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346 Ind. Eng. Chem. Res.

2006, 45, 346-351

Detailed Composition-Based Model for Predicting the Cetane Number of Diesel


Fuels
Prasenjeet Ghosh* and Stephen B. Jaffe†
Compositional Modeling Group, ExxonMobil Process Research Laboratories, Paulsboro Technical Center,
Paulsboro, New Jersey 08066

We have developed a simple composition-based model for predicting the cetane number of diesel fuels with
general applicability to any diesel fuel regardless of the refining process it originates from. The cetane number
is correlated to a total of 129 different hydrocarbon lumps determined by a combination of supercritical fluid
chromatography, gas chromatography, and mass spectroscopic methods. A total of 203 diesel fuels are
considered in this study derived from various diesel-range refinery process streams and their commercial
blends. Across the multitude of such process streams and blends, the model predicts the cetane number with
a standard error of 1.25 numbers, which is well within the experimental error of the measurement.

1. Introduction injection system, and a computer that is used to control the


Cetane number (CN) is a measure of the ignition quality of experiment, record the data, and provide interpretation of the
the diesel fuel and is determined by a standard engine test as data. The basic concept of the IQT is the measurement of the
specified by ASTM (ASTM D613).1 The ignition quality is time from the start of fuel injection into the combustion chamber
quantified by measuring the ignition delay, which is the period to the start of combustion. The thermodynamic conditions in
between the time of injection and the start of combustion the combustion chamber are influenced by the charge pressure
(ignition) of the fuel. A fuel with a high CN has a short ignition (combustion air), chamber temperature, and fuel injection
delay period and starts to combust shortly after it is injected quantity. These conditions are precisely controlled to provide
into an engine. The ignition quality of the diesel fuel depends consistent measurement of the ignition delay time. The measured
on its molecular composition. Some of the simpler molecular ignition delay time is correlated by an equation to a derived
components such as the n-paraffins can ignite in a diesel engine CN. We call it deriVed to highlight the fact that the CN was
with relative ease, but others like aromatics have more stable not measured in the actual ASTM engine. However, in terms
ring structures that require higher temperature and pressure to of actual numbers, the IQT-based derived CN is the same as
ignite. what we would have measured if we had run the fuel through
The ASTM D6131 test method defines the CN of a diesel the actual ASTM engine. The reproducibility errors on IQT-
fuel as the percentage by volume of normal cetane (C16H34), in based derived CN are tighter than the those of ASTM D613
a blend with 2,2,4,4,6,8,8-heptamethylnonane (sometimes called and vary between 1 and 2 numbers. The present work is
HMN or isocetane), which matches the ignition quality of the therefore based on IQT measurements on the various diesel fuels
diesel fuel being rated under the specified test conditions. By and their commercial blends.
definition, normal cetane has been assigned a CN of 100, Numerous attempts have been made in the past to correlate
whereas HMN has a CN of 15. The ASTM D613 method the CN with various physical and chemical attributes of the
involves running the fuel in a single-cylinder compression- diesel fuel. These include correlations based on either bulk
ignition engine with a continuously variable compression ratio properties such as API gravity, boiling points, and aniline points
under a fixed set of conditions. Although it has been the or based on molecular composition, measured by gas chroma-
traditional test method for CN, it was soon recognized that the tography (GC)2 or inferred from different spectroscopic methods
test suffered from many disadvantages, some of which include such as Fourier transform infrared spectroscopy, nuclear mag-
a relatively large fuel sample volume requirement (∼1 L), netic resonance (1H NMR, 13C NMR), etc. An exhaustive com-
significant time consumption (approximately a few hours), and pilation of the correlations based on bulk properties can be found
a relatively high reproducibility error. ASTM documents a in ref 3, among which the most commonly used correlation is
maximum reproducibility error of 3-4 numbers for this test.1 the ASTM D47374,5 equation. The D4737 equation correlates
Consequently, there have been many attempts to develop the API gravity and the T10, T50, and T90 points on the boiling
alternate tests to replace the ASTM D613 method. These include curve to the CN of the fuel and is summarized in eq 1
devising better engine tests and developing correlative models
to predict the CN from bulk properties of the fuel that may be CN ) 45.2 + 0.0892T10N + (0.131 + 0.901BN)T50N +
measured more quickly and reliably. Among the different engine (0.0523 - 0.42BN)T90N + [0.00049(T10N2 - T90N2)] +
tests developed, the Ignition Quality Tester (IQT) has been the
most promising for reliable measurement of CNs of middle 107BN + 60BN2 (1)
distillates and alternate fuels. It uses much smaller sample
volumes (<50 mL) and requires much shorter times (<10 min) where d ) specific gravity at 60 °F, BN ) e-3.5(d-0.85) - 1,
for completion of the test. The IQT consists of a constant- T10N ) T10 - 215, T50N ) T50 - 260, T90N ) T90 - 310, and
volume combustion chamber that is electrically heated, a fuel Tx is the temperature (in °C) at which x vol % of the sample
has distilled off. Despite its empirical nature, this equation has
* To whom correspondence should be addressed. E-mail: enjoyed enviable success in describing the CN of various diesel
prasenjeet.ghosh@exxonmobil.com. fuels and their blends and is used extensively within the
† petroleum industry. However, with the increasing trends toward
E-mail: stephen.b.jaffe@exxonmobil.com.

