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GPA Standard 2174-93

Obtaining Liquid Hydrocarbon


Samples for Analysis by
Gas Chromatography

Adopted as Tentative Standard, 1974


Adopted as a Standard, 1979
Revised 1983, 1993
Reprinted 1996, 1997, 1998, 2000

Gas Processors Association


6526 East 60th Street
Tulsa, Oklahoma 74145
DISCLAIMER

GPA publications necessarily address problems of a general nature and may be used by anyone desiring to
do so. Every effort has been made by GPA to assure accuracy and reliability of the information contained in
its publications. With respect to particular circumstances, local, state, and federal laws and regulations
should be reviewed. It is not the intent of GPA to assume the duties of employers, manufacturers, or
suppliers to warn and properly train employees, or others exposed, concerning health and safety risks or
precautions.

GPA makes no representation, warranty, or guarantee in connection with this publication and hereby
expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the
violation of any federal, state, or municipal regulation with which this publication may conflict, or for any
infringement of letters of patent regarding apparatus, equipment, or method so covered.

FOREWORD

This 1993 revision of GPA Publication 2174 is based on the original 2174 publication, first published in
1974 and revised in 1983. It has been expanded and revised to include additional natural gas liquidi
sampling procedures. These changes are primarily the result of a cooperative analytical study directed by a
Gas Processors Association work group through Technical Committee Section B. Testing was performed on
eight (8) potential sampling methods. Ten laboratories and eighteen volunteers were eventually involved in
gathering 320 samples that covered over 7,000 data points. Criteria for an acceptable sampling method
required that it demonstrated minimal variability, was representative of the source, and was user friendly.
Details of the project addressed experimental design, sample collection, logic of the evaluation process, and
statistical analysis; final conclusions were presented in the Proceedings of the Gas Processors Association's
67th Annual Convention, March 1988, in Dallas, Texas.

Sampling methods found to be acceptable from the chromatographic analysis of the 10 common components
of the natural gas liquids and which are covered in the work group report are:
1. Floating Piston Cylinder (original GPA Standard 2174)

2. Water Displacement (total H 2 0 removal - 80% replaced by hydrocarbons; 20% displaced for outage)

3. Water Displacement (partial H 2 0 removal - 70% replaced by hydrocarbons; 20% displaced for
outage; 10% remaining in cylinder)

4. Ethylene Glycol Displacement (total glycol removal - 80% replaced by hydrocarbons; 20% displaced
for outage)

Proper samples can be obtained when using any of the four methods listed, provided a strict adherence to
detail is maintained. It is recommended that the potential users of these methods study the work group
report prior to selection of an applicable method.
OBTAINING LIQUID HYDROCARBON SAMPLES FOR ANALYSIS BY GAS
CHROMATOGRAPHY
1. SCOPE at the bottom. It is strongly recommended that the samples be
obtained under the supervision of a person knowledgeable in the
1.1 The specific purpose of this method is to describe the phase behavior of hydrocarbon systems and experienced in all
equipment and procedures for obtaining representative samples sampling operations.
of natural gas liquids and the subsequent preparation of those
samples for laboratory analysis by gas chromatography. The 3.4 The scope of this m e t h o d does not include
procedures described in this method may be used for obtaining recommendations for the location of the sampling point in a line
samples for analysis by methods other than gas chromatography. or vessel, although the importance of the proper sampling
A S A M P L E PROBE MUST BE USED TO O B T A I N A location cannot be overemphasized.
REPRESENTATIVE SAMPLE.
3.5 A certain amount of information about a sample is
2. OUTLINE OF METHODS necessary before it can be intelligently handled in the laboratory.
Essential information includes the sample source, sample date,
2.1 A hydrocarbon fluid sample is transferred under cylinder identification, sample source pressure and temperature,
pressure from a source into a sample container by one of the ambient temperature, type of analysis required, and the sampling
following methods: method used. There may be additional related facts such as
field-determined results and operating conditions which will
a. Floating Piston Cylinder Method assist in the evaluation of the analytical data. This information
must accompany the filled sample cylinder.
b. Water Displacement Method 1 (total H20 removal - 80%
replaced by hydrocarbons; 20% displaced for outage) 3.6 If the hydrocarbon fluid samples are to be transported by
common carrier within the United States, the sample containers
c. Water Displacement Method 2 (partial H20 removal - must meet the specifications of and be labeled and packaged
70% replaced by hydrocarbons; 20% displaced for outage; 10% according to the Hazardous Materials Regulations of the
remaining in cylinder) Department of Transportation.

