Conversion of mixtures of C
The present disclosure provides methods and materials for oligomerization of lower olefins (e.g., C 2 -C 8 ) to transportations fuels including diesel and/or jet fuel. The oligomerization employs, in certain embodiments, tungstated zirconium catalysts. Surprisingly, the oligomerizations proceed smoothly in high yields and exhibit little to no sensitivity to the presence of significant amounts of oxygenates (e.g., water, lower alcohols such as C 2 -C 8 alcohols) in the feed stream. Accordingly, the present disclosure is uniquely suited to the production of fuels derived from bio-based alcohols, wherein olefins produced from such bio-based alcohols typically contain high levels of oxygenates.
1. A process for converting one or more C 2 -C 8 linear or branched olefins to jet and/or diesel fuel, comprising contacting a feed stream comprising the one or more C 2 -C 8 linear or branched olefins with a first catalyst and a second catalyst to afford a mixture comprising at least 70 wt % C 12 or greater alkenes, wherein the first catalyst comprises tungstted zirconium, molybdenum zirconium, or a combination thereof and the second catalyst comprises an acidic ZSM-5 catalyst.
2. The process of claim 1 , wherein the one or more C 2 -C 8 linear or branched olefins comprise at least about 50 wt % of butenes.
3. The process of claim 2 , wherein the one or more C 2 -C 8 linear or branched olefins comprise at least about 75 wt % of butenes.
4. The process of claim 3 , wherein the one or more C 2 -C 8 linear or branched olefins comprise at least about 90 wt % of butenes.
5. The process of claim 4 , wherein said butenes comprises at least about 75 wt % isobutene.
6. The process of claim 4 , wherein said butenes comprises at least about 75 wt % of linear butenes.
7. The process of claim 1 , further comprising dehydrating one or more C 2 -C 8 linear or branched alcohols with a third catalyst to provide the feed stream comprising one or more C 2 -C 8 linear or branched olefins.
8. The process of claim 7 , wherein said third catalyst comprises Zeolites, Group IB-VIIB metal doped zeolites) doped zeolites, or combinations thereof.
9. The process of claim 7 , wherein said third catalyst comprises an acidic ZSM-5 catalyst.
10. The process of claim 9 , wherein said acidic ZSM-5 further comprises from about 0.01 wt % to about 5 wt % zinc.
11. The process of claim 9 , wherein said acidic ZSM-5 further comprises from about 0.01 wt % to about 20 wt % zirconium.
12. The process of claim 7 , wherein said third catalyst comprises an acidic Ferrierite catalyst.
13. The process of claim 12 , wherein said acidic Ferrierite further comprises from about 0.01 wt % to about 5 wt % zinc.
14. The process of claim 12 , wherein said acidic Ferrierite further comprises from about 0.01 wt % to about 20 wt % zirconium.
15. The process of claim 7 , wherein the feed stream comprising one or more C 2 -C 8 linear or branched olefins comprises at least 0.5 wt % oxygenates.
16. The process of claim 15 , wherein the feed stream comprising one or more C 2 -C 8 linear or branched olefins comprises at least 1 wt % oxygenates.
17. The process of claim 16 , wherein the feed stream comprising one or more C 2 -C 8 linear or branched olefins comprises at least 2 wt % oxygenates.
18. The process of claim 17 , wherein the feed stream comprising one or more C 2 -C 8 linear or branched olefins comprises at least 3 wt % oxygenates.
19. The process of claim 15 , wherein said oxygenates comprise water and one or more C 2 -C 8 linear or branched alcohols.
20. The process of claim 1 , wherein a single-pass converstion of said C 2 -C 8 olefin is at least about 50%.
21. The process of claim 20 , wherein the single-pass conversion of said C 2 -C 8 olefin is at least about 60%.
22. The process of claim 21 , wherein the single-pass conversion of said C 2 -C 8 olefin is at least about 70%.
23. The process of claim 22 , wherein the yield of said C 12 or greater alkenes is at least about 75%.
24. The process of claim 1 , wherein said first catalyst comprises nickel and/or cobalt doped tungstated zirconium catalysts, nickel and/or cobalt doped molybdenum zirconium catalysts, or combinations thereof.
25. The process of claim 1 , wherein said first catalyst is tungstated zirconium catalyst.
26. The process of claim 25 , wherein said tungstated zirconium catalyst comprises about 85 wt % zirconium and about 15 wt % tungsten.
27. The process of claim 25 , wherein said tungstated zirconium catalyst further comprises from about 0.01 to about 3 wt % of nickel.
28. The process of claim 25 , wherein said tungstated zirconium catalyst further comprises from about 0.01 to about 3 wt % of cobalt.
29. The process of claim 1 , wherein said first catalyst is nickel and/or cobalt doped molybdenum zirconium catalyst.
30. The process of claim 29 , wherein said molybdenum zirconium catalyst comprises about 85 wt % zirconium and about 15 wt % molybdenum.
31. The process of claim 29 , wherein said molybdenum zirconium catalyst further comprises from about 0.01 to about 3 wt % of nickel.
32. The process of claim 29 , wherein said molybdenum zirconium catalyst further comprises from about 0.01 to about 3 wt % of cobalt.
33. The process of claim 1 , wherein said first catalyst further comprises acidic Ferrierite, zeolites, Group IB-VIIB metal doped zeolites, doped zeolites, an acidic zeolite catalyst, or combinations thereof.
34. The process of claim 1 , wherein said acidic ZSM-5 further comprises from about 0.01 wt % to about 5 wt % zinc.
35. The process of claim 1 , wherein said acidic ZSM-5 further comprises from about 0.01 wt % to about 20 wt % zirconium.
36. The process of claim 1 , wherein said first catalyst comprises an acidic Ferrierite catalyst.
37. The process of claim 36 , wherein said acidic Ferrierite further comprises from about 0.01 wt % to about 5 wt % zinc.
38. The process of claim 31 , wherein said acidic Ferrierite further comprises from about 0.01 wt % to about 20 wt % zirconium.