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Профессиональный Документы
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Harry N. Giles is retired from the Department of Energy Clifford O. Mills is retired from CONOCO where he served
where he was manager of crude oil in numerous capacities. At retire-
quality programs for the Strategic ment, after 35 years, he was a labo-
Petroleum Reserve. This included ratory consultant with an emphasis
development and management of on crude oil analysis. Mr. Mills has
analytical programs for monitoring been involved with ASTM methods
quality of stocks, and research relat- development since the early 1980s.
ed to the biological and geochemi- Until recently, he was chairman
cal aspects of petroleum stockpiling. of ASTM D02.05 on Properties of
He was employed by the Department of Energy for over 30 Fuels, Petroleum Coke and Carbon Material, and also chaired
Crude Oils
Fuels. He is chairman emeritus of IASH, and was elected
to honorary membership in 2009. Currently, he serves as
Executive Director of the Crude Oil Quality Association.
www.astm.org
ISBN: 978-0-8031-7014-8
Stock #: MNL68
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Crude Oils: Their Sampling, Analysis,
and Evaluation
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ii
Giles, Harry N.
Crude oils: their sampling, analysis, and evaluation/Harry N. Giles and Clifford O. Mills.
p. cm.
Includes bibliographical references and index.
ISBN: 978-0-8031-7014-8
1. PetroleumAnalysis. I. Mills, Clifford O. II. Title.
TP691.G545 2010
665.5dc22 2010031882
Copyright 2010 ASTM International, West Conshohocken, PA. All rights reserved. This material may not be repro-
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iii
Foreword
THIS PUBLICATION, Crude Oils: Their Sampling, Analysis, and Evaluation, was sponsored by ASTM com-
mittee D02 on Petroleum Products and Lubricants. The authors are Harry N. Giles, Consultant, 2324 N.
Dickerson Street, Arlington, Virginia 22207 and Clifford O. Mills, Consultant, 1971 E. Tower Road, Ponca
City, Oklahoma 74604. This is Manual 68 in the ASTM International manual series.
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v
Acknowledgments
This manual is based on the ASTM International Technical Intertek; KBW Process Engineers; Koehler Instruments; Arden
and Professional Training Course of the same name that has Strycker, Northrop Grumman Mission Systems; Patrice Per-
been taught by the authors at several locations worldwide kins, PetroTech Intel; Professor G. Ali Mansoori, University
numerous times since 2005. This manual would not have of IllinoisChicago; Professor Bahman Tohidi, Institute of
been possible without the support and encouragement of Petroleum Engineering; Heriot-Watt University; Dan Villa-
many of our colleagues and participants in the course. We lanti, Triton Analytics; Anne Brackett Walker, W. L. Walker
are grateful to many individuals and companies for provid- Co.; and David Fish, Welker Engineering. We apologize if
ing us some of the material included herein. We appreciate we neglected to mention someone that has assisted us; this
their willingness to share this information because it makes is not intentional. Dr. Arden Strycker of Northrop Grum-
our task easier illustrating some of the topics. The following man Mission Systems kindly reviewed the manuscript and
individuals and companies provided some of the material provided many valuable comments that helped us improve
included in this course: Baker Hughes and Larry Kremer; the contents. We also thank the staff at ASTM Interna-
Canadian Crude Quality Technical Association and Andre tional, who helped in making the course a reality, and the
Lemieux; Chevron Energy Technology Company and Anne Sha- members of the Publications Department for their guid-
fizadeh; Crude Oil Quality Association; DynMcDermott Petro- ance, support, and, most of all, their patience during the
leum Operating Co.; Google and the WorldWideWeb; preparation of this manual.
Harry N. Giles
Arlington, VA
Clifford O. Mills
Ponca City, OK
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vii
Contents
Glossary of Terms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Chapter 1: Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Brief History of Crude Oil Exploitation and Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Strategic Importance of Crude Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Chapter 2: Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Manual Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Automatic Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Sampling for Vapor Pressure Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Mixing and Handling of Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Sample Chain of Custody . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Sample Archive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
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viii CONTENTS
Appendix 3: Excerpts from Standards Used for Sampling, Handling, and Analysis . . . . . . . . . . . . . . . . . . . . . . . . 44
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
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ix
Glossary of Terms
AdditivesSubstance added to a crude oil stream in rela- Opportunity crudeA crude oil priced below market value.
tively minor amounts to facilitate its production and trans- An opportunity crude may be production from a new field
portation and minimize adverse effects on equipment. These with little or no processing history, a distressed cargo, or a
include pour point depressants, drag reducing agents, demul- crude oil with a known history that reduces refinery profit-
sifiers, and corrosion inhibitors. ability. This latter can result from the crude having a high
total acid number, sulfur content, and/or metals, problem-
API gravityA special function of relative density (specific atic contaminants, or is difficult to upgrade or has unattrac-
gravity) 60/60F, represented by: tive yields.
API = 141.5/(specific gravity 60/60F) 131.5 Referee test methodAn analytical method designated in test-
[ASTM D1298] ing protocols to be used in case of disputes.
AssayA combination of physical and chemical data that Relative density (specific gravity)The ratio of the mass of a
uniquely describe a crude oil. given volume of liquid at a specific temperature to the mass
BitumenA category of crude oil that is black, highly viscous, of an equal volume of pure water at the same or different
and semisolid at normal temperatures, will not flow without temperature. Both reference temperatures must be explicitly
dilution, and generally has an API of less than 10. stated. [ASTM D1298]
Challenging (or challenged) crudeSee Opportunity crude. Representative sampleA portion extracted from a total vol-
ume that contains the constituents in the same proportion
CompatibilityThe capacity of two or more crude oils to be as are present in the total volume. [ASTM D4057]
commingled without asphaltenes or waxes precipitating or floc-
culating out of the mixture. SamplingAll the steps required to obtain an aliquot repre-
sentative of the contents of any tank, pipe, or other system
CondensateLiquid mixture usually recovered from natural and to place the sample into a suitable laboratory sample
gas consisting primarily of hydrocarbons from approximately container. [ASTM D6470]
C6C12-15, and having an API gravity greater than 45. The mix-
ture may also contain hydrogen sulfide, thiols, carbon dioxide, Slop oilA combination of off-specification fuel, water, refin-
and nitrogen. Some consider condensate to be a light, sweet ery wastes, and transmix. Slop oil is usually processed in the
crude oil. Other terms include gas condensate, natural gas generating refinery but is occasionally exported or shipped
liquids, lease condensate, and natural gasoline. domestically for use as an inexpensive feedstock for process-
ing in atmospheric units.
ContaminantAny material added to a crude oil stream that
is not naturally occurring or exceeds the concentration nor- StabilityThe ability of a crude oil when produced, trans-
mally present. ported, and/or stored to endure without physical or chemical
change, such as flocculation or precipitation of asphaltenes
Crude oilNaturally occurring hydrocarbon mixture, generally and/or waxes.
in a liquid state, which may also contain compounds of sulfur,
nitrogen, oxygen, metals, and other elements. [ASTM D4175] StratificationThe intentional layering of different crudes oils
in a storage container taking advantage of differences in their
DegradationA lessening in quality of a crude oil stream com- density. Cf. Differentiation.
monly resulting from mixing of another stream of poorer quality.
Degradation of a crude oil can also result from biological activity. Synthetic crude oilStream derived by upgrading oil-sands
bitumen and extra-heavy crude oil. Upgrading processes include
DifferentiationNatural development of a density differential hydroprocessing and coking to yield a more fungible, lighter,
from top to bottom in a storage container. Cf. Stratification. less viscous stream.
ImpurityNonhydrocarbons naturally occurring in crude oil. TransmixTransportation mixture is the material present at
These typically include sediment; water; salts; organic acids; the interface between different quality crude oils batched in
heteroatomic compounds of sulfur, nitrogen, and oxygen; a common carrier pipeline system. Generally, at a terminal,
and metalsparticularly nickel and V. the mixture will be relegated to the lower quality crude oil.
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1
Introduction
This manual is intended for whoever is involved with sam- probably more crude oil analyses are routinely performed
pling and analysis of crude oils after they are produced and on a daily basis using inherently similar methods than are
stabilized; essentially the mid- and downstream sectors of the analyses on any single refined petroleum product except, possi-
industry. They will be the operators of pipelines and tankers bly, gasoline.
that transport the crude oil, the terminals that temporarily The overriding issue when performing comprehensive
store it, laboratory personnel that are responsible for its crude oil assays is economics. Crude oils are assayed to
characterization, refiners that eventually process it, and trad- determine (a) the slate of products that can be produced
ers responsible for its sale or acquisition. with a given refinerys process technology, (b) the processing
Crude oils are a highly complex combination of hydro- difficulties that may arise as a result of inherent impurities
carbons; heterocyclic compounds of nitrogen, oxygen, and and contaminants, and (c) the downstream processing and
sulfur; organometallic compounds; inorganic sediment; and upgrading that may be necessary to optimize yields of high-
water. More than 600 different hydrocarbons have been pos- value specification products. Today, analytical data are typi-
itively identified in crude oil, and it is likely that thousands cally stored in electronic databases that can be accessed by
of compounds occur, many of which probably will never be computer models that generate refinery-specific economic
identified. In a study sponsored by the American Petroleum valuations of each crude oil or crude slate; that is, a mixture
Institute (API) in the 1960s, nearly 300 individual hydrocar- of crude oils processed together. Linear programming (LP)
bons were identified in Ponca City, Oklahoma, crude oil [1,2]. models are available from several commercial vendors, but
In another API project beginning in the 1950s, some 200 indi- several companies have developed their own models to meet
vidual sulfur compounds were identified in a 20-year system- the needs of their specific refinery configurations.
atic study of four crude oils [3]. In the ensuing 50+ years, Analyses are also performed to determine whether each
hundreds, and perhaps thousands, of other hydrocarbons and batch of crude oil received at a terminal or the refinery gate
sulfur compounds have been identified using increasingly meets expectations. Can the crude oil be commingled into a
more sophisticated instrumentation. Not only is the composi- common stream pipeline system, or does it need to be batched?
tion of crude oil highly complex, it is also highly variable from Does the crude receipt match the database assay so that the
field to field, and even within a given field it is likely to exhibit projected economic valuations and operational strategies are
inhomogeneity from reservoir to reservoir. Physical and chemi- valid? Has any unintentional contamination or purposeful adul-
cal characterization of this complex mixture is further compli- teration occurred during gathering, storage, or transport of the
cated for the analyst by the fact that crude oils are not pure crude oil that may increase the processing cost or decrease the
solutions but commonly contain colloidally suspended compo- value of the refined products? The information needed to
nents, dispersed solids, and emulsified water. answer these questions is often refinery-specifica function of
Compared with refined products such as gasoline and the refinerys operating constraints and product slateand, al-
aviation turbine fuel, there is relatively little in the literature most certainly, has considerable financial consequences.
on the analysis and characterization of crude oils. Indeed, for To obtain the desired information, two different analyti-
many years, there were relatively few ASTM methods specific cal schemes are commonly used; namely, an inspection assay
to crude oils, although several ASTM methods had been and a comprehensive assay. Inspection assays usually involve
adapted for their analysis. This situation may have resulted, determination of a few key whole crude oil properties such
at least in part, from the historical tendency of refinery as API gravity, sulfur content, and pour pointprincipally as
chemists to independently develop or modify analytical meth- a means of determining if major changes in a crude oil
ods specific to their needs and, subsequently, for the methods streams characteristics have occurred since the last compre-
to become company proprietary. In recent years, the unique hensive assay was performed. Additional analyses may be
problems associated with sampling and analysis of crude oils performed to help ensure that the quality of the cargo or
have received more attention, and more methods for determin- shipment received is that which is expected; to ascertain the
ing selected constituents and characteristics of crude oils have quantity of impurities such as salt, sediment, and water; and
been standardized. to provide other critical refinery-specific information. Inspec-
A series of articles [4-9] illustrates the diversity of crude tion assays are routinely performed on all shipments received
oil assay practices used by major refiners in the United States at a terminal or refinery. On the other hand, the comprehen-
and Austria. The dissimilarity of published results [10] and as sive assay is complex, costly, and time-consuming and is nor-
provided by several companies on their Web sites [11] is a mally performed only when a new field comes on stream for
reflection of this independent development of analytical which a company has an equity interest, a crude that has not
schemes, although standardized approaches to crude oil analy- previously been processed arrives at a refinery, or when the
sis have been published [12-15]. Despite the complexity of crude inspection assay indicates that significant changes in the streams
oil composition and the diversity of analytical methodology, composition have occurred. Except for these circumstances,
1
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2 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
a comprehensive assay of a particular crude oil stream may success, Sillimans report became an important document in
not be updated for several years. promoting commercial development at Titusville, which is
Moreover, many major pipeline companies require a com- located in Venango County.
prehensive assay when accepting a new crude oil stream for Thereafter, developments in the petroleum industry
transportation in their system on a common stream basis. spread worldwide but were most prevalent in North America
Thereafter, an inspection assay is used for checking the qual- and in the Caspian Sea region. Many significant developments
ity of shipments. in the exploitation and use of crude oil took place in Azerbai-
jan and Russia in the mid- to late 19th century. Azerbaijan is
BRIEF HISTORY OF CRUDE OIL the oldest known oil-producing region in the world, and it
EXPLOITATION AND USE was there that Russian engineer F. N. Semyenov drilled the
Herodotus, the ancient Greek historian, recorded about 440 first modern oil well in 1848. The first offshore well was also
BCE that the Mesopotamians in 40th century BCE used bitu- drilled in the Azerbaijan area of the Caspian Sea at the end
men to caulk their ships and as an adhesive [16]. This is of the 19th century [23]. Ludvig and Robert Nobel, brothers
thought to be the first recorded use of petroleum by a civili- of Alfred, the inventor of dynamite and benefactor of his
zation. Herodotus also recorded that beginning about 1000 namesake Nobel Prize, were responsible for considerable devel-
BCE, the ancient Egyptians used crude oil or a derivative in opment of Azerbaijans petroleum resources and for several
their mummification process. The term mummy is derived technological advances. Beginning in 1877, they had a fleet
from the Persian word mummeia, meaning pitch or asphalt. of tankers, several railway tank cars, and a pipeline built for
Many ancient civilizations including those of the Persians and transporting crude oil. The brothers introduced the use of
Sumerians used bitumen for medicinal purposes, a practice tanks to store crude oil, rather than in the commonly used
also known to have been used by pre-Columbian cultures in open vessels and pits [24]. This practice resulted in large losses
the Americas. Further documentation of the medicinal uses of through evaporation and oil penetrating into the ground and
petroleum was provided by Georgius Agricola, the 16th cen- significant ecological damage that persisted for decades. By
tury German physician and scientist in his De Natura Fossil- 1900, Azerbaijan was the worlds largest producer of crude oil.
ium [17]. In that, he reported that It is used in medicine Totten provides a comprehensive timeline of the impor-
Spread on cattle and beasts of burden it cures mange and tant events in the history of the petroleum industry from
Pliny writes that the Babylonians believed it to be good for ancient times to the present [19]. Table 1 provides a summary
jaundice They also believed it to be a cure for leprosy (and) of some of the highlights in ancient and modern exploitation
it is used as an ointment for the gout. In this latter respect, it and use of crude oil.
has been reported by several writers that, in 1539, oil in some Zayn Bilkadi, in his introduction to Babylon to Baku
form was exported from Venezuela to Spain for use in treating [25], accurately portrayed the importance of petroleum in
gout suffered by the Holy Roman emperor Charles V. In his todays world.
Travels, Marco Polo wrote of its use in the 13th century in
the Caspian Sea region to treat mange in camels and as a ther- There is one natural material which touches almost
apeutic ointment for various skin conditions in humans [18]. every facet of our lives; it assists us to travel long dis-
From the writings of Agricola and others on the medicinal vir- tances, it is an ingredient in many of our medicines, it
tues of petroleum, it is no wonder that centuries later snake oil is used in the manufacture of our clothes and in the
salesmen were so successful in marketing their concoctions microchips we build into our computers. In fact, it is
many of which contained crude oil or some derivative. essential to our daily existence.
The earliest known oil wells were drilled in China in
347 CE to depths of as much as 240 m using bits attached That material is, of course, crude oil.
to bamboo shafts. In 1594, a well was hand dug near Baku, A few of the superlatives that can be attributed to crude
Azerbaijan to a depth of 35 m [19]. Hand dug wells contin- oil are
ued to be used in Azerbaijan until the mid-19th century for Volume produced each day worldwide is sufficient to
recovery of crude oil [18]. fill a string of railroad tank cars over 2100 km in length
The modern history of petroleum perhaps dates from Basis of worlds first trillion dollar industry
1846 when Abraham Gesner developed a process for extracting Worlds most actively traded commodity
what he termed keroselain from coal [20]. In 1853, Ignacy Largest single item in balance of payments and exchanges
Lukasiewicz, a Polish pharmacist, made improvements to Ges- between nations
ners process and used it to distill kerosene from seep oil [21]. Employs most of worlds commercial shipping tonnage
In 1854, Benjamin Silliman, a chemist and professor of sci- More than 1 million km of pipelines are dedicated to its
ence at Yale University, became the first person known to frac- transportation
tionate petroleum by distillation. This was followed in 1855 by
his Report on the Rock Oil, or Petroleum, from Venango Co., STRATEGIC IMPORTANCE OF CRUDE OIL
PA, with special reference to its use for illumination and other Early in the 20th century, Winston Churchill successfully
purposes [22]. In this, he documented that half of the crude oil argued that the British Navy should switch from coal to
he studied could be economically exploited as an illuminant and petroleum to power its warships [26]. In 1907, the Oil & Gas
that much of the remaining byproducts had commercial value. Journal in an article titled When Will the United States
The first commercial oil discovery in North American was Navy Wake Up! reported on the British Admiralty convert-
made in 1858 in Ontario, Canada, when a 3-m deep hand dug ing its warships from use of coal to crude oil as fuel [27].
pit encountered a pool of crude oil. This predated by one year The article went on to state that Japan is also aware of the
the more famous well drilled by Colonel Edwin Drake near fact that coal is so scarce in (the Pacific Ocean) that the use
Titusville, Pennsylvania, to a depth of 21 m. Following Drakes crude oil as fuel is absolutely imperative to insure success or
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CHAPTER 1 n INTRODUCTION 3
Sillimans report was followed just 1 year later by a Beginning in 1924, API began supporting several research
report that dealt with the artificial destructive distillation projects on the heteroatomic composition of crude oil. The
and characterization of Burmese Naphtha, or Rangoon Tar first two of these, initiated in 1926, were to isolate and study
[32]. In this, it was noted that the material contains indeed sulfur and nitrogen compounds. This was followed in 1927
so great a variety of substances, and some of them in so by a project on the metallic constituents of crude oil [34].
exceedingly minute a proportion, that even the large amount These and several other studies that continued into the 1960s
of material at our disposal was insufficient for the complete used separation, analysis, and compound identification techni-
examination of several constituents, the presence of which ques, some of which might seem primitive by modern stand-
we had succeeded in establishing beyond a doubt. In the ards, yet they succeeded in separating and identifying over
course of the investigation, several aromatic compounds 600 individual hydrocarbons and over 200 individual sulfur
were separated and studied in great detail. compounds. Unquestionably, these studies have been funda-
By the end of the 19th century, great strides had been mentally important in our understanding of the origin, chemis-
made in determining the composition of crude oil, mostly try, and geochemical history of crude oil.
by Russian scientists and engineers involved in its refining. In the last 40 years, advances in instrumentation have
allowed the petroleum chemist to separate and identify
It was clear that crude oil was a greatly varying mix- crude oil components that are characterized as novel by
ture of widely different hydrocarbons, a mixture of some investigators [35]. However, these are present in such
straight-chain paraffins (sometimes with short side infinitesimally small concentrations that they do not have
chains), of aromatic hydrocarbons deriving from ben- even a trivial effect on refining or product quality, yet they
zene, and cyclic hydrocarbons or naphthenes having a may provide important insight into the origin of petroleum
ring structure with five or six carbon atoms as nucleus. and its transformation in the reservoir. These techniques
Besides these saturated hydrocarbons there might also include gas chromatography (GC), mass spectrometry (MS),
be present small quantities of unsaturated olefins, sul- atomic absorption and inductively coupled plasma (ICP) spec-
phur, nitrogen and oxygen compounds, which gave each trometry, and numerous multihyphenated techniques such as
crude a special character and compelled the refiner to GC-MS, atomic emission spectrometry (AES)-ICP, and ICP-MS,
take its composition into account [33]. among others [36].
