Ind. Eng. Chem. Res.

2006, 45, 337-345

337

GENERAL RESEARCH
Development of a Detailed Gasoline Composition-Based Octane Model
Prasenjeet Ghosh,* Karlton J. Hickey, and Stephen B. Jaffe
Compositional Modeling Group, ExxonMobil Process Research Laboratories, Paulsboro Technical Center,
Paulsboro, New Jersey 08066

We present a model that predicts the research and motor octane numbers of a wide variety of gasoline process
streams and their blends including oxygenates based on detailed composition. The octane number is correlated
to a total of 57 hydrocarbon lumps measured by gas chromatography. The model is applicable to any gasoline
fuel regardless of the refining process it originates from. It is based on the analysis of 1471 gasoline fuels
from different naphtha process streams such as reformates, cat-naphthas, alkylates, isomerates, straight runs,
and various hydroprocessed naphthas. Blends of these individual process streams are also considered in this
work. The model predicts the octane number within a standard error of 1 number for both the research and
motor octane numbers.
1. Introduction
Octane number (ON) is one of the most important properties
of gasoline streams and is a measure of its antiknock property.
It is defined as the volume percentage of i-octane in a blend of
n-heptane and i-octane, which produces the same knock intensity
as the test fuel under standard test conditions in an ASTM
internal combustion engine. ASTM defines two different types
of ONs, the research octane number (RON) and the motor octane
number (MON), which are evaluated using the ASTM D2699
and the ASTM D2700 tests, respectively.1,2 Both methods use
the same standard test engine but differ in the operating
conditions. RON is measured in an engine running at 600 rpm
and a fuel/air mixture at a temperature of 60 F, while MON is
measured with the engine running at 900 rpm and a fuel/air
mixture at a temperature of 300 F. The slower engine speed
and the lower fuel/air temperature as required in the RON test
are representative of the fuel performance for city driving, while
the faster engine speeds and higher fuel/air temperature represent
the fuel performance for highway driving.
Knock results from the premature combustion of the gasoline
due to compression in the engine.3 As the fuel/air mixture is
compressed in the internal combustion engine, certain molecules
in gasoline tend to self-ignite even before they reach the ignition
spark, thereby creating a resistive expansive motion in the
compression stroke of the engine and hence the knock. Depending on the thermal stability of the molecule (which depends on
its molecular structure) and the ensuing radicals, certain
molecules tend to combust sooner (and knock more) than others.
Consequently, ON is a direct function of the molecular
composition of the gasoline fuel, and any modeling effort should
explicitly acknowledge it.
Numerous studies in the past have attempted to mathematically describe the ON as a function of the gasoline composition.
* To whom correspondence should be addressed. E-mail:
prasenjeet.ghosh@exxonmobil.com.
E-mail: karlton.j.hickey@exxonmobil.com.
E-mail: stephen.b.jaffe@exxonmobil.com.

Lovell et al.4 were an early group to identify that aromatics

and branched i-paraffins have higher ONs than the corresponding paraffins. In the middle 1950s, the American Petroleum
Institute (API) Research Project 455-7 analyzed the purecomponent ONs for over 300 different hydrocarbon molecules,
and several reliable correlations relating gasoline composition
to ON were developed. The work not only quantified the ON
trends with molecular structure and size, it also studied the
nonlinear interactions between different molecular types toward
ON.7 However, the work was primarily focused on purecomponent studies with a limited number of binary or ternary
gasoline blends. Commercial gasoline contains many different
molecules in the C4-C13 range, and the more recent papers in
the literature have therefore focused on predicting the octane
number of such multicomponent mixtures. Anderson et al.8
developed a useful method for predicting the RON of different
gasolines based on the gas chromatographic (GC) analysis of
the sample. A total of 31 molecular lumps were considered to
describe the composition of gasoline, and the contribution of
each lump was added linearly to compute the octane number
of the fuel. Although simple in its structure, the method by
Anderson et al.8 is rather restrictive in its use and is known to
show an error of around 2.8 numbers on average for catalytically
cracked naphthas.9 Part of the less than satisfactory predictions
is perhaps the assumption of linearity in octane blending because
octane blending is known to exhibit nonlinear interactions (both
synergistic and antagonistic) among the various constituent
hydrocarbon molecular classes (e.g., paraffins, olefins, aromatics,
etc.).7 Sasano10 described a procedure similar to that of Anderson
et al.8 to predict ON of the gasoline fuel from its composition
measured by GC. The ON of the fuel is calculated as the linear
volumetric average of the ON of each molecule in the fuel,
which, in turn, is calculated using a linear correlative model.
Van Leeuwen et al.11 used nonlinear regression methods,
specifically projection pursuit regression and neural networks,
to correlate the gasoline composition from GC to ON. However,
both these techniques require much fine-tuning and experience
to develop. This is especially true for neural network based

