IP Library › Granted Patent US 10,258,967
Granted Patent B2
US 10,258,967 · App. 15/559,458 · Granted Apr 16, 2019

PT and/or PD egg-shell catalyst and use thereof

Inventors: Peter Witte (Utrecht, NL); Lei Zhang (De Meern, NL); Robert Terorde (Maarn, NL)
Assignee: BASF Corporation
B01J23/44B01J21/18B01J23/42B01J23/52B01J35/0006B01J35/006B01J35/008B01J35/0013B01J35/0066B01J35/023B01J35/026B01J35/1014B01J35/1019B01J35/1023B01J35/1028B01J37/0203B01J37/0211B01J37/0219B01J37/0221B01J37/031B01J37/035B01J37/038B01J37/16C07C29/17
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Quick Facts
Patent No.
US 10,258,967
App. No.
15/559,458
Granted
Apr 16, 2019
Kind
B2
Abstract

The present invention is in the field of catalysis. More particularly, the present invention is directed to supported precious metal catalysts, preferably palladium and/or platinum metal catalysts, having a high metal loading, a high degree of dispersion and a high degree of edge-coating. The present invention is further directed to a process for producing these catalysts, as well as to the use of these catalysts in chemical reactions.

Claims (32)

1. A precious metal catalyst, wherein said catalyst comprises nanocrystallites of precious metal on a powder support, wherein the nanocrystallites have an average size of from 1 to less than 5 nm, wherein the catalyst comprises precious metal in an amount of at least 1.0 wt. %, based on the weight of the catalyst, and wherein the precious metal is palladium and/or platinum metal; and,

wherein the palladium metal catalyst has a surface enrichment value of from at least 6.5 to at most 150; and,

wherein the platinum metal catalyst has a surface enrichment value of from at least 1.5 to at most 150, and,

wherein the surface enrichment value (SEV) is determined from the following formula (I):

SEV=(XPS wt. %−ICP wt. %)/ICP wt. %;  (I)

wherein XPS wt. % is the X-ray photoelectron spectroscopy (XPS) measurement and ICP wt. % is the inductively coupled plasma (ICP) measurement of the precious metal content in weight percent of said catalyst.

2. The catalyst according to claim 1 ,

wherein the palladium metal catalyst has a surface enrichment value of at least 8; and, wherein the palladium metal catalyst has a surface enrichment value of at most 120; and,

wherein the platinum metal catalyst has a surface enrichment value of at least 2; and, wherein the platinum metal catalyst has a surface enrichment value of at most 120.

3. The catalyst according to claim 1 , wherein the catalyst comprises palladium and/or platinum metal in an amount of between more than 1.0 wt. % and 20 wt. %, based on the weight of the catalyst.

4. The catalyst according to claim 1 , wherein the nanocrystallites have an average size of between 1 and 4 nm.

5. The catalyst according to claim 1 , wherein the support is selected from the group consisting of silica, alumina, zirconia, titanium oxide, ceria, magnesium oxide, zinc oxide, metal silicates, metal aluminates, zeolites, carbon nanotubes, carbon nanofibres, graphitic carbon and activated carbon and combinations thereof.

6. The catalyst according to claim 1 , wherein the Dv(90) particle size distribution of the powder support is between 1 and 500 micron.

7. The catalyst according to claim 1 , wherein the BET surface area of the powder support is between 100 and 3000 m 2 /g.

8. The catalyst according to claim 1 , wherein the micropore surface area of the powder support is between 10 and 1000 m 2 /g.

9. Process for preparing a precious metal catalyst, wherein said process comprises the steps of:

reducing a precious metal compound in an aqueous solution by contacting said solution with a reducing agent, a stabilizing agent and optionally a coordinating agent thereby forming a colloidal precious metal suspension;

contacting the suspension with a powder support at a pH value of between 9.5 and 11; and,

recovering the precious metal catalyst.

10. Process according to claim 9 , wherein the precious metal is selected from platinum, palladium, iridium, rhodium, ruthenium, silver, gold and combinations thereof.

11. Process according to claim 9 , wherein the suspension is contacted with a powder support at a pH value of between 9.5 and 10.5.

12. Process according to claim 9 , wherein a coordinating agent is used in the reduction step of said process when the precious metal compound to be reduced is a palladium and/or gold metal compound, optionally in combination with one or more other precious metal compounds.

13. Process according to claim 9 , wherein the reducing agent is selected from the group consisting of a quaternary ammonium salt, sodium formate, formic acid, sodium citrate, citric acid, hydrazine, C 1 -C 4 alcohols, diols, polyols, borohydrides, formaldehyde, hypophosphite, metal alkalydes, hydrogen and combinations thereof;

wherein the stabilizing agent is selected from the group consisting of a quaternary ammonium salt, donor ligands, polymers, surfactants and combinations thereof; and,

wherein the coordinating agent is urea and/or ammonia.

14. Process according to claim 9 , wherein the support is selected from the group consisting of silica, alumina, zirconia, titanium oxide, ceria, magnesium oxide, zinc oxide, metal silicates, metal aluminates, zeolites, carbon nanotubes, carbon nanofibres, graphitic carbon and activated carbon and combinations thereof.

15. A precious metal catalyst obtainable by the process of claim 9 .

16. A process, comprising performing a reaction in the presence of a precious metal catalyst according to claim 15 , wherein the reaction is a hydrogenation/dehydrogenation, isomerization, oxidation, hydrogenolysis or hydro-dewaxing reaction.

17. The catalyst according to claim 1 , wherein the nanocrystallites of at least one precious metal are edge-coated on the powder support.

18. The process according to claim 9 , wherein the precious metal suspension is edge-coated on the powder support.

19. The precious metal catalyst according to claim 9 , wherein the stabilizing agent is a quaternary ammonium salt.

20. The process according to claim 9 , wherein the coordinating agent is urea.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 30, 2018
From: BASF NEDERLAND B.V.
To: BASF CORPORATION
Reel/Frame 045928/0553 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 5, 2017
From: WITTE, PETER; ZHANG, LEI; TERORDE, ROBERT
To: BASF NEDERLAND B.V.
Reel/Frame 043793/0656 →
Priority Claims (2)
NL 2014493 · Mar 20, 2015 · national
NL 2016001 · Dec 22, 2015 · national
Continuity (1)
Related Publication 20180117566A1 · May 3, 2018
Cited By (3)
US 12,370,533 US 12,678,773 US 12,702,969