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2
Sampling
The basic objective of sampling is to obtain a small portion drums, barrels, and other containers. This practice addresses,
(spot sample) for analysis that is truly representative of the in detail, the various factors that need to be considered in
material contained in a large bulk container, vessel, or pipe- obtaining a representative sample. These considerations
line shipment. Often, the spot sample may be as little as one include the analytical tests to be conducted on the sample, the
part in greater than ten million. Frequently, a series of spot types of sample containers to be used, and any special instruc-
samples may be collected and composited for analysis, tions required for special materials such as crude oils to be
which can help to minimize randomness and nonhomogene- sampled. Test Method D5854 provides additional guidance for
ity and make for a somewhat more representative sample. sample mixing and handling. In many liquid manual sampling
Samples to be composited must be thoroughly mixed and applications, it must be kept in mind that the material to be
volumetrically proportional. sampled contains a heavy component (e.g., free water) that
Crude oil to be sampled may be in static storage in an tends to separate from the main component. Unless certain
above- or underground tank or a marine vessel, or it may be conditions can be met to allow for this, an automatic sampling
flowing through a pipeline or vessel offloading line. For system as described in ASTM D4177 is highly recommended.
static storage, samples are collected manually using several
different devices. For streams flowing in a pipeline, auto- Apparatus
matic sampling methods are used. In establishing a sampling Sample containers come in various shapes, sizes, and materi-
protocol, the analytical tests to be performed will dictate the als. To be able to select the right container for a given appli-
volume of sample needed, type(s) of container(s) to be used, cation, one must have knowledge of the material to be
and precautions necessary to preserve sample integrity. The sampled to ensure that there will be no interaction between
latter consideration is especially important for samples to be the sampled material and the container that would affect the
collected for vapor pressure determination or measurement integrity of the other. Additional considerations in the selec-
of hydrogen sulfide (H2S) content. tion of sample containers are the type of mixing required to
The importance of adhering to a rigorous sampling pro- remix the contents before transferring the sample from the
tocol to ensure that samples are representative of the bulk container and the type of laboratory analyses that are to be
material cannot be overemphasized. Representative samples conducted on the sample. For most samples, the container
are required for the determination of chemical and physical must be large enough to contain the required sample vol-
properties used to establish standard volumes and compli- ume without exceeding 80% of the container capacity. The
ance with contractual specifications. Maintaining composi- additional capacity is required for thermal expansion of the
tional integrity of these samples from the time of collection sample and to enhance sample mixing efficiency.
until they are analyzed requires care and effort.
Moreover, it is critically important that the sampling pro- SAMPLE MIXING SYSTEMS
cedure does not introduce any contaminant into the sample The sample container should be compatible with the mixing
or otherwise alter the sample so that subsequent test results system for remixing samples that have stratified to ensure
are affected. Procedures for collection and handling of sam- that a representative sample is available for transfer to an
ples for H2S determination are especially critical because of intermediate container or the analytical apparatus. This is
the highly reactive nature and volatility of this compound. especially critical when remixing crude oil samples to ensure
Appendix 1 provides recommended procedures suitable for a representative sample. When separation of entrained con-
collection and handling of samples for determination of H2S stituents such as sediment and water is not a major concern,
in crude oil. These were developed by the U.S. Department of adequate mixing may be achieved by such methods as shak-
Energys Strategic Petroleum Reserve in support of its crude ing (manual or mechanical) or use of a shear mixer. How-
oil assay program and underwent rigorous field and labora- ever, manual and mechanical shaking of the sample
tory testing [37]. With proper handling, samples do not exhibit container are not recommended methods for mixing a sam-
detectable loss of their H2S for a minimum of 10 days. ple for sediment and water analysis. Tests have shown it is
difficult to impart sufficient mixing energy to mix and main-
MANUAL SAMPLING tain a homogeneous representative sample.
ASTM D4057: Practice for Manual Sampling of Petroleum and
Petroleum Products1,2 provides procedures for manually SAMPLE TRANSFERS
obtaining samples, the vapor pressure of which at ambient The number of intermediate transfers from one container to
conditions is below 101 kPa (14.7 psi), from tanks, pipelines, another between the actual sampling operation and testing
1
Appendix 2 lists the ASTM and other standards referenced in this manual.
2
Appendix 3 provides excerpts from the Scope and certain other sections for most of the ASTM standards cited in this manual.
5
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6 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
should be minimized to the maximum extent possible. The MIXING AND HANDLING OF SAMPLES
loss of light hydrocarbons as the result of splashing, loss of ASTM D5854: Practice for Mixing and Handling of Liquid
water due to clingage, or contamination from external sour- Samples of Petroleum and Petroleum Products covers the
ces, or a combination thereof, may distort test results. The handling, mixing, and conditioning procedures that are
more transfers between containers, the greater the likelihood required to ensure that a representative sample is delivered
one or more of these problems may occur. from the primary sample container or receiver into the ana-
lytical test apparatus or into intermediate containers. This
SAMPLE STORAGE practice also provides a guide for selecting suitable contain-
Except when being transferred, samples should be main- ers for crude oil samples for various analyses.
tained in a closed container to prevent loss of light compo- Further guidance and precautions to be observed in
nents. Samples should be protected during storage to sampling for specific tests such as water determination and
prevent weathering or degradation from light, heat, or other measurement of vapor pressure are provided in discussion
potentially detrimental conditions. Refrigerated storage at of the relevant test methods elsewhere in this manual.
approximately 5C will help preserve compositional integrity
when samples are stored for protracted periods. Sample Containers
No single container type will meet requirements of all sam-
SPECIAL PRECAUTIONS pling operations or restrictions necessary to ensure sample
Crude oil almost invariably contains sediment and water, compositional integrity for different tests. Sample containers
which will rapidly settle out, and may contain H2S, an must be clean and free from all substances that might con-
extremely toxic gas. Sampling of tanks through a stand pipe taminate the material being sampled, such as water, dirt,
that is not slotted or perforated will not yield a representa- washing compounds, naphtha or other solvent, soldering
tive sample. When crude oil is to be tested for vapor pres- fluxes, acid, rust, and oil. Table 1 provides a guide for select-
sure, care must be exercised in sample collection and ing the sample container most suitable for various crude oil
handling, and reference should be made to ASTM D5842. analyses. It is impossible to cover all sampling container
requirements; therefore, when questions arise as to a con-
AUTOMATIC SAMPLING tainers suitability for a given application, experience and
ASTM D4177: Practice for Automatic Sampling of Petroleum testing should be relied upon. Regardless of the container
and Petroleum Products covers information for the extraction type, before a sample is transferred from one container to
of representative samples of petroleum from a flowing stream another, a homogenous mix must be created and maintained
and storing them in a sample receiver. Several precautions until the transfer is complete. Even new containers should
must be observed in the use of automatic systems when sam- be inspected for cleanliness before use.
pling crude oil. Free and entrained water must be uniformly
dispersed at the sample point. The sample must be maintained Sample Mixing Methods
in the sample receiver without altering the sample composi- Sample mixing methods can be divided into three general
tion. Venting of hydrocarbon vapors during receiver filling and categories of power mixing, shaking, and no mixing. These
storage must be minimized. A properly designed, installed, categories vary greatly in severity depending on the equip-
tested, and operational automatic sample system is to be pre- ment used, the type of analytical test to be conducted, and
ferred to manual sampling and is more likely to provide a rep- the characteristics of the sample. Further, power mixers are
resentative test specimen that can be delivered into the of two subtypesinsertion and closed loop. Overmixing with
analytical apparatus. power mixers may create an oil and water emulsion that will
affect the accuracy of certain analytical tests. Power mixers
SAMPLING FOR VAPOR PRESSURE may entrain air into the sample that could affect certain ana-
DETERMINATION lytical tests. Loss of vapor normally associated with rise in
ASTM D5842: Practice for Sampling and Handling of Fuels for temperature may also occur, which could affect test results
Volatility Measurements covers procedures and equipment for for water, Reid vapor pressure (RVP), and density. Shaking
obtaining, mixing, and handling representative samples of vol- simply involves manually or mechanically shaking the sam-
atile fuels. Although directed to products such as gasoline and ple container to redisperse separated constituents such as
reformulated fuels, the guidance provided is also useful in sediment and water. If a sample is known to be homogene-
sampling and handling of crude oils and condensates. ous, no mixing is required; however, this is rarely the case
Vapor pressure is extremely sensitive to evaporation with crude oils. Nevertheless, samples should not be mixed
losses and to slight changes in composition. The precautions when the analytical tests to be conducted may be affected by
required to ensure the representative character of the sam- air, which could be introduced by power mixing or shaking.
ple are numerous and depend on the tank, carrier, con- When the results will be affected by interference from extra-
tainer, or pipe from which the sample is being obtained; the neous material such as water and sediment, the sample
type and cleanliness of the sample container; and the sam- should not be shaken. Table 2 lists the recommended mixing
pling procedure that is used. For example, ASTM D323 procedure to be used before a sample is transferred from a
requires that the sample shall be taken in 1-L containers container for certain crude oil tests.
filled 7080 %. The sample container and its contents have
to be cooled to a temperature of 01C before the container SAMPLE CHAIN OF CUSTODY
is opened. With crude oils with a pour point greater than Chain-of-custody procedures are a necessary element in a pro-
1C, this requirement can affect results. Directions for sam- gram to ensure ones ability to support data and conclusions
pling cannot be made explicit enough to cover all cases, and adequately in a legal or regulatory situation. ASTM D4840:
extreme care and good judgment are necessary. Guide for Sample Chain-of-Custody Procedures contains a
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TABLE 1Summary of Container Materials for Crude Oils (ASTM D5854)
Type of Analysis
Neutrali-
Hydro-Carbon zation Pour Trace Vapor
Density Chloride Distribution Number Point Salt S and W Sulfur Metals Pressure Viscosity
Downloaded/printed by
Immediate use S P NP P S S S P P S S
Storage6 months S P NP P S S S P P S S
Reuse S P NP P S S S P S S S
Stainless steel
Immediate use S S S S S S S S S S S
Storage6 months S S S S S S S S S S S
Reuse S S S S S S S S S S S
Epoxy-lined steel
Immediate use P S S S S S P S S S S
Storage6 months P S S S S S P S S S S
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Reuse S S S S S S S S S S S
Immediate use S S S S S S S S NR S S
Storage6 months NR NR NR NR NR NR NR NR NR NR NR
Reuse NR NR NR NR NR NR NR NR NR NR NR
Immediate use S S NP S S S S S P S S
Reuse S S NP S S S S S S S S
n
Immediate use S S NP S S S S S P S S
Storage6 months S NR NP NR NR NR NR NR NR NR NR
Reuse S NR NP NR NR NR NR NR NR NR NR
SAMPLING
Note 1The containers listed in this summary should not be used without consulting the appropriate paragraphs of this practice for detail advice.
Note 2Where REUSE is indicated, containers should be cleaned in accordance with 6.7 prior to reuse.
Note 3 Legend:
NR = not recommended
NP = not practical
7
P = preferred
5 = suitable
8 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
SUMMARY
TABLE 2Summary of Recommended Mixing In any sampling operation, whether manual or automatic, it
Procedures for Crude Oils must be kept in mind that crude oils are not homogeneous.
Recommended Mixing Procedure They contain sediment and water that can settle out and
asphaltenes and waxes that can flocculate or precipitate out
Test Purpose Power None under certain conditions. In pipeline shipments, different
Density X crudes will commonly be batched, and some mixing will
take place between the heads and tails of these. When crude
Sediment and water X oils are discharged into a storage tank, there will frequently
Vapor pressure X be a tank heel that may be of different quality. During stor-
age in a tank, crudes oilseven a single crudecan differenti-
Sulfur by X ray X ate and exhibit a density differential from top to bottom.
Other tests Note 1 Note 1 Also, sediment and water present in the incoming crude oil
will settle during storage. Conversely, sediment and water
Note 1 = Refer to specific analytical test procedure. already present in a tank heel can be resuspended by the
turbulence created when further crude oil is pumped in.
Crude oil can also exhibit a density differential from one
side of a tank to the opposite because of heating by the
comprehensive discussion of potential requirements for a sam- Suns rays. At a terminal, when storage capacity is at a pre-
ple chain-of-custody program and describes the procedures mium, operators may intentionally layer similar quality
involved. The purpose of these procedures is to provide crudes in a tank. Collection of a representative sample may
accountability for and documentation of sample integrity from be impeded by the presence of deadwood in ships compart-
the time samples are collected until they are disposed of. ments and tank stand pipes that are not slotted or perfo-
rated. In sampling a pipeline, flow must be turbulent and
SAMPLE ARCHIVE not laminar. With dense or viscous crude oils, this can
Samples, or representative portions thereof, should be main- become problematic.
tained in a sample archive for a minimum of 45 days, although In conclusion, it was accurately said Sampling is truly
the time requirement can be from 30 to 180 days. Archived an art. Failure to use proper techniques can cost companies
samples may be needed in case of disputes, should additional huge sums of money daily. Sampling is too critical to be
data become necessary, or to conform to contractual require- left to guess work, old outdated methods, or unproven
ments or environmental or governmental regulations. techniques [38].
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MNL68-EB/Nov. 2010
3
Inspection Assays
INTRODUCTION been adapted to and are widely used and accepted for crude
The testing of crude oils to determine their quality and to oil analysis.
assess refining characteristics generally involves two sequen-
tial but complimentary series of tests. An inspection analysis API GRAVITY AND DENSITY
as described in this chapter is performed initially to deter- Accurate determination of the density or API gravity of
mine a few to numerous whole crude oil properties. This is crude oil is necessary for the conversion of measured vol-
followed by a detailed comprehensive analysis described in umes to volumes at the standard temperature of 15.56C
the next chapter that involves distillation of the crude oil (60F) using ASTM D1250: Petroleum Measurement Tables.
into several fractions or cuts that are analyzed to determine API gravity is a special function of relative density (specific
their suitability for use or blending into a host of refined gravity) represented by the following:
products.
Inspection assays comprise a relatively limited number 141:5
API gravity; degrees 131:5
of tests generally restricted to the whole crude oil. On the specific gravity 60=60 F
basis of published data, there is little agreement as to what 1
constitutes an inspection assay. Because the data are primar-
ily for intracompany use, there is little driving force for a No statement of reference temperature is required because
standard scheme. At a bare minimum, American Petroleum 60F is included in the definition. Fig. 1 depicts the relation-
Institute (API) gravity and sulfur, sediment, and water con- ship between the two. A specific gravity of 1.00that of
tent are usually determined, although it is useful to also waterequates to an API gravity of 10.0.
know the pour point, which provides some basic perception
of the crude oils fluidity and composition. A more detailed API Gravity History
inspection assay might consist of the following tests: API In 1916, the U.S. National Bureau of Standards adopted the
gravity (or density or relative density), total sulfur content, Baume scale as the standard for measuring the specific grav-
pour point, viscosity, carbon residue, salt content, total acid ity of liquids less dense than water. The Baume scale, devel-
number (neutralization number), and water and sediment oped in 1768, used solutions of sodium chloride (NaCl) in
content. Individual shippers and refiners may substitute or water for degree calibration. When adopted, a large margin
add tests (e.g., trace metal or organic halide tests) that may of error was unintentionally introduced as later found in
be critical to their operations. Combining the results from investigation by the U.S. National Academy of Sciences. This
these few tests and high-temperature simulated distillation resulted in hydrometers in the United States being manufac-
data of a current crude oil batch with the archived data tured with a modulus of 141.5 rather than the correct
from a comprehensive assay, the process engineer will be Baume scale modulus of 140. By 1921, the scale was so
able to estimate generally the product slate that the crude firmly established that API created the API gravity scale,
will yield and any extraordinary processing problems that which recognized the scale being used by the industry [40].
may be encountered. Density and API gravity are also factors indicating the
In the early 1990s, the API formed an Ad Hoc Crude Oil quality of crude oils. Generally, the heavier (lower the API
Quality Task Force. The report of this task group recom- gravity) the crude oil the greater the quantity of heavier
mends a set of crude oil quality testing procedures that, if components that may be more refractory and require
adopted by a shipper or refiner, would help ensure the qual- greater upgrading or more severe cracking to produce sala-
ity of crude oil from the wellhead to the refinery [39]. These ble products. Conversely, the lighter the crude oil the greater
procedures include tests for API gravity, sediment and water the quantity of easily distillable products. Crude oil prices
content, organohalide compounds, salt, sulfur, and neutrali- are frequently posted against values in kilograms per cubic
zation number, among others. Although not a standard, it is metre (kg/m3) or in degrees API. However, this property
an important aid to members of the petroleum industry in alone is an uncertain indication of quality and must be cor-
protecting the quality of common stream crude petroleum related with other properties.
from contamination by foreign substances or crude petro- The relative density (specific gravity) or density of a
leum of unspecified makeup. The report is also a useful crude oil may also be reported in analyses. Relative density
guide for an inspection program using mostly standardized is the ratio of the mass of a given volume of liquid at a spe-
procedures widely accepted in the industry for monitoring cific temperature to the mass of an equal volume of pure
the quality of mercantile commodity. water at the same or a different temperature. Both reference
It is important to note that, in the following discussion temperatures must be explicitly stated. Density is simply the
of test methods, crude oil may not be included in the title mass of liquid per unit volume at 15C, with the standard
or even in the scope. However, many test methods have unit of measurement being kg/m3.
9
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10 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
1.1 than for lighter crude oils. Sediment and water do not readily
settle out, and air bubbles are not easily seen.
Sp. Gr., 60/60 deg F
These older techniques have now largely been replaced sulfide. H2S is also known to be produced by action of sul-
by two instrumental methods: ASTM D2622: Test Method for fate-reducing bacteria (SRB) in storage tanks, in the legs of
Sulfur in Petroleum Products by X-Ray Spectrometry and offshore production platforms used for storage, and in the
ASTM D4294: Test Method for Sulfur in Petroleum Products dead legs of pipelines. Studies have shown that the H2S pres-
by Energy-Dispersive X-Ray Fluorescence Spectroscopy. ent in some crude oil reservoirs has unequivocally resulted
A fundamental assumption in ASTM D2622 is that the from SRB activity [41]. Sulfate reduction in the reservoir by
sample and standard matrices are well matched. When the ele- SRB introduced with water used for enhanced oil recovery is
mental composition of the sample differs significantly from now widely accepted as the most significant mechanism con-
that of the standard, errors in the sulfur determination can tributing to formation of H2S in crude oils [42].
result. For crude oils, this matrix mismatch is usually the In analyses, it is important to report H2S as dissolved
result of differences in the carbon-hydrogen ratio. Presence of (existent; that which is naturally present) or evolved (poten-
interfering heteroatomic species is less likely to be a contribut- tial; that which results from decomposition of sulfur com-
ing factor. This test method provides rapid and precise pounds on heating or distillation). Elemental sulfur and
measurement of total sulfur with a minimum of sample prep- many thiols will decompose when heated and form H2S.
aration. However, the equipment tends to be more expensive Thiols or mercaptans are considerably more prevalent
than for alternative test methods, such as ASTM D4294. in crude oils than H2S. They are the least stable sulfur com-
In the round-robin studies used to develop precision pounds and many decompose on heating to form H2S. This
data for ASTM D2622 and ASTM D4294, the highest level of reaction can begin at less than 100C, with maximum evolu-
sulfur in a sample was 4.6 mass percent. Samples containing tion at approximately 200C [43]. Thiols may be distributed
more than 5.0 mass percent should be diluted to bring the across a wide boiling range, extending from the lightest frac-
sulfur concentration of the diluted material within the scope tion well into vacuum gas oil, and can give rise to evolution
of the test method. However, samples that are diluted can of H2S across much the same boiling range. Free sulfur is
have higher errors than nondiluted samples. known to occur in crude oils and it will also decompose on
As with ASTM D2622, a fundamental assumption in heating to form H2S.
