Title of Invention	A METHOD OF ISOMERIZATION OF LIGHT GASOLINE FRACTIONS
Abstract	Title: A method of isomerization of light gasoline fractions. A method of isomerization of light gasoline fractions by contacting a raw material with a catalyst containing a hydrogenating component, Group 3B, 4A, 7A and 8A metal oxides and an oxygen-containing sulphur ion, at elevated temperature and pressure, in the presence of hydrogen, characterized in that as the oxide component the catalyst contains the following composition of metal oxides: xFe2O3 yMnO2 zTiO2 nAI2O3 rnZrO2, with the following mole coefficient values: x= (0.06-3.6) 10-3; y= (0.11-2.3) 10-3; z= (0.12-2.5) 10-3; n= (7.8-21.5) 10-2; m= (63.3-74.7) 10-2, and a mass ratio of said oxygen-containing sulphur ion to said composition of metal oxides is 0.042-0.178.

Title of Invention

A METHOD OF ISOMERIZATION OF LIGHT GASOLINE FRACTIONS

Abstract

Title: A method of isomerization of light gasoline fractions. A method of isomerization of light gasoline fractions by contacting a raw material with a catalyst containing a hydrogenating component, Group 3B, 4A, 7A and 8A metal oxides and an oxygen-containing sulphur ion, at elevated temperature and pressure, in the presence of hydrogen, characterized in that as the oxide component the catalyst contains the following composition of metal oxides: xFe2O3 yMnO2 zTiO2 nAI2O3 rnZrO2, with the following mole coefficient values: x= (0.06-3.6) 10-3; y= (0.11-2.3) 10-3; z= (0.12-2.5) 10-3; n= (7.8-21.5) 10-2; m= (63.3-74.7) 10-2, and a mass ratio of said oxygen-containing sulphur ion to said composition of metal oxides is 0.042-0.178.

