Analysis of Aromatic
Hydrocarbons
by Charles H. Pfeiffer
INTRODUCTION
THE HISTORYOF INDUSTRIALanalyses of aromatic hydrocar-
bons began in the 1920s when the production of benzene
from coke by-products became commercially viable. By the
1930s, the rapid growth in demand for benzene as well as the
commercial production of heavier aromatics led to the for-
mulation of a considerable number of empirical analytical
procedures. At this time, ASTM Committee D16 on Aromatic
Hydrocarbons was formed. In the more than 50 years that
this group has been active, the changes in analytical tech-
niques have progressed hand-in-hand with the advancements
in process technology and the expansion in the demand for
high-purity aromatic products.
As coal was heated in the absence of oxygen to produce
coke, the lighter chemicals were vaporized and separated
from the coal. Cooling the vapors condensed a highly aro-
matic liquid. Fractional distillation was used to separate the
hydrocarbons into narrow-boiling fractions representing sin-
gle aromatics, such as benzene, or groups of aromatics, such
as xylenes. The contaminants were largely sulfur-, oxygen-,
and nitrogen-containing hydrocarbons.
Estimates of the purity of these products were determined
in laboratories using procedures such as ASTM Test Methods
D850, Distillation of Industrial Aromatic Hydrocarbons and
Related Materials, 1 and D852, Solidification Point of Ben-
zene. t Contaminants in the products caused corrosion and
product degradation in the downstream units. The following
ASTM Test Methods were developed to address these prob-
lems: ASTM Test Methods D853, Hydrogen Sulfide and Sul-
fur Dioxide Content (Qualitative) of Industrial Aromatic Hy-
drocarbons/ D848, Acid Wash Color of Industrial Aromatic
H y d r o c a r b o n s / a n d D849, Copper Strip Corrosion of Indus-
trial Aromatic Hydrocarbons. ~
As processes improved, aromatic hydrocarbons became
available at substantially higher purities. The higher product
purities opened up new industrial applications and required
new standards. To make these materials easier to buy, sell,
and trade, ASTM Test Methods D1015, Freezing Points of
High-Purity Hydrocarbons,2 D 1016, Purity of Hydrocarbons
from Freezing Points, 2 and D 1078, Distillation Range of Vola-
tile Organic Liquids/ were published. Later, methods that
gave more specific compositional information would sup-
plant these empirical tests.
1Appears in this publication.
2Annual Book of ASTM Standards, Vol. 05.01.
41
7
Eventually all of the light aromatics obtainable from the
coking operation were being used and shortages occurred.
The world needed another source, and that source was petro-
leum. Even as early as the late 1920s, crude oil was evaluated
as a source of light aromatics. Not until the late 1940s, how-
ever, did the development of catalytic reforming and liquid-
liquid extraction provide large quantities of aromatic hydro-
carbons for use by the chemical industry and as a blending
ingredient in high-octane gasoline.
CURRENT PRACTICES
Cyclohexane, made from benzene, is a chemical intermedi-
ate in the production of nylon. Polyester is made from
p-xylene, which is extracted from mixed xylenes. Synthetic
rubber is made from styrene, which is made from ethylben-
zene. Resins are made from phenol, which is made from
cumene. Each of these feedstocks and intermediates requires
a specific purity level as well as limits on specific impurities
and groups of impurities. ASTM test methods were developed
and revised in ASTM Committee D16 as each of these needs
were identified and as requirements for each of the materials
changed.
Gas chromatography (GC) has become a primary tech-
nique for determining hydrocarbon impurities in individual
aromatic hydrocarbons and the composition of mixed aro-
matic hydrocarbons. Although a measure of purity by GC is
often sufficient, GC is not capable of measuring absolute
purity; not all possible impurities will pass through the GC
column, and not all those that do will be measured by the
detector. Absolute purity is best measured by distillation
range or freeze or solidification points. Despite this caveat,
GC is a standard, widely used technique and is the basis of
many current ASTM Committee D16 test methods for aro-
matic hydrocarbons. Most of these methods, listed below,
were written with, or converted to, fused silica capillary col-
umns.