ASTM D4294 is that the sample and standard matrices are These components are commonly determined by nona-
well matched. Moreover, spectral interferences may arise queous potentiometric titration with silver nitrate (UOP 163:
from the presence of silicon, calcium, and halideselements Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocar-
commonly present in the inorganic sediment inherently pres- bons by Potentiometric Titration). The presence of free sul-
ent in crude oils. In modern instruments, these may be com- fur in samples complicates interpretation of the titration
pensated for with the use of built-in software. ASTM D4294 curves. A newer test method developed specifically for fuel
also provides rapid and precise measurement of total sulfur oils may prove applicable to crude oils with further testing
with a minimum of sample preparation, and the instrumenta- (IP 570 Determination of Hydrogen Sulfide in Fuel Oils
tion is less costly than that for ASTM D2622. Of the two Rapid Liquid Phase Extraction Method). The test method is
methods, ASTM D4294 has slightly better repeatability and automatic, suitable for laboratory or field use, and provides
reproducibility and is also adaptable to field applications. results in approximately 15 min. Crude oils were not included
Sediment, water, and waxes commonly present in crude in the interlaboratory study that developed the methods preci-
oil samples can settle onto the Mylar film sealing the test sion data, and a new round robin will need to be conducted to
cell and interfere in sulfur determination by both of the X-ray obtain these.
methods. Before analysis, water and particulates should be H2S is very volatile and highly reactive, and unless pre-
removed from the sample by centrifugation or settling, but cautions are taken in the collection and preservation of sam-
care must be taken that sample integrity is not compromised. ples, results will not be representative (Appendix 1). A test
ASTM D7343 Optimization, Sample Handling, Calibra- kit has been developed that is very useful for rapidly deter-
tion, and Validation of X-ray Fluorescence Spectrometry mining H2S concentration in liquid samples in the field [44].
Methods for Elemental Analysis of Petroleum Products and This kit has an accuracy of approximately 20 % for H2S. A
Lubricants provides information relating to sampling, cali- commonly used field technique for determining H2S concen-
bration, and validation of X-ray fluorescence instruments tration in head space gases is the so-called Drager tube,
applicable to determination of sulfur by ASTM D2622 and keeping in mind that concentration in the head space can-
D4294. This practice includes sampling issues such as the not be equated to liquid concentration. This is especially
selection of storage vessels, transportation, and subsampling. applicable to marine cargoes as reported in the International
Treatment, assembly, and handling of technique-specific Safety Guide for Oil Tankers and Terminals. It is important
sample holders and cups are also included. Technique- to distinguish between concentrations of H2S in the atmos-
specific requirements during analytical measurement and phere, expressed in ppmv, and concentrations in liquid
validation of measurement are described. petroleum expressed in ppmw. For example, a crude oil con-
taining 70 ppmw H2S has been shown to give rise to a con-
Hydrogen Sulfide and Thiols or Mercaptans centration of 7,000 ppmv in the gas stream [45].
Hydrogen sulfide (H2S) is a highly toxic and corrosive gas
that occurs naturally in some but not all crude oils. H2S can WATER AND SEDIMENT
be formed by thermal decomposition of elemental sulfur and The water and sediment content of crude oil results princi-
thiols, and even crude oils that do not contain the compound pally from production and transportation practices. Water,
naturally may produce the gas on heating or during distilla- with its dissolved salts, may occur as easily removable sus-
tion. Reservoir souring by H2S may occur from reduction pended droplets or as an emulsion. The sediment dispersed
of bisulfite chemicals used as oxygen scavengers, thermal in crude oil may be comprised of inorganic minerals from
decomposition of sulfur compounds, or dissolution of iron the production horizon or from drilling fluids, as well as
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12 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
scale and rust from pipelines and tanks used for oil trans- For both of the Karl Fischer methods, thiols and sul-
portation and storage. Usually water is present in far greater fides (S and H2S) are known to interfere, but at levels of
amounts than sediment, but, collectively, it is unusual for less than 500 lg/g (ppm) the interference from these com-
them to exceed 1 % (v/v) of the crude oil on a delivered pounds is insignificant except at low water levels (<0.02
basis. Water and sediment can foul heaters, distillation tow- mass percent). If thiol and H2S contents are accurately
ers, and exchangers and can contribute to corrosion and to known and water levels are very low, corrections can be
deleterious product quality. Also, water and sediment are approximated for the interfering compounds. The interfer-
principal components of the sludge that accumulates in stor- ence from thiol sulfur follows the theoretical stoichiometry
age tanks and must be disposed of periodically in an envi- of 1 to 0.28; that is, 1,000 lg/g (ppm) of thiol sulfur can gen-
ronmentally acceptable manner. erate a response equivalent to 280 lg/g (ppm) water. The
Further, water bottoms in storage tanks can promote interference from H2S sulfur follows the theoretical stoichi-
microbiological activity and, if the system is anaerobic, pro- ometry of 1 to 0.56; that is, 1,000 lg/g (ppm) of H2S sulfur
duction of corrosive acids and H2S can result. This is not can generate a response equivalent to 560 lg/g (ppm) water.
usually a problem with crude oils because stocks are nor- However, the validity of correcting measured water contents
mally rotated on a regular basis. Nevertheless, anaerobic for known thiol/sulfide levels has not been rigorously deter-
degradation of crude oil stocks and production of H2S has mined and corrections should be made with caution.
been known to happen, and the operator must be aware of Because of the relatively small sample size involved in
the potential for this occurring and the analyst must take the two Karl Fischer methods, in transferring samples by
this into consideration in evaluating results. syringe it is important that no air bubbles be present. Heavy
Knowledge of the water and sediment content is also and viscous oils can be difficult to measure by syringe, and
important in accurately determining net volumes of crude sample aliquots should be drawn by mass rather than
oil in sales, taxation, exchanges, and custody transfers. When volume.
a significant amount of free water is present in a marine
cargo, identification of its probable source should be a Sediment
major consideration. Guidelines that include basic sampling, An accurate method for sediment entails extraction with hot
testing, and analytical procedures and interpretation and toluene in a refractory thimble (ASTM D473: Test Method
presentation of results for this process have been published for Sediment in Crude Oils and Fuels Oils by the Extraction
by API in their Manual of Petroleum Measurement Stand- Method). A somewhat less time-consuming method of deter-
ards [46]. mining sediment involves dissolving a sample in hot toluene
Several test methods exist for the determination of and filtering the solution under gravity through a membrane
water and sediment in crude oil. Some of these are specific filter (ASTM D4807: Test Method for Sediment in Crude Oil
to water alone, others to sediment alone, and one other to a by Membrane Filtration). Fig. 2 is a photomicrograph of
combination of sediment and water. sediment recovered from a crude oil by extraction and mem-
brane filtration. Most of the grains are less than approxi-
Water mately 20 lm in their largest dimension.
Techniques for measuring water content are heating under In assays, sediment values are commonly reported as
reflux conditions with a water immiscible solvent that distills volume percent, rather than in mass percent as determined
as an azeotrope with the water (ASTM D4006: Test Method by these methods. A major portion of the sediment is prob-
for Water in Crude Oil by Distillation), potentiometric titra- ably sand (silicon dioxide, which has a density of 2.32 g/mL)
tion (ASTM D4377: Test Method for Water in Crude Oils by with lesser amounts of other materials having somewhat
Potentiometric Karl Fischer Titration), or the more generally lower densities arbitrarily assumed to be 2.0 g/mL. To obtain
preferred coulometric titration (ASTM D4928: Test Method a value in volume percent for the sediment, divide the mass
for Water in Crude Oils by Coulometric Karl Fischer Titra-
tion). The latter two Karl Fischer methods include a homoge-
nization step designed to redisperse any water that has
separated from the crude oil while the sample has been
stored. Because the two Karl Fischer methods are quite simi-
lar, it has been proposed that they be combined into a single
method with two partsone for potentiometric titration and
the second for coulometric titration. Water may also be
determined by centrifugation, as discussed in the following
subsection on water and sediment.
The precision of the distillation method, especially at
low levels, can be affected by water droplets adhering to sur-
faces in the apparatus and therefore not settling into the
water trap to be measured. To minimize the problem, all
apparatus must be chemically cleaned at least daily to remove
surface films and debris, which hinder free drainage of water
in the test apparatus. At the conclusion of the distillation, the
condenser and trap should be carefully inspected for water
droplets adhering to surfaces. These should then be carefully Fig. 2Photomicrograph in plain transmitted light of sediment
dislodged using a tetrafluoroethylene (TFE) pick or scraper recovered from a crude oil by extraction and membrane filtration
and transferred to the water layer. (Courtesy of Baker Hughes).
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CHAPTER 3 n INSPECTION ASSAYS 13
percent sediment by 2.0 and multiply by the relative density especially magnesium chloride, can be hydrolyzed to hydro-
of the crude oil according to the following equation: chloric acid according to the following reaction:
S MgCl2 H2 O ! 2 HCl MgO 3
Sv 3 relative density of oil 2
2:0
The hydrochloric acid evolved is extremely corrosive, necessi-
where: tating the injection of a basic compound, such as ammonia,
Sv = the sediment content of the sample as a percentage by into the overhead lines to minimize corrosion damage. Salts
volume and and evolved acids can also contaminate overhead and residual
S = the sediment content of the sample as a percentage by products, and certain metallic salts can deactivate catalysts. A
mass. thorough discussion of the effects of salt on crude processing
This calculation is for convenience only, and the preci- is included in a manual on impurities in petroleum [47].
sion and bias have not been established. For many years the salt content has been routinely
Excessive reuse of thimbles in ASTM D473 is to be determined by comparing the conductivity of a solution of
avoided because, over time, the pores become clogged with crude oil in a polar solvent to that of a series of standard
inorganic material resulting in falsely high results. Also, the salt solutions in the same solvent [ASTM D3230: Test Method
use of toluene in laboratories is coming under increasing for Salts in Crude Oil (Electrometric Method)]. This test
scrutiny by safety and health groups, and a future ban on its method provides an approximate measure of the chloride
use is not inconceivable. No alternative solvent has been content of the crude oil being tested on the basis of mea-
identified to date, although some laboratories are known to surement of its conductivity. The chloride content is
use Varsol and aviation turbine (jet) fuel in lieu of toluene. obtained by reference to a calibration curve prepared using
a given mixture of salts. Because conductivity varies with
Sediment and Water varying salt composition, unless the composition of salts in
Centrifugal separation of the water and sediment [ASTM the sample being tested is the same as the calibration mix-
D4007: Test Method for Water and Sediment in Crude Oil by ture, results will be affected. Also, temperature and other
the Centrifuge Method (Laboratory Procedure)] is rapid and conductive materials such as sediment and water present in
relatively inexpensive, but the amount of water detected is the crude oil sample will affect results. These factors contrib-
almost invariably lower than the actual water content. This can ute to the relatively poor precision of the method.
result from inaccuracy in reading the interface between oil With crude oils having a viscosity in excess of approxi-
and water and emulsified water not being totally separated. mately 700 cSt at ambient laboratory conditions, it can be
ASTM D96: Test Method for Water and Sediment in very difficult to transfer the test sample using a pipet as
Crude Oil by Centrifuge Method (Field Procedure) covers the required by ASTM D3230. With highly viscous oils, a 10-mL
determination of sediment and water in crude oil during graduated cylinder is a practical alternative, provided it is
field custody transfers. This method may not always provide used to transfer the crude oil and neutral oil. However, pre-
the most accurate results, but it is considered the most prac- cision of the method is based only on use of a 10-mL pipet
tical method for field determination of sediment and water. and may not apply when using a 10-mL graduated cylinder.
The method is still widely used although it was withdrawn ASTM D6470: Test Method for Salt in Crude Oils (Poten-
with no replacement by ASTM in 2000. A technically equiva- tiometric Method) is less affected by salt composition and
lent version of the method is available as Chapter 10.4 in the has considerably better precision than the older method.
API Manual of Petroleum Measurement Standards. H2S and thiols interfere in the determination of salts by
For all of the methods for sediment and water determi- potentiometric titration, and a step is provided in this test
nation, sample homogenization is critically important and method for eliminating these before determination.
analyses must be conducted immediately after mixing to pre- As with many test methods, sample homogenization is
clude settling. Loss of light ends will also affect results, and critically important in salt determination. Waxy samples and
care must be exercised during mixing so that the tempera- those solid at room temperature must be heated to 3C above
ture does not rise more than 10C. their pour point to facilitate test sample withdrawal. A nonaer-
ating high-speed shear mixer is suitable for small laboratory
SALT CONTENT sample containers up to approximately 500 mL. However, it is
The salt content of crude oil is highly variable and, as with important that the temperature not be allowed to rise more
water and sediment, results principally from production prac- than 10C during mixing, otherwise excessive loss of light ends
tices used in the field and, to a lesser extent, from its handling can occur or the dispersion can become unstable.
aboard tankers bringing it to terminals. The bulk of the salt The results of ASTM D3230 are in pounds per thousand
present will be dissolved in coexisting free and emulsified barrels (PTB), the common industry reporting factor. Those
water and can be removed in desalters, but small amounts of of ASTM D6470 are in milligrams per kilogram (mg/kg), in
salt may be dissolved in the crude oil itself and present as a conforming to metric practice. Conversion between the two
crystalline solid. Salt may be derived from reservoir or forma- is accomplished using the following simple formulas:
tion waters or from other waters used in secondary recovery
operations. Aboard tankers, nonsegregated ballast water of Salt; mg=kg X=d 4
varying salinity may also be a source of salt contamination. Salt; mg=kg 2:853 Y=d 5
Salt in crude oil may be deleterious in several ways.
Even in small concentrations, salts will accumulate in distil- where:
lation towers, heaters, and exchangers, leading to fouling X = measured concentration, mg/m3,
that requires expensive cleanup. More importantly, during Y = measured concentration, PTB, and
flash vaporization of crude oil, certain metallic salts, d = specimen density at 15C, kg/m3.
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14 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
Regardless of the method used, it is necessary to use determination of the temperature to which a sample must
other methods (e.g., atomic absorption, inductively coupled be heated to redissolve all wax may require measurement of
argon plasma spectrophotometry, or ion-chromatography) to its wax disappearance temperature (WDT). Further discus-
determine the composition of the salts present. sion of this is provided in the succeeding chapter on crude
oil compatibility and stability.
FLUIDITYPOUR POINT AND VISCOSITY Viscosity is determined by measuring the time for a vol-
Pour point and viscosity determinations of crude oils are ume of liquid to flow under gravity through a calibrated glass
performed principally to ascertain their handling character- capillary viscometer [ASTM D445: Test Method for Kinematic
istics at low temperatures. However, there are some general Viscosity of Transparent and Opaque Liquids (and the Calcu-
relationships about crude oil composition that can be lation of Dynamic Viscosity)]. Although the preferred unit of
derived from pour point and viscosity data. Commonly, the kinematic viscosity is millimeter squared per second (mm2/s),
lower the pour point of a crude oil the more naphthenic or many older analyses report it in centistokes (cSt). These units
aromatic it is, and the higher the pour point the more paraf- are equivalent, with 1 mm2/s equaling 1 cSt.
finic it is. There are numerous exceptions to this rule of ASTM D7279: Test Method for Kinematic Viscosity of
thumb, and other data must be used to verify a crude oils Transparent and Opaque Liquids by Automated Houillon
character. Viscosity is also affected by the aromaticity or par- Viscometer is beginning to be used in several petroleum lab-
affinicity of the sample. Those crude oils with a greater con- oratories in addition to ASTM D445. The test method is
centration of paraffins generally have a lower viscosity than applicable to material having a viscosity of 21500 cSt at
crude oils having a relatively large proportion of aromatic 20150C, and requires only approximately 1 mL of sample.
and naphthenic compounds. The method is rapid and provides results in approximately
Pour point is determined by cooling a preheated sample 15 min, making it especially useful in determining viscosity
at a specified rate and examining its flow characteristics at of blends. Although the Scope of the method only refers to
intervals of 3C. ASTM D97: Test Method for Pour Point of fresh and used lube oils, it is increasingly being used for
Petroleum Products is the most widely used procedure for crude oils.
this measurement, although crude oils are not mentioned in At one time, the petroleum industry measured viscosity
the methods Scope. An alternative procedure specifically for by means of the Saybolt viscometer and expressed values in
testing the pour point of crude oils is described in ASTM units of Saybolt Universal Seconds (SUS) or Saybolt Furol
D5853: Test Method for Pour Point of Crude Oils. Seconds (SFS). This practice is now largely obsolete in the
Both test methods use the same apparatus but differ in industry. ASTM D2161: Practice for Conversion of Kinematic
the test procedures and the lower limit of determination. In Viscosity to Saybolt Universal Viscosity or to Saybolt Furol
ASTM D97, a single value is determined in defining pour Viscosity establishes equations that may be used for calculat-
point, whereas in ASTM D5853, maximum (upper) and mini- ing kinematic viscosities from SUS and SFS data that appear
mum (lower) pour point values may be measured. The maxi- in older literature.
mum (upper) pour point is defined as the temperature By determining viscosity at two temperatures such as
obtained after the test specimen has been subjected to a pre- 25C and 40C, viscosity at any other temperature over a lim-
scribed treatment designed to enhance gelation of wax crys- ited range may be interpolated or extrapolated using viscos-
tals and solidification of the test specimen. The minimum ity-temperature charts (ASTM D341: Viscosity-Temperature
(lower) pour point temperature is that obtained after the test Charts for Liquid Petroleum Products). It must be kept in
specimen has been subjected to a prescribed treatment mind that these charts are not linear. Also, the lowest temper-
designed to delay gelation of wax crystals and solidification ature at which viscosity is determined should be at least 5C
of the test specimen. The maximum and minimum pour higher than the pour point. Otherwise, the crude oil may not
point temperatures provide a temperature window in which exhibit Newtonian behavior.
a crude oil, depending on its thermal history, might appear For waxy crude oils and those with a pour point greater
in the liquid and solid state. The test method is especially than approximately 25C and very viscous material such as
useful for the screening of the effect of wax interaction bitumen, it is best to determine viscosity at three tempera-
modifiers (pour point depressants) on the flow behavior of tures to ensure the material is Newtonian at the test temper-
crude oils. However, in practice few laboratories using ASTM ature. For these types of material, the lowest temperature at
D5853 are determining the minimum pour point on the which viscosity is measured may need to be 20C higher
basis of published data. Further, ASTM D97 has no defined than the pour point.
lower limit of applicability, whereas ASTM D5853 only cov- A common source of error in determining viscosity
ers determination down to 36C. when using test method ASTM D445 is the presence of par-
The pour point of crude oils is very sensitive to trace ticulates lodged in the capillary bore. If sediment is present,
amounts of high melting waxes, and meticulous care must which is commonly the case with crude oils, samples should
be exercised to ensure waxes present are completely melted first be filtered or centrifuged. Samples should also be air
or homogeneously dispersed. Crude oils stored below their free. Homogenization can introduce air bubbles that will
cloud point will deposit waxes. The wax coming out of solu- affect test results, and it may be necessary to allow samples
tion will preferentially be the high melting wax, which is the to stand for a period of time to allow entrained air to dis-
type that has the most pronounced influence on pour point perse. Temperature control is critically important in obtain-
temperature. This wax is also the most difficult to redissolve ing accurate and precise viscosity measurements.
or homogeneously disperse in the crude oil. Heating the
crude oil to 20C above the expected pour point will usually VAPOR PRESSURE
result in the wax going back into solution, but caution must Vapor pressure is an important physical property of crude
be observed to avoid loss of light ends. An accurate oils impacting shipping, storage, and refinery handling
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CHAPTER 3 n INSPECTION ASSAYS 15
practices. The greater the vapor pressure of a crude oil, the ambient temperatures. When collecting samples from pressur-
greater the potential for atmospheric emission of hydrocar- ized systems, sampling may be done in accordance with ASTM
bons and other volatile compounds such as H2S. With the D4177 rather than ASTM D4057. When using a floating piston
increasingly more stringent environmental limitations on cylinder, it is advisable to use a gas such as argon as the back
emission of these compounds, it is important that the vapor pressure agent rather than air, nitrogen, or helium. The larger
pressure be known so that crude oil stocks can be stored molecular size of argon molecules relative to the other gases
and handled in an appropriate manner. helps minimize leakage across the O-ring seals on the floating
ASTM D323: Test Method for Vapor Pressure of Petro- piston cylinder and integrity of the sample can be maintained
leum Products (Reid Method) is the oldest of the several for a longer period. When a floating piston cylinder has been
methods used for determining vapor pressure of crude oils. used for sample collection, chilling and air saturation of the
The RVP differs from the true vapor pressure of the sample sample are not required before the vapor pressure
under test because of some small sample vaporization and measurement.
the presence of water vapor and air in the sample chamber The extreme sensitivity of vapor pressure measurements
used in the test. ASTM D323 is not an easy test to perform to evaporative losses and the resultant changes in composi-
and it is time-consuming. However, an automatic vapor pres- tion require the utmost precaution and the most meticulous
sure instrumental method did not become standardized until care in the collection and handling of samples, regardless of
1991 with the publication of ASTM D5191: Test Method for the test method to be used. Moreover, vapor pressure deter-
Vapor Pressure of Petroleum Products (Mini Method). No mination is required to be performed on the first specimen
crude oil samples were included in the interlaboratory study withdrawn from the sample container. The remaining sam-
to determine the precision of this method. Hence, its use for ple in the container is not to be used for a second vapor
crude oil vapor pressure measurement is specifically outside pressure determination because results will be affected
of the methods Scope, yet the method is routinely used for by the additional handling. The effect of taking more than
the determination of crude oil vapor pressure by several one test specimen from the same sample container was
laboratories. evaluated as part of the 2003 ILS study previously men-
ASTM D323 and ASTM D5191 provide different meas- tioned. A precision effect was observed between the first and
ures of vapor pressure that are affected by the different test second replicates taken from the 1-L and 250-mL containers
conditions, and ASTM D323 generally provides results that evaluated.
are somewhat higher than those of ASTM D5191. The latter The procedures for sampling and vapor pressure deter-
technique also does not take into account dissolved water in mination of crude oil are complex, especially if the crude oil
the sample in determining total pressure. Moreover, the two has a pour point greater than 01C or if its vapor pressure
methods are restricted to samples collected from a nonpres- is greater than the ambient atmospheric pressure.
surized source such as a storage tank or oil tanker. ASTM Manual 51 Distillation and Vapor Pressure Mea-
ASTM D323 and ASTM D5191 prescribe that sampling surement in Petroleum Products includes detailed discussion
is to be done in accordance with ASTM D4057. Normally, of the several ASTM test methods used to measure vapor
1-L containers filled between 70 and 80 % of capacity with pressure of crude oil (i.e., D323, D5191, and D6377) [48].
sample are used for vapor pressure determination. However, This will provide the analyst a better understanding of the
samples taken in containers of sizes other than those pre- details of each method and how they apply to determination
scribed in Practice D4057, such as 250 mL, can be used if it of this parameter. A separate, complimentary chapter pro-
is recognized that the precision could be affected. In the vides a more in-depth discussion of the importance of crude
case of referee testing, the 1-L sample container shall be oil vapor pressure measurements as they relate to determin-
mandatory. Regardless of the size of sample container used, ing regulatory compliance.
it shall not be filled beyond 80 % of its capacity.