10.1021/ie0508132 CCC: $33.50 © 2006 American Chemical Society


Published on Web 11/24/2005
Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 347

low sulfur diesel fuels and the addition of cetane improvers in


the fuel, the results of this equation have become progressively
less satisfactory, and newer and better models are sought. In
contrast to bulk property correlations, many predictive models
based on molecular composition have also been proposed to
predict CN. These include models based on NMR6-8 and FTIR9
spectra and the molecular composition measured by a combina-
tion of liquid chromatography and GC-mass spectroscopy (MS)
techniques.2,10,11 Although composition-based, most of these
models are linear (and occasionally nonlinear) principal com-
ponent regression models and do show encouraging results in
predicting CN. However, the lack of a phenomenologically
motivated mathematical structure for the functional form and
the assumption of linearity (in most cases) make such models
inadequate for extrapolation. Further, these models are typically
refinery or application specific and require frequent updating,
thus restrictive in their application for any diesel fuel. Figure 1. Schematic showing the difference between cetane number of
the diesel fuel (CN), pure-component cetane numbers (CNA and CNB), and
The underlying common thesis of all of the above models is
the corresponding blend cetane numbers (B CN CN
A and B B ) for a typical
the implicit or partial acknowledgment of the molecular binary blend. Notice that the blend numbers are obtained by extrapolating
composition of the diesel fuel, whether it is through density, the tangent to the cetane curve to the pure-component limit.
the boiling curves, or the NMR and FTIR spectra. Because CN
depends on the molecular composition of the fuel, we believe Equation 3 is analogous to the equation for any partial molar
that an explicit and complete acknowledgment of the detailed property, where the partial molar property (B CN i ) depends on
molecular composition is necessary to build a predictive model. the composition of the diesel fuel it blends into. B CN i is
This is a prerequisite to make the model quantitatively superior parametrized by two parameters, a slope a (1) i and an intercept
and robust in its predictions, especially when used in extrapola- a (0)
i , thereby implying a linear variation of blend values with
tion. Our objective in this study is to develop such a predictive diesel composition. Equation 3 is based on the experimental
model as a function of the molecular composition of the fuel. observation made for octane numbers and gasoline fuels in our
This model would be used to support various product quality laboratory and by analogy extended for CNs.13-15 For instance,
predictions for diesel fuels in ExxonMobil’s refineries world- in ref 14, it was shown that the blend numbers of various
wide. Because the model depends purely on composition, it n-paraffins varied almost linearly with the overall octane number
would also be integrated into our existing network of detailed of the gasoline fuel. Because both octane numbers and CNs
process kinetic models.12 It will also be used in identifying the are dictated by similar combustion chemistries (autoignition
important hydrocarbon molecules that have a significant impact reactions) of the fuel, we believe that the observations for one
on the diesel fuel quality and that are important for meeting may be extended to the other.
future transportation fuel specifications. The details of such a Although the variation of the blend value of the individual
model development are presented in the next section. molecules with the CN of the diesel fuel is taken to be linear,
this does not imply a linear relationship of the fuel composition
2. Development of the Cetane Model
to its CN. Using the definition for CN from eq 2 in eq 3, it is
The development of the cetane model is analogous to that of easy to see that eq 3 captures multicomponent interaction.
the octane model for gasoline fuels reported in ref 13. Each
Equation 3 requires two parameters, a (0) i and a (1)
i , for each
diesel fuel, regardless of the process stream (e.g., kero cut, heavy
molecule; however, it is possible to eliminate one of these
cat naphtha, light cycle oil, heavy gas oil, etc.) is a mixture of
parameters using the special case when the diesel fuel is a pure
many hydrocarbon molecules, each contributing to the CN of
component. For instance, if the diesel fuel is pure n-cetane, then
the diesel fuel. Let CN denote the measured cetane number for
the CN of the fuel is the same as the pure-component number
the diesel fuel while CNi represent the pure-component cetane
for n-cetane, which, in turn, is the same as its blend value. This
number of each molecule i in the fuel. Because a molecule i
boundary condition is necessary to ensure that the model returns
may not necessarily always contribute its pure-component cetane
the pure-component value when the fuel is a pure-component
number to the diesel fuel, each molecule’s contribution toward
stream. Application of this boundary condition yields
the fuel cetane number is quantified by its blend value, denoted
by B CN
i . The blend value of a molecule depends on the overall CNi ) a (0)
i + a i CNi w a i ) (1 - a i )CNi
(1) (0) (1)
(4)
composition of the fuel it is part of. Figure 1 shows the
difference between CNi and B CN i using the example of a binary Further, if we define βi ) 1 - a (1)
i , eq 4 may be rewritten as
blend. By definition, CN is a linear volumetric blend of the
blend contributions of all of the different molecules present in
i ) βiCNi
a (0) (5)
the diesel fuel; thus, it follows that

