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

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. Depend-
ing 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 mathemati-
cally 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.
10.1021/ie050811h CCC: $33.50 © 2006 American Chemical Society
Published on Web 11/24/2005
and branched i-paraffins have higher ONs than the correspond-
ing paraffins. In the middle 1950s, the American Petroleum
Institute (API) Research Project 455-7 analyzed the pure-
component 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 pure-
component 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
338 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 varia-
tions 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 catego-
ries: first, predicting the ON of individual hydrocarbon
molecules in gasoline by correlating molecular structure descrip-
tors 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 math-
ematical 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 col-
lectively 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 tradition-
ally 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 today’s 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),
and the corresponding blend octane numbers (BON ON
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 pure-
component octane number to the gasoline fuel, each molecule’s
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 volume-
blended 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 ap-
proximated as a linear function of the gasoline ON. Therefore
) a(0)
BON i + ai (ON)
(1)
i (2)
Equation 2 is analogous to the equation for any partial molar
property, where the partial molar property (BON i ) depends on
the composition of the gasoline fuel it blends into. BON i is
parametrized by two parameters, a slope a(1) i and an intercept
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.

Figure 2. Variation of blending ON of n-paraffins in different refinery
naphtha fuels.
Although eq 2 requires two parameters, a(0) i and a(1)
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
ONi ) a(0)
i + ai (ONi) w ai ) (1 - ai )ONi
(1) (0) (1)
(3)
If we define βi ) 1 - a(1)
i , eq 2 may be rewritten as
i ) βiONi
a(0) (4)
Rearranging eqs 1, 2, and 4, we get
∑i ViβiONi lumps
∑ ViβiONi
ON ) ) (5)
∑i Viβi ∑ Viβi
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.
βi’s are the adjustable parameters and represent whether a
molecule contributes beneficially or detrimentally to the ON
Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 339
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 contribu-
tion is detrimental if BON < ONi. For the two cases (a) βi < 1
i
and ONi < ON or (b) βi > 1 and ONi > ON, the lump i
contributes beneficially to the fuel ON. For the other two cases
(a) βi > 1 and ONi < ON or (b) βi < 1 and ONi > ON, it
contributes detrimentally to the fuel ON. βi ) 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 pure-
component 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.
( V1β1
) V2β2
( )
ON1 e ON ) ON1 + ON2 e
V1β1 + V2β2 V1β1 + V2β2
ON2 (6)
340 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:

12 V2V1
k(a)
y) (7)
1 + k(b)
12 V2

where k(a) (b)

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.

12 V2V1
k(a) + 13 V3V1
k(a) + 23 V2V3
k(a)
y) (8) Using eqs 2-4 in eq 9 and rearranging the various terms, we
1+ 12 V2 +
k(b) 13 V3 +
k(b) 23 V3
k(b) get

Equation 8 has six interaction parameters: k(a) (b)

12 and k12 for the
1-2 interaction, k13 and k13 for the 1-3 interaction, and k(a)
(a) (b)
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
∑ ViβiONi + IP∑P ViβiONi
PONA
ON ) (11)
∑ Viβi + IP(∑P Viβi - ∑P Vi)
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 dif-

( )
ferentiate the lump for most of the process streams. For instance,
PNVN + kPOVO
k(a) (a) it is possible to analytically measure the different aromatics by
ON ) ∑ ViBON
i + ∑P VjBON
j (9) carbon number for most of the naphtha process streams by
PONA 1+ PNVN +
k(b) POVO
k(b) 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,
where VN and VO represent the total naphthenes and olefins in for the aromatics, our lump definition has been restricted to
the gasoline sample. Mathematically, VN ) ∑i∈naphthenesVi and total aromatics by carbon number only.
VO ) ∑i∈olefinsVi. Note that in eq 9, while the first sum runs over (b) ON Differentiation. When analytical differentiation is
P, O, N, and A (i.e., paraffins, olefins, naphthenes, and possible across similar molecular lumps, we have defined
aromatics) molecules, the second sum runs only over the separate lumps only if their ONs are widely different and their
paraffinic molecules. If the interaction term is denoted by I, eq relative distributions differ across various process streams. For
9 may be more succinctly rewritten as example, we consider separate lumps for mono-, di-, and
trimethyl-i-paraffins at each carbon number as opposed to a
ON ) ∑
PONA
(1 + Ii)ViBON
i (10) 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
where

