Systems and processes for conversion of ethylene feedstocks to hydrocarbon fuels

Patent metadata

Field	Value
Publication number	US-9771533-B2
Application number	US-201414528185-A
Country	US
Kind code	B2
Filing date	Oct 30, 2014
Priority date	Oct 30, 2014
Publication date	Sep 26, 2017
Grant date	Sep 26, 2017

Abstract

Systems, processes, and catalysts are disclosed for obtaining fuels 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 for converting feedstocks to distillate-range hydrocarbon fuels, comprising:
oligomerizing an ethylene-containing feed over a first catalyst at a temperature selected from about 40° C. to about 220° C. to form a water-free first oligomerization product in a first reaction stage, wherein the water-free first oligomerization product contains a majority concentration of mixed olefins with a carbon number from about C4 to about C8;
oligomerizing the mixed olefins in the water-free first oligomerization product over a second catalyst at a temperature from about 150° C. to about 350° C. to form a two-step oligomerization product at a yield greater than or equal to about 20% containing mixed open-chain linear and branched olefins with a carbon number from about C8 to about C23; and
combining together selected portions of (a) the two-step oligomerization product and a first hydrocarbon product or (b) the two-step oligomerization product, the first hydrocarbon products, and a second hydrocarbon product to form a blend comprising any selected ratio of open-chain and closed-chain hydrocarbons;
wherein the first hydrocarbon product is derived from an ethanol-containing feed and comprises a majority concentration of mixed cycloparaffin hydrocarbons and mixed closed-chain aromatic hydrocarbons with a carbon number between about C3 to about C12; and the second hydrocarbon product comprises a selected quantity of alkylated aromatic hydrocarbons.

2. The process of claim 1 , further including mixing the water-free first oligomerization product with the first hydrocarbon product to make a feed, and alkylating the feed over an alkylation catalyst to form the second hydrocarbon product comprising alkylated aromatic hydrocarbons.

3. The process of claim 2 , wherein the second hydrocarbon product contains more hydrocarbons with carbon numbers greater than C8 than the feed.

4. The process of claim 2 , wherein the second hydrocarbon product contains more hydrocarbons with carbon numbers greater than C10 than the feed.

5. The process of claim 1 , further including hydrotreating the blend to yield a majority of fuel range hydrocarbons boiling in the range of temperatures from about 120° C. to about 390° C.

6. The process of claim 1 , further including hydrotreating each of the first hydrocarbon product, the second hydrocarbon product, and/or the two-step oligomerization product prior to combining the selected portions together to yield a majority of fuel range hydrocarbons boiling in the range of temperatures from about 120° C. to about 390° C.

7. The process of claim 1 , further including optionally fractionating the two-step oligomerization product at a selected fractionation temperature to obtain individual fractions, a fraction containing distillate-range olefins boiling at or higher than the fractionation temperature and a light fraction boiling at or below the fractionation temperature.

8. The process of claim 7 , wherein the fractionation temperature is selected in the range from about 100° C. to about 140° C.

9. The process of claim 7 , wherein the fractionation temperature is selected in the range from about 140° C. to about 180° C.

10. The process of claim 7 , further including hydrogenating the distillate-range olefins to form a mixture of open-chain hydrocarbons including linear and branched open-chain paraffins.

11. The process of claim 10 , wherein a majority of open-chain hydrocarbons in the mixture are in the jet fuel range.

12. The process of claim 10 , wherein a majority of open-chain hydrocarbons in the mixture are in the diesel fuel range.

13. The process of claim 7 , further including mixing the light fraction with the first hydrocarbon product containing aromatic hydrocarbons to make a feed, and alkylating the feed over an alkylation catalyst to form the second hydrocarbon product comprising alkylated aromatic hydrocarbons.

14. The process of claim 13 , wherein the second hydrocarbon product contains more hydrocarbons with carbon numbers greater than C8 than the feed.

15. The process of claim 13 , wherein the second hydrocarbon product contains more hydrocarbons with carbon numbers greater than C10 than the feed.

16. The process of claim 1 , further including mixing ethylene or an ethylene-containing feed with the first hydrocarbon product containing aromatic hydrocarbons to make a feed, and alkylating the feed over an alkylation catalyst to form the second hydrocarbon product comprising alkylated aromatic hydrocarbons.

17. The process of claim 16 , wherein the second hydrocarbon product contains more hydrocarbons with carbon numbers greater than C8 than the feed.

18. The process of claim 16 , wherein the second hydrocarbon product contains more hydrocarbons with carbon numbers greater than C10 than the feed.

19. The process of claim 1 , further including combining selected ratios of the first hydrocarbon product containing aromatic hydrocarbons and the second hydrocarbon product containing alkylated aromatic hydrocarbons to make a feed and hydrogenating the feed to obtain a mixture of closed-chain hydrocarbons including closed-chain aromatics and closed-chain paraffins.

20. The process of claim 19 , wherein the hydrogenation includes converting from 0% to about 33% of the closed-chain aromatics to closed-chain paraffins.

21. The process of claim 19 , wherein the hydrogenation includes converting from about 33% to about 66% of the closed-chain aromatics to closed-chain paraffins.

22. The process of claim 19 , wherein the hydrogenation includes converting from about 66% to about 100% of the closed-chain aromatics to closed-chain paraffins.

23. The process of claim 19 , further including combining a selected ratio of the mixture containing closed-chain hydrocarbons and a mixture containing open-chain hydrocarbons including linear and branched open-chain paraffins to make a fuel blend, wherein the mixture containing open-chain hydrocarbons is obtained from a fraction derived from fractionation of the two-step oligomerization product containing distillate-range olefins boiling at or higher than the fractionation temperature that is further hydrogenated.

24. The process of claim 23 , further including fractionating the fuel blend to obtain individual fractions, a fraction containing distillate-range hydrocarbons boiling in the range of temperatures from about 120° C. to about 300° C., a light fraction boiling below a temperature of about 120° C., and a heavy fraction boiling above a temperature of about 300° C.

25. The process of claim 24 , wherein the distillate-range hydrocarbons are in the jet fuel range.

26. The process of claim 24 , wherein the light fraction contains hydrocarbons in the gasoline fuel range.

27. The process of claim 23 , further including fractionating the fuel blend to obtain individual fractions, a fraction containing distillate-range hydrocarbons boiling in the range of temperatures from about 160° C. to about 390° C., a light fraction boiling below a temperature of about 160° C., and a heavy fraction boiling above a temperature of about 390° C.

28. The process of claim 27 , wherein the distillate-range hydrocarbons are in the diesel fuel range.

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

30. The process of claim 1 , fu

Assignees

• Battelle Memorial Institute

Inventors

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

Classifications

• C10G69/123

  alkylation · CPC title

• C07C2/12

  with crystalline alumino-silicates {or with catalysts comprising} molecular sieves · CPC title

• C10G45/00

  Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds · CPC title

• C10G29/205 Primary

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

• C10G2300/1092

  C2-C4 olefins · CPC title