IP Library Granted Patent US 9,139,783
Granted Patent B2
US 9,139,783 · App. 14/051,495 · Granted Sep 22, 2015

Hydroprocessing light cycle oil in liquid-full reactors

Inventors: Hasan Dindi (Wilmington, DE); Alan Howard Pulley (Lee's Summit, MO); Thanh Gia Ta (New Castle, DE); Vincent Adam Kuperavage, Jr. (Philadelphia, PA)
Assignee: E I DU PONT NEMOURS AND COMPANY
C10G65/12C10G7/00C10G45/22C10G2300/1037C10G2300/4081C10G2400/04
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Quick Facts
Patent No.
US 9,139,783
App. No.
14/051,495
Granted
Sep 22, 2015
Kind
B2
Abstract

A process for the hydroprocessing of a low-value light cycle oil (LCO) hydrocarbon feed to provide a high-value diesel-range product. The process comprises a hydrotreatment stage followed by a hydrocracking stage, each of which is conducted under liquid-full reaction conditions wherein substantially all the hydrogen supplied to the hydrotreating and hydrocracking reactions is dissolved in the liquid-phase hydrocarbon feed. Ammonia and optionally other gases formed during hydrotreatment are removed in a separation step prior to hydrocracking. The LCO feed is advantageously converted to diesel in high yield with little loss of hydrocarbon to naphtha.

Claims (35)

1. A process for hydroprocessing a hydrocarbon feed, comprising:

(a) contacting the hydrocarbon feed with hydrogen and a first diluent to form a first liquid feed, wherein hydrogen is dissolved in said first liquid feed, and wherein the hydrocarbon feed is a light cycle oil (LCO) having a polyaromatic content greater than 25% by weight, a nitrogen content greater than 300 parts per million by weight (wppm), and a density greater than 890 kg/m 3 at 15.6° C.;

(b) contacting the first liquid feed mixture with a first catalyst in a first liquid-full reaction zone to produce a first effluent;

(c) recycling a portion of the first effluent for use as all or part of the first diluent in step (a);

(d) separating at least a portion of the first effluent not recycled in a separation zone into at least three fractions comprising: (i) a low boiling fraction comprising ammonia and optionally other gases, (ii) a diesel fraction comprising a diesel-range product having a density no more than 870 kg/m 3 at 15.6° C., a polyaromatic content no more than 13% by weight, and a sulfur content no more than 60 wppm, and (iii) a high boiling fraction having a nitrogen content less than 100 wppm;

(e) contacting at least a portion of the high boiling fraction with hydrogen and a second diluent to produce a second liquid feed, wherein hydrogen is dissolved in said second liquid feed;

(f) contacting the second liquid feed with a second catalyst in a second liquid-full reaction zone to produce a second effluent having a density less than 875 kg/m 3 at 15.6° C. and a polyaromatic content less than 15% by weight; and

(g) recycling a portion of the second effluent for use as all or part of the second diluent in step (e);

wherein the at least three fractions comprise a naphtha fraction, and the diesel fraction is at least 90% by volume based on the total volume of the diesel and naphtha fractions.

2. The process of claim 1 further comprising: (h) separating at least a portion of the second effluent not recycled to generate at least a diesel fraction comprising a diesel-range product having a density no more than 870 kg/m 3 at 15.6° C., a polyaromatic content no more than 13% by weight, and a sulfur content no more than 60 wppm.

3. The process of claim 2 wherein the diesel fractions in separating steps (d) and (h) are either separately collected or combined as diesel blending component or diesel fuel.

4. The process of claim 1 wherein the total amount of hydrogen fed to the first and the second liquid-full reaction zones is 200-530 N l/l (1125-3000 scf/bbl).

5. The process of claim 1 wherein both the first liquid-full reaction zone and the second liquid-full reaction zone have, independently, a temperature in the range of about 300° C. to about 450° C., a pressure in the range of about 3.45 MPa (34.5 bar) to about 17.3 MPa (173 bar), and a liquid hourly space velocity (LHSV) of from about 0.1 hr −1 to about 10 hr −1 .

6. The process of claim 1 wherein the high boiling fraction has a nitrogen content less than 10 wppm.

7. The process of claim 1 wherein the LCO in step (a) has a sulfur content of more than 500 wppm and the second effluent in step (f) has a sulfur content no more than 50 wppm.

8. The process of claim 1 wherein the LCO in step (a) has a cetane index less than 30 and the second effluent in step (f) has a cetane index no less than 35.

