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iy
Manual on
UU Hee TALE
ELE ey
bth Edition
1, W. Brews, efter Manual on
Hydrocarbon
Analysis:
6th Edition
A. W. Drews
editor
ASTM Manual Series: MNL3
ASTM Stock #: MNL3
tly 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959 ‘Library of Congress Cataloging-in-Publication Data
Manual on hydrocarbon analysis—6th ed./A. W. Drews, editor
(ASTM manual series: MNL 3)
ASTM Stock #: MNL3
Includes bibliographical references and index
ISBN 0-803 1-2080-X
1. Petroleum products—Analysis. 2. Hydrocarbons—Analysis.
I. Drews, A.W. IL. Series.
TP691.M358 1998
665.5—de21 O8-25886
cp
Copyright © 1998 by the AMERICAN SOCIETY FOR TESTING AND MATERIALS, West
‘Conshohocken, PA. All ights reserved. This matenal may not be reproduces or copied, in whole
Fin pat, in any printed, mechanical, electoic, fim, or otter distribution and storage media,
without fe wrttan consent cf the publsher.
Photocopy Rights:
‘Authorization to photocopy items for Internal, personal, or educational cl
‘the internal, personal, or educational classroom use of spectfc cents, is granted b)
‘American Society for Testing and Materials (ASTM) provided that the appropriate
;paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923; Tel: 5
"750-8400; online: http//www.copyright.com/.
NOTE: This manuel does not purport to addrese allof the slaty concerns, any, associated with
its use tis the responsiblity ofthe user of ths manual 1 establish appropriate sefety and health
Practices and determine tne appiieabily of regulatory limitations pror to use,
NOTE: The Society is not responsible, as a body, for the statements and opinions a
vanced in this publication.
Printed in Rltirnore
Sine 1998 Contents
INTRODUCTORY INFORMATION
Introduction 3
Table 1—Summary of Product Types Produced from Petroleum 4
Table 2—Summary of ASTM Test Methods (by subject) 5
Table 3—Number of Isomeric Paraffins Tt
Table 4—Summary of Hydrocarbon Types in Petroleum Fractions u
a1 Ty
1 Analysis of C; and Lighter Hydrocarbons by N. G. Johansen 15
Introduction 15
Current Practices 15
Future Trends 16
2 Analysis of Gasoline and Other Light Distillate Fuels by J, M. McCann 18,
Introduction 18
Curent Practi 13
Future Trends 20
3 Analysis of Kerosine, Diesel, and Aviation Turbine Fuel by G. Hemighaus 22
Introduction
Current Practice
Future Trends 23
4 Analysis of Viscous Oils by T. M. Warne 25
Introduction 25
Current Practices 25
Future Trend 0
5 Analysis of Waxes by A. D. Barker 31
Introduction 31
Current Practices 31
Future Trends 32
6 Analysis of Crude Oils by A.J. Lubeck 34
Introduction 34
Current Practices 35
Future Trends 39
7 Analysis of Aromatic Hydrocarbons by C. H. Pfeiffer a
Introduction 4
Current Practices al
Future Trend: 4: vi CONTENTS
Par 2—ASTM Test MerHops
The test methods in this section re arranged in alphanumeric sequence. The page numbers apply only to this manual and
rot to thestardard documents as they appear inthe annual ASTM Book of Standards. See'Table 2 for alist of test methods
by subject. The following isa list of al test methods included in Part 2. It includes all test methods refecenced in theseven
chapiers except as indicated in the chapters, It does not inchide all of the test methods cited in Table 2
bs Test Method for Penetration of Bituminous Materials a
36 Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus) 50
D56 ‘Test Method for Flash Point by Tag Closed ‘Tester 4
bso Test Method for Distillation of Petroleum Products at Atmospheric Pressure o4
D87 Test Method for Melting Point of Petroleum Wax (Cooling Curve) 77
D9 ‘Test Method for Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure) 80
97 Test Method for Pour Foint of Petroleum Oils 87
D127 Test Method for Drop Melting Point of Petroleum Wax Including Petrolatur 95
D130_ Test Method for Detection of Copper Corrosion from Petroleum Products by the Copper Stip 97
Tarnish Test
D hod fc siduc of um Prod
D287 Test Method for API Gravity of Crude Petrolcum and Petroleum Products (I
D323 __Test Method for Vapor Pressure of Petroleum Products (Reid Method) 112
D341 Viscosity-Temperafure Charts tor Liguid Petroleum Products. 120
Da4S Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (@nd the Calculation’ 125
of Dynamic Viscosity)
baa7___Test Method for Distillation of Mant Spray Oils 134
D473____Test Method for Sediment in Crude Oils and Fuels Oils by the Extraction Method 37
Dai “Test Method for Ash from Petroleum Product 141
1D824____Test Method for Ramsbottom Carbon Residue of Petroleum Products| 144
DéL1_Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and 152
Hydrocarbon Solvents
Test Method for Acid Number of Petroleum Products by Potentiometric Titration 159
“Test Method for Oil Content of Petraleum Waxes ti
Test Method for Acid Wash Color of Industrial Aromatic Hydrocarbons 17
‘Test Method for Copper Strip Corrosion of Industrial Aromatic Hydrocarbons 175
Test Method far Dstillation of Industrial Aromatic Hydrocarbons and Related Materials 17
“Test Method for Solidification Point of Benzene 182
Test Method for Hydrogen Sulfide and Sulfur Dioxide Content Qualitative) of Industrial 184
‘Aromatic Hydrocarbons,
D972___Test Method for Evaporation Loss of Lubricating Greases and Oils 186
a rst Method for Calculated Ceisne Index of Dishllate Fuels 20
D107 Test Method for Distillation Range of Volatile Organic Liquids 193
DI133. Test Method for Kauri-Butanol Value of Hy¢rocerbon Solvents 200
1142 ‘Test Method for Water Vapor Content of Gascous Fuels by Measurement of Dew-Point 202
Temperature
DLIS9Tést Method for Bromine Number of Petroleum Distillates and Commercial Aliphatic Olefins by 213
Electromettic Titration
1209 Test Method fur Color of Clear Liguids (Platinumn-Cobalt Seale) 240
DI218 Test Method for Refractive Index and Refractive Dispersion of Hydrocarbon Liguids 243
D250 Guide for Petroleum Measurement Tables 2a
1265 Practice for Sampling Liquefied Petroleum (LP) Gases (Manual Method) 249
1298 Practice for Density, Relative Density (Specific Gravity) or API Gravity of Crude Petroleum and. 252
