Part l--Discussion of Analyses

by Product Type
Analysis of Cs and Lighter
Hydrocarbons
by Neil G. Johansen
INTRODUCTION
THE LIGHTHYDROCARBONS--methane (C~), ethane (C2), pro-
pane (Ca), and the butanes (C4), either in the gas phase or
liquefied, are primarily used for heating, motor fuels, and as
feedstocks for chemical processing. The pentanes/pentenes
(C5) are products of natural gas or petroleum fractionation or
refinery operations (i.e., reforming and cracking) that are
removed for use as chemical feedstocks. The olefins--ethene
(ethylene), propene (propylene), butenes (butene-1, isobutyl-
ene, cis- and trans-butene-2, and the butadienes), pentenes,
and pentadienes are materials produced by various refining
processes involving the use of the saturated hydrocarbons as
feedstocks.
Mixtures of these hydrocarbons are commonly encoun-
tered in material testing, and the composition varies depend-
ing upon the source and intended use of the material. Other
non-hydrocarbon constituents of these mixtures are impor-
tant analytes since they may be useful products or may be
undesirable as a source of processing problems. Some of
these components are helium, hydrogen, argon, oxygen, ni-
trogen, carbon monoxide, carbon dioxide, sulfur, and nitro-
gen containing compounds, as well as heavier hydrocarbons.
Desired testing of these hydrocarbon mixtures usually in-
volves the determination of bulk physical or chemical proper-
ties and component speciation and quantitation.
ASTM addresses the characterization and specification of
the C~ to C5 hydrocarbon materials and products through
several venues. Committee D03 is responsible for gaseous
fuels; Committee D02, Subcommittee H is responsible for
liquefied petroleum gas; Committee D02, Subcommittee D is
responsible for hydrocarbons for chemical and special uses,
while Committee D02, Subcommittee 4 has responsibility for
test methods involving hydrocarbons in general. Committees
D19 (Water) and D22 (Sampling and Analysis of Atmo-
spheres) address environmental concerns involving light
hydrocarbons.
CURRENT PRACTICES
Sampling
One of the more critical aspects for the analysis of light
hydrocarbons is the question of sampling. Sampling of gas-
eous and liquefied materials is addressed in a variety of
specific sampling methods, and many of the test methods
themselves contain additional sampling requirements. Nota-
15
1
ble among these are ASTM Standard Practices D5287, Auto-
matic Sampling of Gaseous Fuels,1 D5503, Natural Gas Sam-
ple-Handling and Conditioning Systems for Pipeline
Instrumentation, I D1265, Sampling Liquefied Petroleum
(LP) Gases (Manual Method), l and D3700, Containing Hy-
drocarbon Fluid Samples Using a Floating Piston Cylinder?
Sampling of low-pressure materials is described in ASTM
Standard Practices D4057, Manual Sampling of Petroleum
and Petroleum Products/ D4177, Automatic Sampling of
Petroleum and Petroleum Products, ~ and D5842, Sampling
and Handling of Fuels for Volatility Measurement. 1
The preparation of gaseous and liquid blends is described
in ASTM Standard Practices D4051, Preparation of Low-
Pressure Gas Blends, 2 and D4307, Preparation of Liquid
Blends for Use as Analytical Standards. 1
While sampling of C1 and C2 hydrocarbons is typically per-
formed using stainless steel cylinders, either lined or unlined,
other containers are employed dependent upon particular
situations; for example, glass cylinder containers or PVF sam-
pling bags. The preferred method for sampling C a and C4
hydrocarbons is by the use of piston cylinders, ASTM Stan-
dard Practice D3700, although sampling these materials as
gases is also acceptable in many cases. The sampling of C5
and higher hydrocarbons is dependent upon the vapor pres-
sure of the sample. Piston cylinders or pressurized steel cylin-
ders are advisable for high-vapor pressure samples (contain-
ing significant amounts of light gases), while atmospheric
sampling may be used for low-vapor pressure samples.
Analysis
ASTM test methods for gaseous fuels and petroleum prod-
ucts have been developed over many years, extending back
into the 1930s. Bulk physical property tests, such as density
and heating value, as well as some compositional tests, such
as the Orsat analysis and the mercuric nitrate method for the
determination of unsaturation, were widely used. Mass spec-
trometry became the method of choice for compositional
analysis of light hydrocarbons, and ASTM Test Method
D2650, Chemical Composition of Gases by Mass Spectrome-
try/ was standardized in 1967 to replace several older meth-
ods. Currently the mass spectrometry method has been re-
placed, in practice, by gas chromatography as the technique
of choice for fixed gas and hydrocarbon speciation.