10.1021/ie050811h CCC: $33.50 2006 American Chemical Society

Published on Web 11/24/2005

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Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006

approaches, where the determination of the number of layers

in the network, number of nodes in each layer, the kind of
transfer functions for each node, etc., is highly user-dependent.
Also, the lack of an underlying phenomenological structure and
the inherent opacity in such models make them less reliable in
the extrapolative mode. More recently, Meusinger and Moros
used genetic algorithms and neural networks to quantify the
partial ON of each gasoline component in the mixture based
on the structural elements of the molecule.12,13 Other relevant
work in this area includes the work by Lugo et al.,14 Twu and
Coon,15 and Albahri,16 who have all employed different variations of the correlating gasoline composition to its octane.
Although the literature is replete with many relevant papers,
most of the work falls into one of the two following categories: first, predicting the ON of individual hydrocarbon
molecules in gasoline by correlating molecular structure descriptors such as topological indices, length of the backbone carbon
chain, degree of branching, type of carbon atom based on
spectroscopy, etc., to the pure-component ON and, second,
predicting the ON of the actual gasoline fuel by correlating the
molecular composition of the gasoline fuel to its ON. In this
work, we are interested in accomplishing the second objective.
In principle, any model that achieves the second objective should
also be able to predict (or reconcile) the ON of the individual
hydrocarbon molecule because a pure component is merely the
limiting value of a mixture. However, most of these published
mixture models do not achieve this. Part of this lack of
reconciliation in the published models originates from their
purely empirical and statistical nature of the underlying mathematical structure used to develop the models, making them
rather restrictive for extrapolation. Further, most of the published
models have focused on developing correlations that work well
with individual or a very few naphtha process streams collectively like fluidized catalytically cracked (FCC) naphtha,
reformates, or some light straight-run (LSR) naphtha streams.
The streams were so chosen that the ONs varied in a narrow
range between 80 and 95 numbers. Although this has traditionally been the most important range for commercial gasoline
fuels, it would be beneficial to have a model that can work
with a much extended range of ONs between 30 and 120
numbers. This is especially critical in todays refinery blending
operations, where many different blend components (i.e.,
naphthas from different processes) with widely different ONs
need to be economically blended. Finally, none of the above
work predict the octane number of gasoline fuels that contain
oxygenates such as methyl tert-butyl ether (MTBE), ethanol
(EtOH), or tert-amyl methyl ether (TAME), which are finding
increasing use in commercial gasoline.
We attempt to address some of the questions raised in the
previous paragraph. Specifically, our objectives are 2-fold: first,
to develop a predictive model for ON, both RON and MON
for any gasoline fuel, dependent solely on the composition and
independent of the refining process stream and, second, to extend
the range of applicability of the model to a much broader range
of octanes from 30 to 120 numbers. In developing such a model,
we would like to ensure that, in the limiting case of a pure
component, the model predicts the pure-component octane
number. Further, we would also like to extend the model to
fuels containing different oxygenates. The details of such a
model development are presented in the next section.
2. Development of the Octane Model
Each gasoline fuel, regardless of the process stream (e.g.,
reformate, FCC, LSR, etc.), is a complex mixture of many

Figure 1. Schematic showing the difference between octane numbers of

the gasoline sample (ON), pure-component octane numbers (ONA and ONB),
ON
and the corresponding blend octane numbers (BON
A and BB , respectively)
for a typical binary blend. Notice that the blend numbers are obtained by
extrapolating the tangent to the octane curve to the pure-component limit.

different hydrocarbon molecules, each contributing to the ON

of the gasoline fuel. Let ON denote the measured octane number
for the gasoline fuel while ONi represents the pure-component
octane number for each molecule i in the fuel. Because a
molecule i may not necessarily always contribute its purecomponent octane number to the gasoline fuel, each molecules
contribution toward the fuel octane number is quantified by its
blend value, denoted by BON
i . The blend value of a molecule
depends on the overall composition of the fuel it is part of.
Figure 1 schematizes the difference between ONi and BON
i . By
definition, ON is a linear volumetric blend of the blend
contributions of all of the different molecules present in the
gasoline fuel. Therefore

ON )

i ViBON
i

(1)

where Vi is the volume fraction of molecule i in the sample.

