Lubricating base oil production

Patent metadata

Field	Value
Publication number	US-10196575-B2
Application number	US-201414541684-A
Country	US
Kind code	B2
Filing date	Nov 14, 2014
Priority date	Nov 15, 2013
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

Abstract

A process is provided for producing a heavy lubricating base oil by hydrocracking a lubricating oil feedstock at high yield. The lubricating oil feedstock contains a hydroprocessed stream that is difficult to process using a conventional catalyst system. The catalyst used in the process includes a mixed metal sulfide catalyst that comprises at least one Group VIB metal and at least one Group VIII metal. The process also provides for hydroisomerization and hydrofinishing process steps to prepare the lubricating base oil.

First claim

What is claimed is:

1. A process for hydrocracking a lubricating oil feedstock comprising:
blending a straight run crude oil distillate feedstock and a hydroprocessed feedstream to form a lubricating oil feedstock having a nitrogen content of greater than 300 ppm and a sulfur content of greater than 0.1 wt. %; wherein the crude oil distillate has a viscosity at 100° C. in a range from 3 cSt to 30 cSt and the hydroprocessed feedstream has a viscosity at 100° C. in a range from 2 cSt to 30 cSt;
hydrocracking the lubricating oil feedstock with a hydrogen-containing treat gas over a self-supported mixed metal sulfide catalyst under hydrocracking conditions to form a hydrocrackate, wherein at least 10 wt. % of the feedstock is converted to products which boil below the initial boiling point of the feedstock;
separating the hydrocrackate by atmospheric distillation or vacuum distillation into at least a gaseous product that contains ammonia, and a liquid fraction that boils above the initial boiling point of the feedstock and has a nitrogen content of less than 50 ppm;
dewaxing the liquid fraction in the presence of a hydrogen-containing treat gas stream over a shape selective intermediate pore size molecular sieve catalyst at hydroisomerization conditions, to produce a dewaxed effluent having a pour point of less than −5° C.; and
providing the dewaxed effluent to a hydrofinishing reaction zone for hydrogenating the dewaxed effluent over a hydrofinishing catalyst;
to form a heavy lubricating base oil having a viscosity index of greater than 95 and a viscosity at 100° C. of 10 cSt or greater;
wherein the self-supported mixed metal sulfide catalyst comprises at least one Group VIB metal and at least one Group VIII metal and is prepared by drying at a temperature of 200° C. or less, then sulfidizing a self-supported charge-neutral hydroxide catalyst precursor composition of the formula:
A v [(M P )(OH) x (L) n y ] z (M VIB O 4 )

wherein A is at least one of an alkali metal cation, an ammonium, an organic ammonium and a phosphonium cation, M P is at least one of a Group VIII metal, Group IIB metal, Group IIA metal, Group IVA metal or combinations thereof, P is an oxidation state with M P having an oxidation state of +2 or +4 depending on the selection of M P , M VIB is at least a Group VIB metal having an oxidation state of +6, L is at least one oxygen-containing ligands, and L has a neutral or negative charge n<=0; M P :M VIB has an atomic ratio between 100:1 and 1:100; v−2+P*z−x*z+n*y*z=0; and 0<y≤−P/n; 0<x≤P; 0<v≤2; 0<z;
wherein the hydroxide catalyst precursor has an X-ray diffraction pattern which is amorphous with broad peaks or the hydroxide catalyst precursor has an X-ray diffraction pattern with at least a crystalline peak at Bragg angle between 52.7° to 53.2° theta.

2. The process of claim 1 , wherein the self-supported mixed metal sulfide catalyst contains no zeolite or molecular sieve.

3. The process of claim 1 , wherein the hydroprocessed feedstream has a nitrogen content of greater than 300 ppm and a sulfur content of greater than 0.1 wt. %, optionally wherein the hydroprocessed feedstream is derived from a process of hydrocracking at least one of a crude oil, a gas oil, a vacuum gas oil, a residual fraction, a solvent-deasphalted petroleum residuum, an FCC tower bottoms, a petroleum distillate, and combinations thereof.

4. The process of claim 1 , wherein the lubricating oil feedstock is hydrocracked in a layered catalyst system or in a single reaction stage.

5. The process of claim 1 , wherein the lubricating oil feedstock comprises up 20 wt. % of the hydroprocessed feedstream.

6. The process of claim 1 , wherein the lubricating oil feedstock further comprises a crude oil distillate boiling in a temperature range of 650° F. to 1300° F. and having a nitrogen content of greater than 500 ppm, optionally wherein the weight ratio of the crude oil distillate to the hydroprocessed feedstream is within the range from 99:1 to 80:20.