Full Text	The invention relates to isomerization of light gasoline fractions to produce a high octane gasoline component, and may- be used in oil-refining and petrochemical industries. There are known a method for producing a catalyst useful in hydrocarbon isomerization, a catalyst produced by this method and use thereof (Patent RU N 2 191 627, IPC7 B01J 31/44, 1996) A raw material being isomerized is contacted with a catalyst which is a noble metal selected from platinum, palladium, ruthenium, osmium or iridium on an alumina support, containing up to 20 mass-% of such active components as silicon and titanium dioxides, magnesium or zirconium oxide. The alumina is pre-treated with an aluminium halide compound having a hydrocarbon substituent. The catalyst may be promoted with tin, lead, germanium, bismuth, cobalt, nickel, indium, zinc, uranium, thallium, zirconium or mixtures thereof. Isomerization is conducted at a temperature of 100-200°C in the presence of hydrogen, where hydrogen: raw material mole ratio is 0.01-5. A gas-raw material mixture is fed on a fixed-bed catalyst under a pressure of 0.2-4.0 MPa. The disadvantage of this method is low stability of isomerization (concentration of the most branched isomer 2,2-dimethylbutane (2,2-DMB) in the mixture of all hexane isomers decreases after 200 hours of operation from 28 mass-% to 14 mass-%). Known is a layered catalyst for paraffin isomeriziation (EP N 1 002 579, IPC7 B01J 37/02, 1999), a top layer of which t l comprises platinum in the' amount of 0.05-10 mass-%. A catalyst core is a zirconium oxide or a mixture of zirconium and aluminium oxides, containing 0.5-5 mass-% of sulfur. An intermediate layer comprises one of the following metals: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, preferably Mn, Fe, Ni, in the amount of 0.05-2 mass-%. An atomic ratio of the intermediate layer metal to the top layer metal is more than 3. Isomerization process is conducted at a temperature of 100-200°C and pressure of 0.03-4 MPa, in the presence of hydrogen (hydrogen:feedstock mole ratio is 0.05-5:1). The disadvantage of this process of isomerization of light gasoline fractions is low stability of isomerization (concentration of the most branched isomer 2,2-DMB in the mixture of all hexane isomers decreases after 200 hours of operation from 28 mass-% to 20 mass-%). The most similar method is isomerization of light gasoline fractions at a temperature of 170-270°C and pressure of 0.8-4.0 MPa, with hydrogen:raw material mole ratio equal to (0.2-10):1, with the use of a catalyst for isomerization of light paraffin C4-C6 hydrocarbons (Patent RU N' 2 171 713, IPC7 B01J 23/40, 2000) containing 0.2-1.0 mass-% platinum or palladium, 0.05-2.5 mass-% chlorine and 0.5-10 mass-% sulfate-ion, which are deposited on a mixture of aluminium and zirconium oxides. The aluminium oxide being pre-promoted with titanium and manganese used in the following mass ratios TiO:Al2O3=0.005-0.05 and MnO2:Al2O3 = 0. 001-0. 05. The disadvantage of this method is low stability of isomerization (concentration of the most branched 2,2-DMB isomer in the mixture of all hexane isomers decreases after 200 hours of operation from 34 mass-% to 25 mass-%). The proposed method of isomerization of light gasoline fractions provides a high stability of isomerization. The method of isomerization of light gasoline fractions is carried out by contacting a raw material with _ a catalyst containing the following composition of metal oxides: xFe203-yMnO2 • zTiO2-nAl2O3-mZrO2/ with a hydrogenating component and an oxygen-containing sulphur ion applied thereon, wherein mole coefficients in the composition of oxides are as follows: x=(0.06-3.6) -10-3; y= ( 0 .11-2 . 3 ) 10-3 ; z= ( 0 .12-2 . 5) • 10-3 ; n=(7.8-21.5) -10-2; m= (63 . 3-74 . 7) -10-2, and a mass ratio of sulphur ion to metal composition is 0.042-0.178. As the hydrogenating component of the catalyst use is made of a Group 8A metal: platinum and/or palladium, and/or iridium, and/or rhodium, and/or ruthenium, and as the oxygen-containing sulphur ion - a sulphuric acid ion, with the following mass ratio of catalyst components: Group 8A metal 0.1-0.8 sulphuric acid ion 4-15 metal compositions to 100 The process is conducted at a temperature of 100-220°C and pressure of 1.0-3.5 MPa, using hydrogen: raw material mole ratio=(0.3-l0):1. Mode of carrying out isomerization process. A raw material (pentane-hexane fraction) is mixed with a hydrogen-containing gas, maintaining the hydrogen: raw material mole ratio equal to (0.3-10):1. Further, the gas-raw material mixture is heated and supplied to a reactor, where it is brought into contact with the above described catalyst (hourly space velocity 0.5-4 hr-1) . In the reactor, isomerization of paraffin hydrocarbons C5-C6, hydrogenation of unsaturated and aromatic compounds and partial cracking of hydrocarbons with C1-C4 gases formation take place. Catalyst preparation. A composition of metal oxides is prepared by mixing iron, manganese, titanium, zirconium and aluminium hydroxides, maintaining the required mole ratio of oxides, with the following extrusion, drying and calcination at a temperature of 500-900°C. The obtained composition of metal oxides is impregnated with platinum and/or palladium, and/or iridium, and/or rhodium, and/or ruthenium compound solutions. To provide the required ratio of an oxygen-containing sulphur ion to a composition of oxides a sulphuric acid is added to the impregnating solution. After the impregnation is complete the catalyst is calcinated at a temperature of 400-700°C. For illustration of this method experiments were carried out for which a continuous flow pilot plant was used. A catalyst charge was 4 cm3. Isomerization process was conducted using a temperature range of 100-220°C, pressure 1.0- 3.5 MPa, hourly space velocity (V) 0.5-4.0 hr-1 and a mole ratio of hydrogen:raw material=(0.3-10) :1 (Q) . As the raw material a hydrofined straight run HK-70°C gasoline fraction was used, having octane number as determined by F-2 method - 67 items of the composition, mass-%: The reaction products were