The current precision statements in ASTM D5191 were TOTAL ACID NUMBER
derived from a 2003 Interlaboratory Study (ILS) using sam- The acids present in crude oil contribute to increased rates
ples in 250-mL and 1-L clear glass containers. The differen- of corrosion in the refinery and can contribute to instability
ces in precision results obtained from 250-mL and 1-L in refined products. Surface activity imparted by acids can
containers were found to be statistically significant, whereas also make for difficulty in desalting of crude oils. Total acid
there was no statistically observable bias detected between number, as determined by ASTM D664: Test Method for
250-mL and 1-L containers. Tables 2 and 3 and Figs. 1 and 2 Acid Number of Petroleum Products by Potentiometric Titra-
in ASTM D5191 provide more specific details on precision tion, provides an indication of the acid content of a crude
differences as a function of container size. oil. Test results will also indicate the presence of remnant
ASTM D6377: Test Method for Determination of Vapor inorganic acids such as hydrochloric acid and hydrofluoric
Pressure of Crude Oil: VPCRx (Expansion Method) covers acid used in production well workover operations. Organic
determination for vapor-liquid ratios of from 4:1 to 0.02:1. acids such as acetic acid (CH3COOH) and formic acid
When the vapor pressure measurement is done for a 4:1 ratio (HCOOH) are sometimes used in acidizing wells particularly
at 37.8C, the observed vapor pressure can be compared to the for high-temperature applications. If not neutralized, they
vapor pressure obtained by ASTM D323. A vapor-liquid ratio too will be determined in the analysis. Salts of heavy metals
of 0.02:1 mimics closely the situation of an oil tanker and may have acidic characteristics and react during the determi-
approaches the true vapor pressure. This method may be used nation of the acid number. The method does not differenti-
for analyzing samples from a pressurized source such as a ate acid species (e.g., carboxylic, naphthenic, or inorganic)
pipeline collected using a floating piston cylinder in accord- and does not provide any indication of relative acid strength.
ance with ASTM D3700. This method is also useful for sam- Although no general correlation is known between acid
ples that will boil at normal atmospheric pressures and number and the corrosive tendency of oils toward metals,
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16 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
Fig. 3Correlation of Conradson (D189) and Ramsbottom (D524) carbon residue tests.
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CHAPTER 3 n INSPECTION ASSAYS 17
Fig. 5Nomograph for determining characterization factor (K) from viscosity (cSt) at 100F and API gravity (UOP 375).
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18 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
R2 = 0.7337
80.0
80
Paraffins, vol %
60.0
60
40.0
Vol %
40
20.0
20
0.0
11.0 11.5 12.0 12.5 13.0
K factor 0
85
5
Fig. 6K-factor versus paraffin content of 178 crude oils.
12
15
17
20
23
26
29
relationship between the two factors. Moreover, across the B.P. deg C
boiling range of a crude oil, chemical character can shift
Fig. 8Variation in paraffin, naphthene, and aromatic content
quite dramatically between fractions. This is well illustrated
for a 31.0 API West African crude oil with K = 11.9.
in Figs. 8 and 9 for two crude oils having the same K-factor
and nearly the same API gravity. Despite these obvious short-
comings, the K-factor is determined and reported on virtu- Nickel and vanadium nearly invariably are the most
ally every detailed crude oil assay. abundant trace element constituents of crude oil. However,
Other parameters used to characterize petroleum, includ- until recently, relatively little systematic analytical work had
ing refractivity intercept, viscosity gravity constant, and car- been carried out on many other trace elements. With height-
bon-to-hydrogen weight ratio, are discussed by Riazi [52]. ened environmental awareness and susceptibility of many
catalysts to poisoning or deactivation by trace metals, more
TRACE ELEMENTS work is being done on determining their presence in crude
Knowledge of the trace element constituents in crude oil is oils. Published reports indicate that over 30 trace metals
important because they can have an adverse effect on petro- definitively occur in crude oils [56,57]. An extensive review
leum refining, product quality, and the environment. Among of the literature published through 1973 provides informa-
the problems associated with trace elements are catalyst poi- tion on the occurrence and concentration of 45 trace ele-
soning in the refinery and excessive atmospheric emissions ments [58]. Using highly sophisticated techniques such as
in combustion of fuels. Elements such as iron, arsenic, and neutron activation analysis and with the greatly improved
lead are catalyst poisons. Vanadium compounds can cause sensitivity of modern detectors, it is likely that even more
refractory damage in furnaces, and sodium compounds have elements will be found, but probably in sub-parts-per-billion
been found to cause superficial fusion on fire brick [53]. concentrations.
Some organometallic compounds are volatile, which can In handling of crude oils, several trace metals are of
lead to contamination of distillate fractions and a reduction considerable interest because of their potential impact on
in their stability or malfunctions of equipment when they the environment resulting from atmospheric emissions when
are combusted [54]. Concentration of the nonvolatile orga- fuels are burned, or from discharge of process streams or
nometallics in heavy products such as premium coke can disposal of wastes. In the Netherlands, in support of the
have a significant impact on price, marketability, and use. North Sea Action Plan to reduce emissions, a detailed study
Knowledge of trace element concentrations is also useful in of crude oils imported into the country was conducted in
exploration in correlating production from different wells
and horizons in a field [55].
60
60
Vol. %
40
40
20
20
0
0 75 125 175 225 275 325
11 11.5 12 12.5 13 B.P. deg C
K factor
Fig. 9Variation in paraffin, naphthene, and aromatic content
Fig. 7K-factor versus naphthene content for 178 crude oils. for a 30.7 API Gulf of Mexico crude oil with K = 11.9.
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CHAPTER 3 n INSPECTION ASSAYS 19
the 1990s [59]. The study found that cadmium, zinc, and mercury, whereas ASTM D7623 is applicable to samples con-
copper were not indigenous to the crude oils studied but taining between 5 and 400 ng/mL of mercury.
were the result of contamination by associated water and/or Selenium has become a priority pollutant because of its
particles from the producing wells. Chromium was found to high toxicity to aquatic wildlife. In refineries, it partitions into
be indigenous for the most part and associated with the wastewater streams and can be discharged from treatment
hydrocarbon matrix. Some inorganic chromium was thought plants into the environment where it rapidly bioaccumulates.
to be present as a contaminant. The study was unable to As with mercury, selenium can be present as different
determine the origin of arsenic found in the crude oils, but species that behave differently and complicate identification
it was considered to probably be a contaminant. The inten- and remediation. Selenate [Se(VI)], selenite [Se(IV)], selenide
tion to study mercury was abandoned because a reliable [Se(-II)], colloidal selenium (Se), and selenocyanate (SeCN)
analysis technique was not found at the time of the study. have all been observed in wastewaters [62]. In this study,
Two metals currently of considerable environmental which comprised 16 different crude oils, a large variability
concern are mercury and selenium, both of which occur nat- was observed in the total concentration of selenium in the
urally in crude oil at varying concentrations. Mercury is of samples (<10 to 960 lg kg1).
concern as an air and water pollutant, and selenium is of Several trace metals are now customarily included in
concern as a water pollutant. crude oil analyses. Among these are calcium, copper, iron,
There is substantial evidence indicating that mercury mercury, nickel, selenium, sodium, and vanadium. The suite
can occur in crude oil as volatile, dissolved, and particulate of elements determined will be dictated by refinery processes,
(suspended) speciesall of which differ considerably in their product slate, regulation, and environmental considerations.
chemical structure and behavior. Supporting the presence of Several analytical methods are available for the routine deter-
volatile species, elemental mercury has been found con- mination of many trace elements in crude oil. Among the
densed in cooler regions in refinery distillation towers and techniques used for trace element determinations are flame-
in cryogenic heat exchangers that liquefy petroleum gases. less and flame atomic absorption spectrophotometry (AAS)
Further, replicate laboratory analyses on the same sample (ASTM D5863: Test Methods for Determination of Nickel,
have found decreases in concentration over time [60]. Mer- Vanadium, Iron, and Sodium in Crude Oils and Residual
cury has also been found in sludge that accumulates in stra- Fuels by Flame Atomic Absorption Spectrometry) and induc-
tegic stockpiles of crude oil, clearly indicating the tively coupled argon plasma spectrophotometry [ASTM
occurrence of particulate or suspended species [61]. Finally, D5708: Test Method for Determination of Nickel, Vanadium,
mercury can be present in various petroleum distillation and Iron in Crude Oils and Residual Fuels by Inductively-
fractions across a broad boiling range. Coupled Plasma (ICP) Atomic Emission Spectrometry]. Some
Mercury is among the most difficult of the metals pres- of these techniques allow direct aspiration of the samples
ent in crude oils to accurately determine, and its concentra- (diluted in a solvent) instead of the time-consuming sample
tion is generally at low parts-per-million to parts-per-billion preparation procedures such as wet ashing (acid decomposi-
levels. In a study of 103 crude oils from the United States, tion) or flame or dry ashing (removal of volatile/combustible
Europe, Africa, and Asia, total mercury concentrations constituents). A modified version of ASTM D5185: Test
ranged from 0.02 to 10 ng/g [61]. This is about an order of Method for Determination of Additive Elements, Wear Metals,
magnitude lower than anticipated based on historical data. and Contaminants in Used Lubricating Oils and Determina-
Contamination is a significant issue whenever samples tion of Selected Elements in Base Oils by Inductively Coupled
contain the target analyte at such low levels. ASTM D7482: Plasma Atomic Emission Spectrometry is being used by some
Practice for Sampling, Storage, and Handling of Hydrocar- laboratories for the determination of elements such as lead
bons for Mercury Analysis covers the types of and preparation and phosphorus in crude oils.
of containers most suitable for the handling of hydrocarbon Inductively coupled plasmaatomic emission spectrome-
samples for the determination of total mercury. This practice try (ICP-AES) is one of the more widely used analytical techni-
was developed for sampling streams where the mercury speci- ques in the oil industry for multielement analysis. The
ation is predominantly elemental mercury (Hg(0)) present as advantages of using an ICP-AES analysis include high sensitiv-
a mixture of dissolved Hg(0) atoms, adsorbed Hg(0) on partic- ity for many elements, relative freedom from interferences,
ulates, and suspended droplets of metallic mercury. linear calibration over a wide dynamic concentration range,
UOP 938 Total Mercury and Mercury Species in Liquid single or multielement capability, and ability to calibrate the
Hydrocarbons is widely used for determining total mercury instrument on the basis of elemental standards irrespective of
content of crude oils. The method is applicable to samples their elemental chemical forms within limits such as solubility
containing 0.1 to 10,000 ng/mL. An appendix provides a pro- and volatility assuming direct liquid aspiration. Thus, the tech-
cedure that can be used to differentiate between elemental nique has become a method of choice in many oil industry
mercury, organic nonionic mercury, and ionic (inorganic laboratories for metal analysis. ASTM D7260: Practice for Opti-
and organic) mercury species. mization, Calibration, and Validation of Inductively Coupled
ASTM D7622: Test Method for Total Mercury in Crude Plasma-Atomic Emission Spectrometry (ICP-AES) for Elemen-
Oil Using Combustion and Direct Cold Vapor Atomic tal Analysis of Petroleum Products and Lubricants summarizes
Absorption Method with Zeeman Background Correction, the protocols to be followed during calibration and verifica-
and ASTM D7623: Total Mercury in Crude Oil Using Com- tion of instrument performance. With the low levels at which
bustion-Gold Amalgamation and Cold Vapor Atomic Absorp- many elements of interest are present, these protocols are of
tion Method provide two other methods for determination of the utmost importance in obtaining accurate data.
total mercury in crude oil. This latter test method uses the Despite the advantages of ICP-AES, several laboratories
same instrumentation as that used in UOP 938. ASTM D7622 continue to use AAS because detection limits are often bet-
is applicable to samples containing from 5.0 to 350 ng/mL of ter. X-ray fluorescence spectrophotometry is also sometimes
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20 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
used, although matrix effects can be a problem. The method Like sulfur, nitrogen concentration increases with
to be used is generally a matter of individual preference and increasing boiling point, but unlike sulfur, usually only trace
instrumentation availability. quantities of nitrogen are found in the fractions boiling below
Many advances have been made in techniques for trace approximately 343C. API Research Project 52 identified
and ultratrace sample preparation and elemental analysis numerous nitrogen compounds present in crude oils and
including AAS, ICP-MS, isotope dilution mass spectrometry, reported on many of the problems they cause in refining and
and other multihyphenated methods. Several of these are with product quality [65]. As a group, they can contaminate
discussed in ASTM STP 1468 [36]. refinery catalysts sometimes when even trace quantities are
present in feedstocks. Nitrogen compounds also contribute to
Sample Preparation for Elemental Analysis refined product instability, are responsible for formation and
The test methods used for analysis of crude oils for their ele- precipitation of gums in some fuels, and become an environ-
mental metals content use various analytical techniques. mental pollutant when fuels are burned because of emission
Some of these test methods require little or no sample prep- of oxides of nitrogen (NOx). Further, they tend to be the most
aration, some others require only simple dilution, and others difficult class of compounds to hydrogenate and are of
require elaborate sample decomposition before the sample increasing concern to refiners. The nitrogen content remain-
is analyzed for its elemental content. ASTM D7455: Practice ing in the product from a hydrotreater is a measure of the
for Sample Preparation of Petroleum and Lubricant Prod- effectiveness of the hydrotreating process.
ucts for Elemental Analysis covers alternative ways of pre- Three test methods are available for the determination of
paring a sample for elemental analysis. The means of total nitrogen. ASTM D3228: Test Method for Total Nitrogen in
preparation of samples may vary from no special steps to Lubricating Oils and Fuel Oils by Modified Kjeldahl Method is
extensive procedures dependent on the sample matrix and a manual method rarely used for analysis of crude oils. The test
the measurement technique to be used. Adoption of uniform method is time-consuming and involves hazardous substances
practices for sample preparation is beneficial in standardiz- such as sulfuric acid and mercuric oxide. During the test proce-
ing the procedures and obtaining consistent results among dure, H2S is evolved and mercuric sulfide is produced. More-
laboratories. This becomes especially important in cases of over, it is not applicable to nitrogen present in heterocyclic
dispute, such as in contract compliance, and because of envi- compounds, in which case lower results will be obtained
ronmental, industrial hygiene, and regulatory concerns. compared with the actual total nitrogen concentration.
The two methods commonly used for determination of
MICROWAVE DIGESTION total nitrogen in crude oils both involve chemiluminescent
The traditional method of digestion/ashing of samples for detection. ASTM D4629: Test Method for Trace Nitrogen in
trace element analysis as described in ASTM D5708 is time- Liquid Petroleum Hydrocarbons by Syringe/Inlet Oxidative
consuming, and up to 24 h may be necessary to decompose Combustion and Chemiluminescence Detection covers deter-
heavy or bituminous material. Moreover, during the process, mination of trace quantities of nitrogen in the range 0.3 to
elements of interest may be lost by spattering and foaming, 100 mg/kg. This test method has been successfully applied in
the risk of contamination is ever present, and the sample may interlaboratory studies to samples with higher concentra-
not be totally decomposed. Microwave digestion of samples tions by dilution to bring the concentration to within the
has become commonplace in many laboratories worldwide as range covered by the test methods Scope and, as such, is
an excellent alternative means for rapidly decomposing even frequently used for determination of total nitrogen content
refractory samples and with essentially no loss of elements of of crude oils having a wide range in concentration. ASTM
interest during the process or contamination. D5762: Test Method for Nitrogen in Petroleum and Petroleum
This technique involves high-pressure dissolution in Products by Boat-Inlet Chemiluminescence covers determina-
sealed vessels at elevated temperatures to attain rapid sample tion of total nitrogen at concentrations of 4010,000 mg/kg.
decomposition and analyte dissolution [63]. Basically, the Because some nitrogen compounds are volatile and to
sample is sealed in a Teflon vessel with a combination of prevent contamination, it is advisable that samples be ana-
nitric acid (HNO3), hydrochloric acid (HCl), and hydrogen per- lyzed as soon as possible after their collection. ASTM D7455
oxide (H2O2) and digested for approximately 1 h at approxi- discussed earlier in the section on trace metals provides
mately 200C. The result in a precipitate-free, clear yellow information relevant to sample preparation for their nitro-
solution that can be diluted and run directly by AAS. If the gen determination.
sample is to be analyzed by ICP-MS, it may be necessary to There are no standard test methods for determining
evaporate the excess HNO3 before dilution and analysis. basic nitrogen in crude oil. It usually suffices to determine
total nitrogen and assume that approximately 30% is basic
NITROGEN CONTENT in character. This ratio appears to be approximately constant
The nitrogen constituents in crude oils are divided into two throughout the boiling range of a crude oil.
major classesbasic and nonbasic. Basic nitrogen constitu- Instrumental fast neutron activation analysis has been
ents include such compounds as pyridines and quinolines, used to directly determine nitrogen in crude oils in the
and the nonbasic constituents are typified by carbazoles, range of 0.0140.490 % [66]. This provides an accurate and
indoles, and pyrroles [34]. The classification of nitrogen rapid means of determining nitrogen, but few laboratories
compounds as basic or nonbasic is based on whether they have the requisite instrumentation. Identification and distri-
can be titrated with perchloric acid in a 50:50 solution of bution of nitrogen compounds in middle distillate fuels
glacial acetic acid and benzene. Compounds extracted by derived from crude oils from several sources has also been
acids are basic; the compounds that cannot be extracted are done by gas chromatography (GC)/MS [67]. This technique
nonbasic [64]. In general, basic compounds account for also does not lend itself to routine laboratory determinations
approximately 30% of the total nitrogen present. of the nitrogen concentration of crude oil.
