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2, March-April, 2012)
To ensure a quality gasoline stock, it is necessary to determine the means by which the total content of
aromatic hydrocarbons is reduced in the gasoline. In that context, a unique method of diluting the reformates is to
appreciably increase the content of branched paraffin hydrocarbons in commercial gasolines. For this purpose, it
is necessary to revise substantially the structure of active petroleum refineries within the framework of the traditional
expensive approach in order to explore the possibility of a multiple increase in the isomerization yield of plants
producing light gasoline fractions with a simultaneous increase in the yield of oxygenate-production processes.
A similar cycle of measures will hardly be possible to implement in the continuing worldwide recession.
Promising high-octane gasoline should contain 20-30 wt. % of isoparaffin hydrocarbons, the introduction
of which will raise the octane number of the light fractions (40-85C), render the distribution of anti-knock
characteristics more uniform with respect to the distillation curve, and ensure a reduction in the content of
aromatic and olefin hydrocarbons in the gasolines.
The set of production processes that have been formulated in worldwide refining over many years has
not, even in perspective, permitted a continuously expanding vehicular fleet operating on high-quality gasolines
containing a significant amount of isoparaffin components. At the present time, and in the near future, reforming
Table 1
Indices
Temperature, C
340
360
380
400
22.3
37.4
42.2
propane
0
4.4
0.1
6.0
0.6
14.0
1.0
17.2
isobutene
8.9
11.7
15.9
16.0
n-butane
2.8
4.5
6.9
8.0
19.5
26.4
32.2
31.2
including
isopentane
9.0
12.8
16.9
16.6
n-pentane
0.9
1.4
2.0
2.1
2,3-dimethylbutane + 2-methylpentane
3.9
4.6
4.8
4.9
3-methylpentane
n-hexane
1.3
0.7
2.7
1.0
3.0
1.3
2.9
1.4
2,4-dimethylpentane
0.3
0.3
0.6
0.5
methylcyclopentane
benzene
3.4
0
3.6
0
3.5
0.1
2.7
0.1
64.4
51.3
30.4
26.6
isobutane:n
3.2
2.6
2.3
2.0
isopentane:n
10.0
9.1
8.5
7.9
isohexane:n
7.4
6.8
5.7
5.2
86.5
86
86
85.5
Gas
including
methane, ethane
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is and will remain the fundamental process by which the basic volume of high-octane gasolines is produced in
Russia, and also abroad [1]. To convert to automotive gasolines with improved ecological characteristics, it is
necessary to reform the gasoline stock, since the gasolines currently produced are characterized by a high content
of reformates and low-octane components.
A reformate of 60-65 wt. % consists of aromatic hydrocarbons, and only 30-40 wt. % of paraffin
hydrocarbons. As a result, the content of aromatic hydrocarbons in gasoline should not exceed 25 wt. % in
conformity with Euro-5 standards and the stringent ecological standards of the United States [2].
Substantial reorientation on processes employed for the production of isoparaffin hydrocarbons is required
to fulfill these ecological requirements. One of these priority processes ensuring the production of C 5-C 8 isoparaffins
is destructive hydroisomerization of low-octane gasoline fractions. This process can be used to obtain the light
high-octane component of automotive gasolines, and also a feedstock for petrochemistry. The process in question
was developed by the Institute of Petrochemical Processes of the Academy of Sciences of Azerbaijan SSR. A
zeolite-containing NiAlSi catalyst with a highly disperse distribution of nickel was developed for its industrial
implementation [3].
Prior to conducting experiments, the catalyst, which is charged into a reactor, was activated in a dry-air
current for a period of 3 h at 550C, and reduced by hydrogen over a period of 8-10 h at 480C under a pressure
of 2 MPa. The low-octane straight-run 85-195C fraction, the characteristics of which are cited below, was used as
feedstock. The feedstock contained no unsaturated hydrocarbons, benzene, and n-hexane.