analyzed by flow gas-liquid chromatography using an OV-101 capillary column with a liquid phase. Degree of isomerization was assessed by 2,2-DMB proportion in the total amount of hexane isomers. Example 1 Raw material is mixed with hydrogen in a mole ratio of hydrogen to starting material = 5, heated to 150 °C and at a hourly space velocity of 2 hr'1 and under a pressure of 2.8 MPa is supplied to a reactor filled with a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 2 Isomerization process is carried out similarly to that as described in Example 1, except that feed space velocity is 0.5 hr"1, hydrogen:raw material mole ratio is 0.3 and the process is carried out under a pressure of 3.5 MPa and at a temperature of 100°C, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 3 Isomerization process is carried out similarly to that as described in Example 1, except that feed space velocity is 4.0 hr"1, hydrogen:raw material mole ratio is 10 and the process is carried out under a pressure of 1.0 MPa and at a temperature of 220°C, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 4 Isomerization process is carried out similarly to that as described in Example 1, except that feed space velocity is 0.5 hr-1, hydrogen:raw material mole ratio is 0.3 and the process is carried out under a pressure of 3.5 MPa and at a temperature of 100°C, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 5 Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 6 Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 7 Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 8 Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a weight ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2.' Example 9 Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 10 Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 11 (comparative) Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Isomerization process in comparative examples 12-20 is carried out similarly to that as described in Example 11. Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 21 (comparative) Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2. Example 22 (comparative) Isomerization process is carried out similarly to that as described in Example 1, using a catalyst having the following composition, mass-%: Mole coefficient values in the composition of oxides and a mass ratio of sulphuric acid ion to composition of oxides are provided in Table 1. Conditions under which the process is carried out and results are provided in Table 2 . The results which were obtained show high stability of the process of isomerizat'ion of light gasoline fractions (Ex. 1-10). However, these results can be obtained only with the claimed metal oxide mole coefficients in the composition and the claimed ratio of oxygen-containing sulphur ion to composition of metal oxides. Thus, with lowering mole coefficients of iron (ex. No.11), manganese (ex. No.13), titanium (ex. No.15), zirconium (ex. No.19) and aluminium (ex. No.17) oxides 2,2-DMB proportion in the total amount of C6 isomers decreases after 200 hours of operation by 17.9-21.1%. Increasing mole coefficients of iron (ex. No.12), manganese (ex. No.14), titanium (ex. No.16), aluminium (ex. No.18) and zirconium (ex. No.20) oxides above the claimed value decreases stability of isomerization process by 18.8-24.6%. As to a mass ratio of oxygen-containing sulphur ion to composition of metal oxides, both in the cases of this value decrease (ex. No.21) or its increase (ex. No.22) with respect to the claimed range 2,2-DMB proportion in the total amount of C6 isomers falls by 23-24%. WE CLAIM: 1. A method of isomerization of light gasoline fractions by contacting a raw material with a catalyst containing a hydrogenating component, Group 3B, 4A, 7A and 8A metal oxides and an oxygen-containing sulphur ion, at elevated temperature and pressure, in the presence of hydrogen, characterized in that as the oxide component the catalyst contains the following composition of metal oxides: xFe2O3 yMnO2 zTiO2 nAI2O3 rnZrO2, with the following mole coefficient values: x= (0.06-3.6) 10-3; y= (0.11-2.3) 10-3; z= (0.12-2.5) 10-3; n= (7.8-21.5)-10-2; m= (63.3-74.7) 10-2, and a mass ratio of said oxygen-containing sulphur ion to said composition of metal oxides is 0.042-0.178. 2. A method of isomerization of light gasoline fractions as claimed in claim 1, wherein as the hydrogenating component of the catalyst use is made of Group 8A metal(s) selected from the group consisting of: platinum, palladium, iridium, rhodium, ruthenium, mixture of platinum and palladium, mixture of platinum and iridium, mixture of platinum and rhodium, and mixture of platinum and ruthenium. 3. A method of isomerization of light gasoline fractions as claimed in claim 2, wherein as the oxygen-containing sulphur ion use is made of a sulphuric acid ion. 4. A method of isomerization of light gasoline fractions as claimed in claim 3, wherein the catalyst contains from 0.1 to 0.8 mass-% of Group 8A metal, from 4 to 15 mass-% of sulphuric acid ion and a composition of metal oxides with mass- % supplementing the total mass of the catalyst to 100%. 5. A method of isomerization of light gasoline fractions as claimed in claim 1, wherein the process is conducted at a temperature of 100-220°C and pressure of 1.0-3.5 MPa, with hydrogen: raw material mole ratio of (0.3-10): 1. ABSTRACT Title: A method of isomerization of light gasoline fractions. A method of isomerization of light gasoline fractions by contacting a raw material with a catalyst containing a hydrogenating component, Group 3B, 4A, 7A and 8A metal oxides and an oxygen-containing sulphur ion, at elevated temperature and pressure, in the presence of hydrogen, characterized in that as the oxide component the catalyst contains the following composition of metal oxides: xFe2O3 yMnO2 zTiO2 nAI2O3 rnZrO2, with the following mole coefficient values: x= (0.06-3.6) 10-3; y= (0.11-2.3) 10-3; z= (0.12-2.5) 10-3; n= (7.8-21.5) 10-2; m= (63.3-74.7) 10-2, and a mass ratio of said oxygen-containing sulphur ion to said composition of metal oxides is 0.042-0.178.

