Catalytic dewaxing processes using alumina free coated catalyst

• US 5,804,058 A
• Filed: 06/13/1996
• Issued: 09/08/1998
• Est. Priority Date: 06/13/1995
• Status: Expired due to Term

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Maesen, Theodorus Ludovicus Michael, Huve, Laurent Georges, Grandvallet, Pierre
• Primary Examiner(s): Griffin, Walter D.
• Assistant Examiner(s): NORTON, NADINE GEORGIANNA
• Application Number:
  US08/662,596
• Time in Patent Office: 817 Days
• Field of Search: 208/27, 208/111, 208/110, 208/112, 208/109, 208/108
• US Class Current: 208/111.1
• CPC Class Codes: B01J 2229/16 to increase the Si/Al ratio; Dealumination
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/65 of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
• CPC Class Codes: C10G 45/64 containing crystalline alumino-silicates, e.g. molecular sieves

Abstract

A process is disclosed for the catalytic dewaxing of a hydrocarbon oil feed comprising waxy molecules, which process comprises:

contacting a feed under catalytic dewaxing conditions with a catalyst composition comprising a molecular sieve containing crystallites covalently bound alumina moieties in its framework and having pores with a diameter in the range of from 0.35 to 0.80 nm and recovering a product having a reduced pour point, wherein the molecular sieve has been modified to reduce the mole percentage of alumina by coating the surface of the crystallites with a refractory inorganic oxide which is essentially free of alumina.

Claims

1. In a process for the catalytic dewaxing of a hydrocarbon oil feed consisting essentially of a gas oil and a lubricating base oil, wherein both have waxy molecules therein, which process comprises the steps of:

(a) contacting the feed under catalytic dewaxing conditions with a catalyst composition comprising a molecular sieve containing crystallites covalently bound alumina moieties in its framework and having pores with a diameter in the range of from 0.35 to 0.80 nm, wherein said crystallites have a surface, and

(b) recovering a product having a reduced pour point,

wherein the improvement of the process consists of modifying said molecular sieve to reduce the mole percentage of alumina by coating said surface of said crystallites with a refractory inorganic oxide which is essentially free of alumina.

2. A process according to claim 1 wherein the molecular sieve is an aluminosilicate zeolite which has been modified by subjecting it to a dealumination treatment.

3. A process according to claim 2 wherein the mutual ratio of the SiO₂ /Al₂ O₃ molar ratio of the zeolite after dealumination to the SiO₂ /Al₂ O₃ molar ratio of the zeolite before dealumination, is in the range of from 1.1 to 3.0.

4. A process according to claim 1 wherein the catalyst composition also comprises a low acidity refractory oxide binder material which is essentially free of alumina.

5. A process according to claim 1 wherein the catalyst composition comprises a hydrogenation component.

6. A process according to claim 1 wherein the catalyst composition is predominantly selective for cracking of waxy molecules.

7. A process according to claim 6 wherein the catalyst composition comprises a molecular sieve selected from the group consisting of ZSM-5, ferrierite and mixtures thereof.

8. A process according to claim 1 wherein the catalyst composition is predominantly selective for isomerizing waxy molecules.

9. A process according to claim 8, wherein the catalyst composition comprises a molecular sieve selected from the group consisting of ZSM-23, SSZ-32 and mordenite.

10. A process according to claim 1 for the catalytic dewaxing of a hydrocarbon oil feed comprising waxy molecules, wherein the catalyst composition in said process is a combination of isomerization and cracking, which said process comprises the steps of:

(a1) contacting the hydrocarbon oil feed under isomerization conditions with a selective isomerization catalyst composition,

(a2) contacting the product of step (a1) under cracking conditions with a selective cracking catalyst composition, and

(b) recovering a product having a reduced pour point.

11. A process according to claim 10 wherein the selective isomerization catalyst composition used in step (a1) is a catalyst composition selected from the group consisting of ZSM-23, SSZ-32 and mordenite.

12. A process according to claim 11 wherein process steps (a1) and (a2) are carried out in a series flow mode or stacked bed configuration with a first bed of selective isomerization catalyst above a second bed of selective cracking catalyst.

13. A process according to claim 10 wherein the molecular sieve present in the selective isomerization catalyst composition used in step (a1) comprises larger pores than the molecular sieve present in the selective cracking catalyst used in step (a2).

14. A process according to claim 4, wherein the low acidity refractory oxide binder material is silica.