# US 2014/0197074 A1 · Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds

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- Number: US 2014/0197074 A1
- Document ID: US20140197074A1
- Status: Published application
- Kind: A1
- Application number: 13/741,101
- Filed: 2013-01-14
- Published: 2014-07-17
- Earliest claimed: 2013-01-14
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Abdennour Bourane; Omer Refa Koseoglu; Zinfer Ismagilov; Svetlana Yashnik; Mikhail Kerzhentsev; Valentin Parmon
- Web page: https://patentgrep.com/patent/US20140197074A1

## CPC

- C10G 67/16: plural parallel stages only
- B01J 23/005: {Spinels}
- B01J 23/80: with zinc, cadmium or mercury
- B01J 23/83: with rare earths or actinides
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/45: Nanoparticles
- B01J 35/50: characterised by their shape or configuration
- B01J 35/613: {10-100 m2/g}
- B01J 35/647: {2-50 nm}
- B01J 37/031: {Precipitation}
- C10G 27/04: with oxygen or compounds generating oxygen
- C10G 45/02: to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/4056: Retrofitting operations
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Desulfurization of hydrocarbon feeds is achieved by flashing the feed at a target cut point temperature to obtain two fractions. A first fraction contains refractory organosulfur compounds, which boils at or above the target cut point temperature. A second fraction boiling below the target cut point temperature is substantially free of refractory sulfur-containing compounds. The second fraction is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone operating under mild conditions to reduce the quantity of organosulfur compounds to an ultra-low level. The first fraction is contacted with gaseous oxidizing agent over an oxidation catalyst having a formula CuxZn1-xAl2O4 in a gas phase catalytic oxidation reaction zone to convert the refractory organosulfur compounds to SOx and low sulfur hydrocarbons. The by-product SOx is subsequently removed, producing a stream containing a reduced level of organo sulfur compounds.

## Claims

### Claim 1

A method of processing a hydrocarbon feed to remove undesired organosulfur compounds comprising:
a. flashing the hydrocarbon feedstock to provide a low boiling temperature fraction that contains a reduced level of organosulfur compounds and a high boiling temperature fraction having refractory organosulfur compounds;
b. subjecting the low boiling temperature fraction to a hydrodesulfurizing process to produce a hydrotreated effluent;
c. contacting the high boiling temperature fraction with a gaseous oxidizing agent and an oxidizing catalyst having a formula CuxZn1-xAl2O4 wherein x ranges from 0 to 1 to convert refractory organosulfur compounds into sulfur-free hydrocarbons and SOx by breaking the C—S bonds;
d. removing the by-product SOx in a separation zone from the sulfur-free hydrocarbons; and
e. recovering an ultra-low sulfur level hydrocarbon product.

### Claim 2 (depends on 1)

The method of claim 1, wherein the oxidizing catalyst comprises copper oxide in an amount ranging from 10 weight percent (wt %) to 50 wt %, zinc oxide in an amount ranging from 5 wt % to less than 20 wt %, and aluminum oxide in an amount ranging from 20 wt % to 70 wt %, wherein said catalytic composition has an X-ray amorphous oxide phase, and highly dispersed crystalline ZnO and CuO.

### Claim 3 (depends on 1)

The method of claim 1, wherein the temperature cut point in step (a) is about 340° C.

### Claim 4 (depends on 1)

The method of claim 1, wherein the low boiling temperature fraction includes aliphatic organosulfur compounds.

### Claim 5 (depends on 4)

The method of claim 4, wherein the aliphatic organosulfur compounds include sulfides, disulfides, and mercaptans.

### Claim 6 (depends on 4)

The method of claim 4, wherein the low boiling temperature fraction further includes thiophene and alkyl derivatives of thiophene.

### Claim 7 (depends on 1)

The method of claim 1, wherein the high boiling temperature fraction includes dibenzothiophene, alkyl derivatives of dibenzothiophene and long-chain alkylated derivatives of benzothiophene having a boiling point in the range of the high boiling temperature fraction.

### Claim 8 (depends on 1)

The method of claim 1, wherein the hydrocarbon feed is a straight run gas oil boiling in the range of about 180° C. to about 450° C.

### Claim 9 (depends on 8)

The method of claim 8, wherein the hydrodesulfurizing process is operated at mild operating conditions.

### Claim 10 (depends on 9)

The method of claim 9, wherein the hydrogen partial pressure is less than about 55 bars.

### Claim 11 (depends on 9)

The method of claim 9, wherein the hydrogen partial pressure is about 25 bars to about 40 bars.