1Appears in this publication.
2Annual Book of ASTM Standards, Vol. 05.02.
16 MANUAL ON HYDROCARBON ANALYSIS
Natural and Reformed Gas
ASTM Test Method D1945, Analysis of Natural Gas by Gas
Chromatography, ~and ASTM Practice D 1946, Analysis of Re-
formed Gas by Gas Chromatography, 1 describe procedures
for the determination of hydrogen, helium, oxygen, nitrogen,
carbon monoxide, carbon dioxide, methane, ethene, ethane,
propane, butanes, pentanes, and hexanes-plus in natural and
reformed gases by packed column gas chromatography.
These compositional analyses are used to calculate many
other properties of gases, such as density, heating value, and
compressibility. The first five components listed are deter-
mined using a molecular sieve 13X column (argon carrier
gas), while the remaining components are determined using
polydimethylsiloxane partition or porous polymer columns.
The hexanes-plus analysis is accomplished by backflushing
the column after the elution of pentane or by the use of a
bacldlushed precolumn.
Important constituents of natural gas not accounted for in
these analyses are moisture (water) and hydrogen sulfide, as
well as other sulfur compounds. Water content is determined
by ASTM Test Methods D 1142, Water Vapor Content of Gas-
eous Fuels by Measurement of Dew-Point Temperature, ~
D5454, Water Vapor Content of Gaseous Fuels Using Elec-
tronic Moisture Analyzers, ~ or D4888, Water Vapor in Natu-
ral Gas Using Length-of-Stain Detector Tubes) ASTM Test
Method D5504, Sulfur Compounds in Natural Gas and
Gaseous Fuels by Gas Chromatography and Chem-
iluminescence, I best accomplishes sulfur compound deter-
mination, although ASTM Test Methods D 1988, Mercaptans
in Natural Gas Using Length-of-Stain Detector Tubes, ~ and
D4810, Hydrogen Sulfide in Natural Gas Using Length-of-
Stain Detector Tubes, ~ can also be used with some loss in
accuracy.
Liquefied Petroleum (LP) Gases
Propane, iso-butane, and butane generally constitute this
sample type and are used for heating, motor fuels, and as
chemical feedstocks. ASTM Test Methods D2597, Analysis of
Demethanized Hydrocarbon Liquid Mixtures Containing Ni-
trogen and Carbon Dioxide by Gas Chromatography,l D2163,
Analysis of Liquefied Petroleum (LP) Gases and Propene Con-
centrates by Gas Chromatography, l and D2504, Noncondens-
able Gases in C2 and Lighter Hydrocarbon Products by Gas
Chromatography, ~ are methods for determining light hydro-
carbons and some fixed gases in LP gases. Total sulfur is
determined by ASTM Test Method D2784, Sulfur in Liquefied
Petroleum Gases (Oxy-Hydrogen Burner or Lamp). ) Sulfur
compound determination is made using ASTM Test Method
D5623, Sulfur Compounds in Light Petroleum Liquids by Gas
Chromatography and Sulfur Selective Detection. ~Trace total
organic and bound nitrogen is determined using ASTM
Test Method D4629, Trace Nitrogen in Liquid Petroleum
Hydrocarbons by Syringe/Inlet Oxidative Combustion and
Chemiluminescence Detection.~ The current test method for
heavy residues in LP gases is ASTM Test Method D2158,
Residues in Liquefied Petroleum (LP) Gases, t which involves
evaporation of an LP Gas sample, measuring the volume of
residue and observing the residue for oil stain on a piece of
filter paper.
Light Olefins (C2, C3, C. and C5)
Characteristics and corresponding test methods for these
materials have been outlined in three ASTM standard guides:
D5234, Analysis of Ethylene Product, ~ D5273, Analysis of
Propylene Concentrates, 1 and D5274, Analysis of 1,3-
Butadiene Product. 1 A proposed Guide for the Analysis of
Isoprene is being developed. These guides list properties to be
measured and the range of values expected, as well as appro-
priate test methods where available.
