Catalytic dewaxing process

• US 7,077,948 B1
• Filed: 11/16/1999
• Issued: 07/18/2006
• Est. Priority Date: 11/18/1998
• Status: Expired due to Term

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Barre, Guy, Darnanville, Jean-Paul, Huve, Laurent Georges
• Primary Examiner(s): GRIFFIN, WALTER DEAN
• Application Number:
  US09/856,022
• Time in Patent Office: 2,436 Days
• Field of Search: 208/111.01, 208/111.35, 208/120.01, 208/120.35, 208/58, 208/59, 208/97
• US Class Current: 208/111.35
• CPC Class Codes: C10G 45/64 containing crystalline alumino-silicates, e.g. molecular sieves

Abstract

Process for the catalytic dewaxing of a hydrocarbon oil feed including waxy molecules and more than 500 ppmw of sulphur or sulphur containing compounds by contacting the oil feed under catalytic dewaxing conditions with a catalyst composition comprising at least a hydrogenation component, dealuminated aluminosilicate zeolite crystallites and a low acidity refractory oxide binder material which is essentially free of alumina.

Claims

1. A process for the catalytic dewaxing of a hydrocarbon oil feed obtained by the vacuum distillation of the residue of an atmospheric distillation of a crude petroleum feedstock, wherein said hydrocarbon oil feed has a boiling range between 300°

C. and 620°

C. includes waxy molecules and more than 1000 ppmw of sulphur or sulphur containing compounds and said hydrocarbon oil feed has not been subjected to a hydrotreating step to reduce sulfur and nitrogen content, by contacting said hydrocarbon oil feed under catalytic dewaxing conditions with a catalyst composition comprising a Group VIII metal hydrogenation component selected from the group consisting of platinum palladium and nickel, dealuminated aluminosilicate zeolite crystallites and a low acidity refractory oxide binder material which is essentially free of alumina.

2. The process of claim 1, in which said hydrocarbon oil feed further comprises more than 10 ppmw of nitrogen or nitrogen containing compounds.

3. The process of claim 1, in which the low acidity binder is silica.

4. The process of claim 1, in which the aluminosilicate zeolite crystallites have a Constraint Index of between 2 and 12.

5. The process of claim 4, in which the aluminosilicate zeolite crystallites include MFI type zeolite.

6. The process of claim 1, in which the dealuminated aluminosilicate zeolite crystallites are obtained by contacting the zeolite crystallites with an aqueous solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula:

(A)_2/bSiF₆

in which ‘

A’

is a metallic or non-metallic cation other than H+ having the valence ‘

b’

.

7. The process of claim 6, in which an extrudate of the aluminosilicate zeolite crystallites and the low acidity binder is contacted with the aqueous solution of the fluorosilicate salt.

8. The process of claim 1, in which said hydrocarbon oil feed is a solvent extracted waxy raffinate that has been obtained further by the solvent extraction of the vacuum distillate obtained by the vacuum distillation of the residue of said atmospheric distillation of said crude petroleum feedstock.

9. The process of claim 6, where ‘

A’

is an ammonium cation.

10. The process of claim 1, in which the hydrogenation component is palladium.

11. The process of claim 1, in which the hydrogenation component is nickel.

21. The process of claim 7, wherein said catalyst composition has an absence of a Group VIB metal component.

12. A process for the catalytic dewaxing of a hydrocarbon oil feed obtained by the vacuum distillation of the residue of an atmospheric distillation of a crude petroleum feedstock, wherein said hydrocarbon oil feed has a boiling range between 300°

C. and 620°

C. includes waxy molecules and more than 1000 ppmw of sulphur or sulphur containing compounds compounds and said hydrocarbon oil feed has not been subjected to a hydrotreating step to reduce sulfur and nitrogen content, by contacting said hydrocarbon oil feed under catalytic dewaxing conditions with a catalyst composition comprising a nickel hydrogenation component, dealuminated aluminosilicate zeolite crystallites and a low acidity refractory oxide binder material which is essentially free of alumina.

13. The process of claim 12, wherein said hydrocarbon oil feed further comprises more than 10 ppmw of nitrogen or nitrogen containing compounds.

14. The process of claim 13, wherein said low acidity binder is silica.

15. The process of claim 14, wherein said aluminosilicate zeolite crystallites have a Constraint Index of between 2 and 12.

16. The process of claim 15, wherein said aluminosilicate zeolite crystallites include MFI type zeolite.

17. The process of claim 16, wherein said dealuminated aluminosilicate zeolite crystallites are obtained by contacting the zeolite crystallites with an aqueous solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula:

(A)_2/bSiF₆

in which ‘

A’

is a metallic or non-metallic cation other than H+ having the valence ‘

b’

.

18. The process of claim 17, wherein an extrudate of the aluminosilicate zeolite crystallites and the low acidity binder is contacted with the aqueous solution of the fluorosilicate salt.

