Liquid-full hydroprocessing to improve sulfur removal using one or more liquid recycle streams

• US 8,926,826 B2
• Filed: 04/28/2011
• Issued: 01/06/2015
• Est. Priority Date: 04/28/2011
• Status: Active Grant

• Current Assignee: Refining Technology Solutions, LLC (DuPont de Nemours, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Dindi, Hasan, Murillo, Luis Eduardo
• Primary Examiner(s): Singh, Prem C
• Assistant Examiner(s): Doyle, Brandi M
• Application Number:
  US13/096,309
• Publication Number:
  US 20120273390A1
• Time in Patent Office: 1,349 Days
• Field of Search: 208/59, 208/49, 208/108, 208/210, 208/251.H, 208/254.H
• US Class Current: 208/49
• CPC Class Codes: C10G 2300/1051 Kerosene having a boiling range of about 180 - 230 °C
• CPC Class Codes: C10G 2300/1055 Diesel having a boiling range of about 230 - 330 °C
• CPC Class Codes: C10G 2300/1059 Gasoil having a boiling range of about 330 - 427 °C
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/4018 Spatial velocity, e.g. LHSV, WHSV
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2300/802 Diluents
• CPC Class Codes: C10G 45/22 with hydrogen dissolved or suspended in the oil
• CPC Class Codes: C10G 65/04 including only refining steps
• CPC Class Codes: C10G 65/12 including cracking steps and other hydrotreatment steps

Abstract

The present invention provides a process for hydroprocessing hydrocarbons in liquid full reactors with one or more independent liquid recycle streams. The process operates as a liquid-full process, wherein all of the hydrogen dissolves in the liquid phase and one or more of the recycle streams may actually be zero. Hydrocarbons can be converted in the process to provide liquid products such as clean fuels with multiple desired properties.

Claims

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

(a) providing two or more reaction stages disposed in sequence and in liquid communication, wherein each reaction stage contains at least one catalyst bed, and each catalyst bed contains at least one catalyst;

(b) contacting the feed with (i) a diluent and (ii) hydrogen, to produce a feed/diluent/hydrogen mixture, wherein the hydrogen is dissolved in the feed/diluent/hydrogen mixture;

(c) contacting the feed/diluent/hydrogen mixture with a first catalyst in a first reaction stage, to produce a first product effluent;

(d) recycling a portion of the first product effluent as a first recycle stream for use in the diluent in step (b)(i) at a first recycle ratio of from about 0.1 to about 10;

(d′

) optionally having one or more current reaction stages between the first reaction stage and a final reaction stage, wherein step (d′

) comprises (i) providing a preceding product effluent, which is the product effluent from a preceding reaction stage, to the current reaction stage;

(ii) optionally contacting the preceding product effluent with hydrogen;

(iii) optionally contacting the preceding product effluent with a current recycle stream;

(iv) contacting the preceding product effluent with a current catalyst to produce a current product effluent;

(v) optionally recycling a portion of the current product effluent as the current recycle stream at a current recycle ratio of from about 0.1 to about 10; and

(vi) feeding the current product effluent to a subsequent reaction stage;

(e) contacting at least a portion of a product effluent from the reaction stage preceding the final reaction stage, and optionally hydrogen, with a final catalyst in the final reaction stage, to produce a final product effluent;

wherein each contacting step (c), optional step (d′

)(iv), and (e) is performed under liquid-full reaction conditions, wherein the recycle ratio in a reaction stage cannot be larger than the recycle ratio in a preceding reaction stage, and wherein the final reaction stage has no recycle stream.

2. The process of claim 1 wherein the at least a portion of a product effluent from the reaction stage preceding the final reaction stage is contacted with hydrogen to produce a product effluent/hydrogen mixture which is contacted with the final catalyst in step (e).

3. The process of claim 1, wherein one or more current reaction stages is present between the first reaction stage and the final reaction stage.