“Liguid Petroleum Products by Hydrometer Method
D1319___‘Tést Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator 2st
Adsorption
1322 Test Method for Smoke Point of Aviation Tusbine Fucks 268
1492. Test Method for Bromine Index of Aromatic Hydrocarbors by Coulometrie Titration 209
Diss2___Test Method for Sulfur in Fetroleum Products (High-Temperature Method) 2n
i685 Test Method for Traces of Thiophens in Benzene by Spectrophotometry 2
DI747__Test Method for Refractive Index of Viscous Materials 28)
1840 Test Method for Naphthalene Hydrocarbons in Aviation Turbine Fucls by Ultm Violet 284
Spectrophotometry x CONTENTS
6160 _Test Method for Determination of Polychlorinated Biphenvls (PCBs) in Waste Materials by Ga
Chromatography
D6212 Test Method for Total Sulfur in Aromatic Compounds by Hydrogenolysis and Rateometrie 1054
Colorimetry
1039 Table 2—Summary of ASTM Test Methods
INTRODUCTORY INFORMATION §
‘Number of Carbon Atoms
Pailng Range of Normal Palins st 760 mm He, °C
cc,
6ito 89
Gre
a6
c.06 [Ges | Cte [ee
eter | rsstode | aresis | 2358
Physical Methods
DS, Penetration of bituminous materials
‘36, Ring and tall softening point
56, Flash by te closed cup tester
186, Distilation of petroleum products
B87, Melting pein of wax
x
»
*
oe
1002, Flash and fre Cleveland open cup
193, Flash and fire by Peesky-Martns closed cup
197, Pour point
D127, Meting pint of wax
D189, Conradson carbon residue
Pa
Hox
'D287, API gravity by hydrometer
1323, Vapor pressure (Reid metbod)
‘D445, Kinematic viscosity
‘D447, Disullation of plant spray oils
D473, Sediment by extraction
foreee)
mH OH
D482, Ash from petroleum produets
1DS24, Ramsbottom carbon residue
D611, Aniline point
10721. Oil content of petroleum waxes
D850, Distillatin of industrial aromatics
vere [coe oe [ee nee
xx [><
“
*
‘D852, Solidification point of benzene
D972, Evaporation losses of areases & oils
1015, Purity fom freezing point
1016, Puity from freezing point
11078, Distillation of volatile organic Higuids
wu
D142, Water vapor of gescous fuels
1160, Distillaion st redaced pressure
DI2I8, Refractive index & dispersion
1267, Vapor pressure of LP gases
1298, Relative demsity of liquids
1D1322, Smoke point of aviation turbine fuels
11493, Solidification point of organic chemicals
1657, Relative density of light hydrocarbons
DI74?, Refractive index of viscous materials
DIQ07, Refractive index of insalating oils
ux
“x
1837, Volatiiy of LP gases
12138; Residue in L? gases
2171, Viscosity of asphalts
1D2386, Freezing poiat of aviation fuels
2800, Cloud point of petroleum oils
xo
wx INTRODUCTORY INFORMATION 9
Table 2 - continued
Gly] Cam
weit | ae7tein | 385
‘Number of Carbon Atoms roe ot
Paling Range of Normal Paraiins a 760 mm Ha, °C site's | 210-36
1D2624, Fetal condvciviyof sation and distil fuels x x
'D2699, Knock characteristics by research octane x
12700, Koock characteristics by motor oxtane x
12713, Drynes of ropane (valve freeze) x
27RD, Solubility of ied gases in igus x | x
1D2878, Estimating vapor pressure of lubricating ois x x
D28KS, Keock characteristics by online analyzers x
3235, Soivent extractables in waxes
13241, Thermal oxil. stab. of aviation turbine fuel SPTOT) x
1D3700, Sampling using floating piston cylinder x x x
exe
13948, Water separation charac. of aviation turbine fuel
‘4057, Minual sampling of petroloum x x
A177, Automatic ssmpling of petroleum x x
'D4291, Ethylene glycol in used engine ol
14307, Preparation oftiquid bends x
HH
dene bee
xx
'D4419, Transition temperatures of Wax by DSC
1D4740, Stability of residual oils by spot test
S184, Aland Si in fuel cls by ICP-AES and AAS
S234, Guide for amilysis of elaylene x
5273, Guide for analysis of propylene
x
seve oe
S274, Guide for alysis of batadiene
109287, Automatic sampling of gaseous fuels x
5386, Color of liquids x
15503, Natural gas sample-hasdling
5842, Sampling of fuels for volatility
Pa
‘Non-Hydrocarbon Methods
19S, Water by distillation
1D96, Water and sediment in crude oils x x
D129, Sulfur by bomb method
‘D808, Chlorine in petroleam products
D853, 11,§ and $0, ia aromation x
aK
pene pene
pee ee
11265, Sulfur ty temp method x x x
1582, Sulfur ty high-temperature method x x x
16S, Thiophene in benzene x
DI98R. Mereapians in natal pas x x
2420, Liydrogensufide in LP gases x
2622, Sulfur by X-ray x x
12709, Water aad sediment in fuels
2784, Sulfur in LP gases
3120, Trace sulfur by oxidative microcoulometry
13227, Mercapians in dsillates (potentiometric)
ose
xe
xx
vee
xm Part 1—Discussion of Analyses
by Product Type MNLB-EB/un, 1998,
Analysis of Gasoline and
Other Light Distillate Fuels
by James M. McCann
INTRODUCTION
‘THE CHALLENGE 10 nevELOP more accurate and precise test
methods for the analysis of gasoline or automotive spark-
ignition engine fuel has been tremendously influenced by
federal and state regulations covering the production of re
formulated gasolines (REG) with tight limits on many param
eters [/]) Examples of these new fuels include U.S, Environ
mental Protection Ageney (EPA) RFG and Californie Air
Resources Board (CARB) Phase 2 Gesoline. The regulated
RFG test parameters include vapor pressure, distillation,
benzene content, to1al aromatics, toval olefins, individual
oxygenates, oxygen content, and total sulfur. Regulatory re
‘quirements haveenhanced the need for better test methods to
control manufacturing and the distribution of gasolines, The
addition of alcohol and ether as important blending compo-
nents to gasoline to meet air quality standards has necessi:
tated modifying some existing (est methods and the develop:
‘ment ofnew procedures. The desire to reduce manufacturing
costs, coupled with the regulatory requirements, have en
hanced the application of more cost effective test methods
inchiding rapid screening procedures and wider use of on
line analyzers. In this chapter, a brief history of ASTM
method development for hydrocarbon analysis of gasoline is
given. The focus, however, will be on some ofthe test parame
ters required for toda
many of the new test methodologies.
