Polyolefins from non-conventional feeds

• US 20070123659A1
• Filed: 11/30/2005
• Published: 05/31/2007
• Est. Priority Date: 11/30/2005
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Wu, Margaret, Yang, Norman, Kramer, Anatoly
• Granted Patent: US 7,456,329 B2
• Time in Patent Office: Days
• US Class Current: 525/338
• CPC Class Codes: C10G 69/126 polymerisation, e.g. oligomerisation
• CPC Class Codes: C10M 107/10 containing aliphatic monomer having more than 4 carbon atoms
• CPC Class Codes: C10M 2205/0285 used as base material
• CPC Class Codes: C10N 2030/08 Resistance to extreme temperature

Abstract

Polyolefins made in accordance with the present invention are produced by polymerizing an unsaturated olefin or combination of unsaturated olefins to produce an unsaturated polyolefin, isomerizing the unsaturated polyolefin in the presence of an acid catalyst under conditions to produce a substantially unsaturated-isomerized polyolefin, and hydrogenating the unsaturated-isomerized polyolefin to produce a saturated isomerized polyolefin. A lube oil comprising the inventive saturated isomerized polyolefin is also disclosed.

Claims

1. A process for preparing a saturated isomerized polyolefin comprising:

polymerizing a feed stock comprising an unsaturated olefin to form an unsaturated polyolefin;

isomerizing the unsaturated polyolefin in the presence of an acid catalyst in a substantially hydrogen-free environment to form an unsaturated-isomerized polyolefin; and

hydrogenating the unsaturated-isomerized polyolefin to form the saturated isomerized polyolefin.

2. The process according to claim 1, wherein the unsaturated olefin comprises unsaturated, linear alpha-olefins;

unsaturated, normal internal-olefins;

unsaturated, branched alpha-olefins;

unsaturated, branched internal-olefins;

or a combination thereof.

3. The process according to claim 2, wherein the linear alpha-olefins comprise C₈ or greater linear alpha-olefins or a combination thereof.

4. The process according to claim 2, wherein the linear alpha-olefins comprise C₁₀ to C₂₄ linear alpha-olefins or a combination thereof.

5. The process according to claim 2, wherein the normal internal-olefins comprise C₁₀ or greater normal internal-olefins.

6. The process according to claim 2, wherein the normal internal-olefins comprise C₁₂ to C₂₄ normal internal-olefins.

7. The process according to claim 2, wherein the branched alpha-olefins comprise C₈ or greater branched alpha-olefins.

8. The process according to claim 2, wherein the branched alpha-olefins comprise C₁₂ to C₂₄ branched alpha-olefins.

9. The process according to claim 2, wherein the branched internal-olefins comprise C₈ or greater branched internal-olefins.

10. The process according to claim 2, wherein the branched internal-olefins comprise C₁₂ to C₂₄ branched internal-olefins.

11. The process according to claim 1, wherein the unsaturated olefin comprises C₈₊ alpha-olefins and polymers thereof either individually or in any combination thereof;

C₁₀₊ dimers, trimers, co-dimers, co-trimers, and higher oligomers of normal alpha-olefins either individually or in any combination thereof;

C₁₀₊ linear internal olefins and polymers thereof either individually or in any combination thereof;

C₈₊ branched alpha- or internal-olefins and polymers thereof either individually or in any combination thereof;

C₂₅₊ linear poly-alpha-olefins, branched poly-alpha-olefins, linear internal-polyolefins, and branched internal-polyolefins either individually or in any combination thereof;

or a mixture of any combination of the unsaturated olefins and polyolefins.

12. The process according to claim 11, wherein the feed stock further comprises C₂ to C₆ unsaturated olefins.

13. The process according to claim 1, wherein the acid catalyst has an alpha value of at least 1.

14. The process according to claim 1, wherein the acid catalyst is a zeolite having a Constraint Index of about 12 or less.

15. The process according to claim 1, wherein the acid catalyst is a zeolite having a Constraint Index of about 2 to about 12.

16. The process according to claim 1, wherein the acid catalyst is selected from the group consisting of ZSM-3, ZSM-4, ZSM-5, ZSM-11, ZSM-12, ZSM-14, ZSM-18, ZSM-20, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, Zeolite Beta, ultrastable Y, dealuminized Y, clinoptilolite, mordenite, faujasite, offretite, and any combination thereof.

17. The process according to claim 1, wherein the acid catalyst is a homogeneous acid catalyst selected from Friedel-Crafts catalysts, Bronsted acids, Lewis acids, or any combination thereof.

18. The process according to claim 1, wherein the acid catalyst is a homogeneous acid catalyst selected from BF₃, BCl₃, BBr₃, AlCl₃, AlBr₃, SbF₅, TiCl₃, TiCl₄, SnCl₄, PF₅, SnF₄, H₂SO₄, HCOOH, HF, HCl, HBr, triflic acid, or a combination thereof.

