IP Library Granted Patent US 10,220,379
Granted Patent B2
US 10,220,379 · App. 14/693,967 · Granted Mar 5, 2019

Catalyst and its use for the selective hydrodesulfurization of an olefin containing hydrocarbon feedstock

Inventors: Opinder Kishan Bhan (Katy, TX); David Andrew Komar (Magnolia, TX)
Assignee: Shell Oil Company
B01J35/109B01J23/882B01J23/883B01J27/19B01J27/199B01J35/108B01J35/1019B01J35/1042B01J35/1061B01J35/1066B01J35/1076B01J37/0036C10G45/08C10G45/38C10G69/04C10G2300/1037C10G2300/202C10G2300/305C10G2300/701C10G2400/02
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Quick Facts
Patent No.
US 10,220,379
App. No.
14/693,967
Granted
Mar 5, 2019
Kind
B2
Abstract

A catalyst and its use for selectively desulfurizing sulfur compounds present in an olefin-containing hydrocarbon feedstock to very low levels with minimal hydrogenation of olefins. The catalyst comprises an inorganic oxide substrate containing a nickel compound, a molybdenum compound and optionally a phosphorus compound, that is overlaid with a molybdenum compound and a cobalt compound. The catalyst is further characterized as having a bimodal pore size distribution with a large portion of its total pore volume contained in pores having a diameter less than 250 angstroms and in pores having a diameter greater than 1000 angstroms.

Claims (19)

1. A selective hydrodesulfurization catalyst comprising: a calcined catalyst particle made by calcining a shaped particle of a co-mulled mixture, comprising an inorganic oxide support material, molybdenum trioxide, and a nickel compound, to provide a calcined shaped particle; wherein said calcined shaped particle is further impregnated with an impregnation solution having a material absence of a nickel component to thereby provide an overlayer of a cobalt compound and a molybdenum compound and is subjected to a further calcination step to produce said calcined catalyst particle, said calcined catalyst particle being characterized by having a bimodal pore size distribution with at least 20% of the total pore volume being in pores having a diameter less than 250 angstroms and at least 10% of the total pore volume being in pores having a diameter greater than 1000 angstroms.

2. A catalyst as recited in claim 1 , wherein said calcined shaped particle is impregnated with a impregnating solution containing an amount of molybdenum and cobalt sufficient to provide a calcined catalyst particle having a molybdenum content of from 9 wt % to 23 wt % and a cobalt content of from 2 wt % to 8 wt %, each of said percentages calculated as the metal.

3. A catalyst as recited in claim 2 , wherein said calcined shaped particle contains from 12 wt % to 19 wt % molybdenum, from 3 wt % to 7 wt % cobalt and from 0.5 wt % to 2 wt % nickel, each of said percentages calculated as the metal.

4. A catalyst as recited in claim 3 , wherein said calcined catalyst particle has at least 30% of the total pore volume in pores having a diameter less than 250 angstroms and at least 15% of the total pore volume in pores having a diameter greater than 1000 angstroms.

5. A catalyst as recited in claim 4 , wherein said calcined shaped particle is impregnated with a impregnating solution containing an amount of molybdenum and cobalt sufficient to provide a calcined catalyst particle having a molybdenum content of from 12 wt % to 19 wt % and a cobalt content of from 3 wt % to 6 wt %, each of said percentages calculated as the metal.

6. A catalyst as recited in claim 4 , wherein said calcined catalyst particle has at least 40% of the total pore volume in pores having a diameter less than 250 angstroms and at least 20% of the total pore volume in pores having a diameter greater than 1000 angstroms.

7. A catalyst as recited in claim 1 , wherein said calcined shaped particle further comprises a phosphorus compound.

8. A catalyst as recited in claim 7 , wherein the total amount of molybdenum present in said calcined catalyst particle is from 14 wt % to 18 wt %, the total amount of cobalt present in said catalyst is from 3 wt % to 5 wt % and the total amount of phosphorous present in said catalyst is from 0.4 wt % to 1 wt %, each of said percentages calculated as the element.

9. A catalyst as recited in claim 8 , wherein said calcined catalyst particle is overlaid with phosphorus.

10. A catalyst as recited in claim 1 , wherein said calcined catalyst particle has at least 5% of the total pore volume in pores having a diameter greater than 5000 angstroms.

11. A process for selectively hydrodesulfurizing sulfur compounds contained in an olefin-containing hydrocarbon feedstock with minimal hydrogenation of olefins, which process comprises:

contacting in a reactor under selective hydrodesulfurization conditions said olefin-containing hydrocarbon feedstock with a calcined catalyst particle made by calcining a shaped particle of a co-mulled mixture comprising an inorganic oxide support material, molybdenum trioxide and a nickel compound to provide a calcined shaped particle; wherein said calcined shaped particle is further impregnated with an impregnation solution having a material absence of a nickel component to thereby provide an overlayer of a cobalt compound and a molybdenum compound and is subjected to a further calcination step to produce said calcined catalyst particle, said calcined catalyst particle being characterized by having a bimodal pore size distribution with at least 20% of the total pore volume being in pores having a diameter less than 250 angstroms and at least 10% of the total pore volume being in pores having a diameter greater than 1000 angstroms.

12. A process as recited in claim 11 , wherein said catalyst has a molybdenum content of from 9 wt % to 23 wt %, a cobalt content of from 2 wt % to 8 wt %, a nickel content of from 0.5 wt % to 2 wt %, and a phosphorus content of from 0.1 wt % to 3.5 wt %, each of said percentages calculated as the element.

13. A process as recited in claim 12 , wherein said olefin containing feedstock is a cracked gasoline or cracked naphtha feedstock.

14. A process as recited in claim 13 , wherein the reactor is a polishing reactor.

15. A process as recited in claim 11 , wherein said calcined catalyst particle has at least 30% of the total pore volume in pores having a diameter less than 250 angstroms and at least 15% of the total pore volume in pores having a diameter greater than 1000 angstroms.

16. A process as recited in claim 14 , wherein the sulfur content of the cracked gasoline feedstock is reduced to below 15 ppmw.

17. A process as recited in claim 16 , wherein said calcined catalyst particle has at least 40% of the total pore volume in pores having a diameter less than 250 angstroms and at least 20% of the total pore volume in pores having a diameter greater than 1000 angstroms.

18. A process as recited in claim 11 , wherein said calcined catalyst particle has at least 5% of the total pore volume in pores having a diameter greater than 5000 angstroms.

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 Feb 8, 2016
From: BHAN, OPINDER KISHAN; KOMAR, DAVID ANDREW
To: SHELL OIL COMPANY
Reel/Frame 037681/0293 →
Continuity (2)
Provisional Application 61987047 · May 1, 2014
Related Publication 20150314282A1 · Nov 5, 2015