Full Text

The invention relates to isomerization of light gasoline
fractions to produce a high octane gasoline component, and may-
be used in oil-refining and petrochemical industries.
There are known a method for producing a catalyst useful in
hydrocarbon isomerization, a catalyst produced by this method
and use thereof (Patent RU N 2 191 627, IPC7 B01J 31/44, 1996) A raw material being isomerized is contacted with a catalyst
which is a noble metal selected from platinum, palladium,
ruthenium, osmium or iridium on an alumina support, containing
up to 20 mass-% of such active components as silicon and
titanium dioxides, magnesium or zirconium oxide. The alumina is
pre-treated with an aluminium halide compound having a
hydrocarbon substituent. The catalyst may be promoted with tin,
lead, germanium, bismuth, cobalt, nickel, indium, zinc, uranium,
thallium, zirconium or mixtures thereof. Isomerization is
conducted at a temperature of 100-200°C in the presence of
hydrogen, where hydrogen: raw material mole ratio is 0.01-5. A
gas-raw material mixture is fed on a fixed-bed catalyst under a
pressure of 0.2-4.0 MPa.
The disadvantage of this method is low stability of
isomerization (concentration of the most branched isomer
2,2-dimethylbutane (2,2-DMB) in the mixture of all hexane
isomers decreases after 200 hours of operation from 28 mass-% to
14 mass-%).
Known is a layered catalyst for paraffin isomeriziation (EP

N 1 002 579, IPC7 B01J 37/02, 1999), a top layer of which
t l
comprises platinum in the' amount of 0.05-10 mass-%. A catalyst
core is a zirconium oxide or a mixture of zirconium and
aluminium oxides, containing 0.5-5 mass-% of sulfur. An
intermediate layer comprises one of the following metals: Ti, V,
Cr, Mn, Fe, Co, Ni, Cu, Zn, preferably Mn, Fe, Ni, in the amount
of 0.05-2 mass-%. An atomic ratio of the intermediate layer
metal to the top layer metal is more than 3. Isomerization
process is conducted at a temperature of 100-200°C and pressure
of 0.03-4 MPa, in the presence of hydrogen (hydrogen:feedstock
mole ratio is 0.05-5:1).
The disadvantage of this process of isomerization of light
gasoline fractions is low stability of isomerization
(concentration of the most branched isomer 2,2-DMB in the
mixture of all hexane isomers decreases after 200 hours of
operation from 28 mass-% to 20 mass-%).
The most similar method is isomerization of light gasoline
fractions at a temperature of 170-270°C and pressure of 0.8-4.0
MPa, with hydrogen:raw material mole ratio equal to (0.2-10):1,
with the use of a catalyst for isomerization of light paraffin
C4-C6 hydrocarbons (Patent RU N' 2 171 713, IPC7 B01J 23/40,
2000) containing 0.2-1.0 mass-% platinum or palladium,
0.05-2.5 mass-% chlorine and 0.5-10 mass-% sulfate-ion, which
are deposited on a mixture of aluminium and zirconium oxides.
The aluminium oxide being pre-promoted with titanium and
manganese used in the following mass ratios TiO:Al2O3=0.005-0.05
and MnO2:Al2O3 = 0. 001-0. 05.

