Catalyst composition for the selective conversion of synthesis gas to light olefins

Patent metadata

Field	Value
Publication number	US-9694345-B2
Application number	US-201414889483-A
Country	US
Kind code	B2
Filing date	Jun 25, 2014
Priority date	Jun 28, 2013
Publication date	Jul 4, 2017
Grant date	Jul 4, 2017

Abstract

A catalyst composition and process for preparing it and for using it to enhance the selectivity to light (C2 to C3) olefins in a Fischer-Tropsch conversion of synthesis gas is disclosed. The catalyst composition is an iron-based catalyst on an yttria/zirconia support. In a Fischer-Tropsch reaction the selectivity to ethylene may be enhanced by at least 20 mole percent and to propylene by at least 4 mole percent, in comparison with use of an otherwise identical catalyst that is free of yttria, in an otherwise identical Fischer-Tropsch reaction.

First claim

The invention claimed is:

1. A catalyst comprising
an iron compound comprising iron carbides and, optionally, an alkali metal, alkaline earth metal, or a combination thereof,
on a support comprising zirconia and yttria,
the iron being present in an amount ranging from 1 weight percent to 20 weight percent, based on combined weight of the iron and the support;
the yttria being present in an amount ranging from 1 mole percent to 95 mole percent, based on combined moles of yttria and zirconia, and
the optional alkali metal, alkaline earth metal or combination thereof being present in an amount ranging from 0 mole percent to 6 mole percent, based on moles of the iron.

2. The catalyst of claim 1 , wherein the support is substantially free of silica, tungsten oxide and sulfate dopants.

3. The catalyst of claim 1 further comprising a sulfate promoter on the support in an amount ranging from 0.1 mole percent to 5 mole percent, based on the moles of the iron.

4. The catalyst of claim 1 wherein the yttria is present in an amount ranging from 1 mole percent to 75 mole percent, based on combined moles of the yttria and zirconia.

5. The catalyst of claim 1 wherein the yttria is present in an amount ranging from 1 mole percent to 20 mole percent, based on combined moles of the yttria and zirconia.

6. A process for converting synthesis gas to olefins, comprising contacting synthesis gas and the catalyst of claim 1 under reaction conditions sufficient to convert, at a selected carbon monoxide conversion percentage, at least a portion of the synthesis gas to a mixture of hydrocarbons that has an ethylene content and a propylene content, each of the ethylene content and the propylene content being greater than the ethylene content and the propylene content resulting from use of an otherwise identical catalyst that is substantially free of yttria, under otherwise identical reaction conditions and at a carbon monoxide conversion percent that is within 2 percent of the selected carbon monoxide conversion percent.

7. The process of claim 6 , wherein the ethylene and propylene contents resulting from use of the catalyst of claim 1 are, respectively, at least 20 percent greater and at least 4 percent greater than the ethylene content and the propylene content resulting from use of the otherwise identical catalyst.

8. A catalyst prepared by a process comprising
(1) dispersing an iron-containing compound and, optionally, an alkali metal, an alkaline earth metal, or a combination thereof, on a particulate catalyst support comprising zirconia and yttria;
the amount of the iron-containing compound ranging from 1 weight percent to 20 weight percent, based on combined weight of the iron and the support;
the amount of the optional alkali metal, alkaline earth metal, or combination thereof ranging from 0 mole percent to 6 mole percent, based on combined moles of the alkali metal, the alkaline earth metal, or combination thereof and the iron; and
the amount of yttria ranging from 0.1 mole percent to 95 mole percent, based on combined moles of yttria and zirconia;

(2) thermally at least partially decomposing the iron-containing compound to form a catalyst precursor composition comprising an iron oxide;
(3) subjecting the catalyst precursor composition to at least partial carburization in a carbon monoxide-containing atmosphere to convert at least some of the iron oxides to iron carbides.

9. The catalyst prepared by the process of claim 8 , wherein the iron-containing compound comprises Fe(II), Fe(III) or both.

10. The catalyst of claim 1 , wherein the iron compound is in amounts from 4 weight percent to 15 weight percent, based on combined weight of the iron and the support.

11. The catalyst of claim 10 , wherein the support is substantially free of silica and tungsten oxide.

12. The catalyst of claim 10 , wherein the yttria is present in an amount ranging from 1 mole percent to 75 mole percent, based on combined moles of the yttria and zirconia.

13. The catalyst of claim 10 , wherein the yttria is present in an amount ranging from 1 mole percent to 20 mole percent, based on combined moles of the yttria and zirconia.

14. A catalyst comprising:
iron, a sulfate promoter, and optionally, an alkali metal, alkaline earth metal, or a combination thereof,
on a support comprising zirconia and yttria,
the iron being present in an amount ranging from 1 weight percent to 20 weight percent, based on combined weight of the iron and the support;
the sulfate promoter being present in an amount ranging from 0.1 mole percent to 5 mole percent, based on the moles of the iron;
the yttria being present in an amount ranging from 1 mole percent to 95 mole percent, based on combined moles of yttria and zirconia; and
the optional alkali metal, alkaline earth metal or combination thereof being present in an amount ranging from 0 mole percent to 6 mole percent, based on moles of the iron.

Assignees

• Dow Global Technologies Llc

Inventors

• Davidian Thomas
• Ruitenbeek Matthijs
• Chojecki Adam
• Koeken Adrianus

Classifications

• B01J21/066 Primary

  Zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J23/78

  with alkali- or alkaline earth metals · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J23/83

  with rare earths or actinides · CPC title

• B01J37/084

  Decomposition of carbon-containing compounds into carbon · CPC title