d. Ethylene Glycol Displacement Method (total glycol 3.7 This method assumes all procedures begin with clean,
removal - 80% replaced by hydrocarbons; 20% displaced for leak-free sample cylinders. Cylinders must be thoroughly
outage) cleaned prior to sampling with an appropriate volatile solvent or
by following manufacturers' recommendations. The use of
NOTE 1: Methods b, c, and d may not be applicable to the analysis detergent/water solutions or steam is not recommended for the
of certain samples containing reactive non-hydrocarbons such as sulfur cleaning of floating piston cylinders.
compounds, carbon dioxide, etc.
3.8 For floating piston cylinders, it is desirable in most
3. GENERAL INFORMATION cases to use an "inert" charge gas for the piston cylinder which
is not present in the sample so that a leak in the cylinder itself
3.1 The objective of any sampling operation is to secure, in can be easily detected during the analysis. The use of natural
a suitable container, an adequate portion of a hydrocarbon fluid gas as a back pressure fluid is not recommended because a leak
under pressure, having the same composition as the stream being across the piston may result in compromising the sample with
sampled. hydrocarbons (or other components) which were not actually
present at the source. A method to insure a leak-free cylinder is
3.2 Particular emphasis should be given to the necessity of to pressure test both sides of the piston cylinder. This is
obtaining accurate, representative samples for analysis since accomplished by pressurizing the displacement chamber with
analyses, regardless of the care and accuracy of the laboratory inert gas to a typical operating pressure with valve C opened
tests, may be useless if the samples are not valid. (see Fig. 1). Next, close valves C and D and note the pressure
reading on gauge N. After a period of five minutes, a decrease
3.3 It is not possible, nor is it the intent of this method, to in pressure as indicated at gauge N and a corresponding increase
provide a procedure that will be applicable for all sampling in pressure at gauge M would indicate a leak across the piston.
situations. The sample source here is a s s u m e d to be a A pressure drop only at gauge N indicates a leaky fitting, valve,
homogeneous, single-phase liquid. All samples must be gauge, or rupture disc. The inert gas should be removed from
obtained using a probe designed to secure product from the the displacement end and the above procedure repeated for the
center one-third of the flowing stream. The location of the sample side. It is also possible to analyze the inert gas side of
probe fitting should be on the top or side of the line rather than
El

SAMPLE
SOURCE
A

FITTING
PROBE

R1

SAMPLE

PISTON

INERT GA~

INDICATOR

Figure 1. Typical Visual Indicator Sampling System

the cylinder to determine hydrocarbon concentration if leakage design) may prevent the flashed product from returning to the
occurs in that direction. Cylinders should be tested at least on an original homogeneous mixture.
annual basis.
3.10 Duplicate Samples
3.9 Care must be exercised when sampling liquids having a
vapor pressure higher than atmospheric pressure to prevent 3.10.1 When resampling is difficult or impossible, it is
flashing of lighter components when transferring product from advisable to take duplicate samples as a precaution against
the source to a sample cylinder, or from a primary sample accidental loss. These duplicate samples must be taken using
cylinder to a secondary cylinder. For floating piston cylinders, the same sampling method and from the same sampling location.
precautions should also be taken to ensure that the inert gas The sample sequence should be noted on the sample information
pressure in the piston cylinder never drops below the sampling tag.
pressure or the product's vapor pressure at the existing source
temperature, thus p r e v e n t i n g flashing of the sample. 4. APPARATUS
Theoretically, the product in the vapor state could be returned to
liquid phase, but the physical restrictions of the piston cylinder 4.1 Sample Containers
(e.g., rupture disc, valve dead space, and stirring assembly