ASTM standanfization of methods for hydrocarbon analy:
sis started in 1942 when Committee B02, Technical Division
oon Gascline, established a subgroup to standardize a proce-
lure for the determination of aromatics in gasolines for use
by the military. This method was fist issued in March of 1943,
as Emergeney Standard ES 45, Test for Olefins, Aromatics,
Paraffins, and Nophthenes in Aviation Gasoline (Without Dis
tillation Into Fractions). This method was a combination of
several procedures, some of which are still commonly used.
In 1948, a procedure was described by A. L. Conrad and,
later refined by D. W. Cridle and R. L. LeTourneau for deter
_mining olefins, aromatics, and saturates in cracked gasoline,
This procedure evolved into ASTM Test Method D1319, Hy-
drocarbon Types in Liquid Petroleum Products by Fluores
cent Indicator Adsorption,’ often abbreviated as “FIA.”
‘s reformulate! gasolines including
"The italic numbers in brackets ref
this chapter,
“1044 Annual Book of ASTM Standards, Part II
“appears in this publication.
tothe references atthe end of
Copseight© 1998by ASTM Interatonal
During the early 1950s, instrumental analytical techniques,
such as mass spectrometry, infrared, and ultraviolet spectros
copy, were being explored and used for hydrocarbon compo-
sition and structural analysis. Beginning with the mid 1950s,
publications on gas chromatography began to appear in the
literature, and this new technique was soon being used for
analyzing a wide variety of hydrocarbon streams. As com
mercial instrumentation was developed, the application of
‘gas chromatography grew rapidly, with volumes of informa-
tion being published from its beginning up to the present
time. Recently, more rapid spectrometry methods such as
infrared and near-infrared and the use of hyphenated analyti
cal techniques, for example GC-MS, have been applied.
CURRENT PRACTICES
Analysis of Gasoline Range Hydrocarbons
The following is a review of applicable test methods that
can be used to measure some of the key parameters in gaso-
Tine range hydrocarbons
Distillation
The primary method specified for determining boiling
range of gasoline continues to be ASTM Test Method D86,
Distillation of Petroleum Products at Atmospheric Pressure.”
‘Theuse of automated instrumentation has been incorporated.
into the method. ASTM Test Method D3710, Boiling Range
Distribution of Gasoline and Gasoline Fractions hy Gas Chro-
matography," (GO), can be used for determining the boiling
point properties of oxygenate-free gasoline distillates. ASTM
3710 has the advantage that it uses a smaller sample size
and can be more easily automated, but D3710 data are not
directly equivalent to that obtained by D86 distillation. ASTM
3710 data are being used by some companies and vendors
by applying correlations to predict D8» distillation data for
various refinery streams. Improvements in the GC simulated
distillation procedures have been implemented in some labo:
ratories and are being evaluated in ASTM 102.04, Section H.
Improvements include rapid gas chromatography techniques
using very narrow bore capillary gas chromatography col:
tums that will potentially reduce analysis time to a few min-
utes [2]
Vapor Pressure
‘The vapor pressure of gasoline is a critical physical test
parameter for today’s gasoline. ASTM Test Method D323, Analysis of Kerosine, Diesel,
NNL3-EB/Iun, 1998
and Aviation Turbine Fuel
by Gregory Hemighaus
INTRODUCTION
KEROSINE, DIESEL, AND AVIATION turbine fuel (jt fuel) are
embers of the class of petroleum products known as middle
distillates. As the name implies, these preduets are heavier
than gasoline but lighter than’ gas oils. Middle distillates
cover the beiling range from approximately 175°C to 375°C
(BS0°F io 700°F) and the carbon number range from about C,
10 Gs
Besides these products, gas turbine fuel, fuel oil (heating
cil), and some marine ues are also classified as middle distil
lates because they have a wide boiling range that overlaps the
lighter fuels. These products have similar properties but dif
ferent specifications as appropriate for their intended use.
‘Methods for determining physical properties ofthese prod:
uwcts are well established. They are listed in Table 2 and most
will not be discussed further. Table 2 also lists methods for
elemental analysis of middle distilates. This chapter will fo
us on compositional analysis of these preducts.
