Iron and cobalt based fischer-tropsch pre-catalysts and catalysts

• US 9,114,378 B2
• Filed: 03/15/2013
• Issued: 08/25/2015
• Est. Priority Date: 03/26/2012
• Status: Active Grant

• Current Assignee: Brigham Young University (The Church of Jesus Christ of Latter-Day Saints)
• Original Assignee: Brigham Young University (The Church of Jesus Christ of Latter-Day Saints)
• Inventors: Woodfield, Brian F., Bartholomew, Calvin H., Hecker, William, Ma, Xuchu, Xu, Fen, Astle, Lynn, Brunner, Kyle
• Primary Examiner(s): Hailey, Patricia L
• Application Number:
  US13/836,850
• Publication Number:
  US 20130274093A1
• Time in Patent Office: 893 Days
• Field of Search: 502/326, 502/327, 502/330, 502/331, 502/338, 518/713, 518/715, 518/717, 518719-721
• US Class Current: 1/1
• CPC Class Codes: B01J 23/745 Iron
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/78 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 27/22 Carbides
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/035 Precipitation on carriers
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/082 Decomposition and pyrolysis
• CPC Class Codes: C10G 2/332 of the iron-group

Abstract

A method of making iron and cobalt pre-catalysts and catalysts in activated, finished form suitable for use in Fischer-Tropsch synthesis. The pre-catalysts are prepared by mixing an iron or cobalt salt, a base, and a metal oxide textural promoter or support. The reaction is carried out in a solvent deficient environment. The resulting product is then calcined at temperatures of about 300-500° C. to produce a metal oxide. The catalysts are prepared by reducing the metal oxide in the presence of hydrogen at temperatures of about 300-500° C. and carbiding the reduced metal in the case of iron.

Claims

1. A process for preparing an iron or cobalt based pre-catalyst consisting essentially of

(a) reacting a metal salt selected from the group consisting of a solid iron salt and a solid cobalt salt with a solid base in the presence of a solid textural promoter, with no solvent added to produce a cobalt or iron oxide nanoparticle catalyst precursor in the pores of said textural promoter;

and

(b) calcining the product of step (a) to produce an iron or cobalt based pre-catalyst.

2. The process of claim 1 wherein the metal salt is an iron salt.

3. The process of claim 2 wherein a copper salt, a potassium salt and the textural promoter are provided in step (a) and mixed together in one step prior to heating, and wherein the calcining step is carried out at a temperature of about 150-750°

C.

4. The process of claim 2 wherein the iron salt is selected from the group consisting of iron nitrate, iron oxalate, iron acetate, iron chloride and mixtures thereof and the calcining step is carried out at a temperature of 150-750°

C.

5. The process of claim 2 wherein the base is selected from the group consisting of ammonium carbonate, ammonium bicarbonate, ammonium sesquicarbonate, ammonium chloride, ammonium oxalate, ammonium sulfate, ammonium hydroxide, ammonium nitrate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and mixtures thereof.

6. The process of claim 5 wherein the base is ammonium bicarbonate or ammonium carbonate.

7. The process of claim 2 wherein the iron salt is iron nitrate and the base is selected from the group consisting of ammonium carbonate, ammonium bicarbonate and mixtures thereof.

8. The process of claim 2 wherein the textural promoter is a metal oxide selected from the group consisting of alumina, silica, ceria, titania and mixtures thereof.

9. The process of preparing a catalyst wherein the pre-catalyst of claim 1 is prepared from an iron salt and the pre-catalyst is heated in the presence of hydrogen to reduce the resulting product which reduced product is then heated in the presence of carbon monoxide to produce iron carbide.

10. The process of claim 9 wherein the textural promoter is present in the amount of about 10-30% or 50-90% by weight based on the weight of the catalyst produced.

11. The process of claim 1 wherein the metal salt is a cobalt salt.

12. The process of claim 11 wherein a noble metal salt selected from the group consisting of Ru, Pt, Pd, Re and mixtures thereof is provided in step (a).

13. The process of claim 12 wherein the cobalt salt, the base, the noble metal salt and textural promoter are mixed together in one step prior to the heating step, and the calcining step is carried out at a temperature of about 150-750°

C.

14. The process of claim 11 wherein the cobalt salt is selected from the group consisting of cobalt nitrate, cobalt oxalate, cobalt acetate, cobalt citrate, cobalt chloride and mixtures thereof.

15. The process of claim 11 wherein the base is selected from the group consisting of ammonium carbonate, ammonium bicarbonate, ammonium sesquicarbonate, ammonium chloride, ammonium oxalate, ammonium sulfate, ammonium hydroxide, ammonium nitrate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and mixtures thereof.

16. The process of claim 15 wherein the cobalt salt is cobalt nitrate and the base is ammonium bicarbonate, ammonium carbonate or mixtures thereof.

17. The process of claim 11 wherein the textural promoter is a metal oxide selected from the group consisting of alumina, silica, titania, ceria, and mixtures thereof.

18. A process for preparing a catalyst wherein the pre-catalyst prepared by the process of claim 11 is prepared from a cobalt salt and the pre-catalyst is heated in the presence of hydrogen to reduce the cobalt oxide.

19. The process of claim 18 wherein the textural promoter is present in the amount of about 10-30% or 50-90% by weight of the catalyst produced.

20. The process of claim 1 wherein water present in the reaction of step (a) with no solvent added facilitates the reaction.

21. A process for preparing an iron or cobalt based pre-catalyst consisting essentially of:

(a) reacting a solid metal salt selected from the group consisting of an iron salt or a cobalt salt with a solid base, with no solvent added to produce a nanoparticle iron or cobalt oxide catalyst precursor;

(b) adding a solid textural promoter to the product of step (a) to produce a pre-catalyst, and

(c) calcining the product of step (b).