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CHAPTER 3 n INSPECTION ASSAYS 21
ORGANIC HALIDES of the separated material will differ from that obtained
Organic halides do not occur naturally in crude oils. They using n-heptane [73]. Fig. 10 depicts this variation in relative
mainly chloride speciesare among the most egregious con- terms in the mass percent of asphaltenes that will precipitate
taminants, and their presence commonly results from sol- from a given crude oil as a function of the carbon number
vents used in cleaning operations at production sites and in of the n-alkane precipitant from n-C3 through n-C10.
pipelines and tanks. Their presence may also result from Asphaltenes are the organic molecules of highest molec-
illicit disposal of waste solvents. These compounds are ular mass and carbon-hydrogen ratio normally occurring in
potentially damaging to refinery processes. For example, crude oil. They are highly aromatic in character, and their
HCl can be produced in hydrotreating or reforming reactors, composition normally includes a disproportionately high
after which the highly corrosive acid can accumulate in con- quantity of the sulfur, nitrogen, and metals present in crude
densing regions of the refinery. Large or unexpected concen- oil. If the colloidal suspension of these molecules is dis-
trations of the resulting acids cannot be effectively turbed through excess stress or incompatibility, they can give
neutralized, and damage can result. Organic halide species rise to problems during storage and handling.
can also poison catalysts in reformers and adversely affect When crude oil is produced from the reservoir, the
gasoline yields. depressurization that occurs can result in flocculation of
After enactment of the Resource Conservation and asphaltenes [7476]. Further flocculation can take place dur-
Recovery Act (RCRA) in 1976, there have been numerous ing transportation and in refinery processing where the pre-
reports of incidents involving the presence of organic halides cipitates can foul pipelines, preheat trains, and result in
in crude oil feedstocks and their consequences. In 1981, in an desalter upsets (Fig. 11). In desalter units, asphaltene precipi-
article in Oil Daily, it was noted that the consequences of tates can stabilize emulsions, resulting in an increase in the
organically-combined chlorine in crude are by no means trivi- solids and oil carried under to the wastewater treatment facil-
al [68]. A report by the U.S. General Accounting Office dis- ity. Asphaltenes can stabilize emulsions and result in excessive
closed 40 cases of crude oil contamination that occurred salts and water being carried over to other refinery units
between 1981 and 1989, most involving disposal of organic where they can foul equipment and contaminate products.
chlorides into crude oil [69]. In 2000, it was reported that Asphaltene flocculation and its causes have been the
a series of sudden tube leaks in overhead exchangers of a subject of considerable study, as well summarized by James
crude tower of a major Gulf Coast refinery was attributed to G. Speight [77] and discussed in papers related to the Deep-
repeated contamination of the crude charge with organic Star Project [78]. G. A. Mansoori and his collaborators at the
chlorides [70]. In this latter case, a single supplier had University of Illinois at Chicago have devoted considerable
repeatedly dumped contaminated crude oil containing from study to deposition of heavy organic material during crude
3 to 3,000 mg/L organic chlorides into one of the refinerys oil production and refinery processing and to characteriza-
pipelines over a 10-month period. To combat organic chloride tion of the deposits [7981].
contamination, one major crude oil common carrier pipeline Another common cause of destabilization and precipita-
instituted a program that resulted in a significant reduction tion is the blending of incompatible crude oils, such as one
in incidents in its system [71]. Despite these widely publicized that is paraffinic with one that is more asphaltenic or aro-
incidents, the use of halogenated solvents continues to be pro- matic in character [82,83]. Asphaltenes are also the last mol-
moted for removing wax buildup in pipelines [72]. ecules in a product to combust completely; thus, their
Total organic halide content of the naphtha fraction can occurrence may be one indicator of black smoke propensity.
be effectively determined using ASTM D4929: Test Method ASTM D6560: Test Method for Determination of Asphal-
for Determination of Organic Chloride Content in Crude Oil. tenes (Heptane Insolubles) in Crude Petroleum and Petro-
In performing the test, it is imperative that the sample be leum Products covers a procedure for their determination.
distilled to obtain a naphtha fraction before chloride deter- The test method requires that the crude oil first be topped
mination as described in the test method to eliminate poten- to an oil temperature of 260C before analysis. However,
tial interference by inorganic salts. Other titratable halides many laboratories are performing the test without first top-
such as hydrogen bromide (HBr) and hydrogen iodide (HI) ping the sample. Analyses of topped and untopped samples
will also give a positive response. Some commonly encoun- of the same crude oil have shown that the results can differ
tered organic chloride compounds such as dichloromethane
have a relatively low boiling point and can be lost before
analysis because of exposure. Consequently, it is important
that samples be analyzed as soon as possible after collection. TABLE 1Common Organic Chloride
ASTM D7455 discussed earlier in the section on trace metals Compounds
provides information relevant to sample preparation for Boiling
organic chloride determination. Table 1 lists some of the orga- Compound Point, C
nochloride compounds commonly used as solvents, cleaning
agents, and in industrial processes and their boiling points. Dichloromethane (methylene chloride) 40
Trichloromethane (chloroform) 62
ASPHALTENES
By definition, asphaltenes are wax-free material insoluble in Tetrachloromethane (carbon tetrachloride) 77
n-heptane, but soluble in hot toluene. In classical references,
1,2-Dichloroethane (ethylene dichloride) 84
benzene is used rather than toluene; however, because of its
known carcinogenicity, it has largely been banned in labora- 1,1,1-Trichloroethane (trichloroethylene) 87
tories. Other solvents such as n-pentane or n-hexane may be
Tetrachloroethylene (perchloroethylene) 121
used in the determination, but the quantity and properties
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22 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
the boiling curve in the region C4C8. Fig. 12 shows typical hydrate inhibitor occurs mostly in production of crude oils
uncorrected and corrected distillation curves for a crude oil from deep waters such as the Outer Continental Shelf of the
analyzed by this test method and using the suggested light- Gulf of Mexico, offshore West Africa, and in areas of the North
end analysis procedure. Sea. It may also be used in cold climates to assist in thawing
Determination of boiling point distribution by HTSD is pumps and pipelines. With the growing number of subsea
useful for rapidly obtaining information on the potential wells in ever deeper water, the use of methanol is likely to
mass percent yield of products. These data provide refiners increase, posing a growing problem for refiners. For crude oil
the ability to quickly evaluate crude oils and to select those produced from the Gulf of Mexico, methanol contamination
with economic advantages and more favorable refining mar- commonly occurs after hurricanes after production restarts
gins [84]. The information it provides can be input to linear and until pipelines have been warmed by the produced oil.
programming (LP) models and used in establishing opera- Because the methanol is water miscible, it gets carried with
tions conditions in the refinery. Data on the boiling point water present in the crude oil to the refinery where it comes
distribution also serve as a rapid method for screening for out in the water effluent from the desalter unit. When it
the presence of diluents or residuum, constituting what is reaches the wastewater treatment system, it can drastically
commonly referred to as dumbbell crude. upset the balance of the system. The bacteria used in the plant
Further discussion on application of GC to determination to digest oily components prefer the methanol, leaving hydro-
of boiling point distribution can be found in ASTM Manual 51 carbons and some other toxic substances untreated. Large
[48]. This includes important considerations such as instru- incursions of methanol can lead to a bug kill that effectively
ment requirements, column selection, carrier gas, analysis deactivates the system. Either of these situations can result in
software, data interpretation, and a comparison to physical discharge of pollutants and environmental excursions that
distillation. However, GC-simulated distillation does not pro- exceed permitted levels. Increasingly, refiners are setting lim-
vide any material for quality assessments. This requires that its on the content of methanol they receive, generally a maxi-
samples be fractionated by conventional physical or potstill mum of 50 parts per million (ppm).
distillation methods, which are described in the next chapter. Methanol that partitions into the crude oil phase can
lower its apparent WAT, complicating accurate determina-
OTHER TESTS tion of this characteristic [85].
Other properties that are generally determined on a more Currently, there is no standard test method for deter-
limited basis include, but are not limited to, the following. mining methanol in crude oils containing water. ASTM
D7059: Test Method for Determination of Methanol in Crude
Methanol Oil by Multidimensional Gas Chromatography is applicable
Methanol, as with organic halides, does not occur naturally in only to crude oils containing a maximum of 0.1 % (v/v)
crude oils but is introduced artificially to prevent formation of water. As such, it is not applicable to analysis of most pro-
gas hydrateslarge matrixes of methane and water that can duction quality crude oil streams that commonly contain
block or impede flow in pipelines. Use of methanol as a 0.251.0 % (v/v) water. Several instrument manufacturers
4
Comprehensive Assays and
Fraction Evaluations
TRUE BOILING POINT DISTILLATION of all fractions, including the liquefied gas cut and the resi-
In addition to the whole crude oil tests performed as part of due. Distillation yields by volume of all fractions and the res-
the inspection assay, a comprehensive or full assay requires idue are calculated from mass and density. From these data,
that the crude oil be fractionally distilled and the fractions curves corresponding to TBP in mass or volume percent, or
characterized by appropriate tests. This characterization is both, versus AET are plotted. The method does not prescribe
necessary to enable the refiner to assess the quantity and specific cutpoint temperatures, which are to be agreed upon
quality of products recoverable from a given crude oil and by interested parties before beginning the distillation. The
to determine if that product slate economically satisfies the fractions yielded can be analyzed as produced or combined
market requirements of a particular refinery. Refiners tailor to produce samples specific to what is needed for analytical
a comprehensive assay to their individual needs, and the studies and engineering and product quality evaluations.
number of cuts or fractions taken may vary from as few as The sample to be distilled must have been obtained in
4 to 24 or more. The following ten fractions provide the accordance with ASTM Practice D4057 or D4177 and must
basis for a moderately thorough evaluation: be received in a sealed container and show no evidence of
leakage. Before opening the sample, it must be cooled to
between 0 and 5C. If, on opening, it appears waxy or too
C2C4 Gas viscous to handle, the temperature should be raised to 5C
above its pour point. After thorough mixing, the samples
C579C Light naphtha
water content is to be determined. If the water content
79121C Medium naphtha exceeds 0.3 % volume, the sample should be dehydrated
before fractional distillation. Attempts to distill wet crude
121191C Heavy naphtha
oil samples in glass columns can result in bumping and
191277C Kerosine breakage of the glassware, posing a potential fire hazard.
Moreover, the presence of water will affect the accuracy of
277343C Distillate fuel oil
distillation yields in the naphtha range. These effects are
343455C Light vacuum gas oil (LVGO) more pronounced for heavy crude oils containing low
amounts of hydrocarbons boiling below 100C. A suitable
455566C Heavy vacuum gas oil (HVGO)
practice for dehydration of wet crude oils is described in an
343C+ Atmospheric (long) residuum appendix to ASTM D2892.
Beyond an AET of 400C, it is necessary to continue the
566C+ Vacuum (short) residuum
distillation at further reduced pressures under conditions
that provide approximately a one-theoretical plate fractiona-
tion. ASTM D5236: Test Method for Distillation of Heavy
Commonly, from 5 to 50 L of crude oil are needed for Hydrocarbon Mixtures (Vacuum Potstill Method) enables the
a comprehensive assay, depending on the number of cuts to distillation to be continued to a temperature of up to
be taken and the tests to be performed on the fractions. approximately 565C AET at a pressure of 0.013 kPa. This
Fractionation of the crude oil begins with a true boiling test method details the procedures for the production of dis-
point (TBP) distillation using a fractionating column having tillate fractions in the gas oil and lubricating oil range as
an efficiency of 1418 theoretical plates and operated at a well as the production of standard residue and provides for
reflux ratio of 5:1. ASTM D2892: Test Method for Distillation the determination of standard distillation curves to the high-
of Crude Petroleum (15-Theoretical Plate Column) details est AET possible by conventional distillation. The maximum
procedures for the production of a liquefied gas fraction, achievable AET is dependent on the heat tolerance of the
various distillate cuts, and an atmospheric residuum. The dis- charge. It will be significantly lower for heat-sensitive sam-
tillation may be used for all fractions up to a maximum cut- ples and might be somewhat higher for nonheat-sensitive
point of approximately 400C atmospheric equivalent material.
temperature (AET) provided reduced pressure is used to As with ASTM D2892, the mass and density of each cut
avoid cracking. The quantity of sample to be distilled will be or fraction are obtained and distillation yields by mass are
dependent on the number of cuts to be made and the vol- calculated from the mass of all fractions and the residue.
ume of the various fractions needed for subsequent analyses. Distillation yields by volume of all fractions and the residue
The mass and density of each cut or fraction are obtained are calculated from mass and density. From these data, dis-
and distillation yields by mass are calculated from the mass tillation curves in mass or volume percent, or both, versus
25
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26 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
AET are plotted. The method does not prescribe specific cut- collected in a single receiver. Thus, unlike ASTM D2892 and
point temperatures, which are to be agreed upon by inter- D5236, the method does not provide material that can be
ested parties before beginning the distillation. The fractions characterized. Results are strictly limited to providing data
yielded can be analyzed as produced or combined to pro- from which the initial boiling point, the final boiling point,
duce samples specific to what is needed for analytical stud- and a distillation curve relating volume percent distilled and
ies and engineering and product quality evaluations. atmospheric equivalent boiling point temperature can be
The sample to be distilled using ASTM D5236 can be the prepared. Moreover, the method is only useful up to a maxi-
residue from ASTM D2892, or it can be a heavy crude oil mum liquid temperature of approximately 400C at a pres-
obtained in accordance with ASTM Practice D4057 or sure of 0.13 kPa (640C AET).
D4177. The latter must be received in a sealed container and A detailed discussion of these three ASTM methods used
show no evidence of leakage. On opening, if the sample for crude oil distillation is provided in the ASTM MNL51
looks waxy or is solid, it should be warmed to liquefy it and cited earlier in the discussion on vapor pressure [48]. This
be thoroughly mixed before proceeding with the distillation. includes their field of application; important parameters;
If, upon examination, there is evidence of water present in comments on terminology, precision, and accuracy; and a
the sample (>0.1 % volume) a preliminary distillation should comparison of ASTM D2892 and D5236.
be performed as described in the test method Annex. Fig. 2 graphically depicts typical boiling range curves
This test method can also be used for heavy crude oils for a heavy (22API) and a light (38API) crude oil.
with initial boiling points greater than 150C, but distillation Wiped-wall or thin-film molecular stills have short resi-
curves and fraction qualities are not comparable to what dence times mimicking those in refinery distillation units.
would be obtained on similar material using ASTM D2892. Consequently, they can be used to separate higher boiling
In graphing boiling point data from ASTM D2892 and fractions under conditions that minimize cracking of ther-
D 5236 on a single continuous curve, there will be an offset at mally labile constituents that would otherwise occur with
the switchover point between the two sets of data. Several fac- ASTM D5236 in which residence times are longer. However,
tors are responsible for this mismatch. First, ASTM D2892 in wiped-wall stills, cutpoints cannot be directly selected
uses a 15-theoretical plate column, whereas ASTM D5236 uses because vapor temperature in the distillation column cannot
a 1-theoretical plate column. This affects the separation effi- be measured accurately under operating conditions. Instead,
ciency of the two methods. Also, the overlap at each cutpoint the wall (film) temperature, pressure, and feed rate that will
for ASTM D2892 is only approximately 1520C, whereas for produce a cut equivalent to a ASTM D1160 or D5236 fraction
ASTM D5236, the overlap can be 5070C. Graphing the data with a given endpoint are determined from in-house correla-
for the two methods will produce a curve similar to that tions developed by matching yields between the wiped-wall
depicted in Fig. 1. Further discussion of yield curves is pro- distillation and the ASTM D1160 or D5236 distillation. ASTM
vided in Chapter 3 of Manual 51 from which the graph is D7169 should be useful in determining cutpoints of the
taken [48]. Fortunately, many of the computer crude oil data higher boiling fraction material recovered by wiped-wall dis-
management programs available today and widely used will tillation. Despite this indirect approach, wiped-wall stills are
produce a smooth boiling point curve that reasonably approxi- often used because they allow higher endpoints to be
mates the theoretical TBP curve for a particular crude oil. attained than with ASTM D1160 or D5236 and can easily pro-
Using ASTM D1160: Test Method for Distillation of vide large quantities of material for characterization.
Petroleum Products at Reduced Pressure, samples are dis- After fractionation of the crude oil, each of the fractions
tilled at reduced pressure under conditions designed to pro- is analyzed to determine one or more of its physical and/or
vide approximately a one-theoretical plate separation. The chemical characteristics depending on the needs of the ana-
test uses only a 200-mL charge and all distilled material is lyst or refiner. In the following discussion, the properties or
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Volume and mass percent D2892 and X X X X X X X X X X
yields D5236
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Carbon residue, mass D4530 X X X X X
percent
40C X X X
55C X X X X
80C X X X X
100C X
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120C X
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Naphthalenes, volume D1840 X X
percent
Penetration D5 X
correlative methods, especially in LP models, for determina- The quality of cargoes arriving at refineries may not
tion of the gross composition of this fraction. conform to what is known or expected for that stream. This
can be the result, among other causes, of new production
VACUUM GAS OIL FRACTIONS coming on-stream and being commingled with existing pro-
Density or specific gravity, total sulfur, total nitrogen, aniline duction or field maintenance. The analyst or refiner can use
point, viscosity, acid number, cloud and pour points, and the so-called Flash Assay Tool [97] to update an existing
carbon residue would normally be determined on these frac- comprehensive assay on the stream in question with a mini-
tions. Cetane index would be determined on the LVGO if the mum of data. The tool uses HTSD and various whole crude
material is to be used as diesel fuel oil blending stock. If the properties such as American Petroleum Institute (API) grav-
HVGO is to be used as catalytic cracker feedstock, asphal- ity or density and total sulfur content to adjust the older
tenes, nickel and vanadium, and hydrogen and carbon con- assay. The new assay, together with a refinery LP model,
tents would also be determined. Lube stock evaluations can then be used to make quick decisions such as purchas-
would include determination of wax content. Basic nitrogen ing and running an opportunity (challenging) crude oil. The
is also typically determined on these fractions. However, in flash assay can also be used to indicate when another full
general, the ratio of basic to total nitrogen is on the order of assay should be run. With the proliferation of new streams
0.3:1 for many crude oils and virgin stocks [34]. The types of and with new production frequently being added into exist-
nitrogen compounds present in various crude oils appear to ing streams, a flash assay can result in considerable cost and
be essentially the same, although the actual amounts may time savings. With the relatively limited data incorporated
vary considerably [94]. Consequently, for most assays it is into flash assay updates, it must be kept in mind that preci-
sufficient to determine total nitrogen and to assume that sion and accuracy are not optimum.
approximately one third is basic in character. Moreover, todays trend is toward automated, real-time anal-
ysis using on-line detectors to the extent permitted by available
RESIDUUM instrumentation. Some of this instrumentation has the capability
Tests of the residuum fractions usually include density or spe- to provide data suitable for custody transfer determination of
cific gravity, total sulfur, total and basic nitrogen, acid num- crude oil properties, but this is currently quite limited. However,
ber, viscosity, trace metals, asphaltenes, and carbon residue. it seems likely that significant advances in this area will be
Hydrogen/carbon ratio and pour point determinations on the accomplished in the near future, further removing the laboratory
atmospheric (long) and vacuum (short) residua are also analyst from routine characterization of crude oil feedstocks.
important. Refiners are increasingly minimizing production
of material that formerly went into heavy fuels such as No. 6 SUMMARY
and bunker oil as markets for these products diminish. Crude oils, unlike refined products, do not have specifications.
Determination of the properties of asphalt, such as pen- As such, it is fundamentally important that assays provide suf-
etration (ASTM D5: Test Method for Penetration of Bitumi- ficient and accurate data so that the producers, traders, refin-
nous Materials), softening point [ASTM D36: Test Method ers, and other users of the data can achieve several objectives.
for Softening Point of Bitumen (Ring-and-Ball Apparatus)], Moreover, the analytical test methods and procedures used
and viscosity would also be included in some assays. How- must be defined so that different laboratories can be reason-
ever, penetration and softening point tests were developed ably expected to obtain comparable data on replicate samples.
in an era of less traffic and significantly lower pavement From the time a crude oil stream is produced until it
loadings and are no longer suitable for evaluating asphalt to reaches a refinery and is processed, several factors can
be used as a binder. Newer Performance Grade tests such affect its quality. Depressurization and cooling at the well-
as Dynamic Shear Rheometer, Rolling Thin Film Oven, and head can result in flocculation of asphaltenes and crystalliza-
Direct Tension Test have been developed [95]. tion of waxes. Production making up a defined stream varies
In the preceding discussion, the properties listed for each over time because of several factors, including well mainte-
fraction and for the whole crude oil assay are not exhaustive nance and workovers, reservoir aging, and commingling of
but are illustrative of those used to evaluate quality. As noted new production. During subsequent marine transportation,
earlier, refiners tailor their analytical scheme to their particu- two or more crude oils of somewhat different quality may
lar crude oil and product slates, although one refiner is be commingled on the same vessel.
reported to have said, The best crude oil assay is a 100,000 bbl In common carrier pipeline systems, crude oils of differ-
run through my refinery [96]. Although this opinion carries ent quality are commonly batched. Interfacial mixing will
some validity, the assay tests presented here provide data that take place between the head and tail of sequential batches
are sufficient for most refiners to evaluate crude oil streams. until they reach a breakout terminal. At the terminal, the
With the proliferation of computer LP models and their crude oil may be stored in a tank containing a heel of dif-
associated assay libraries [9], many refiners no longer need to ferent quality.
perform comprehensive assays as frequently as in the past. Assays provide assurance that the crude oil received is
Often, an inspection assay is all that is required for them to what is expected and help to define the changes that have
plan for changes in processing that will be necessitated by taken place during transportation and storage. Refinery oper-
varying levels of impurities or small changes in crude oil com- ation personnel use assays to assess handling and processing
position resulting from changes in the production com- characteristics of a new stream or one that has changed in
mingled to make up the crude oil stream. Most importantly, quality. Assays provide important information on the pres-
an inspection assay can be completed much more rapidly ence and concentration of impurities and contaminants that
than a comprehensive assay and requires considerably less may affect refinery process systems. Moreover, they are
material. Collectively, these can result in savings in analysts important to the producer because they provide the data
time and shipping and handling expenses. needed to demonstrate acceptability of a stream in a common
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CHAPTER 4 n COMPREHENSIVE ASSAYS AND FRACTION EVALUATIONS 31
carrier pipeline system. Furthermore, assays are used in vari- However, the data available are seldom from recent ship-
ous ways in ascertaining compatibility of different streams. ments or cargoes.
