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Gasoline Blending Research Paper
Gasoline Blending Research Paper
(3)
Eqn.(2) provides one logical starting point for any attempt to predict octane
numbers from composition. Because there is no blending effect for blending
identical components, the simplest nontrivial expession which obeys these
conditions is that of eqn.(2) plus the term b
12
x
1
x
2
as proposed by Morris et al.
(1975). This expression for correction on octane number is symmetrical. For a
general description of blending behavior, this equation is not adequate.
Additional terms are needed to represent adequately the blending behavior of
octane number for a binary. One particularly successful series expansion was
introduced by Redlich and Kister (1948). However, the Redlich-Kister equation
can not be rigorously extended to multicomponent systems. Note that the first-
order term of the Redlich-Kister expansion is term used in the eqn.(1) by Morris
et al. (1975). A correlation of the form given by Morris but extended to a more
6
complex form such as Redlich-Kister expansion would do a more accurate job
of correlating blend octane numbers, but it would still suffer from the limitations
discussed earlier.
A different approach from Morris et al. (1975) is proposed here. Instead of
adding b
12
x
1
x
2
to eqn.(2), eqn.(3) is rewritten in a more general form as:
a x
i
x
j
a
ij
j i
=
(4)
where
a
ij
a
i
a
j
k
ij
= +
1
2
1 ( )( ) (5)
A binary interaction parameter, k
ij
, is introduced into the blending correlation
to correct the assumed mathematic average mean rule for the "a
ij
" parameter in
the eqn.(5). This correlation is very effective in representing the octane blending
behavior of gasoline cuts. If symmetric binary interaction parameters, k
ij
= k
ji
,
are assumed, then the expression of eqn.(5) for correction on octane number is
symmetrical. For asymmetric correction, asymmetric binary interaction
parameters, (i.e. k
ij
k
ji
), can be used for a
ij
in eqn.(4):
a
ij
a
i
a
j
k
ij
k
ij
k
ji
x
i
= + +
1
2
1
2
( )[( ) ( ) ] (6)
Eqns.(4) and (6) can be generalized for the blend of a multicomponent system
as follows (Twu et al., 1991):
( ) ( ) a x
i
x
j
a
i
a
j
k
ij
j i
= +
1
2
1
+ +
x
i
x
j
a
i
a
j
k
ij
k
ji
i
j
1
2
1 3
1 3
3
( ) ( )
/
/
(7)
If k
ij
= k
ji
, eqns.(4) and (5) are recovered. By using different values of k
ij
and
k
ji
in eqn.(7), any blending behavior can be correlated using this blending
correlation. Blends made from constitutes of equal or nearly equal octane
ratings are said to be matched. Typical blending data will normally fall into
one of the six different types shown in Figs 1 to 6. Figure 1 shows the octane
7
bonus from blending two matched components. The mixing of an olefin and a
paraffin show positive deviation, and belong to this class. Figure 2 shows
negative deviations. As an example, aromatic and olefin blends of varying olefin
concentrations show a slightly negative deviation. The blend deviations can also
be both positive and negative over the range of blend compositions as illustrated
in Fig. 3. The locus of octane numbers of match blends shown in Fig. 1 and 2
is a parabolic curve. However, blending deviations for components show that
these curves do not necessary have a symmetric shape (Fig. 4 and 5). The
order of magnitude of the bonus or negative value and the skewedness of the
curves, which can be simulated by varying values of k
ij
and k
ji
, will vary greatly
from system to system. Finally, isooctane blending linearly with n-heptane is
reproduced in Fig.6 using eqn.(7) with k
ij
= k
ji
= 0.
