Upgrading paraffins to distillates and lubricant basestocks

Patent metadata

Field	Value
Publication number	US-9688626-B2
Application number	US-201514956477-A
Country	US
Kind code	B2
Filing date	Dec 2, 2015
Priority date	Dec 16, 2014
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

A process for converting light paraffins (especially C 3 -C 5 ) to middle distillate and higher boiling range liquid hydrocarbons by (1) oxygen or air oxidation of iso-paraffins to alkyl hydroperoxides; (2) conversion of alkyl hydroperoxides to dialkyl peroxides; (3) radical coupling of paraffins using the dialkyl peroxides as radical initiators forming heavier hydrocarbon products; and (4) fractionation of the heavy hydrocarbon products. The net reaction is catalytically converting light paraffins to heavier hydrocarbons using oxygen or air to effect the conversion.

First claim

The invention claimed is:

1. A process for the conversion of a feed comprising paraffins to fuel which comprises:
1. separating the feed into a first fraction comprising isoparaffins and a second fraction consisting of paraffins;
2. oxidizing the first fraction comprising isoparaffins with air or oxygen to form alkyl hydroperoxides;
3. converting the alkyl hydroperoxides to dialkyl peroxides;
4. coupling paraffins in the second fraction using the dialkyl peroxides as radical initiators to form hydrocarbon products of higher molecular weight;
5. separate the hydrocarbon products of higher molecular weight to obtain a product comprising fuel boiling range hydrocarbons; and
6. hydrofinishing the product comprising fuel boiling range hydrocarbons to remove trace oxygenates or unsaturation.

2. A process according to claim 1 , where the paraffins in step 4 are isoparaffins, normal-paraffins, neoparaffins, cyclic paraffins, or mixtures thereof with carbon numbers in the range of 2 to 12 with the same or different carbon numbers as the isoparaffins of step 2.

3. A process according to claim 1 where the feed is light virgin naphtha.

4. A process according to claim 1 where the feed is liquefied petroleum gas (LPG).

5. A process according to claim 1 where the feed is a mixture of propane, butanes and pentanes.

6. A process according to claim 1 in which the paraffins comprise butanes.

7. A process according to claim 6 in which the feed comprises a mixture of n-butane and iso-butane comprising 5 to 90 wt % iso-butane.

8. A process according to claim 6 in which the feed is n-butane which is isomerized to form iso-butane.

9. A process according to claim 1 in which the paraffins comprise pentanes.

10. A process according to claim 9 in which the feed comprises a mixture of n-pentane, iso-pentane, cyclo-pentane, or neo-pentane.

11. A process according to claim 10 in which the feed is n-pentane.

12. A process according to claim 1 which includes the step of fractionating the hydrocarbon products from step (4) to separate the hydrocarbon products of higher molecular weight.

13. A process according to claim 1 in which the iso-paraffins are oxidized to a mixture of alkyl hydroperoxides and alkanols.

14. A process according to claim 1 in which the alkyl hydroperoxides are converted to dialkyl peroxides by reaction of the alkyl hydroperoxides with alkanol.

15. A process according to claim 14 in which the alkyl hydroperoxides are converted to dialkyl peroxides by reaction of the alkyl hydroperoxides with C 4 or C 5 alkanol.

16. A process according to claim 1 in which the hydrocarbon products of higher molecular weight formed by the coupling of the feed consisting of C 3 , C 4 or C 5 paraffins with the dialkyl peroxide are fractionated to separate lower C 4 or C 5 alkanol and the separated alkanol is partially or fully recycled to step 3 for the formation of dialkyl peroxides.

17. A process according to claim 1 in which the hydrofinishing is performed at a temperature in the range of 150-350° C. and a hydrogen pressure of 1400-7000 KPag (200-1000 psig).

18. A process according to claim 17 in which the hydrofinishing is performed with a catalyst comprising a metal or an alloy on a support.

19. A process according to claim 18 in which the metal or alloy comprises Pt, Pd, Rh, Ru, Ir, Co, Ni, Fe, Cu, Mo, W, Re, or Sn.

20. A process according to claim 18 in which the support comprises alumina, silica, zirconia, titania, carbon, aluminosilicates, zeolites (natural or synthetic), or silicoaluminophosphates (SAPO).

21. A process according to claim 1 in which the hydrocarbon products of higher molecular weight formed by the coupling of the feed consisting of C 4 or C 5 paraffins with the dialkyl peroxide are fractionated to separate lower C 4 or C 5 alkanol and the alkanol is dehydrated to form iso-olefins.

22. A process according to claim 1 in which the hydrocarbon products of higher molecular weight formed by the coupling of the feed consisting of C 4 or C 5 paraffins with the dialkyl peroxide are fractionated to separate lower C 4 or C 5 alkanol and the alkanol is converted into ether by reacting with an alcohol.

23. A process according to claim 21 where the iso-olefins are converted by oligomerization to higher molecular weight products gasoline, kero-jet, diesel, or lubricant basestocks.

24. A process according to claim 21 where the iso-olefins are converted by alkylation to higher molecular weight products gasoline, kero-jet, or diesel.

25. A process according to claim 1 in which the oxidation of step 2 is carried out at a temperature of 110-150° C. and a pressure of 2000-5500 kPag.

26. A process according to claim 1 in which the oxidation of step 2 is carried out at a temperature of 130-140° C. and a pressure of 2000-3500 kPag.

27. A process according to claim 1 in which the conversion of alkyl hydroperoxides to dialkyl peroxides in step 3 is carried out by reactive distillation.

28. A process according to claim 1 in which the coupling reaction of step 4 is carried out at a temperature of 100-170° C. at a pressure of 3,500-10,000 kPag.

Assignees

• Wang Kun
• Ho Suzzy Chen Hsi
• Olmstead William N
• Exxonmobil Res & Eng Co

Inventors

• Wang Kun
• Ho Suzzy Chen Hsi
• Olmstead William N

Classifications

• C10G2400/08

  Jet fuel · CPC title

• C07C409/16

  the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides · CPC title

• C10G69/126

  polymerisation, e.g. oligomerisation · CPC title

• C07C2/84

  catalytic · CPC title

• C10L1/04

  essentially based on blends of hydrocarbons · CPC title