19. The process according to claim 1, wherein the acid catalyst is a boron halide, an aluminum halide, or a combination thereof.

20. The process according to claim 1, wherein the acid catalyst is selected from the group consisting of MCM-22, MCM-36, MCM-49, MCM-56, MCM-68, and a combination thereof.

21. The process according to claim 1, wherein the acid catalyst comprises zeolites;

homogeneous acid catalysts;

acidic resins;

acidic solid oxides;

acidic silicoaluminophosphates;

Group IVB metal oxides;

oxide, hydroxide, or free metal forms of Group VIII metals, Group IVA metals, Group VB metals, and Group VIIB metals;

or any combination thereof.

22. The process according to claim 1, wherein the acid catalyst comprises a Group VIIIB metal deposited on a zeolite.

23. The process according to claim 1, wherein the saturated isomerized polyolefin has a pour point of less than or equal to about −

30°

C.

24. The process according to claim 1, wherein the saturated isomerized polyolefin has a pour point of less than or equal to about −

40°

C.

25. The process according to claim 1, wherein the saturated isomerized polyolefin has a pour point of less than or equal to about −

50°

C.

26. The process according to claim 1, wherein the saturated isomerized polyolefin has a viscosity of less than about 200 cSt at 100°

C.

27. The process according to claim 1, wherein the saturated isomerized polyolefin has a viscosity of less than about 10 cSt at 100°

C.

28. The process according to claim 1, wherein the saturated isomerized polyolefin has a viscosity of less than about 50 cSt at 40°

C.

29. The process according to claim 1, wherein the saturated isomerized polyolefin has a viscosity index of greater than or equal to about 50.

30. The process according to claim 1, wherein the saturated isomerized polyolefin has a viscosity index of greater than or equal to about 100.

31. The process according to claim 1, wherein the saturated isomerized polyolefin has a viscosity index of greater than or equal to about 120.

32. The process according to claim 1, wherein the saturated isomerized polyolefin has a volatility of less than or equal to a C₈-C₁₀ poly-alpha-olefin having a comparable molecular weight.

33. The process according to claim 1, wherein the acid catalyst is a zeolite containing one or more Group VI B to VIIIB metal elements.

34. The process according to claim 1, wherein the acid catalyst is a zeolite containing one or more metals selected from the group consisting of Pt, Pd, Ni, Co, Rh, Ir, Ru, W, Mo, and a combination thereof.

44. A lube oil comprising the saturated-isomerized polyolefin of claim 1.

35. A process for preparing a saturated isomerized polyolefin comprising:

polymerizing a feed stock comprising an unsaturated olefin to form an unsaturated polyolefin;

isomerizing the unsaturated polyolefin by contacting the unsaturated polyolefin with an acidic zeolite catalyst at a temperature of about 200°

C. to about 475°

C. in an essentially hydrogen free environment, to produce an unsaturated-isomerized polyolefin, wherein the zeolite catalyst has a constraint index of less than or equal to 12; and

hydrogenating the unsaturated-isomerized polyolefin to produce a saturated isomerized polyolefin.

36. The process according to claim 35, wherein the unsaturated olefin comprises C₈₊ alpha-olefins and polymers thereof either individually or in any combination thereof;

C₁₀₊ dimers, trimers, co-dimers, co-trimers, and higher oligomers of normal alpha-olefins either individually or in any combination thereof;

C₁₀₊ linear internal olefins and polymers thereof either individually or in any combination thereof;

C₈₊ branched alpha- or internal-olefins and polymers thereof either individually or in any combination thereof;

C₂₅₊ linear poly-alpha-olefins, branched poly-alpha-olefins, linear internal-polyolefins, and branched internal-polyolefins either individually or in any combination thereof;

or a mixture of any combination of the unsaturated olefins and polyolefins.

37. The process according to claim 36, wherein the feed stock further comprises C₂ to C₆ unsaturated olefins.

38. The process according to claim 35, wherein the zeolite catalyst is selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and a combination thereof.

39. The process according to claim 35, wherein the zeolite catalyst is ZSM-22, ZSM-23 or ZSM-48.

40. The process according to claim 35, wherein the catalyst is a zeolite having a Constraint Index of about 2-12.

41. The process according to claim 35, wherein the catalyst further comprises a homogeneous acid catalyst;

an acidic resin;

an acidic solid oxide;

an acidic silicoaluminophosphate;

a Group IVB metal oxide;

an oxide of a Group VIII, IVA, or VB metal, a hydroxide of a Group VIII, IVA, or VB metal, a free of Group VIII, IVA, or VB metal;

or any combination thereof.

42. The process according to claim 35, wherein the acid catalyst is a zeolite containing one or more Group VI B to VIIIB metal elements.

43. The process according to claim 35, wherein the acid catalyst is a zeolite containing one or more metals selected from the group consisting of Pt, Pd, Ni, Co, Rh, Ir, Ru, W, Mo, and a combination thereof.

45. A lube oil comprising the saturated-isomerized polyolefin of claim 35.