Because of the number of isomers in this carbon number
range (see Table 3), complete speciation of individual hydro
carbons is not possible for midale distillates. Composivional
analysis of middle distillates is obtained in terms of hydrocar-
bon group type totals These grougs are most often defined by
a chromatographie separation or a mass spectral 7-series
CURRENT PRACTICES
Distillation
‘One of the most important physical parameters defining
these products is their boiling range distribution, Histori
cally, this has been measured by ASTM Test Method D86,
Distillation of Petroleum Products at Atmospheric Pressure.
ASTM D86 is a low-efficiency, one theoretical plate distilla
tion, This hes been adequate for product specification pur-
poses; however, engineering studies require true boiling
point (TBP) data, TBP data can be provided by ASTM Test
Method D2832, Distillation of Crude Petroleum (15-Theore!
cal Plate Column).’ However, this method is rather difficult,
time consuming, and expensive to run. TBP data are most
often obtained using ASTM Test Method D2887, Boiling
Range Distribution of Petroleum Fractions by Gas Chroma-
tography! (simulated distillation). Use of simulated distilla
tion has been recently reviewed (i ]?
"Appears in this publication,
Copyright©: 199%by ASTM Intemational
Chromatographic Methods
The first level of compositional information is group-ype
totals. ASTN Test Method D1319, Hydrocarbon Types in
Liquid Petroleum Products by Fluorescent indicator Adsorp-
tion.’ gives volume percent saturates, olefins, and aromatics
in materials that boil below 315°C (600°). This covers jet
fuels but notall diese! fuels, most of which havean end point
above 315°C. Despite this limitation, the method has been
used widely for diese! fuel due to the lack of @ suitable
alternative.
In 1988 the California Air Resources Board issued regula-
tions that limited the aromatic content of diesel fuel sold in
California starting in 1993. This heightened avareness that
ASTM D1319 was not appropriate for diesel fuels led to
‘efforts being initiated though ASTM to develop a suitable
alternative. This led to the development of ASTM Test
Method D5186, Determination of the Aromatic Content and
Polynuclear Aromatic Content of Diesel Fuels and Aviation
‘Turbine Fuels by Supercritical Fluid Chromatography." This,
method does not separate saturates and olefins, so it cannot
be used! as a replacement for ASTM D1319. Another compli-
cation in comparing the two methods is that ASTM D1319
ives results in volume-porcent while ASTM D5186 results
are in mass-percent.
‘Another approach to the determination of aromatics in
middle distillates is high performance liquid chromateera-
phy, (HPLC), with refractive index (RD) detection [2]. The
Institute of Petroleum has standardized this cechnique as
TP-391, ASTM is currently considering this method and may
adopt it as a standard
HPLC with dielectric constant detection [3] was consid
ered by ASTM, but problems with detector stability prevented
standardization
Coupled Chromatographic Techniques
The combination of HPLC with GC can provide more de
tailed compositional information than either technique
alone. Typically HPLC is used to separate a particular hydro.
carton group (saturates, mono-aromatics, di-aromatics) and
transfer it to a high-resolution GC column that can resolve
many of the individual compounds [4,5 J. Supercritical fluid
chromatography, (SFC), can be used instead of HPLC to
make the primary separation [6], These are rather sophisti
the italic face nambers in brackets refer to references at the end
of this chapter. 26 MANUAL ON HYDROCARBON ANALYSIS
Refractive index
Refractive index isthe ratio of the velocity of light in air to
the velocity of light in the measured substance, The numeri-
cal value of the refractive index varies inversely with the
‘wavelength of light used and the temperature at which the
measurements are taken. The refractive index of a substance
is related to its chemical composition and may be used to
draw conclusions about molecular structure
Two ASTM test methods are available for measuring the
refractive index of viscous liquids. Both methods are limited
to lighter-colored samples for best aecuracy. Both methods
‘were written for instruments which are no longer manufac
tured,
ASTM Test Method D1218, Refractive Index and Refractive
Dispersion of Hydrocarbon Liquids," is designed to use the
Bausch & Lomb Precision Refractometer. This model is no
Jonger manufactured. ASTM Test Method D1747, Refractive
Index of Viscous Materials," uses the Abbe type (Valentine)
rehiaetometer, which is no longer made. In both cases, other
refmactometers are available, but no cooperative work has
been conducted to verify equivalence. There are also limita:
tions on the availability of thermometers with suitable range
andaccaracy that will fit the instruments. ASTM Subcommit
tee D02.04.0D plans cooperative testing of modern commer
cial refractometers to develop precision data, but data are not
yet available
Molecular Weight
Since viscous oils are commonly broad-boiling mixtures,
‘measurements of molecular weight commonly provide mass:
averageor number-average measurements. A variety of meth:
ods are available
‘Molecular weight may be calculated from viscosity data
using ASTM Test Method 2502, Estimation of Molecular
Weight (Relative Molecular Mass) of Petroleum Oils from
Viscosity Measurements. The current version requires centi-
stoke viscosity at 100 and 210°F, The method is generally
applicable to “average” petroleum fractions with molecular
‘weight in the range 250 10 700. Samples with unususl compo-
sition, such as aromatic-free white mineral oils, or oils with
very narrow boiling range, may give atypical result.
For samples with higher molecular weight (up to 3000 or
more) with unusual composition or for polymers, ASTM Test
‘Method D2503, Relative Molecular Mass (Molecular Weight)
of Hydrocarbons by Thermoelectric Measurement of Vapor
Pressure,’ is recommended. This method uses a vapor pres-
sure osmomeler to determine molecular weight. Low boiling
samples may notbe suitable if their vapor pressure interferes
with the method, The method has only been standardized by
ASTM for samples up to.a molecular weight of 800.
