SYSTEMS AND METHODS FOR ISOPRENE PURIFICATION

Abstract

Methods for the selective hydrogenation of acetylenic compounds in a product stream that includes isoprene. A method of selectively hydrogenating an acetylenic hydrocarbon in the presence of isoprene may include obtaining a hydrocarbon mixture comprising an acetylenic hydrocarbon, isoprene, and butadiene or cyclopentadiene, or both. If cyclopentadiene is present, the hydrocarbon mixture may comprise greater than 2 wt. % cyclopentadiene. The method may further include contacting the hydrocarbon mixture and hydrogen (H.sub.2) with a hydrogenation catalyst under reaction conditions that are more selective to the hydrogenation of the acetylenic hydrocarbon than the isoprene.

Claims

1-16. (canceled)

17. A method of selectively hydrogenating an acetylenic hydrocarbon in the presence of isoprene, the method comprising: (a) obtaining a hydrocarbon mixture comprising (i) an acetylenic hydrocarbon, (ii) isoprene, (iii) butadiene and (iv) greater than 10 wt. % cyclopentadiene; and (b) contacting the hydrocarbon mixture and hydrogen (H.sub.2) with a hydrogenation catalyst under reaction conditions that are more selective to hydrogenation of the acetylenic hydrocarbon than the isoprene to produce an effluent comprising a hydrogenated compound.

18. The method of claim 17, wherein the hydrogenation catalyst comprises nickel, palladium, or platinum, or combinations or alloys thereof.

19. The method of claim 17, wherein less than 10% of the isoprene is hydrogenated.

20. The method of claim 17, wherein the acetylenic hydrocarbon is 2-butyne.

21. The method of claim 17, wherein the wherein the hydrogenation catalyst comprises platinum.

22. The method of claim 17, wherein the reaction conditions include a pressure in a range of less than 50 to 8 bar(g).

23. The method of claim 17, wherein the reaction conditions include a weight hourly space velocity (WHSV) in a range of 1 to 4 h.sup.−1.

24. The method of claim 17, wherein an amount of cyclopentadiene in the hydrocarbon mixture is 5 to 25 wt. %.

25. The method of claim 17, wherein the hydrogenation catalyst comprises nickel.

26. The method of claim 17, wherein the hydrogenation catalyst comprises palladium.

27. The method of claim 17, wherein there is a complete hydrogenation of the acetylenic hydrocarbon.

28. The method of claim 17, wherein, the method does not include a dimerization reaction involving cyclopentadiene.

29. The method of claim 17, wherein the butadiene is added to a product stream from a pyrolysis or cracking process to form the hydrocarbon mixture.

30. The method of claim 17, wherein the cyclopentadiene is added to a product stream from a pyrolysis or cracking process to form the hydrocarbon mixture.

31. The method of claim 17, wherein the contacting occurs in a fixed-bed reactor.

32. The method of claim 18, wherein there is a complete hydrogenation of the acetylenic hydrocarbon.

33. The method of claim 18, wherein, the method does not include a dimerization reaction involving cyclopentadiene.

34. The method of claim 18, wherein the butadiene is added to a product stream from a pyrolysis or cracking process to form the hydrocarbon mixture.

35. The method of claim 18, wherein the cyclopentadiene is added to a product stream from a pyrolysis or cracking process to form the hydrocarbon mixture.

36. The method of claim 18, wherein the contacting occurs in a fixed-bed reactor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

[0020] FIG. 1 shows a system for the selective hydrogenation of acetylenic compounds in presence of isoprene, according to embodiments of the invention; and

[0021] FIG. 2 shows a method for the selective hydrogenation of acetylenic compounds in presence of isoprene, according to embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0022] A method has been discovered for the selective hydrogenation of acetylenic compounds in a product stream that includes isoprene. The method implements operating conditions (e.g., temperature, pressure, weight hourly space velocity (WHSV)) that minimize the loss of isoprene in the hydrogenation process.

