Fuel 83 (2004) 517523

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A new non-linear calculation method of isomerisation gasoline research

octane number based on gas chromatographic data
N. Nikolaoua,1, C.E. Papadopoulosa,*, I.A. Gagliasb, K.G. Pitarakisc,2
a
T.E.I Kavalas, Department of Petroleum and Natural Gas Technology, School of Technological Applications, Kavala, Greece
b
Hellenic Petroleum S.A., Aspropyrgos Attikis, Greece
c
Water Supply and Sewerage Municipal Of Larissa, Terma Tyherou St., 41222-Larissa, Greece
Received 3 March 2003; revised 23 September 2003; accepted 25 September 2003; available online 14 October 2003

Abstract
A new simple no-linear calculation method of isomerisation gasoline Research Octane Number (RON) is presented. The calculation
method effectively utilizes the compositional data from high-resolution capillary GC analysis, and the measured pure and blending RON
values of various HCs, which are widely published. The method, which is a simple non-linear method, utilizes calculable weighting factors,
which are specific for each gasoline blend, and showed an excellent agreement with the RON values of various refinery isomerates samples as
they measured in a standard CFR engine.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Non-linear methods; Gasoline; Isomerates; Octane number calculation; Gas chromatography

1. Introduction as an Antiknock Index or Pump Octane which is the average

Gasoline is a multicomponent or complex mixture that
may comprise of several hundred hydrocarbons. It actually
varies from refinery to refinery and there is not such a thing
as a single criterion that can characterise gasoline purity and
quality in general. The new environmental and performance
considerations have introduced several difficulties in gaso-
line production and have made a standard general definition
of gasoline quality a very difficult task.
So, new specifications [1] for the unleaded gasoline were
drawn and increased demands on the quality of gasoline as
indicated by its octane numbers (Research octane number or
RON and Motor octane number or MON), among others,
have been placed. The RON accounts for fuel performance
under low severity engine operation while the MON for
more severe operation that might be incurred at high speed
or high load. In practise the octane of a gasoline is reported
* Corresponding author. Tel.: 30-23210-20562; fax: 30-23210-
56246.
E-mail addresses: cpapad@otenet.gr (C.E. Papadopoulos); nicnik@
otenet.gr (N. Nikolaou).
1
Tel: 30-2510 46223-1.
2
Tel: 30-2410 687240-1.
0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2003.09.011
of RON and MON
RON MON
AI 1
2
Both RON and MON are still measured in a standardised
single cylinder, variable compression ratio (from 4:1 to
18:1), internal combustion engine (Cooperative Research
Fuel-CFR engine), following the standard methods ASTM-
D2699 [3] and D2700 [4], respectively. Both RON and
MON are relative values based on accepted standard fuel
mixtures. The engine is operated at a constant speed (RPMs)
for both RON and MON and the compression ration is
increased until the onset of knocking. Engine speed is set at
600 rpm for RON and 900 rpm for MON.
Petroleum industry has always been used empirical
performance standards of its gasoline products, such as
RON and MON. Only after gas chromatography became
widely available, compositional standards and constraints
on gasolines composition have started to be applied.
The direct determination of RON (and MON) with the
standard CFR engine is a complicated, relatively expensive
operation. CFR engines require constant maintenance and
frequent calibrations [5].
518 N. Nikolaou et al. / Fuel 83 (2004) 517523
The fast, easy and accurate determination of octane
number is important for refiners today, since optimisation of
refining process at a reasonable cost is an ever-increasing
requirement.
1.1. Gasoline compositional data by analytical techniques
There are various existing analytical techniques to obtain
gasoline compositional data from which calculation of
octane numbers can be done. The main disadvantage of
most them, for an accurate octane prediction is their limiting
detail in terms of the compositional data they can provide. A
detailed gasoline compositional analysis can always allow a
more accurate calculation of octane number. Thus, analyti-
cal techniques such as fluorescent indicator adsorption
(FIA) [2], Near infra-red (NIR) [6,8]. Nuclear magnetic
resonance (NMR) [7,8], e.g. can provide only limited
compositional information, corresponding to structural
