Method of enhancing an aromatization catalyst

• US 8,362,310 B2
• Filed: 04/01/2011
• Issued: 01/29/2013
• Est. Priority Date: 07/28/2006
• Status: Active Grant

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Inventors: Brown, Scott H., Cheung, Tin-Tack Peter, Glova, David J., Hasenberg, Daniel M., Holtermann, Dennis L., Khare, Gyanesh P., Knorr, Daniel B. Jr., Blessing, Christopher D.
• Primary Examiner(s): Dang, Thuan D
• Application Number:
  US13/078,524
• Publication Number:
  US 20110184217A1
• Time in Patent Office: 669 Days
• Field of Search: 585/418, 585/419, 208/137, 208/138, 208/139
• US Class Current: 585/418
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2400/30 Aromatics
• CPC Class Codes: C10G 35/095 containing crystalline alumino-silicates, e.g. molecular sieves C10G35/065 takes precedence

Abstract

A hydrocarbon aromatization process comprising adding a nitrogenate, an oxygenate, or both to a hydrocarbon stream to produce an enhanced hydrocarbon stream, and contacting the enhanced hydrocarbon stream with an aromatization catalyst, thereby producing an aromatization reactor effluent comprising aromatic hydrocarbons, wherein the catalyst comprises a non-acidic zeolite support, a group VIII metal, and one or more halides. Also disclosed is a hydrocarbon aromatization process comprising monitoring the presence of an oxygenate, a nitrogenate, or both in an aromatization reactor, monitoring at least one process parameter that indicates the activity of the aromatization catalyst, modifying the amount of the oxygenate, the nitrogenate, or both in the aromatization reactor, thereby affecting the parameter.

Claims

1. A hydrocarbon aromatization process comprising:

adding a nitrogenate to a hydrocarbon stream to produce an enhanced hydrocarbon stream, wherein the hydrocarbon stream is substantially free of sulfur and wherein the nitrogenate comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone;

contacting the enhanced hydrocarbon stream with an aromatization catalyst in a reaction zone, wherein the aromatization catalyst comprises a non-acidic L-zeolite support, platinum, and one or more halides; and

recovering an effluent comprising aromatic hydrocarbons.

2. The process of claim 1 further comprising separating a hydrogen recycle stream from the effluent, wherein the hydrogen recycle stream has a water content of from about 1 ppmv to about 100 ppmv.

3. The process of claim 2 further comprising drying the hydrogen recycle stream to produce a dried hydrogen recycle stream having a water content of less than about 1 ppmv and feeding the dried hydrogen recycle stream to the hydrocarbon stream or the enhanced hydrocarbon stream.

4. The process of claim 1 further comprising controlling the addition of the nitrogenate to the hydrocarbon stream to maintain one or more process parameters within a desired range.

5. The process of claim 1 further comprising controlling the addition of the nitrogenate to the hydrocarbon stream to increase the production of one or more aromatic compounds in the reaction zone effluent by at least about 1 percent over pre-addition levels.

6. The process of claim 1 further comprising controlling the addition of the nitrogenate to the hydrocarbon stream to increase the catalyst selectivity to benzene in the reaction zone effluent by at least about 1 percent over pre-addition levels.

7. The process of claim 1 further comprising prior to the addition of the nitrogenate, treating the hydrocarbon stream to remove all or a portion of any nitrogenates, oxygenates, or both therein to produce a treated hydrocarbon stream.

8. The process of claim 7 wherein the oxygenate removed from the hydrocarbon stream comprises water, and wherein the treated hydrocarbon stream has a water content of less than about 1 ppmv.

9. The process of claim 1 wherein the aromatization process comprises a plurality of reactors, and the nitrogenate is added to one or more of the reactors.

10. The process of claim 1 wherein the one or more halides are fluoride, chloride, bromide, iodide, or combinations thereof.

11. The process of claim 1 wherein the nitrogenate is used in combination with an oxygenate.

12. A hydrocarbon aromatization process comprising:

adding a nitrogenate to a hydrocarbon stream to produce an enhanced hydrocarbon stream, to a hydrogen recycle stream to produce an enhanced recycle stream, or to both, wherein the hydrocarbon stream is substantially free of sulfur and wherein the nitrogenate comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone;

contacting the enhanced recycle stream, alone or in combination with the enhanced hydrocarbon stream with an aromatization catalyst, wherein the aromatization catalyst comprises a non-acidic L-zeolite support, platinum, and one or more halides;

recovering an effluent comprising aromatic hydrocarbons; and

controlling the addition of the nitrogenate to the hydrocarbon stream, the recycle stream, or both in order to maintain one or more process parameters within a desired range,

wherein the nitrogenate is controlled to maintain a Teq across one or more reactors in the process, wherein the Teq in the one or more reactors is decreased in comparison to a Teq that occurs in the absence of the nitrogenate.