A third method is also available, ASTM Test Method
12678, Estimating Apparent Vapor Pressures and Molecular
Weights of Lubricating Oils," provides a procedure to cale
late these properties from test data on evaporation. The pro-
cedure is based on ASTM Test Method D972, Evaporation
Loss of Lubricating Greases and Oils.’ The sample is partly
evaporated at a temperature of 256 to 500°C; fluids not stable
in this temperature range may require special treatment [/]*
The italic numbers in brackets refer tothe listof references at the
cond of this chapter
Other approaches to determining molecular weigh! include
distillation (gas chromatography) and mass spectroscopy.
These are discussed separately.
Disiillaiion
Four distillation methods are in common use for determin.
ing the boiling range and for collecting fractions from viscous
oils.
ASTM Test Method D1160, Distillation of Petroleum Prod:
ucts at Reduced Pressure,’ is probably the best known and
most widely used of the methods for distillation of higher
boiling petroleum products. The methed isa vacuum distlla
tion, applicable to samples that can be at least partially vola-
tilized ai temperature up to 400°C and pressure in the range 1
to 50 mm Hg, The distilatio. temperature at vacuum is
comerted to atmospheric equivalent temperatures.
ASTM Test Method D447, Distillation of Plant Spray Oils,”
is a method designed for characterization of these narrow-
hoiling fractions. (Optimal persistence with minimal damage
to plant fruit and foliage is obtained when narrow boiling
petroleum fractions of appropriate volatility are used.)
ASTM Test Method D2892, Distillation of Crude Petroleum
(5-Theoretical Plate Column),' applies to a wide range of
products. The procedure uses a column with 15 theoretical
plates and a 5:1 reflux ratio. The distillation is started at
atmospheric pressure until the vapor temperature reaches
210°C. Distillation is continued at vacuum (100 mm Hg) until
the vapor temperature again reaches 210°C or cracking is
observed.
With very heary crudes or viscous products, a preferred
altemate distillation method is ASTM Test Method D5236,
Distillation of Heavy Hydrocarbon Mixtures (Vacuum Porstll
Method).' This method should be used instead of ASTM
12802 for heavy crudes above a 490°C cutpoint.
Unless a distillation method is required by specification or
the collected fractions are needed for further testing, gas
chromatographic methods have become preferred for deter-
mining the boiling range of petroleum fractions. ASTM Test.
Method D2887, Boiling Range Distribution of Petroleum
Fractions by Gas Chromatography,' gives detailed informa-
tion for samples with a final boiling point no higher than
538°C (1000°F) al atmospheric pressure and a boiling range
greater than 55°C(100°F). Some laboratories have used modi
fied procedures 10 analyze fractions boiling higher than
538°C, ASTM Subcommittee D02.04 has prepared a draft
method that covers products boiling to 838°C; this method
should be standardized in the near future.
Chemical Composition
Elemental Analysis
In elemental analysis of viscous olls, the analyst is most
commonly interested in the presence of contaminant metals,
nitrogen, and sulfur preseat in the hydrocarbon fraction. For
finished products, additional information issought regarding
elements contributed by additives. While there exist many
classical, wet chemical methods for determination of metals
and certain elements, routine analysis generally involves in-
strumenial methods based on spectrometric techniques in-
cluding atomic absorption, emission, X-ray and plasma spec-
trometry. 30 MANUAL ON HYDROCARBON ANALYSIS
ASTM Test Method DS292, Aromatic Carbon Contents of
Hydrocarbon Oils by High Resolution Nuclear Magnetic Res-
fonance Spectroscopy, permits determination of aromatic
hydrogen and aromatic carbon content of gas oils, lubricat
ing oils, and other hydrocarben fractions that are complet
soluble in chloroform and carbon tetrachloride at ambient
temperatures. Concentrations as low as 0.1 mol-% hydrogen
and 0.5 mole carbon can be determined, Olefins and pheno-
lic compounds above | mass-% interfere.
‘ASTM Committee D02 has standardized three methods for
hydrocarbon compositional analysis using mass spectrome.
try. One of these is ASTM Tes: Method D2786, Hydrocarbon
‘Types Analysis of Gas-Oil Saturates Fractions by High
onizing Voltage Mass Spectrometry.' A complementary
method is ASTM Test Method D3239, Aromatic Types Analy.
sis of Gas-Oil Aromatic Fractions by High Tonizing Voltage
Mass Spectromeitry.! These methods require preliminary sep
aration using elution chromatography, ASTM D2549, or sim:
ilar method. A thitd method, ASTM Test Method 12425,
Hydrocarbon Types in Middle Distillates by Mass Spectrome.
try,' may be applicable to some visecus oil samples in the
lower molecular weight range.
‘The procedures used in these methods were originally de.
veloped and reported in 1969 [121 They were developed
using the Consolidated Electrodynamics Corp. Type 103 se
vies (Model 21-100 and later the DuPont 21-103 and 21-104
instruments). These instruments are no longer in production,
While newer instruments are reported to give satisfactory
results, the procedures for their use have not been standard:
ized, Efforts are now in progress to provide test methods,
using newer, lower-cost instruments. The use of quadrupole
instruments and a combination of mass spectroscopy with
gas of liquid chromatography should produce useful new
procedures,
FUTURE TRENDS
‘As noted in previous editions, the trend in hydrocarbon
analysis is away from manual test methods and increasingly
favors automated instrumental methods. Commercial instru:
‘ments are available that will perform many of the procedures
described in this chapter. While ASTM committees have stan:
dardized tests based on some of these instruments, commer
cial development is rapid and new analytical instruments are
constantly available. This trend is expected to continue. A
‘major challenge is to match standard test methods with new
equipment so that methods do not become obsolete,
‘Combining separation and analysis techniques (hyphen-
ated techniques) can produce powerlul tools for characteriz-
ing viscous oils. Thus, iquid chromatography or gas chroma-
tography can be used to separate a sample for subsequent
acterization by mass spectromeuy (LC/MS or GC/MS).
