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Chemistry and Technology of Fuels and Oils, Vol. 48, No. 2, May, 2012 (Russian Original No.

2, March-April, 2012)

DESTRUCTIVE HYDROISOMERIZATION A NEW METHOD OF REDUCING


BENZINE CONTENT IN COMMERCIAL GASOLINE

Kh. I. Abad-Zade, Z. A. Gasymova, G. S. Mukhtarova, N. Kh. Efendieva,


A. N. Kyazimova, and R. G. Ibragimov

A destructive process of hydroisomerization of straight-run 85-185C gasoline fraction followed by


close fractionation of the products into a high-octane low-boiling (85C) isocomponent and a fraction
with a final BP of 85C is proposed. The latter is free of benzene-forming hydrocarbons and is submitted
to catalytic reforming under mild conditions. Gasoline with octane number 86 (MM) and
containing ~51 wt. % of aromatic hydrocarbons, including less than 0.5 wt. % of benzene, is obtained by
compounding the isocomponent and the reformate in 25:75 ratio.
Key words: destructive hydroisomerization, isocomponent, reforming, reformate, high-octane gasoline.
Stringent requirements as to the content of toxic substances in the exhausts of vehicles dictates the need
to alter the composition of the motor fuels reduce the sulfur and aromatic-hydrocarbon contents, particularly
benzene, while simultaneously improving the operational characteristics an increase in octane number, better
vaporability, and a reduction in the difference in the octane number of the gasoline as a whole and the fraction that
boils-off to 100C. This requires serious changes in the procedure used to produce the gasoline components and
balance their compounding.
Fulfillment of requirements regarding benzene content and the sums of aromatic hydrocarbons in gasoline
represents a major problem, since the basic high-octane component of automotive gasolines produced in large
part by petroleum refineries is a reformate containing benzene and the sums of the aromatic hydrocarbons in
which 7 and 70 wt. % are obtained, respectively. Moreover, the aromatic hydrocarbons are concentrated in the
high BP fractions of the reformate. The reformate fraction that boils-off to 100C has an octane number
of 71-73 (MM), and the octane number is therefore distributed nonuniformly with respect to boiling point. Even
though the gasoline is evaluated as high-octane on the whole, knocking may be observed during transitional
operating regimes of an engine running on this gasoline.
____________________________________________________________________________________________________
Yu. G. Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
Baku. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 31 33, March April, 2012.
130

0009-3092/12/48020130 2012 Springer Science+Business Media, Inc.

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

Yield of products, wt. %


16.1

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

Isocomponent (IBP of 85C)

Resid > 85C


Ratio

Octane number (MM) of isocomponent

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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

Sulfur content, wt. % . . . . . . . . . . . . . .


Octane number based on MM . . . . . . . . . . . .

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.

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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

Yield of products, wt. %


Stable reformate
Hydrogen
Characteristics of reformate
Density at 20C, kg/m3
Fractional composition, C
IBP

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

destructive hydroisomerization of the straight-run 85-185C gasoline fraction followed by separation of


the hydroisomerizate into an isocomponent (IBP 85C fractions) and > 85C resid;
reforming of the > 85C of the hydroisomerization under mild conditions (temperature of 475C) to
eliminate demethylation of the alkyl aromatic hydrocarbons, which leads to the formation of benzene; and,
compounding of the isocomponent and reformate in a 25:75 ratio with the production of high-octane
gasoline with a benzene content of less than 0.5 wt. % and an aromatic-hydrocarbon content of ~ 51 wt. %.
Table 3 presents results of compounding of the isocomponent and reformate. The procedure proposed
can be implemented at all petroleum refineries. Destructive hydroisomerization of the 85-195C fraction may replace
preliminary hydrotreatment of the reforming feedstock.
REFERENCES
1.
2.

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.

USSR Authors Certificate 727213.

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