The disadvantage of this method is low stability of
isomerization (concentration of the most branched 2,2-DMB isomer
in the mixture of all hexane isomers decreases after 200 hours
of operation from 34 mass-% to 25 mass-%).
The proposed method of isomerization of light gasoline
fractions provides a high stability of isomerization.
The method of isomerization of light gasoline fractions is
carried out by contacting a raw material with _ a catalyst
containing the following composition of metal oxides:
xFe203-yMnO2 • zTiO2-nAl2O3-mZrO2/ with a hydrogenating component
and an oxygen-containing sulphur ion applied thereon, wherein
mole coefficients in the composition of oxides are as follows:
x=(0.06-3.6) -10-3; y= ( 0 .11-2 . 3 ) 10-3 ; z= ( 0 .12-2 . 5) • 10-3 ;
n=(7.8-21.5) -10-2; m= (63 . 3-74 . 7) -10-2,
and a mass ratio of sulphur ion to metal composition is
0.042-0.178.
As the hydrogenating component of the catalyst use is made
of a Group 8A metal: platinum and/or palladium, and/or iridium,
and/or rhodium, and/or ruthenium, and as the oxygen-containing
sulphur ion - a sulphuric acid ion, with the following mass
ratio of catalyst components:
Group 8A metal 0.1-0.8
sulphuric acid ion 4-15
metal compositions to 100
The process is conducted at a temperature of 100-220°C and
pressure of 1.0-3.5 MPa, using hydrogen: raw material mole

ratio=(0.3-l0):1.
Mode of carrying out isomerization process.
A raw material (pentane-hexane fraction) is mixed with a
hydrogen-containing gas, maintaining the hydrogen: raw material
mole ratio equal to (0.3-10):1. Further, the gas-raw material
mixture is heated and supplied to a reactor, where it is brought
into contact with the above described catalyst (hourly space
velocity 0.5-4 hr-1) . In the reactor, isomerization of paraffin
hydrocarbons C5-C6, hydrogenation of unsaturated and aromatic
compounds and partial cracking of hydrocarbons with C1-C4 gases
formation take place.
Catalyst preparation.
A composition of metal oxides is prepared by mixing iron,
manganese, titanium, zirconium and aluminium hydroxides,
maintaining the required mole ratio of oxides, with the
following extrusion, drying and calcination at a temperature of
500-900°C.
The obtained composition of metal oxides is impregnated
with platinum and/or palladium, and/or iridium, and/or rhodium,
and/or ruthenium compound solutions. To provide the required
ratio of an oxygen-containing sulphur ion to a composition of
oxides a sulphuric acid is added to the impregnating solution.
After the impregnation is complete the catalyst is calcinated at
a temperature of 400-700°C.
For illustration of this method experiments were carried
out for which a continuous flow pilot plant was used.
A catalyst charge was 4 cm3. Isomerization process was

conducted using a temperature range of 100-220°C, pressure 1.0-
3.5 MPa, hourly space velocity (V) 0.5-4.0 hr-1 and a mole ratio
of hydrogen:raw material=(0.3-10) :1 (Q) . As the raw material a
hydrofined straight run HK-70°C gasoline fraction was used,
having octane number as determined by F-2 method - 67 items of
the composition, mass-%:

The reaction products were analyzed by flow gas-liquid

chromatography using an OV-101 capillary column with a liquid
phase.
Degree of isomerization was assessed by 2,2-DMB proportion
in the total amount of hexane isomers.
Example 1
Raw material is mixed with hydrogen in a mole ratio of
hydrogen to starting material = 5, heated to 150 °C and at a
hourly space velocity of 2 hr'1 and under a pressure of 2.8 MPa
is supplied to a reactor filled with a catalyst having the
following composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 2
Isomerization process is carried out similarly to that as
described in Example 1, except that feed space velocity is
0.5 hr"1, hydrogen:raw material mole ratio is 0.3 and the
process is carried out under a pressure of 3.5 MPa and at a
temperature of 100°C, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 3
Isomerization process is carried out similarly to that as
described in Example 1, except that feed space velocity is
4.0 hr"1, hydrogen:raw material mole ratio is 10 and the process
is carried out under a pressure of 1.0 MPa and at a temperature
of 220°C, using a catalyst having the following composition,
mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 4
Isomerization process is carried out similarly to that as
described in Example 1, except that feed space velocity is
0.5 hr-1, hydrogen:raw material mole ratio is 0.3 and the

process is carried out under a pressure of 3.5 MPa and at a
temperature of 100°C, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 5
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 6
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following

composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 7
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 8
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following

composition, mass-%:

Mole coefficient values in the composition of oxides and a
weight ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.'
Example 9
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 10
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following

composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 11 (comparative)
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Isomerization process in comparative examples 12-20 is
carried out similarly to that as described in Example 11.
Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.