9. A process for hydroprocessing a hydrocarbon feed, comprising:

(a) contacting the hydrocarbon feed with hydrogen and a first diluent to form a first liquid feed, wherein hydrogen is dissolved in said first liquid feed, and wherein the hydrocarbon feed is a light cycle oil (LCO) having a polyaromatic content greater than 25% by weight, a nitrogen content greater than 300 parts per million by weight (wppm), and a density greater than 890 kg/m 3 at 15.6° C.;

(b) contacting the first liquid feed mixture with a first catalyst in a first liquid-full reaction zone to produce a first effluent;

(c) recycling a portion of the first effluent for use as all or part of the first diluent in step (a);

(d) directing at least a portion of the first effluent not recycled and a second component to a separation zone to generate at least three fractions comprising: (i) a low boiling fraction comprising ammonia and optionally other gases, (ii) a diesel fraction comprising a diesel-range product having a density no more than 870 kg/m 3 at 15.6° C., a polyaromatic content no more than 13% by weight, and a sulfur content no more than 60 wppm, and (iii) a high boiling fraction having a nitrogen content less than 100 wppm;

(e) contacting at least a portion of the high boiling fraction with hydrogen and a second diluent to produce a second liquid feed, wherein hydrogen is dissolved in said second liquid feed;

(f) contacting the second liquid feed with a second catalyst in a second liquid-full reaction zone to produce a second effluent having a density less than 875 kg/m 3 at 15.6° C. and a polyaromatic content less than 15% by weight;

(g) recycling a portion of the second effluent for use as all or part of the second diluent in step (e); and

(h) providing at least a portion of the second effluent not recycled as all or part of the second component in step (d).

10. The process of claim 9 wherein the at least a portion of the first effluent not recycled and the second component are admixed before being introduced into the separation zone in step (d).

11. The process of claim 9 wherein the diesel fraction in step (d) is collected as diesel blending component or diesel fuel.

12. The process of claim 9 wherein the total amount of hydrogen fed to the first and the second liquid-full reaction zone is 200-530 N l/l (1125-3000 scf/bbl).

13. The process of claim 9 wherein both the first liquid-full reaction zone and the second liquid-full reaction zone have, independently, a temperature in the range of about 300° C. to about 450° C., a pressure in the range of about 3.45 MPa (34.5 bar) to about 17.3 MPa (173 bar), and a liquid hourly space velocity (LHSV) of from about 0.1 hr −1 to about 10 hr −1 .

14. The process of claim 9 wherein the at least three fractions further comprises a naphtha fraction and the diesel fraction is at least 75% by volume based on the total volume of the diesel and naphtha fractions.

15. The process of claim 9 wherein the high boiling fraction has a nitrogen content less than 10 wppm.

16. The process of claim 9 wherein the LCO in step (a) has a sulfur content of more than 500 wppm and the second effluent in step (f) has a sulfur content no more than 50 wppm.

17. The process of claim 9 wherein the LCO in step (a) has a cetane index less than 30 and the second effluent in step (f) has a cetane index no less than 35.

18. The process of claim 1 wherein the first catalyst is a hydrotreating catalyst, and the second catalyst is a hydrocracking catalyst.

19. The process of claim 9 wherein the first catalyst is a hydrotreating catalyst, and the second catalyst is a hydrocracking catalyst.

Assignments (8)
RELEASE OF SECURITY INTEREST RECORDED AT REEL/FRAME 059593/0951 Recorded Nov 19, 2024
From: MADISON PACIFIC TRUST LIMITED
To: REFINING TECHNOLOGY SOLUTIONS, LLC
Reel/Frame 069389/0366 →
SECURITY INTEREST Recorded Nov 15, 2024
From: BELCO TECHNOLOGIES CORPORATION; REFINING TECHNOLOGY SOLUTIONS, LLC; MECS, INC.
To: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
Reel/Frame 069284/0388 →
SECURITY INTEREST Recorded Nov 15, 2024
From: BELCO TECHNOLOGIES CORPORATION; REFINING TECHNOLOGY SOLUTIONS, LLC; MECS, INC.
To: MSD ADMIN SERVICES, LLC, AS COLLATERAL AGENT
Reel/Frame 069286/0861 →
IP SECURITY AGREEMENT SUPPLEMENT Recorded Apr 4, 2022
From: REFINING TECHNOLOGY SOLUTIONS, LLC
To: MADISON PACIFIC TRUST LIMITED, AS SECURITY AGENT
Reel/Frame 059593/0951 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 31, 2020
From: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC
To: REFINING TECHNOLOGY SOLUTIONS, LLC
Reel/Frame 053369/0191 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ENTITY FOR ASSIGNEE PREVIOUSLY RECORDED AT REEL: 49879 FRAME: 212. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Sep 6, 2019
From: E. I. DU PONT DE NEMOURS AND COMPANY
To: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC
Reel/Frame 050301/0065 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 26, 2019
From: E. I. DU PONT DE NEMOURS AND COMPANY
To: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC
Reel/Frame 049879/0212 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 14, 2013
From: DINDI, HASAN; PULLEY, ALAN HOWARD; TA, THANH GIA; KUPERAVAGE, VINCENT ADAM, JR
To: E. I. DU PONT DE NEMOURS AND COMPANY
Reel/Frame 031597/0398 →
Continuity (2)
Continuation In Part 13669540 · Nov 6, 2012
Related Publication 20140124409A1 · May 8, 2014