4. The process of claim 3, wherein step (d′

) comprises (i) providing a preceding product effluent, which is the product effluent from a preceding reaction stage, to the current reaction stage;

(ii) contacting at least a portion of the preceding product effluent with hydrogen to produce a preceding product effluent/hydrogen mixture, wherein the hydrogen is dissolved in the preceding product effluent/hydrogen mixture;

(iii) contacting the preceding product effluent/hydrogen mixture with a current catalyst to produce a current product effluent; and

(iv) feeding the current product effluent to a subsequent reaction stage.

5. The process of claim 3, wherein step (d′

) comprises (i) providing a preceding product effluent, which is the product effluent from a preceding reaction stage, to the current reaction stage;

(ii) contacting the preceding product effluent with a current recycle stream;

(iii) contacting the preceding product effluent and the current recycle stream with a current catalyst to produce a current product effluent;

(iv) recycling a portion of the current product effluent as the current recycle stream at a current recycle ratio of from about 0.1 to about 10; and

(v) feeding the current product effluent to a subsequent reaction stage.

6. The process of claim 3, wherein step (d′

) comprises, for each current reaction stage, (i) providing a preceding product effluent, which is the product effluent from a preceding reaction stage, to the current reaction stage;

(ii) contacting the preceding product effluent with hydrogen;

(iii) contacting the preceding product effluent with a current recycle stream;

(iv) contacting the preceding product effluent with a current catalyst to produce a current product effluent;

(v) recycling a portion of the current product effluent as the current recycle stream; and

(vi) feeding the current product effluent to a subsequent reaction stage, wherein the recycle ratio of current recycle stream to product effluent from the preceding reaction stage is from about 0.1 to about 10.

7. The process of claim 6 wherein each of the first and the current reaction stage contains one independent liquid recycle stream with a corresponding recycle ratio.

8. The process of claim 7 wherein the recycle ratio of a reaction stage is larger than the recycle ratio of a subsequent reaction stage.

9. The process of claim 1 having two reaction stages.

10. The process of claim 1, wherein each catalyst bed has a temperature from about 204°

C. to about 450°

C., a pressure from about 3.45 MPa (34.5 bar) to 17.3 MPa (173 bar), and a hydrocarbon feed rate to provide a liquid hourly space velocity (LHSV) of from about 0.1 to about 10 hr<sup>−

1</sup>.

11. The process of claim 1, wherein the diluent comprises the first recycle stream and an organic liquid selected from the group consisting of light hydrocarbons, light distillates, naphtha, diesel, propane, butane, pentane, hexane and combinations thereof.

12. The process of claim 1, wherein the diluent is the first recycle stream.

13. The process of claim 1, wherein each reaction stage contains at least one catalyst bed and fresh hydrogen is added at the inlet of each catalyst bed.

14. The process of claim 1, wherein at least one catalyst is a hydrotreating catalyst or a hydrocracking catalyst.

15. The process of claim 14, wherein one or more catalyst beds which contain a hydrotreating catalyst are followed by one or more catalyst beds which contain a hydrocracking catalyst.

16. The process of claim 14 wherein the hydrotreating catalyst comprises a metal and an oxide support wherein the metal is a non-precious metal.

17. The process of claim 14 wherein the hydrocracking catalyst comprises a metal and an oxide support wherein the metal is a non-precious metal.

18. The process of claim 1, wherein each catalyst comprises a metal which is a combination of metals selected from the group consisting of nickel-molybdenum (NiMo), cobalt-molybdenum (CoMo), nickel-tungsten (NiW) and cobalt-tungsten (CoW).

19. The process of claim 1, wherein there is no separation of ammonia, hydrogen sulfide and remaining hydrogen from the product effluent from a first catalyst bed or the product effluent from a preceding catalyst bed prior to feeding the product effluent to a subsequent catalyst bed.

20. The process of claim 1, wherein ammonia and hydrogen sulfide are removed from the product effluent from a first catalyst bed or the product effluent from a preceding catalyst bed prior to feeding the product effluent to a subsequent catalyst bed.

21. The process of claim 1, wherein the first recycle ratio is from about 0.1 to about 6.