Assay data are input to refinery LP models to optimize Finally, detailed assays are costly and can take weeks to
crude oil blends and predict product yields. These data are complete. The data they provide may not be representative
directionally correct, but they do not replicate refinery con- of the shipment recently received, especially if it is an oppor-
ditions. Assays do not indicate how the fraction material will tunity crude oil. Assays do not account for variations
behave in process units such as reformers, catalytic crackers, between cargoes and may not be representative of current
or cokers or how the process streams will interact with the production quality. Furthermore, and perhaps most impor-
many and complex catalysts used today. Moreover, they do tant of all, assays are fundamentally dependent on the care
not provide data on the storage stability of refined products. and attention paid to sampling and handling.
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MNL68-EB/Nov. 2010
5
Quality Assurance
Petroleum laboratories, large and small, should have a quality Three times yearly, program participants receive sam-
assurance program that helps provide confidence to all inter- ples. The laboratory performs the tests that they normally
ested parties that the analytical data it provides fall within the conduct within their own facility using the specified ASTM
limits of precision and accuracy defined in the ASTM test methods cited in the program. Single determinations by
methods used. These data are important in the following each laboratory are required because the program does not
respects, and inaccurate data can have severe financial and allow the reporting of averages of replicate determinations.
operational consequences: Final summary reports provided to participants contain
Conformity to what is expected, that is, Is the crude oil Each participating laboratorys test results (coded for
I am receiving what I am expecting and what I am pay- confidentiality)
ing for? Statistical analyses of test data
If I am a shipper, does the crude oil meet common Charts plotting test results versus laboratory code
stream pipeline specifications? If not, it may be neces- Other pertinent information
sary for me to batch my crude oil at additional cost. These final statistical summary reports will help
Are the data I am providing accurate for payment of laboratories
customs duty? Monitor strengths and weaknesses of their laboratorys
Are the concentrations of impurities and contaminants performance.
I have determined correct for planning refinery opera- Compare test results and calculated statistical parame-
tions and making deductions from the cost of the ters with other laboratories worldwide.
crude oil? Demonstrate proficiency in the specific analysis to meet
Are my data accurate for regulatory and environmental, laboratory accreditation requirements.
safety, and health reporting requirements? Monitor process performance over time as part of each lab-
ASTM Internationals Crude Oil Interlaboratory Cross- oratories quality control (QC) program and prompt the
check Program (ILCP) is a statistical quality assurance pro- respective laboratory to investigate their process if the qual-
gram that enables facilities to assess their performance in ity changesparticularly if precision degrades over time.
conducting test methods within their own laboratories when In some cases the retained ILCP sample may be used by
their data are compared against those of other participating the laboratory for future check standards of some tests
laboratories. In early 2010, over 140 laboratories worldwide in which no standards are commercially available.
participated in the crude oil ILCP program. Table 1 lists the An example of the statistical data summary provided in
properties and test methods used in the program at that time. a crude oil ILCP test report is shown in Table 2.
32
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CHAPTER 5 n QUALITY ASSURANCE 33
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6
Crude Oil Compatibility and Stability
The blending of compositionally different crude oils and Fuel Oil Stability Analyzer (Optical Detection) is a procedure
condensate with crude oil can result in significant problems involving titration and optical detection of precipitated
in transportation, storage, and refining. This is usually mani- asphaltenes for determining the stability and compatibility
fested by agglomeration or flocculation of waxes and/or of crude oils. Stability in this context is the ability to main-
asphaltenes. These can accumulate and clog tubular compo- tain asphaltenes in a peptized or dissolved state and not
nents such as pipelines and heat exchangers or contribute to undergo flocculation or precipitation. Similarly, compatibil-
sludge buildup in tanks, requiring costly and time-consuming ity relates to the property of mixing two or more crude oils
cleanup and equipment downtime. without precipitation or flocculation of asphaltenes occur-
The problem has been recognized for many years, but ring. In the test, different mixtures of the crude oil of inter-
no standard method has been developed that reliably pre- est plus xylene are titrated with n-heptane to cause
dicts whether particular blends will be incompatible, quantify precipitation of asphaltenes. The titrated mixture is continu-
the extent to which waxes and asphaltenes will accumulate, ously circulated through an optical system that detects pre-
nor when onset of incompatibility will begin once compo- cipitated asphaltenes by back-scattering of visible light.
nents are mixed. This latter is complicated by the fact that Stability and compatibility parameters as defined in the
considerable empirical evidence indicates there can be an method are then calculated.
induction period of three or more days before onset. ASTM D7157: Test Method for Determination of Intrinsic
Stability of Asphaltene-Containing Residues, Heavy Fuel Oils,
ASPHALTENES and Crude Oils (n-Heptane Phase Separation; Optical Detec-
Historically, two test methods used for testing compatibility tion) is a procedure for quantifying the intrinsic stability of
of residual fuel oil mixtures have been applied to crude oil the asphaltenes in an oil. The method uses an integrated auto-
blends. ASTM D4740: Test Method for Stability and Compati- mated analytical measurement system with an optical probe
bility of Residual Fuels by Spot Test and a modified version for the detection of asphaltene precipitation from a toluene
of ASTM D4870: Test Method for Determination of Total solution of the sample. Three test specimens are dissolved in
Sediment in Residual Fuels. ASTM D4740 is a simple test to three different quantities of toluene. The three solutions are
perform, but the results are subjective and not quantitative. automatically and simultaneously titrated with n-heptane to
In determining compatibility of crude oils, two oils are cause precipitation of the asphaltenes. A computer program
mixed in a predetermined ratio and the blend tested and calculates stability parameters and subsequently the intrinsic
rated for compatibility against ASTM D4740 Adjunct Refer- stability of the oil in terms defined in the method.
ence Spots (Fig. 1). Crude oil blends may exhibit an induc-
tion period and evidence of incompatibility may not become WAXES
evident for several days. If, on initial testing, a blend seems As discussed earlier, waxes are a complex mixture of mostly
compatible, it may be advisable to retest the mixture several normal- and iso-alkanes having chain lengths of greater than
days later to determine if a change in rating has occurred. approximately 30 carbon atoms that contribute to several
ASTM D4870, as modified, provides a quantitative measure problems in crude oil production, transportation, storage,
of the amount of inorganic and insoluble organic material and handling. Among these, they congeal in pipelines and
in a blend of crude oils of interest. In the modified version other production equipment restricting flow [102], and they
of the test method, a 10-g sample of the blend is mixed at agglomerate and contribute to sludge buildup in tanks. As
60C then filtered at 60C through the apparatus described offshore production moves into deeper and colder waters,
in the test method. The test does not differentiate inorganic concern about wax deposition in subsea pipelines becomes
from organic sediment, and the former must be determined increasingly relevant. Moreover, precipitation of waxes dur-
by a method such as ASTM D473 and subtracted from the ing marine transportation can result in relatively significant
total to obtain the organic sediment content. remain-on-board (ROB) losses when the vessel discharges.
Other test methods, which range from simple to complex, This is an especially important consideration for cargoes
include modified Shell Spot test [98], Asphaltene Stability that undergo considerable cooling from the time they are
Index [99], Oil Compatibility Model [100], and Automated loaded until discharge. For example, a cargo may be loaded
Flocculation Titrimetry [101]. The latter method was devel- at an Arabian Sea port at a temperature of approximately
oped for determining compatibility of heavy oils and asphalts 38C and then discharged at a transshipment terminal in
but has been applied to blending of crude oils. Canada at a temperature of 20C after a voyage through
Two automated instrumental test methods seem promis- frigid ocean waters.
ing for determining stability and compatibility of crude oils. Cloud point or wax appearance temperature (WAT) is
ASTM D7112: Test Method for Determining Stability and probably the single most important measure of the potential
Compatibility of Heavy Fuel Oils and Crude Oils by Heavy for a crude oil to deposit waxes as it cools. Cloud point is
34
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CHAPTER 6 n CRUDE OIL COMPATIBILITY AND STABILITY 35
-1000
-3000
-5000
Cooling
RF/Hz
Heating
-7000
-11000
WAT WDT
-13000
10 15 20 25 30 35 40 45 50 55 60
T/C
Fig. 2Measurement of wax appearance and disappearance temperatures using changes in the resonant frequency of a quartz crystal
microbalance (Courtesy of Professor B. Tohidi).
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36 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
presence of pour point depressants will drastically affect the same sample using DSC. A newer technique for determining
samples WAT. WAT and WDT involves measuring changes in resonant fre-
Contrasting with WAT is the wax disappearance tempera- quency (RF) of a sample with a quartz crystal microbalance as
ture (WDT), the temperature at which the last wax crystal is in illustrated in Fig. 2 [107]. Although WAT and WDT should ther-
equilibrium with the liquid phase. This latter is measured while modynamically be the same, the WAT is invariably 320C
heating the sample rather than cooling the sample as is done lower than the WDT [103]. These differences result from sub-
for WAT. WAT and WDT can conveniently be measured on the cooling and superheating of the sample [108].
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7
Crude Oil as Fuel
Crude oil has been used directly as a fuel for power genera- replaced other sources of energy to fire cement kilns in
tion in several applications for more than 100 years. Among Cuba [116]. During the 1990s, thermoelectric power stations
the earliest documented uses was as fuel for the Cleveland in the Republic of Macedonia were fueled by some 1 million
City Cable Railway power plant in Cleveland, Ohio, in 1891 tons of crude oil every year [117]. In 2004, China purchased
[109]. In 1892, it was reported there are some such progres- three diesel engines from a Finnish company for installation
sive brick manufacturers in Chicago, who use neither coal on one of its offshore production platforms specifically to
nor wood in the drying or burning of their clay products. generate electricity using crude oil from the oilfields pro-
Crude oil is the fuel which they employ. [110]. In 1893, a duction as fuel [118]. In 2006, Japan used on the order of
very extensive trial of crude petroleum fuel was made in Chi- 90100 thousand barrels per day of crude oil to fire some of
cago in connection with the Worlds Fair [111]. The arti- its thermal power plants [119]. And, contrary to the admoni-
cle went on to caution the main things to bear in mind in tions in the report on the 1893 Worlds Fair and in the 1915
burning crude oil are, (1) the liability to fires and explosions encyclopedia article about crude oils dangers, several tanker
from the ignition of vapor given off by the oil. Crude oil operators have, at times, surreptitiously and unlawfully
was used to power a railroad locomotive in a trial run in diverted some of their cargo to power their ships. These inci-
Corsicana, Texas, in 1895. dents have not been without disastrous consequences, and
fires and explosions have occurred.
An experiment was made in using the crude oil from Cost and availabilityespecially in remote operational
the oil wells at Corsicana, Texas for fuel for the loco- areasare certainly factors influencing the selection of crude
motive in hauling passenger trains between Corsicana oil over conventional burner, diesel, and gas turbine fuels.
and Hillsboro, which proved satisfactory and arrange- Other factors must also be considered, among them safety,
ments have been made to continue use oil in that environmental emissions, and the effect that use of crude oil
locomotive, and also in the switch locomotive at Corsi- will have on the performance and maintenance of engines,
cana [112]. turbines, and boilers.
No specifications have been established for crude oil to
A history of Anheuser-Busch, the American brewing giant, be used in these applications, but certain properties critical
mentions that Adolphus Busch obtained the American rights to the operation of burners, engines, and turbines must be
to build diesel engines in 1897 and that the companys first taken into consideration. Among these are flash point, sul-
engine was installed in the Anheuser Busch power plant in fur, ash content, pour point, viscosity, wax content, carbon
1898. Although not stating explicitly that crude oil was used residue, and metals contentespecially vanadium, nickel, and
to fuel this engine, the history states as now is well known, sodium. Because crude oils usually have relatively low flash
the Diesel engine operates very economically, using crude oil points, their use as a fuel has an associated fire hazard and
as fuel [113]. inherent risk of explosion necessitating that storage facilities
In 1915, The New International Encyclopedia stated be appropriately configured. Furthermore, crude oils selected
nearly all crude oil can be used by fuel (for ships). If it con- for use as burner fuels must have suitable fluidity properties
tains very little sulphur or asphalt, it is suitable for heavy oil to ensure they are pumpable and can be aspirated in the
engines of the Diesel type. The article went on to state that burner or turbine. Moreover, the crude oil should have low
crude oil is not, however, much used for either of these pur- ash and sulfur contents. These are important environmental
poses and the reasons are the presence of the more vola- considerations from the standpoints of fly ash (particulates)
tile oils renders storage dangerous. [114]. and sulfur dioxide emissions. The asphaltic residuum from
In 1975, crude oils with a wide range of properties were burning of crude oils can build up on heat transfer surfaces,
investigated for direct use as fuel in U.S. Army high-speed reducing their efficiency, and can clog burners. Crude oils to
diesel engines [115]. Results of this study indicated that, with be used for gas turbines must also have low concentrations of
proper selection and pretreatment, crude oils are feasible for trace metals to ensure that turbine blades are not adversely
emergency use. affected.
In recent years, crude oil has been used as fuel under The standard test methods described elsewhere in this
boilers, in gas turbines used for standby power generation, manual for characterizing crude oils as refinery feedstocks
and in diesel engines worldwide. Since 1990, crude oil has are equally applicable to determining its use as a fuel.
37
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8
Future Needs in Crude Oil Characterization
The average quality of crude oil being processed in refineries detectors that provide selectivity for other constituents
is becoming higher in sulfur and heavier [120]; that is, a of interest (e.g., nitrogen and organometallics) are also
greater content of heavy ends or residuum. With the growing commercially available and being increasingly used for
demand for transportation fuels, the refiner is faced with characterizations.
mounting pressure to make better use of the bottom of the The supply of high-acid crude oils (i.e., those with a
barrelthe residuum that formerly went into low-quality total acid number >1.0) is increasing substantially on a
products such as No. 6 and bunker fuel oils. Diminishing global basis. To adequately assess and plan the effective
worldwide demand for these latter fuels is exacerbating the refinery processing of these, it is important to know the acid
need to use this material to produce other products, especially species present. Naphthenic acids in particular can be espe-
lighter fuels [121]. Moreover, as environmental restrictions cially detrimental throughout a refinery. Several crude oils
increasingly limit sulfur and aromatics in transportation and today contain high concentrations of calcium that will con-
burner fuel oils, refiners are facing new challenges to econom- tribute to formation of egregious naphthenic acid soaps.
ically producing a marketable slate of products from heavier, These soaps can cause formation of highly stable emulsions
higher sulfur feedstocks. These challenges generally require that can be carried through to wastewater treatment plants.
new or expanded processing and treatment technology at the Naphthenic acids can be very corrosive, but it is important
refinery. This, in turn, translates into the need for new analyti- to know their species because they behave differently
cal test methods in the laboratory to adequately evaluate feed- depending on the varying conditions of temperature, flow
stocks and monitor product quality (Table 1). velocity, and metallurgy existing within a refinery. ASTM
However, existing analytical methods may not be suita- D664, which is used almost universally for determining the
ble for characterizing many of todays crude oil streams. The acid content of a crude oil, provides no information on the
scope of these methods may not be sufficiently broad to acid species present or their relative strength. A rapid and
cover the range in quality of some of the heavier and higher reliable method for characterizing the components contrib-
sulfur crude oils, nonconventional streams such as bitumen, uting to the acidity of a crude oil and their relative strength
and synthetic crude oil derived from Canadian oil sands is needed.
and Venezuelan heavy oils. Table 2 summarizes some of the Upgrading the bottom of the barrel involves converting
improvements needed to existing test methods to make them moreideally allof the residuum into a more salable, higher-
more applicable to these streams. In making revisions to test valued product (i.e., 100% residuum conversion). Whatever
methodology, it may be necessary to conduct new interlabor- the means to this end, improved characterization methods are
atory round-robin studies to validate the precision state- necessary for process design, crude oil evaluation, and opera-
ments. With the consolidations within the industry and the tional control. Characterization methods that define the boil-
growing demands being placed on the analyst, this may not ing range and the hydrocarbon type distribution of heavy
be practical. residuum are of growing importance. High-temperature gas
The Canadian Crude Quality Technical Association has chromatography simulated distillation (HTSD) has been used
used the extensive experience of its members to compile a to obtain cutpoint data up to an atmospheric equivalent boil-
manual, Heavy Oil and Bitumen Analytical Methods [122]. ing point temperature of 740C [123].
This manual provides a review of existing test methods for The distributions of hydrocarbon types in gas oil and
eight parameters commonly used in assessing quality of heavier materials are important in evaluating them as feed-
heavy oils and bitumen and discusses their capabilities and stocks for further processing. Some older mass spectromet-
limitations. When available, precision data obtained from ric methods for determining hydrocarbon types are being
round-robin studies on heavy oils and bitumen are included. updated for use with modern quadrupole mass spectrome-
The analytical sections in this manual are not a substitute ters, either with batch inlets or with gas chromatographic
for standardized test methods specific to heavy oils and bitu- inlets (GC/MS). Another technique that has been successfully
men, but they do help users to make informed decisions on applied for determining hydrocarbon types in these materi-
method selection, sample preparation, test modifications, als involves the use of high-performance liquid chromatogra-
and interpretation of resultant data. phy (HPLC), which can provide information comparable to
Sulfur reduction processes are sensitive to amount and the mass spectrometric methods. Standardized HPLC techni-
structure of the sulfur compounds being removed. Tests that ques are now being used to determine aromatic hydrocar-
can provide information about both are becoming increas- bon types in middle distillate and aviation fuels.
ingly important. Several laboratories have combined gas chro- With the large volumes of crude oil being moved in
matography with sulfur-selective detectors to provide data todays markets and with the growing availability of opportu-
on the boiling range distribution of the sulfur compounds nity or challenged crude oils comes increasing pressure to
and probable molecular types. In addition, gas chromatography determine key properties in less time and with a high degree
38
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CHAPTER 8 n FUTURE NEEDS IN CRUDE OIL CHARACTERIZATION 39
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D96 Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure) (withdrawn 2000)
D287 API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method)
D445 Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
D473 Sediment in Crude Oils and Fuel Oils by the Extraction Method
D1298 Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method
D1480 Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
D2161 Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or to Saybolt Furol Viscosity
D3228 Total Nitrogen in Lubricating Oils and Fuel Oils by Modified Kjeldahl Method
D4007 Water and Sediment in Crude Oil by the Centrifuge Method (Laboratory Procedure)
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42 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
ASTM Title
D4629 Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe/Inlet Oxidative Combustion and Chemiluminescence
D5002 Density and Relative Density of Crude Oils by Digital Density Analyzer
D5134 Detailed Analysis of Petroleum Naphthas through n-Nonane by Capillary Gas Chromatography
D5185 Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of
Selected Elements in Base Oils by Inductively-Coupled Plasma Atomic Emission Spectrometry (ICP-AES)
D5291 Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants
D5307 Determination of the Boiling Range Distribution of Crude Petroleum by Gas Chromatography
D5708 Determination of Nickel, Vanadium, and Iron in Crude Oils and Residual Fuels by Inductively-Coupled Plasma (ICP)
Atomic Emission Spectrometry
D5854 Practice for Mixing and Handling of Liquid Samples of Petroleum and Petroleum Products
D5863 Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption
Spectrometry
D6299 Applying Statistical Quality Assurance Techniques to Evaluate Analytical Measurement System Performance
D6560 Determination of Asphaltenes (Heptane Insolubles) in Crude Petroleum and Petroleum Products
D6822 Density, Relative Density, and API Gravity of Crude Petroleum and Liquid Petroleum Products by Thermohydrometer
Method
D7112 Determining Stability and Compatibility of Heavy Fuel Oils and Crude Oils by Heavy Fuel Oil Stability Analyzer
(Optical Detection)
D7157 Determination of Intrinsic Stability of Asphaltene-Containing Residues, Heavy Fuel Oils, and Crude Oils (n-Heptane
Phase Separation; Optical Detection)
D7169 Boiling Point Distribution of Samples with Residues Such as Crude Oils and Atmospheric and Vacuum Residues by
High-Temperature Gas Chromatography
D7279 Kinematic Viscosity of Transparent and Opaque Liquids by Automated Houillon Viscometer
D7343 Optimization, Sample Handling, Calibration, and Validation of X-Ray Fluorescence Spectrometry Methods for Ele-
mental Analysis of Petroleum Products and Lubricants
(Continued)
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APPENDIX 2: REFERENCED ASTM AND OTHER STANDARDS 43
ASTM Title
D7455 Sample Preparation of Petroleum and Lubricant Products for Elemental Analysis
D7622 Total Mercury in Crude Oil Using Combustion and Direct Cold Vapor Atomic Absorption Method with Zeeman Back-
ground Correction
D7623 Total Mercury in Crude Oil Using Combustion-Gold Amalgamation and Cold Vapor Atomic Absorption Method
IP Title
389 Determination of Wax Appearance Temperature (WAT) of Middle Distillate Fuels by Differential Thermal Analysis
(DTA) or Differential Scanning Calorimetry (DSC)
UOP Title
163 Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocarbons by Potentiometric Titration
375 Calculation of UOP Characterization Factor and Estimation of Molecular Weight of Petroleum Oil
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 45
Fig. 3Comparison of percent sediment and water versus unloading time period.
adsorbed Hg(0) on particulates (e.g., carbonaceous or min- D287 Test Method for API Gravity of Crude
eral fines and ferric oxide), and suspended droplets of Petroleum and Petroleum Products
metallic mercury. (Hydrometer Method)
1.3 The presence of suspended droplets of metallic mercury 1. SCOPE
(often called colloidal mercury, because the droplet 1.1 This test method covers the determination by means of a
size can be very small) can make obtaining a representa- glass hydrometer of the American Petroleum Institute (API)
tive sample very difficult for various reasons (e.g., non- gravity of crude petroleum and petroleum products nor-
isokinetic sampling of the liquid can result in over- or mally handled as liquids and having a RVP (Test Method
undercollection of suspended droplets and collection of D323) of 180 kPa (26 psi) or less. Gravities are determined at
mercury that has accumulated in dense larger drops and 15.56C (60F ) or converted to values at 60F by means of
pools on the bottom of piping and in sample taps). Pay standard tables.
strict attention to the detailed procedure (Section 7) to Note 1The international version of this test method is
ensure representative samples are collected. described in Practice D1298.
