PROCESS FOR THE REDUCTION OF SULFUR, NITROGEN AND THE PRODUCTION OF USEFUL OXYGENATES FROM HYDROCARBON MATERIALS VIA ONE-POT SELECTIVE OXIDATION

• US 20080121565A1
• Filed: 09/20/2007
• Published: 05/29/2008
• Est. Priority Date: 10/12/2006
• Status: Active Grant

• Current Assignee: Kocat, Inc.
• Original Assignee: Kocat, Inc.
• Inventors: YOO, Jin S., KIM, Ho Dong, LEE, Sang-Chul
• Granted Patent: US 7,591,943 B2
• Time in Patent Office: Days
• US Class Current: 208/216R
• CPC Class Codes: C07C 51/265 having alkyl side chains which are oxidised to carboxyl groups
• CPC Class Codes: C07C 63/00 Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 63/04 Monocyclic monocarboxylic acids
• CPC Class Codes: C07C 63/15 all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
• CPC Class Codes: C07C 63/26 1,4 - Benzenedicarboxylic acid
• CPC Class Codes: C07C 63/307 Monocyclic tricarboxylic acids

Abstract

The present invention relates to a process of reducing sulfur- or nitrogen-containing compounds and also producing oxygenates, which can be used as an excellent octane booster in the reformulated gasoline and as a cetane booster for the future oxygenated diesel in a one-pot reaction.

Claims

1. A one-pot process for reducing a sulfur- or a nitrogen-containing compound and producing an oxygenate in a hydrocarbon substrate, which comprises the steps of:

(a) placing an MC-type homogeneous catalyst in a reactor;

(b) adding the hydrocarbon substrate in the reactor; and

(c) introducing an oxidant into the reactor;

wherein the MC-type homogeneous catalyst is selected from the group consisting of Co/HBr, Mn/HBr, Co/Mn/HBr and Co/Mn/M′

/HBr (M′

is selected from the group consisting of K, Rb, Cs, Mo, Fe, Zr, Hf, Mn, Ti, Ni, Ru, Nb, Mo, W, Ta, Sb, Re, Rh, Pr, Sm and Ce) and the oxidant is an O₂/CO₂ mixture.

5. The process according to claim 1, which further comprises the pretreatment step of removing a nitrogen-containing compound in the hydrocarbon substrate prior to the step (a).

2. A one-pot process for reducing a sulfur- or a nitrogen-containing compound, a metal and producing an oxygenate in a hydrocarbon substrate, which comprises:

(a) converting the sulfur- or the nitrogen-containing compound in the hydrocarbon substrate into a sulfur- or a nitrogen-containing precursor, respectively, and also converting a benzylic or an allylic compound in the hydrocarbon substrate into the oxygenate at the same time via a selective oxidation of the hydrocarbon substrate in the presence of an MC-type homogeneous catalyst and an oxidant; and

(b) conducting a post-treatment selected from the group consisting of a filtration, a fractionation, a selective adsorption, a solvent extraction, a catalytic destruction, a selective oxidation, a pyrolysis and a combination thereof;

wherein the MC-type homogeneous catalyst is selected from the group consisting of Co/HBr, Mn/HBr, Co/Mn/HBr and Co/Mn/M′

/HBr (M′

is selected from the group consisting of K, Rb, Cs, Mo, Fe, Zr, Hf, Mn, Ti, Ni, Ru, Nb, Mo, W, Ta, Sb, Re, Rh, Pr, Sm and Ce), and the oxidant is an O₂/CO₂ mixture.

6. The process according to claim 2, wherein the MC-type homogeneous catalyst is selected from the group consisting of Co/HBr, Mn/HBr, Co/Mn/HBr, Ni—

Co/Mn/HBr and Zr—

Co/Mn/HBr.

7. The process of claim 2, wherein the oxidant is an O₂/CO₂ mixture, and the volumetric ratio of O₂/CO₂ is 20-50%/80-50%.

8. The process of claim 7, wherein the volumetric ratio of O₂/CO₂ is 30-40%/70-60%.

9. The process of claim 7, wherein the volumetric ratio of O₂/CO₂ is 35-40%/65-60%.

10. The process of claim 8, wherein the O₂/CO₂ mixture comprises 5-30 vol % of helium or argon.

11. The process of claim 8, wherein the O₂/CO₂ mixture comprises less than 20 vol % of nitrogen.

12. The process according to claim 2, wherein the hydrocarbon substrate is at least one selected from the group consisting of:

(a) FCC product selected from the group consisting of gasoline, light cycle naphtha (LCN), heavy cycle naphtha (HCN), heavy oil fraction (middle distillate), light cycle oil (LCO), heavy cycle oil (HCO) and clarified oil (CLO);

(b) hydrogenated (HDS or HDN) counterparts of (i) the FCC products;

(c) heavy oil, bunker C oil or atmospheric and vacuum distilled resid bottoms;

(d) asphaltene separated from crude oil;

(e) long crude oil;

(f) tar sand, oil sand or peat;

(g) hydrogenated liquefied coal or H-coal;

(h) chemically cleaned coal that underwent deashing, desulfurizing and denitrogenating processes; and

(i) cokes, graphite or shale oil.