groups such as aromatics, olefins and saturates. This limited
compositional (analytical) detail makes these methods not
to be the most accurate for an octane number prediction,
with an exception those cases where a gasoline mixture
mainly consists of some predominant group.
To the contrary, GC methods with the use of modern
capillary columns can provide an almost excellent HCs
separation and detailed compositional data, far beyond the
aromatic, olefin etc. groups [9,10].
1.2. Octane number calculation methodsnew method
proposed
Even though GC data offer detailed gasolines compo-
sitional information, a common problem of all analytical
methods for an accurate calculation of octane number is the
non-linear blending characteristics of the octane contri-
butions from the individual components (or the structural
groups) in a gasoline, which is a highly complex mixture.
Thus, octane numbers measured directly for pure com-
pounds cannot be simply (linearly) combined, according to
the gasoline composition, to calculate the octane number of
that gasoline. The non-linearity in the combination of pure
components octane numbers is the most significant
complication to the accurate calculation of gasoline octane
numbers as well as to other fuel properties.
Other researchers have done many efforts for the
prediction of gasolines octane number utilising GC data
of reformed gasoline [9,11,12]. Most of the methods
developed utilise the basic equation (linear) of octane
number for a blend of n-heptane and iso-octane which is:
Octane number RONn-heptaney1 RONiso-octaney2
2 tration of HC components in a gasoline.
where y1 and y2 are the volume fractions of n-heptane and
iso-octane in the blend respectively, RON (n-heptane) is
equal to 0 (the octane number of pure n-heptane) and RON
(iso-octane) is equal to 100 (the octane number of pure iso-
octane).
Eq. (2) is generally extended and used for a gasoline
consisting of k components as:
X
k
RONG RONi yi 3
i1
Wherever Eq. (3) has been employed by others to predict
research octane number from GC data, the RONi values
used are not those of pure hydrocarbons present in ASTM
STP 225 [13], but are blending octane numbers that have
been usually obtained by comparison with measured data
and using multiple linear regression analysis [7]. This has
been done so, because in systems other that blends of n-
heptane and iso-octane the octane numbers of the constitu-
ent components (Blending octane numbers from ASTM
STP 225), or in other cases the partial octane numbers
(employing the directly relevant term from thermodyn-
amics), are functions of their concentration and of the
overall composition of the gasoline blend.
Some of the published methods referred above, for the
prediction of octane number from GC data, might be
criticised for two main disadvantages:
Although GC methods can give detailed compositional
data, as it was already said, the grouping of the analysed
HCs into similar structural groups such as paraffins,
olefins etc. for the octane number prediction, which has
been usually the case, automatically removes the main
advantages offered by GC methods themselves. This
grouping procedure is based on the weak assumption that
these structural groups behave similarly during the
combustion of different gasolines [7].
Another disadvantage of the conventional methods
available is that the blending or effective octane numbers
that have been obtained under some specific conditions
are equally applied in Eq. (3) for all types of gasoline
blends. For example, measured blending (and pure)
octane numbers of a wide range of hydrocarbons has
been published in API project 45 [13] and some of them
are shown in Table 1. These blending octane numbers
were estimated from the measured (CFR) octane number
of a blend of 48%v/v iso-octane, 32%v/v n-heptane and
20%v/v of the specific HC. It must be recognised that
these blending octane numbers have given some
qualitative information in terms of the RON perform-
ance, related with specific HCs in these simple blends,
however, this has been extended and used under another
weak assumption that these blending octane numbers are
the same (constants) for any number, type and concen-
Recently, and with the continuous advancement of
computational power, some new and quite promising non-
linear utilisation methods, based on pattern recognition,
 N. Nikolaou et al. / Fuel 83 (2004) 517523 519

Table 1
Octane number data for various HCs present in isomerization gasolines

Ordered by retention time Boiling point (8C) Type of H/C Molecular weight Pure RON Pure MON Blending RON