Experimental studies in our laboratory over many years have
revealed that the blend value of a molecule i varies almost
linearly with the ON of the gasoline fuel it is part of, or blended
into. These results have been reported previously in refs 17 and
18. A typical result highlighting this observation is shown in
Figure 2.18 The figure plots the variation of the blend values of
various n-paraffins (nC5-nC9) against the ON of the three
different refinery naphtha fuels in which they were volumeblended into. For each of the paraffins, the figure shows that
the blending value of n-paraffin increases linearly as the ON of
the refinery naphtha fuel increases. We have observed similar
results over many other such studies. Thus, in general, we may
postulate that the blend value of molecule i may be approximated as a linear function of the gasoline ON. Therefore
(1)
) a(0)
BON
i
i + ai (ON)

(2)

Equation 2 is analogous to the equation for any partial molar

property, where the partial molar property (BON
i ) depends on
is
the composition of the gasoline fuel it blends into. BON
i
parametrized by two parameters, a slope a(1)
and
an
intercept
i
a(0)
i . Although the variation of the blend value of the individual
molecules with the ON of the gasoline fuel is taken to be linear,
this does not imply a linear relationship of the fuel composition
to its ON. Using the definition for ON from eq 1 in eq 2, it is
easy to see that eq 2 captures multicomponent interaction.

Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 339

Figure 2. Variation of blending ON of n-paraffins in different refinery

naphtha fuels.

Although eq 2 requires two parameters, a(0)

and a(1)
i
i , for
each molecule, it is possible to eliminate one of these parameters
using the special case when the gasoline fuel is a pure
component. For instance, if the gasoline fuel is pure toluene,
then its ON is the same as the pure-component ON for toluene,
which is the same as its blend value. Application of this
boundary condition yields
(1)
(0)
(1)
ONi ) a(0)
i + ai (ONi) w ai ) (1 - ai )ONi

(3)

If we define i ) 1 - a(1)
i , eq 2 may be rewritten as

a(0)
i ) iONi

(4)

Rearranging eqs 1, 2, and 4, we get

ON )

i ViiONi lumps
ViiONi
)

i Vii

Vii

(5)

lumps

This is the basic octane prediction model, where the summation

index i runs over all of the molecules present in the gasoline
fuel. However, a typical gasoline fuel contains an enormous
number of different molecules, so some molecular lumping is
necessary to build a practical model. Such lumping is reflected
in the second part of eq 5, where we have replaced the summing
variable i with lumps to indicate that the sum runs over all
of the molecular lumps relevant for the octane model. A lump
defines the compositional level of abstraction that the model
uses. It could be a single molecule like n-heptane or a group of
similar molecules such as C10 aromatics. Note that, in light of
this lumping, the term pure-component ON for lump i may not
always necessarily reflect the ON of a single molecule. For
molecular lumps that correspond to single molecules, ONi is
the pure-component ON of that single molecule, but for
molecular lumps that correspond to a group of similar molecules,
ONi is the average of the pure-component ONs of all of the
different molecules in that lump. These lumps are described in
more detail in section 3.
is are the adjustable parameters and represent whether a
molecule contributes beneficially or detrimentally to the ON

Figure 3. Typical nonlinear interactions between two species x1 and x2.

For instance, x1 could be a paraffin while x2 could be a olefin. Curve a
indicates positive interaction, curve b indicates no interaction, and curve c
indicates negative interaction.

