The distribution of distillation temperatures of liquid and

High-temperature Simulated semifluid products, including petroleum fractions and

Distillation Applications in products, is an important process and practical considera-
tion. At present, the distribution of distillation temperatures
Petroleum and Renewable is often investigated by simulated distillation (SimDist).
SimDist is a gas chromatography (GC) technique, which
Energy separates individual hydrocarbon components in the
order of their boiling points, and is used to simulate the
Dan C. Villalanti, Kandi A. Fuchs, Debbie C. expensive and time-consuming laboratory-scale method
known as true boiling point (TBP) distillation. The most
Dowling
used SimDist method, American Society for Testing and
Triton Analytics Corporation, Houston, TX, USA Materials International (ASTM) D2887,(1) covers the
boiling range 36–545 ∘ C (97–1013 ∘ F), which includes the
n-alkanes (n-paraffins) of chain length from C5 to C44 .
1 Introduction 1 The most popular high-temperature simulated distillation
2 History 2 (HTSD) method, ASTM D7169,(2) covers the boiling range
3 Comparison of American Society for Testing and 36–720 ∘ C (97–1328 ∘ F), which includes the n-alkane range
Materials International Distillation and Simulated of about C5 –C100 . A key difference between ASTM D2887
Distillation Methods 2 and D7169 is the ability of the latter technique to handle
3.1 Physical Distillation Methods 2 residue-containing samples (i.e. material boiling >720 ∘ C,
1328 ∘ F). The use of SimDist and laboratory-scale physical
3.2 Simulated Distillation Methods 3
distillation procedures is important in the characterization
4 American Society for Testing and Materials of petroleum crude oil properties and refined products
International D7169 Methodology 3 in the operational decisions of any refinery to improve
4.1 Sample Preparation 4 both product yields and quality, and aids the refiner in the
4.2 Blank Run 4 ability to rapidly evaluate opportunity crudes for selection
4.3 Calibration 5 of those with economic advantages and more favorable
4.4 Determination of Hydrocarbon Yield as a refinery profit margins. As a result of the Bakken Crude
Function of Boiling Point 5 Oil incident, the US Department of Transportation (DOT)
5 Quality Control and Instrument enhanced tank car standards regarding the classification
Performance 7 of products shipped via rail including crude oil. The
goal is better classification and characterization of mined
5.1 Statistical Analysis of Quality Control
gases and liquids, which is accomplished through the use
Samples 7
of HTSD coupled with detailed hydrocarbon analysis
5.2 Instrument Performance and Maintenance 7 (DHA) to understand the front end, which allows for an
5.3 Interlaboratory ‘Round-Robin’ accurate determination of initial boiling point (IBP). The
Test Results 8 use of SimDist methods in today’s environment proves to
6 Case Studies and/or Applications 8 be a valuable tool not just for refiners (upstream technolo-
6.1 Petroleum Refining 8 gies, flow assurance, fracking, and polymer chemistry) but
6.2 Crude Oil Characterization 13 also for environmental forensics, biofuel and renewable
6.3 Environmental 16 energy development, and compliance with regulatory
6.4 Renewable Energy (Biomass) 17 rules.
6.5 Legal and Regulatory Rules 19
Acknowledgments 20 1 INTRODUCTION
Abbreviations and Acronyms 20
Related Articles 22 SimDist is a GC technique that separates hydrocarbon
References 22 components in the order of boiling points. The separation
is accomplished with a chromatography column coated
with a nonpolar (hydrocarbon-like) stationary phase and
uses a gas chromatograph equipped with a temperature-
programmable inlet system and oven. A flame ionization
Update based on the original article by Dan C. Villalanti, Joseph C. Raia, and
Jim B. Maynard, Encyclopedia of Analytical Chemistry, ©2000, John Wiley & detector (FID) is used for detection and measurement of
Sons, Ltd. the hydrocarbon analytes. The SimDist analysis results

