Sulfiding process for aromatic transalkylations

Patent metadata

Field	Value
Publication number	US-10450243-B2
Application number	US-201514861707-A
Country	US
Kind code	B2
Filing date	Sep 22, 2015
Priority date	Dec 19, 2014
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

A process is provided for producing xylene by transalkylation including introducing sulfur into a reactor containing a catalyst system prior to first introduction of hydrocarbon feedstock into the reactor; introducing hydrocarbon feedstock into the reactor upon the concentration of sulfur downstream of the catalyst system meeting a predetermined sulfur breakthrough concentration; continuing sulfur introduction for a period of time after first introducing hydrocarbon feedstock into the reactor; reducing the concentration of sulfur introduced upon ΔT decreasing to or below a predetermined sulfur reduction threshold; and discontinuing sulfur introduction upon ΔT decreasing to or below a predetermined sulfur shutoff threshold.

First claim

What is claimed is:

1. A process for producing xylene by transalkylation of two or more hydrocarbon feedstocks, the process comprising:
(a) introducing sulfur into a reactor containing a catalyst system prior to first introduction of the two or more hydrocarbon feedstocks into the reactor in an initial sulfiding period;
(b) measuring a concentration of sulfur downstream of the catalyst system and continuing introducing sulfur into the reaction until the concentration of sulfur downstream of the catalyst system has met a predetermined sulfur breakthrough concentration;
(c) introducing the two or more hydrocarbon feedstocks into the reactor after the sulfur concentration downstream of the catalyst system meets the predetermined sulfur breakthrough concentration;
(d) transalkylating at least some of the two or more hydrocarbon feedstocks in the presence of the catalyst system to produce xylene;
(e) continuing sulfur introduction in a de-edging period for 1-24 hours after introducing the two or more hydrocarbon feedstocks into the reactor in (c);
(f) measuring the temperature of the reactor upstream of the catalyst system and the temperature of the reactor downstream of the catalyst system to calculate ΔT,
wherein ΔT is the difference between the temperature in the reactor upstream of the catalyst system and the temperature in the reactor downstream of the catalyst system;

(g) reducing the concentration of sulfur introduced into the reactor when ΔT is less than or equal to a predetermined sulfur reduction threshold; and
(h) discontinuing sulfur introduction when ΔT is less than or equal to a predetermined sulfur shutoff threshold, wherein the sulfur shutoff threshold is less than the sulfur reduction threshold.

2. The process of claim 1 wherein the sulfur concentration reduction of step (g) is performed over a period of 1-24 hours to a concentration of 0.1-50 ppm by volume, and sulfur introduction is continued at a concentration of 0.1-50 ppm by volume if ΔT remains above the sulfur shutoff threshold.

3. The process of claim 1 further comprising: (i) measuring ΔT and reintroducing sulfur upon ΔT increasing to or above a predetermined sulfur reintroduction threshold.

4. The process of claim 3 wherein the predetermined sulfur reintroduction threshold is equal to or greater than the predetermined sulfur shutoff threshold.

5. The process of claim 4 wherein the predetermined sulfur reintroduction threshold is between 10° C. and 30° C.

6. The process of claim 1 wherein the sulfur concentration is reduced to a concentration of 1-5 ppm by volume, and continuing sulfur introduction at a concentration of 1-5 ppm by volume if ΔT remains above the predetermined sulfur shutoff threshold.

7. The process of claim 1 wherein the sulfur concentration reduction of step (g) is performed in step-wise increments.

8. The process of claim 1 wherein sulfur is introduced into the reactor during steps (a)-(c) at a concentration of 100-1000 ppm by volume.