19. The process of claim 18, wherein ‘

A’

is an ammonium cation.

20. The process of claim 19, wherein said catalyst composition has an absence of a Group VIB metal component.

22. A catalytic dewaxing process, comprising:

vacuum distilling a residue from an atmospheric distillation of a crude petroleum feedstock that contains a sulfur compound and a nitrogen compound to yield a vacuum distillate having a boiling range between 300°

C. and 620°

C.;

subjecting said vacuum distillate to a solvent extraction with a solvent to thereby yield a solvent extracted waxy raffinate having a reduced aromatics content from that of said vacuum distillate, wherein said solvent extracted waxy raffinate contains waxy molecules and more than 1000 ppmw of sulfur or sulfur containing compounds; and

without being subjected to a hydrotreating step to reduce the sulfur and nitrogen content of said solvent extracted waxy raffinate, contacting said solvent extracted waxy raffinate, under catalytic dewaxing conditions, with a catalyst composition comprising dealuminated aluminosilicate zeolite crystallites, a low acidity refractory oxide binder material which is essentially free of alumina, and a Group VIII metal hydrogenation component selected from the group consisting of platinum, palladium and nickel.

23. A dewaxing process as recited in claim 22, wherein said solvent extracted waxy raffinate further contains more than 10 ppmw of nitrogen or nitrogen compounds.

24. A dewaxing process as recited in claim 23, wherein the low acidity refractory oxide binder of said catalyst composition is silica.

25. A dewaxing process as recited in claim 24, wherein the dealuminated aluminosilicate zeolite crystallites of said catalyst composition have a Constraint Index of between 2 and 12.

26. A dewaxing process as recited in claim 25, wherein the dealuminated aluminosilicate zeolite crystallites of said catalyst composition include MFI type zeolite.

27. A dewaxing process as recited in claim 26, wherein the dealuminated aluminosilicate zeolite crystallites of said catalyst composition are obtained by contacting the zeolited crystallites with an aqueous solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula:

(A)_2/bSiF₆ in which ‘

A’

is a metallic or non-metallic cation other than H+ having the valence ‘

b’

.

28. A dewaxing process as recited in claim 27, wherein in the preparation of said catalyst composition the dealuminated aluminosilicate zeolite crystallites and low acidity refractory oxide binder material are formed into an extrudate and then contacted with said aqueous solution of fluorosilicate salt prior to the incorporation into said extrudate said Group VIII metal hydrogenation component.

29. A dewaxing process as recited in claim 28, wherein ‘

A’

is an ammonium cation.

30. A dewaxing process as recited in claim 29, wherein said catalyst composition has an absence of a Group VIB metal component.

31. A catalytic dewaxing process, comprising:

vacuum distilling a residue from an atmospheric distillation of a crude petroleum feedstock that contains a sulfur compound and a nitrogen compound to yield a vacuum distillate having a boiling range between 300°

C. and 620°

C. and containing more than 1000 ppmw of sulfur or sulfur containing compounds; and

without being subjected to a hydrotreating step to reduce the sulfur or nitrogen content of said vacuum distillate, contacting said vacuum distillate, under catalytic dewaxing conditions, with a catalyst composition comprising dealuminated aluminosilicate zeolite crystallites, a low acidity refractory oxide binder material which is essentially free of alumina, and a Group VIII metal hydrogenation component selected from the group consisting of platinum, palladium and nickel.

32. A dewaxing process as recited in claim 31, wherein said vacuum distillate further contains more than 10 ppmw of nitrogen or nitrogen compounds.

33. A dewaxing process as recited in claim 32, wherein the low acidity refractory oxide binder of said catalyst composition is silica.

34. A dewaxing process as recited in claim 33, wherein the dealuminated aluminosilicate zeolite crystallites of said catalyst composition have a Constraint Index of between 2 and 12.

35. A dewaxing process as recited in claim 34, wherein the dealuminated aluminosilicate zeolite crystallites of said catalyst composition include MFI type zeolite.

36. A dewaxing process as recited in claim 35, wherein the dealuminated aluminosilicate zeolite crystallites of said catalyst composition are obtained by contacting the zeolited crystallites with an aqueous solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula:

(A)_2/bSiF₆ in which ‘

A’

is a metallic or non-metallic cation other than H+ having the valence ‘

b’

.

37. A dewaxing process as recited in claim 36, wherein in the preparation of said catalyst composition the dealuminated aluminosilicate zeolite crystallites and low acidity refractory oxide binder material are formed into an extrudate and then contacted with said aqueous solution of fluorosilicate salt prior to the incorporation into said extrudate said Group VIII metal hydrogenation component.

38. A dewaxing process as recited in claim 37, wherein ‘

A’

is an ammonium cation.

39. A dewaxing process as recited in claim 38, wherein said catalyst composition has an absence of a Group VIB metal component.