Hydrocarbon analysis of ethene is accomplished using
ASTM Test Methods D2505, Ethylene, Other Hydrocarbons,
and Carbon Dioxide in High-Purity Ethylene by Gas Chroma-
tography, l and ASTM Test Method D6159, Hydrocarbon Im-
purities in Ethylene by Gas Chromatography.l D6159 is a new
test method using wide-bore (0.53-mm) capillary columns,
including a A1203/KCI PLOT column. Currently, ASTM Test
Method D2504 is recommended for determination of non-
condensable gases, and ASTM Test Method D2505 is used for
the determination of carbon dioxide; however, a new method
is under development in ASTM to address these analyses.
ASTM Test Methods D2712, Hydrocarbon Traces in Pro-
pylene Concentrates by Gas Chromatography, 1 and D2163,
also a gas chromatographic method, are currently recom-
mended for the determination of hydrocarbon impurities in
propene. ASTM Test Method D4864, Determination of Traces
of Methanol in Propylene Concentrates by Gas Chromatogra-
phy, l is used for methanol determination. ASTM Test Method
D5303, Trace Carbonyl Sulfide in Propylene by Gas Chroma-
tography, 1 is used for carbonyl sulfide determination with a
flame photometric detector. ASTM Test Method D3246, Sul-
fur in Petroleum Gas by Oxidative Microcoulometry, 1 is cur-
rently recommended for the determination of total sulfur,
and the method is being revised to be more generally applica-
ble to light hydrocarbon analysis.
Commercial butylenes, high-purity butylenes, and butane-
butylene mixtures are analyzed for hydrocarbon constituents
by ASTM Test Method D4424, Butylene Analysis by Gas
Chromatography) Hydrocarbon impurities in 1,3-butadiene
are determined by ASTM Test Method D2593, Butadiene Pu-
rity and Hydrocarbon Impurities by Gas Chromatography)
Butadiene dimer and styrene are determined in butadiene
using ASTM Test Method D2426, Butadiene Dimer and Sty-
rene in Butadiene Concentrates by Gas Chromatography)
Carbonyls in C4 hydrocarbons are determined by a titrimetric
technique using ASTM Test Method D4423, Determination of
Carbonyls in C4 Hydrocarbons. ~ ASTM Test Method D5799,
Determination of Peroxides in Butadiene, t is used for perox-
ide determination.
FUTURE TRENDS
In general, gas chromatography will undoubtedly continue
to be the method of choice for characterization of light hydro-
carbon materials. New developments in higher-speed tech-
niques for gas chromatographic instrumentation and data
processing will lead to new and revised test methods. New
and improved detection devices and techniques, such as
chemiluminescence, atomic emission, and mass spectros-
copy, will enhance selectivity, detection limits, and analytical
productivity. Laboratory automation through autosampling,
 CHAPTER 1--ANALYSIS OF Cs AND LIGHTER HYDROCARBONS
computer control, and data handling will provide improved
precision and productivity, as well as simplified method
operation.
Development of test methods for process (on-line) analysis
and validation of these analyses are continuing under the
direction of ASTM Committee D02.0D, Section l and D02.25.
A proposed gas chromatographic/selective detection method
is under development for the trace analysis of sulfur com-
pounds in ethene and propene.
ASTM Test Method D2163 is quite old. It utilizes lower
resolution packed columns, a less sensitive detector, and
manual peak area measurement. Thus, it is technically out of
date, and Committee D02.0D is currently in the process of
developing a revision for the determination of hydrocarbons
in LP gases and lower-purity mixtures of C3 and C4 hydrocar-
bons. The revision will still be performance based, but the
recommended column will be the A1203/KC1 PLOT column, as
used in the recently standardized ASTM Test Method D6159,
17
as well as in another test method under development for
high-purity propene.
A continuing problem for LP gas characterization is the
accurate determination of heavy residues (i.e., oils) in LP gas.
New test methods have been proposed using procedures simi-
lar to those employed in gas chromatographic simulated dis-
tillation, and this development work is continuing. The devel-
opment of test methods for C5 hydrocarbons (olefins) has
begun recently and should result in ASTM standards in the
near future. Various petroleum refinery process streams, of-
ten containing olefinic compounds, are generically referred
to as "refinery gas." Although no ASTM test method is avail-
able for this determination, several instrumentation and
technology suppliers market automated gas chromato-
graphic systems as "refinery gas analyzers." ASTM standard-
ization of this technology would be beneficial to users of these
analyzers.