13. The process of claim 12 wherein the T_eq decreases from about 0.1 percent to about 25 percent.

14. The process of claim 12 wherein the nitrogenate is used in combination with an oxygenate.

15. A hydrocarbon aromatization process comprising:

monitoring the presence of a nitrogenate in the aromatization process;

monitoring at least one parameter of the aromatization process that indicates the activity of an aromatization catalyst, wherein the aromatization catalyst comprises a non-acidic L-zeolite support, platinum, and one or more halides; and

modifying the amount of the nitrogenate in the aromatization process, thereby affecting the parameter,

wherein the modification comprises increasing an amount of the nitrogenate added in the aromatization process to a first level, then decreasing the amount of the nitrogenate added in the aromatization process to a second level,

wherein the nitrogenate is added to a hydrocarbon stream is substantially free of sulfur, and

wherein the nitrogenate comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone.

16. The process of claim 15 wherein the parameter is benzene production, and wherein upon the modification of the amount of the nitrogenate in the aromatization process, benzene production is increased by at least about 1 percent as compared to the benzene production prior to modifying the amount of the nitrogenate.

17. The process of claim 15 wherein the parameter is a useful life of the aromatization catalyst, and wherein the useful life of the aromatization catalyst is increased by at least about 5 percent as compared to a similar catalyst in which the amount of the nitrogenate has not been modified.

18. The process of claim 15 wherein the parameter is a useful life of the aromatization catalyst, and wherein the modification increases the useful life of the aromatization catalyst as compared to either a first similar aromatization catalyst in which the amount of the nitrogenate is maintained at the first level or a second similar aromatization catalyst in which the amount of the nitrogenate is maintained at the second level.

19. A hydrocarbon aromatization process comprising:

adding a nitrogenate to a recycle stream to produce an enhanced recycle stream, wherein the nitrogenate comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone;

contacting the enhanced recycle stream and a hydrocarbon stream with an aromatization catalyst in a reaction zone, wherein the hydrocarbon stream is substantially free of sulfur, wherein the catalyst comprises a non-acidic L-zeolite support, platinum, and one or more halides; and

recovering an effluent comprising aromatic hydrocarbons.

20. The process of claim 19 further comprising separating a stream from the effluent to produce the hydrogen recycle stream, wherein the hydrogen recycle stream has a water content of from about 1 ppmv to about 100 ppmv.

21. The process of claim 20 further comprising treating the hydrogen recycle stream to remove all or a portion of any nitrogenates therein to produce a treated hydrogen recycle stream having a water content of less than about 1 ppmv and then adding the nitrogenate to the treated hydrogen recycle stream prior to addition to the hydrocarbon stream.

22. The process of claim 21 wherein the nitrogenate removed from the recycle stream comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone.

23. The process of claim 19 further comprising controlling the addition of the nitrogenate to the recycle stream to maintain one or more process parameters within a desired range.

24. The process of claim 23 wherein the nitrogenate addition is controlled to maintain a T_eq across one or more reactors in the process.

25. The process of claim 24 wherein the T_eq in the one or more reactors is decreased in comparison to a T_eq that occurs in the absence of the nitrogenate.

26. The process of claim 25 wherein the T_eq decreases from about 0.1 percent to about 25 percent.

27. The process of claim 19 further comprising controlling the addition of the nitrogenate to the recycle stream to increase the production of one or more aromatic compounds in the reaction zone effluent by at least about 1 percent over pre-addition levels.

28. The process of claim 19 further comprising controlling the addition of the nitrogenate to the recycle stream to increase the catalyst selectivity to benzene in the reaction zone effluent by at least about 1 percent over pre-addition levels.

29. The process of claim 19 wherein the aromatization process comprises a plurality of reactors, and the nitrogenate is added to one or more of the reactors.

30. The process of claim 19 wherein the nitrogenate comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone.

31. The process of claim 19 wherein the one or more halides are fluoride, chloride, bromide, iodide, or combinations thereof.

32. The process of claim 19 further comprising adding the nitrogenate to the hydrocarbon stream to produce an enhanced hydrocarbon stream;

contacting both the enhanced hydrocarbon stream and the enhanced recycle stream with the aromatization catalyst; and

controlling the addition of the nitrogenate to the enhanced hydrocarbon stream, the enhanced recycle stream, or both in order to maintain one or more process parameters within a desired range.

33. The process of claim 19 wherein the nitrogenate is used in combination with an oxygenate.

34. A hydrocarbon aromatization process comprising:

adding a nitrogenate to a hydrocarbon stream to produce an enhanced hydrocarbon stream, to a recycle stream to produce an enhanced recycle stream, or to both, wherein the hydrocarbon stream is substantially free of sulfur and wherein the nitrogenate comprises ammonia or one or more ammonia precursors that form ammonia in the reaction zone;

contacting the enhanced hydrocarbon stream or the enhanced recycle stream with an aromatization catalyst, wherein the aromatization catalyst comprises a non-acidic L-zeolite support, platinum, and one or more halides;

recovering an effluent comprising aromatic hydrocarbons; and

increasing an amount of the nitrogenate added to the hydrocarbon stream or to the recycle stream.