4
4.1.1 Floating Piston Cylinders
4.1.1.6 Other types of floating piston cylinders are available
4.1.1.1 The container required for this method is constructed which have no visual method of determining the sample volume
of metal tubing, honed and polished on the inside surface. The directly. For these cylinders, a displacement cylinder, cylinder
cylinder is preferably closed with removable end caps to provide Y (Fig. 2), is fabricated from metal tubing. This cylinder must
access to remove and service the moving piston. The end caps be designed to meet the same pressure requirements as the piston
are drilled and tapped for valves, gauges, and relief valves. The cylinder and have a volume of no more than 80 percent of the
cylinder is designed consistent with the maximum pressure pressurizing volume of the piston cylinder.
anticipated during sampling and to be nonreactive to materials
being sampled, the pressurizing fluid, the cleaning solvents and 4.1.2 Double Valve Cylinders
the expected corrodants. The volume of the cylinder will
depend on the amount of sample needed for the laboratory 4.1.2.1 Metal sample containers of a type which insure
analysis. maximum safety and which are corrosion resistant to the product
being sampled should be used. Stainless steel containers are
4.1.1.2 The cylinder itself contains a moving piston recommended to minimize problems of surface adsorption of
equipped with o-rings, teflon rings, or other devices to effect a heavy components (hexanes and heavier components) and to
leak-free seal between the sample and the pressurizing fluid minimize the reaction of carbon dioxide or other contaminants
while allowing it to move freely within the cylinder. The use of with the container. Sample containers and valves must have a
guide rings is recommended to assure smooth piston travel. The working pressure equal to or exceeding the maximum pressure
piston and sealing device must be non-reactive to the sample, the anticipated in sampling, storage, or lransportation of the sample
pressurizing fluid, the cleaning solvents, and expected container. Soft-seated valves are preferable to those having
corrodants. metal-to-metal seats. The size of the container depends upon the
amount of sample required for the laboratory tests to be
CAUTION: Some types of lubricating fluids will absorb performed.
appreciable amounts of the C6+ fraction from the gas being
sampled, thus compromising the integrity of the sample. It is N O T E 2: DOT regulations regarding the use of pressure relief
recommended that non-absorbing lubricating greases, such as, devices on these cylindersmust be followed.
but not limited to DuPont's KrytoxAC or AD, be used to prevent
4.2 Sample Transfer System
this difficulty. Further details regarding non-absorbing
lubricating greases can be obtained from the piston cylinder
4.2.1 Transfer lines, valves, and gauges in the transfer
manufacturers.
system shall be designed consistent with maximum anticipated
pressure and be resistant to all expected corrodants. (Stainless
4.1.1.3 All valves and safety devices must meet the
steel is preferred.) The transfer lines should have a minimum
appropriate material and pressure requirements for safe design.
diameter of 1/4 inch (6.35 mm) and be as short as is practical.
The pressure reliefs may be of spring or rupture disc types.
These allow a partial or complete loss of contents due to thermal The use of filters and dryers is discouraged.
expansion or over-pressurization. Should relieving occur, the
4.3 Composite Sampling Mechanism
sample should be considered compromised.
4.3.1 A composite sampling mechanism is a device which is
4.1.1.4 Some piston-type cylinders are fabricated from non-
used to obtain a representative sample from a flowing product
magnetic materials such as the 300 series stainless steel. The
stream over a given period of time. The unit consists of a
piston likewise is fabricated of stainless steel but has magnets
sample probe, either a flow-through sample injection valve,
attached to the precharge side of the piston. As the piston moves
whether automatic or manual (see Figures 3 and 4) or a probe-
the length of the cylinder, the magnetic field generated by the
mounted sample pump (Fig. 5) and utilizes a floating piston
magnets flips a series of bi-colored flags. This system, or
cylinder as its collection chamber. The system must include a
systems of similar configuration, indicates the piston position
method to mix the product sample in the collection chamber.
and the volume of product in the cylinder.
This is necessary regardless of whether the original floating
piston cylinder is removed and used for laboratory analysis or a
4.1.1.5 Some piston-type cylinders are fabricated with a rod
transfer of the product sample is made into a secondary cylinder
attached to the piston which extends through the end cap on the
as described herein. (Figure 6 depicts a typical automatic
inert gas back pressure chamber with appropriate sealing devices
sampler and the various parts required. Figure 5 depicts a
to prevent the inert gas from leaking. The Iraveling rod provides
typical proportional sampler using an injection pump and the
an indication of the piston position and the volume of the
various parts required.)
i product sample in the cylinder. Again, some variations of this
style may exist.
L B
SAMPLE
SOURCE

R I ~ M

I 1

PISTON--~ CYLI~D
IN EROAST .;, o o
SAMPLE
ER
I

R2 ....

-t
-t
t

AIR
(ATMOSPHERIC
CY:DER
PRESSURE)
I

Figure 2. DisplacementCylinder Sampling System


4.4 Sample Filters 5. SAMPLING PROCEDURES

4.4.1 The sample filter is an optional device used to protect 5.1 Floating Piston Cylinder Method
the sampling valve from scoring due to the presence of foreign
contaminants such as metal shavings, dirt, etc., in a NGL 5.1.1 Technique of using a cylinder equipped with visual
sample. The filter should be of a small total volume, of an indicator for liquid phase samples of "spot" or "instantaneous"
inline-type design, and contain a replaceable/disposable element. type (see Figure 1)

CAUTION: A filter may introduce error if not handled 5.1.1.1 With sample side of cylinder evacuated (from
properly. The filter should be clean and free of any residual cleaning operation) and valve C open, fill displacement end with
product from previous samples so that a buildup of heavy-end inert gas to a pressure at least 10 psi (69 kPa) above sampling
hydrocarbon components does not result. (This may be pressure. Close valve D.
accomplished by a heating~cooling process or inert gas purge, A

etc.) The filter element should be 15 micron size or larger so 5.1.1.2 Open valve A at sample source and thoroughly blowl
that during the purging process NGL is not flashed, causing out any accumulated material. Close valve A at sample source, v
fractionation and bubble formation.