13. The process of claim 12, wherein the hydrocarbon substrate is a transportation fuel selected from the group consisting of:

(a) a reformulated gasoline that has underwent desulfurization and denitrogenation through a hydrogenation process, followed by a selective oxidation for increasing the amount of oxygenates;

(b) a light cycle oil, a heavy cycle oil, a heavy oil fraction or a mixture thereof that has underwent a hydrogenation; and

(c) a reformulated diesel that has underwent desulfurization and denitrogenation through a hydrogenation process, followed by a selective oxidation for increasing the amount of oxygenates.

14. The process according to claim 2, wherein

the benzylic or allylic compound is selected from the group consisting of tetralin;

alkyltetralin derivative;

partially hydrogenated naphthalene and naphthene;

alkylbenzene derivative selected from the group consisting of xylene, cumene, isopropylbenzene, mesitylene, psuedocuemene and durene; and

a mixture thereof; and

the oxygenate is selected from the group consisting of alcohols, ketones, aldehydes, organic acid esters, aromatic or aliphatic organic acids, ethers and a mixture thereof.

15. The process of claim 2, wherein

the sulfur-containing compound is selected from the group consisting of dialkyldibenzothiophene (4,6-DMDBT, 2,5-DMDBT), 4-alkyldibenzothiophene (4-MDBT), dibenzothiophene (DBT), alkylbenzothiophene, benzothiophene (BT), dialkylthiophene, thiophene, diphenylsulfide, thiophenol, methylphenylsulfide, alkyldisulfide and a mixture thereof;

and

the sulfur-containing precursor is a sulfoxide or a sulfone type oxygenate of the sulfur-containing compound.

16. The process of claim 2, wherein

the nitrogen-containing compound is pyridine, quinoline, pyrrole, indole, carbazole, alkyl derivative thereof, aromatic and aliphatic amines thereof and a mixture thereof;

the nitrogen-containing precursor is a N-oxide, an oxime, a nitron, a nitrosobenzene, a nitrobenzene or an indigo type oxygenate of the nitrogen-containing compound.

17. The process of claim 2, wherein the biphasic system is a nonpolar/polar system selected from the group consisting of oil/acetonitrile, oil/DMF, oil/acetic acid, oil/pyrrolidone, oil/NaOH aqueous solution, oil/NaHCO₃ aqueous solution, oil/Na₂CO₃ aqueous solution, oil/acetic acid-water mixture, oil/t-BuOH, oil/MeOH and a combination thereof.

18. The process according to claim 2, wherein the oxidation is performed at 140-190°

C. under 10-15 atm.

19. The process according to claim 2, wherein

the sulfur-containing compound and the nitrogen-containing compound are removed to less than 10 ppm and 5 ppm, respectively;

and

the oxygenate is produced in the amount of higher than 2.2-2.7 wt % on a basis of oxygen.

3. A one-pot process for reducing a sulfur- or a nitrogen-containing compound and producing an oxygenate in a hydrocarbon substrate, which comprises:

(a) placing an MC-type homogeneous catalyst in a biphasic system;

(b) adding the hydrocarbon substrate in the biphasic system; and

(c) introducing an oxidant into the biphasic system;

wherein the MC-type homogeneous catalyst is selected from the group consisting of Co/HBr, Mn/HBr, Co/Mn/HBr and Co/Mn/M′

/HBr (M′

is selected from the group consisting of K, Rb, Cs, Mo, Fe, Zr, Hf, Mn, Ti, Ni, Ru, Nb, Mo, W, Ta, Sb, Re, Rh, Pr, Sm and Ce), and the oxidant is an O₂/CO₂ mixture.

4. A one-pot process for reducing a sulfur- or a nitrogen-containing compound and producing an oxygenate in a hydrocarbon substrate, which comprises:

(a) converting the sulfur- or the nitrogen-containing compound in the hydrocarbon substrate into a sulfur- or a nitrogen-containing precursor, respectively, and also converting a benzylic or an allylic compound in the hydrocarbon substrate into the oxygenate at the same time via a selective oxidation of the hydrocarbon substrate in a biphasic system comprising an MC-type homogeneous catalyst and an oxidant; and

(b) removing a layer that comprises the a sulfur- or a nitrogen-containing precursor;

wherein the MC-type homogeneous catalyst is selected from the group consisting of Co/HBr, Mn/HBr, Co/Mn/HBr and Co/Mn/M′

/HBr (M′

is selected from the group consisting of K, Rb, Cs, Mo, Fe, Zr, Hf, Mn, Ti, Ni, Ru, Nb, Mo, W, Ta, Sb, Re, Rh, Pr, Sm and Ce), and the oxidant is an O₂/CO₂ mixture.