# US 7,744,749 B2 · Diesel oil desulfurization by oxidation and extraction

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- Number: US 7,744,749 B2
- Document ID: US7744749B2
- Status: Granted
- Kind: B2
- Application number: 11/222,729
- Filed: 2005-09-08
- Published: 2007-03-08
- Granted: 2010-06-29
- Earliest claimed: 2005-09-08
- Assignees: Saudi Arabian Oil Company
- Inventors: Gary M. Martinie; Farhan M. Al-Shahrani; Bashir O. Dabbousi
- Web page: https://patentgrep.com/patent/US7744749B2

## CPC

- C10G 27/00: Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G 21/16: Oxygen-containing compounds
- C10G 21/20: Nitrogen-containing compounds
- C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03}
- C10G 27/10: in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
- C10G 27/12: with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates (plumbites or plumbates C10G19/06)
- C10L 1/08: for compression ignition
- C10G 2300/1055: Diesel having a boiling range of about 230 - 330 °C
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/4006: Temperature
- C10G 2300/44: Solvents
- C10G 2400/04: Diesel oil
- 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
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS

## Abstract

The reduction in the sulfur-containing content of diesel fuel is achieved by oxidation in the presence of a catalyst followed by a liquid-liquid countercurrent extraction.

## Claims

### Claim 1

A process for reducing the sulfur content of diesel fuel comprising the steps of:
a. contacting a diesel fuel containing sulfur compounds in a reactor with an oxidant selected from the group consisting of sulfuric acid, peracetic acid, hydrogen peroxide, sodium hypochlorite, perchloric acid, nitric acid, sodium or potassium peroxidisulfate or peroxymonosulfate, and mixtures thereof, in the presence of a homogeneous or heterogeneous oxidation catalyst selected from the group consisting of {(C8H17)4N}3PW4O24, Mo2W7O30.2N(CH2PO)3, MoO2NH(CHCH3CH2O)2, N(CH2PO)3(WO5)9, H5BiMo12O40.4H2O, and Na4C32H12N8S4O12Co(II)O2, at a temperature in the range of from about 50° C. to about 150° C. for a period of time sufficient to oxidize the sulfur compounds; and
b. removing the oxidized sulfur compounds from the diesel fuel by liquid-liquid countercurrent extraction with a water-soluble polar solvent.

### Claim 2 (depends on 1)

The process according to claim 1, including the steps of:
a. stripping the solvent from the diesel fuel; and
b. polishing the diesel fuel by passing it through an adsorbent to remove the remaining sulfur compounds.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the reactor is a countercurrent reactor.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the reactor is stirred, agitated, oscillated, or static.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the solvent is selected from the group consisting of aqueous solutions of acetonitrile and methanol.

### Claim 6 (depends on 2)

The process according to claim 2, wherein the polishing is effected by an adsorbent bed consisting of polar organic groups coated on or bound to a support selected from the group consisting of silica, alumina, and carbon.

### Claim 7 (depends on 5)

The process of claim 5, wherein the solvent contains from about 10% to 30% water by volume.

### Claim 8 (depends on 7)

The process of claim 7, wherein the solvent contains 10% water by volume.

### Claim 9 (depends on 1)

The process of claim 1, wherein the concentration of sulfur in the treated diesel fuel is reduced to less than 10 ppm by weight.

### Claim 10

A process for reducing the sulfur content of diesel fuel containing sulfur compounds comprising:
a. introducing an aqueous oxidant and a heterogeneous or homogenous catalyst selected from the group consisting of {(C8H17)4N}3PW4O24, Mo2W7O30.2N(CH2PO)3, .XH2O, MoO2NH(CHCH3CH2O)2, N(CH2PO)3(WO5)9, H5BiMo12O40.4H2O, and Na4C32H12N8S4O12Co(II)O2, into the top of a reactor column;
b. contacting the oxidant and catalyst in countercurrent flow in the reactor with a diesel fuel boiling in the range of from about 240° C. to about 360° C.;
c. continuously oxidizing the sulfur compounds in the diesel oil;
d. continuously extracting oxidized compounds from the diesel oil produced in the reactor by contact with an aqueous solution of a polar solvent in a column;
e. removing traces of aqueous solution from the diesel fuel in a stripper column;
f. recovering the aqueous solution; and
g. adsorbing remaining sulfur compounds from the diesel fuel with an absorbent selected from the group consisting of activated carbon, silica gel and alumina.

### Claim 11 (depends on 10)

The process of claim 10, wherein the aqueous solution is selected from the group consisting of aqueous methanol and aqueous acetonitrile.

### Claim 12 (depends on 10)

The process according to claim 10, wherein the concentration of sulfur compounds in the diesel fuel is reduced to less than 10 ppm by weight.

### Claim 13 (depends on 6)

The process of claim 6 in which the solid support is coated with polar polymers selected from the group consisting of polysulfone, polyacrylonitrite, polystyrene, polyester terephthlate and polyurethane.

### Claim 14 (depends on 1)

The process of claim 1 in which the diesel fuel to be treated is a low sulfur hydrotreated diesel containing about 1000 ppm by weight of sulfur.

### Claim 15 (depends on 1)

The process of claim 1, wherein the oxidation catalyst is {(C8H17)4N}3PW4O24.

### Claim 16 (depends on 1)

The process of claim 1, wherein the oxidation catalyst is Mo2W7O30.2N(CH2PO)3.

### Claim 17 (depends on 1)

The process of claim 1, wherein the oxidation catalyst is MoO2NH(CHCH3CH2O)2.

### Claim 18 (depends on 1)

The process of claim 1, wherein the oxidation catalyst is N(CH2PO)3(WO5)9.

### Claim 19 (depends on 1)

The process of claim 1, wherein the oxidation catalyst is H5BiMo12O40.4H2O.

### Claim 20 (depends on 1)

The process of claim 1, wherein the oxidation catalyst is Na4C32H12N8S4O12Co(II)O2.

### Claim 21 (depends on 10)

The process of claim 10, wherein the oxidation catalyst is {(C8H17)4N}3PW4O24.

### Claim 22 (depends on 10)

The process of claim 10, wherein the oxidation catalyst is Mo2W7O30.2N(CH2PO)3.

### Claim 23 (depends on 10)

The process of claim 10, wherein the oxidation catalyst is MoO2NH(CHCH3CH2O)2.

### Claim 24 (depends on 10)

The process of claim 10, wherein the oxidation catalyst is N(CH2PO)3(WO5)9.

### Claim 25 (depends on 10)

The process of claim 10, wherein the oxidation catalyst is H5BiMo12O40.4H2O.

### Claim 26 (depends on 10)

The process of claim 10, wherein the oxidation catalyst is Na4C32H12N8S4O12Co(II)O2.

### Claim 27 (depends on 3)

The process of claim 3, further comprising
introducing oxidant and catalyst into the countercurrent reactor from an oxidant-catalyst storage tank, and
recycling residual catalyst and spent or residual oxidant from the countercurrent reactor to the oxidant-catalyst storage tank.

### Claim 28 (depends on 27)

The process of claim 27, further comprising adding make-up catalyst and/or oxidant to the oxidant-catalyst storage tank.

### Claim 29 (depends on 10)

The process of claim 10, further comprising
introducing oxidant and catalyst into the countercurrent reactor from an oxidant-catalyst storage tank, and
recycling residual catalyst and spent or residual oxidant from the countercurrent reactor to the oxidant-catalyst storage tank.

### Claim 30 (depends on 29)

The process of claim 29, further comprising adding make-up catalyst and/or oxidant into the oxidant-catalyst storage tank.