IP Library Granted Patent US 9,371,496
Granted Patent B2
US 9,371,496 · App. 13/897,756 · Granted Jun 21, 2016

Catalyst and process for hydroconversion of a heavy feedstock

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Quick Facts
Patent No.
US 9,371,496
App. No.
13/897,756
Granted
Jun 21, 2016
Kind
B2
Abstract

A hydroconversion catalyst comprising a Group VIB metal component, a Group VIII metal component and a carrier material is disclosed wherein said catalyst has a total surface area of 240 to 360 m 2 /g; a total pore volume of 0.5 to 0.9 cc/g; and a pore volume distribution such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å and less than 10% of pore volume are in pores present as macropores of diameters greater than 250 Å.

Claims (19)

1. A hydroprocessing catalyst for treating heavy hydrocarbon feedstocks, wherein said catalyst comprises: a calcined particle comprising a co-mulled mixture made by co-mulling inorganic oxide powder or powders, solution or solutions containing molybdenum and Group VIII metals and optionally water, acid and flocculating agent, and then forming said co-mulled mixture into a particle that is calcined to thereby provide said calcined particle, said calcined particles having:

a. a total surface area of 240 to 360 m 2 /g;

b. a total pore volume of 0.5 to 0.9 cc/g; and

c. a pore volume distribution such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å, greater than 5% of the total pore volume is in pores of diameter greater than 210 Å, and less than 10% of pore volume are in pores present as macropores of diameters greater than 250 Å.

2. The catalyst of claim 1 , wherein said calcined particle has a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall.

3. The catalyst of claim 1 , wherein said inorganic oxide material is selected from the group consisting of alumina, silica and alumina-silica.

4. The catalyst of claim 1 , wherein said calcined mixture has a molybdenum content in the range of from 1 weight percent to 24 weight percent with the weight percent being based upon the molybdenum as MoO 3 and the total weight of the calcined mixture, a nickel content in the range of from 0.2 weight percent to 6 weight percent based on the nickel as NiO and the total weight of the calcined mixture, and a phosphorous content in the range from 0 weight percent to 6 weight percent, with the weight percent being based upon the phosphorous as P 2 O 5 and the total weight of the calcined mixture.

5. The catalyst of claim 2 , wherein each calcined particle has an outer circle diameter of D O , an inner circle diameter of D I , and a height of H; the ratio of D O to D I is between about 1.5 to 3.0; the ratio of H to D O is between about 1 to about 4; and the outer circle diameter D o is between about 0.75 and 2 millimeters.

6. The catalyst of claim 5 , wherein the catalyst has a total surface area of 245-285 m 2 /g, a total pore volume of 0.65-0.75 cc/g, and a pore volume distribution such that greater than 75% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.10 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å and 0-9% of pore volume are in pores present as macropores of diameters greater than 250 Å.

7. The catalyst of claim 1 , wherein said calcined mixture has a molybdenum content in the range of from 7.5 weight percent to 11 weight percent with the weight percent being based upon the molybdenum as MoO 3 and the total weight of the calcined mixture, a nickel content in the range of from 1.5 weight percent to 3.5 weight percent based on the nickel as NiO and the total weight of the calcined mixture, and a phosphorous content in the range from 0 weight percent to 2 weight percent, with the weight percent being based upon the phosphorous as P 2 O 5 and the total weight of the calcined mixture.

8. The catalyst of claim 5 , wherein said calcined particle has three truncated lobes with rounded intersections of the lobes.

9. A method of making a highly stable heavy hydrocarbon hydrodesulfurization, metal removal and pitch conversion catalyst, wherein said method comprises:

a. forming a co-mulled mixture by co-mulling solid inorganic oxide powders, solution or solutions containing molybdenum and Group VIII metals and optionally water, acid and flocculating agent;

b. extruding said co-mulled mixture into particles to form a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall wherein each lobe; and

c. calcining said particles at temperatures such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å, greater than 5% of the total pore volume is in pores of diameter greater than 210 Å, and less than 10% of pore volume are in pores present as macropores of diameters greater than 250 Å; and

d. wherein said calcined particle has a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall, wherein each calcined particle has an outer circle diameter of D O , an inner circle diameter of D I , and a height of H; the ratio of D O to D I is between about 1.5 to 3.0; the ratio of H to D O is between about 1 to about 4; and the outer circle diameter D o is between about 0.75 and 2 millimeters.

10. The method of claim 9 , wherein said calcining step is conducted under a controlled temperature condition in which the calcination temperature is in the range of from about 482° C. (900° F.) to about 787.7° C. (1450° F.) for a calcination time period that is effective to provide said calcined mixture having a desired pore structure.

11. The method of claim 10 , wherein said inorganic oxide material is selected from the group consisting of alumina, silica and alumina-silica.

12. A process comprising: contacting a heavy hydrocarbon feedstock having a nickel content in the range of from 0.1 ppmw to 250 ppmw, a vanadium content in the range of from 0.3 ppmw to 250 ppmw, and a sulfur content in the range of from 0.5 wt % to 8 wt % with any one of the catalyst of claims 1 through 8 .

Assignments (2)
CHANGE OF NAME Recorded Mar 7, 2022
From: SHELL OIL COMPANY
To: SHELL USA, INC.
Reel/Frame 059694/0819 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 14, 2013
From: KESTER, JOHN GEORGE; KOMAR, DAVID ANDREW; SHERWOOD, DAVID EDWARD
To: SHELL OIL COMPANY
Reel/Frame 030616/0156 →