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DOI: 10.1002/9780470027318.a1819.pub2
2 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
provide a quantitative percent mass yield as a function
of boiling point of the hydrocarbon components of the
sample. The chromatographic elution times are calibrated
to the atmospheric equivalent boiling point (AEBP) of
the n-alkanes as described in the ASTM method by using
the n-alkane (n-paraffin) reference material. In order to
validate and recalibrate distillation temperature distri-
bution determined by the SimDist method, reference
materials with a known distribution of boiling points
are used.
SimDist and laboratory-scale physical distillation
methods are routinely used for determining boiling
ranges of petroleum crude oils. The boiling point with
yield profile data of crude is used in operational decisions
by refinery engineers to improve product yields and
quality. SimDist data is valuable for use in the application
of computer modeling of refining processes for improve-
ments in unit design and process optimization. Precise
yield correlations between HTSD and crude assay distil-
lation (a procedure that uses methods ASTM D2892(3)
and D5236(4) ) have allowed HTSD to be successfully
used in place of physical distillation procedures.
SimDist methods are more widely utilized today for
environmental applications; for example, in charac-
terizing hydrocarbons that can be present as soil and
water contaminants and in the renewable energy market
through the development of biofuels derived from waste
oils, wood chips, oil from algae, biomass, and so on.
SimDist methods continue to assist in the enhancement
of flow assurance through studies involving pipeline
wax deposition and the continued development of new
and enhanced products such as asphalt production and
roofing materials. SimDist methods are used to ensure
compliance with regulatory matters as well as being used
as aids in legal matters. The use of the different SimDist
methods continues to evolve over time.
2 HISTORY
SimDist was first reported in the 1960s by Eggertsen
et al.(5) and Green et al.(6,7) as a method of simulating
the time-consuming laboratory-scale physical distillation
procedure by using GC. The SimDist technique is based
on the fundamental assumption that individual nonpolar
hydrocarbon components elute in the order of their
boiling points from a GC column coated with nonpolar
(hydrocarbon-like), stationary phase. The elution, or
retention time, is dependent upon the vapor pressure
of the component and its affinity with the stationary
phase. This varies with different types of hydrocarbons.
For example, aromatic hydrocarbons and cycloalkanes
(naphthenes) generally elute earlier than n-alkanes
having the same boiling point. In SimDist, experimental
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DOI: 10.1002/9780470027318.a1819.pub2
conditions are selected to give limited column efficiency
and resolution unlike many GC techniques that achieve
high-resolution separation of components. The lower
resolution analysis conditions provide distillation data
that agree with physical distillation.
SimDist became an ASTM standard test method in 1973
under the designation D2887, ‘Boiling Point Range Distri-
bution of Petroleum Fractions by Gas Chromatography’.
The current edition is designated D2887-16a, ‘Standard
Test Method for Boiling Range Distribution of Petroleum
Fractions by Gas Chromatography’. This method covers
the determination of the boiling range distribution of
petroleum product and fractions having a final boiling
point (FBP) of 545 ∘ C (1013 ∘ F) or lower at atmospheric
pressure.
HTSD, ASTM D7169, was originally approved by
ASTM in 2005. The current edition is designated D7169-
16, ‘Standard Test Method for Boiling Point Distribution
of Samples with Residues Such as Crude Oils and Atmo-
spheric and Vacuum Residues by High Temperature
Gas Chromatography’. This method extends the ASTM
D2887 determination of the boiling range distribution
of hydrocarbons to an FBP limit of 720 ∘ C (1328 ∘ F) or
n-C100 equivalent.
3 COMPARISON OF AMERICAN SOCIETY
FOR TESTING AND MATERIALS
INTERNATIONAL DISTILLATION AND
SIMULATED DISTILLATION METHODS
A summary of ASTM physical distillation and SimDist
methods is presented schematically in Figure 1 and
discussed in detail as follows.
3.1 Physical Distillation Methods
Laboratory-scale physical distillation methods are
routinely used by petroleum refineries for determining
the boiling ranges of crude oils and their products. ASTM
D86(8) has been used as a quality control (QC) test since
the 1920s; it is one of the oldest test methods in ASTM’s
repertoire. This method is a one-plate distillation that
covers the range of materials boiling up to about 254 ∘ C
(490 ∘ F).
ASTM D1160(9) is a similar method, but is conducted
at reduced pressure and covers the determination of
the range of boiling points for petroleum products that
can be partially or completely vaporized at a maximum
liquid temperature of 400 ∘ C (752 ∘ F). This temperature
corresponds to an atmospheric equivalent temperature
(AET) of about 600 ∘ C when run under 1 mmHg (the
lowest pressure permitted). Petroleum products and frac-
tions in this range may decompose if distilled at atmo-
spheric pressure.
HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY
D7169
D2887E
D2887
ASTM methods
C14
D3710
C 125°
Boiling point
F 257°
C14
D86
D1160
D2892
C9
D5236
Figure 1 Summary of ASTM physical and simulated distillation.
ASTM D2892 is used for samples with a wide boiling
range, such as crude petroleum, up to a final cut temper-
ature of 400 ∘ C (752 ∘ F) AET. The method can also
be applied to any petroleum mixture except liquefied
petroleum gases (LPGs), very light naphthas, and frac-
tions having IBPs above 400 ∘ C (752 ∘ F). This test method
uses a fractionating column having an efficiency of 14–18
theoretical plates operated at a reflux ratio of 5:1 and
provides for the determination of yields of material as
both mass and volume. A graph of temperature versus
mass percent distilled can be produced, and this distilla-
tion curve corresponds to a laboratory technique which
is defined at 15/5 (15 theoretical plate, 5:1 reflux ratio)
or TBP.
ASTM D5236 is for distillation of heavy hydrocarbon
mixtures such as heavy crude oils, petroleum distillates,
residues, and synthetic mixtures with IBPs greater than
150 ∘ C (300 ∘ F). This method provides for the deter-
mination of standard distillation curves to the highest
AET possible by conventional distillation. The maximum
achievable temperature up to 565 ∘ C (1050 ∘ F) AET is
dependent upon the heat tolerance of the charge.
3.2 Simulated Distillation Methods
SimDist methods adopted as ASTM test methods are
D2887, D7169, D3710,(10) D5307,(11) ASTM D6352,(12)
ASTM D7213,(13) and ASTM D7500.(14) ASTM D2887
covers the determination of the boiling range distribution
of petroleum products and fractions having a FBP of
545 ∘ C (1013 ∘ F) or lower at atmospheric pressure; it is
most equivalent to ASTM D2892. The method is limited
to samples having a boiling range greater than 55.5 ∘ C
(100 ∘ F), and having a vapor pressure sufficiently low to
permit sampling at ambient temperature.
ASTM D7169 covers the determination of the boiling
point distribution and cut point intervals of crude oils and
residues through a temperature of 720 ∘ C (1328 ∘ F).
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3
C100
C60
C44
250° 375° 500° 625° 720°
482° 707° 932° 1157° 1328°
C56
C25
C48
The method is applicable to a wide range of fully
eluting and noncompletely eluting materials, which
include petroleum crude oil, cat crack feed and products,
hydrotreater feed and products, atmospheric residue,
vacuum gas oils, deasphalted oils, and vacuum tower
bottoms (pitch). Technological advances in capillary
GC columns and stationary phases together with either
programmed temperature vaporization (PTV) inlets
or on-column injection techniques provide adequate
separation from C5 to C100 n-paraffins.
ASTM D3710 covers the determination of the boiling
range distribution of gasoline and gasoline components
with an FBP of 260 ∘ C (500 ∘ F) or lower. ASTM D5307
covers the determination of the boiling range distribution
of water-free crude petroleum through 538 ∘ C (1000 ∘ F),
with material boiling above 538 ∘ C (1000 ∘ F) reported as
residue.
Other methods are also available including ASTM
D6352, which covers the determination of the boiling
range distribution of petroleum distillate fractions having
an IBP greater than 174 ∘ C (345 ∘ F) and an FBP of less
than 700 ∘ C (1292 ∘ F) representing C10 to C90 ; ASTM
D7213, which covers the determination of the boiling
range distribution of light and medium petroleum distil-
late fractions beyond the scope of ASTM D2887 (538 ∘ C)
and below ASTM D6352 (700 ∘ C); and ASTM D7500,
which covers the determination of the boiling range
distribution of distillates and lubricating base oils in
boiling range from 100 to 735 ∘ C.
4 AMERICAN SOCIETY FOR TESTING AND
MATERIALS INTERNATIONAL D7169
METHODOLOGY
The proper choice of GC conditions and equipment is
essential in routinely utilizing ASTM D7169 (HTSD). The
4 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
instrumentation for HTSD is typically equipped with a
PTV injector and FID. To accomplish the goal of eluting
heavy materials up to the equivalent of C100 , a thin-
film nonpolar stationary phase is used. The film thick-
ness of the capillary column varies from 0.09 to 0.17 μm,
which, with a 0.5-mm internal diameter (ID), results in a
phase ratio (volume of the column vs the volume of the
stationary phase) high enough to permit the elution of
materials from the column at temperatures up to 435 ∘ C
(815 ∘ F) under temperature programming. The tempera-
ture conditions of the column, oven, and injector are set
initially at either near ambient or subambient (−20 ∘ C),
and then programmed at a specified linear rate to a final
temperature of about 430 ∘ C. Subambient initial condi-
tions are required to cover a wide boiling range of samples
and this is accomplished with the use of a carrier gas such
as helium. Since HTSD utilizes an external standard tech-
nique, all samples must be injected from an autosampler
to ensure reproducibility of sample volume on the column
for each sample. The detector signal is recorded as area
slices (time intervals) for consecutive increasing retention
times. SimDist software is used for data acquisition and
result calculations.
4.1 Sample Preparation
Ensure a homogeneous sample is prepared for analysis.
A consequence of the conditions necessary for HTSD
is a limited concentration capacity of the column due
to the small amount of stationary phase. This limita-
tion requires appropriate dilution of both the standards
and the sample, usually in carbon disulfide. Liquid
hydrocarbon samples such as petroleum crude oils,
150 000
100 000
FID response
50 000
0
0 10
Chromatographic retention time (min)
Figure 2 Analysis of carbon disulfide solvent blank using HTSD.
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gas oils, and solid or semisolid residue materials, such
as vacuum tower bottoms and asphaltic materials, are
typically prepared at a concentration of about 0.5–2.5
mass percent in the solvent, whereas environmental
samples such as oil contaminated soils and waters are
generally prepared at higher concentrations on the order
of about 50 mass percent solvent to sample to improve
sensitivity.
4.2 Blank Run
Because of the highly inert conditions of high-purity
fused silica and special treated metal GC columns,
along with the gentle injection techniques, and the short
time at maximum temperature, little or no evidence
of cracking is normally seen in HTSD. Because of the
column breakdown (bleed) during the final portion of
an HTSD analysis and the need to dilute the sample, as
noted previously, a blank GC run using only the solvent
is recorded in the data system. An acceptable blank
run shows a stable plateau at the highest temperature
of the oven and no indication of carryover or residual
sample elution. Identification of an acceptable blank
run is important as it is then subtracted from all subse-
quent GC runs in the analysis sequence including the
calibration, QC, and testing samples (Figure 2). This
blank subtraction accomplishes two important goals:
first it removes the signal present for the solvent, which
occurs just following the start of the analysis near the
determination of any light-end material present; and
second the column bleed is compensated. The assump-
tion during this process is that the solvent blank and the
column bleed profiles are constant during the calibration
Enlargement of baseline
showing column bleed at final
temperature of 432 °C (810 °F)
20 30 40 min
HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 5