Conditions under which the process is carried out and
results are provided in Table 2.
Example 21 (comparative)
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2.
Example 22 (comparative)
Isomerization process is carried out similarly to that as
described in Example 1, using a catalyst having the following
composition, mass-%:

Mole coefficient values in the composition of oxides and a
mass ratio of sulphuric acid ion to composition of oxides are
provided in Table 1.
Conditions under which the process is carried out and
results are provided in Table 2 .

The results which were obtained show high stability of the
process of isomerizat'ion of light gasoline fractions (Ex. 1-10).
However, these results can be obtained only with the
claimed metal oxide mole coefficients in the composition and the
claimed ratio of oxygen-containing sulphur ion to composition of
metal oxides.
Thus, with lowering mole coefficients of iron (ex. No.11),
manganese (ex. No.13), titanium (ex. No.15), zirconium (ex.
No.19) and aluminium (ex. No.17) oxides 2,2-DMB proportion in
the total amount of C6 isomers decreases after 200 hours of
operation by 17.9-21.1%.
Increasing mole coefficients of iron (ex. No.12), manganese
(ex. No.14), titanium (ex. No.16), aluminium (ex. No.18) and
zirconium (ex. No.20) oxides above the claimed value decreases
stability of isomerization process by 18.8-24.6%.
As to a mass ratio of oxygen-containing sulphur ion to
composition of metal oxides, both in the cases of this value
decrease (ex. No.21) or its increase (ex. No.22) with respect to
the claimed range 2,2-DMB proportion in the total amount of C6
isomers falls by 23-24%.

WE CLAIM:
1. A method of isomerization of light gasoline fractions by contacting a raw
material with a catalyst containing a hydrogenating component, Group 3B,
4A, 7A and 8A metal oxides and an oxygen-containing sulphur ion, at
elevated temperature and pressure, in the presence of hydrogen,
characterized in that as the oxide component the catalyst contains the
following composition of metal oxides:
xFe2O3 yMnO2 zTiO2 nAI2O3 rnZrO2,
with the following mole coefficient values:
x= (0.06-3.6) 10-3;
y= (0.11-2.3) 10-3;
z= (0.12-2.5) 10-3;
n= (7.8-21.5)-10-2;
m= (63.3-74.7) 10-2,
and a mass ratio of said oxygen-containing sulphur ion to said
composition of metal oxides is 0.042-0.178.

2. A method of isomerization of light gasoline fractions as claimed in claim 1,
wherein as the hydrogenating component of the catalyst use is made of Group
8A metal(s) selected from the group consisting of:
platinum,
palladium,
iridium,
rhodium,
ruthenium,
mixture of platinum and palladium,
mixture of platinum and iridium,
mixture of platinum and rhodium, and
mixture of platinum and ruthenium.
3. A method of isomerization of light gasoline fractions as claimed in claim 2,
wherein as the oxygen-containing sulphur ion use is made of a sulphuric acid ion.
4. A method of isomerization of light gasoline fractions as claimed in claim 3,
wherein the catalyst contains from 0.1 to 0.8 mass-% of Group 8A metal, from 4
to 15 mass-% of sulphuric acid ion and a composition of metal oxides with mass-
% supplementing the total mass of the catalyst to 100%.

5. A method of isomerization of light gasoline fractions as claimed in claim 1,
wherein the process is conducted at a temperature of 100-220°C and pressure of
1.0-3.5 MPa, with hydrogen: raw material mole ratio of (0.3-10): 1.

ABSTRACT
Title: A method of isomerization of light gasoline fractions.
A method of isomerization of light gasoline fractions by contacting a raw material
with a catalyst containing a hydrogenating component, Group 3B, 4A, 7A and 8A
metal oxides and an oxygen-containing sulphur ion, at elevated temperature and
pressure, in the presence of hydrogen, characterized in that as the oxide
component the catalyst contains the following composition of metal oxides:
xFe2O3 yMnO2 zTiO2 nAI2O3 rnZrO2, with the following mole coefficient values: x=
(0.06-3.6) 10-3; y= (0.11-2.3) 10-3; z= (0.12-2.5) 10-3; n= (7.8-21.5) 10-2; m=
(63.3-74.7) 10-2, and a mass ratio of said oxygen-containing sulphur ion to said
composition of metal oxides is 0.042-0.178.

A METHOD OF ISOMERIZATION OF LIGHT GASOLINE FRACTIONS

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