D2306 Cs Aromatic Hydrocarbon Analysis by Gas Chroma-
tography ~
D2360 Trace Impurities in Monocyclic Aromatic Hydrocar-
bons by Gas Chromatography 1
D3054 Purity and Benzene Content of Cyclohexane by Gas
Chromatography I
D3760 Analysis of Isopropylbenzene (Cumene) by Gas
Chromatography ~
D3797 Analysis of o-Xylene by Gas Chromatography ~
42 MANUAL ON HYDROCARBON ANALYSIS
D3798 Analysis of p-Xylene by Gas Chromatography ~
D4492 Analysis of Benzene by Gas Chromatography 1
D4534 Benzene Content of Cyclic Products by Gas Chroma-
tography 1
D4735 Determination of Trace Thiophene in Refined Ben-
zene by Gas Chromatography ~
D5060 Determining Impurities in High-Purity Ethylben-
zene by Gas Chromatography ~
D5135 Analysis of Styrene by Capillary Gas Chrom-
atography 1
D5713 Analysis of High Purity Benzene for Cyclohexane
Feedstock by Capillary Gas Chromatography 1
D5917 Trace Impurities in Monocyclic Aromatic Hydrocar-
bons by Gas Chromatography and External Calibra-
tion 1
D6144 Analysis of AMS (a-Methylstyrene) by Gas Chroma-
tography I
When classes of hydrocarbons, such as olefins, need to be
measured, techniques such as bromine index are used. ASTM
Test Method D1492, Bromine Index of Aromatic Hydrocar-
bons by Coulometric Titration/ continues as a useful
method, but D1491, Bromine Index of Aromatic Hydrocar-
bons by Potentiometric Titration, 3 was withdrawn in 1985
because of health concerns regarding its use of carbon tetra-
chloride as a solvent. It was eventually replaced by D5776,
Bromine Index of Aromatic Hydrocarbons by Electrometric
Titration,~ which is based on D2710, Bromine Index of Petro-
leum Hydrocarbons by Electrometric Titration, ~but uses the
less toxic 1-methyl-2-pyrrolidinone as a solvent.
Impurities other than hydrocarbons are of concern in the
petroleum industry. For example, many catalytic processes
are sensitive to sulfur contaminants. Consequently, ASTM
committees responded by developing a series of state-of-the-
art methods to determine trace concentrations of sulfur-con-
taining compounds. These methods included ASTM Test
Methods D 1685, Traces of Thiophene in Benzene by Spectro-
photometry/D3961, Trace Quantities of Sulfur in Liquid Ar-
omatic Hydrocarbons by Oxidative Microcoulometry,
D4045, Sulfur in Petroleum Products by Hydrogenolysis and
Rateometric Colorimetry, 1 and D4735, Trace Thiophene in
Refined Benzene by Gas ChromatographyJ Chloride-con-
taining impurities are determined by ASTM Test Methods
D5194, Trace Chloride in Liquid Aromatic Hydrocarbons/
and D5808, Determining Organic Chloride in Aromatic Hy-
drocarbons and Related Chemicals by Microcoulometry. l Ni-
trogen-containing impurities are determined by ASTM Test
Method D6069, Trace Nitrogen in Aromatic Hydrocarbons by
Oxidative Combustion and Reduced Pressure Chem-
iluminescence DetectionJ Many of these test methods have
sensitivity to 1 mg/kg, reflecting the needs of industry to de-
termine very low levels of these contaminants.
In addition to those tests previously mentioned, a number
of other ASTM Test Methods are regularly used for the analy-
sis of aromatics and are listed below:
D847 Acidity of Benzene, Toluene, Xylenes, Solvent Naph-
thas, and Similar Industrial Aromatic Hydrocar-
bons 4
3Discontinued; see 1985 Annual Book of ASTM Standards, Vol.
06.03.
