Integrated hydrocarbon desulfurization with oxidation of disulfides and conversion of SO2 to elemental sulfur

Abstract

A process to produce a sulfur-free hydrocarbon product stream from a liquid hydrocarbon disulfide product, e.g., of the Merox Process, includes subjecting the hydrocarbon disulfide to a catalytic oxidation step to produce SO.sub.2 which is separated from the remaining desulfurized hydrocarbons that form the clean sulfur-free hydrocarbon product stream; the SO.sub.2 is introduced into a Claus processing unit with the required stoichiometric amount of hydrogen sulfide (H.sub.2S) gas to produce elemental sulfur.

Claims

1. In the process for treating a liquid hydrocarbon feedstream to remove mercaptans present in the stream by a. contacting the mercaptan-containing hydrocarbon feedstream with an aqueous caustic solution to oxidize the mercaptans and produce a spent caustic solution and mercaptan-free hydrocarbons; b. subjecting the spent caustic and hydrocarbons to a wet air oxidation step to regenerate the spent caustic and produce a liquid hydrocarbon disulfide product; c. separating the regenerated aqueous caustic solution from the hydrocarbon disulfide and recycling the caustic to step (a); the improvement comprising: d. oxidizing the hydrocarbon disulfide product to sulfur dioxide and a hydrocarbon product stream that is substantially free of sulfur; e. separating and recovering the hydrocarbon product stream; f. reacting the sulfur dioxide with H.sub.2S in a predetermined stoichiometric ratio to produce an elemental sulfur product and water; and g. recovering the sulfur.

2. The process of claim 1 in which the caustic is selected from the group consisting of aqueous solutions of sodium hydroxide, ammonia, potassium hydroxide, and combinations thereof.

3. The process of claim 1 which includes subjecting the H.sub.2S to an oxidation reaction to convert a predetermined portion of the H.sub.2S to sulfur dioxide in order to achieve a stoichiometric ratio of 2H.sub.2S:SO.sub.2 to complete the sulfur-producing reaction:
2H.sub.2S+SO.sub.2.fwdarw.3S+2H.sub.2O.

4. The process of claim 1 in which the hydrocarbon disulfide is oxidized in the presence of a catalyst.

5. The process of claim 4 in which the catalyst is selected from the group consisting of catalytic compositions comprising copper oxide in an amount ranging from 10 weight percent (wt %) to 50 wt %, zinc oxide in an amount ranging from 5 wt % to less than 20 wt %, and aluminum oxide in an amount ranging from 20 wt % to 70 wt %, wherein said catalytic composition has an X-ray amorphous oxide phase, and a formula Cu.sub.xZn.sub.1xAl.sub.2O.sub.4, wherein x ranges from 0 to 1, highly dispersed crystalline ZnO and CuO alone and said composition further comprises CeO.sub.2 in the form of particles ranging in diameter from 5 nm to 10 nm, in an amount ranging from 0.1 wt % to 10 wt % of said catalytic composition, and combinations thereof.

6. The process of claim 5 in which the catalyst composition comprises from 20 wt % to 45 wt % CuO, from 10 wt % to less than 20 wt % ZnO, and from 20 wt % to 70 wt % Al.sub.2O.sub.3.

7. The process of claim 6 in which the catalyst composition comprises from 30 wt % to 45 wt % CuO, from 12 wt % to less than 20 wt % ZnO, and from 20 wt % to 40 wt % Al.sub.2O.sub.3.

8. The process of claim 4 in which the oxidation catalyst is CuCr.sub.2O.sub.4/CeO.sub.2/Al.sub.2O.sub.3.

9. The process of claim 1 in which the liquid hydrocarbon disulfide product has a sulfur content in the range of from 10 to 60 wt %.

10. The process of claim 1 in which the hydrocarbon disulfide is contacted with the oxidation catalyst at a temperature in the range of from 200 C. to 600 C.

11. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O.sub.2:C in a range of from 1:100 to 1:10 and a molar ratio of O.sub.2:S is in the range of from 1:1 to about 150:1.

12. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a weight hourly space velocity (WHSV) that is in the range of from 1 h1 to 100 h1.

13. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a gas hourly space velocity (GHSV) that is in the range of from 1,000 h1 to 25,000 h1.

14. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 30 bars.

15. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 5 bars, a weight hourly space velocity (WHSV) that is in the range of from 10h1 to 30h1, and a as hourly space velocity (GHSV) that is in the range of from 5,000 h1 to 10,000 h1.

16. The process of claim 1. in which the hydrocarbon disulfide is contacted with the oxidation catalyst at a temperature in the range of from about 250 C. to about 550 C.

17. The process of claim 1 in which the hydrocarbon disulfide is contacted with the oxidation catalyst at a temperature in the range of from about 300 C. to about 500 C.

18. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O.sub.2:C in a range of from 1:50 to 1:10 and a molar ratio of O.sub.2:S is in the range of from 1:1 to about 150:1.

19. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O.sub.2:C in a range of from 1:20 to 1:10 and a molar ratio of O.sub.2:S is in the range of from 1:1 to about 150:1.

20. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O.sub.2:C in a range of from 1:100 to 1:10, and a molar ratio of O.sub.2:S is in the range of from 10:1 to 100:1.

21. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O.sub.2:C in a range of from 1:100 to 1:10 and a molar ratio of O.sub.2:S is in the range of from 20:1 to 50:1.

22. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a weight hourly space velocity (WHSV) that is in the range of from 5 h1 to 50 h1.

23. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a weight hourly space velocity (WHSV) that is in the range of from 10 h1 to 30 h1.

24. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a gas hourly space velocity (GHSV) that is in the range of from 5,000 h1 to 15,000 h1.

25. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a gas hourly space velocity (GHSV) that is in the range of from 5,000 h1 to 10,000 h1.

26. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 10 bars.

27. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 5 bars.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be described in greater detail below and with reference to the attached drawings in which:

(2) FIG. 1 is a simplified schematic illustration of the process;

(3) FIG. 2 is a comparative plot of the percent conversion of dimethyldisulfide (DMDS) for two different catalyst systems with a ratio of O.sub.2/S equal to 12; and

(4) FIG. 3 is a comparative plot of the percent conversion of DMDS for varying ratios of O.sub.2/S for the two catalyst systems shown in FIG. 2.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(5) Referring now to the schematic illustration FIG. 1, the integrated process of the invention for treating liquid hydrocarbon disulfide products, e.g., by-products of the Merox process, comprises the following steps: (a) a mercaptan oxidation step to produce spent caustic solution and mercaptan-free hydrocarbons; (b) a wet air oxidation step to regenerate the spent caustic solution and produce by-product liquid hydrocarbon disulfides; (c) an oxidation step to oxidize the hydrocarbon disulfides to produce sulfur dioxide (SO.sub.2) and hydrocarbons which are separated to provide a sulfur-free liquid hydrocarbon product stream; and (d) a gaseous desulfurization step in which SO.sub.2 is reacted with hydrogen sulfide to produce elemental sulfur.

(6) It will be understood by one of ordinary skill in the art that steps (a) and (b) correspond to the conventional Merox process and step (d) corresponds to the conventional Claus process. The liquid mercaptan hydrocarbon stream can have a sulfur content of from about 10 to about 60 wt %.

(7) Addition of the oxidation step (c) between the Merox and Claus processes efficiently converts hydrocarbon disulfides into sulfur dioxide and light hydrocarbon gases and/or liquids which can be used as clean fuel in the refinery. The sulfur dioxide generated is sent to the Claus process unit and fully or partially eliminates the need for the conventional thermal hydrogen sulfide conversion step, because there is no need to produce sulfur dioxide from a portion of the H.sub.2S as in the conventional Claus process to react with the remaining hydrogen sulfide in the production of elemental sulfur.

(8) Oxidation of Dimethyldisulfide

(9) A comparative study was undertaken of the activity of the catalyst systems: MoO.sub.3/Al.sub.2O.sub.3 and CuCr.sub.2O.sub.4/12% CeO.sub.2 in the oxidative desulfurization of octane containing 0.5 W % of S as dimethyldisulfide (DMDS) under a representative range of conditions. The reactions were carried out under conditions that included the same GHSV=10000 h1 and temperatures in the range of 300 C. plus or minus 30 C. The catalyst loading was 2 cm.sup.3, and the O.sub.2/S ratio was varied in the range of from 12-60, and a WHSV h.sup.1 as indicated below. The results are summarized in Table 1 and the data is illustrated in FIGS. 2 and 3. As shown by the data, 100 W % conversion of DMDS was achieved over the CuCr.sub.2O.sub.4/CeO.sub.2/Al.sub.2O.sub.3 catalyst, at an O.sub.2/S ratio of 26 and the other conditions as indicated.

(10) TABLE-US-00001 TABLE 1 DMDS DS in GHSV, WHSV, Conversion. liquid, # Catalysts Temp., C. O.sub.2/S h.sup.1 h.sup.1 W % W % 1 MoO.sub.3/Al.sub.2O.sub.3 300 60 10000 16 51 2 MoO.sub.3/Al.sub.2O.sub.3 330 12 10000 41 36 46 3 MoO.sub.3/Al.sub.2O.sub.3 300 28 10000 27 35 4 MoO.sub.3/Al.sub.2O.sub.3 300 57 10000 15 51 5 MoO.sub.3/Al.sub.2O.sub.3 270 14 10000 30 49 46 6 CuCr.sub.2O.sub.4/CeO.sub.2/Al.sub.2O.sub.3 291 26 10000 26 100 85 7 CuCr.sub.2O.sub.4/CeO.sub.2/Al.sub.2O.sub.3 315 13 10000 19 88 8 CuCr.sub.2O.sub.4/CeO.sub.2/Al.sub.2O.sub.3 310 13 10000 30 70 70

(11) From the above description and examples, it is apparent that the present invention provides an economical and effective method for the recovery of a clean, sulfur-free hydrocarbon fuel from liquid disulfides, including specifically the liquid hydrocarbon disulfides produced in the caustic processing of mercaptan-containing hydrocarbon product streams. The disclosed process has widespread applicability to large scale operations such as refineries and gas processing plants where the disulfides can be processed to remove their sulfur constituent and provide an environmentally acceptable clean-burning hydrocarbon fuel.

(12) Modifications and variations on the process can be made and derived from the above description and the scope of the invention is to be determined by the claims that follow.