# US 10,369,546 B2 · Process for oxidative desulfurization with integrated sulfone decomposition

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- Number: US 10,369,546 B2
- Document ID: US10369546B2
- Status: Granted
- Kind: B2
- Application number: 15/894,341
- Filed: 2018-02-12
- Published: 2018-08-09
- Granted: 2019-08-06
- Earliest claimed: 2011-07-31
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Omer Refa Koseoglu; Abdennour Bourane
- Web page: https://patentgrep.com/patent/US10369546B2

## CPC

- B01J 23/06: of zinc, cadmium or mercury
- B01J 21/04: Alumina
- B01J 23/007: {Mixed salts}
- B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C10G 29/04: Metals, or metals deposited on a carrier
- C10G 29/16: Metal oxides
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

The process provided herein is concerned with disposal of oxidized sulfur compounds formed by oxidative desulfurization. The process uses solid base catalyst pretreated with a base and eliminates the need to separate the sulfones from the hydrocarbon streams and recover the hydrocarbons.

## Claims

### Claim 1

A process for reducing the concentration of oxidized sulfur compounds from a mixture of liquid hydrocarbons and the oxidized sulfur compounds, the process comprising:
a. contacting the mixture of hydrocarbons and oxidized sulfur compounds with a solid base catalyst composition in the presence of a caustic solution,
the solid base catalyst composition comprising separate components or a mixture of zinc oxide, aluminum oxide, zinc aluminates, layered double hydroxides, and magnesium/aluminum layered double hydroxide,
the contacting occurring under conditions effective to promote catalytic decomposition of a portion of the oxidized sulfur compounds into SOx compounds;
b. removing SOx compounds from the hydrocarbon mixture; and
c. recovering a hydrocarbon product having a reduced concentration of oxidized sulfur compounds.

### Claim 2 (depends on 1)

The process as in claim 1, wherein the solid base catalyst composition includes a layered double hydroxide of the general formula (I)
ZnAl2O4.x(ZnO).y(Al2O3) (I)
wherein x and y are independently between 0 and 2, and
wherein the total proportion of ZnAl2O4 in the formula (I) is at least 10 percent by weight.

### Claim 3 (depends on 2)

The process as in claim 2, wherein the layered double hydroxide comprises 100% by weight of the solid base catalyst composition.

### Claim 4 (depends on 2)

The process as in claim 2, wherein the layered double hydroxide comprises at least 50% by weight of the solid base catalyst composition.

### Claim 5 (depends on 2)

The process as in claim 2, wherein the layered double hydroxide comprises at least 1% by weight of the solid base catalyst composition.

### Claim 6 (depends on 1)

The process as in claim 1, wherein the solid base catalyst is a porous material in the form of powder, extrudates or spheres.

### Claim 7 (depends on 1)

The process as in claim 1, wherein the solid base catalyst has a surface area in the range of from 10 m2/g to 600 m2/g.

### Claim 8 (depends on 1)

The process as in claim 1, wherein the solid base catalyst has a surface area in the range of from 50 m2/g to 600 m2/g.

### Claim 9 (depends on 1)

The process as in claim 1, wherein the solid base catalyst has a pore volume in the range of from 0.1 cm3/g to 0.5 cm3/g.

### Claim 10 (depends on 1)

The process as in claim 1, wherein the solid base catalyst has a pore volume in the range of from 0.3 cm3/g to 0.5 cm3/g.

### Claim 11 (depends on 1)

The process as in claim 1, wherein the solid base catalyst has a pore distribution of 0.001 microns to 0.1 microns.

### Claim 12 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 200° C. to 600° C.

### Claim 13 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 300° C. to 400° C.

### Claim 14 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 300° C. to 350° C.

### Claim 15 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted with the solid base catalyst in the presence of a caustic solution, wherein the base is dissolved in the mixture of hydrocarbons and oxidized sulfur compounds.

### Claim 16 (depends on 15)

The process of claim 15, wherein the amount of the caustic solution is in the range of from 0.05 to 30 percent by weight based on the total quantity of solid base catalyst.

### Claim 17 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a liquid hourly space velocity in the range of from about 0.1 h−1 to about 10 h−1.

### Claim 18 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a liquid hourly space velocity in the range of from about 0.1 h−1 to about 4 h−1.

### Claim 19 (depends on 1)

The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a liquid hourly space velocity in the range of from about 0.5 h−1 to about 2 h−1.