Binary Interaction Parameters
The selection of either symmetric binary interaction parameters (k
ij
= k
ji
) or
asymmetric binary interaction parameters (k
ij
k
ji
) for blending the octane
number of gasoline cuts is determined on the basis of a rather empirical analysis
of the goodness of fit. For some mixtures, an accurate description of mixture
behavior requires asymmetric binary interaction parameters. For blending
gasoline cuts, the use of asymmetric binary interaction parameters does not
appear necessary and a very simple blending correlation, eqns.(4) with (5), is
therefore adopted for gasoline blends in this work. Note that this simplification
is still covered by the more general correlation given as eqn.(7).
For octane number blends of gasoline cuts, the use of one symmetric binary
interaction parameter per binary component provides adequate representation
for gasoline blending, based on the quality of the data available. The reason
may be because of complicated mixtures with various types of hydrocarbon in
each gasoline cut. The fact that the contents of blends has so many different
types of hydrocarbons makes it plausible that the sum of the individual blending
deviations may be approximated by a segment of a symmetric parabola over a
limited range of compositions; the results indicate that this assumption is very
satisfactory.
Standard laboratory inspection data of gasoline cuts usually include research
and motor octane numbers and their contents of olefins, aromatics, and
8
saturates. In this paper we shall consider olefins, aromatics, or saturates as
components and the gasoline cut as a mixture of these components.
Depending on the laboratory analysis, a gasoline cut may be reported as a
mixture of either three components (olefins, aromatics, and saturates) or four
components (olefins, aromatics, paraffins, and naphthenes), or five, etc. The
more detailed the analysis, the more accurate are the correlated results that can
be achieved.
Although the same name (such as aromatics) is given to the component
contained in different gasoline cuts, they are really different components because
gasoline cuts are complicated mixtures with various types of aromatics. This
means that the octane number of the aromatics from one gasoline cut is different
from the octane number of the aromatics from another gasoline cut. Therefore,
if two gasoline cuts containing olefins, aromatics, and saturates components are
blended together, the number of different components in this blend is
considered to be six components, not three.
Because there is no any information available on the octane numbers of the
components in a gasoline cut, we propose in this paper that the same octane
number of the gasoline cut be assigned to its components. For example, if the
research octane number (RON) of the gasoline cut is 97.8, then the RONs of its
component olefins, aromatics, and saturates are all assumed to be 97.8. This
approach is internally consistent because the RON of the gasoline cut is
recovered by blending these three components together with binary interaction
parameters in eqn.(5) set to zero. This methodology results in zero binary
interaction parameters between components inside the same gasoline cut, but
non-zero binary interaction parameters between gasoline cuts. In other words,
to blend two three-component gasoline cuts, A and B, the binary interaction
parameters between components inside gasoline cuts A and B are all zero, but
binary interaction parameters between component i (e.g. aromatics) in cut A and
component j (e.g. olefins) in cut B are non-zero. Furthermore, if i and j are both
the same hydrocarbon type (e.g., aromatics in cut A and aromatics in cut B), the
binary interaction parameter between them is assumed to be zero (i.e., k
ii
=0).
The total number of binary interaction parameters for blending two three-
component gasoline cuts is only 3 (i.e., binary interaction parameters between
aromatics in cut A and olefins in cut B, aromatics in cut A and saturates in cut
9
B, olefins in cut A and saturates in cut B). The advantage of this methodology
is that only three binary interaction parameters are required for the correlation for
blending any number of gasoline cuts having components olefins, aromatics,
and saturates.
The binary interaction parameters between components have been derived
from the regression of blending data of gasoline cuts. These binary interaction
parameters between components are then used to generate internally consistent
binary interaction parameters between gasoline cuts. To obtain the general
relationship of binary interaction parameters between components and gasoline
cuts, lets assume that gasoline cut X is a mixture of m components with
compositions x
1
, x
2
, ..., x
m
, and the gasoline cut Y is a mixture of the same m
components with compositions y
1
, y
2
, ..., y
m
. For two three-component
gasoline cuts, X and Y, m is equal to 6 with non-zero compositions x
1
, x
2
, x
3
, y
4
,
y
5
, and y
6
and zero compositions y
1
, y
2
, y
3
, x
4
, x
5
, and x
6
or vice versa. The
binary interaction parameter between gasoline cuts X and Y, K
XY
, is related to
the binary interaction parameters between components by
( ) ( )
( ) ( )
K
x
i
y
j
x
j
y
i
a
i
a
j
k
ij
x
i
x
j
y
i
y
j
a
i
a
j
k
ij
XY
j
m
i
m
j
m
i
m
=
+ +
+ +
1
1
2
1
1
2
1
( )
( )
(8)
where k
ij
is binary interaction parameter between component i (e.g. aromatics) in
cut X and component j (e.g. olefins) in cut Y.