1.4 When representative test portions are collected and ana-
lyzed in accordance with acceptable procedures, the total 4. SUMMARY OF TEST METHOD
mercury is representative of concentrations in the sample. 4.1 This test method is based on the principle that the gravity
of a liquid varies directly with the depth of immersion of a
4. SUMMARY OF PRACTICE body floating in it. The floating body, which is graduated
4.1 This practice describes the sampling, storage, transport, by API gravity units in this method, is called an API
and handling of hydrocarbon samples used for determin- hydrometer.
ing mercury, and the precautions that need to be taken to 4.2 The API gravity is read by observing the freely floating API
prevent sample contamination and loss of analyte. hydrometer and noting the graduation nearest to the appa-
rent intersection of the horizontal plane surface of the liquid
TEST METHODS with the vertical scale of the hydrometer after temperature
D97 Test Method for Pour Point of equilibrium has been reached. The temperature of the sam-
Petroleum Products ple is read from a separate accurate ASTM thermometer in
1. SCOPE the sample or from the thermometer, which is an integral
1.1 This test method is intended for use on any petroleum part of the hydrometer (thermohydrometer).
product. A procedure suitable for black specimens (such
as crude oils) is described. D323 Test Method for Vapor Pressure of Petroleum
1.2 Currently there is no ASTM test method for automated Products (Reid Method)
Test Method D97 pour point measurements. 1. SCOPE
1.1 This test method covers procedures for the determina-
4. SUMMARY OF TEST METHOD tion of vapor pressure (see Note 1) of gasoline, volatile
4.1 After preliminary heating, the sample is cooled at a speci- crude oil, and other volatile petroleum products with a
fied rate and examined at intervals of 3C for flow char- vapor pressure of less than 180 kPa (26 psi).
acteristics (Fig. 4). The lowest temperature at which Note 1Because the external atmospheric pressure is
movement of the specimen is observed is recorded as the counteracted by the atmospheric pressure initially present in
pour point. the vapor chamber, the RVP is an absolute pressure at
37.8C (100F) in kilopascals (pounds-force per square inch).
RVP differs from the true vapor pressure of the sample
because of some small sample vaporization and the presence
of water vapor and air in the confined space.
D473 Test Method for Sediment in Crude Oils 4. SUMMARY OF TEST METHOD
and Fuel Oils by the Extraction Method 4.1 The sample is brought to a specified temperature and a
1. SCOPE test portion is transferred to a hydrometer cylinder that
1.1 This test method covers the determination of sediment in has been brought to approximately the same temperature.
crude oils by extraction with toluene. The precision The appropriate hydrometer, also at a similar tempera-
applies to a range of sediment levels from 0.01 to 0.40 % ture, is lowered into the test portion and allowed to settle.
mass, although higher levels may be determined. After temperature equilibrium has been reached, the
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 49
hydrometer scale is read (Fig. 7), and the temperature of with sulfur concentrations below 60 mg/kg, the repeatabil-
the test portion is taken. The observed hydrometer read- ity standard deviation (Sr) was 1.5 mg/kg. An estimate of the
ing is reduced to the reference temperature by means of limit of detection is 3 3 3 Sr, and an estimate of the limit
the Petroleum Measurement Tables. If necessary, the of quantitation is 10 3 3 Sr. However, because instrumen-
hydrometer cylinder and its contents are placed in a con- tation covered by this test method can vary in sensitivity,
stant temperature bath to avoid excessive temperature the applicability of the test method at sulfur concentrations
variation during the test. below approximately 20 mg/kg must be determined on an
individual basis.
D1480 Test Method for Density and 1.3 Samples containing more than 5.0 mass percent sulfur can
Relative Density (Specific Gravity) of Viscous be diluted to bring the sulfur concentration of the diluted
Materials by Bingham Pycnometer material within the scope of this test method.
1. SCOPE 1.4 Volatile samples may not meet the stated precision because
1.1 This test method describes two procedures for the measure- of selective loss of light materials during the analysis.
ment of the density of materials that are fluid at the desired 1.5 A fundamental assumption in this test method is that the
test temperature. Its application is restricted to liquids of standard and sample matrix are well matched. Matrix
vapor pressures below 600 mm Hg (80 kPa) and viscosities mismatch can be caused by carbon-to-hydrogen ratio dif-
below 40,000 cSt (mm2/s) at the test temperature. The ferences between samples and standards or by the pres-
method is designed for use at any temperature between ence of other heteroatoms.
20C and 100C. It can be used at higher temperatures;
however, in this case, the precision section does not apply. D2892 Test Method for Distillation of Crude
1.2 This test method provides a calculation procedure for Petroleum (15-Theoretical Plate Column)
converting density to specific gravity. 1. SCOPE
1.1 This test method covers the procedure for the distillation
4. SUMMARY OF TEST METHOD of stabilized crude petroleum (see Note 1) to a final cut
4.1 The liquid sample is introduced into the pycnometer, equi- temperature of 400C atmospheric equivalent tempera-
librated to the desired temperature, and weighed. The den- ture (AET). This test method uses a fractionating column
sity or specific gravity is then calculated from this weight having an efficiency of 1418 theoretical plates operated
and the previously determined calibration factor, and a at a reflux ratio of 5:1. Performance criteria for the neces-
correction is applied for the buoyancy of air. sary equipment are specified. This test method offers a
compromise between efficiency and time to facilitate the
D2622 Test Method for Sulfur in Petroleum comparison of distillation data between laboratories.
Products by Wavelength Dispersive X-ray Note 1Defined as having a RVP less than 82.7 kPa (12 psi).
Fluorescence Spectrometry 1.2 This test method details procedures for the production of
1. SCOPE a liquefied gas, distillate fractions, and residuum of stand-
1.1 This test method covers the determination of total sulfur ardized quality on which analytical data can be obtained
in petroleum and petroleum products that are single as well as the determination of yields of the above frac-
phase and either liquid at ambient conditions, liquefiable tions by mass and volume. From the preceding informa-
with moderate heat, or soluble in hydrocarbon solvents. tion, a graph of temperature versus mass percent
These materials include crude oil among others. distilled can be produced. This distillation curve corre-
1.2 Interlaboratory studies on precision covered various materi- sponds to a laboratory technique, which is defined at
als with sulfur concentrations ranging from approximately 15/5 (15-theoretical plate column, 5:1 reflux ratio) or
3 mg/kg to 5.3 mass percent. For a subset of these samples, true boiling point (TBP).
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50 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
4. SUMMARY OF TEST METHOD 4.5 From these data, the TBP curves in mass percent, volume
4.1 A weighed sample of 130 L of stabilized crude petroleum percent, or both versus AET are drawn.
is distilled to a maximum temperature of 400C AET in a
fractionating column having an efficiency at total reflux D3230 Test Method for Salts in Crude Oil
of at least 14, but not greater than 18, theoretical plates (Electrometric Method)
(Fig. 8). 1. SCOPE
4.2 A reflux ratio of 5:1 is maintained at all operating pres- 1.1 This test method covers the determination of the approxi-
sures, except that at the lowest operating pressures mate chloride (salts) concentration in crude oil. The range
between 0.674 and 0.27 kPa (5 and 2 mm Hg), a reflux of concentration covered is 0500 mg/kg or 0150 lb/
ratio of 2:1 is optional. In cooperative testing or in cases 1,000 bbl as chloride concentration/volume of crude oil.
of dispute, the interested parties must mutually agree on 1.2 This test method measures conductivity in the crude oil
the stages of low pressure, the reflux ratios, and the tem- that is due to the presence of common chlorides such as
peratures of cutpoints before beginning the distillation. sodium, calcium, and magnesium. Other conductive
4.3 Observations of temperature, pressure, and other varia- materials may also be present in the crude oil.
bles are recorded at intervals and at the end of each cut 1.3 Acceptable concentration units are grams per cubic metre
or fraction. (g/m3) or pounds per thousand barrels (PTB; lb/1,000 bbl).
4.4 The mass and density of each cut or fraction are obtained.
Distillation yields by mass are calculated from the mass of 4. SUMMARY OF TEST METHOD
all fractions, including liquefied gas cut and the residue. 4.1 This test method measures the conductivity of a solution of
Distillation yields by volume of all fractions and the resi- crude oil in a mixed alcohol solvent when subjected to an
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density. electrical stress. This test method measures conductivity
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 51
due to the presence of inorganic chlorides and other 3. SUMMARY OF TEST METHOD
conductive material in the crude oil. A homogenized test 3.1 The sample is heated under reflux conditions with a water-
specimen is dissolved in a mixed alcohol solvent and immiscible solvent that codistills with the water in the sam-
placed in a test cell consisting of a beaker and a set of elec- ple. Condensed solvent and water are continuously separated
trodes. A voltage is impressed on the electrodes, and the in a trapthe water settles in the graduated section of the
resulting current flow is measured. The chloride (salt) con- trap, and the solvent returns to the distillation flask (Fig. 9).
tent is obtained by reference to a calibration curve of cur- An appendix provides a summary of a round-robin testing
rent versus chloride concentration of known mixtures. program that showed that the distillation test method as prac-
Calibration curves are based on standards prepared to ticed is somewhat more accurate than the centrifuge test
approximate the type and concentration of chlorides in the method (D4007) for determining water in crude oils.
crude oils being tested.
D4007 Test Method for Water and Sediment in
D4006 Test Method for Water in Crude Crude Oil by the Centrifuge Method
Oil by Distillation (Laboratory Procedure)
1. SCOPE 1. SCOPE
1.1 This test method covers the determination of water in 1.1 This test method describes the laboratory determination
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52 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
5. INTERFERENCES
5.1 Spectral interferences result when some sample compo-
nent element or elements emit X rays that the detector
cannot resolve from sulfur X-ray emission. As a result,
the lines produce spectral peaks that overlap with each
other. Spectral interferences may arise from samples
Fig. 9Example of typical distillation apparatus for D4006. containing water, silicon, calcium, potassium, and hal-
ides if present at concentrations greater than one tenth
centrifuge procedure. This centrifuge method for deter- of the measured concentration of sulfur or more than a
mining water and sediment in crude oils is not entirely few hundred milligrams/kilogram.
satisfactory. The amount of water detected is almost 5.2 Matrix effects are caused by concentration variations of
always lower than the actual water content. When a the elements in a sample. These variations directly influ-
highly accurate value is required, the revised procedures ence X-ray absorption and change the measured inten-
for water by distillation, Test Method D4006, and sedi- sity of each element. These types of interferences are
ment by extraction, Test Method D473, shall be used. always present in X-ray fluorescence analysis and are
Note 1Test Method D4006 has been determined to be completely unrelated to spectral interferences.
the preferred and most accurate method for the determina- 5.3 Both types of interferences are compensated for in con-
tion of water. temporary instruments with the use of built-in software. It
is recommended that these interferences be checked from
3. SUMMARY OF TEST METHOD time to time and that the software corrections offered by
3.1 Equal volumes of crude oil and water-saturated toluene the manufacturer not be accepted at face value.
are placed into a coneshaped centrifuge tube. After cen- Note 1In the case of petroleum materials that contain
trifugation, the volume of the higher density water and suspended water, it is recommended that the water be
sediment layer at the bottom of the tube is read removed before testing or that the sample be thoroughly
(Fig. 10). homogenized and immediately tested. The interference is
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 53
Fig. 10Procedure for reading water and sediment when using an ASTM 100-mm cone-shaped centrifuge tube.
greatest if the water creates a layer over the transparent film D4530 Test Method for Determination of
because it will attenuate the X-ray intensity for sulfur. One Carbon Residue (Micro Method)
such method to accomplish the removal of water is to centri- 1. SCOPE
fuge the sample first under ambient sealed conditions, tak- 1.1 This test method covers the determination of the amount
ing care that the sample integrity is not compromised. of carbon residue formed after evaporation and pyrolysis
of petroleum materials under certain conditions and is
D4377 Test Method for Water in Crude Oils intended to provide some indication of the relative coke-
by Potentiometric Karl Fischer Titration forming tendency of such materials.
1. SCOPE 1.2 The test results are equivalent to the Conradson Carbon
1.1 This test method covers the determination of water in Residue test (see Test Method D189).
the range from 0.02 to 2 % in crude oils. Mercaptan and 1.3 This test method is applicable to petroleum products
sulfide (S or H2S) sulfur are known to interfere with that partially decompose on distillation at atmospheric
this test method. pressure and was tested for carbon residue values of
0.1030 % (m/m). Samples expected to be below 0.10
3. SUMMARY OF TEST METHOD weight % (m/m) residue should be distilled to remove
3.1 After homogenizing the crude oil with a mixer, an aliquot 90 % (v/v) of the flask charge. The 10 % bottoms
of the crude, in a mixed solvent, is titrated to an electro- remaining is then tested for carbon residue by this test
metric endpoint using Karl Fischer reagent. (Fig. 11). method.
1.4 Ash-forming constituents, as defined by Test Method
5. INTERFERENCES D482, or nonvolatile additives present in the sample will
5.1 Several substances and classes of compounds associated add to the carbon residue value and be included as part
with condensation or oxidation-reduction reactions interfere of the total carbon residue value reported.
in the determination of water by Karl Fischer reagent. In
crude oils, the most common interferences are mercaptans 4. SUMMARY OF TEST METHOD
and sulfides. At levels of less than 500 lg/g (ppm) (as sulfur), 4.1 A weighed quantity of sample is placed in a glass vial
the interference from these compounds is insignificant. and heated to 500C under an inert (nitrogen)
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54 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
atmosphere in a controlled manner for a specific time. with viscosities between approximately 0.2 and 10 cSt
The sample undergoes coking reactions, and volatiles (mm2/s) at room temperature. This test method is appli-
formed are swept away by the nitrogen. The carbona- cable to naphthas, distillates, and oils containing 0.3100
ceous-type residue remaining is reported as a percent of mg/kg total nitrogen. For liquid hydrocarbons contain-
the original sample as carbon residue (micro). ing more than 100 mg/kg of total nitrogen, Test Method
4.1.1 When the test result is expected to be below 0.10 % D5762 can be more appropriate. This test method has
(m/m), the sample can be distilled to produce a 10 % been successfully applied during interlaboratory studies
(v/v) bottoms, before performing the test. to sample types outside of the range of the scope by
dilution of the sample in an appropriate solvent to bring
D4629 Test Method for Trace Nitrogen in Liquid the total nitrogen concentration and viscosity to within
Petroleum Hydrocarbons by Syringe/Inlet Oxidative the range covered by the test method. However, it is the
Combustion and Chemiluminescence Detection responsibility of the analyst to verify the solubility of the
1. SCOPE sample in the solvent and that direct introduction of the
1.1 This test method covers the determination of the trace diluted sample by syringe into the furnace does not
total nitrogen naturally found in liquid hydrocarbons cause low results because of pyrolysis of the sample or
boiling in the range from approximately 50C to 400C solvent in the syringe needle.
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 55
adapted from Test Method D86 for the distillation of Heavier crudes can require measurements at higher tem-
petroleum products. The naphtha cut is washed with peratures to eliminate air bubbles in the sample.
caustic, repeatedly when necessary, until all hydrogen
sulfide is removed. The naphtha cut, free of hydrogen 4. SUMMARY OF TEST METHOD
sulfide, is then washed with water, repeatedly when nec- 4.1 Approximately 0.7 mL of crude oil sample is introduced
essary, to remove inorganic halides (chlorides). into an oscillating sample tube and the change in oscil-
3.2 There are two alternative test methods for determination lating frequency caused by the change in the mass of the
of the organic chloride in the washed naphtha fraction, tube is used in conjunction with calibration data to
as follows. determine the density of the sample.