of the gasoline fuel. A contribution is considered beneficial if

the blend value of the molecule/lump (BON
i ) is greater than its
pure-component octane number (ONi). Likewise, the contribution is detrimental if BON
< ONi. For the two cases (a) i < 1
i
and ONi < ON or (b) i > 1 and ONi > ON, the lump i
contributes beneficially to the fuel ON. For the other two cases
(a) i > 1 and ONi < ON or (b) i < 1 and ONi > ON, it
contributes detrimentally to the fuel ON. i ) 1 is the special
case where the lump contributes equally to its pure-component
octane number.
Equation 5 forms the core of the octane model and is suitable
for predicting octanes of reformates, LSR, and alkylate streams.
Although nonlinear in composition, the extent of nonlinearity
expressed in it is insufficient to fully capture the nonlinear
interaction between paraffins and olefins and/or paraffins and
naphthenes, which may be important for cat-naphtha fuels.
Published studies in the literature6,7 and independent research
in our laboratories reveal that hydrocarbons belonging to the
same molecular class blend linearly; i.e., paraffins blend linearly
with other paraffins, olefins blend linearly with other olefins,
and so on. However, a blend of paraffins and olefins may exhibit
significant deviation from linearity. Such nonlinear interaction
in a binary blend is qualitatively described in Figure 3. Figure
3a shows a positive interaction or equivalently a positive
deviation from linearity, Figure 3c shows a negative interaction,
and Figure 3b shows no interaction. Paraffins and naphthenes
also exhibit similar deviations from linearity. In contrast, olefins
and naphthenes tend to blend linearly. The blending behavior
of aromatics as a group is somewhat unclear because of the
differences in the blending behavior of individual aromatic
molecules and also because of the difficulty in measuring the
high ONs of such blends. Also, note from Figure 3 that, for
certain blends, the ON of the blend may actually be higher or
lower than both the individual ON extremes defined by the purecomponent numbers. The mathematical structure of eq 5 is
incapable of describing this behavior because it will always be
bounded between the extremes of pure-component numbers for
the two components of the binary blend, as shown in eq 6.

ON1 e ON )

V11
V22
ON1 +
ON2 e
V11 + V22
V11 + V22
ON2 (6)

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Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006

The nonlinear interaction of Figure 3 may be quantitatively

described by the following mathematical function for a binary
blend:

y)

k(a)
12 V2V1

(7)

1 + k(b)
12 V2

(b)
where k(a)
12 and k12 are interaction parameters. By appropriately
choosing these interaction parameters, we can describe positive,
negative, and no blending interactions. The structure has been
borrowed from the more familiar rate expression for inhibiting
and synergistic pyrolysis kinetics which tend to exhibit similar
behavior. For a ternary blend where there are multiple binary
interactions, i.e., between V1 and V2, between V1 and V3, and
likewise between V2 and V3, eq 7 may be written as

Figure 4. Pure-component RONs for various i-octane isomers.

y)

k(a)
12 V2V1
1+

k(a)
13 V3V1

k(b)
12 V2 +

k(a)
23 V2V3

k(b)
13 V3 +

(8)

k(b)
23 V3

(b)
Equation 8 has six interaction parameters: k(a)
12 and k12 for the
(a)
(b)
1-2 interaction, k13 and k13 for the 1-3 interaction, and k(a)
23
and k(b)
23 for the 2-3 interaction, respectively. It is easy to see
from eqs 7 and 8 that if nonlinear interaction has to be modeled
for every binary interaction in a typical gasoline fuel, it would
lead to a large number of interaction parameters; e.g., even for
a very lumped description of a typical gasoline fuel with 50
different molecular lumps, this leads to 50C2 ) 1225 binary
interactions where nCr ) n!/r!(n - r)!. Consequently, the
nonlinear interaction will be modeled only at the P/O/N/A level
(i.e., at the level of the total paraffins, total olefins, total
naphthenes, etc., and not at the individual molecule level).
For the purposes of this paper, we will consider the nonlinear
interaction between paraffins and naphthenes and between
paraffins and olefins. Thus, a correction similar to eq 8 can now
be added to eq 1 to model the nonlinear interactions in octane
blending. Thus

ON )

PONA

ViBON
i

(a)
k(a)
PNVN + kPOVO

1+

k(b)
PNVN +

k(b)
POVO

P VjBON
j

(9)

where VN and VO represent the total naphthenes and olefins in

the gasoline sample. Mathematically, VN ) inaphthenesVi and
VO ) iolefinsVi. Note that in eq 9, while the first sum runs over
P, O, N, and A (i.e., paraffins, olefins, naphthenes, and
aromatics) molecules, the second sum runs only over the
paraffinic molecules. If the interaction term is denoted by I, eq
9 may be more succinctly rewritten as

ON )

where

Ii )

[(

(1 + Ii)ViBON

i
PONA

(a)
k(a)
PNVN + kPOVO

(b)
1 + k(b)
PNVN + kPOVO
0
otherwise

for i P

(10)

Using eqs 2-4 in eq 9 and rearranging the various terms, we

get

ON )

