PRECURSOR OF A CATALYTIC STRUCTURE, A CATALYTIC STRUCTURE, A METHOD OF FABRICATING THE SAME, AND A SYSTEM AND A METHOD FOR USING THE SAME

• US 20080045400A1
• Filed: 03/21/2007
• Published: 02/21/2008
• Est. Priority Date: 08/15/2006
• Status: Active Grant

• Current Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Original Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Inventors: Ginosar, Daniel M., Rollins, Harry W., Petkovic, Lucia M.
• Granted Patent: US 7,592,291 B2
• Time in Patent Office: Days
• US Class Current: 502/8
• CPC Class Codes: B01J 29/005 Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
• CPC Class Codes: B01J 29/035 Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
• CPC Class Codes: B01J 29/041 Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
• CPC Class Codes: B01J 29/061 containing metallic elements added to the zeolite
• CPC Class Codes: B01J 29/072 Iron group metals or copper
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/46 Iron group metals or copper
• CPC Class Codes: B01J 29/80 Mixtures of different zeolites
• CPC Class Codes: B01J 37/0018 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 Class Codes: C07C 1/20 starting from organic compounds containing only oxygen atoms as heteroatoms
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2529/46 Iron group metals or copper
• CPC Class Codes: C07C 2529/84 Aluminophosphates containing other elements, e.g. metals, boron
• CPC Class Codes: C07C 2529/85 Silicoaluminophosphates (SAPO compounds)
• CPC Class Codes: C10G 2/33 characterised by the catalyst used

Abstract

A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

Claims

1. A method of fabricating a catalytic structure, comprising:

forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent; and

heating the reaction mixture under confined volume conditions to produce a precursor of a catalytic structure comprising zinc oxide and copper oxide, the zinc oxide having a sheet-like morphology or a spherical morphology.

2. The method of claim 1, wherein forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent comprises selecting the zinc salt from a compound selected from the group consisting of a zinc alkoxide, zinc acetate, zinc carbonate, zinc carbonate hydroxide, zinc citrate, zinc lactate, zinc nitrate, zinc oxalate, zinc stearate, zinc sulfate, and combinations thereof.

3. The method of claim 1, wherein forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent comprises selecting the copper salt from a compound selected from the group consisting of copper acetate, copper acetate monohydrate, copper acetate hydrate, copper carbonate, copper formate hydrate, copper gluconate, copper hydroxide, copper methoxide, copper nitrate, copper nitrate hydrate, copper tartrate hydrate, and combinations thereof.

4. The method of claim 1, wherein forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent comprises selecting the hydroxyl ion source from a compound selected from the group consisting of hexamethylenetetramine, ammonium hydroxide, ethylene diamine, triethanolamine, ammonia, hydrazine, and combinations thereof.

5. The method of claim 1, wherein forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent comprises selecting the structure-directing agent from a compound selected from the group consisting of sodium citrate, potassium citrate, citric acid, poly(vinyl alcohol), poly(vinyl pyrrolidone), and combinations thereof.

6. The method of claim 1, wherein forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent comprises forming a reaction mixture that comprises zinc nitrate, copper nitrate, hexamethylenetetramine, and sodium citrate.

7. The method of claim 1, wherein forming a reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent comprises forming a reaction mixture comprising between about 0.01 M and about 1 M of the zinc salt, between about 0.01 M and about 1 M of the copper salt, between about 0.02 M and about 2 M of the hydroxyl ion source, and between about 0.05 mM and about 0.5 M of the surface-directing agent.

8. The method of claim 1, wherein heating the reaction mixture under confined volume conditions comprises heating the reaction mixture to a temperature between about 80°

C. and about 200°

C.

9. The method of claim 1, wherein heating the reaction mixture under confined volume conditions comprises heating the reaction mixture to a temperature between about 95°

C. and about 120°

C.

10. The method of claim 1, wherein heating the reaction mixture under confined volume conditions comprises heating the reaction mixture for between about 1 hour and about 4 hours.

11. The method of claim 1, wherein heating the reaction mixture under confined volume conditions comprises producing a mixture of zinc- and copper-containing precipitates comprising zinc oxide and copper oxide.