Research into suitable methods for the analysis of viscousoils,
is underway, but no standard tests have yet been prepared.
Extensive research oa beth proten and carbon-13 nuclear
‘magnetic resonance spectroscopy shows promise as a tool for
the analysis of lubricant base oils and other viscous oils. Both,
near-infrared spectroscopy (NIR) and Fourier-transform IR
(ETIR) are the subjects of active research into methods to
characterize hydrocarbons and for quality control during
production of petroleum products. Standard test methods us-
ing these techniques should become available in the future,
REFERENCES
(Coburn, J. F, “Lubricant Vapor Pressure Derived From Exapo-
ration Loss,” Transzctions, American Society of Lubricating En-
sineers, ASLTA, Val. 12, 1969, pp. 129-134
2) Coat, 1B. and HD, J.B. Jndusiial & Engineering Chemistry,
Vol.20, 1928, p. 641
[5] Barman, BN, Jounal of Chromaiographic Science, Wil. 34, No
5, 1996, pp. 219-225,
4) Sassiat, Pet al, val. Chim. Acta, Vol. 306, No. 1, 1995, pp.
73-19.
[5] Kagdival, R. et al, Proceedings, Adv. Pro. Appl. Lube Base
Stocks, 1994, pp. 295-302
[6] Jain, M. C. etal, Adv. Prod. Appl. Lube Base Stocks, 1994, pp.
272-279,
(7) Hui, R. and Rosset, R., Anal. Chim. Acia, Vol. 314, No.3, 1995,
pp. 1650-1657,
{8} Machtalere, G etal, Anal. Chim. Acta, Vol. 322, Nos. -2, 1996,
pp. 31-41
{9} Lambroupoulos, N. et sl, Journal of Chromatography; Vol. 749,
Nos. 1-2, 1996, pp. 87-94,
[101 Brandes. G., Brennstoff:Chemie, Vol. 37
Vol. 11, No. 10, 1958,
[21] Powell, I R. and Compton, D. A.C, Lab Eing., Vol. 49, No. 3
1993, pp. 233-239.
[12} Robinson, C. J. and Cook, G,L., Analytical Chemistry A, Vo. 41
1968, p. 1548 f.
956; Endol werd Kohl, Analysis of Crude Oils'
by Axel J. Lubeck
INTRODUCTION
‘Ceupe OIL are a highly complex combination of hydrocar:
bons; heterecyelic compounds of nitrogen, oxygen, and sul:
fur;organometallic compounds; inorganic sediment; and wa:
ter. Approximately 600 different hy¢rocarbons have been
identified in crude oil, and iti likely that thousands of com.
pounds occur, many of which probably will never be iden
fied. In a study sponsored by the American Petroleum Ins!
tute (APD), nearly 300 individual hydrocarbons were
identified in Ponca City, Oklahoma crude ofl [1,2]? Some 200
individual sulfur compounds were identified in 2 20.year
systematic siudy of four crude oils[3 J. Not onkyis the compo:
sition of crude oil highly complex, it is also highly variable
from field-to-ield, and even within a given field itis likely to
exhibit inhomogeneity. Physical and chemical characteriz
tion of this complex mixture is further complicated for the
analyst by the fact that crude oils are not pure solutions, but
commonly include colloidally suspended components, dis
persed solids, and emulsified water
Compared to refined products such as gasoline and avia:
tion turbine fuel, there is relatively liule tn the literature on
the analysis and characterization of crude oils. Indeed, for
‘many years, there were relatively few ASTM methods specific
to crude oils, although a number of ASTM methods had been
adapted for use in analyzing crudes, This situation may have
resulted, atleast in part, from the historical tendency of refin
ery chemists to independently develop or modify analstical
methods specific to their needs and subsequently for the
methods to become company proprictery. In recent years, the
unique problems associated with sampling and analysis of
rude oils have received more attention, and more methods
for determining selected constituents and characteristics of
crude oils are new being standardized,
Aseries of articles [4-9] illustrate the diversity of crude oil
assay practices employed by major refiners in the United
States and Austria. The dissimilarity of results reported in the
literature [16 Js reflection of thisindependent development
of analytical schemes, even though standardized approaches
to crude oil analysis have previously been published [11,12 }
Despite the complexity of erude oil compesition and the di-
versity of analytical methodology, probably more crude oil
analyses are routinely performed on a daily basis using inher
"This chapter is an updated and medifiel version of the chapter,
authored by Ht N, Giles found inthe previous edition ofthis manual,
“The italic numbers in brackets refer (othe listof references atthe
end of this chapter
34
Copyright© 199Sby ASTM International
MNLS-EBUun, 1998,
cently similar methods than are analyses on any single refined
petroleum product except, possibly. gasoline.
The overriding issue when performing comprehensive
crude oll assays is economics. Crude oils are assayed o deter:
mine: (a) the slate of products thet can be produced with
given refinery’s process technology; (b) the processing. diffi-
culties that may arise as a result of inkerent impurities; and
(©) the downstream processing and upgrading that may be
necessary to optimize yields of high-value, specification prod:
ucts. The analytical results ace typically stored in an elec
tronic database that can be accessed by computer medels
that generate refinery-specific economic valuations of each
crude or crude slate (i.e, mixture of crudes processed to
gether)
Analyses are also performed to determine whether each
batch of crude oil received at the refinery gate meets expecta
tions. Does the crude receipt match the database assay sothat
the projected economic valuations and operational strategies
are valid? Has any tinintentional contamination or purpose
ful adulteration occurred during gathering, storage, or trans-
port of the crude oil that may increase the processing cost or
decrease the valve of the refined products? The information
needed to answer these questions is often refinery-specific—a
function of the refinery’s operating constraints and product,
slate
‘To obiain the desired information, two different analytical
schemes are commonly used, namely, an inspection assay
anda comprehensive assay. Inspection assays usually involve
determination ofa few key whole crude oil properties such as
API gravity, sulfur content, and pour point—principally as a
means of determiningiif major changes in a crude oil stream’s,
characteristics have occurred since the last comprehensive
assay was performed. Additional analyses may be performed
to help ensure that the cargo or shipment received is that
which is expected; to ascertain the quantity of impurities
such as calt, sediment, and water; and to provide other criti-
cal refinery-specific information. Inspection assays are rou-
tinely performed on all shipments received at a refinery. The
comprehensive assay, on the other hand, is complex, costly,
and time-consuming and is normally performed only when a
new field comes on stream, or when the inspection assay
indicates that significant changes
have occurred. Except for these circumstances, a comprehen
sive assay of a particular crude oil stream may not beupdated
for several years.