After generating the binary interaction parameters between cuts, the calculation
of octane number of gasoline blends can be simplified greatly. For gasoline
blends, eqns.(4) and (5) become:
a z
i
z
j
a
ij
j i
=
(9)
where
a
ij
a
i
a
j
K
ij
= +
1
2
1 ( )( ) (10)
z
i
and a
i
are volume fraction and octane number of gasoline cut i. K
ij
is the
binary interaction parameter between gasoline cuts i and j, which is given by
10
eqn.(8). An exception to this occurs if a gasoline cut is split into two identical
gasoline cuts. The K
ij
between these two gasoline cuts must be set to zero by
the user because they are identical components, rather than being calculated
from eqn.(8). This is to remain consistent with the approach we proposed
earlier, which sets all k
ijs
within a cut to be zero.
Application to Gasoline Blends
Use of the proposed blending correlation in this work is best illustrated by an
example problem. The extensive blend data used to develop the binary
interaction parameters were taken from Healy et al.(1959). The compiled data
covered a wide range of commercial blending stocks and finished gasoline
blends. A total of 161 blends and 157 gasoline cuts were used in this study.
The blending components used were typical refinery gasoline stocks
consisting of straight run, catalytically cracked, thermally cracked, catalytically
reformed, thermally reformed gasolines, natural gasoline, aromatic
concentration, isomer, polymer, alkylate, isopentane, as well as n-pentane and n-
butane. The data required for each gasoline cut are octane number, olefin
contents, aromatic contents, saturated contents, and proportion by volume. For
the example shown here, the properties of the gasoline cuts and blends and
blend compositions are from Healy et al.(1959). Table 1 shows these properties
of the gasoline cuts.
Table 1. Laboratory Inspection of Gasoline Cuts
----------------------------------------------------------------------------------------------
Hydrocarbon-type analysis, volume %
---------------------------------------------------
Gasoline cuts RON MON Olefins (O) Aromatics (A) Saturates (S)
----------------- ------ ------- ------------- ----------------- ----------------
Reformate (1) 97.8 87.0 1.4 63.1 35.5
Thermally
cracked (2) 70.4 65.1 32.5 9.8 57.7
Catalytically
cracked (3) 92.6 80.2 53.3 23.9 22.8
Polymerized (4) 96.8 82.3 100.0 0.0 0.0
Light straight
run I (5) 58.0 58.0 1.3 3.8 94.9
11
Light straight
run II (6) 61.9 62.0 0.7 2.4 96.9
---------------------------------------------------------------------------------------------
We have assigned component numbers O, A, and S to olefins, aromatics, and
saturates, which are the components contained in the gasoline cuts, respectively.
We also assign gasoline cut number 1, 2, 3, 4, 5, and 6 to reformate, thermally
cracked, catalytically cracked, polymerized, light straight run I, and light straight
run II, respectively. Eleven blends with blend compositions were made from
these six gasoline cuts.