ViiONi + IPP ViiONi

PONA

Vii + IP(P Vii - P Vi)

(11)

PONA

This is the complete octane model. Note that when I ) 0, eq

11 reduces identically to eq 5. Also, in the limiting case when
the gasoline fuel is a pure component (Vi ) 1), eq 11 yields
ON ) ONi, thereby returning the pure-component octane
number.
3. Defining the Molecular Lumps
Next we need to define the various molecular lumps that will
be used in the octane model. The molecular lumps have been
selected based on the following two criteria:
(a) Analytical Differentiation. We have defined separate
lumps where it is possible to analytically measure and differentiate the lump for most of the process streams. For instance,
it is possible to analytically measure the different aromatics by
carbon number for most of the naphtha process streams by
different GC techniques; however, it is not always possible to
differentiate between the various aromatic isomers at each
carbon number with current analytical techniques. Consequently,
for the aromatics, our lump definition has been restricted to
total aromatics by carbon number only.
(b) ON Differentiation. When analytical differentiation is
possible across similar molecular lumps, we have defined
separate lumps only if their ONs are widely different and their
relative distributions differ across various process streams. For
example, we consider separate lumps for mono-, di-, and
trimethyl-i-paraffins at each carbon number as opposed to a
single lump for the total i-paraffins at each carbon number. Such
delumping is necessary for two reasons: first, the ONs of the
branched i-paraffins vary widely with the degree of branching
and, second, the relative distribution of branched isomers is very
different across different naphtha streams. Figure 4 plots the
pure-component ONs of all of the i-octane isomers and shows
that, depending upon the particular isomer of i-octane, whether
it is a mono-, di-, or trimethyl isomer, its ON could vary between
25 and 100 numbers. The relative distribution of these isomers
is also different in different naphtha process streams, as shown

Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 341

Table 1. Typical Measured Isomer Distribution (wt %) for
i-Octanes
stream type

monomethyls

dimethyls

trimethyls

alkylates
reformates

0
68.9

18.5
31.1

81.5
0

in Table 1 for alkylates and reformates. Trimethyl-i-octanes

dominate C8 i-paraffins in alkylates, whereas monomethyl-ioctanes dominate C8 i-paraffins in reformates. The observations
reported for i-octane are also true for other i-paraffins. Consequently, i-paraffins are modeled as three lumps at each carbon
number in the model based on their degree of branching. The
situation is somewhat different for aromatics or olefins. At each
carbon number, the variation in the RONs for the aromatic
isomers is only between 5 and 10 ONs (see Figure 6), which is
not significant enough to introduce noticeable errors in the
predictions across the various process streams, especially
because the relative abundance of the individual isomers is small
and their distribution does not change appreciably either across
the process streams. The situation is similar for i-olefins, where
the ON does not change significantly depending on whether
the particular i-olefin is a mono-, di-, or trimethylolefin. In
addition, there is great difficulty in analytical speciation of these
individual isomers for most of the process streams. For streams
where such detailed information might be available, e.g.,
aromatic isomer distribution in reformates, the fact that the
isomers are always at equilibrium makes the delumping unnecessary as a single lump with an average ON of the lump
(reconciled with the equilibrium isomer distribution) would be
adequate.
On the basis of the above two criteria, we have considered a
total of 57 compositional lumps in this work to describe any
naphtha stream. These include 32 lumps for n- and i-paraffins,
6 lumps for naphthenes, 7 lumps for aromatics, 9 lumps for
olefins and cyclic olefins, and 3 lumps for oxygenates. The
lumps range from individual molecules to a group of similar
molecules at various levels of abstraction. Although the oxygenates are ON improvers, they are treated in the model similar to
all of the hydrocarbon lumps. These lumps are summarized in
Table 2.
Once the lumps have been defined, the next step is to specify
their pure-component ONs. The pure-component RONs and