in thestream'scomposi 38 MANUAL ON HYDROCARBON ANALYSIS.
Following fractionation of the crude oil, each of the Frac:
tions is analyzed to determine one or more of its physical or
chemical characieristies depending on the needs of the re-
finer. All of the various tests that could be performed on each
Of the fractions are too numerous to be included here. In the
following discussion, the properties or constituents generally
measured in a detailed analysis of each of the above eight
fractions are listed.
Gas
Typically, the gas or debutanization lraction is analyzed by
high-resolution gas chromategraphy for quantitative deter
mination of individual C; to C, and total C,~ hydrocarbons.
Relative density (specific gravity) can be calculated from the
compositional analysis.
Light Naphtha
Density or specific gravity by hydrameter or (ASTM Test
Method D402, Density and Relative Density of Liquids by
Digital Density Meter,” total sulfur (ASTM Test Method
12622, ASTM Test Method D3120, Trace Quantities of Sulfur
in Light Liquid Petroleum Hydrocarbons by Oxidative Mi
cerocoulometry, or ASTM Test Method D5453, Determination
of Total Sulfur in Light Hydrocarbons, Motor Fuels, and Oils
by Ultraviolet Fluorescence),’ mercapian sulfur [ASTM Test
Method D3227, Mercapian Sulfur in Gasoline, Kerosine
Aviation Turbine, and Distillate Fuels (Potentiometric
Method],’ hydrogen sulfide, and organic chlorides are typi
cally determined on this fraction. Because this fraction is
important both as a petrochemical feedstock and a8 a aso:
line blending component, it is likely that it would also be
analyzed by high-resolution gas chromatography for quanti:
tative determination of its paraffin, isoparaffin, aromatic,
naphthene (cycleparaffin), and olefin, ifany, components (PI
ANO analysis). Octane numbers would also be determined
for this fraction if it wore to be included as a gasoline blend:
ing component. Typically, octane numbers are determined
using special engines that require relatively large volumes of
sample (ASTM Test Method 12699, Knock Characteristics of
Motor Fuels by the Research Methods and ASTM Test
Method 2700, Knock Characteristics of Motor and Aviation
Fuels by the Motor Method).° Some companies are now using
semi-micro methods that require considerably less sample
than the above standard methods for determination of octane
numbers [22]. Other laboratories use PIANO data to calcu
Jate octane numbers [5 ]
Medium and Heavy Naphthas
Density or specific gravity, total sulfur, mercaptan sulfur,
hydrogen sulfide, organic chloride, and PIANO determina:
tions would normally be determined on these fractions. In:
cluded in the information that can be derived from the PI
ANO analysis are the concentrations of benzene and benzene
precursors (compounds that ultimately form benzene in a
refinery’s reforming nit). ‘These data are important because
of govemmental regulations limiting the maximum concen:
tration of benzene in reformulated gasoline.
“Annual Book of ASTM Standards, Vol. 05.04
Kerosine
‘Typically, density or specific gravity, total sulfur, mereap-
tan sulfur, hydrogen sulfide, aniline point (ASTM Test
Method D611, Aniline Point nd Mixed Aniline Point of Pe-
troleum Products and Hydrocarbon Solvents), total acid or
neutralization number, naphthalenes content (ASTM Test
Method D1840, Naphthalene Hydrocarbons in Aviation Tur-
bine Fuels by UV Spectrophotometry).* smoke point (ASTM.
Test Method D132, Smoke Point of Aviation Turbine
Fuels), total nitrogen (see Note 1), viscosity, and freezing
point (ASTM Test Method D2586, Freezing Point of Aviation
Fuels)* would be determined for this fraction and a cetane
index calculated (ASTM Test Method D976, Calculated
Cetane Inder of Distillate Puck or ASTM Test Method D4737
for Calculated Cetane Index by Four Variable Equation).
Other tests that might be performed, depending on the in-
tended end use of the fraction, are flash point (ASTM Test
Method DS6, Flash Point by Tag Closed Tester), corrosive-
ness (ASTM Method D120, Detection of Copper Corrosion
from Petroleum Products by the Copper Strip Tarnish Test),
and thermal stability [ASTM Test Method D3241, Thermal
Oxidation Stability of Aviation Turbine Fuels (FTOT Proce-
dure)]?
Note 1—In gereral, the ratio of basi to total nitrogen is,
practically corstant at O.3:1 for erude oils and virgin,
Stocks, It also appears that the types of nitrogen com-
pounds present in various crude oils are essentially the
Same, although the actual amounts may vary considera
bly [23]. Consequently, in most asseys its sufficient to
determine total nitrogen (by the modified Kjeldahl or
chemiluminescence methods).