[( ]
different across different naphtha streams. Figure 4 plots the

)
pure-component ONs of all of the i-octane isomers and shows
PNVN + kPOVO
k(a) (a)
that, depending upon the particular isomer of i-octane, whether
for i ∈ P it is a mono-, di-, or trimethyl isomer, its ON could vary between
Ii ) 1 + k(b)
PNVN + kPOVO
(b)
25 and 100 numbers. The relative distribution of these isomers
0 otherwise 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 MONs for most of the lumps have been chosen from the values
i-Octanes reported in the API-45 project.5,6 For lumps that correspond to
stream type monomethyls dimethyls trimethyls individual molecules, e.g., n-butane, n-pentane, etc., the pure-
alkylates 0 18.5 81.5 component values are taken as is from ref 6, while for lumps
reformates 68.9 31.1 0 that correspond to a group of similar molecules such as
monomethyl-i-octanes, an average value is chosen based on the
in Table 1 for alkylates and reformates. Trimethyl-i-octanes
ONs of all of the different monomethyl-i-octane isomers. Two
dominate C8 i-paraffins in alkylates, whereas monomethyl-i-
important trends emerge from this dataset: first, ON decreases
octanes dominate C8 i-paraffins in reformates. The observations
with the carbon number and, second, ON increases with the
reported for i-octane are also true for other i-paraffins. Conse-
degree of branching at the same carbon number. Such trends
quently, i-paraffins are modeled as three lumps at each carbon
are shown for the paraffins and aromatics in Figures 5 and 6,
number in the model based on their degree of branching. The
respectively, where the pure-component ONs are plotted against
situation is somewhat different for aromatics or olefins. At each
the number of carbon atoms in the hydrocarbon molecule. These
carbon number, the variation in the RONs for the aromatic
trends have been used to estimate the pure-component ONs of
isomers is only between 5 and 10 ONs (see Figure 6), which is
the lumps that are not reported in ref 6. The final set of pure-
not significant enough to introduce noticeable errors in the
component RONs and MONs for the various molecular lumps
predictions across the various process streams, especially
in the model is shown in Table 2.
because the relative abundance of the individual isomers is small
and their distribution does not change appreciably either across
4. Experimental Program
the process streams. The situation is similar for i-olefins, where
the ON does not change significantly depending on whether An extensive database of 1471 gasoline fuels was collected
the particular i-olefin is a mono-, di-, or trimethylolefin. In from many naphtha process streams found in the petroleum
addition, there is great difficulty in analytical speciation of these refinery. These include 143 alkylates, 165 cat-naphtha (FCC)
individual isomers for most of the process streams. For streams gasolines, 440 reformates, 366 hydroprocessed naphtha streams,
where such detailed information might be available, e.g., 117 SCANfining [Selective CAtalytic Naphtha Refining, a
aromatic isomer distribution in reformates, the fact that the proprietary ExxonMobil Technology] products, 40 LSR naph-
isomers are always at equilibrium makes the delumping un- thas, 13 isomerates, and 187 finished blends of these different
necessary as a single lump with an average ON of the lump process streams. Fuels with oxygenates contained TAME,
(reconciled with the equilibrium isomer distribution) would be MTBE, and EtOH in the range of 2-10 vol % oxygenates. Each