The three binary interaction parameters between components, which are
derived from the regression of these 11 blending data of 6 gasoline cuts, are
shown in Tables 2A and 2B. As mentioned previously, these three binary
interaction parameters between components are then used to generate binary
interaction parameters between gasoline cuts through eqn.(8), which are given in
Tables 3A and 3B. These binary interaction parameters between cuts are then
used in eqns.(9) and (10) to predict the octane numbers of gasoline blends. The
predicted results for these 11 blends are given in Tables 4A and 4B. The
accuracy of prediction of the blend octane numbers obtained isexcellent with an
average absolute deviation percent (AAD%) less than 0.5% for both research
octane number (RON) and motor octane number (MON). Note that the
deviations of the research octane numbers of the last two blends containing light
straight run II are much larger than the others exhibited in Table 4A, indicating a
possible data inconsistency in the light straight run II gasoline cut. If these last
two blends are excluded, the deviation of the prediction of the octane number of
the blends of this group will be much less than 0.5%.
Table 2A
The binary interaction parameters between components for RON
-------------------------------------------------------------------------------
k
OA
= 0.0364
k
OS
=-0.0891 k
AS
=-0.0954
-------------------------------------------------------------------------------
12
Table 2B
The binary interaction parameters between components for MON
-------------------------------------------------------------------------------
k
OA
= 0.1479
k
OS
=-0.1571 k
AS
=-0.0760
-------------------------------------------------------------------------------
Table 3A
The binary interaction parameters between gasoline cuts for RON
------------------------------------------------------------------------------------------------
K
12
= -0.0416
K
13
= -0.0266 K
23
= -0.0446
K
14
= -0.0087 K
24
= -0.0479 K
34
= -0.0116
K
15
= -0.0597 K
25
= -0.0386 K
35
= -0.0670 K
45
= -0.0832
K
16
= -0.0604 K
26
= -0.0385 K
36
= -0.0683 K
46
= -0.0855 K
56
= -0.0074
------------------------------------------------------------------------------------------------
Table 3B
The binary interaction parameters between gasoline cuts for MON
------------------------------------------------------------------------------------------------
K
12
= -0.0192
K
13
= 0.0026 K
23
= -0.0529
K
14
= 0.0375 K
24
= -0.0762 K
34
= -0.0005
K
15
= -0.0480 K
25
= -0.0563 K
35
= -0.0944 K
45
= -0.1435
K
16
= -0.0489 K
26
= -0.0571 K
36
= -0.0973 K
46
= -0.1487 K
56
= -0.0075
------------------------------------------------------------------------------------------------
Table 4A
The predicted RON for gasoline blends from the binary interaction parameters
between components.
--------------------------------------------------------------------------------------------------
volume fractions of gasoline cuts in blends RON
------------------------------------------------------ ------------------
I z
1
z
2
z
3
z
4
z
5
z
6
Expt. Calc. Dev%
-- ----- ----- ----- ----- ----- ----- ------- ------- --------
1 0.41 0.04 0.32 0.09 0.14 0.00 91.80 91.62 -0.19
2 0.23 0.03 0.52 0.09 0.12 0.00 91.40 91.22 -0.19
3 0.26 0.03 0.52 0.07 0.12 0.00 91.80 91.36 -0.47
4 0.41 0.03 0.35 0.07 0.14 0.00 91.40 91.70 0.33
5 0.41 0.03 0.44 0.00 0.12 0.00 91.50 91.98 0.53
13
6 0.34 0.03 0.43 0.05 0.14 0.00 91.20 91.23 0.03
7 0.00 0.11 0.46 0.00 0.43 0.00 78.00 77.88 -0.16
8 0.41 0.12 0.00 0.00 0.47 0.00 78.20 78.22 0.03
9 0.35 0.12 0.00 0.05 0.48 0.00 77.60 77.98 0.49
10 0.16 0.11 0.20 0.09 0.00 0.44 80.00 80.85 1.06
11 0.23 0.10 0.29 0.00 0.00 0.38 84.00 82.73 -1.52
---- ------
AAD% 0.45
Table 4B
The predicted MON for gasoline blends from the binary interaction parameters
between components.
