Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

Patent metadata

Field	Value
Publication number	US-9932531-B2
Application number	US-201715494758-A
Country	US
Kind code	B2
Filing date	Apr 24, 2017
Priority date	Oct 30, 2014
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

Systems, processes, and catalysts are disclosed for obtaining fuel and fuel blends containing selected ratios of open-chain and closed-chain fuel-range hydrocarbons suitable for production of alternate fuels including gasolines, jet fuels, and diesel fuels. Fuel-range hydrocarbons may be derived from ethylene-containing feedstocks and ethanol-containing feedstocks.

First claim

What is claimed is:

1. A process, comprising:
a) passing a feedstock comprising ethylene to a gas purification zone to remove water, providing a purified feedstock;
b) passing the purified feedstock to a first oligomerization stage to oligomerize the ethylene in the purified feedstock by contacting the ethylene with a catalyst comprising a metal deposited on a support at a temperature from about 40° C. to 220° C. to form a first oligomerization product, wherein the first oligomerization product comprises a majority concentration of mixed olefins with a carbon number from about C4 to about C8; and
c) passing the first oligomerization product to a second oligomerization stage to oligomerize the mixed olefins by contacting the mixed olefins with a solid acid catalyst at a temperature from greater than 150° C. to about 450° C. to form a second oligomerization product, wherein the second oligomerization product contains mixed linear olefins and branched olefins with a carbon number from about C8 to about C23 in a yield of greater than or equal to 20% useful as fuels and fuel blend stocks.

2. The process of claim 1 , wherein the ethylene-containing feedstock is derived from ethanol.

3. The process of claim 1 , wherein the ethylene-containing feedstock is derived from methanol.

4. The process of claim 1 , wherein the second oligomerization product further comprises aromatic compounds at a concentration of less than or equal to about 4% by weight.

5. The process of claim 1 , wherein the second oligomerization product further comprises aromatic compounds at a concentration from about 4% to about 20% by weight.

6. The process of claim 1 , further comprising fractionating the second oligomerization product to obtain a distillate-range olefin fraction containing distillate-range olefins with a carbon number greater than or equal to C8, and a light fraction containing olefins with a carbon number less than C8.

7. The process of claim 6 , wherein the distillate-range olefin fraction is hydrotreated to yield a mixture of linear and branched paraffins a majority boiling from about 120° C. to about 300° C.

8. The process of claim 6 , wherein the distillate-range olefin fraction includes open chain linear and branched hydrocarbons with a carbon number from about C8 to about C16.

9. The process of claim 8 , wherein the about C8 to about C16 fraction is hydrotreated to form a mixture boiling from about 120° C. to about 300° C.

10. The process of claim 1 , further comprising fractionating the second oligomerization product to obtain a distillate-range olefin fraction containing distillate-range olefins with a carbon number greater than or equal to C11, and a light fraction containing olefins with a carbon number less than C11.

11. The process of claim 10 , wherein the distillate-range olefin fraction is hydrotreated to yield a mixture of linear and branched paraffins a majority boiling from about 160° C. to about 390° C.

12. The process of claim 10 , wherein the distillate-range olefin fraction includes open chain linear and branched hydrocarbons with a carbon number from about C11 to about C23.

13. The process of claim 12 , wherein the about C11 to about C23 fraction is hydrotreated to form linear and branched paraffins which boil in the range from about 160° C. to about 390° C.

14. The process of claim 1 , further comprising fractionating the second oligomerization product to obtain a distillate-range olefin fraction containing distillate-range olefins boiling higher than about 120° C., and a light fraction boiling below about 120° C.

15. The process of claim 14 , wherein the distillate-range olefin fraction is hydrotreated to yield open-chain linear and branched paraffins.

16. The process of claim 14 , further including hydrotreating the light fraction to form open-chain linear and branched paraffins that boil in the gasoline fuel range.

17. The process of claim 14 , wherein the light fraction is recycled to the second oligomerization stage.

18. The process of claim 1 , further comprising fractionating the second oligomerization product to obtain a distillate-range olefin fraction containing distillate-range olefins boiling higher than about 160° C., and a light fraction boiling below about 160° C.

19. The process of claim 18 , wherein the distillate-range olefin fraction is hydrotreated to yield open-chain linear and branched paraffins.

20. The process of claim 18 , further comprising hydrotreating the light fraction to form open-chain linear and branched paraffins that boil in the gasoline fuel range.

21. The process of claim 18 , wherein the light fraction is recycled to the second oligomerization stage.

22. The process of claim 1 , further comprising hydrotreating the second oligomerization product to obtain a hydrotreated product comprising open-chain linear and branched paraffins.

23. The process of claim 22 , wherein the hydrotreated product is fractionated to obtain a light fraction comprising paraffins boiling below 120° C. and a distillate paraffin fraction boiling above 120° C.

24. The process of claim 23 , wherein the distillate paraffin fraction boils in the range from about 120° C. to 300° C.

25. The process of claim 23 , wherein the distillate paraffin fraction comprises open chain linear and branched paraffins with a carbon number from about C8 to about C16.

26. The process of claim 23 , wherein the light fraction boils in the gasoline fuel range.

27. The process of claim 22 , wherein the hydrotreated product is fractionated to obtain a light fraction comprising paraffins boiling below 160° C. and a distillate paraffin fraction boiling above 160° C.

28. The process of claim 27 , wherein the distillate paraffin fraction boils in the range from about 160° C. to 390° C.

29. The process of claim 27 , wherein the light fraction boils in the gasoline fuel range.

30. The process of claim 27 , wherein the distillate paraffin fraction comprises open chain linear and branched paraffins with a carbon number from about C11 to about C23.

31. The process of claim 1 , wherein the catalyst comprises nickel (Ni) on a silica-aluminate support with a nickel concentration of from about 0.2% to about 5% by weight.

32. The process of claim 1 , wherein the support is a Y zeolite, a Beta zeolite, an HZSM-5 zeolite, a Mordenite zeolite, a Ferrierite zeolite, an Al-MCM-41 zeolite, an MCM-48 zeolite, an MCM-22 zeolite, an SAPO-34 zeolite, a Chabazite zeolite, a Group I metal-exchanged zeolite, a Group II metal-exchanged zeolite, and/or any combination thereof.

33. The process of claim 31 , wherein the silica-aluminate support is a Grace 3111 amorphous silicoaluminate support, a Grace 3113 amorphous silicoaluminate support, a Grace 3115 amorphous silicoaluminate support, a Grace 3125 amorphous silicoaluminate support, a Grace X501 amorphous silicoaluminate support, a Group I metal-exchanged amorphous silicoaluminate support, a Group II metal-exchanged amorphous silicoaluminate support, and/or any combination thereof.

34. The process of claim 1 , wherein the solid acid catalyst is a Y zeolite, a Beta zeolite, an HZSM-5 zeolite, a Mordenite zeolite, a Ferrierite zeolite, an AI-MCM-41 zeolite, an MCM-48 zeolite, an MCM-22 zeolite, an SAPO-34 zeolite, a Chabazite zeolite, a hydroge

Assignees

• Battelle Memorial Institute

Inventors

• Lilga Michael A
• Hallen Richard T
• Albrecht Karl O
• Cooper Alan R
• Frye John G
• Ramasamy Karthikeyan Kallupalayam

Classifications

• C10G2300/1092

  C2-C4 olefins · CPC title

• C10G2400/02

  Gasoline · CPC title

• C10G2300/4081

  Recycling aspects · CPC title

• B01J29/7615

  Zeolite Beta · CPC title

• C10G69/126 Primary

  polymerisation, e.g. oligomerisation · CPC title