MONs for most of the lumps have been chosen from the values
reported in the API-45 project.5,6 For lumps that correspond to
individual molecules, e.g., n-butane, n-pentane, etc., the purecomponent values are taken as is from ref 6, while for lumps
that correspond to a group of similar molecules such as
monomethyl-i-octanes, an average value is chosen based on the
ONs of all of the different monomethyl-i-octane isomers. Two
important trends emerge from this dataset: first, ON decreases
with the carbon number and, second, ON increases with the
degree of branching at the same carbon number. Such trends
are shown for the paraffins and aromatics in Figures 5 and 6,
respectively, where the pure-component ONs are plotted against
the number of carbon atoms in the hydrocarbon molecule. These
trends have been used to estimate the pure-component ONs of
the lumps that are not reported in ref 6. The final set of purecomponent RONs and MONs for the various molecular lumps
in the model is shown in Table 2.
4. Experimental Program
An extensive database of 1471 gasoline fuels was collected
from many naphtha process streams found in the petroleum
refinery. These include 143 alkylates, 165 cat-naphtha (FCC)
gasolines, 440 reformates, 366 hydroprocessed naphtha streams,
117 SCANfining [Selective CAtalytic Naphtha Refining, a
proprietary ExxonMobil Technology] products, 40 LSR naphthas, 13 isomerates, and 187 finished blends of these different
process streams. Fuels with oxygenates contained TAME,
MTBE, and EtOH in the range of 2-10 vol % oxygenates. Each
of these 1471 fuels was analyzed for its detailed composition
using a multitude of different GC techniques. RON and MON
were also measured on these fuels. Because the composition
was measured through multiple GC columns, each measuring
certain carbon number ranges of the composition, a thorough
data-reconciliation procedure was employed to reconcile the
analysis by the different analytical measurements. For example,
fuel samples with both the overall PIONA analysis and the
specific GC analysis (which yield detailed information in a
particular carbon number range) were checked to ensure that
the two analyses were consistent. Likewise, the compositional
information based on GC and PIONA was reconciled with the
boiling point curve wherever available. Further, many repeats

Table 2. Various Lumps Considered in the Present Octane Model along with Their Pure-Component RONs and MONs

Paraffins
n-butane
isobutane
n-pentane
i-pentane
n-hexane
C6 monomethyls
2,2-dimethylbutane
2,3-dimethylbutane
n-heptane
C7 monomethyls
C7 dimethyls
2,2,3-trimethylbutane
n-octane
C8 monomethyls
C8 dimethyls
C8 trimethyls
n-nonane
C9 monomethyls
C9 dimethyls
C9 trimethyls
n-decane
C10 monomethyls
C10 dimethyls
C10 trimethyls

RON

MON

94
102
62
92
24.8
76
91.8
105.8
0
52
93.76
112.8
-15
25
69
105
-20
15
50
100
-30
10
40
95

89.6
97.6
62.6
90.3
26
73.9
93.4
94.3
0
52
90
101.32
-20
32.3
74.5
98.8
-20
22.3
60
93
-30
10
40
87

RON

MON

Paraffins (contd.)
n-undecane
C11 monomethyl
C11 dimethyls
C11 trimethyls
n-dodecane
C12 monomethyl
C12 dimethyls
C12 trimethyls

-35
5
35
90
-40
5
30
85

-35
5
35
82
-40
5
30
80

Naphthenes
cyclopentane
cyclohexane
m-cyclopentane
C7 naphthenes
C8 naphthenes
C9 naphthenes

100
82.5
91.3
82.0
55
35

84.9
77.2
80
77
50
30

Aromatics
benzene
toluene
C8 aromatics
C9 aromatics
C10 aromatics
C11 aromatics

102.7
118
112
110
109
105

105
103.5
105
101
98
94

RON

MON

Aromatics (contd.)
C12 aromatics

102

90

Olefins/Cyclic Olefins
n-butenes
n-pentenes
i-pentenes
cyclopentene
n-hexenes
i-hexenes
total C6 cyclic olefins
total C7d
total C8d

98.7
90
103
93.3
90
100
95
90
90

82.1
77.2
82
69.7
80
83
80
78
77

Oxygenates
MTBE
TAME
EtOH

115.2
115
108

97.2
98
92.9

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Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006

Figure 5. Variation of pure-component RONs for various paraffins (adapted from ref 5).