--------------------------------------------------------------------------------------------------
volume fractions of gasoline cuts in blends MON
------------------------------------------------------ ------------------
I z
1
z
2
z
3
z
4
z
5
z
6
Expt. Calc. Dev%
-- ----- ----- ----- ----- ----- ----- ------- ------- --------
1 0.41 0.04 0.32 0.09 0.14 0.00 81.40 80.66 -0.90
2 0.23 0.03 0.52 0.09 0.12 0.00 79.60 80.03 0.54
3 0.26 0.03 0.52 0.07 0.12 0.00 80.20 80.16 -0.04
4 0.41 0.03 0.35 0.07 0.14 0.00 80.80 80.73 -0.09
5 0.41 0.03 0.44 0.00 0.12 0.00 80.40 80.96 0.70
6 0.34 0.03 0.43 0.05 0.14 0.00 80.50 80.32 -0.22
7 0.00 0.11 0.46 0.00 0.43 0.00 72.70 72.29 -0.56
8 0.41 0.12 0.00 0.00 0.47 0.00 72.40 72.62 0.30
9 0.35 0.12 0.00 0.05 0.48 0.00 73.00 72.41 -0.80
10 0.16 0.11 0.20 0.09 0.00 0.44 74.40 74.97 0.76
11 0.23 0.10 0.29 0.00 0.00 0.38 75.80 75.98 0.24
---- ------
AAD% 0.47
To develop a universal set of binary interaction parameters between
components, a total of 161 blends from 157 gasoline cuts from Healy et
al.(1959) were used. The binary interaction parameters between components for
research and motor octane number derived from this large databank of gasoline
blends are given in Tables 5A and 5B. The overall average absolute deviation
percent (AAD%) for all 161 blends from 157 gasoline cuts is only 1.00% for
research octane number and 1.19% for motor octane number. These results
indicate that the proposed methodology enables the new correlation to
accurately predict octane number of a large number of very different gasoline
blends using only 3 generalized binary interaction parameters.
14
Table 5A
The universal set of the binary interaction parameters between components for
RON
--------------------------------------------------------------------------------------------------
k
OA
= 0.0670
k
OS
=-0.1021 k
AS
=-0.0232
--------------------------------------------------------------------------------------------------
Table 5B
The universal set of the binary interaction parameters between components for
MON
--------------------------------------------------------------------------------------------------
k
OA
= 0.0354
k
OS
=-0.0800 k
AS
= 0.0271
--------------------------------------------------------------------------------------------------
The increase of the AAD% of predicted research octane number from 0.5%
for blends from one group to 1.00% for all blends from all groups was not
unexpected. The contents of each gasoline cut are very complex and each cut
contains many different types of hydrocarbons. In spite of this complexity, the
laboratory analysis lumps the contents of each gasoline cut into only three
hydrocarbon types. The slight AAD% increase for all blends from all groups
may be due to this insufficient data analysis for gasoline cuts or data
inconsistency between groups. If the contents of the gasoline cut can be
analyzed in more detail in the laboratory analysis, the accuracy of prediction of
the octane number of the blends is expected to increase. Due to this data
inconsistency between groups, it is advised that it would be advantageous to re-
evaluate the binary interaction parameters for the specific group of blends by
optimization techniques if increased accuracy is desired. However, considering
the minimum information used in the equation, the accuracy of the prediction of
octane number from this work for any kind of gasoline blends is excellent.
Conclusion
We have shown that an interaction based correlation using the proposed
approach can be used to predict the research or motor octane numbers of
15
gasoline blends. An ultimately detailed analysis of gasoline cut is not necessary.
The correlation can describe blending behavior over the entire composition
range of gasoline cuts. The component type-oriented interaction approach is
general and will predict accurately, without doing additional blending study,
blending behavior for new gasoline cut.
The correlation proposed in this work has been found to fit the data quite
closely for blends of many gasoline cuts. The regression gives realistic values
for the binary interaction parameters between components. A unique set of
binary interaction parameters was found for the equation for the prediction of
octane number of any gasoline blends. The binary interaction parameters
between components contained in gasoline cuts have been converted to binary
interaction parameters between gasoline cuts through a general equation to
simplify the calculations of gasoline blends.