9. The process of claim 1 wherein the predetermined sulfur breakthrough concentration is between 1-200 ppm by volume.

10. The process of claim 1 wherein the predetermined sulfur reduction threshold is between 25° C. and 75° C.

11. The process of claim 1 wherein the predetermined sulfur shutoff threshold is between 5° C. and 25° C.

12. The process of claim 1 wherein the sulfur is introduced in the form of dimethyl disulfide.

13. The process of claim 1 wherein the sulfur is introduced in a mixture of hydrogen sulfide and hydrogen gas.

14. The process of claim 1 wherein the catalyst system comprises at least a first catalyst residing in an first catalyst bed and second catalyst residing in a second catalyst bed, wherein the second catalyst bed is downstream of the first catalyst bed, and wherein the first catalyst comprises a molecular sieve and a hydrogenation component, and the second catalyst comprises a molecular sieve.

15. The process of claim 14 wherein the catalyst system further comprises a third catalyst residing in a third catalyst bed, wherein the third catalyst bed is downstream of the second catalyst bed, and wherein the second catalyst additionally comprises a hydrogenation component, and the third catalyst comprises a molecular sieve.

16. The process of claim 15 wherein each hydrogenation component comprises platinum.

17. The process of claim 16 wherein each hydrogenation component further comprises tin.

18. A process for sulfiding a transalkylation catalyst comprising the steps of:
(a) providing a reactor containing a catalyst system for producing xylene by transalkylation of two or more hydrocarbon feedstocks;
(b) introducing sulfur into the reactor upstream of the catalyst in an initial sulfiding period;
(c) measuring a concentration of sulfur downstream of the catalyst system and continuing introducing sulfur into the reaction until the concentration of sulfur downstream of the catalyst system has met a predetermined sulfur breakthrough concentration;
(d) introducing the two or more hydrocarbon feedstocks into the reactor after the concentration of sulfur downstream of the catalyst system meets the predetermined sulfur breakthrough concentration;
(e) continuing sulfur introduction for 1-24 hours after first introducing the two or more hydrocarbon feedstocks into the reactor in a de-edging period;
(f) measuring the temperature of the reactor upstream of the catalyst system and the temperature of the reactor downstream of the catalyst system to calculate ΔT,
wherein ΔT is the difference between the temperature in the reactor upstream of the catalyst system and the temperature in the reactor downstream of the catalyst system;

(g) reducing the concentration of sulfur introduced when ΔT is less than or equal to a predetermined sulfur reduction threshold; and
(h) discontinuing sulfur introduction when ΔT is less than or equal to a predetermined sulfur shutoff threshold, wherein the predetermined sulfur shutoff threshold is less than the predetermined sulfur reduction threshold.

19. The process of claim 18 wherein the predetermined sulfur breakthrough concentration is between 1-200 ppm by volume.

20. The process of claim 18 wherein the predetermined sulfur reduction threshold is between 25° C. and 75° C.

21. The process of claim 18 wherein the predetermined sulfur shutoff threshold is between 5° C. and 25° C.

22. The process of claim 18 wherein the sulfur concentration reduction of step (g) is performed over a period of 1-24 hours to a concentration of 0.1-50 ppm by volume, and sulfur introduction is continued at a concentration of 0.1-50 ppm by volume if ΔT remains above the sulfur shutoff threshold.

23. The process of claim 22 wherein the sulfur concentration is reduced to a concentration of 1-5 ppm by volume, and comprises continuing sulfur introduction at a concentration of 1-5 ppm by volume if ΔT remains above the predetermined sulfur shutoff threshold.

24. The process of claim 18 wherein the sulfur concentration reduction of step (g) is performed in step-wise increments.

25. The process of claim 1 wherein the hydrocarbon feedstocks comprise benzene and/or xylenes.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Zheng Xiaobo
• Tinger Robert G
• Bender Timothy P
• Keville Kathleen M
• Andrews Jeffrey L

Classifications

• B01J29/7469

  MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3 · CPC title

• C07C2529/80

  Mixtures of different zeolites · CPC title

• C10G29/205

  by reaction with hydrocarbons added to the hydrocarbon oil · CPC title

• C07C6/06 Primary

  at a cyclic carbon-to-carbon double bond · CPC title

• C10G2300/1096

  Aromatics or polyaromatics · CPC title