12. The method of claim 11, further comprising drying the mixture of zinc- and copper-containing precipitates at a temperature between about 80°

C. and about 550°

C.

13. The method of claim 1, further comprising reducing the copper oxide particles.

14. The method of claim 13, wherein reducing the copper oxide particles comprises forming a catalytic structure comprising copper metal and zinc oxide, wherein the zinc oxide has a sheet-like morphology or a spherical morphology.

15. The method of claim 14, wherein the catalytic structure further comprises at least one of at least one promoter and at least one additional catalytic material.

16. The method of claim 13, wherein reducing the copper oxide particles comprises forming a catalytic structure consisting essentially of copper metal and zinc oxide.

17. The method of claim 13, wherein reducing the copper oxide particles comprises forming a catalytic structure consisting of copper metal and zinc oxide.

18. A method of hydrogenating a carbon oxide, comprising:

contacting a catalytic structure with hydrogen and at least one of carbon monoxide and carbon dioxide, the catalytic structure comprising;

zinc oxide and copper metal, the zinc oxide having a sheet-like morphology or a spherical morphology and the copper metal comprising particles of copper metal.

19. The method of claim 18, wherein contacting a catalytic structure with hydrogen and at least one of carbon monoxide and carbon dioxide comprises contacting the catalytic structure with hydrogen and the at least one of carbon monoxide and carbon dioxide at a temperature between about 200°

C. and about 500°

C. and at a pressure between about 0.5 megapascals and about 10 megapascals.

20. The method of claim 18, wherein contacting a catalytic structure with hydrogen and at least one of carbon monoxide and carbon dioxide comprises forming an alcohol selected from the group consisting of methanol, ethanol, propanol, butanol, and combinations thereof.

21. The method of claim 18, wherein contacting a catalytic structure with hydrogen and at least one of carbon monoxide and carbon dioxide comprises supplying a mixture of hydrogen and at least one of carbon monoxide and carbon dioxide to a reactor containing the catalytic structure.

22. The method of claim 21, further comprising:

removing reaction products and unreacted reactants from the reactor;

cooling the reaction products and unreacted reactants; and

separating the unreacted reactants from the reaction products, the reaction products comprising an alcohol selected from the group consisting of methanol, ethanol, propanol, butanol, and combinations thereof.

23. The method of claim 22, further comprising recombining the separated unreacted reactants with the mixture supplied to the reactor.

24. A precursor to a catalytic structure, comprising:

zinc oxide and copper oxide, wherein the zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide.

25. The precursor of claim 24, wherein the copper oxide is dispersed on the zinc oxide.

26. The precursor of claim 24, wherein the copper oxide has an average particle size of less than about 100 nm.

27. The precursor of claim 24, wherein the precursor consists essentially of zinc oxide and copper oxide.

28. The precursor of claim 24, wherein the precursor lacks a support material.

29. The precursor of claim 24, wherein the precursor consists of zinc oxide and copper oxide.

30. A catalytic structure, comprising:

zinc oxide and copper metal, wherein the zinc oxide has a sheet-like morphology or a spherical morphology and the copper metal comprises particles of copper metal.

31. The catalytic structure of claim 30, wherein the copper metal is dispersed on the zinc oxide.

32. The catalytic structure of claim 30, wherein the catalytic structure consists essentially of zinc oxide and copper metal.

33. The catalytic structure of claim 30, further comprising at least one of at least one promoter and at least one additional catalytic material.

34. The catalytic structure of claim 30, wherein the catalytic structure lacks a support material.

35. The catalytic structure of claim 30, wherein the catalytic structure consists of zinc oxide and copper metal.

36. A system for producing an alcohol from hydrogen and at least one of carbon monoxide and carbon dioxide, the system comprising:

a reactor configured to receive a reactant mixture comprising hydrogen and at least one of carbon monoxide and carbon dioxide; and

a catalytic structure disposed within the reactor, the catalytic structure comprising zinc oxide and copper metal, wherein the zinc oxide has a sheet-like morphology or a spherical morphology and the copper metal comprises particles of copper metal.