Selective hydrogenation catalyst and methods of making and using same

Patent metadata

Field	Value
Publication number	US-9636659-B2
Application number	US-201514799440-A
Country	US
Kind code	B2
Filing date	Jul 14, 2015
Priority date	Mar 7, 2012
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

A composition comprising an extruded inorganic support comprising an oxide of a metal or metalloid, and at least one catalytically active metal, wherein the extruded inorganic support has pores, a total pore volume, and a pore size distribution, wherein the pore size distribution displays at least two peaks of pore diameters, each peak having a maximum, wherein a first peak has a first maximum of pore diameters of equal to or greater than about 120 nm and a second peak has a second maximum of pore diameters of less than about 120 nm, and wherein greater than or equal to about 5% of a total pore volume of the extruded inorganic support is contained within the first peak of pore diameters.

First claim

What is claimed is:

1. A composition comprising:
an inorganic support comprising an oxide of a metal or metalloid;
a halide; and
at least one catalytically active metal,
wherein the inorganic support has pores, a total pore volume, and a pore size distribution;
wherein the pore size distribution displays at least two peaks of pore diameters, each peak having a maximum; wherein a first peak has a first maximum of pore diameters of from greater than 1,000 nm to about 6,000 nm; wherein a second peak has a second maximum of pore diameters of less than about 120 nm; and wherein greater than or equal to about 15% of the total pore volume of the inorganic support is contained within the first peak of pore diameters.

2. The composition of claim 1 , wherein the inorganic support is an extruded inorganic support.

3. The composition of claim 1 , wherein the inorganic support is an agglomerated inorganic support.

4. The composition of claim 1 , wherein the oxide of a metal or metalloid consists essentially of silica, titania, alumina, or aluminate.

5. The composition of claim 1 wherein the oxide of a metal or metalloid consists essentially of a spinel.

6. The composition of claim 1 , having a total pore volume of from about 0.1 cc/g to about 0.6 cc/g as determined by differential mercury intrusion.

7. The composition of claim 6 , wherein the inorganic support has a surface area of from about 3 m 2 /g to about 27 m 2 /g.

8. The composition of claim 1 , wherein the first peak is non-Gaussian and has a peak width at half height that is greater than the peak width at half height of the second peak.

9. The composition of claim 1 , further comprising a Group 10 metal.

10. The composition of claim 1 , further comprising a Group 1B metal.

11. The composition of claim 1 , wherein the halide is chloride.

12. The composition of claim 1 , wherein the at least one catalytically active metal comprises palladium and silver; the halide comprises chloride; and the oxide of a metal or metalloid comprises α-alumina.

13. The composition of claim 1 , wherein the at least one catalytically active metal comprises palladium and the palladium is present in the composition in an amount of from about 0.005 wt. % to about 2 wt. % based on the total weight of the composition.

14. The composition of claim 13 wherein greater than about 90 wt. % of the palladium is concentrated near the periphery of the composition.

15. A method of preparing a hydrogenation catalyst comprising:
forming a mixture comprising an oxide of a metal or metalloid, a pore former, and water;
drying the mixture to form a dried mixture;
calcining the dried mixture to from a calcined mixture;
contacting the calcined mixture with a halide-containing compound to form a halided support;
reducing the amount of halide in the halided support to form a cleaned halided support; and
contacting the cleaned hatided support with a Group 10 metal and a Group 1B metal to form a hydrogenation catalyst,
wherein a pore size distribution for the hydrogenation catalyst displays at least two peaks of pore diameters, each peak having a maximum, wherein a first peak has a first maximum of pore diameters of from greater than 1,000 nm to about 6,000 nm, wherein a second peak has a second maximum of pore diameters of less than about 120 nm, and wherein greater than or equal to about 15% of a total pore volume of the hydrogenation catalyst is contained within the first peak of pore diameters.

16. The method of claim 15 , wherein the forming the mixture comprises extruding the mixture to form an extrudate.

17. The method of claim 15 , wherein the forming the mixture comprises agglomerating the mixture to form an agglomerate.

18. The method of claim 15 , wherein the hydrogenation catalyst has a total pore volume of from about 0.1 cc/g to about 0.6 cc/g as determined by differential mercury intrusion.

19. The method of claim 18 , wherein the hydrogenation catalyst has a surface area of from about 3 m 2 /g to about 27 m 2 /g.

20. The method of claim 15 , wherein the halide is chloride.

21. The method of claim 15 , wherein the Group 10 metal comprises palladium; the Group 1B metal comprises silver; the halide comprises chloride; and the oxide of a metal or metalloid comprises α-alumina.

22. A method for selectively hydrogenating a highly unsaturated hydrocarbon to a less unsaturated hydrocarbon in an olefin rich hydrocarbon stream comprising introducing into a reactor a hydrocarbon fluid stream comprising a highly unsaturated hydrocarbon in the presence of hydrogen and a catalyst composition under conditions effective to convert the highly unsaturated hydrocarbon to a less unsaturated hydrocarbon, wherein at least 50% of the catalyst composition comprises the hydrogenation catalyst produced according to claim 15 .

23. The method of claim 22 , wherein the Group 10 metal comprises palladium; the Group 1B metal comprises silver; the halide comprises chloride; and the oxide of a metal or metalloid comprises α-alumina.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Cheung Tin-Tack Peter
• Bergmeister Iii Joseph
• Kelly Stephen L

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• B01J23/44

  Palladium · CPC title

• B01J37/24

  Chlorinating · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• B01J23/005

  Spinels · CPC title