Iron-based catalysts and treatment process therefor for use in Fischer-Tropsch reactions

Patent metadata

Field	Value
Publication number	US-9643164-B2
Application number	US-201414894561-A
Country	US
Kind code	B2
Filing date	Jun 25, 2014
Priority date	Jun 28, 2013
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

A Fischer-Tropsch catalyst, useful for conversion of synthesis gas to olefins, is prepared from a catalyst precursor composition including iron oxide and an alkali metal on a substantially inert support, and then treated by a process including as ordered steps (1) reduction in a hydrogen-containing atmosphere at a pressure of 0.1 to 1 M Pa and a temperature from 280° C. to 450° C.; (2) carburization in a carbon monoxide-containing atmosphere at a pressure from 0.1 to 1 M Pa and a temperature from 200° C. to less than 340° C.; and (3) conditioning in a hydrogen- and carbon monoxide-containing atmosphere at a pressure from 0.1 to 2 MPa and a temperature from 280° C. to 340° C. The resulting catalyst exhibits at least one improvement selected from (1) increased overall activity; (2) reduced break-in time; (3) slowed rate of deactivation; and (4) increased time to onset of deactivation; when compared to an otherwise identical catalyst precursor composition treated by one or some, but not all, of the given steps and/or under different conditions.

First claim

The invention claimed is:

1. A process for producing a catalyst comprising sequential steps in order as follows:
(1) subjecting a catalyst precursor composition that comprises iron oxide and at least one alkali metal, and optionally, at least one alkaline earth metal, on a particulate support,
the iron oxide being present in an amount ranging from 1 percent by weight to 20 percent by weight, based upon the combined weight of iron and the particulate support,
the alkali metal being present in an amount ranging from greater than 0 mole percent to 10 mole percent, based on moles of iron in the iron-containing compound, and the alkaline earth metal being in an amount ranging from 0 mole percent to 10 mole percent, based upon the combined weight of the iron-containing compound and the support,
to reduction in a first atmosphere containing hydrogen at a hydrogen pressure ranging from 0.1 megapascal to 1 megapascal, at a temperature from 300° C. to 475° C.
to form an at least partially reduced catalyst precursor composition;

(2) subjecting the at least partially reduced catalyst precursor composition to carburization in a second atmosphere having a composition containing at least 50 volume percent carbon monoxide and less than 10 volume percent hydrogen,
at a carbon monoxide pressure ranging from 0.1 megapascal to 1 megapascal
at a temperature ranging from 200° C. to less than 340° C., to form an at least partially carburized catalyst precursor composition; and

(3) subjecting the at least partially carburized catalyst precursor composition to conditioning
in an atmosphere containing hydrogen and carbon monoxide
in a molar ratio ranging from 0.5 to 3,
wherein there is a maximum of 50 volume percent of inert gas, and
wherein the combined hydrogen and carbon monoxide pressures total ranges from 0.1 megapascal to 2 megapascals,

at a temperature ranging from 200° C. to 340° C.,
to form an at least partially conditioned, particulate catalyst that comprises iron carbide.

2. The process of claim 1 wherein the alkali metal is selected from potassium and sodium.

3. The process of claim 1 wherein the particulate support comprises a material selected from an alpha-alumina, titania, zirconia, silicon carbide, carbon nanofibers, and combinations thereof.

4. The process of claim 3 wherein the material is an alpha-alumina, titania, or zirconia having a surface area of less than 100 square meters per gram; a silicon carbide or carbon nanofiber having a surface area of less than 500 square meters per gram; or a combination thereof.

5. A catalyst composition prepared by the process of claim 1 .

6. The catalyst according to claim 5 , wherein the catalyst has a break-in period that is shorter by at least 20 percent than that of a catalyst prepared from an identical catalyst precursor composition, but without at least one of step (1) and step (2).

7. The catalyst according to claim 5 , wherein the catalyst has a maximum carbon monoxide conversion percentage that is greater by at least 10% percent than that of a catalyst prepared from an identical catalyst precursor composition, but without at least one of step (1) and step (2).

8. The catalyst according to claim 5 , wherein the catalyst has a deactivation rate that is reduced by at least 50 percent when compared with than that of a catalyst prepared from an identical catalyst precursor composition, but without at least one of step (1) and step (2).

9. The catalyst according to claim 5 , wherein the at least partially conditioned, particulate catalyst is characterized as having
(1) a mean particle size ranging from five nanometers to seven nanometers, and
(2) a particle size distribution wherein at least ninety weight percent of the catalyst particles have a particle size ranging from two nanometers to nine nanometers.

10. A Fischer-Tropsch process comprising:
subjecting the catalyst composition according to claim 5 to high temperatures, wherein high temperature is defined by 300° C. to 350° C.

Assignees

• Dow Global Technologies Llc

Inventors

• Davidian Thomas
• Ruitenbeek Matthijs
• Koeken Adrianus
• Vos Marjolein
• Wielemaker Marco F

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J23/78 Primary

  with alkali- or alkaline earth metals · CPC title

• C07C11/02

  Alkenes · CPC title

• C07C11/06

  Propene · CPC title