DE1074182B - Process for the autofining of petroleum distillates - Google Patents

Description

GERMAN

The invention relates to an autofining method for the catalytic desulfurization of petroleum hydrocarbons, as described in the British patents 654152, 663 038, 669 536, 669 552, 669 553, 697 222, 697 226 and 697 724 is described.

According to this process, sufficient desulfurization of lower-boiling petroleum distillates, such as gasoline and luminous oil, is often achieved at the relatively low pressures of 7 kg / cm ² .

In order to achieve a corresponding desulfurization of the higher-boiling petroleum distillates, such as gas oils, is however, it is generally necessary after the British Patent 697083 described to work at the equilibrium pressure method, in which the higher Pressures occur. For the autofining treatment of lower-boiling raw materials with lower ones Equipment suitable for pressure does not necessarily have to be able to operate at the higher pressures under equilibrium pressure conditions be suitable. However, it is desirable that the higher-boiling petroleum ao Destulate can be desulphurized in these plants using the autofining process.

It has now been found that higher-boiling petroleum distillates, a single autofining treatment at pressures below equilibrium pressure is insufficient desulphurized by returning or re-treating the product from the first treatment can be further desulfurized under essentially the same conditions.

The subject matter of the invention is thus a method for the auto-finishing of petroleum fractions obtained by an auto-lining treatment not sufficiently desulfurized at pressures below the autofining equilibrium pressure , which is characterized in that the starting materials at pressures below the autofining equilibrium pressure subjected to an autofining treatment and then the product with reduced sulfur content autofinished one or more times.

The products from the autofining desulphurisation can be sent to the same autofining zone for further treatment can be returned or fed over fresh catalysts under autofining conditions.

The invention is particularly suitable for the autofining treatment of gas oils.

The catalysts used preferably consist of the oxides of cobalt and molybdenum as such or in the form of compounds which are applied to a metal oxide carrier, usually aluminum oxide. The catalysts advantageously contain a small amount, preferably between 0.1 and 6.0 percent by weight of fluorine, as described in British Patent 719,627. The use of such catalysts increases the degree of desulphurization in this case, in which one cannot use the equilibrium method for autofining
of petroleum distillates

Applicant:

The British Petroleum Company Limited, London

Representative: Dr.-Ing. A. ν. Kreisler, patent attorney,
Cologne 1, Deichmannhaus

Claimed priority:
Great Britain from. March 22, 1955

John Arthur Edgar Moy and John Rowland,

SutLbury-on-Thames, Middlesex (Great Britain),

have been named as inventors

pressure works, not enlarged, but the Lower pressures obtain a greater overall yield of hydrogen, which is advantageous in other refining processes can be applied.

The invention is illustrated in the following examples:

example 1

A Kuwait gas oil is used in a pilot plant with 100 ecm catalyst capacity under the following conditions subjected to an autofining treatment:

Temperature 416 ° C

Pressure, 8 kg / cm ²

Space velocity 2 V / V / hour

Return speed 357 cm ³ / cm ³

Duration 40 hours

The starting material had the following data:

Specific gravity, 16 ° / 16 ° 0.8435

Initial Boiling Point (ASTM Destflation), ° C 248

Final boiling point, ⁰ C ... 360

Sulfur content, weight percent 1.26

Bromine number 3.7

Aromatics (ASTM D 875), percent by volume. 14

The liquid product is washed with caustic soda and water to remove dissolved hydrogen sulfide, and then passed over a fresh catalyst filling under the same conditions. It'll be two Kinds of catalyst related, namely a catalyst made of oxides of alumina applied to

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I 0/4

Cobalt and molybdenum and a catalyst of similar composition that activates with aluminum fluoride is. The following results are obtained:

Chemical composition

des at 550 ° C
'' stable catalyst

sator material
in components /
100 g catalyst

catalyst

of the non-fluorine-containing catalyst five times of an autofining treatment subject. Thereafter, the sulfur content of the product is reduced to 0.17 percent by weight. The following results are obtained:

Mixed oxides of cobalt and

Molybdenum on aluminum oxide

15.75
3.2
0

Mixed oxides of cobalt and molybdenum on aluminum oxide, with aluminum fluoride activated

14.4

3.2 3.36

Duration in hours

Sulfur content of the product, percent by weight

Total hydrogen formation, m ³ / t

Liquid product, data after the first treatment

Specific gravity, 16 ^O / 16 ° 0.8365 0.8390

Initial Boiling Point (ASTM), ⁰ C 110 104

Final Boiling Point (ASTM), 354 355 ° C so

Bromine number 10.2 10.7

Aromatics (ASTM D 875), volume percent 13.5 12.5

Sulfur content, percent by weight. 0.54 0.55

Sulfur removal,% 57 56

Total hydrogen formation, m ³ / t 22 26

Liquid product, data after the second treatment

Specific gravity, 16 ^O / 16 ° 0.8350 0.8375

Initial Boiling Point (ASTM), 89 94 ° C

Final Boiling Point (ASTM), ⁰ C 355 359

Bromine number 9.8 11.8

Aromatics (ASTM D 875), volume percent 14.0 16.0

Sulfur content, percent by weight .. 0.40 0.44

Sulfur removal,% 26 22

Total hydrogen formation, m ³ / t 5.8 8.2

Example 2

The same starting material as in Example 1 is made under the conditions of Example 1 using number of treatments
1 I 2 I 3 I 4 I 5

6.4

21

5.2

21

20th , 0

20th

Claims (4)

Patent claims: 1. A method for autofining petroleum fractions which are not sufficiently desulfurized by an autofining treatment at pressures below the autofining equilibrium pressure, in particular gas oils, characterized in that the starting materials are subjected to an autofining treatment at pressures below the autofining equilibrium pressure and the product with a reduced sulfur content is subjected one or more times auto-mated. 2. The method according to claim 1, characterized in that the products for re-treatment in the same autofining zone can be returned. 3. The method according to claim 1, characterized in that the products for re-treatment be conducted under autofining conditions over fresh catalysts. 4. Process according to Claims 1 to 3, characterized in that the catalysts used in both process stages consist of the oxides of cobalt and molybdenum as such or as compounds which are applied to a carrier consisting essentially of aluminum oxide and optionally 0.1 to 6 ° / ₀ containing fluorine. © 909 727/46 »1.60