∑i Vi B CN
Rearranging eqs 2, 3, and 5, we get
CN ) i (2)
∑i Vi βiCNi lumps
∑ Vi βiCNi
where Vi is the volume fraction of molecule i in the fuel. We CN ) ) (6)
assume that the blend value (B CN
i ) of molecule i in a diesel fuel
varies linearly with the diesel CN. Therefore, ∑i Vi βi ∑
lumps
Vi βi

i ) a i + a i CN
B CN (0) (1)
(3) This is the final form of the cetane prediction model, where the
348 Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006

summation index i runs over all of the molecules present in the Table 1. Various Molecular Lumps Considered in the Cetane Model
diesel fuel. However, a typical diesel fuel contains innumerable molecular class carbon number range
different hydrocarbon molecules. Therefore, some amount of n-paraffins nC5 to nC16+
molecular lumping is necessary to build any realistic model. monobranched i-paraffins iC5 to iC25+
This is reflected in the second part of eq 6, where we replace multibranched i-paraffins iC5 to iC25+
the summing variable i with “lumps” to indicate that the sum alkylcyclohexanes cyclohexane to C10+ cyclohexanes
runs over only the molecular lumps relevant for the cetane decalins decalin to C4+ decalins
naphthalenes naphthalene to C13+ naphthalenes
model. A lump defines the compositional level of abstraction alkylbenzenes benzene to C14+ benzenes
that the model uses. It could be a single molecule like n-cetane tetralins tetralin to C15+ tetralins
or a group of similar molecules such as C18 i-paraffins. Note olefins C5 to C18+ olefins
that, in light of this lumping, the term pure-component CN for
lump i may not always necessarily reflect the CN of a single Table 2. Pure-Component CN for the Various Lumps Considered in
molecule. For molecular lumps that correspond to single the Modela
molecules, CNi is the pure-component CN of that single lump CNi lump CNi lump CNi
molecule, but for molecular lumps that correspond to a group
nC5 31.72 multi-iC18 60 benzene 10.7
of similar molecules, CNi is the average of the pure-component nC6 39.97 multi-iC19 60 C1 benzene 2.6
CNs of all of the different molecules in that lump. These lumps nC7 54.61 multi-iC20 60 C2 benzene 7.4
are described in greater detail in the next section. nC8 61.56 multi-iC21 60 C3 benzene 7.6
βi’s are the adjustable parameters of the model and represent nC9 85.4 multi-iC22 62 C4 benzene 10
whether a molecule contributes beneficially or detrimentally to nC10 80.91 multi-iC23 64 C5 benzene 9
nC11 84.74 multi-iC24 65 C6 benzene 9
the CN of the diesel fuel. A contribution is considered beneficial nC12 83.15 multi-iC25+ 70 C7 benzene 37.5
if the blend value of the molecule/lump (B CN i ) is greater than nC13 88 C8 benzene 39.2
its pure-component cetane number (CNi). Likewise, the con- nC14 100.4 C9 benzene 50.1
nC15 96.3 cyclohexane 18.5 C10 benzene 56.8
tribution is detrimental if B CN
i < CNi. For the two cases (a) βi nC16+ 100 C1 cyclohexane 24.9 C11 benzene 56.3
< 1 and CNi < CN and (b) βi > 1 and CNi > CN, the lump i C2 cyclohexane 34.1 C12 benzene 62.8
contributes beneficially to the fuel CN. For the other two cases, mono-iC5 25 C3 cyclohexane 40 C13 benzene 50.5
(a) βi > 1 and CNi < CN and (b) βi < 1 and CNi > CN, it mono-iC6 29.5 C4 cyclohexane 61.8 C14+ benzene 40
contributes detrimentally to the fuel CN. βi ) 1 is the special mono-iC7 33.4 C5 cyclohexane 62
mono-iC8 41.9 C6 cyclohexane 64.5 tetralin 11.7
case where the lump contributes equally to its pure-component mono-iC9 42 C7 cyclohexane 78.5 C1 tetralin 6.7
CN. mono-iC10 47.3 C8 cyclohexane 83.7 C2 tetralin 3.5