Figure 6. Variation of pure-component RONs for various aromatics (adapted from ref 5).

were run on the RON and MON measurements of each fuel to

ensure high fidelity in the dataset.
5. Results
5.1. Parameter Estimation: Constrained Least-Squares
Formulation. A constrained least-squares minimization problem
was solved using the Levenberg-Marquadt algorithm in order
to regress the parameters of the model. The adjustable parameters were allowed to vary between a lower bound of 0 and

an upper bound of 10. Although, in principle, may be <0,

the restriction of g 0 was necessary to avoid singularity in
eq 11. Softer constraints in the form of inequality constraints
were also employed to ensure that did not vary arbitrarily
with the carbon number within the same molecular class but
rather maintained the directional trend with the carbon number
and branching as shown previously in Figures 5 and 6.
The experimental dataset was partitioned into a training set
(90% of the samples) and a testing set (10% of the samples),
and many such partitions (total partitions considered ) 200)

Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 343

Figure 7. Model predictions for RONs for various process streams and blends. N ) number of samples. SE ) standard error.
Table 3. Parameter Values
molecular class

molecular lumps

(RON)

(MON)

n-paraffins
i-paraffins
naphthenes
aromatics
olefins/cyclic olefins
oxygenates
interaction parameters

nC4-nC12
C4-C12 mono-, di-, and trimethyl-i-paraffins
C5-C9 naphthenes
benzene-C12 aromatics
C4-C12 linear, branched, and cyclic olefins
MTBE, EtOH, TAME
(b)
(a)
(b)
k(a)
PN, kPN, kPO, kPO

2.0559
2.0204
1.6870
3.3984
8.9390
3.9743
0.2, 2.4, 0.4, 3.6

0.3092
0.4278
0.2821
0.4773
10.0000
2.0727
0.2, 2.4, 0.4, 3.6

were considered to ensure the robustness of the parameter

estimates. Many different initial guesses were assumed and the
parameters reoptimized to ensure that the optimization problem
was not trapped in an inferior local solution. Sensitivity analysis
in the form of a local perturbation of the parameters was also
performed to see whether the parameters returned to the same
optimal or not.
Although the final set of parameter values () for all of the
individual molecular lumps used in this model cannot be
disclosed in the publication for proprietary reasons, the average
values of these parameters, grouped by P, I, O, N, and A classes,
are reported in Table 3. Also included in the table (last row)
are the four interaction parameters used in the model. The results
based on these average parameter values are satisfactory, though
we may point out that the use of individual values for the
different molecular lumps enhances model predictions. The
results presented below are based on the individual parameters.
5.2. Prediction Statistics. The results of the model are shown
in Figures 7 and 8 for both RON and MON across the 1471
gasoline fuels. The plots summarize not only the overall
performance of the model but also the performance across the
individual process streams. The overall standard errors (SEs)
defined as x(meas - pred)2/n for RON and MON are 1.01
and 1.05 numbers, respectively, on all of these process streams

Table 4. Model Performance across Various Process Streams

RON
total
alkylates
cat-naphthas
reformates
hydroprocessed naphtha
products
SCANfining products
LSR naphtha
isomerates
process blends

MON

SE

st dev

SE

st dev

1.0194
0.8822
0.6732
0.8869
1.2359

1.0296
0.9122
0.6065
0.9115
1.2352

1.0572
0.6935
0.5468
0.9132
1.1718

1.0263
0.6505
0.5846
0.9889
1.1094

1.2188
1.4531
0.7683
0.9095

1.2278
1.3800
0.6734
0.9104

1.1926
1.3921
0.7522
1.3255

1.1033
1.2598
0.2977
1.2048

and blends. The individual SE and the standard deviation are

summarized in Table 4. The FCC gasoline fuels are predicted
with the highest accuracy (SE ) 0.67), while the predictions
on the straight-run fuels have the highest error (SE ) 1.45)
relative to other process streams. The higher relative error is
due to the higher measurement error in the ONs of straight-run
naphtha fuels, which have octanes in the range of 40-70
numbers where the octane test itself is less than satisfactory.
The process blends, many of which have 2-10 vol % oxygenates, are also predicted quantitatively, suggesting that the model
structure is sufficient to capture the effect of oxygenates on the
gasoline fuel. The prediction results on all of the process streams

344

Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006

Figure 8. Model predictions for MONs for various process streams and blends. N ) number of samples. SE ) standard error.
Table 5. Comparison of Model Predictions with and without Data
Reconciliation of the Measured Composition
SE (Standard Error)

Figure 9. Error distribution for RON across the various samples.