and sample analysis. It is the HTSD operator’s responsi- mass distribution data known for physical distillation
bility to verify these criteria for statistically meaningful of the reference oil, and the statistical error of the
results. difference between HTSD data versus actual boiling
point data is reported (Table 1). The difference must
4.3 Calibration remain within the acceptable limits established for the
HTSD method, which is a maximum squared deviation
The HTSD calibration is comprised of two items: the of 139.
first is an n-alkane calibration reference (hydrogenated
polyolefin wax, Polywax 655, which covers the boiling
4.4 Determination of Hydrocarbon Yield as a Function
range C5–C100) as shown in Figure 3; and the second is a
of Boiling Point
reference oil that has been physically distilled by ASTM
D2892 and D5236, as shown in Figure 4. The HTSD analysis result gives a chromatogram of
The Polywax is used to calibrate chromatography detector signal response as a function of chromatography
elution times of the hydrocarbon components to the retention time and a tabulated report of boiling point
AEBP of the n-paraffin. The physically distilled refer- distribution of hydrocarbon yield at specific boiling cut
ence oil is used as the external standard to calibrate points in cumulative percent mass of sample (Figure 5
the chromatography system for all sample percent and Table 2). The report shows percent mass of material
recovery calculations. In addition, the HTSD analysis recovered in the analysis, IBP, FBP, and whether mate-
results found for the reference oil are compared to the rial boiling at higher than 720 ∘ C (1328 ∘ F) is present.

Component BP(°F) Rt(min)

C5 97 0.115
C6 – 0.5442

C6 156 0.544
2.000e+005 C7 208 0.752
C8 259 1.349
C9 304 2.396
C10 345 3.693
1.800e+005 C11 385 5.021
C12 421 6.303
C13 455 7.520
C14 489 8.671
1.600e+005 C15 520 9.761
C16 549 10.796
C17 576 11.781
C18 601 12.714
1.400e+005 C20 651 14.480
C24 736 17.576
C28 808 20.278
C32 871 22.616
C46 – 29.2602

1.200e+005 C36 925 24.748

C50 – 30.7844

C40 972 26.681

C46 1033 29.260
C8 – 1.3487

C40 – 26.6812

C50 1067 30.784

FID response

1.000e+005 C56 1112 32.835

C60 1139 34.073
C56 – 32.8355

C66 1175 35.787

C9 – 2.3959

C36 – 24.7480

C70 1197 36.845

C5 – 0.1150

C28 – 20.2779
C10 – 3.6929

C76 1227 38.330

C60 – 34.0728

8.000e+004 C80 1247 39.248

C20 – 14.4801

C86 1276 40.565

C11 – 5.0207

C16 – 10.7961
C12 – 6.3030

C17 – 11.7805

C32 – 22.6164
C13 – 7.5204

C90 1292 41.392

C14 – 8.6708
C15 – 9.7609

C24 – 17.5759

C96 1314 42.564

C66 – 35.7865
C18 – 12.7144

6.000e+004 C100 1328 43.320

C70 – 36.8449
C76 – 38.3299

4.000e+004
C80 – 39.2484

C100 – 43.3200
C86 – 40.5654
C90 – 41.3916
C96 – 42.5642

2.000e+004

0.000e+000

–2.000e+004
0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 3 Analysis of C5 –C100 n-alkane calibration reference mixture using HTSD.

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6 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005

8.000e+004

6.000e+004

End time 38.0000

Start time 8.0000

4.000e+004

FBP 1016
2.000e+004
IEP 684

0.000e+000

–2.000e+004
0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 4 Analysis of physically distilled reference oil using HTSD.