[0023] Embodiments of the invention include a method of selectively hydrogenating an acetylenic hydrocarbon (e.g., 2-butyne, CH.sub.3—C≡C—CH.sub.3) in the presence of isoprene. The method includes obtaining a hydrocarbon mixture comprising an acetylenic hydrocarbon, isoprene, and butadiene or cyclopentadiene, or both. The hydrocarbon mixture may include greater than 2 wt. % cyclopentadiene, if present. Embodiments of the invention may further include contacting the hydrocarbon mixture and hydrogen (H.sub.2) with a hydrogenation catalyst under reaction conditions that are more selective to the hydrogenation of the acetylenic hydrocarbon than the isoprene.

[0024] FIG. 1 shows system 10 for the selective hydrogenation of acetylenic compounds in presence of isoprene, according to embodiments of the invention. FIG. 2 shows method 20 for the selective hydrogenation of acetylenic compounds in presence of isoprene, according to embodiments of the invention. Method 20 may be implemented with system 10. Embodiments of the invention, as illustrated in FIG. 1, include the selective hydrogenation of components of hydrocarbon feed 100. Hydrocarbon feed 100 may be a C.sub.4 cut (fraction) and/or a C.sub.5 cut from a catalytic cracking process, for example, that produces ethylene. According to embodiments of the invention, hydrocarbon feed 100 is a mixture of different compounds, including isoprene and acetylenic compounds (e.g., C.sub.4 and/or C.sub.5 acetylenic compounds). In embodiments of the invention, cyclopentadiene may be present with the isoprene in hydrocarbon feed 100 as a byproduct of hydrocarbon pyrolysis. Alternatively or additionally, cyclopentadiene may be added to a product stream (e.g., a product stream from a pyrolysis or cracking process) to form hydrocarbon feed 100, as it is theorized that the presence of cyclopentadiene may help in the minimization of isoprene loss in the hydrogenation process. Similarly, it is theorized that the presence of butadiene may help in the minimization of isoprene loss in the hydrogenation process. In view of this, butadiene may also be added to a product stream (e.g., a product stream from a pyrolysis or cracking process) to form hydrocarbon feed 100 to minimize such isoprene loss in the hydrogenation process. Thus, hydrocarbon feed 100 may include one or more acetylenic hydrocarbons, isoprene, and butadiene or cyclopentadiene (C.sub.5H.sub.6), or both. In embodiments of the invention in which cyclopentadiene is present, hydrocarbon feed 100 may include greater than 2 wt. % cyclopentadiene. Further, in embodiments of the invention, the amount of cyclopentadiene in the hydrocarbon mixture is 5 to 25 wt. %. Hydrocarbon feed 100 may include 3 wt. % to 25 wt. % cyclopentadiene. In embodiments of the invention, hydrocarbon feed 100 is a liquid.

[0025] Consistent with the foregoing, method 20 may include, at block 200, obtaining a hydrocarbon mixture (e.g., hydrocarbon feed 100) comprising an acetylenic hydrocarbon, isoprene, and butadiene or cyclopentadiene, or both. The hydrocarbon mixture may include greater than 2 wt. % cyclopentadiene, if present. Obtaining this hydrocarbon mixture may include adding butadiene and/or cyclopentadiene to a hydrocarbon stream that includes isoprene. At block 201, method 20 may then include flowing hydrocarbon feed 100 to reactor 101 (FIG. 1). In embodiments of the invention, reactor 101 may be a fixed-bed reactor configured to hydrogenate particular components of hydrocarbon feed 100.

[0026] For example, reactor 101, as shown in FIG. 1, includes catalyst 102. Catalyst 102 may be a hydrogenation catalyst adapted to selectively hydrogenate acetylenic compounds. Catalyst 102 may be a selection from: nickel (Ni) catalyst, palladium (Pd) catalyst, platinum (Pt) catalyst, alloys thereof, and combinations thereof. According to embodiments of the invention, catalyst 102 selectively hydrogenates acetylenic compounds due to the much stronger adsorption of these compounds by catalyst 102, as compared to other compounds of hydrocarbon feed 100. These acetylenic compounds, in embodiments of the invention, stay adsorbed on catalyst 102 until complete saturation. Active sites of catalyst 102 available for hydrogen adsorption are different from those available for adsorption of acetylenics compounds. Because acetylenic compounds having triple bonds are more reactive than diolefins having double bonds, short contact time may allow complete hydrogenation of the acetylenic compounds before saturation of diolefins. According to embodiments of the invention, there is no direct competition between hydrogen and the acetylenic compounds for the same sites because hydrogen molecules are so small that they can find free sites even though the catalytic surface is completely covered by the strongly adsorbed acetylenic compounds.

