Catalyst and process of hydrocarbon feedstock reformation to hydrogen and carbon monoxide

• US 8,709,378 B2
• Filed: 01/16/2008
• Issued: 04/29/2014
• Est. Priority Date: 01/16/2008
• Status: Expired due to Fees

• Current Assignee: The United States of America As Represented By The Secretary of Agriculture
• Original Assignee: The United States Of America As Represented By The Secretary Of The Army
• Inventors: Lee, Ivan Chihang
• Primary Examiner(s): SAHA, BIJAY S
• Application Number:
  US12/014,910
• Publication Number:
  US 20140073499A1
• Time in Patent Office: 2,295 Days
• Field of Search: None
• US Class Current: 423/700
• CPC Class Codes: B01J 2229/186 not in framework positions
• CPC Class Codes: B01J 29/126 Y-type faujasite
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0238 the reforming step being a carbon dioxide reforming step
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0455 Purification by non-catalytic desulfurisation
• CPC Class Codes: C01B 2203/0485 the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/066 with fuel cells
• CPC Class Codes: C01B 2203/1064 Platinum group metal catalysts
• CPC Class Codes: C01B 2203/107 Platinum catalysts
• CPC Class Codes: C01B 2203/1082 Composition of support materials
• CPC Class Codes: C01B 3/40 characterised by the catalyst
• CPC Class Codes: Y02P 20/141 Feedstock
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A catalytic composition is particularly well suited for hydrocarbon conversion to synthesis gas at a temperature of between 800 and 1000° Celsius. The catalytic composition includes a noble metal cluster having an X-Y-Z axial mean linear dimension of between 2 and 15 Angstroms and a super cage structure surrounding the noble metal cluster. The super cage structure stabilizes the noble metal cluster against aggregation at temperatures of 1000° Celsius. A process for reforming hydrocarbon feedstock to hydrogen and carbon monoxide is also provided that conversion to greater than 80% of theoretical yield.

Claims

1. A catalytic composition for increasing the rate of conversion of a sulfur-containing hydrocarbon feedstock and an oxygen donor to hydrogen and carbon monoxide at temperatures less than or equal to 1000°

Celsius, the catalytic composition comprising;

a Y-zeolite that comprises

an exterior surface,

an interior volume having an interior cross-sectional area ranging from 36 to 225 square Angstroms, and

a passage providing fluid communication for a hydrocarbon having at least 6 carbon atoms between the exterior surface and the interior volume; and

a noble metal cluster having an X-Y-Z axial mean linear dimension of between 2 and 15 Angstroms within the interior volume,

wherein the Y-zeolite stabilizes the X-Y-Z axial mean linear dimension of the noble metal cluster against aggregation at temperatures up to 1000°

Celsius

and further wherein the catalytic composition increases the rate of conversion of a sulfur-containing hydrocarbon feedstock and an oxygen donor to hydrogen and carbon monoxide at temperatures less than or equal to 1000°

Celsius at a yield of said conversion of at least 80 percent.

2. The catalytic composition of claim 1 wherein the noble metal cluster is formed of a noble metal selected from the group consisting of rhodium, platinum, palladium and combinations thereof.

3. The catalytic composition of claim 1 wherein the noble metal cluster is formed of a noble metal consisting of rhodium.

4. The catalytic composition of claim 1 wherein the sulfur-containing hydrocarbon feedstock is selected from the group consisting of Jet-A, Jet-A1, JP-4, JP-5, JP-8, kerosene, gasoline, diesel fuel and mixtures thereof.

5. The catalytic composition of claim 4 wherein the Y zeolite is a rare earth stabilized Y zeolite comprising at least one rare earth atom selected from the group consisting of samarium, dysprosium, and erbium.

6. The catalytic composition of claim 1 wherein the catalytic composition comprises at least one rare earth atom selected from the group consisting of samarium, dysprosium, and erbium.

7. The catalytic composition of claim 1 wherein the Y zeolite has an exterior surface area of between 170 and 350 meters² per gram at 925°

Celsius.

8. The catalytic composition of claim 1 wherein the catalytic composition comprises a nanotube selected from the group consisting of a tungsten carbide nanotubes and a titanium carbide nanotubes.