Table 1 Results for reference oil using physical distillation (target values) versus HTSD (determined values)
Reference check
Recovered (mass%) Target values Determined values
BP (∘ F) dBP (∘ F) BP (∘ F) dBP (∘ F)
10.0 791 5.0 791 0.0
20.0 817 5.0 817 0.0
30.0 834 5.0 834 0.0
40.0 850 5.0 850 0.0
50.0 864 7.0 864 0.0
60.0 877 7.0 878 1.0
70.0 891 7.0 892 1.0
80.0 907 7.0 908 1.0
90.0 928 7.0 929 1.0
Maximum squared deviation = 139.
Found squared deviation = 4.
Squared test passed.

The IBP is the temperature (corresponding to the The HTSD result can also be expressed in a carbon
retention time) at which a cumulative yield is equal number distribution format, which gives a graphical plot
to 0.5% of the total sample. The FBP is the tempera- and tabulated report of yield at each n-alkane carbon
ture (corresponding to the retention time) at which a number in incremental and cumulative percent mass
cumulative yield is equal to 99.5% of the total sample. (Figure 6).

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HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 7

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005

8.000e+004
IBP 121

6.000e+004

End time 45.2167

4.000e+004
Start time 0.0233

2.000e+004

0.000e+000

–2.000e+004
0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 5 Base oil analysis using HTSD.

5 QUALITY CONTROL AND INSTRUMENT range (Figure 7) and indicate corrective action needs to
PERFORMANCE be taken before a sample analysis is reported.

5.1 Statistical Analysis of Quality Control Samples

QC and quality assurance (QA) procedures adopted for
HTSD are rigorously followed to ensure the integrity
of HTSD and produce statistically meaningful results.
A QC material should be analyzed with every sequence
and depending on the length of the sequence it may
need to be repeated within the sequence. As noted in
Section 4.3, the QC for each HTSD run is the reference
oil; however, other materials can also be utilized such as
gas oil, lube feed stocks, hydrotreated residue, or crude
oils of different specific gravity (e.g. California crude vs
Gulf of Mexico crude). When determining which type of
sample to use as the QC, you must know the physical
distillation mass distribution data to compare the HTSD
data to identify the statistical error difference. The mean
and standard deviation (SD) of the temperature versus
percent yield need to be tracked over time as excursions
beyond ±2 or 3 SD limits will signal an out-of-control
5.2 Instrument Performance and Maintenance
Careful operator evaluation of the system performance is
necessary for accurate HTSD data. Visual inspection of
the n-alkane calibration reference (Polywax) is useful in
evaluating system performance. Chromatographic peak
shape symmetry of the n-alkanes and changes in their
retention times can give an indication of the condition
of the chromatography column and also the GC injector
liner. The solvent blank analysis is also important in moni-
toring any shifts in baseline during the analysis.
Performance is affected by variables such as loss of
the stationary phase at high temperatures (i.e. resulting
in loss of film thickness and sample capacity) and the
unavoidable buildup from residue containing samples of
nonvolatile materials, such as metals, and asphaltenes
in the injector or the column. Corrective action often
involves replacing the GC injector liner, cutting off a short

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8 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

Table 2 Tabulated report showing BP distribution by % and cut points from an HTSD analysis of base oil (Figure 5)
BP distribution table – percent
Recovered BP (∘ F) Recovered BP (∘ F) Recovered BP (∘ F) Recovered BP (∘ F)
(mass%) (mass%) (mass%) (mass%)
IBP 116.6 26.0 502.8 52.0 767.0 78.0 1028.8
1.0 151.4 27.0 512.6 53.0 776.8 79.0 1040.4
2.0 186.2 28.0 521.0 54.0 786.8 80.0 1052.0
3.0 209.8 29.0 533.2 55.0 796.2 81.0 1063.8
4.0 233.0 30.0 544.0 56.0 806.0 82.0 1075.4
5.0 245.0 31.0 550.2 57.0 815.6 83.0 1087.4
6.0 263.8 32.0 561.8 58.0 825.2 84.0 1099.6
7.0 277.0 33.0 573.0 59.0 835.4 85.0 1112.0
8.0 289.4 34.0 579.4 60.0 845.2 86.0 1124.8
9.0 304.4 35.0 590.2 61.0 855.2 87.0 1137.8
10.0 317.2 36.0 600.0 62.0 865.2 88.0 1150.8
11.0 329.0 37.0 607.4 63.0 875.0 89.0 1164.0
12.0 343.0 38.0 618.8 64.0 884.4 90.0 1177.4
13.0 351.2 39.0 628.0 65.0 893.8 91.0 1190.8
14.0 363.8 40.0 639.6 66.0 903.4 92.0 1204.8
15.0 376.6 41.0 650.6 67.0 912.8 93.0 1219.2
16.0 386.6 42.0 660.6 68.0 922.6 94.0 1234.2
17.0 400.2 43.0 671.8 69.0 932.2 95.0 1250.4
18.0 413.4 44.0 681.8 70.0 942.0 96.0 1267.6
19.0 422.4 45.0 693.0 71.0 952.0 97.0 1284.8
20.0 434.4 46.0 703.0 72.0 962.4 98.0 1302.2
21.0 446.8 47.0 714.4 73.0 973.0 99.0 1322.6
22.0 456.2 48.0 724.8 74.0 983.8 FBP 1335.2
23.0 469.4 49.0 735.8 75.0 994.6
24.0 481.0 50.0 746.2 76.0 1005.8
25.0 490.4 51.0 756.4 77.0 1017.0

BP distribution table – cut points

BP (∘ F) Recovered Fraction BP (∘ F) Recovered Fraction BP (∘ F) Recovered Fraction
(mass%) (mass%) (mass%) (mass%) (mass%) (mass%)
100.0 0.3 0.3 600.0 36.0 10.2 1100.0 84.0 8.5
200.0 2.4 2.2 700.0 45.7 9.8 1200.0 91.7 7.6
300.0 8.4 6.0 800.0 55.4 9.7 1300.0 97.9 6.2
400.0 17.0 8.6 900.0 65.7 10.3
500.0 25.8 8.8 1000.0 75.5 9.8

length of the column at the inlet, or replacing the column weight% at certain temperatures to demonstrate repro-
with a new one. ducibility among the participating labs. Figure 8 repre-
sents an example of the report at temperature ∘ C at 10%,
5.3 Interlaboratory ‘Round-Robin’ Test Results 50%, and 90% weight recovery.