adequate. of these 1471 fuels was analyzed for its detailed composition
On the basis of the above two criteria, we have considered a using a multitude of different GC techniques. RON and MON
total of 57 compositional lumps in this work to describe any were also measured on these fuels. Because the composition
naphtha stream. These include 32 lumps for n- and i-paraffins, was measured through multiple GC columns, each measuring
6 lumps for naphthenes, 7 lumps for aromatics, 9 lumps for certain carbon number ranges of the composition, a thorough
olefins and cyclic olefins, and 3 lumps for oxygenates. The data-reconciliation procedure was employed to reconcile the
lumps range from individual molecules to a group of similar analysis by the different analytical measurements. For example,
molecules at various levels of abstraction. Although the oxygen- fuel samples with both the overall PIONA analysis and the
ates are ON improvers, they are treated in the model similar to specific GC analysis (which yield detailed information in a
all of the hydrocarbon lumps. These lumps are summarized in particular carbon number range) were checked to ensure that
Table 2. the two analyses were consistent. Likewise, the compositional
Once the lumps have been defined, the next step is to specify information based on GC and PIONA was reconciled with the
their pure-component ONs. The pure-component RONs and 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
RON MON RON MON RON MON
Paraffins Paraffins (cont’d.) Aromatics (cont’d.)
n-butane 94 89.6 n-undecane -35 -35 C12 aromatics 102 90
isobutane 102 97.6 C11 monomethyl 5 5
n-pentane 62 62.6 C11 dimethyls 35 35 Olefins/Cyclic Olefins
i-pentane 92 90.3 C11 trimethyls 90 82 n-butenes 98.7 82.1
n-hexane 24.8 26 n-dodecane -40 -40 n-pentenes 90 77.2
C6 monomethyls 76 73.9 C12 monomethyl 5 5 i-pentenes 103 82
2,2-dimethylbutane 91.8 93.4 C12 dimethyls 30 30 cyclopentene 93.3 69.7
2,3-dimethylbutane 105.8 94.3 C12 trimethyls 85 80 n-hexenes 90 80
n-heptane 0 0 i-hexenes 100 83
C7 monomethyls 52 52 Naphthenes total C6 cyclic olefins 95 80
C7 dimethyls 93.76 90 cyclopentane 100 84.9 total C7d 90 78
2,2,3-trimethylbutane 112.8 101.32 cyclohexane 82.5 77.2 total C8d 90 77
n-octane -15 -20 m-cyclopentane 91.3 80
C8 monomethyls 25 32.3 C7 naphthenes 82.0 77 Oxygenates
C8 dimethyls 69 74.5 C8 naphthenes 55 50 MTBE 115.2 97.2
C8 trimethyls 105 98.8 C9 naphthenes 35 30 TAME 115 98
n-nonane -20 -20 EtOH 108 92.9
C9 monomethyls 15 22.3 Aromatics
C9 dimethyls 50 60 benzene 102.7 105
C9 trimethyls 100 93 toluene 118 103.5
n-decane -30 -30 C8 aromatics 112 105
C10 monomethyls 10 10 C9 aromatics 110 101
C10 dimethyls 40 40 C10 aromatics 109 98
C10 trimethyls 95 87 C11 aromatics 105 94
342 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 param-
eters β were allowed to vary between a lower bound of 0 and
an upper bound of 10. Although, in principle, β may be <0,
the restriction of β g 0 was necessary to avoid singularity in
eq 11. Softer constraints in the form of inequality constraints
were also employed to ensure that β 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 β(RON) β(MON)
n-paraffins nC4-nC12 2.0559 0.3092
i-paraffins C4-C12 mono-, di-, and trimethyl-i-paraffins 2.0204 0.4278
naphthenes C5-C9 naphthenes 1.6870 0.2821
aromatics benzene-C12 aromatics 3.3984 0.4773
olefins/cyclic olefins C4-C12 linear, branched, and cyclic olefins 8.9390 10.0000
oxygenates MTBE, EtOH, TAME 3.9743 2.0727
interaction parameters k(a) (b) (a) (b)
PN, kPN, kPO, kPO
0.2, 2.4, 0.4, 3.6 0.2, 2.4, 0.4, 3.6

