Process for synthesizing iron carbide Fischer-Tropsch catalysts

Patent metadata

Field	Value
Publication number	US-9833774-B2
Application number	US-201515300139-A
Country	US
Kind code	B2
Filing date	May 14, 2015
Priority date	May 16, 2014
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

Preparation of a catalyst suitable for use in Fischer-Tropsch Synthesis reactions using a two step process in which the steps may be performed in either order. In step a), impregnate an iron carboxylate metal organic framework selected from a group consisting of iron-1,3,5-benzenetricarboxylate (Fe-(BTC), Basolite™ F-300 and/or MIL-100 (Fe)), iron-1,4 benzenedicarboxylate (MIL-101(Fe)), iron fumarate (MIL-88 A (Fe)), iron-1,4 benzenedicarboxylate (MIL-53 (Fe)), iron-1,4 benzenedicarboxylate (MIL-68 (Fe)) or iron azobenzenetetracarboxylate (MIL-127 (Fe)) with a solution of a promoter element selected from alkali metals and alkaline earth metals. In step b) thermally decompose the iron carboxylate metal organic framework under an inert gaseous atmosphere to yield a catalyst that is a porous carbon matrix having embedded therein a plurality of discrete aliquots of iron carbide. If desired, add a step intermediate between steps a) and b) or preceding step b) wherein the metal organic framework is impregnated with an oxygenated solvent solution of a polymerizable additional carbon source and the polymerizable additional carbon source is thereafter polymerized.

First claim

What is claimed is:

1. A process for preparing a Fischer-Tropsch Synthesis catalyst comprising two steps as follows: a) impregnating an iron based metal organic framework with a solution of a promoter element selected from alkali metals and alkaline earth metals; and b) thermally decomposing the metal organic framework at a temperature within a range of from 400° C. to 1000° C., under an inert gaseous atmosphere to yield a catalyst that is a porous carbon matrix having embedded therein a plurality of discrete aliquots of iron carbide, the discrete aliquots having a mean particle size of from greater than 0 nanometer to no more than 100 nanometers and being present in a total amount within a range of from 10 weight percent to no more than 60 weight percent, based upon total catalyst weight.

2. The process of claim 1 , wherein the iron based metal organic framework consists of a carboxylate metal organic framework selected from a group consisting of iron-1,3,5-benzenetricarboxylate, iron 1,4 benzenedicarboxylate, iron fumarate, and iron azobenzenetetracarboxylate.

3. The process of claim 1 , wherein the inert gaseous atmosphere comprising at least one gas selected from a group consisting of nitrogen, helium and argon.

4. The process of claim 1 , further comprising a step that precedes step b) wherein the iron based metal organic framework is impregnated with an organic solvent solution or aqueous solution of a polymerizable additional carbon source and the polymerizable additional carbon source is polymerized under an inert gaseous atmosphere at a temperature within a range of from 50° C. to 200° C. for a period of time within a range of from one hour to forty eight hours to yield a polymer-modified iron based metal organic framework.

5. The process of claim 4 , wherein the organic solvent is at least one solvent selected from a group consisting of alcohols, ethers, esters, ketones and aldehydes, and the polymerizable additional carbon source is furfuryl alcohol, the furfuryl alcohol being present in an amount within a range of from greater than zero volume percent to less than or equal to 100 volume percent, each volume percent being based upon total alcohol solution volume.

6. The process of claim 4 , wherein the polymerizable additional carbon source is selected from pyrrole and sucrose.

7. The process of claim 4 , wherein the organic solvent is an alcohol selected from a group consisting of methanol, ethanol, propanol, butanol and mixtures thereof.

8. The process of claim 4 wherein the temperature is within a range of from 80° C. to 150° C. and the time is less than or equal to 24 hours.

9. The process of claim 1 , wherein the promoter element is an alkali metal, an alkaline earth metal or a combination of two or more of the preceding, and wherein the promoter is present in an amount that yields an promoter metal/iron atomic ratio within a range of from greater than zero to less than or equal to 0.2.

10. The process of claim 1 wherein the metal organic framework is applied as synthesized.

11. The process of claim 1 wherein the catalyst is applied in Fischer-Tropsch Synthesis without prior activation.

12. A process for preparing a Fischer-Tropsch Synthesis catalyst comprising two steps as follows: a) thermally decomposing an iron based metal organic framework at a temperature within a range of from 400° C. to 1000° C., under an inert gaseous atmosphere; and b) impregnating the iron based metal organic framework with a solution of a promoter element selected from alkali metals and alkaline earth metals to yield a catalyst that is a porous carbon matrix having embedded therein a plurality of discrete aliquots of iron carbide, the discrete aliquots having a mean particle size of from greater than 0 nanometer to no more than 100 nanometers and being present in a total amount within a range of from 10 weight percent to no more than 60 weight percent, based upon total catalyst weight.

13. The process of claim 12 , wherein the iron based metal organic framework consists of a carboxylate metal organic framework selected from a group consisting of iron-1,3,5-benzenetricarboxylate, iron-1,4-benzenedicarboxylate, iron fumarate, and iron azobenzenetetracarboxylate.

14. The process of claim 12 , wherein the inert gaseous atmosphere comprising at least one gas is selected from the group consisting of nitrogen, helium and argon.

15. The process of claim 12 , further comprising a step that precedes step a) wherein the metal organic framework is impregnated with an organic solvent solution or aqueous solution of a polymerizable additional carbon source and the polymerizable additional carbon source is polymerized under an inert gaseous atmosphere at a temperature within a range of from 50° C. to 200° C. for a period of time within a range of from one hour to forty eight hours to yield a polymer-modified iron based metal organic framework.

16. The process of claim 15 , wherein the organic solvent is at least one solvent selected from a group consisting of alcohols, ethers, esters, ketones and aldehydes, and the polymerizable additional carbon source is furfuryl alcohol, the furfuryl alcohol being present in an amount within a range of from greater than zero volume percent to less than or equal to 100 volume percent, each volume percent being based upon total alcohol solution volume.

17. The process of claim 15 , wherein the polymerizable additional carbon source is selected from pyrrole and sucrose, wherein the organic solvent is an alcohol selected from a group consisting of methanol, ethanol, propanol, butanol and mixtures thereof, and wherein the temperature is within a range of from 80° C. to 150° C. and the time is less than or equal to 24 hours.

18. The process of claim 12 , wherein the promoter element is an alkali metal, an alkaline earth metal or a combination of two or more of the preceding, and wherein the promoter is present in an amount that yields a promoter metal/iron atomic ratio within a range of from greater than zero to less than or equal to 0.2.

19. The process of claim 12 , wherein the iron based metal organic framework is applied as synthesized.

20. The process of claim 12 , wherein the catalyst is applied in Fischer-Tropsch Synthesis without prior activation.

Assignees

• Dow Global Technologies Llc

Inventors

• Santos Castro Vera P
• Chojecki Adam
• Meima Garmt R
• Koeken Adrianus
• Ruitenbeek Matthijs
• Davidian Thomas
• Jorge Gascon
• Makkee Michiel
• Kapteijn Freek
• Wezendonk Tim A

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/023

  Operations & Transport · mapped topic