and their blends are within the measurement error; therefore, it

is unlikely that the average error can be further reduced for a
model that spans such a diverse set of naphtha fuels.
An important requirement of any regression model is that its
predictions are unbiased with respect to its inputs. To ensure
this, the frequency distribution of the model errors is plotted in
Figure 9. The abscissa in the figure represents the error level in
the model predictions, while the ordinate represents the number
of fuels predicted at these various error levels. Approximately
75% of the samples are predicted within (1.0 ON, 93% ()75
+ 18) are predicted within (2.0 ON, and 99% of the samples
are predicted within (3.0 ON. The frequency distribution of
Figure 9 closely resembles a normal distribution, suggesting
that the model is independent of any inherent bias. Further, the
plot of the prediction error against each of the compositional
lumps also revealed no directional trend of the composition with
the model error.
5.3. Independent Model Validation and Prediction Improvement via Data Reconciliation. To test the pure predictive
capabilities of the model, an independent dataset comprising

refinery 1
refinery 2
refinery 3
refinery 4
refinery 5
refinery 6
refinery 7

model predictions
(using the measured
composition as is)

model predictions
(using autotuned
compositions)

0.9105
0.5457
0.7016
1.0197
1.1686
0.7850
1.2074

0.8444
0.4482
0.7069
1.0085
1.1682
0.7833
0.8436

many commercial gasoline fuels from seven different refineries

worldwide was collected. The gasoline fuels collected were
blends of various refinery process streams such as alkylates,
reformates, FCC-naphtha, and so on. The individual process
streams are therefore the blend components of the final
gasoline blend. On each individual blend component, the
composition was measured using a combination of GCs along
with RON and MON. In addition, some bulk properties such
as gravity and the boiling point curve were also measured. On
the final gasoline blends, only RON and MON were measured.
On the basis of the measured composition of the blend
components and using the blend recipe (i.e., the volumetric ratios
of how the components were blended), the composition of the
final gasoline blend was calculated and RON and MON were
predicted using eq 11. A comparison of the model predictions
against the measured RON for these fuels is shown in the first
column of Table 5. The results are segmented based on the
performance in each individual refinery. The table shows that,
on average, the model predicts all of the data with a SE of (0.9
number, which is within the experimental error of the different

Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 345

measurements, thus providing credence to the robustness and

reliability of the model. Similar results are obtained for MON
as well.
However, a part of the error in the model predictions
originates from the error in measuring the composition itself
and the elimination of which might improve the model predictions. We will use a data-reconciliation formulation, which we
call autotuning, to eliminate this error contribution. Autotuning,
described in eq 12, attempts to make minimal changes in the
measured composition subject to the constraints that target
measured properties are matched exactly or very closely
approximated within an  tolerance, where  is a very small
number, g0.

min
w

w - wmeasured
wmeasured

s.t.
Pj -  e Pj(w) e Pj + 

j ) 1, ..., m

(12)

wi ) 1

wg0
In eq 12, wmeasured is the vector of raw measured composition
from the GC, w the autotuned composition reconciled to a
number of different measured properties, and Pj the various
target measured properties. Because the formulation of eq 12
results in a highly underdetermined set of equations, the choice
of the number and type of property constraints is important to
obtain a better autotuned composition. The following property
constraints were used in this work: (a) RON, (b) MON, (c)
gravity at 60 F, (d) total paraffin/i-paraffin ratio, (e) total
olefins, and (f) boiling point curve. The results based on the
autotuned compositions of the blend components are shown in
the second column of Table 5. Remarkably, using an autotuned
composition consistently improves the ON predictions for the
gasoline blends across all of the seven refineries. On average,
the SE improved from (0.9 numbers to (0.8 numbers. This
improvement may seem marginal, but even a 0.1 number
improvement in the prediction error below a (1 number has a
significant economic consequence.
6. Conclusions
We have developed a composition-based predictive model
for both RON and MON that can be universally applied across
a wide variety of gasoline fuels derived from different naphtha
process streams and blends. Each gasoline fuel is compositionally represented by 57 different molecular lumps and by a
combination of different GCs and correlated to the ON. The
model structure permits a wide range of composition extrapolation from pure components to real gasoline blends. Its predictions are within a SE of (1 number for both RON and MON
across the multitude of gasoline fuels. The model is applicable
for a broad range of ONs from 30 to 120. Further improvements

in the model predictions are demonstrated using a datareconciliation algorithm used in tandem with the predictive
model.
Acknowledgment
We express our appreciation to N. L. Avery, D. I. Hoel, M.
R. Apelian, K. D. Rose, R. J. Quann, and C. R. Kennedy for
their many helpful discussions and suggestions.
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ReceiVed for reView July 11, 2005

ReVised manuscript receiVed October 10, 2005
Accepted October 14, 2005
IE050811H