The precision of HTSD was determined initially by the

statistical examination of the interlaboratory test results
for five crude oils and five residues; at which time the
repeatability and the reproducibility was identified based
on the percent mass of hydrocarbon yield with temper-
ature given for each crude type and laboratory. ASTM
Committee D-2 conducts quarterly interlaboratory crude
oil checks (round-robin) under their Proficiency Testing
Program, which includes the HTSD method. Statistical
analysis of the data obtained from each participating
laboratory is reported in % weight recovery and total
6 CASE STUDIES AND/OR APPLICATIONS
6.1 Petroleum Refining
Refining processes are used to transform crude oil into
useful products such as LPG, gasoline, kerosene, jet fuel,
diesel oil, and fuel oils. Each product represents different
temperature cuts from the crude oil as demonstrated in
Figure 9. To optimize each type of unit at the refinery
(atmospheric, vacuum, and residual), the refinery will

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HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 9

100.00

10.00
% Weight

1.00

0.10

0.01
0–5

11

17

23

29

35

41

47

53

59

65

71

77

83

89

95

101

107
Carbon number
% wt Cum % wt

Figure 6 n-Alkane carbon number distribution from HTSD analysis of base oil (Figure 5).

HTSD QA % OFF @ 360°F instrument 1 (40 PTS)

12.4

12.3

12.2
% OFF
12.1 MEAN
+2SD
–2SD
12
+3SD
% OFF

–3SD
11.9

11.8

11.7

11.6

11.5

11.4
0803A

0811A

0821A

0914A

0927A

1006A

1016A

1106A

1113A

1203A

1217A

1230A

0115A

0122A

0128A

Sequence date

Figure 7 QC X-chart for reference sample (% OFF at 360 ∘ F) using HTSD.

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10 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

High-temperature simulated distillation – D7169

Temperature °C at 10% weight recovery
28.44 124.33

21.33 117.22
3 Sigma range limit these test data

14.22 110.11

7.11 103
Deviation

0 95.89

–7.11 88.78

–14.22 81.67

3 Sigma range limit these test data

–21.33 74.56

–28.44 67.45
1 3 7 2 6 4 1 1 6 1 2 2 2 5 5 1 1 3 3 1 1 1 2 1 9 1 2 1 2 2 1 9 2 1 1 1 1 1 7 8 1 2 2 1 9 2 2 1 6 6 2 1 8 1 1 8 2 1 9
7 9 8 3 9 2 3 7 5 4 0 6 1 0 7 5 1 1 5 2 7 2 6 8 8 8 8 2 1 1 6 0 2 3 9 0 5 9 5 0 1 2 5 1 1 2 2 0 1 2 1 7 5 7 0 0 7
4 0 0 6 1 7 8 6 6 8 5 1 8 6 1 2 9 2 2 2 7 0 7 3 4 7 1 0 7 4 0 3 7 1 5

Lab code (presented vertically)

28
Median
0.01 0.99
24

20
Number of labs

16

12

0
3

.1

5
–7

.0

.1

3
87

01

15
8.

2.
80

94
66

1–

–1

–1

2
–

–1

–1
05

15

.2

3
80

25

8.

35
94
.

.
73

87

10
1.

5.
10

11

Distribution range of test results

Figure 8 HTSD interlaboratory round-robin HTSD results for a crude oil. (Used with the written consent of ASTM International
from Proficiency Testing Program (PTP) for crude oils by D7169. © ASTM International, 2018.)

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HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 11

High-temperature simulated distillation – D7169

Temperature °C at 50% weight recovery
37.76 305.1

28.32 295.66
3 Sigma range limit these test data

18.88 286.22
Deviation

9.44 276.78

0 267.34

–9.44 257.9

–18.88 248.46

3 Sigma range limit these test data

–28.32 239.02

–37.76 229.58
2 1 7 3 1 1 2 1 1 1 9 1 1 2 2 1 2 8 2 1 1 9 7 1 6 1 2 2 6 4 1 1 1 5 1 9 1 1 1 5 4 2 8 2 2 1 2 9 6 1 2 1 1 6 3 2 8
3 7 8 9 6 5 0 2 3 4 1 8 7 6 0 5 2 5 1 2 1 6 9 8 5 3 1 2 0 2 1 0 1 7 0 8 5 5 5 0 5 8 2 1 0 2 7 9 2 0 9 7 1 2 7
0 6 6 8 7 5 0 1 1 2 6 2 8 2 6 1 2 0 8 9 0 0 3 3 1 7 4 4 5 7 7 1 7 7

Lab code (presented vertically)

21

Median
18 0.01 0.99

15
Number of labs

12

0
5

25

65

45

25
.6

.4

.0

8
.

8.

4.

.
7

55

63

71

86

02
24

27

29
–2

–2

–2

–3
9–

3–

1–

7–
.7

5
9.

5.

3.

1.

8.

6.

4.
7
23

24

25

26

27

27

28

29

Distribution range of test results

Figure 8 (Continued)

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12 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

High-temperature simulated distillation – D7169

Temperature °C at 90% weight recovery
82.64 600.57

61.98 579.91
3 Sigma range limit these test data

41.32 559.25

20.66 538.59
Deviation

0 517.93

–20.66 497.27

–41.32 476.61

3 Sigma range limit these test data

–61.98 455.95

–82.64 435.29
1 2 2 9 1 1 1 1 2 1 1 1 1 2 6 8 1 1 2 1 7 2 2 8 7 1 9 1 9 6 2 1 4 1 1 2 1 1 1 4 3 9 1 6 5 6 1 1 2 2 2 2 5 1 1 3 2
7 1 3 1 7 7 4 6 0 3 8 2 0 2 0 5 1 5 0 2 8 6 2 9 3 6 5 7 9 1 8 2 1 5 1 5 0 0 5 9 8 1 5 7 1 5 2 1 2 2 0 0 7 9 8
4 0 1 6 1 6 7 0 5 0 2 0 8 2 2 8 2 3 0 1 9 1 8 6 5 3 6 7 7 4 4 7 1 7 7

Lab code (presented vertically)

35

30 Median
0.01 0.99

25
Number of labs

20

15

10

0
45

05

25

65

85
6

.8

4
1.

1.

2.

2.

2.

.
01

22

02
46

48

54

56

58
–5

–5

–6
3–

5–

1–

3–

5–
.7

7
1.

1.

1.

2.

2.

2.

