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

Patent metadata

Field	Value
Publication number	US-10220379-B2
Application number	US-201514693967-A
Country	US
Kind code	B2
Filing date	Apr 23, 2015
Priority date	May 1, 2014
Publication date	Mar 5, 2019
Grant date	Mar 5, 2019

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.

First claim

That which is claimed is:

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.

Assignees

• Shell Oil Co

Inventors

• Bhan Opinder Kishan
• Komar David Andrew

Classifications

• B01J27/199

  with chromium, molybdenum, tungsten or polonium · CPC title

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title

• C10G2300/1037

  Hydrocarbon fractions · CPC title

• C10G2300/701

  Use of spent catalysts · CPC title

• C10G2400/02

  Gasoline · CPC title