Slurry oil upgrading while preserving aromatic content

• US 9,375,656 B2
• Filed: 06/19/2014
• Issued: 06/28/2016
• Est. Priority Date: 01/09/2009
• Status: Active Grant

• Current Assignee: Phillips 66 Company
• Original Assignee: Phillips 66 Company
• Inventors: Subbiah, Ayyappan, Choudhary, Tushar V.
• Primary Examiner(s): Boyer, Randy
• Application Number:
  US14/308,802
• Publication Number:
  US 20140299510A1
• Time in Patent Office: 740 Days
• US Class Current: 1/1
• CPC Class Codes: B01D 15/08 Selective adsorption, e.g. chromatography
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/283 based on silica
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3475 in the liquid phase
• CPC Class Codes: C10B 55/00 Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material cracking oils C10G
• CPC Class Codes: C10B 57/045 containing mineral oils, bitumen, tar or the like or mixtures thereof
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 67/06 including a sorption process as the refining step in the absence of hydrogen

Abstract

Methods relating to methods for producing a needle coke precursor from slurry oil having low levels of nitrogen and sulfur. Nitrogen-containing compounds are removed by chromatography, followed by hydrotreating at relatively mild conditions that focus on the more easily-removed sulfur-containing compounds while largely preserving aromatic content of the slurry oil. The resulting needle coke precursor can be converted to a premium needle coke in a delayed coking system.

Claims

1. A process for producing needle coke from slurry oil, comprising:

a) providing a slurry oil comprising aromatic compounds, nitrogen containing compounds and sulfur-containing compounds;

b) contacting the slurry oil with a chromatography substrate that retains at least a portion of the nitrogen-containing compounds, thereby producing an upgraded slurry oil;

c) hydrotreating the upgraded slurry oil at a pressure in the range from 1 to 350 psig with a hydrodesulfurization catalyst to remove sulfur-containing compounds from the upgraded slurry oil, thereby producing a needle coke precursor comprising less than about 0.5 percent (by weight) sulfur-containing compounds, wherein the hydrotreating is performed at a temperature that preserves at least 70 percent of the aromatic compounds comprising at least three aromatic rings that were originally present in the slurry oil feedstock;

d) converting the needle coke precursor to needle coke in a coking system.

2. The method according to claim 1, wherein the hydrodesulfurization generates hydrogen sulfide from sulfur-containing compounds in the upgraded slurry oil and strips the hydrogen sulfide from the upgraded slurry oil.

3. The method according to claim 1, wherein the slurry oil comprises at least 70 percent (by weight) aromatic compounds that, in turn, comprise from three to six aromatic rings.

4. The method according to claim 1, wherein the hydrotreating is performed at a temperature that preserves at least 80 percent of the aromatic compounds comprising at least three aromatic rings that were originally present in the slurry oil.

5. The method according to claim 1, wherein the hydrotreating is performed at a temperature that preserves at least 90 percent of the aromatic compounds comprising at least three aromatic rings that were originally present in the slurry oil.

6. The method according to claim 1, wherein the nitrogen-containing compounds within the slurry oil are adsorbed onto the chromatography substrate.

7. The method according to claim 1, wherein the chromatography substrate is contained within a chromatography reactor and the slurry oil is passed through the chromatography reactor to decrease the level of nitrogen-containing compounds to a threshold level of 0.75 wt. percent or less.

8. The method according to claim 7, wherein the slurry oil mixture is passed through the chromatography reactor multiple times to decrease the level of nitrogen-containing compounds in the slurry oil to below the threshold level.

9. The method of claim 7, wherein the threshold level is 0.5 wt. percent or less.

10. The method of claim 7, wherein the threshold level is 0.2 wt. percent or less.

11. The method of claim 7, wherein the threshold level is 0.1 wt. percent or less.

12. The method of claim 7, wherein the threshold level is 500 ppmw or less.

13. The method according to claim 1, wherein the chromatography substrate is contained within multiple chromatography reactors in a swing configuration, wherein the slurry oil mixture is passed through at least one chromatography reactor while one or more additional chromatography reactors are regenerated.

14. The method according to claim 7, wherein decreasing the level of nitrogen-containing compounds to the threshold level or below enables the hydrotreating to occur at less severe conditions of temperature, pressure, or both to remove sulfur-containing compounds to below 0.5 wt. percent, wherein the less severe conditions cause the preservation of at least 70 wt. percent of aromatic compounds comprising at least three aromatic rings that were originally present in the slurry oil.

15. The method according to claim 14, wherein the less severe conditions cause the preservation of at least 80 wt. percent of aromatic compounds comprising at least three aromatic rings that were originally present in the slurry oil.

16. The method according to claim 14, wherein the less severe conditions cause the preservation of at least 90 wt. percent of aromatic compounds comprising at least three aromatic rings that were originally present in the slurry oil.

17. The method according to claim 7, wherein decreasing the level of nitrogen-containing compounds to below the threshold level causes increased activity of the hydrotreating catalyst, thereby lowering the temperature or pressure required during hydrotreating to remove sulfur-containing compounds from the slurry oil to a level below about 0.5 wt. percent.