2.
1
44

46

48

50

52

54

56

58

Distribution range of test results

Figure 8 (Continued)

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HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 13

800 800

700 700
Heavy diesel oil

600 600

Cetane (hexadecane) C16H34

No 2 diesel No 1 diesel
500 500

Tridecane C13H28
Temperature (°F)

JP-5, Jet A

400 400

JP-4 Premium motor

gasoline
300 300
Octane C8H18
Iso-octane C8H18
Aviation gasoline
200 200
Ethanol
Methanol

Pentane C5H12
100 100

0 10 20 30 40 50 60 70 80 90 100
Percent evaporated

Figure 9 Distillation characteristics of fuels.

utilize both laboratory-scale distillation and HTSD to
evaluate production and identify areas of improvement.
The laboratory-scale distillation is valuable as it simulates
the actual plant process and is relied on the evalua-
tion of unit performance. Refinery engineers must ulti-
mately use lab data to make operational decisions to
improve product yields and product quality. Refiners are
always interested in the value of incremental product
and feedstock; laboratory analytical data is useful in
gaining insight into necessary unit design or operation
changes.(15) For example, the quantity of asphaltenes in
the overflash stream can be used to estimate entrainment;
HTSD analysis of the ‘overflash’ stream and vacuum
residue, in conjunction with the asphaltene analysis, will
indicate if the unit has enough wash oil. A crude vacuum
unit produces heavy distillate for downstream processing
in a fluidized catalytic cracker (FCC) or hydrotreater.
Optimizing heavy vacuum gas oil (HVGO) production
requires an understanding of the feedstock distillation
curve and incremental gas oil contaminants in the region
where it is yielded; Figure 10 represents an HTSD analysis
used to characterize refinery vacuum tower products and
the identification of the distillation curve; and Figure 11 is
a pictorial presentation of the cuts.
6.2 Crude Oil Characterization
The ability to accurately evaluate opportunistic crudes
and crudes from currently producing fields has increas-
ingly important economic considerations in refining
margins. The crude assay distillation procedure is defined
by the methodologies found in ASTM D2892 and D5236.

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14
300 000
250 000
FID response
200 000
150 000
100 000
50 000
0
0 10
Chromatographic retention time (min)
Figure 10 Vacuum tower products analysis using HTSD.
Figure 11 Vacuum tower products (HTSD – Figure 10).
A comparison of the yield curves (expressed in mass
percent) of a crude assay to HTSD were presented for
100 typical crudes spanning the range of light, interme-
diate, and heavy API gravities for which 10 distillation cut
points were compared. The study reported by Villalanti
et al.(16) categorized the crudes based on API gravity,
which is a function of relative density (specific gravity)
that is widely used in the petroleum industry. A full
wide boiling range (naphtha and residue containing) QA
sample was utilized in the study. The comparison of the
distillation yield curves (percent mass) as determined by
crude assay and by HTSD showed good agreement. In
general, the difference was better than ±2% mass over
the cut point range of IBP to 538 ∘ C (1000 ∘ F). The only
exception to this is the region around 399 ∘ C (750 ∘ F).
The deviation in this region is caused by the change from
high-efficiency (15 plates) ASTM D2892 distillation to
low-efficiency (one plate) ASTM D5236 distillation. The
distillation at this point goes from TBP distillation to
non-TBP distillation. This results in a larger deviation for
HTSD versus physical distillation at the crossover and
beyond and also introduces a bias between ASTM D2892
and D5236. The fact that HTSD has no crossover effects
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PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS
Plot Range
1 875–900
2 900–925
3 925–950
4 950–975
5 975–1000
6 1000–1025
7 1025–1050
8 1050–1075
9 1075–1100
10 1100–1125
11 1125–1150
20 30 40
is one of its main advantages for modeling and moni-
toring purposes. The study cited the advantages of HTSD
to include method precision, faster turnaround and less
expense than laboratory physical distillation, valuable
business tool for evaluating new crudes and confirming
crude quality before purchase, and ensuring crude
product integrity during transportation and delivery.
Product adulteration can occur whether intentionally or
not and HTSD is a monitoring tool for product integrity.
For example, the blending of pitch (defined as 538 ∘ C+ or
1000 ∘ F+) into crudes has been spotted at concentration
levels of about 1.5% mass and lower.(17)
Crude oil characterization is important relative to flow
assurance, as the gelling of waxy crudes and the deposi-
tion of wax on the inner walls of pipelines present a costly
problem in the production, transportation, and storage
of oil.(18) Many crude oils contain significant quanti-
ties of wax, which will readily crystallize under special
conditions of pressure and temperature affecting the oil
viscosity and gelation. Waxy crude oils are characterized
by a high content of paraffin. Figure 12 represents
a normal crude analysis and Figure 13 represents a
waxy deposit from a crude pipeline. As shown by the
HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 15

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005

8.000e+004

6.000e+004

End time 143.9400

Start time 0.0267

4.000e+004

FBP 135
2.000e+004

0.000e+000

–2.000e+004
0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 12 Analysis of crude oil using HTSD.

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005

8.000e+004
IBP 156

6.000e+004
End time 43.9400

4.000e+004

2.000e+004

0.000e+000

–2.000e+004
0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 13 Analysis of pipeline wax deposit using HTSD.

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16 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

HTSD analysis, the waxy deposit is highly paraffinic.
Wax deposits represent a long-standing problem in
the petroleum industry resulting in numerous research
projects relative to flow rates, residence time, wax concen-
tration, and temperature differences as all of these items
impact operating efficiency and production and increases
the cost relative to prevention and remediation. Accu-
rately modeling deposition in pipelines can be complex
and difficult, while precipitation is mainly a function
of thermodynamic variables such as composition, pres-
sure, and temperature; deposition is also dependent
on flow hydrodynamics, heat and mass transfer, and
solid–solid and surface–solid interactions. The study of
wax deposits will remain a focus of flow assurance groups
as researchers develop valid models to predict wax depo-
sition in pipelines under different operational conditions,
and engineers develop chemical packages and other tools
to prevent the wax deposits from accumulating.
6.3 Environmental
From 1989 when the Valdez Oil Spill occurred in Alaska to
recently in 2014 with the Bakken Oil Spill, environmental
issues remain at the forefront of concern. The potential
sources of environmental contamination that do not
always make the headlines include hydrocarbon and
metals from urban runoff and municipal outfalls; pesti-
cides from farming; petroleum hydrocarbons, metals, and
chemicals in oil and gas production; petroleum hydro-
carbons in petroleum refining and pipeline operations;
polycyclic aromatic hydrocarbons (PAHs), tars, and
metals associated with coal gasification and processing;
chemicals in manufacturing; and the handling and storage
of transportation fuels and oil. The occurrence of hydro-
carbon contamination found in the environment often
leads to an investigation to assess the nature and extent of
contamination to assist in the remediation and restoration
process both on land and in water. Because hydrocar-
bons have a distinguishing compositional pattern or
‘fingerprint’, the identification of potential sources
can be narrowed when compared to known standards.
HTSD is useful for characterizing hydrocarbons, which
can be present as soil (surface and subsurface) and water
contaminants. Figure 14 represents a soil sample analyzed
by HTSD. For this particular analysis, the soil was placed
in a vial with carbon disulfide; it was sonicated and

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005

8.000e+004

6.000e+004
End time 44.9500
Start time 0.6600

4.000e+004
IBP 286

2.000e+004

0.000e+000

–2.000e+004

0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 14 Analysis of soil sample using HTSD.