The model depicted in eq 6 is simple and demonstrates the mono-iC11 48 C9 cyclohexane 90 C3 tetralin 7.9
contribution of each molecular lump toward the fuel CN. Its mono-iC12 50 C10+ cyclohexane 90 C4 tetralin 8
mono-iC13 50.2 C5 tetralin 9
inputs are the volumetric composition of the fuel (Vi), the pure- mono-iC14 52 C6 tetralin 12
component CNs of the different molecules (or molecular lumps) mono-iC15 52 decalin 40 C7 tetralin 15
(CNi), and their blend contributions parametrized by βi. The mono-iC16 55 C1 decalin 40 C8 tetralin 17.9
model structure is consistent in predicting both the CN of a mono-iC17 60 C2 decalin 35 C9 tetralin 18
mono-iC18 65.6 C3 decalin 35 C10 tetralin 20
typical diesel fuel and that of a pure component. In the limiting
mono-iC19 70.7 C4+ decalin 30.6 C11 tetralin 21
case when the diesel fuel is a pure component (Vi ) 1), the mono-iC20 83.1 C12 tetralin 22
model returns the pure-component cetane number (CNi). mono-iC21 80 C13 tetralin 23
mono-iC22 80 naphthalene 22.6 C14 tetralin 24
mono-iC23 80 C1 naphthalene 0 C15+ tetralin 25
3. Defining the Molecular Lumps mono-iC24 80 C2 naphthalene 5
We now need to define the various molecular (or composi- mono-iC25+ 80 C3 naphthalene 10 C5 olefin 20
C4 naphthalene 14 C6 olefin 23.8
tional) lumps that will be used in the cetane model. The multi-iC5 10 C5 naphthalene 16 C7 olefin 47
molecular lumps are based on the following two criteria: first, multi-iC6 12 C6 naphthalene 16.5 C8 olefin 45
significant CN difference and, second, analytical resolution. multi-iC7 14 C7 naphthalene 17 C9 olefin 50
Thus, two molecules (or molecular lumps) are considered multi-iC8 15.5 C8 naphthalene 17.5 C10 olefin 60.2
multi-iC9 35 C9 naphthalene 18 C11 olefin 65
distinct and included separately in the model if there is a multi-iC10 40 C10 naphthalene 18.5 C12 olefin 71.3
significant difference in their pure-component CNs and if the multi-iC11 45 C11 naphthalene 19 C13 olefin 75
analytical resolution between these two molecules (or molecular multi-iC12 50 C12 naphthalene 19.5 C14 olefin 79.7
lumps) is also available. We have chosen a total of 129 multi-iC13 54 C13+ naphthalene 20 C15 olefin 83
multi-iC14 56 C16 olefin 86.5
molecular lumps in this work belonging to 9 different hydro-
multi-iC15 57.5 C17 olefin 87
carbon classes. These include 12 lumps for normal paraffins, multi-iC16 60 C18+ olefin 90
21 lumps for each of the monobranched and multibranched multi-iC17 60
i-paraffins, 11 lumps for alkylcyclohexanes, 5 lumps for a mono-iC means a monomethyl i-paraffin with a total of x carbon atoms.
x
decalins, 15 lumps for alkylbenzenes, 14 lumps for naphthalenes, Cx cyclohexanes represent alkylcyclohexanes only with a total of x carbon
16 lumps for tetralins, and 14 lumps for olefins. These lumps atoms in the alkyl chain. A similar convention is followed for the other
are summarized in Table 1. In choosing these lumps, a number molecular classes.
of additional assumptions were made as noted below:
(i) The branching position is ignored in the lumping of mono- (iii) Alkyl side chains in all ring molecules are assumed to
and multibranched i-paraffins because such detail is difficult be n-alkyl.
to measure by the present analytical capabilities in diesel-range (iv) Alkylcyclohexanes are 1-ring cyclohexanes with n-alkyl
fuels. side chains.
(ii) Multibranched i-paraffins represent all i-paraffins with (v) Decalins represent multiring naphthenes (g2 rings) with
two or more branches. n-alkyl side chains.
Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 349

