Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

• US 7,879,749 B2
• Filed: 08/15/2006
• Issued: 02/01/2011
• Est. Priority Date: 08/15/2006
• Status: Expired due to Fees

• Current Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Original Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Inventors: Rollins, Harry W., Petkovic, Lucia M., Ginosar, Daniel M.
• Primary Examiner(s): Singh; Prem C
• Application Number:
  US11/464,566
• Publication Number:
  US 20080045403A1
• Time in Patent Office: 1,631 Days
• Field of Search: 585639-640, 518/713, 518/714, 518/715, 518/721, 502/62, 502/64, 502/71, 502/77, 502/78, 502/79
• US Class Current: 502/62
• 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 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 3/45 containing iron group metals or compounds thereof
• CPC Class Codes: C10G 3/47 containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 3/49 containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: C10G 3/50 in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: Y02P 30/40 : Ethylene production

Abstract

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Claims

1. A method of synthesizing hydrocarbon molecules having two or more carbon atoms, the method comprising:

contacting hydrogen and at least one of carbon monoxide and carbon dioxide with a catalytic structure at a temperature greater than about 200°

C. and a pressure greater than about 0.5 megapascals, the catalytic structure comprising;

a zeolite material comprising;

a first plurality of pores substantially defined by interstitial spaces within a crystal structure of the zeolite material, the first plurality of pores comprising a plurality of micropores; and

a second plurality of pores dispersed throughout the zeolite material, the second plurality of pores comprising a plurality of mesopores; and

at least one catalytic material differing from the zeolite material disposed within pores of at least one of the first plurality of pores and the second plurality of pores, the at least one catalytic material comprising a plurality of particles of the catalytic material having an average particle size of less than about 500 angstroms;

catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen within at least one of the first plurality of pores and the second plurality of pores using the at least one catalytic material; and

catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol within at least one of the first plurality of pores and the second plurality of pores using the zeolite material.

2. The method of claim 1, wherein contacting at least one of carbon monoxide and carbon dioxide with a catalytic structure comprises supplying a mixture of hydrogen and at least one of carbon monoxide and carbon dioxide to a reactor containing the catalytic structure.

3. The method of claim 1, further comprising:

removing reaction products and unreacted reactants from the reactor;

cooling the reaction products and unreacted reactants; and

separating unreacted reactants from the reaction products, the reaction products comprising hydrocarbon molecules having two or more carbon atoms.

4. The method of claim 2, further comprising recombining the separated unreacted reactants with the mixture supplied to the reactor.

5. The method of claim 1, wherein contacting hydrogen and at least one of carbon monoxide and carbon dioxide with a catalytic structure comprises contacting hydrogen and at least one of carbon monoxide and carbon dioxide with a plurality of pellets each comprising the zeolite material and the at least one catalytic material.

6. The method of claim 1, further comprising selecting the plurality of particles of the catalytic material to comprise a plurality of metallic particles.

7. The method of claim 6, further comprising selecting each metallic particle of the plurality of metallic particles to comprise at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, and cesium.

8. The method of claim 6, further comprising selecting the plurality of particles of the catalytic material to comprise a plurality of metal oxide particles.

9. The method of claim 8, further comprising selecting each metal oxide particle of the plurality of metal oxide particles to comprise at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.

10. The method of claim 1, further comprising selecting the at least one catalytic material to comprise copper and zinc oxide.

11. The method of claim 1, further comprising forming the second plurality of pores to comprise a plurality of elongated channels.

12. The method of claim 11, further comprising forming each elongated channel of the plurality of elongated channels to be generally cylindrical and have an average diameter in a range extending from about 20 angstroms to about 500 angstroms.

13. The method of claim 11, further comprising forming the second plurality of pores to comprise a plurality of generally spherical pores.

14. The method of claim 1, further comprising selecting the zeolite material to comprise a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.

15. The method of claim 14, further comprising selecting the zeolite material to comprise an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

16. The method of claim 15, further comprising selecting the zeolite material to comprise ZSM-5.