1 20.5 n-C4 58.123 93.8 89.6 113.0

2 9.5 2,2-DM-C3 72.15 85.5 80.2 100.0
3 27.9 iso-C5 (2-M-C4) 72.15 92.3 90.3 100.0
4 36 n-C5 72.15 61.7 62.6 62.0
5 49.7 2,2-DM-C4 86.177 91.8 93.4 89.0
6 49.6 Cyclo-C5 70.134 101.3 85 141.0
7 58 2,3-DM-C4 86.177 103.5 94.3 96.0
8 60.2 iso-C6 (2-M-C5) 86.177 73.4 74.5 82.0
9 63.2 3-M-C5 86.177 74.5 74.3 86.0
10 68.7 n-C6 86.177 24.8 26 19.0
11 79.2 2,2-DM-C5 100.203 92.8 95.6 89.0
12 71.8 M-cyclo-C5 84.161 91.3 80 107.0
13 80.5 2,4-DM-C5 100.203 83.1 83.8 76.0
14 80.7 2,2,3-TM-C4 100.203 112.1 104.3 112.0
15 86.1 3,3-DM-C5 100.203 80.8 86.6 84.0
16 80.8 Cyclo-C6 84.161 83 77.2 110.0
17 90 iso-C7 (2-M-C6) 100.203 42.4 46.4 40.0
18 89.8 2,3-DM-C5 100.203 91.9 88.5 88.0
19 87.9 1,1-DM-Cyclo-C5 98.188 92.3 89.3 96.0
20 91.8 3-M-C6 100.203 52 55.8 56.0
21 90.7 1,3-DM-cis-cyclo-C5 98.188 79.2 73.1 98.0
22 91.7 1,3-DM-trans-cyclo-C5 98.188 80.6 72.6 90.0
23 93.4 3-E-C5 98.188 65 69.3 64
24 98.5 n-C7 100.203
25 100.9 M-cyclo-C6 98.188 74.8 71.1 104
26 103.5 E-cyclo-C5 112.215 67.2 61.2 61.2

have been proposed [7] for the prediction of octane
number.
In the new calculation method proposed by the authors,
the following equations for the prediction of isomerisation
gasoline research octane number (RONG) are used. Similar
equations can be equally applied for MON:
X
N
RONG Ki RONi yi
i1
where yi ; are volume fractions of HCs present in the
gasoline and obtained by GC, RONi is the measured
(published) pure HC research octane number and Ki is a
weighting factor that is calculated from:
XN
RONi yi BRONi
Ki Xi1
N 5
BRONi yi RONi
i1
where BRONi is the measured (published) blending
research octane number of each HC.
The product Ki RONi in Eq. (4), gives a calculated
effective or blending octane number, characteristic for the
specific gasoline, which also depends, except on the known
pure and blending octane numbers, on the number, type and
concentration of the HCs present in the specific gasoline.
Thus there is not limit in the number of the HCs present and
analysed by the GC, as long as there are data available for
their pure and blending octane numbers.
2. Experimental
The demand for increased octane number in gasoline
production from refineries in consequence of the reduction,
4
under the new specifications, of high octane ratings
aromatics and olefins led to the investigation of any possible
alternative processes for octane number improvements. For
example, one of the best processing options for light straight
run (LSR) has been determined to be the isomerisation.
Isomerisation units rearrange the molecules from straight-
chain, low-octane hydrocarbons to branched-chain, high-
octane hydrocarbons known as isomers. This is done for two
reasons:
They create extra isobutane feed for alkylation.
They improve the octane number of straight run pentanes
and hexanes and hence make them into better petrol
blending components. So, the resulting isomerate is a
superior gasoline blending stock.
Twenty (20) pure refinery isomerates samples, with
different number and components concentrations were
collected and their research octane number (RON) was
520 N. Nikolaou et al. / Fuel 83 (2004) 517523

Fig. 1. A typical gas chromatogram obtained for an isomerization gasoline sample and column/detector characteristics.