3.2.1 Test Method A, Sodium Biphenyl Reduction and
PotentiometryThe washed naphtha fraction of a D5191 Test Method for Vapor Pressure of
crude oil specimen is weighed and transferred to a Petroleum Products (Mini Method)
separatory funnel containing sodium biphenyl rea- 1. SCOPE
gent in toluene. The reagent is an addition com- 1.1 This test method covers the use of automated vapor pres-
pound of sodium and biphenyl in ethylene glycol sure instruments to determine the total vapor pressure
dimethyl ether. The free radical nature of this rea- exerted in vacuum by volatile liquid petroleum products
gent promotes very rapid conversion of the organic containing air. This test method is suitable for testing sam-
halogen to inorganic halide. In effect, this reagent ples with boiling points above 0C (32F) that exert a vapor
solubilizes metallic sodium in organic compounds. pressure between 7 and 130 kPa (1.0 and 18.6 psi) at 37.8C
The excess reagent is decomposed, the mixture (100F) at a vapor-to-liquid ratio of 4:1. Measurements are
acidified, and the phases are separated. The aqueous made on liquid sample sizes in the range from 1 to 10 mL.
phase is evaporated to 2530 mL, acetone is added, No account is made for dissolved water in the sample.
and the solution is titrated potentiometrically. Note 1Samples can also be tested at other vapor-to-liq-
3.2.2 Test Method B, Combustion and Microcoulometry uid ratios, temperatures, and pressures, but the precision
The washed naphtha fraction of a crude oil speci- and bias statements need not apply.
men is injected into a flowing stream of gas contain- Note 2The interlaboratory studies conducted in 1988
ing approximately 80 % oxygen and 20 % inert gas, and 1991 to determine the precision statements in Test
such as argon, helium, or nitrogen. The gas and sam- Method D5191 did not include any crude oil in the sample
ple flow through a combustion tube maintained at sets. (Nevertheless, the method is used by a considerable
approximately 800C. The chlorine is converted to number of laboratories for determining vapor pressure of
chloride and oxychlorides, which then flow into a crude oils). Test Method D6377 has been shown to be suita-
titration cell where they react with the silver ions in ble for vapor pressure measurements of crude oils.
the titration cell. The silver ions thus consumed are
coulometrically replaced. The total current required 4. SUMMARY OF TEST METHOD
to replace the silver ions is a measure of the chlorine 4.1 A known volume of chilled, air-saturated sample is intro-
present in the injected samples. duced into an evacuated, thermostatically controlled test
chamber, the internal volume of which is five times that of
5. INTERFERENCES the total test specimen introduced into the chamber. After
5.1 Test Method AOther titratable halides will also give a injection into the test chamber, the test specimen is
positive response. These titratable halides include hydro- allowed to reach thermal equilibrium at the test tempera-
gen bromide (HBr) and hydrogen iodide (HI). ture, 37.8C (100F). The resulting rise in pressure in the
5.2 Test Method BOther titratable halides will also give a pos- chamber is measured using a pressure transducer sensor
itive response. These titratable halides include HBr and HI and indicator. Only total pressure measurements (sum of
(HOBr and HOI do not precipitate silver). Because these the partial pressure of the sample and the partial pressure
oxyhalides do not react in the titration cell, approximately of the dissolved air) are used in this test method, although
50 % microequivalent response is detected. some instruments can also measure the absolute pressure
5.2.1 This test method is applicable in the presence of of the sample.
total sulfur concentration of up to 10,000 times the
chlorine level. D5236 Test Method for Distillation of Heavy
Hydrocarbon Mixtures (Vacuum Pot still Method)
D5002 Test Method for Density and Relative 1. SCOPE
Density of Crude Oils by Digital Density Analyzer 1.1 This test method covers the procedure for distillation of
1. SCOPE heavy hydrocarbon mixtures having initial boiling points
1.1 This test method covers the determination of the density greater than 150C (300F), such as heavy crude oils,
or relative density of crude oils that can be handled in a petroleum distillates, residues, and synthetic mixtures. It
normal fashion as liquids at test temperatures between uses a pot still with a low-pressure-drop entrainment sep-
15C and 35C. This test method applies to crude oils arator operated under total takeoff conditions (Fig. 12).
with high vapor pressures provided appropriate precau- Distillation conditions and equipment performance crite-
tions are taken to prevent vapor loss during transfer of ria are specified and a typical apparatus is illustrated.
the sample to the density analyzer. 1.2 This test method details the procedures for the produc-
1.2 This test method was evaluated in round-robin testing using tion of distillate fractions of standardized quality in the
crude oils in the 0.75- to 0.95-g/mL range. Lighter crude oil gas oil and lubricating oil range as well as the produc-
can require special handling to prevent vapor losses. tion of standard residue. In addition, it provides for the
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 57
determination of standard distillation curves to the high- 3.2 Test Method BOne to 20 g of sample are weighed into a
est AET possible by conventional distillation. beaker and decomposed with concentrated sulfuric acid
1.3 The maximum achievable AET is dependent upon the by heating to dryness. Great care must be used in this
heat tolerance of the charge. For most samples, a tem- decomposition because the acid fumes are corrosive and
perature up to 565C (1050F) can be attained. This the mixture is potentially flammable. The residual carbon
maximum will be significantly lower for heat-sensitive is burned off by heating at 525C in a muffle furnace. The
samples (e.g., heavy residues) and might be somewhat inorganic residue is digested with nitric acid evaporated to
higher for non-heat-sensitive samples. incipient dryness, dissolved in dilute nitric acid, and made
1.4 The recommended distillation method for crude oils up up to volume. The solution is nebulized into the plasma of
to a cutpoint of 400C (752F) AET is Test Method an atomic emission spectrometer. The intensities of light
D2892. This test method can be used for heavy crude emitted at characteristic wavelengths of the metals are
oils with initial boiling points greater than 150C measured sequentially or simultaneously. These intensities
(302F). However, distillation curves and fraction qual- are related to concentrations by the appropriate use of cali-
ities obtained by these methods are not comparable. bration data.
1.5 This test method also contains an Annex for Dehydration
of a Wet Sample of Oil. D5762 Test Method for Nitrogen in Petroleum and
Petroleum Products by Boat-Inlet
4. SUMMARY OF TEST METHOD Chemiluminescence
4.1 A weighed volume of sample is distilled at absolute pres- 1. SCOPE
sures between 6.6 and 0.013 kPa (50 and 0.1 mm Hg) at 1.1 This test method covers the determination of nitrogen in liq-
specified distillation rates. Cuts are taken at preselected uid hydrocarbons in the concentration range from 40 to
temperatures. Records of vapor temperature, operating 10,000 lg/g nitrogen. For light hydrocarbons containing less
pressure, and other variables are made at intervals, includ- than 100 lg/g nitrogen, Test Method D4629 can be more
ing at each cutpoint. appropriate.
4.2 The mass of each fraction is obtained. Distillation yields
by mass are calculated from the mass of each fraction 3. SUMMARY OF TEST METHOD
relative to the total mass recovery. 3.1 A hydrocarbon sample is placed on a sample boat at room
4.3 The density of each fraction is obtained. Distillation temperature. The sample and boat are advanced into a
yields by volume are calculated from the volume com- high-temperature combustion tube where the nitrogen is
puted for each fraction at 15C (59F) relative to the oxidized to NO in an oxygen atmosphere. The NO contacts
total recovery. ozone and is converted to excited NO2. The light emitted
4.4 Distillation curves of temperature versus mass or volume as the excited NO2 decays is detected by a photomultiplier
percent or both are drawn using the data from 4.2 and 4.3. tube, and the resulting signal is a measure of the nitrogen
contained in the sample.
D5708 Test Methods for Determination of Nickel,
Vanadium, and Iron in Crude Oils and Residual Fuels D5853 Test Method for Pour Point of Crude Oils
by Inductively Coupled Plasma (ICP) Atomic 1. SCOPE
Emission Spectrometry 1.1 This test method covers two procedures for the determi-
1. SCOPE nation of the pour point temperatures of crude oils
1.1 These test methods cover the determination of nickel, down to 36C. One method provides a measure of the
vanadium, and iron in crude oils and residual fuels by maximum (upper) pour point temperature; the other
inductively coupled plasma (ICP) atomic emission spec- method provides a measure of the minimum (lower)
trometry. Two different test methods are presented. pour point temperature. [In practice, few laboratories
1.2 Test Method AICP is used to analyze a sample dissolved using this test method to determine the minimum
in an organic solvent. This test method uses oil-soluble (lower) pour point).]
metals for calibration and does not purport to quantita-
tively determine or detect insoluble particulates. 3. TERMINOLOGY
1.3 Test Method BICP is used to analyze a sample that is 3.1.2 Maximum (Upper) Pour Point, nThe pour point
decomposed with acid. obtained after the test specimen has been subjected
1.4 The concentration ranges covered by these test methods to a prescribed treatment designed to enhance gela-
are determined by the sensitivity of the instruments, the tion of wax crystals and solidification of the test
amount of sample taken for analysis, and the dilution specimen.
volume. Typically, the low concentration limits are a few 3.1.3 Minimum (Lower) Pour Point, nThe pour point
tenths of a milligram per kilogram. obtained after the test specimen has been subjected to
a prescribed treatment designed to delay gelation of
3. SUMMARY OF TEST METHOD wax crystals and solidification of the test specimen.
3.1 Test Method AApproximately 10 g of the sample are dis-
solved in an organic solvent to give a specimen solution con- 4. SUMMARY OF TEST METHOD
taining 10 % (m/m) of sample. The solution is nebulized 4.1 After preliminary heating, the test specimen is cooled at a
into the plasma, and the intensities of the emitted light at specified rate and examined at intervals of 3C for flow
wavelengths characteristic of the analytes are measured characteristics. The lowest temperature at which move-
sequentially or simultaneously. The intensities are related to ment of the test specimen is observed is recorded as the
concentrations by the appropriate use of calibration data. pour point.
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58 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
D5863 Test Methods for Determination of nor detect insoluble particulates. Hence, this test method
Nickel, Vanadium, Iron, and Sodium in Crude may underestimate the metal content, especially sodium,
Oils and Residual Fuels by Flame Atomic present as inorganic sodium salts.
Absorption Spectrometry 1.4 The concentration ranges covered by these test methods
1. SCOPE are determined by the sensitivity of the instruments, the
1.1 These test methods cover the determination of nickel, amount of sample taken for analysis, and the dilution
vanadium, iron, and sodium in crude oils and residual volume. A specific statement is given in Note 1.
fuels by flame atomic absorption spectrometry (AAS). Note 1If it is desired to extend the lower concentration
Two different test methods are presented. limits of the test method, it is recommended that the decom-
1.2 Test Method AFlame AAS is used to analyze a sample position be done in 10-g increments up to a maximum of
that is decomposed with acid for the determination of 100 g. It is not necessary to destroy all of the organic matter
total nickel, vanadium, and iron. each time before adding additional amounts of the sample
1.3 Test Method BFlame AAS is used to analyze a sample and acid. When it is desired to determine higher concentra-
diluted with an organic solvent for the determination of tions, reduce the sample size accordingly.
nickel, vanadium, and sodium. This test method uses oil- 1.5 For each element, each test method has its own unique pre-
soluble metals for calibration to determine dissolved cision. The user can select the appropriate test method on
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APPENDIX 3: EXCERPTS FROM STANDARDS USED FOR SAMPLING, HANDLING, AND ANALYSIS 59
resolution gas chromatograph (GC) analysis of the light- conditions of the test is used to determine the detector
end portion of the sample may be necessary to obtain a response factor. Solvent injections are made, and the
more accurate description of the boiling point curve in the resulting signal is subtracted from the response factor
interval in question. (An appendix provides procedures for standard and the sample chromatogram. Finally, the sam-
conducting a light-end analysis in the region C4C8.) ple solution is injected, and with the use of the response
factor, the amount of sample recovered is calculated
4. SUMMARY OF TEST METHOD (Fig. 15). After converting the retention times of the sam-
4.1 This is a GC method utilizing an inlet and a capillary col- ple slices to temperature, the boiling point distribution
umn, both of which are subject to a temperature pro- can be calculated up to the recovered amount.
gram. A flame ionization detector is used as a transducer
that converts mass to an electrical signal. A data acquisi- D7279 Test Method for Kinematic Viscosity of
tion system operating in the slice mode and chromatogra- Transparent and Opaque Liquids by Automated
phy software is used to accumulate the electronic signal. Houillon Viscometer
A retention time calibration mixture is used to develop a 1. SCOPE
retention time versus boiling point curve. A solution of a 1.1 This test method covers the measurement of the kine-
reference oil that fully elutes from the column under the matic viscosity of transparent and opaque liquids such
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62 CRUDE OILS: THEIR SAMPLING, ANALYSIS, AND EVALUATION
Fig. 15Typical chromatogram (baseline corrected) of a crude oil (injected at 20C) analyzed by D7169.
4. SUMMARY OF TEST METHOD decomposition products other than mercury, the amal-
4.1 Controlled heating of the analysis sample in oxygen gamator is rapidly heated to approximately 600C,
is used to liberate mercury. The sample is heated to releasing mercury vapor. Flowing oxygen carries the
dryness in the instrument and then thermally (at mercury vapor through absorbance cells positioned in
approximately 700C) and chemically decomposed. The the light path of a single wavelength cold-vapor atomic
decomposition products are carried by flowing treated absorption spectrophotometer. Absorbance peak height
air into the catalytic section of the furnace (at approxi- or peak area, as a function of mercury concentration,
mately 850C), where oxidation is completed. The is measured at 253.65 nm.
decomposition products are carried to a gold amalga- Note 1Mercury and mercury salts can be volatized at
mator that selectively traps mercury. After the system low temperatures. Precautions against inadvertent mercury
is flushed with oxygen to remove any remaining loss should be taken when using this test method.
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References
[1] Rossini, F. D., Hydrocarbons in Petroleum, J. Chem. Educ., [25] Bilkadi, Z., Babylon to Baku, Barrett Howe Group Ltd., Wind-
Vol. 37, 1960 pp. 554561. sor, United Kingdom, 1996.
[2] Mair, B. J., Annual Report for the Year Ending, June 30, [26] Considine, T. J. and Dowd, K. M., A Superfluous Petroleum
1967, American Petroleum Institute Research Project 6, Car- Reserve? How Should the SPR Be Used, and What Benefits
negie Institute of Technology, Pittsburgh, PA,1967. Does It Provide? Regulation, The Cato Institute, Washington,
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MNL68-EB/Nov. 2010
Index
A ASTM D5291, 29t
Agricola, 2 ASTM D5307, 22
American Petroleum Institute, 1, 9, 30 ASTM D5708, 19, 20, 28t
API gravity, 1, 910, 10f, 17, 17f, 18, 30, 32t ASTM D5762, 20, 28t
Aromaticity, 14 ASTM D5842, 6
Aromatics (compounds; hydrocarbons), 4, 14, 17, 18f, 38 ASTM D5853, 14, 28t
Arsenic, 18, 19 ASTM D5854, 6, 7t
Ash, 24, 37 ASTM D5863, 19
Asphaltene Stability Index, 34 ASTM D6299, 33
Asphaltenes, 8, 16, 21, 22f, 24t, 29t, 30, 32, 32t, 34, 39t ASTM D6377, 15
Assays (analyses) ASTM D6470, 13, 28t
comprehensive, 12, 9, 24, 2531, 39 ASTM D6560, 21, 22, 29t
inspection, 1, 2, 924, 25, 30 ASTM D6792, 33, 33t
ASTM D5, 29t, 30 ASTM D6822, 10
ASTM D36, 29t, 30 ASTM D7059, 23
ASTM D97, 14, 24t, 32t ASTM D7112, 34
ASTM D129, 10 ASTM D7157, 34
ASTM D189, 16, 17f ASTM D7169, 22, 26, 29t
ASTM D287, 10, 32t ASTM D7279, 14
ASTM D323, 6, 15, 24t, 28t, 32t ASTM D7343, 11
ASTM D341, 14 ASTM D7455, 20, 21
ASTM D445, 14, 24t, 29t, 32t ASTM D7482, 19
ASTM D473, 12, 13, 24t, 28t, 32t, 34 ASTM D7622, 19
ASTM D482, 24 ASTM D7623, 19
ASTM D524, 16 ASTM MNL51, 26
ASTM D664, 15, 16 ASTM Crude Oil Interlaboratory Crosscheck Program,
ASTM D1160, 26 22, 32, 32t
ASTM D1250, 9 Atomic absorption spectrometry. See Spectrometry,
ASTM D1298, 10 atomic absorption
ASTM D1480, 10 Automated Flocculation Titrimetry, 34
ASTM D1552, 10 Automatic sampling, 5, 6
ASTM D2161, 14 Azerbaijan, 2, 3t
ASTM D2622, 11
ASTM D2887, 22 B
ASTM D2892, 22, 25, 26, 26f, 28t Baume scale, 9
ASTM D3228, 20 Bitumen, 2, 3t, 10, 14, 16, 22, 30, 38, 39t
ASTM D3230, 13 Boiling point
ASTM D3279, 22 Distillation, 2527
ASTM D4006, 12 Distribution, 2223
ASTM D4052, 10
ASTM D4057, 5, 15 C
ASTM D4177, 5, 6, 15 Canadian Crude Quality Technical Association, 38
ASTM D4294, 11, 28t Carbon residue, 9, 16, 16f, 17f, 24t, 28t, 30, 32t, 37
ASTM D4377, 12 Conradson, 16
ASTM D4530, 16, 28t Micro, 16, 17t
ASTM D4629, 20 Ramsbottom, 16
ASTM D4740, 34, 35f Caspian Sea, 2, 3t
ASTM D4807, 12 Chain of custody, 6, 8
ASTM D4840, 6 Characterization factor, 1718, 17f. See also UOP
ASTM D4870, 34 Characterization factor
ASTM D4928, 12, 28t Chemiluminescence detection, 20
ASTM D4929, 21, 28t Chromatography
ASTM D5002, 10, 28t Gas, 4, 20, 22, 23, 24t, 27, 38
ASTM D5134, 27, 28t Ion, 4
ASTM D5185, 19 Compatibility, 14, 21, 31, 3435, 39t
ASTM D5191, 15 Conradson carbon residue, 16, 16t, 17t
ASTM D5236, 25, 26, 28t Contamination, 1, 6, 9, 13, 18, 19, 20, 21, 23
67
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68 INDEX
Coulometric titration, 12 K
Crossed polar microscopy, 35 Karl Fischer titration, 12
Crude oil Keroselain, 2, 3t
as fuel, 2, 37 Kerosene, 2, 3t
assay practices, 1
chemical characterization, 1
comprehensive assay, 12, 9, 24, 2531, 39
L
Linear programming, 1, 23, 27, 39
history, 2
Lukasiewicz, Ignacy, 2
importance, 24
inspection assay, 1, 2, 924, 25, 30
physical characterization, 1 M
practices, 1, 2 Manual sampling, 5, 6, 8
strategic importance, 24 Manual of Petroleum Measurement Standards, 12, 13
superlatives, 2 Mass spectrometry. See Spectrometry, mass
Cycloparaffins (naphthenes), 27 Mercaptans. See Thiols
Mercury, 19
D Methanol, 2324, 24t, 35, 39t
Database, electronic, 1 Metals, 4, 9, 18, 19, 24t, 28t, 30, 32t, 37, 39t. See also
Density, 6, 7t, 8t, 910, 24, 24t, 28t, 32t Trace elements
Differential scanning calorimetry, 10, 35 Microwave digestion, 20
Differential thermal analysis, 10, 35 Molecular modeling, 39
Differentiation, 8
Digital Density Analyzer, 10 N
Distillate fuel oil, 10, 20, 25, 27, 27f, 27, 28t, 35 Naphtha, 21, 25, 27
Naphthenes, 4, 17, 18, 18f, 27f, 28t
E National Petroleum Council, 3
Elemental analysis, 11, 19, 20 Naval Petroleum Reserves, 3
Emulsion,6, 11, 21, 38 Navy Special Fuel Oil, 3
Energy Information Administration, 3 Nickel, 18, 19, 30, 37
Nitrogen, 1, 4, 15, 20, 21, 24t, 27, 28t, 30, 32t, 38, 39t
F Nitrogen, basic, 20, 28t, 30, 39t
Flash Assay Tool, 30 Nobel brothers, 2, 3
Flash point, 24, 27, 37
Fluidity, 9, 14, 37 O
Fraction evaluation, 2531 Offshore production, 11, 34, 37
Fractional distillation, 3, 25 Oil Compatibility Model, 34
Future test method needs, 3839 Opportunity crude, 22, 30, 31
Organic halides, 21, 23, 27
G Organometallic compounds, 1, 18
Gas, 2, 10, 27 Oxygen, 1, 4, 10, 11
Gas chromatography. See Chromatography, gas
Gessner, Abraham, 2 P
Paraffinicity, 14
H Paraffins, 4, 14, 17, 18f, 27, 28t
High temperature simulated distillation (HTSD), 9, 22, 23, Petroleomics, 39
29t, 30, 32t, 38 Petroleum stockpiles, 3
Houillon viscometer, 14 PIAN analysis, 27, 28t, 29t
Hydrocarbon types, 38, 39t Pipelines, 1, 2, 5, 11, 12, 21, 23, 24, 34
Hydrocarbons, 1, 4, 6, 15, 19, 20, 23, 25, 27, 38 Potentiometric titration, 11, 12, 13, 15
Hydrogen sulfide, 5, 10, 11, 24, 24t, 27 Pour point, 1, 6, 7t, 9, 10, 13, 14, 15, 24t, 25, 27, 28t, 30, 32t,
Hydrometer, 9, 10 36, 37
Product slate, 1, 9, 19, 22, 24, 25, 30
I
Impurities, 1, 13, 24, 30, 32 Q
Inductively-coupled plasma spectrometry. See Spectrometry, Quality assurance, 3233
inductively-coupled plasma
Inspection assay, 1, 2, 924, 25, 30 R
IP 389, 10, 35 Railway tank cars, 2
IP 570, 11 Referee test methods, 24t, 24, 27
Isoparaffins, 27, 28t Relative density, 9, 10, 13, 24t, 27
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INDEX 69
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Giles | Mills
Harry N. Giles is retired from the Department of Energy Clifford O. Mills is retired from CONOCO where he served
where he was manager of crude oil in numerous capacities. At retire-
quality programs for the Strategic ment, after 35 years, he was a labo-
Petroleum Reserve. This included ratory consultant with an emphasis
development and management of on crude oil analysis. Mr. Mills has
analytical programs for monitoring been involved with ASTM methods
quality of stocks, and research relat- development since the early 1980s.
ed to the biological and geochemi- Until recently, he was chairman
cal aspects of petroleum stockpiling. of ASTM D02.05 on Properties of
He was employed by the Department of Energy for over 30 Fuels, Petroleum Coke and Carbon Material, and also chaired
Crude Oils
Fuels. He is chairman emeritus of IASH, and was elected
to honorary membership in 2009. Currently, he serves as
Executive Director of the Crude Oil Quality Association.
www.astm.org
ISBN: 978-0-8031-7014-8
Stock #: MNL68
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