9. The catalytic composition of claim 1 wherein the noble metal cluster is formed of a noble metal selected from the group consisting of rhodium, platinum, palladium, and combinations thereof.

10. The catalytic composition of claim 1 wherein the noble metal cluster comprises rhodium.

13. The catalytic composition of claim 1 wherein the noble metal cluster is formed of a noble metal selected from the group consisting of rhodium, platinum, palladium, and combinations thereof.

14. The catalytic composition of claim 1 wherein the catalytic composition is formed from Sm—

Na Y-Zeolite powder that comprises a super cage and rhodium metal clusters inserted into the super cage of the Sm—

Na Y-Zeolite powder by degassing the zeolite.

15. The catalytic composition of claim 1 wherein the composition is used in a process for reformation of hydrocarbon feedstock to hydrogen and carbon monoxide comprising:

preheating the catalytic composition to a preheating temperature of between 250 and 400°

Celsius and

exposing the catalytic composition to the hydrocarbon feedstock and a gaseous oxygen atom donating reactant to a reaction temperature for a period of time sufficient to reform hydrocarbon feedstock to hydrogen and carbon monoxide.

17. The catalytic composition of claim 1 wherein the Y zeolite is a rare earth stabilized Y zeolite and the noble metal cluster is formed of a noble metal selected from the group consisting of rhodium, platinum, palladium, and a combination thereof.

18. The catalytic composition of claim 1 wherein the Y zeolite is a rare earth stabilized Y zeolite having an exterior surface area of between 170 and 350 Meters² per gram at 925°

Celsius.

19. The catalytic composition of claim 1 wherein the sulfur-containing hydrocarbon feedstock has a sulfur content of at least 500 parts per million by weight.

20. The catalytic composition of claim 1 wherein the sulfur-containing hydrocarbon feedstock has an average sulfur content of at least 1000 parts per million by weight.

21. The catalytic composition of claim 1 wherein the sulfur-containing hydrocarbon feedstock is JP-8.

22. The catalytic composition of claim 1 wherein the catalytic composition increases the rate of conversion of a sulfur-containing hydrocarbon feedstock and an oxygen donor to hydrogen and carbon monoxide at temperatures in the range of from 800 to 1000°

Celsius.

23. The catalytic composition of claim 1 wherein the catalytic composition increases the rate of conversion of a sulfur-containing hydrocarbon feedstock and an oxygen donor to hydrogen and carbon monoxide at temperatures in the range of from 800 to 1000°

Celsius to a yield of said conversion of at least 84 percent.

24. The catalytic composition of claim 1 wherein the noble metal cluster is attached to the exterior surface of the Y-zeolite.

11. A catalytic composition for increasing the rate of conversion of a hydrocarbon feedstock to hydrogen and carbon monoxide at temperatures less than or equal to 1000°

Celsius, the catalytic composition comprising a Y zeolite comprising

an exterior surface having a surface area of between 170 and 350 meters² per gram at 925°

Celsius, and having cages containing a rare earth atom selected from the group consisting of samarium, dysprosium, and erbium,

an interior volume having a cross-sectional area ranging from 36 to 225 square Angstroms, and

a passage adapted to provide fluid communication for a hydrocarbon having at least 6 carbon atoms between the exterior surface and the interior volume; and

a rhodium cluster having an X-Y-Z axial mean linear dimension of between 2 and 15 Angstroms, within the interior volume,

wherein the Y zeolite stabilizes the X-Y-Z axial mean linear dimension of the rhodium cluster against aggregation at temperatures up to 1000°

Celsius and further wherein the catalytic composition increases the rate of conversion of a hydrocarbon feedstock to hydrogen and carbon monoxide at temperatures less than or equal to 1000°

Celsius to a yield of said conversion of at least 84 percent.

12. The catalytic composition of claim 11 wherein the Y zeolite is stabilized to form rare earth stabilized Y-zeolite and the rare earth atom is selected from the group consisting of 10 ppmw to 2 wt % samarium, 40 ppmw to 3 wt % dysprosium and 20 ppmw to 3 wt % erbium.

16. The catalytic composition of claim 11 wherein the Y zeolite is a rare earth stabilized Y zeolite.