6
iI ~ FLOW THROUGH
ONVALVESAMPLE -- FLOW THROUGH
INJECTI ONV.N.VESAMPLE
INJECTI
~~u
i~~~ T0
114" TO i/2"
TUBING 1/'4" ~/2"
tUBING

UP (5 TO 10 PSi Z~P)

[_ o,,,~,~ ~--t \7
---q
---"-÷-i
PROBE STREAMSAMPLEJ
PROBE

Figure 3. Typical Sample Probe Installation Figure 4. Typical Sample Probe Installation
on Orifice Flange for a Pump

5.1.1.3 Connect piston cylinder to sampling source at 5.1.1.8 Close valves D, C, and A in that order. Open valve
valve A. B to release pressure on the sample line. Disconnect the
cylinder from sample source.
5.1.1.4 With valves B and C closed, open source valve A to
full open position. Observe sample pressure on gauge L. Crack 5.1.1.9 Do not take outage or reduce pressure on piston
valve B and fitting at valve C to purge line. Do not allow cylinder. Check valves C and D for leaks, cap valves to protect
pressure L to drop below original sample pressure. Discontinue threads, p r e p a r e s a m p l e i n f o r m a t i o n tag and box for
purging after a sufficient time and only when liquid product is transportation as per Department of Transportation or applicable
present. If the product flashes without leaving a liquid residue at requirements.
valve B and the fitting at valve C, the operator must use
judgment in determining when to discontinue purging. Close 5.1.2 Technique of using cylinder not equipped with visual
valve B and tighten fitting at valve C. indicator for liquid phase samples, via displacement cylinder, of
"spot" or "instantaneous" type (see Figure 2)
NOTE 3: If the diameter of the indicator rod is of significant size
compared to the piston, then the pressure on the inert gas side will be 5.1.2.1 With sample side of the piston cylinder evacuated
slightly higher than the sample side, i.e., gauge N will read higher than
gauges L and M. This comment applies to all subsequent comments (from cleaning operation) and valve C open, fill displacement
regarding equal pressures on gauges L, M and N. end with inert gas to a pressure at least 10 psi (69 kPa) above
sampling pressure. Close valve D.
5.1.1.5 Adjust pressure on gauge N to equal pressure L by
releasing adequate inert gas through valve D. 5.1.2.2 Open valve A at sample source and thoroughly blow
out any accumulated material. Close valve A at sample source.
5.1.1.6 With v a l v e D c l o s e d , s l o w l y open v a l v e C
completely. There should be no pressure change on gauge N 5.1.2.3 Connect piston cylinder X to sample source at valve
and pressure at gauges L, M and N should all be equal. A and displacement cylinder Y to piston cylinder. Displacement
cylinder Y should be filled with air at atmospheric pressure. For
5.1.1.7 Partially open valve D, slowly allowing inert gas to proper cylinder sizing refer to Section 4.1.1.6.
vent to the atmosphere. To prevent flashing, do not allow
pressure M to drop below sampling pressure. Continue the 5.1.2.4 With valves B and C closed, open sample source
operation until the indicator designates the cylinder contains valve A to full open position. Observe sample source pressure
80% by v o l u m e o f p r o d u c t ( f o l l o w i n g m a n u f a c t u r e r ' s on gauge L. Crack valve B and fitting at valve C to purge line.
instructions). Do not allow pressure L to drop below original sample pressure.

7
Product Minimum
flow 5 Diameters
meter ---Center-stream
sample probe

/11

I
I
"X" pulse per
bbl (ppb) fi
Pressure ~ Probe mounted sample
i supply injection pump

Meter Sol. [ ~ / / /
totalizer
//
i
i //
f 1 ppb
i
I
1/4" to 1/2"
Pulse tubing
divider
circuit
....... Optional .......
1 pulse per
"X" bbls.