Figure 2. Pure-component CNs for different molecular lumps considered in the cetane model. The curves indicate the general trend of cetane variation
across each hydrocarbon class as a function of the number of carbon atoms in the molecule. The chemical structures associated with each class are shown
only for visual clarity. Also, for ease of comparison across both parts a and b, n-paraffin curves are plotted in both parts.

(vi) Alkylbenzenes are 1-ring aromatics with n-alkyl side have the highest CNs, and it increases with the carbon number;
chains. i.e., the longer the backbone carbon chain, the higher the CN.
(vii) Naphthalenes, like decalins, are multiring aromatics (g2 The addition of branches decreases the CN, which explains the
rings) with n-alkyl side chains. Biphenyls are also included in lower CNs for i-paraffins compared to those of n-paraffins. The
this group. greater the degree of branching, the lower the CN. The position
(viii) Tetralins represent multiring (g2 rings) naphthenoaro- of the branch also plays a role (although secondary) in the CN.
matics with n-alkyl side chains. Indanes are included in this If the branching is concentrated at one end of the molecule,
group. leaving a long chain at the other end, then such i-paraffins tend
(ix) Olefins represent all three types of olefins: linear olefins, to have higher CNs. Compared to i-paraffins, olefins have higher
cycloolefins, and benzoolefins. Indenes are also included in this CNs and follow closely the n-paraffin trend. Aromatics and
group. naphthenes typically have lower CNs, unless they have a long
(x) All heteroatom molecules containing sulfur and nitrogen n-paraffinic side chain. Multiring structures have lower CNs
are lumped into naphthalenes because most such structures compared to the corresponding single-ring structures, which can
contain two or more aromatic rings. be seen by comparing the alkylcyclohexanes with alkyldecalins
Parts a and b of Figure 2 show the pure-component CNs for or alkylbenzenes with the corresponding alkyltetralins and
the 129 molecular lumps considered in this work. The data are naphthalenes. Although decalins are slightly higher in CN than
based on an exhaustive compilation of the CNs for various both tetralins and naphthalenes, the difference is marginal. The
hydrocarbon molecules published in the literature. The abscissa actual numerical values for these CN trends, as shown in Figure
represents the total number of carbon atoms in the molecule, 2a,b, are summarized in Table 2. These numbers will be used
while the ordinate indicates its pure-component CN. n-Paraffins for CNi in eq 6. Beyond a certain carbon number, the molecules
350 Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006

Table 3. Parameter Values


molecular class molecular lumps β
n-paraffins nC5 to nC16+ 0.5212
i-paraffins iC5 to iC25+ mono- and multibranched 7.3717
i-paraffins
naphthenes cyclohexane to C10+ naphthenes, 0.0727
decalin to C4+ decalins
aromatics benzene to C14+ aromatics, 3.1967
naphthalene to C13+ naphthalenes,
tetralin to C15+ tetralins
olefins/cycloolefins C5 to C18+ linear olefins, branched olefins, 0.3597
and cycloolefins

are lumped into a single lump, e.g., nC16+. This is because there
is hardly any difference in the pure-component CN of paraffins
beyond nC16. Similar observations hold for the other lumps in
the other molecular classes as well.
To apply eq 6, we must also specify the various adjustable
parameters βi. In principle, each molecular lump in eq 6 should
be associated with a separate fitting parameter βi because it Figure 3. Comparison of model predictions of CN against measured CN.
parametrizes its blend contribution to the fuel cetane. However, The different symbols indicate the predictions for the diesel-range refinery
here we make the simplifying assumption that βi is the same process streams and commercial blends separately. Also shown in the parity
plot are the (1.5 CN error lines.
for all of the molecules in a given molecular class. Therefore,
all n-paraffins, regardless of their carbon chain length, will have
the same βi. Likewise, all aromatics, regardless of their carbon
number, will have the same βi, and so on. This simplification
reduces the number of adjustable parameters to 9, one β for
each molecular class.