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HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 17

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005

8.000e+004

6.000e+004

End time 44.1733

Start time 0.0300

4.000e+004

2.000e+004

0.000e+000

–2.000e+004

0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 15 Analysis of water sample using HTSD.

centrifuged to effectuate the separation process of the
oil, water, and soil.
Figure 15 represents a water sample analyzed by HTSD.
For this particular analysis, the water was placed in a
vial and centrifuged to effectuate the separation process
of the oil and water. Once separation occurred, the oil
layer was pipetted into a separate vial and analyzed. In
both examples, the soil sample and the water sample, the
HTSD result is useful for characterizing the amounts of
petroleum hydrocarbons in the boiling range of naphtha,
gasoline, diesel, and heavier material. The detectable
hydrocarbons can be reported on basis of percent mass
of sample as received or on a normalized percent hydro-
carbon basis.
HTSD identification of compositional data for released
oil facilitates the forensic investigation to distinguish one
oil from another. For example, with the sinking of the
Deepwater Horizon drilling platform in 2010, composi-
tional information for petroleum (gas and oil) released
by the well at the seafloor was essential in evaluating
the fates of hydrocarbons in the sea. It was necessary
to distinguish oil from the Macondo well with hydrocar-
bons released from other sources in the Gulf of Mexico
to fully understand the impact of the Deepwater Horizon
incident.(19) Samples were collected from the Macondo
well as demonstrated in Figure 16.
Woods Hole Oceanographic Institute conducted the
investigation into the Deepwater Horizon oil spill. In
the development of the compositional data, they utilized
HTSD data (Figure 15 represents one of the samples
obtained from the spill) to assist in their understanding
of the far-reaching implications of the spill. Their study
revealed differences in deep water spills versus sea-
surface oil spills; in that components such as benzene,
toluene, ethylbenzene, and total xylenes (collectively
referred to as BTEX) and naphthalenes quickly volatize
and are rapidly lost to the atmosphere within hours to
days in a sea-surface spill; whereas in a deep water spill,
the gas and oil experienced a significant residence time in
the water column with no opportunity for the release of
volatile species to the atmosphere.
6.4 Renewable Energy (Biomass)
In an effort to develop sources of renewable energy,
several markets have advanced including wind, water,

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18 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

Figure 16 Fluids exiting the Macondo well being collected on June 21, 2010 with an IGT sampler.

2.000e+005

1.800e+005

1.600e+005

1.400e+005

1.200e+005
FID response

1.000e+005 Methanol

8.000e+004

6.000e+004
Carbon disulfide
solvent
End time 44.3300
Start time 4.8733

4.000e+004
FBP 1190

2.000e+004
IBP 595

0.000e+000
Light ends C18 C20 Monoglyceride Diglyceride Triglyceride
FAME FAME
–2.000e+004

0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 17 Analysis of a biodiesel using HTSD.

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HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY
solar, and biomass. As interest grows in sustainable
fuel sources, there are currently a number of product
streams being developed from sources including wood
chip biofuel and biodiesel from corn and algae. Figure 17
is an HTSD analysis of a biodiesel demonstrating the
typical markers found in biodiesel.
Biodiesel can be used in its pure form for certain appli-
cations, but it is usually blended with petroleum diesel
especially when it is utilized in a vehicle. There are both
advantages and disadvantages to the use of biodiesel, as
the market continues to develop; the effects of the disad-
vantages will begin to diminish.
6.5 Legal and Regulatory Rules
As noted, the environmental impacts of oil contamina-
tions are of concern and in a number of those instances
legal battles ensue. Characterization of hydrocarbons
involving legal matters is evident in a number of law suits
filed on a regular basis; from spills on land and water, to
plane crashes and even murder investigations. In a civil
matter, a German auto dealership wanted to know if the
oil in a car was original equipment manufacturer (OEM)
Counts
Used BMW
conventional
120 000 motor oil
100 000
80 000
60 000
40 000
Light ends
20 000 blow-by
of used oil
0 10
Figure 18 Overlay HTSD analysis of Virgin synthetic oil and a used motor oil.
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19
brand oil and if the oil was contaminated to refute a claim
by a customer that the dealership damaged the vehicle
engine during the last service of the vehicle. In an effort
to prove or disprove if the oil used was an OEM oil, a
new bottle of Virgin fully synthetic twin power turbo oil
was obtained from the dealership and a sample of the oil
removed from the vehicle was also obtained; an HTSD
analysis was completed on both samples. Figure 18 is an
overlay comparison of the two analyses.
In addition to legal matters, regulatory issues also
impact the legal system with both civil and criminal
filings. There are several entities that regulate laws rela-
tive to the petroleum industry including, but not limited
to, the Environmental Protection Agency (EPA), Occu-
pational Safety and Health Administration (OSHA), and
the DOT.
In May 2015, the DOT announced a final rule(20)
to strengthen safety standards for transportation of
flammable liquids by rail, including new testing and
sampling requirements to improve classification of unre-
fined petroleum-based products placed into transport.
Under the new requirements, the offeror has the responsi-
bility to certify the classification and describe the material
Virgin fully synthetic BMW
twin power turbo oil
Synthetic oligomer pattern
of viscosity index improvers
20 30 40 min
20 PETROLEUM AND LIQUID FOSSIL FUELS ANALYSIS