AC . . . . . . . . . Power
Power interposer
t e:::v:ve-k G
f
I ! [ ~ Pressure
recorder
Mixing L . . . . . . . . . . . . . . . . . . . . . . . . J
device
Inert gas
Pressure C~
regulator
Sample

I
Check valve
Pressure
supply Sample transfer tap

Bleed valve

Figure 5. Typical Proportional Sampler Using an Injection Pump

8
PRODUCT ORIFICE
FLOW METER FLANGE

iiil,. - -

"~ PPB ~__ STREAM


SAMPLE PROBE
METER
TOTALIZER
FILTER
I

I PPB
FLOW-THRU
PULSE SAMPLE

PULSE PER
DIVIDER
CIRCUIT
I
I [

I
INJECTION VALVE

I
BBLS.
AC
I

I-'
POWER POWER
-- --IIID-
.--I
INTERPOSER

INERT GAS o O °oO o

PISTON

SAMPLE

SAMPLE
TRANSFER TAP

(---I ~ BLEED VALVE


PRESSURE
SUPPLY
SAMPLE MIXING DEVICE

Figure 6. Typical Automatic Proportional Sampler


Discontinue purging after a sufficient time and only when liquid 5.1.3.4 All samples must be obtained using a probe. (Refer
product is present. If the product flashes without leaving a to Section 3.3 for specifications and location.) A bypass device
liquid residue at valve B and the fitting at valve C, the operator that causes a differential pressure, such as an orifice plate e
must use judgment in determining when to discontinue purging. small pump, is used to supply fresh liquid to a location
Close valve B and tighten fitting at valve C. filling the sample container, either manually or by use of sample
injection valves. The bypass sample line utilizes short lines of a
5.1.2.5 With valve E closed, open valve D and observe small diameter connecting the fresh sample source to the
pressure on gauge N. Adjust pressure N to equal pressure L by floating piston cylinder receiver (see Figures 3 and 4).
slowly venting inert gas through valve E. Close valve E.
5.1.3.5 The floating piston cylinder should be connected to
5.1.2.6 With valve E closed, slowly open valve C to full the purged sample line via the composite sampling device. Inert
open position. There should be no pressure change indicated on gas pressure or appropriate pressurizing fluid should be applied
gauge N and pressure at gauges L, M and N should all be equal. to the cylinder to force the piston to the starting end of the
sampling cylinder. The inert gas pressure should be maintained
5.1.2.7 Close valve D. Open valve E and properly vent at a pressure which exceeds by 200 psi (1379 kPa) the
pressure through valve F. Close valve F. equilibrium vapor pressure of the fluid sampled under expected
varying temperature conditions. At pressure differences less
5.1.2.8 Slowly open valve D, allowing inert gas from than 200 psi (1379 kPa) the chance for erroneous samples
cylinder X to flow into cylinder Y. Observe gauge M so as not increases.
to allow pressure M to drop. Continue operation until pressure
of all three gauges equalizes. At this point, a volume equal to 5.1.3.6 The automatic sample injection valves will require
cylinder Y has been displaced into cylinder X by the product adjusting to obtain incremental samples at a rate such that the
sample. Sample cylinder X now contains 80% by volume of floating piston cylinder will have adequate capacity to hold the
sample, leaving sufficient inert gas space to insure safe storage sample during its period of sampling. Care should be exercised
and transport. to prevent overfilling of the sample container so that relieving
does not occur, thus changing the composition of the sample and
5.1.2.9 Close valves D, C, and A in that order. Open valves creating a serious safety hazard.
B and F. Disconnect displacement cylinder Y. Disconnect
piston cylinder X from sample source. 5.1.3.7 Increasing or decreasing the volume of sam
desired can be accomplished by changing the volume of the
5.1.2.10 Do not take outage or reduce pressure on piston incremental sample obtained with the injection valve and/or by
cylinder X. Check valves C and D for leaks, cap valves to changing the frequency of the proportioning device which
protect threads, and prepare sample information tag and box for controls the injection valve.
transport as per Department of Transportation or applicable
requirements. 5.1.3.8 The sample obtained by the sampler apparatus and
stored in the floating piston cylinder must be mixed thoroughly
5.1.3 Technique of using floating piston cylinders for liquid by either a mechanical device or a liquid pump and circulating
phase samples of "composite" type via manual or automatic system.
systems (see Figures 5 and 6)
5.1.3.9 The floating piston cylinder used in the above
5.1.3.1 Automatic proportional samplers take small samples system may be removed from the composite sampling device
of the flowing stream proportional to the flow rate. Time after the desired product has been sampled.
increments may be used only when the flow rate is constant.
CAUTION: Under no circumstances should the cylinder be
5.1.3.2 Thorough purging of sample lines, pumps and filled beyond 80% of its capacity with sample.
connections to the sample cylinder is necessary to avoid
contamination of the sample. Sampler systems should be 5.1.3.10 Do not take outage or reduce pressure on the
designed to minimize stagnant areas which could result in the cylinder. Check valves for leaks, cap valves to protect threads,
sample not being representative of the fluid source. and prepare sample information tag and box for transport as per
Department of Transportation or applicable requirements.
5.1.3.3 Precautions shall be taken to avoid vaporization in
sample loop lines when operating near the equilibrium pressure 5.1.3.11 If it is not possible to disconnect the primary
of the liquid. In some instances, it may be necessary to insulate floating piston cylinder from the automatic system, the sample
the sample line and sample container, or control the pressure or may be transferred to a secondary floating piston cylinder. Once
temperature of sample containers containing volatile materials. the sample in the primary cylinder is adequately mixed, proceed

