Reaction system, methods and products therefrom

• US 9,828,557 B2
• Filed: 02/23/2015
• Issued: 11/28/2017
• Est. Priority Date: 09/22/2010
• Status: Active Grant

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Rankin, Jonathan, Clickner, Sarah, Litz, Kyle Erik, Lewis, Larry Neil, Faherty, John, Kolibas, Eric, Hemberger, Stephen, Richardson, John, Rossetti, Mark
• Primary Examiner(s): Robinson, Renee
• Application Number:
  US14/629,169
• Publication Number:
  US 20150184086A1
• Time in Patent Office: 1,009 Days
• CPC Class Codes: B01J 2231/64 Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
• CPC Class Codes: B01J 23/02 of the alkali- or alkaline earth metals or beryllium
• CPC Class Codes: B01J 2531/007 Promoter-type Additives
• CPC Class Codes: B01J 31/0202 Alcohols or phenols
• CPC Class Codes: C10G 19/00 Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
• CPC Class Codes: C10G 19/02 with aqueous alkaline solutions
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/203 Naphthenic acids, TAN
• CPC Class Codes: C10G 2300/308 Gravity, density, e.g. API
• CPC Class Codes: C10G 27/00 Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen
• CPC Class Codes: C10G 29/20 Organic compounds not containing metal atoms
• CPC Class Codes: C10G 29/22 containing oxygen as the only hetero atom
• CPC Class Codes: C10G 32/02 by electric or magnetic means
• CPC Class Codes: C10G 53/12 including at least one alkaline treatment step
• CPC Class Codes: C10G 53/14 including at least one oxidation step

Abstract

A reaction system and method for removing heteroatoms from oxidized-heteroatom-containing hydrocarbon streams and products derived therefrom are disclosed. An oxidized-heteroatom-containing hydrocarbon feed is reacted in a reaction system thereby forming non-ionic hydrocarbon products. The products derived therefrom are useful as transportation fuels, lubricants, refinery intermediates, or refinery feeds.

Claims

1. A method for reducing heteroatom content of a hydrocarbon feed comprising the steps of:

oxidizing the hydrocarbon feed to an oxidized heteroatom-containing hydrocarbon feed;

contacting the oxidized heteroatom-containing hydrocarbon feed with a caustic treatment solution comprising a phenol-derived catalyst, a caustic and a selectivity promoter;

producing from said contacting step, a hydrocarbon product having a heteroatom content that is less than the heteroatom content of the oxidized heteroatom-containing hydrocarbon feed.

2. The method of claim 1 wherein the contacting step occurs under biphasic conditions, producing a hydrocarbon phase and an aqueous phase, wherein the hydrocarbon phase includes the hydrocarbon product having the heteroatom content that is less than the heteroatom content of the hydrocarbon feed, and at least one of a sulfate salt, and sulfite salt and wherein the aqueous phase comprises the caustic and the selectivity promoter.

3. The method of claim 2, further comprising the steps of:

separating the hydrocarbon phase from the aqueous phase;

mixing the hydrocarbon phase with an aqueous wash feed, producing a washed hydrocarbon phase and an aqueous wash phase; and

extracting the washed hydrocarbon phase from the aqueous wash phase.

4. The method of claim 3, wherein the aqueous wash feed is a solution of sodium hydrogen sulfate dissolved in water.

5. The method of claim 4, wherein the sodium hydrogen sulfate has a concentration that is approximately ≦

50% by weight.

6. The method of claim 3, wherein the aqueous wash phase comprises at least one of sodium sulfate, sodium bisulfate, sodium phenoxide, sodium sulfite, sodium hydrogen sulfite, selectivity promoter and one or more caustic byproducts.

7. The method of claim 3, wherein the extracting step includes separating the washed hydrocarbon phase from the aqueous wash feed by providing an electric voltage to the mixture.

8. The method of claim 7, wherein the electric voltage is approximately ≦

2000 v.

9. The method of claim 3, further comprising the steps of:

mixing the washed hydrocarbon phase with a second aqueous wash feed, producing a final hydrocarbon product having a sulfite salt concentration or sulfate salt concentration that is less than the sulfite salt concentration or sulfite salt concentration of the hydrocarbon product and a second aqueous wash phase; and

extracting the final hydrocarbon product from the second aqueous wash phase.

10. The method of claim 9, wherein the second aqueous wash feed comprises a salt dissolved in water.

11. The method of claim 9, wherein the second aqueous wash feed has a density greater than the washed hydrocarbon phase.

12. The method of claim 10, wherein the salt comprises a cation, selected from the group consisting of an alkali metal, alkaline earth metal, and organic heterocyclic-cations, and mixtures thereof, and wherein the salt has an anion selected from the group consisting of one or more halogens, sulfite, sulfate and a combination thereof.

13. The method of claim 10, wherein the second aqueous wash feed further comprises tetra-n-butyl ammonium hydroxide (TBAH).

14. The method of claim 9, wherein the second aqueous wash phase comprises at least one of water, sodium chloride, sodium sulfate, sodium bisulfate, sodium phenoxide, sodium sulfite, sodium hydrogen sulfite, TBAH, selectivity promoter and one or more caustic byproducts.

15. The method of claim 9, wherein the step of extracting step includes separating the final hydrocarbon product from the second aqueous wash phase by providing a second electric voltage to the mixture.

16. The method of claim 9, wherein the second electric voltage is approximately ≦

2000V.

17. The method of claim 1, wherein the phenol-derived catalyst is selected from the group consisting of a novolac resin, a resol resin, a calixarene, lignin, a siloxy phenol, Black liquor and a combination thereof.