Distillate Fuel Oil
‘Tests of the fuel oil fraction normally Include determina-
tion of density or specific gravity, total sulfur, aniline point,
total acid number, naphthalenes content, smoke point, total
nitrogen, viscosity, cloud point (ASTM Test Method D2500,
Cloud Point of Petroleum Oils),’ pour point (ASTM Test
Method D97, Pour Point of Petroleum Oils), and calculation
of cetane index. Corrosiveness, ash (ASTM Test Method
D482, Ash from Petroleum Products),’ and carbon residue
might also be determined in more thorough evaluations.
Gas Oil and Lube Stocks
Density or specific gravity, total sulfur, aniline point, total
nitrogen, viscosity, cloud point, pour point, trace metals (Fe,
Ni, V), and carbon residue would normally be determined on
this fraction, If the fractien is to be used as catalytic cracker
feedstock, asphaltenes would also be determined by precipi-
tation with normal-heptane (ASTM Test Method D3279, Hep-
tane Insolubles).” Wax content determination by solvent
reflux [24] might be included in a lube stock evaluation,
Hydrocarbon-type analysis by mass spectrometry or other
‘means is an important part of lube stock evaluation, but this,
is heyond the scope of this chapter.
Residusm
‘Tests of the residuum typically include density or specific
gravity, total sullur, total nitrogen, viscosity, trace metals,
and carbon residue, Determination of the properties of as
phalt such as penetration (ASTM Test Method D5, Penetra- 42 MANUAL ON HYDROCARBON ANALYSIS
3798
4492
D4s34
Analysis of p-Xylene by Gas Chromatography"
Analysis of Benzene by Gas Chromatography"
Benzene Content of Cyclic Products by Gas Chroma
tography’
Determination of Trace Thiophene in Refined Ben-
zene by Gas Chromaiographs!
Determining Impurities in HighPurity Ethylben
zene by Gas Chromatography"
‘of Styrene by Capillary Gas Chrom-
atography!
Analysis of High Purity Benzo
Feedstock by Capillary Gas Chromatography!
Impurities in Monocyelic Aromauie Hydrocar
bby Gas Chromatography and External Calibra
4735
5060
5135
ps713 ¢ for Cyclohexane
pss17
6144. Analysis of AMS (a Methrlstyrene) by Gas Chroma.
tography!
When classes of hydrocarbons, such as olefins, need io 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 Hydevcar
bons by Potentiometie Titration? was withdrawn in 1985
because of health concerns regarding its use of carbon tetra
chloride as a solvent. It was eventually replaced by DS776.
Bromine Index of Aromatic Fydrocarbons by Electrometric
Titration,’ which is based on D2710, Bromine Index of Petro-
lem Hydrocarbons by Electromettie Titration,’ but uses the
less toxie I-methyl-2-pyrrolidinone as a solvent
Tmptrities other than hydrocarbons are of concern ia the
petroleum industry. For example, many eatalstic processes
are sensitive to sulfur contaminants. Consequently, ASTM,
committees responded by developing @ series of state-of-the:
art methods to determine trace concentrations of sulfur-con
taining compounds. These methods inclided ASTM Test
Methods D1685, Traces of Thiophene in Benzene by Spectro
photometry, D391, Trace Quantities of Sulfurin Liquid Ar
‘omatic Hydrocarbons by Oxidative Microcoulometry,
D4C45, Sulfur in Petroleum Products by Hydrogenclysis and
Ratcomotrie Colorimeuy,” are D4735, Trace Thiophene in
Refined Benzene by Gas Chromatography.’ Chloridecon-
taining impurities are determined by ASTM Test Methods
15194, Trace Chloride in Liquid Aromatic Hydrocarbons,
and D5808, Determining Organic Chloride in Aromatic Hy-
drocarbons ancl Related Chemicals by Microcoulometey/! Ni:
trogen-containing impurities are determined by ASTM Test
Method D6089, Trace Nitrogen in Aromatic Hydrocarbons by
Oxidative Combustion and Reduced Pressure Chem:
luminescence Detection! Many of these test methods have
sensitivity 10 1 mg/kg, reflecting the needs of industry to de-
termine very low levels of these contaminants.
In addition to those tests previously mentioned, « number
of other ASTM Test Methods are regularly used for the analy
sis of aromatics and are listed below:
bea?
Acidity of Benzene, Toluene, Xylenes, Solvent Naph-
thas, and Similar Industrial Aromatic Hydrocar
bons!
Discontinuad, see 1985 Annual Book of ASTM Standards, Vol.
05,08,
1493. Solidification Point of Industrial Orsanic Chemicals!
DISS5_ Calculation of Volume and Weight of Industrial
Aromatic Hydrocarbons*
D1636 Color of Solid Aromatic Hydrocarbons and Related
Materials in the Molten. State (Platinum-Cobalt
Sealey!
D2119 Aldehydes in Styrene Monomer!
2121 Polymer Content of Styrene Monomer*
1D2340_Peroxides in Styrene Monomer’
2935 Apparent Density of Industrial Aromatic Hydrocar-
bons!
3160 Phenol Content of Cumene (Isopropylbenzene) or
AMS (a-Methylstyrene)*
13505 Density or Relative Density of Pure Liquid Chemi-
cals!
13799 Purity of Styrene by Freezing Point Method!
14590 Colorimetric Determination of p-ert-Butyleatechot
in Styrene Monomer or AMS (a-Methylstyrene) by
Spectrophotometry*
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 Committze D16 to write these methods
in @ timely manner has been made possible, in part, by
increased vendor activity, a trend thet is expected to con-
tinue,
For relative density, most labs now use ASTM Test Method
14052, Density and Relative Density of Liquids by Digital
Density Meter.' Distillation methods have been or are being
rewritten to include automated distillation apparatus. For
ttace sulfur, D4045 has become the industry standard. Re-
cenily, this method has been optimized for aromatics analy-
is a ASTM Test Method D6212, Total Sulfur in Aromatic
Compounds by Hydrogenolysis and Rateometric Colorime-
try.’ 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-