10
as in step 5.1.1, treating the primary cylinder as a flowing Ethylene glycol must be the glycol type used. Water must have
~ source. (In this particular transfer situation, as sample is
withdrawn, the master sample container will partially
a pH between 5.0 and 7.0. Water with a pH greater than 7.0
must be acidified to bring the pH within the proper range. (0.1
depressurize. The product vapor pressure at the existing master N H2SO4 is a satisfactory acid solution.)
sampler temperature must be maintained or exceeded to prevent
flashing.) 5.2.2 The total volume of the sample cylinder must be
found, then 80% of the total volume should be calculated. (For
5.2 Water Displacement and Ethylene Glycol Displacement example, if the total volume of the cylinder is 500 ml, then 80%
Methods - Total displacement of the total volume is 400 ml.)

5.2.1 A double valve sample cylinder filled with clean 5.2.3 Open valve A at sample source and thoroughly blow
ethylene glycol or water and a vessel to measure the displaced out any accumulated material. Close valve A at sample source.
liquid are required for these two methods (see Figure 7).

L~

SAMPLE
SOURCE
A
FII-rlNG
PROBE

R1

SAMPLE
CYLINDER

\
ORADUATED
CYLINDER

Figure 7. Liquid Displacement Sampling

11
5.2.4 Connect the sample cylinder to sampling source at 5.3.3 Open valve A at sample source and thoroughly blow
valve A exactly as shown in Figure 7. out any accumulated material. Close valve A at sample source.

5.2.5 With valves B, C, and D closed, open sample source 5.3.4 Connect the sample cylinder to sampling source
valve A to full open position. Observe sample pressure on valve A exactly as shown in Figure 7.
gauge L. Crack valve B and fitting at valve C to purge line. Do
not allow pressure L to drop below original sample pressure. 5.3.5 With valves B, C, and D closed, open sample source
Discontinue purging after a sufficient time and only when liquid valve A to full open position. Observe sample pressure on
product is present. If the product flashes without leaving a gauge L. Crack valve B and fitting at valve C to purge line. Do
liquid residue at valve B and the fitting at valve C, the operator not allow pressure L to drop below original sample pressure.
must use his judgement in determining when to discontinue Discontinue purging after a sufficient time and only when liquid
purging. Close valve B and tighten fitting at valve C. product is present. If the product flashes without leaving a
liquid residue at valve B and the fitting at valve C, the operator
5.2.6 With valve D still closed, slowly open valve C to full must use his judgement in determining when to discontinue
open position. Pressure at gauges L and M should be equal. purging. Close valve B and tighten fitting at valve C.

5.2.7 Slowly open valve D to allow a slow discharge of the 5.3.6 With valve D still closed, slowly open valve C to full
glycol or water displacement liquid into the measuring vessel. open position. Pressure at gauges L and M should be equal.
To prevent flashing, do not allow pressure M to drop below
sampling pressure. Continue operation until 80% by volume of 5.3.7 Slowly open valve D to allow a slow discharge of the
the displacement liquid has been displaced by product in the water into the measuring vessel. To prevent flashing, do not
sample cylinder. allow pressure M to drop below sampling pressure. Continue
operation until 70% by volume of water has been displaced by
5.2.8 Close valves D, C and A in that order. Open valve B product in the sample cylinder.
to release pressure on sample line.
5.3.8 Close valves D, C, and A in that order. Open valve B
5.2.9 With sample cylinder still attached to source valve A, to release pressure on sample line.
slowly open valve D to drain the remaining 20% displacement
liquid from the sample cylinder. After 15 ml has been 5.3.9 With sample cylinder still attached to source valve
withdrawn, the operator should reduce the drain rate and slowly open valve D to drain another 20% of the water from the
carefully extract the remaining water or glycol. (The sample cylinder. (At this point, 10% of the water still remains in
displacement liquid may become cloudy just prior to the end the sample cylinder.) Disconnect sample cylinder from sample
point, although the effect is less noticeable with glycol.) At this source.
time, reduce the rate to 10 ml/min maximum. When the first
indication of product appears, usually a flashing bubble, close 5.3.10 Check valves C and D for leaks, cap valves to protect
valve D immediately with no further loss of product. threads, prepare sample information tag and box for
Disconnect cylinder from sample source. transportation as per Department of Transportation or applicable
requirements.
5.2.10 Check valves C and D for leaks, cap valves to protect
threads, prepare sample information tag and box for 6. LIQUID PHASE LABORATORY HANDLING AND
transportation as per Department of Transportation or applicable PREPARATION
requirements.
6.1 Recommended Procedures for Liquid Phase Samples
5.3 Water Displacement Method - Partial Displacement Prior to Injection of the Sample into the Test Device