4. Experimental Program
A database of 203 diesel fuels was collected from 8 different
refineries in this study. The fuels include 45 different diesel-
range refinery process streams and 158 commercial blends of
these process streams. They were so chosen to reflect a wide
range of diesel properties with CNs varying from 20 to 60. The
CNs on all of these fuels were measured using the IQT method. Figure 4. Error distribution of the model predictions for CN across the
Detailed compositional analysis was also obtained on these fuels various samples.
using a combination of supercritical fluid chromatography
(SFC), GC, and MS methods. The SFC was used to measure parameter values are satisfactory, though we may point out that
the total paraffins, naphthenes, and aromatics by ring class, GC the use of individual β values for the different molecular lumps
was used to measure the boiling point distribution, and MS was enhances model predictions. The results presented below are
used to get the molecular weight distribution. The fuels collected based on the individual β parameters.
spanned a wide range of molecular compositions from highly 5.2. Prediction Statistics. On the basis of the regression of
paraffinic to highly naphthenic to highly aromatic diesel fuels. the parameters β, the prediction results of the model are shown
in Figure 3 for all of the 203 diesel fuels. The plot not only
5. Results
summarizes the overall performance of the model but also
5.1. Parameter Estimation: Constrained Least-Squares highlights the performance separately across the different diesel-
Formulation. A constrained least-squares minimization problem range refinery process streams and the commercial blends as
was solved using the Levenberg-Marquadt algorithm in order indicated by the different symbols. Across all of these fuels,
to regress the parameters of the model. The adjustable param-
eters β were allowed to vary between lower and upper bounds the overall standard error (SE) defined as x∑(meas - pred)2/n
of -10 and +10, respectively. The experimental dataset was for the whole dataset is 1.25 numbers. The individual statistics
partitioned into a training set (90% of the samples) and a testing for the training and the testing datasets are 1.15 and 1.3 numbers,
set (10% of the samples), and many such partitions were respectively. Also shown in this plot are the (1.5 number error
considered to ensure robustness of the parameter estimates. lines which is the typical repeatability error of the cetane
Different initial guesses were assumed and the parameters measurements in the IQT. The results shown in this figure
reoptimized to ensure that the optimization problem was not clearly demonstrate quantitative agreement of the model predic-
trapped in an inferior local solution. Sensitivity analysis in the tions across this multitude of diesel fuels for both the process
form of local perturbation of the parameters was also performed streams and the commercial blends. It is unlikely that the SE
to see whether the parameters returned to the same optimal or could be reduced further because the model predictions are well
not. within the measurement error of the property itself.
Although the final parameter values (β) for all of the An important requirement of any regression model is that its
individual molecular lumps used in this model cannot be predictions are unbiased with respect to its inputs. To ensure
disclosed in the publication for proprietary reasons, the average this, the frequency distribution of the model errors is plotted in
values of these parameters, grouped by P, I, O, N, and A classes, Figure 4. The abscissa in the figure represents the error level in
are reported in Table 3. The results based on these average the model predictions, while the ordinate represents the number
Ind. Eng. Chem. Res., Vol. 45, No. 1, 2006 351

variety of diesel fuels including process streams and their blends.


Each diesel fuel was compositionally represented by 9 different
hydrocarbon classes containing a total of 129 different molecular
lumps measured by a combination of SFC, GC, and MS
methods. The model predicts the CN with a standard error of
(1.25 numbers across the multitude of diesel fuels considered
in this work. The model explicitly acknowledges the detailed
molecular composition of the diesel fuel and incorporates the
pure-component molecular trends of CN. As a result, the model
predictions are expected to be robust and reliable during the
use of the model in extrapolation.

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because the present model builds upon the direct and explicit 1992, 31 (11), 2483.
knowledge of the detailed molecular composition of the diesel (13) Ghosh, P.; Hickey, K. J.; Jaffe, S. B. Development of a Detailed
fuel. Such detailed molecular accounting is critical because it Composition Based Octane Model. Ind. Eng. Chem. Res. 2005, 44, XXXX.
provides more robustness and reliability in the predictions, which (14) Heck, R. H. Contribution of Normal Paraffins to the Octane Pool.
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is important because such models would be most frequently (15) Jaffe, S. B. Control of Gasoline Manufacture. U.S. Patent 4,251,870,
used in the extrapolative mode in the petroleum refinery. 1981.

ReceiVed for reView July 11, 2005


6. Conclusions
ReVised manuscript receiVed October 10, 2005
Accepted October 14, 2005
A general composition-based predictive model for CN is
presented here that can be universally applied across a wide IE0508132