18. The method of claim 17, wherein the calixarene is p-tert-butylcalix[n]arene, where n denotes the number of phenol groups, and is approximately 3 to 30.

19. The method of claim 1, wherein the caustic is selected from the group consisting of an inorganic oxide having a group IA metal, an inorganic oxide having a group IIA metal, an inorganic hydroxide having a group IA element, an inorganic hydroxide having a group IIA element, an alkali metal sulfide, an alkaline earth metal sulfide, an alkali metal carbonate, an alkaline earth metal carbonate, a phosphate salt, a silicate salt, mixtures and molten mixtures thereof.

20. The method of claim 19, wherein the caustic is selected from the group consisting of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, Fr₂O, BeO MgO, CaO, SrO, BaO, Na₂S, K₂S, LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Be(OH)₂, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, Ba(OH)₂, Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, BaCO₃, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, calcium pyrophosphate, magnesium pyrophosphate, barium pyrophosphate, calcium tripolyphosphate, magnesium tripolyphosphate, barium tripolyphosphate, sodium silicate and potassium silicate, calcium silicate, magnesium silicate, barium silicate, green liquor, mixtures and molten mixtures thereof.

21. The method of claim 1, wherein the selectivity promoter is selected from the group consisting of organic alcohol, morpholine, dioxane, dimethylethanolamine, methyldiethanolamine, mono ethanolamine, diethanolamine, triethanolamine, N-acetylglucosamine, glucosamine, crown ether, piperazine, choline hydroxide, benzyltrimethylammonium hydroxide, ethylene glycol, propylene glycol, glycerin, sugar, starches, cellulose, chitosan, hyaluronic acid diethylene glycol, triethylene glycol, polyethylene glycol, chitin and pectin.

22. The method of claim 1, wherein the contacting step occurs at a temperature ≦

250°

C., producing an intermediate selected from the group consisting of a hydrocarbon-containing sulfinate intermediate, a hydrocarbon-containing sulfonate intermediate and a combination of intermediates thereof.

23. The method of claim 22, further comprising the steps of:

removing the caustic treatment solution after the formation of the intermediate; and

reacting the intermediate with water to produce the hydrocarbon product having a heteroatom content that is less than the heteroatom content of the oxidized heteroatom-containing hydrocarbon feed.

24. The method of claim 1, wherein the hydrocarbon product is an aromatic hydrocarbon.

37. The method of claim 1, wherein ≧

20% of heteroatom-containing compounds in the hydrocarbon feed are converted to non-oxygenated, non-heteroatom-containing hydrocarbon compounds including biphenyls.

38. The method of claim 1, wherein ≦

50% of heteroatom-containing compounds in the hydrocarbon feed are converted to oxygenated or heteroatom-containing compounds.

25. A method for reducing heteroatom content of a hydrocarbon feed comprising the steps of:

contacting an oxidized heteroatom containing hydrocarbon feed with a caustic treatment solution;

producing from said contacting step, a hydrocarbon phase having a hydrocarbon product and at least one of a sulfite salt and a sulfate salt, and an aqueous phase;

separating the hydrocarbon phase from the aqueous phase;

mixing the hydrocarbon phase with an aqueous wash feed, wherein the aqueous wash feed is a solution of sodium hydrogen sulfate dissolved in water, producing a washed hydrocarbon phase and an aqueous wash phase; and

extracting the washed hydrocarbon phase from the aqueous wash phase.

26. The method of claim 25, wherein the sodium hydrogen sulfate has a concentration that is approximately ≦

50% by weight.

27. The method of claim 25, wherein the aqueous wash phase comprises at least one of sodium sulfate, sodium hydrogen sulfate, sodium phenoxide, sodium sulfite, sodium hydrogen sulfite, selectivity promoter and one or more caustic byproducts.

28. The method of claim 25, wherein the step of extracting includes separating the washed hydrocarbon phase from the aqueous wash feed by providing an electric voltage to the mixture of the hydrocarbon phase and the aqueous wash feed.

29. The method of claim 28, wherein the electric voltage is approximately ≦

2000V.

30. The method of claim 25, further comprising the steps of:

mixing the washed hydrocarbon phase with a second aqueous wash feed, producing a final hydrocarbon product having a sulfite salt concentration or sulfate salt concentration that is less than the sulfite salt concentration or sulfite salt concentration of the hydrocarbon product and a second aqueous wash phase; and

extracting the final hydrocarbon product from the second aqueous wash phase.

31. The method of claim 30, wherein the second aqueous wash feed comprises a salt dissolved in water wherein the salt comprises a cation selected from the group consisting of alkali metal, alkaline earth metal, and organic heterocyclic-cations, and mixtures thereof and an anion selected from the group consisting of halogens and mixtures thereof.

32. The method of claim 31, wherein the second aqueous wash feed has a density greater than the hydrocarbon phase.

33. The method of claim 30, wherein the second aqueous wash feed further comprises tetra-n-butyl ammonium hydroxide (TBAH).

34. The method of claim 30, wherein the second aqueous wash phase comprises at least one of sodium chloride, sodium sulfate, sodium bisulfate, sodium phenoxide, sodium sulfite, sodium hydrogen sulfite, TBAH, selectivity promoter and one or more caustic byproducts.

35. The method of claim 30, wherein the extracting step includes separating the final hydrocarbon product from the second aqueous wash phase by providing a second electric voltage to the mixture.

36. The method of claim 35, wherein the second electric voltage is approximately ≦

2000V.