5.3.1 A double valve sample cylinder filled with clean water 6.1.1 Floating Piston Cylinders
and a vessel to measure the displaced liquid are required for this
method (see Figure 7). The water used must meet the same 6.1.1.1 For floating piston cylinders refer to Figure 8 and
requirements as in 5.2.1. proceed as follows: Connect a source of inert gas to valve A so
that pressure may be applied to the sample via the floating
5.3.2 The total volume of the sample cylinder must be piston. Apply a pressure not less than 200 psi (1379 kPa) above
found; then 70% and 20% of the total volume should be the vapor pressure of the sample at the temperature of the
calculated. (For example, if the total volume of the cylinder is sample injection valve by opening the valve on the inert gas
500 ml, then 70% of the total volume is 350 ml and 20% is 100 source and valve A. The inert gas pressure is to be maintained
ml.)

42
on the sample container at all times during the analysis via a CAUTION: Extreme care must be used to ensure that no
precharge regulator or similar device. flashing of sample occurs in the inlet sampling line and valve
system. Any measurements should be taken at sample purge
6.1.1.2 The sample should be thoroughly mixed per the valve C, never at sample valve B. The sample line and valve
cylinder manufacturer's recommendations, whether it be by system should remain at 200 psi (1379 kPa) above the vapor
"mixing dasher", "mixing ball" or equivalent, immediately prior pressure of the product.
to each analysis.
6.1.1.6 Operate the liquid sample valve either manually or
6.1.1.3 Connect the sample end of the cylinder, valve B, to automatically to inject the liquid sample into the carrier gas flow
the inlet of the chromatograph liquid sample valve. All immediately ahead of the chromatographic column. The sample
connections and tubing are to be made of material impervious to injection valve should be actuated quickly and smoothly to place
the sample composition with the smallest diameter and shortest the sample onto the column all at once and to ensure continuous
length of plumbing practical, thereby minimizing "dead space". carrier gas flow through the column.
All tubing between the sample cylinder and liquid sample valve
should be the same diameter. 6.1.1.7 When sample injection is complete, close valves B
and A in that order, then close valve on inert gas source. Slowly
6.1.1.4 With valve C closed, open valve B to fill the sample open valve C and vent any remaining unused sample in the
valve and associated lines. system through an appropriate vent.

6.1.1.5 Slowly crack valve C to purge the sample valve and 6.1.1.8 Disconnect the cylinder from the inlet of the
associated lines. Be sure sufficient volume is displaced to purge chromatograph liquid sample valve and the inert gas source.
unmixed areas in the sample cylinder as wellas the sample
injection system. When the purge is complete, close valve C. 6.1.1.9 If the sample is to be reused, do not take an outage

CARRIER CARRIERGAS
GAS I I TO COLUMN

H
LCI~RICDMv~STL~M~P
LP~IP~ /
FLOATINGPISTON
PRESSURE I-I 1
REGULATOR CYLINDER II o ° o. CYLINDER ~ NEEDLE
~ A L V E ~ L"~:
~,Oo.O oo
° Oo -IIII IIIIIII Ij~ OO,LE, II
INERT /o * o * u III I i
GAS @

RELIEF
VALVE
INERT--!
GAS
""i''
~1° ,l*°** - 1111111 I %

NGL RELIEF
VALVE
®

Figure 8. RepressuringSystemand ChromatographValving with Floating Piston

13
or reduce pressure on the piston cylinder. Check valves for pressure of the hydrocarbon sample at operating conditions.
leaks, cap valves to protect threads, and store the cylinder in a Open valves B and C to admit pressurizing fluid into sample
suitable location. cylinder Y.