carefully measured in a standard CFR engine. The same the gasoline was quantitatively determined. In Table 3 are
samples were analysed in a PERKIN ELMER 8700 GC with shown typical calculated weighting factors and effective
a Petrocol DH by Supelco, 150 m capillary column, which is research octane numbers for a specific sample. The
known to have an excellent HCs separation performance. A weighting factors Ki calculated values were close to one.
summary of the GC operating conditions and capillary As it would be normally expected, for a pure component
column characteristics is provided in Fig. 1. Standard yi 1 from Eq. (5) we obtain Ki 1 and subsequently
analysis calculations of area% (normalization) in a standard from Eq. (4) RONG is equal to the pure RON.
integrator incorporated into the chromatograph were used.
The GC TALK software available in the 8700 GC used for
the transfer of compositional data through an RS232 to a
PC, where they were fatherly processed with a Visual Basic Table 2
Typical composition (%w/w) of detected HCs
program.
1 n-C4 0.320 14 2,2,3-TM-C4 0.013
2 2,2-DM-C3 0.031 15 3,3-DM-C5 0.026
3 iso-C5 (2-M-C4) 41.596 16 Cyclo-C6 2.677
3. Results 4 n-C5 12.323 17 iso-C7 (2-M-C6) 0.076
5 2,2-DM-C4 25.818 18 2,3-DM-C5 0.032
6 Cyclo-C5 1.037 19 1,1-DM-cyclo-C5 0.020
A typical chromatogram from a full range isomerisation
7 2,3-DM-C4 2.971 20 3-M-C6 0.066
gasoline blend is shown in Fig. 1 and a typical composition 8 iso-C6 (2-M-C5) 5.398 21 1,3-DM-cis-cyclo-C5 0.020
with the HCs peaks allocated also shown in Table 2. The 9 3-M-C5 2.200 22 1,3-DM-trans-cyclo-C5 0.024
RON and various other data for these HCs are also present 10 n-C6 2.869 23 3-E-C5 0.030
in Table 1. 11 2,2-DM-C5 0.054 24 n-C7 0.029
12 M-cyclo-C5 1.221 25 M-cyclo-C6 0.493
A maximum number of 26 different HCs was detected
13 2,4-DM-C5 0.033 26 E-cyclo-C5 0.011
and allocated. In all the samples more than 98%w/w of
 N. Nikolaou et al. / Fuel 83 (2004) 517523 521

Table 3
Example of calculated weighting factor and effective research octane numbers

Ordered by H/C Volume Weighting Pure RON Measured Calculated

retention time fraction yi factor Ki blending RON blending RON

1 n-C4 0.0043 0.876 93.8 113.0 82.1

2 2,2-DM-C3 0.0003 0.902 85.5 100.0 77.1
3 iso-C5 (2-M-C4) 0.4507 0.974 92.3 100.0 89.9
4 n-C5 0.1335 1.050 61.7 62.0 64.8
5 2,2-DM-C4 0.2342 1.088 91.8 89.0 99.9
6 Cyclo-C5 0.0116 0.758 101.3 141.0 76.8
7 2,3-DM-C4 0.0270 1.137 103.5 96.0 117.7
8 iso-C6 (2-M-C5) 0.0490 0.944 73.4 82.0 69.3
9 3-M-C5 0.0200 0.914 74.5 86.0 68.1
10 n-C6 0.0260 1.377 24.8 19.0 34.1
11 2,2-DM-C5 0.0004 1.100 92.8 89.0 102.1
12 M-cyclo-C5 0.0113 0.900 91.3 107.0 82.2
13 2,4-DM-C5 0.0003 1.153 83.1 76.0 95.8
14 2,2,3-TM-C4 0.0001 1.056 112.1 112.0 118.4
15 3,3-DM-C5 0.0002 1.015 80.8 84.0 82.0
16 Cyclo-C6 0.0249 0.796 83 110.0 66.1
17 iso-C7 (2-M-C6) 0.0006 1.118 42.4 40.0 47.4
18 2,3-DM-C5 0.0003 1.102 91.9 88.0 101.2
19 1,1-DM-cyclo-C5 0.0002 1.014 92.3 96.0 93.6
20 3-M-C6 0.0005 0.979 52 56.0 50.9
21 1,3-DM-cis-cyclo-C5 0.0002 0.852 79.2 98.0 67.5
22 1,3-DM-trans-cyclo-C5 0.0002 0.945 80.6 90.0 76.1
23 3-E-C5 0.0002 1.071 65 64 69.6
24 n-C7 0.0002 0 0 0
25 M-cyclo-C6 0.0039 0.759 74.8 104 56.7
26 E-cyclo-C5 0.0001 1.158 67.2 61.2 77.8

