DE1014692B - Process for the hydrocatalytic desulphurisation of petroleum hydrocarbons - Google Patents

Description

The invention relates to a method for the hydrocatalytic desulfurization of petroleum hydrocarbons, especially the desulfurization of gas oils.

It is known to hydrocatalytically desulfurize gas oils in the vapor phase. Such a process is usually carried out at pressures between 33 and 66 kg / cm ² , temperatures from 400 to -440 °, at high recycling rates, for example 720 m ³ / m ³ . It is also known to treat gas oils in the liquid phase, the oils at temperatures above 200 ° and pressures of at least 10 atm. can flow in a thin layer over the catalysts. Typical process conditions are temperatures of 350 ° and pressures of 50 at. It has already been pointed out that low recycling rates of about 45 to 225 m ³ / m ^{3 are} possible under such conditions.

It has now been found that working at higher temperatures, which is usually only in the vapor phase is possible at lower return speeds than were previously common at such temperatures, is advantageous.

According to the invention, the hydrocatalytic desulfurization of petroleum hydrocarbons is carried out at temperatures of 400 to 440 °, pressures above 20 kg / cm ² , preferably between 33 and 66 kg / cm ² , at room flow rates of the liquid starting material of 0.5 to 20 V / V / Hours. and hydrogen recycle velocities not exceeding 360 m ^s / m ³ .

The catalysts used in the process of the invention preferably consist of cobalt and / or Molybdenum oxides which are applied to a metal oxide carrier, preferably aluminum oxide.

The method according to the invention is particularly suitable for the desulfurization of gas oils. The preferred return speed is 180 m ^s / m ³ . When gas oils are desulfurized under such conditions, although a substantial proportion of the oil in the reactor is in the liquid phase, the method according to the invention is advantageous over known methods which run in the liquid phase in that, because of the higher temperatures used, higher space flow velocities can also be used. Compared to known processes carried out in the vapor phase, the subject of the application has the advantage that the reduction in the return rate of 720 m ³ / m ³ results in a reduction in process costs.

The invention is illustrated in the following examples:

example 1

A straight run Middle Eastern gas oil grading 1.25 weight percent sulfur was added at a space velocity of 8 V / V / hr., 415 °, a

procedure

for the hydrocatalytic desulfurization of petroleum hydrocarbons

Applicant:

The British Petroleum Company Limited, London

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

Claimed Priority: Great Britain April 14, 1954

Frederick William Bertram Porter

and Roy Purdy Northcott,

Sunbury-on-Thames, Middlesex (Great Britain), have been named as inventors

Pressure of 66 kg / cm ² and a gas recirculation rate of 225 m ³ / m ³ over a cobalt-molybdenum oxide on aluminum oxide catalyst using exhaust gases from a catalytic reforming which contained 70 mol percent hydrogen, desulfurized. The product contained 0.1 weight percent sulfur. The hydrogen consumption was 23.4 m ³ / m ³ . The catalyst only needs to be regenerated every 12 months.

Example 2

A mixture of 80 volume percent straight run Middle East gas oil and 20 volume percent Middle East cycle oil of a light catalytic cracking process containing 1.6 weight percent sulfur was fed at a space flow rate of 8 v / v / hr. at 415 °, a pressure of 66 kg / cm ² and a gas recirculation speed of 225 m ³ / m ³ via a catalyst consisting of cobalt-molybdenum oxide on aluminum oxide

lysator, using exhaust gases from a catalytic reforming with a content of 70 mol percent hydrogen, desulfurized. The product contained 0.1 weight percent sulfur. The hydrogen consumption was 36 m ³ / m ³ . The catalyst only needs to be regenerated every 6 months.

Example 3

A mixture of 80 percent by volume straight-run gas oil and 20 percent by volume cycle oil from a light

709 659/389

Catalytic cracking, both from Middle Eastern crude, was carried out in a hydrofining process over a catalyst from cobalt and molybdenum oxides on aluminum oxide under the following conditions and outcomes.

The results of both examples show that under the temperature, pressure and space flow conditions in question, reducing the recycle rate from 720 to 225 m ³ / m ^{3 has} no significant effect on sulfur removal.

Pressure in kg / cm ²

Temperature in ° C

Room flow velocity in V / V / hour

Return speed in m ³ / m ³

Weight percent sulfur in the starting material

Weight percent sulfur in the product

Sulfur removal in%

Trial A Trial B

66 400

8.0 225 1.51

0.06 96.0

66

415

IO

8.0 720 1.47

0.08 94.5

20th

Example 4

In similar experiments as in Example 3 using Ahren cycle oil from a light catalytic Crackverf as a starting material were the disadvantages ₂ applied mentioned conditions and obtained the following results.

Trial A Trial B

Pressure in kg / cm ²

Temperature in ⁰ C

Room flow velocity in V / V / hour

Return speed in m ³ / m ³

Weight percent sulfur in the starting material

Weight percent sulfur in the product

Sulfur removal in%

66 415

8.0 225 2.54

0.12 95.3

35

66 415

8.0 720 2.61

0.09 40 96.5

Claims (6)

Patent claims: 1. A method for hydrocatalytic desulfurization of petroleum hydrocarbons boiling in the gas oil range, in particular, characterized in that the hydrocarbons are mixed with up to 360 m ^s / m ^{s of} hydrogen at room flow rates of the liquid starting material between 0.5 to 20 V / V / hour at temperatures between 400 and 440 ° and pressures of at least 20 kg / cm ² with conversion of the organically bound sulfur in the hydrocarbons into hydrogen sulphide over sulfur-resistant hydrogenation catalysts and the hydrogen sulphide is then separated from the treated hydrocarbons. 2. The method according to claim 1, characterized in that one works at pressures of 33 to 66 kg / cm ² . 3. The method according to claim 1 and 2, characterized in that catalysts are used those made of cobalt and / or applied to a metal oxide carrier, preferably aluminum oxide Molybdenum oxides exist. 4. The method according to claim 1 to 3, characterized in that the hydrocarbons are passed in a mixture with about 180 m ³ / m ^{3 of} hydrogen over the catalysts. Considered publications:
Oil and coal, 6th year (1953), p. 616 to 619, year (1954), No. 12, p. 817/818;
Petroleum Refiner, 32, No. 5 (1953), p. 137. ©? » 659,389 8.