[0027] In embodiments of the invention, method 20 may include, at block 202, flowing hydrogen to reactor 101. With hydrogen present, method 20, at block 203, may involve contacting hydrocarbon feed 100 and hydrogen (H.sub.2) with catalyst 102, in reactor 101 under reaction conditions that are more selective to the hydrogenation of the acetylenic hydrocarbon than isoprene.

[0028] In embodiments of the invention, the reaction conditions within reactor 101 for the selective hydrogenation of acetylenic hydrocarbons may include a temperature in a range of less than 80° C., and all ranges and values therein including ranges 0 to 5° C., 5 to 10° C., 10 to 15° C., 15 to 20° C., 20 to 25° C., 25 to 30° C., 30 to 35° C., 35 to 40° C., 40 to 45° C., 45 to 50° C., 50 to 55° C., 55 to 60° C., 60 to 65° C., 65 to 70° C., 70 to 75° C., and 75 to 80° C., preferably 30 to 50° C. With respect to pressure, the reaction conditions within reactor 101 for the selective hydrogenation of acetylenic hydrocarbons may include a pressure in the range of less than 10 bar(g), and all ranges and values therein including ranges 1 to 2 bar(g), 2 to 3 bar(g), 3 to 4 bar(g), 4 to 5 bar(g), 5 to 6 bar(g), 6 to 7 bar(g), 7 to 8 bar(g), 8 to 9 bar(g), and 9 to 10 bar(g), preferably 5 to 8 bar(g), and values of 1 bar(g), 2 bar(g), 3 bar(g), 4 bar(g), 5 bar(g), 6 bar(g), 7 bar(g), 8 bar(g), 9 bar(g), and 10 bar(g). And with respect to weight hourly space velocity (WHSV), the reaction conditions within reactor 101 for the selective hydrogenation of acetylenic hydrocarbons may include a WHSV in a range less than 8 h.sup.−1, and all ranges and values therein including ranges 1 to 2 h.sup.−1, 2 to 3 h.sup.−1, 3 to 4 h.sup.−1, 4 to 5 h.sup.−1, 5 to 6 h.sup.−1 6 to 7 h.sup.−1, and 7 to 8 h.sup.−1 and values 1 h.sup.−1, 2 h.sup.−1, 3 h.sup.−1, 4 h.sup.−1, 5 h.sup.−1, 6 h.sup.−1, 7 h.sup.−1, and 8 h.sup.−1, preferably 1 to 4 h.sup.−1. In embodiments of the invention in which butyne is present, the reaction conditions may include a mol. % ratio of H.sub.2/butyne of less than 6 mol. %, and all ranges and values therein including ranges of 1 to 2 mol. %, 2 to 3 mol. %, 3 to 4 mol. %, 4 to 5 mol. %, and 5 to 6 mol. %, and values of 1 mol. %, 2 mol. %, 3 mol. %, 4 mol. %, 5 mol. %, and 6 mol. %, preferably 2 to 3 mol. %.

[0029] According to embodiments of the invention, under the reaction conditions of reactor 101, acetylenic compounds of hydrocarbon feed 100 is hydrogenated and effluent stream 104 is flowed from reactor 101, at block 204.

[0030] In embodiments of the invention the acetylenic hydrocarbons of hydrocarbon feed 100 are completely hydrogenated. In embodiments of the invention, method 20 does not include a dimerization reaction involving cyclopentadiene. In embodiments of the invention, less than 10% of the isoprene is hydrogenated. In embodiments of the invention, the acetylenic hydrocarbons can be butyne, preferably 2-butyne, or combinations thereof. In embodiments of the invention, less than 7% of the isoprene is hydrogenated, wherein the mol. % ratio of H.sub.2:butyne is less than 6:1.

[0031] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.