6.1.2 Double Valve Cylinders 6.1.2.2 Mix the sample thoroughly by gently inverting
cylinder Y several times. Fix cylinder Y in a vertical position by
6.1.2.1 For double valve displacement cylinders, refer to means of a ringstand or similar device. Allow it to remain
Figure 9 and proceed as follows: Connect the sample cylinder Y immobile in the vertical position at least 2 minutes before
to cylinder X so pressurizing fluid can enter into the bottom of injection of sample into the chromatograph.
cylinder Y. (The pressurizing fluid should be same type used to
secure the product.) With this configuration the hydrocarbon 6.1.2.3 Connect the sample outlet valve D on cylinder Y to
sample will be taken from the upper portion of the cylinder. the inlet of the chromatograph liquid sample valve. All
Open valve A and pressurize cylinder X with inert gas. connections and tubing are to be made of material impervious to
Maintain a pressure at least 200 psi (1379 kPa) above the vapor the sample composition, utilizing the smallest diameter and

~CHROMATOGRAPH
VENT VALVE
PRESSURE
REGULATOR
© LIQUIDv ALS~VEPLING

I
oi I--]
I i
r 1
TO COLUMN

I
CYLINDER "X" CYLINDER "Y"

- - NGL - -
o GAS ° ! _ LAYER- -
oo o o ° o o i
o oo i
... " .o ." .. .".l i : ...'.." - ".:
• GLYCOL : ! "" GLYCI3L" :
• OR . ~ ' " ~ - OR ""
: WATER "

®I ®
Figure 9. Repressuring System and Chromatograph Valving with Double Valve Displacement Cylinder

14
shortest length of plumbing practical, thereby minimizing "dead 6.1.2.10 Check the valves for leaks, then cap valves to
B space". All tubing between the sample cylinder and liquid protect the threads and store the cylinder in a suitable location.
sample valve should be the same diameter.
7. SAFETY PRECAUTIONS
6.1.2.4 With valve E closed, open valve D to fill the sample
valve and associated lines. 7.1 Sampling hydrocarbon fluids can be hazardous. Persons
responsible for obtaining samples should be familiar with and
6.I.2.5 Slowly crack valve E to purge the sample valve. adhere to safe practices for handling flammable fluids under
When the purge is complete close valve E. pressure.

CAUTION: Extreme care must be used to ensure that no 7.2 In all cases, a 20% (or more) inert gas charge should be
flashing of sample occurs in the inlet sampling line and valve present in all floating piston cylinders and a minimum of 20%
system. Any measurements should be taken at sample purge displacement fluid outage in all double valve sample cylinders.
valve E, never at sample valve D. The sample line and valve
system should remain at 200 psi (1379 kPa) above the vapor 7.3 Disassembly of the Piston Cylinder
pressure of the product.
C A U T I O N : Disassembly of the piston cylinder for
6.1.2.6 Operate the liquid sample valve either manually or maintenance requires special precautions. If either end cap is
automatically to inject the liquid sample into the carrier gas flow removed while pressure is on the cylinder, the end caps and the
immediately ahead of the chromatographic column. The liquid piston can be ejected with such a force as to cause serious inju~.
sample valve should be actuated quickly and smoothly to place to personnel and damage to adjacent equipment.
the sample onto the column all at once and to ensure continuous
carrier gas flow through the column. 7.3.1 Clamp the piston cylinder firmly to a steady work
surface. Caution should be taken not to dent or bend the
6.1.2.7 When sample injection is complete, close valves D cylinder by applying excessive pressure.
and C on cylinder Y and valves B and A on cylinder X, in that
~ order, then close the valve on the inert gas source. Slowly open 7.3.2 Using a suitable venting apparatus (e.g. vent hood),
valve E and vent any remaining unused sample in the system properly vent both ends of the cylinder before attempting to
through an appropriate vent. (If the sample is to be reused remove either end cap.
immediately, do not take an outage or reduce pressure on the
sample cylinder. If the sample is not to be reused immediately, 7.3.3 The work surface at either end of the cylinder should
proceed to next step, 6.1.2.8.) be clear before the end plug is loosened.

6.1.2.8 Disconnect cylinder Y from the inlet of the 7.3.4 Provide a mechanical plunger to dislodge the piston
chromatograph liquid sample valve and disconnect from from the cylinders, provided the plunger is of suitable material
cylinder X. Disconnect Cylinder X from the inert gas source. as to not scratch the cylinder bore. Do not use fluid pressure to.
dislodge the piston.
6.1.2.9 With cylinder Y remaining in the upright position,
remove 20% by volume of the pressurizing fluid for outage. NOTE 4: For reproducible sample volume limits see GPA
publication 2177.
This is accomplished by slowly opening valve C to allow a slow
discharge of the pressurizing fluid into a measuring vessel.

15

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