D1493 Solidification Point of Industrial Organic Chemicals 4
D1555 Calculation of Volume and Weight of Industrial
Aromatic Hydrocarbons4
D1686 Color of Solid Aromatic Hydrocarbons and Related
Materials in the Molten State (Platinum-Cobalt
Scale) 4
D2119 Aldehydes in Styrene Monomer 4
D2121 Polymer Content of Styrene Monomer 4
D2340 Peroxides in Styrene Monomer 4
D2935 Apparent Density of Industrial Aromatic Hydrocar-
bons 4
D3160 Phenol Content of Cumene (Isopropylbenzene) or
AMS (~-Methylstyrene) 4
D3505 Density or Relative Density of Pure Liquid Chemi-
cals 4
D3799 Purity of Styrene by Freezing Point Method 4
D4590 Colorimetric Determination of p-tert-Butylcatechol
in Styrene Monomer or AMS (a-Methylstyrene) by
Spectrophotometry4
FUTURE TRENDS
Timeliness of analyses and the amount of labor required to
perform them continue to grow in importance. Although
many laboratories have limits on staffing, they may still be
able to make a one-time capital purchase of equipment to
make the available staff more productive. Instrumental and
automated methods are replacing chemical and physical
methods in the laboratories, and ASTM is supporting this
trend by writing test methods using contemporary technol-
ogy and by listing these test methods in ASTM specifications.
The ability of ASTM Committee D16 to write these methods
in a timely manner has been made possible, in part, by
increased vendor activity, a trend that is expected to con-
tinue.
For relative density, most labs now use ASTM Test Method
D4052, Density and Relative Density of Liquids by Digital
Density Meter. 1 Distillation methods have been or are being
rewritten to include automated distillation apparatus. For
trace sulfur, D4045 has become the industry standard. Re-
cently, this method has been optimized for aromatics analy-
sis as ASTM Test Method D6212, Total Sulfur in Aromatic
Compounds by Hydrogenolysis and Rateometric Colorime-
tryJ Development in D16.0E on a proposed method, "Total
Sulfur in Aromatic Compounds by Oxyhydropyrolysis and
Difference Photometry," is continuing, utilizing new equip-
ment. Methods for trace sulfur and trace nitrogen by electro-
chemical detection have also been proposed.
The classic platinum-cobalt color method, ASTM Test
Method D1209, Color of Clear Liquids (Platinum-Cobalt
Scale)/which requires subjective visual color comparison, is
slowly being replaced by methods such as ASTM Test Method
D5386, Color of Liquids Using Tristimulus Colorimetry.l This
new standard is currently limited to a maximum color of 30
because, for higher color values, the vendors' algorithms to
convert tristimulus values to Pt-Co color produce different
results. Currently, three major instrument manufacturers are
4Annual Book of ASTM Standards, Vo]. 06.04.
 CHAPTER 7 - - A N A L Y S I S OF AROMATIC HYDROCARBONS
working together on a common algorithm, which may be
published as an appendix to the standard.
The labor requirements of GC methods are also being ad-
dressed. Traditionally, trace analyses by GC have been
quantitated using an internal standard for calibration. These
test methods require careful weighing procedures for each
sample. Now, with the routine use of autosamplers to provide
repeatable injections, an external standard procedure is pre-
ferred as a means of saving analyst time. Trace impurities by
GC, ASTM Test Method D5917, was written as an equivalent
to the internal standard GC method D2360.
Because of continuing concerns over labor requirements,
ASTM Committee D 16 is currently trying to eliminate redun-
dant tests in Committee DI6 Specifications. For example, if a
specification for high-purity benzene includes distillation
range, purity by GC, and solidification point, a density or
43
relative density test is not justified. Similarly, current com-
mercial high-purity aromatic hydrocarbons always pass acid-
ity, copper corrosion, hydrogen sulfide, and sulfur dioxide
tests, so the continuing need for these tests on a routine basis
is being questioned.
More stringent product requirements, advanced catalytic
processing techniques, improved feedstock purification for
specific downstream processes, and health and environmen-
tal requirements are driving the limits of impurities into the
less than parts-per-million range. Efforts to provide quantita-
tive analyses at this level continue. As raw material sources,
product distributions, and methodologies change, efforts to
publish methods based on current technology will continue
to go hand-in-hand with these industrial technological
changes.