Table 4. Model Performance across Various Process Streams

were considered to ensure the robustness of the parameter
estimates. Many different initial guesses were assumed and the RON MON
parameters reoptimized to ensure that the optimization problem SE st dev SE st dev
was not trapped in an inferior local solution. Sensitivity analysis total 1.0194 1.0296 1.0572 1.0263
in the form of a local perturbation of the parameters was also alkylates 0.8822 0.9122 0.6935 0.6505
performed to see whether the parameters returned to the same cat-naphthas 0.6732 0.6065 0.5468 0.5846
optimal or not. reformates 0.8869 0.9115 0.9132 0.9889
hydroprocessed naphtha 1.2359 1.2352 1.1718 1.1094
Although the final set of parameter values (β) for all of the products
individual molecular lumps used in this model cannot be SCANfining products 1.2188 1.2278 1.1926 1.1033
disclosed in the publication for proprietary reasons, the average LSR naphtha 1.4531 1.3800 1.3921 1.2598
values of these parameters, grouped by P, I, O, N, and A classes, isomerates 0.7683 0.6734 0.7522 0.2977
are reported in Table 3. Also included in the table (last row) process blends 0.9095 0.9104 1.3255 1.2048
are the four interaction parameters used in the model. The results and blends. The individual SE and the standard deviation are
based on these average parameter values are satisfactory, though summarized in Table 4. The FCC gasoline fuels are predicted
we may point out that the use of individual β values for the with the highest accuracy (SE ) 0.67), while the predictions
different molecular lumps enhances model predictions. The on the straight-run fuels have the highest error (SE ) 1.45)
results presented below are based on the individual β parameters. relative to other process streams. The higher relative error is
5.2. Prediction Statistics. The results of the model are shown due to the higher measurement error in the ONs of straight-run
in Figures 7 and 8 for both RON and MON across the 1471 naphtha fuels, which have octanes in the range of 40-70
gasoline fuels. The plots summarize not only the overall numbers where the octane test itself is less than satisfactory.
performance of the model but also the performance across the The process blends, many of which have 2-10 vol % oxygen-
individual process streams. The overall standard errors (SEs) ates, are also predicted quantitatively, suggesting that the model
defined as xΣ(meas - pred)2/n for RON and MON are 1.01 structure is sufficient to capture the effect of oxygenates on the
and 1.05 numbers, respectively, on all of these process streams 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)
model predictions model predictions
(using the measured (using autotuned
composition “as is”) compositions)
refinery 1 0.9105 0.8444
refinery 2 0.5457 0.4482
refinery 3 0.7016 0.7069
refinery 4 1.0197 1.0085
refinery 5 1.1686 1.1682
refinery 6 0.7850 0.7833
refinery 7 1.2074 0.8436
Figure 9. Error distribution for RON across the various samples.
many commercial gasoline fuels from seven different refineries
and their blends are within the measurement error; therefore, it worldwide was collected. The gasoline fuels collected were
is unlikely that the average error can be further reduced for a
blends of various refinery process streams such as alkylates,
model that spans such a diverse set of naphtha fuels.
reformates, FCC-naphtha, and so on. The individual process
An important requirement of any regression model is that its
streams are therefore the “blend components” of the final
predictions are unbiased with respect to its inputs. To ensure
gasoline blend. On each individual blend component, the
this, the frequency distribution of the model errors is plotted in
composition was measured using a combination of GCs along
Figure 9. The abscissa in the figure represents the error level in
with RON and MON. In addition, some bulk properties such
the model predictions, while the ordinate represents the number
of fuels predicted at these various error levels. Approximately as gravity and the boiling point curve were also measured. On
75% of the samples are predicted within (1.0 ON, 93% ()75 the final gasoline blends, only RON and MON were measured.
+ 18) are predicted within (2.0 ON, and 99% of the samples On the basis of the measured composition of the blend
are predicted within (3.0 ON. The frequency distribution of components and using the blend recipe (i.e., the volumetric ratios
Figure 9 closely resembles a normal distribution, suggesting of how the components were blended), the composition of the
that the model is independent of any inherent bias. Further, the final gasoline blend was calculated and RON and MON were
plot of the prediction error against each of the compositional predicted using eq 11. A comparison of the model predictions
lumps also revealed no directional trend of the composition with against the measured RON for these fuels is shown in the first
the model error. column of Table 5. The results are segmented based on the
5.3. Independent Model Validation and Prediction Im- performance in each individual refinery. The table shows that,
provement via Data Reconciliation. To test the pure predictive on average, the model predicts all of the data with a SE of (0.9
capabilities of the model, an independent dataset comprising number, which is within the experimental error of the different

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 predic-
tions. 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.
( )
w - wmeasured 2 Society for Testing and Materials Test Method D2700; American Society
min
w 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 composition-
ally 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 extrapola-
tion from pure components to real gasoline blends. Its predic-
tions 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
Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 345
in the model predictions are demonstrated using a data-
reconciliation 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
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