### Claim 12 (depends on 9)

The method of claim 9, wherein the operating temperature is about 300° C. to about 400° C.

### Claim 13 (depends on 9)

The method of claim 9, wherein the operating temperature is about 320° C. to about 380° C.

### Claim 14 (depends on 9)

The method of claim 9, wherein the hydrogen feed rate in the hydrodesulfurizing process step is from about 100 liters of hydrogen per liter of oil to about 1000 liters of hydrogen per liter of oil.

### Claim 15 (depends on 9)

The method of claim 9, wherein the hydrogen feed rate in the hydrodesulfurizing process step is from about 200 liters of hydrogen per liter of oil to about 300 liters of hydrogen per liter of oil.

### Claim 16 (depends on 1)

The method of claim 1, wherein the oxidizing agent is selected from the group consisting of oxides of nitrogen, oxygen, and air.

### Claim 17 (depends on 1)

The method of claim 1, further comprising recovering a hydrotreated hydrocarbon product.

### Claim 18 (depends on 1)

The method of claim 1, further comprising combining the low boiling temperature fraction that has been subjected to a hydrodesulfurization process and the high boiling temperature fraction that has been subjected to gas phase catalytic oxidative desulfurization by breaking the C—S bonds into a reduced-organosulfur content hydrocarbon product.

### Claim 19 (depends on 1)

The method of claim 1 wherein the catalytic composition used in step (c) further comprises CeO2 in the form of particles ranging in diameter from 5 nm to 10 nm, in an amount ranging from 0.1 wt % to 10 wt % of said catalytic composition.

### Claim 20 (depends on 1)

The method of claim 1 wherein the catalytic composition used in step (c) is in granular form.

### Claim 21 (depends on 1)

The method of claim 1 wherein the catalytic composition used in step (c) is formed as a cylinder, a sphere, a trilobe, or a quatrolobe.

### Claim 22 (depends on 21)

The method of claim 21 wherein particles of the catalytic composition have effective diameter of from 1 mm to 4 mm.

### Claim 23 (depends on 21)

The method of claim 21 wherein particles of the catalytic composition have having a specific surface area of from 10 m2/g to 100 m2/g.

### Claim 24 (depends on 21)

The method of claim 21 wherein particles of the catalytic composition have having a specific surface area of from 50 m2/g to 100 m2/g.

### Claim 25 (depends on 21)

The method of claim 21 wherein particles of the catalytic composition have pores with effective diameters of from 8 nm to 12 nm.

### Claim 26 (depends on 21)

The method of claim 21 wherein particles of the catalytic composition have pores with effective diameters of from 8 nm to 10 nm.

### Claim 27 (depends on 21)

The method of claim 21 wherein particles of the catalytic composition have pores with a volume of from about 0.1 cm3/g to about 0.5 cm3/g.

### Claim 28 (depends on 1)

The method of claim 1 wherein the catalytic composition used in step (c) comprises from 20 wt % to 45 wt % CuO, from 10 wt % to less than 20 wt % ZnO, and from 20 wt % to 70 wt % of Al2O3.

### Claim 29 (depends on 1)

The method of claim 1 wherein the catalytic composition used in step (c) comprises from 30 wt % to 45 wt % CuO, from 12 wt % to less than 20 wt % ZnO, and from 20 wt % to 40 wt % Al2O3.

### Claim 30 (depends on 1)

The method of claim 1 wherein x in the catalytic composition used in step (c) is from 0.1 to 0.6.

### Claim 31 (depends on 1)

The method of claim 1 wherein x in the catalytic composition used in step (c) is from 0.2 to 0.5.

### Claim 32

An apparatus for processing a hydrocarbon feed containing undesired organosulfur compounds comprising:
a flashing column operable to flash a hydrocarbon feed at a temperature cut point of about 320° C. to about 360° C., the flashing column including
an inlet for receiving the hydrocarbon feed,
a low boiling temperature outlet for discharging a low boiling temperature fraction, and
a high boiling temperature outlet for discharging a high boiling temperature fraction containing refractory organosulfur compounds;
a hydrodesulfurization zone having an inlet in fluid communication with the low boiling temperature outlet and an outlet for discharging hydtrotreated effluent; and
a gas phase catalytic oxidative desulfurization zone containing an oxidation catalyst and a gaseous oxidizing agent, gas phase catalytic oxidative desulfurization zone having an inlet in fluid communication with the high boiling temperature outlet, and an outlet for discharging low-sulfur hydrocarbons and SOx.