BP distribution table – Percent

2.000e+005
Recovered BP Recovered BP Recovered BP Recovered BP
(mass%) (°F) (mass%) (°F) (mass%) (°F) (mass%) (°F)
1.800e+005 2.0 96.8 26.0 462.4 50.0 738.4 74.0 1008.0
3.0 100.6 27.0 476.8 51.0 749.6 75.0 1022.2
4.0 108.0 28.0 489.6 52.0 760.4 76.0 1037.0
1.600e+005 5.0 132.0 29.0 503.0 53.0 771.2 77.0 1051.4
6.0 153.8 30.0 515.0 54.0 781.8 78.0 1066.0
7.0 157.2 31.0 527.0 55.0 791.8 79.0 1080.8
1.400e+005 8.0 176.6 32.0 539.8 56.0 802.0 80.0 1095.8
9.0 190.8 33.0 551.6 57.0 812.2 81.0 1111.0
10.0 209.0 34.0 562.8 58.0 822.6 82.0 1126.4
1.200e+005 11.0 220.6 35.0 574.4 59.0 833.0 83.0 1142.2
12.0 234.0 36.0 584.6 60.0 843.8 84.0 1157.8
13.0 247.2 37.0 595.6 61.0 854.6 85.0 1174.0
FID response

1.000e+005 14.0 267.6 38.0 605.6 62.0 865.4 86.0 1190.6

15.0 283.8 39.0 617.0 63.0 876.2 87.0 1207.6
16.0 302.2 40.0 627.4 64.0 886.8 88.0 1225.4
8.000e+004 17.0 318.0 41.0 639.0 65.0 897.4 89.0 1244.6
18.0 334.4 42.0 650.2 66.0 908.4 90.0 1265.4
19.0 352.4 43.0 661.0 67.0 919.6 91.0 1286.4
6.000e+004 20.0 370.4 44.0 671.8 68.0 931.0 92.0 1307.8
21.0 386.2 45.0 682.8 69.0 942.8 93.0 1334.6
22.0 404.2 46.0 693.6 70.0 954.8 93.5 1351.0
Start time 0.0267

4.000e+004 23.0 419.8 47.0 704.6 71.0 967.6

End time 4
24.0 433.6 48.0 715.8 72.0 980.6
25.0 448.2 49.0 727.2 73.0 994.0
2.000e+004

0.000e+000

–2.000e+004

0 5 10 15 20 25 30 35 40 45 50
Chromatographic retention time (min)

Figure 19 Crude oil analysis using HTSD.

being shipped, which includes the proper hazard class, Reddy, Woods Hole Oceanographic Institute for infor-
packing group, and shipping name. Flash point and IBP mation on HTSD application relative to the Deepwater
are two properties used to determine the proper packing Horizon oil spill.
group; HTSD in conjunction with a DHA assist in the
determination of IBP. Figures 19 and 20 demonstrate how
HTSD and DHA work together to identify the proper
IBP of a crude oil. HTSD showed that the crude oil
sample had 2% below the initial boiling range of 97 ∘ C or ABBREVIATIONS AND ACRONYMS
C5 . The DHA report showed both C3 and C4 components
in the sample and the summary identified the IBP of the AEBP Atmospheric Equivalent Boiling Point
sample as 31.10 ∘ F. These two analyses were utilized by AET Atmospheric Equivalent Temperature
the offeror to properly classify the crude oil for shipment. ASTM American Society for Testing and Materials
International
BTEX Benzene, Toluene, Ethylbenzene, and Total
Xylenes
DHA Detailed Hydrocarbon Analysis
ACKNOWLEDGMENTS DOT Department of Transportation
EPA Environmental Protection Agency
The authors wish to thank the following colleagues for FBP Final Boiling Point
their valuable contributions to this article: Scott Golden, FCC Fluidized Catalytic Cracker
Process Consulting Services for information on HTSD FID Flame Ionization Detector
applications relative to refinery processes; and Chris GC Gas Chromatography

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1819.pub2
HTSD APPLICATIONS IN PETROLEUM AND RENEWABLE ENERGY 21

Summary report
Group type Total (mass%) Total (vol%) Total (mol%)
Paraffins: 5.8583 6.2599 6.4867
I-Paraffins: 5.6607 5.8814 5.5716
Olefins: 0.0000 0.0000 0.0000
Napthenes: 3.4365 3.0594 2.9821
Aromatics: 1.1281 0.8834 1.0160
Total C14+: 0.0000 0.0000 0.0000
Total unknowns: 0.0164 0.0159 0.0437

Oxygenates:

Total: 0.0000 (mass%) 0.0000 (vol%)

Total oxygen content: 0.0000 (mass%)

Multisubstituted aromatics: 0.3591 (mass%) 0.2815 (vol%)

Average molecular weight: 85.4647
Relative density: 0.6803
Reid vapor pressure @ 100°F: –0.3470
Calculated octane number: 73.3
Motor octane number (Jenkins calculation): 68.8
IBP Molecular weight and relative density data
BP by mass (°F) 31.10 Group Avg Mw. Avg rel. density
BP by vol (°F) 10.90
C1 0.0000 0.0000
Percent carbon: 84.7261
C2 0.0000 0.0000
Bromine number (calc): 0.0000
C3 44.0970 0.5005
C4 58.1240 0.5737
C5 72.0830 0.6263
C6 85.3103 0.6884
C7 97.9972 0.7385
C8 112.1112 0.7473
C9 127.6597 0.7349
C10 0.0000 0.0000
C11 0.0000 0.0000
C12 0.0000 0.0000
C13 0.0000 0.0000
Total sample: 85.50 0.68

Figure 20 Crude oil analysis using DHA.

HTSD High-temperature Simulated Distillation PAH Polycyclic Aromatic Hydrocarbon

HVGO Heavy Vacuum Gas Oil PTV Programmed Temperature Vaporization
IBP Initial Boiling Point QA Quality Assurance
ID Internal Diameter
QC Quality Control
LPG Liquefied Petroleum Gases
OEM Original Equipment Manufacturer SD Standard Deviation
OSHA Occupational Safety and Health SimDist Simulated Distillation
Administration TBP True Boiling Point

Encyclopedia of Analytical Chemistry, Online © 2006–2018 John Wiley & Sons, Ltd.
This article is © 2018 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2018 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a1819.pub2
22
RELATED ARTICLES
Gas Chromatography
Gas Chromatography: Introduction
Petroleum and Liquid Fossil Fuels Analysis
Full Range Crudes, Analytical Methodology of •
Hydrocarbons Analysis: Introduction • Petroleum
Residues, Characterization of • Diesel Fuels Analysis
Process Instrumental Methods
Chromatography in Process Analysis
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