Density at 20C, kg/m 3 . . . . . . . . . . . . . . . . 748
Fractional composition, C
IBP . . . . . . . . . . . . . . . . . . . . . 87
10% . . . . . . . . . . . . . . . . . . . . 100
50% . . . . . . . . . . . . . . . . . . . . 127
90% . . . . . . . . . . . . . . . . . . . .
EP
. . . . . . . . . . . . . . . . . . . .
Average molecular mass . . . . . . . . . . . . . .
Hydrocarbon composition, wt. %
167
196
112.04
aromatic . . . . . . . . . . . . . . . . . .
naphthene . . . . . . . . . . . . . . . . .
140.6
35.58
including C 6 . . . . . . . . . . . . .
paraffin
. . . . . . . . . . . . . . . . .
0.67
50.35
0.03
43
The experiments were conducted on a flow-through laboratory plant with a stationary catalyst bed with a
volume of 200 m 3 at 340-400C, under a pressure of 6 MPa, a bulk feedstock delivery of 1/h, and a hydrogen:feedstock
ratio of 1,000 m 3/m 3. The gas and IBP85 fraction were analyzed by the chromatographic method.
Data on the influence exerted by the temperature of the reaction on the results of destructive
hydroisomerization of the 85-195 fraction (Table 1) indicate that the yield of the isocomponent attains 32.2 wt. %,
and then diminishes somewhat as the temperature is raised to 380C; the yield of gaseous hydrocarbons increases
continuously with increasing temperature; and, the ratio of branched to the normal C 4 -C6 hydrocarbons decreases.
132
The octane number of the isocomponent attains 86.5 (based on the MM) owing to the high content of
the C 5-C 6 isoparaffin hydrocarbons. The isocomponent can be used as a high-octane component of AI-93 automotive
gasoline. In addition to the isocomponent, a significant amount (22.3 wt. %) of the C 1-C- 4 hydrocarbons,
including 11.7 wt. % of isobutane, which can be used to produce methyl-tri-butyl ether, is formed under optimal
conditions (temperature of 360C, pressure of 6 MPa, bulk feed rate of 1/h).
The >85C resid, which is separated by close fractional distillation is characterized by a high content of
naphthene hydrocarbons (42 wt. %), and a low sulfur content (0.001 wt. %), and, consequently, is a high-quality
feedstock for catalytic reforming.
The material balance and characteristics of the product obtained during reforming of the >85C resid of
the close fractional distillation of the hydroisomerizate are presented in Table 2. As is apparent, the yield of
aromatic hydrocarbons and benzene increases, respectively, from 68.5 to 87 wt. % and from 0.6 to 2.6 wt. % as the
temperature is raised from 475 to 520C (the other parameters of the process do not vary).
Thus, the following are proposed for reducing the content of aromatic hydrocarbons, and also benzene
to 0.5 wt. % in commercial gasolines:
Table 2
Indices
Temperature, C
475
500
520
88
85
78
2.3
2.4
2.55
793
807
829
58
58
54
10
103
99
95
50
90
129
128
130
170
175
180
EP
209
102.64
210
102
220
99
68.5
74.0
86.9
0.6
0.75
2.6
17.71
16.38
27.99
Molecular mass
Hydrocarbon composition, wt. %
unsaturated
aromatic
including
benzene
toluol
naphthene
2.9
2.5
0.77
including C6
0.85
0.4
0.23
paraffin (n-hexane)
28.6 (0.91)
23.5 (0.9)
12.33 (0.88)
MM
85.5
89
95
RM
95.5
99
101
Octane number
133
Table 3
Component
content in
compound,
wt. %
aromatic
hydrocarbons
benzene
Reformate
75
68.5
0.6
793
Isocomponent
25
700
Compound
100
51.26
0.45
769.6
Component
Content, wt. %
Octane number
Density, kg/m3
RM
MM
95
85.5
86.5
95
85.8
M. I. Levinbuk, E. F. Kaminskii, and O. F. Glagoleva, Khim. Tekhnol. Topl. Masel, No. 2, 6-11 (2000).
B. K. Nefedov, Neftekhim., 39, No. 5, 343-352 (1999).
3.
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