In Fig. 2 are shown the RON values measured in the
CFR engine and those calculated from the GC data with
the new method proposed. The agreement was very good.
Considering the RON uncertainty of the ASTM method
to ^ 1 RON, and the fact that the standard deviation
of the difference DRON RON(ASTM)-RON(GC) was
sDRON 0:23RON it is easily justified the consistency of
the estimation.
By employing Chebyshevs probability theorem [14],
which holds for any distribution of observations:
1
P0 2 ksDRON , DRON , 0 ksDRON $ 1 2 6
k2
and for an uncertainty ksDRON ^1 RON; we can safely
conclude that at minimum 95% of our observations are
falling within the ^ 1 RON interval, which is a very good

Fig. 2. Measured RON (ASTM) versus calculated RON(GC) from GC data for 20 isomerates. (Uncertainty of RON(ASTM) taken as ^1RON).
522 N. Nikolaou et al. / Fuel 83 (2004) 517523
agreement. In fact, all our calculated RON(GC) values were
well within ^ 0.5 RON of the RON(ASTM) measured
values.
From Fig. 2, it can be easily seen that RON(ASTM)
from the CFR engine is, in most cases, higher than
the RON(GC). This is another fact that provide further
support to this method since this can be explained by the
small loss of information due to GC analysis, in which
slightly less than 100% w/w of the gasoline has been
quantitatively determined in all the samples, with the tail
end loss mainly consisting of HCs with high octane
number ratings. It is also worth noticing in Table 3, that
the calculated blending RONs by this method follow a
negative correlation with the measured blending RONs
published in API project 45, when both they are
compared with the pure RON values. However, this is
the effect of the weighting factor that depends not only
on the specific gasolines composition but also on the
blending RONs.
4. Discussion
The method and the results obtained in this project can
be compared with those obtained by multiple regression
analysis [9] and those regarding catalytic reformed gaso-
line [10,12]. The main advantages of the method presented,
is its simplicity and the fact that it can be easily integrated
in an on line octane number GC analyser for blending
quality control. This analytical non-linear calculation
method it can be also classified as a pattern recognition
method, since it employs past data for RON and Blending
RON values in order to calculate the RON of a new
unknown sample.
In the end, it was realised that a reliable computational
method for the prediction of RON from GC data would
generally need the following information:
1. Number and type of HC components in the gasoline as
well as detail compositional data. Rich qualitative and
quantitative information can be available by modern GC
analysers with capillary columns. The increased number
and the type of HCs present in a refinery isomerate also
increase the number of interaction and non-linear terms,
partitioning the contribution of each single component to
the overall octane number.
2. Octane numbers of pure components provide infor-
mation about the combustion characteristics of each
component. This could be mathematically combined in
some way with blending octane numbers, and so all this
quantitative and qualitative information is more effec-
tively utilised because the octane number predictor
takes into account interaction characteristics between
the components.
5. Conclusions
Octane number (RON or MON) is a fuel performance
quality metric under various but specified engines
operation conditions. Blending is one of the final
operations in refining, in which two or more different
components or structural groups are mixed together to
obtain the desired range of properties in the final
product.
In practise octane numbers do not blend linearly. To
accommodate this, complex blending calculations
employing blending octane numbers as opposed to the
values for pure hydrocarbons are routinely employed.
There is no universal blending program used industry
wide. In fact, for a given oil company, blending
calculations that are refinery specific are not uncommon.
As an improvement over octane numbers of pure
compounds, there are tabulations of blending octane
numbers for both RON and MON. These numbers are
measured by blending 20 vol.% of the specific hydro-
carbon in 80 vol.% of a 60/40 iso-octane/n-heptane
mixture. Although still not indicative of the actual
blending octane number for a specific gasoline compo-
sition, the blending octane numbers are more representa-
tive and could be utilised more effectively by providing
qualitative information when combined in mathematical
models with pure octane numbers.
Further research is necessary to test the applicability
of the method to other gasoline types, as well as
further research on other non-linear utilisation methods
of GC data. Such a research effort has already been
initiated in the Department of Petroleum and Natural
gas Technology. Various non-linear methods are tested
that employ pattern recognition techniques, along with
the utilisation of past RON data, such as those used in
this project.
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