7. The process of claim 1 , comprising a layered catalyst system.

8. The process of claim 1 , wherein the lubricating oil feedstock boils in a temperature range from 500° F. to 1300° F., and has a density in a range from 0.85 to 1.0 g/cm 3 , a nitrogen content in a range from 500 ppm to 3000 ppm, a sulfur content in a range from 0.05% to 4%, and a viscosity at 100° C. in a range from 3 cSt to 30 cSt, or wherein in the range of between 10 wt. % and 50 wt. % of the lubricating oil feedstock is converted to hydrocarbon products which boil below the initial boiling point of the feedstock.

9. The process of claim 1 , wherein the lubricating oil feedstock is hydrocracked in a layered catalyst system comprising a layer of hydrotreating catalyst and a layer of hydrocracking catalyst in a weight ratio within the range 1:10 and 10:1, the hydrocracking catalyst comprising the self-supported mixed metal sulfide catalyst, optionally wherein the lubricating oil feedstock is provided to the hydrotreating catalyst to produce a hydrotreated effluent, the entire volume of which is provided to the hydrocracking catalyst.

10. The process of claim 9 , wherein the hydrotreating catalyst comprises in the range from 0.5% to about 25% by weight of a Group VIII metal component and from about 0.5% to about 25% by weight of Group VIB metal component.

11. The process of claim 1 , wherein the hydrocracking conditions include a temperature of from 450° F. to 900° F. (232° C. to 482° C.); a pressure of from 500 psig to 5000 psig (3.5 MPa to 34.5 MPa gauge); a liquid reactant feed rate, in terms of liquid hourly space velocity (LHSV) of from 0.1 hr −1 to 15 hr −1 (v/v); and a hydrogen feed rate, in terms of H z /hydrocarbon ratio, of from 500 SCF/bbl to 5000 SCF/bbl (89 to 890 m 3 H 2 /m 3 feedstock) of liquid lubricating oil feedstock, or wherein the hydrofinishing conditions include a temperature of from 300° F. to 600° F. (149° C. to 316° C.); a pressure of from 400 psig to 3000 psig (2.76 MPa to 20.68 MPa gauge); a LHSV of from 0.1 hr 1 to 20 hr 1 , and a hydrogen recycle rate of from 400 SCF/bbl to 1500 SCF/bbl (71 to 267 m 3 H 2 /m 3 feed).

12. The process of claim 1 , wherein the liquid fraction boils within the temperature range from 650° F. to 1300° F., and has a viscosity at 100° C. of greater than 10 cSt.

13. The process of claim 1 , further comprising dewaxing the liquid fraction over a shape selective catalyst comprising a dewaxing component selected from SAPO-11, SM-3, SM-7, SSZ-32, and ZSM-23 or combinations thereof, and a noble metal component selected from platinum, palladium, or combinations thereof, at hydroisomerization conditions, which include a temperature of from 500° F. to 775° F. (260° C. to 413° C.); a pressure of from 15 psig to 3000 psig (0.10 MPa to 20.68 MPa gauge); a LHSV of from 0.25 hr −1 to 20 hr −1 ; and a hydrogen to feed ratio of from 2000 SCF/bbl to 30,000 SCF/bbl (356 to 5340 m 3 H 2 /m 3 feed).

14. The process of claim 1 , wherein the heavy lubricating base oil boils within a temperature range from 750° to 1300° F. (399° C. to 704° C.) and has a nitrogen content of less than 20 ppm, or wherein the heavy lubricating base oil boils within a temperature range from 800° F. to 1300° F. and has a viscosity index of greater than 95.

15. The process of claim 1 , wherein the self-supported mixed metal sulfide catalyst comprises molybdenum (Mo) sulfide, tungsten (W) sulfide, nickel (Ni) sulfide, or a combination thereof, wherein the catalyst has a BET surface area of at least 20 m 2 /g and a pore volume of at least 0.05 cm 3 /g.

16. The process of claim 1 , where

Assignees

• Zhan Bi Zeng
• Trevino Horacio
• Maesen Theodorus Ludovicus Michael
• Lei Guan Dao
• Chevron Usa Inc

Inventors

• Zhan Bi-Zeng
• Trevino Horacio
• Maesen Theodorus Ludovicus Michael
• Lei Guan-Dao

Classifications

• C10M101/02 Primary

  Petroleum fractions · CPC title

• C10G65/12

  including cracking steps and other hydrotreatment steps · CPC title

• C10G67/02

  plural serial stages only · CPC title

• C10G47/06 Primary

  Sulfides · CPC title

• B01J29/00

  Catalysts comprising molecular sieves {(molecular sieves per se C01B)} · CPC title