Because of the accuracy of the proposed method in the prediction of octane
numbers, the optimum allocation of components among gasoline grades can be
obtained and the predicted values can be used for quality control of the octane
number of marketed gasolines.
References
Auckland, M.H.T. and Charnock, D.J., The Development of Linear Blending
Indices for Petroleum Properties, J. of the Inst. of Petroleum, 55(545), 322-
329 (1969).
Healy, Jr.W.C., Maassen, C.W., and Peterson, R.T., A New Approach to
Blending Octanes, API Division of Refining, 24th midyear meeting, New
York, May 27, 1959.
Morris, W.E., Interaction Approach to Gasoline Blending, NPRA Paper AM-
75-30, National Petroleum Refiners Association annual meeting, March 1975.
Redlich, O. and Kister, A.T., Thermodynamics of Nonelectrolytic Solution.
Algebraic Representation of Thermodynamic Properties and Classification of
Solutions, Ind. Eng. Chem. 40, 345-348 (1948).
Rusin, M.H., Chung, H.S., and Marshall, J.F., A Transformation Method for
Calculating the Research and Motor Octane Numbers of Gasoline Blends,
Ind. Eng. Chem. Fundam., 20(3), 195-204 (1981).
16
Schoen, W.F. and Mrstik, A.V., Calculating Gasoline Blend Octane Ratings,
Ind. and Engr. Chem., 47(9), 1740-1742 (1955).
Stewart, W.E., Predict Octanes for Gasoline Blend, Petroleum Refiner,
38(12), 135-139 (1959).
Twu, C.H., Bluck, D., Cunningham, J.R., and Coon, J.E., 1991. "A Cubic
Equation of State with a New Alpha Function and a New Mixing Rule", Fluid
Phase Equilibria, 69:33-50.
Zahed, A.H., Mullah, S.A., and Bashir, M.D., Predict Octane Number for
Gasoline Blends, Hydrocarbon Processing, 85-87, May 1993.
17
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
90
92
94
96
O
c
t
a
n
e
N
u
m
b
e
r
o
f
B
l
e
n
d
Figure 1. The blending correlat ion in t his work simulates t he symmetrically
positive deviat ion of blending behavior wit h k
12
=-0. 12 and k
21 =-0.12
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
84
86
88
90
O
c
t
a
n
e
N
u
m
b
e
r
o
f
B
l
e
n
d
Figure 2. The blending correlation in this work simulates the symmetrically
negative deviation of blending behavior with k
12=0. 12 an d k
21
=0.12
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fract ion of Component 1
86
88
90
92
94
96
O
c
t
a
n
e
N
u
m
b
e
r
o
f
B
l
e
n
d
Figure 3. The blending correlation in t his work simulat es t he positive and
negat ive deviation of blending behavior wit h k
12
=- 0. 25 an d k
21 =0.18
18
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
90
92
94
96
98
O
c
t
a
n
e
N
u
m
b
e
r
o
f
B
l
e
n
d
Figure 4. The blending correlation in this work simulates the asymmetrically
positive deviation of blending behavior with k
12
=-0. 30 and k
21
=0.00
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
82
84
86
88
90
O
c
t
a
n
e
N
u
m
b
e
r
o
f
B
l
e
n
d
Figure 5. The blending correlation in this work simulates the asymmetrically
negative deviation of blending behavior with k
12
=0 .30 and k
21
=0.00
0.00 0.20 0.40 0.60 0.80 1.00
Volume Fraction of Component 1
0
20
40
60
80
100
O
c
t
a
n
e
N
u
m
b
e
r
o
f
B
l
e
n
d
Figure 6. The blending correlation in this work reproduces exactly the blending
behavior of isooctane and n-heptane binary with k
12
=0 a nd k
21
=0