Catalyst for producing hydrocarbon from syngas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from syngas

Patent metadata

Field	Value
Publication number	US-9808792-B2
Application number	US-201314424155-A
Country	US
Kind code	B2
Filing date	Aug 19, 2013
Priority date	Sep 3, 2012
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

The present invention provides a catalyst for producing a hydrocarbon from a syngas, including one of a cobalt metal and a combination of a cobalt metal and cobalt oxides; zirconium oxides; and a noble metal; supported by a catalyst support mainly composed of silica, wherein a content of impurities in the catalyst is less than or equal to 0.15 mass %; a producing method and regenerating method thereof; and a producing method of the hydrocarbon by using the catalyst.

First claim

The invention claimed is:

1. A method for producing a catalyst for producing a hydrocarbon from a syngas, the catalyst consisting of: one of a cobalt metal or a combination of a cobalt metal and cobalt oxides; zirconium oxides; a noble metal; a catalyst support containing more than 50 mass % of silica and supporting all of them; and inevitable impurities, wherein the content of the inevitable impurities is less than or equal to 0.15 mass %, the method comprising the steps of:
loading zirconium compounds to be supported by the catalyst support by one of an impregnation method, an incipient wetness method, a precipitation method, or an ion-exchange method;
performing one of a drying treatment or a combination of drying treatment and calcination treatment of the catalyst support after loading of the zirconium compounds;
loading cobalt compounds and the noble metal simultaneously to be supported by the catalyst support; and then
performing one of a reduction treatment or a combination of a calcination treatment and a reduction treatment of the catalyst support after loading of the cobalt compounds and the noble metal, whereby the zirconium oxides exist on the catalyst support, the cobalt metal exists on the zirconium oxides, and the noble metal is present in an outer surface of the catalyst,
wherein in the reduction treatment, a hydrogen flow rate as a reducing gas is 0.1 to 40 mL/min per 1 g of catalyst.

2. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 1 , wherein the loaded zirconium compounds, cobalt compounds and noble metal, as raw materials for production used in one of the impregnation method, the incipient wetness method, the precipitation method, and the ion-exchange method, contain one of alkali metals and alkaline earth metals in a range of less than or equal to 5 mass %.

3. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 1 , wherein the catalyst support mainly composed of silica is produced by gelating silica sol generated by mixing an alkali silicate aqueous solution and an acid aqueous solution together, subjecting the resulting product to at least any of an acid treatment and a water washing treatment, and then drying it.

4. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 3 , wherein water in which content of alkali metals or alkaline earth metals is less than or equal to 0.06 mass % is used in at least one of the acid treatment and the water washing treatment after the gelation of the silica sol.

5. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 3 , wherein the gelation is performed by spraying the silica sol into a gas medium or a liquid medium to mold the silica sol into a spherical shape.

6. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 1 , wherein the cobalt compounds and the zirconium compounds are supported by the catalyst support mainly composed of silica after the concentration of the impurities is reduced by performing cleaning by using at least any one of water, acid, and alkali.

7. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 6 , wherein the cleaning uses one or more of acid and ion-exchange water.

8. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 1 , wherein a flow rate of a reducing gas is 0.5 to 20 mL/min per 1 g of catalyst.

9. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 8 , wherein a flow rate of a reducing gas is 0.5 to 10 mL/min per 1 g of catalyst.

10. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 1 , wherein the loading amount of one of the cobalt metal and the combination of the cobalt metal and the cobalt oxides in the catalyst is 5 to 50 mass % in terms of cobalt metal, and the loading amount of the zirconium oxides is 0.03 to 0.6 in the molar ratio of Zr/Co, and the loading amount of the noble metal is less than or equal to 1 mass %.

11. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 10 , wherein the loading amount of the noble metal is 0.001 to 0.2 mass %.

12. A method for producing a catalyst for producing a hydrocarbon from a syngas, the catalyst consisting of: one of a cobalt metal or a combination of a cobalt metal and cobalt oxides; zirconium oxides; a noble metal; a catalyst support containing more than 50 mass % of silica and supporting all of them; and inevitable impurities, wherein the content of the inevitable impurities is less than or equal to 0.15 mass %, the method comprising the steps of:
loading zirconium compounds to be supported by the catalyst support by one of an impregnation method, an incipient wetness method, a precipitation method, or an ion-exchange method;
performing one of a drying treatment or a combination of drying treatment and calcination treatment of the catalyst support after loading of the zirconium compounds;
loading cobalt compounds to be supported by the catalyst support;
performing one of a drying treatment or a combination of a drying treatment and calcination treatment of the catalyst support after loading of the cobalt compounds;
loading the noble metal to be supported by the catalyst support; and then
performing one of a reduction treatment or a combination of calcination treatment and reduction treatment of the catalyst support after loading of the noble metal, whereby the zirconium oxides exist on the catalyst support, the cobalt metal exists on the zirconium oxides, and the noble metal is present in an outer surface of the catalyst,
wherein in the reduction treatment, a hydrogen flow rate as a reducing gas is 0.1 to 40 mL/min per 1 g of catalyst.

13. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 12 , wherein the loaded zirconium compounds, cobalt compounds and noble metal, as raw materials for production used in one of the impregnation method, the incipient wetness method, the precipitation method, and the ion- exchange method, contain one of alkali metals and alkaline earth metals in a range of less than or equal to 5 mass %.

14. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 12 , wherein the catalyst support mainly composed of silica is produced by gelating silica sol generated by mixing an alkali silicate aqueous solution and an acid aqueous solution together, subjecting the resulting product to at least any of an acid treatment and a water washing treatment, and then drying it.

15. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 14 , wherein water in which content of alkali metals or alkaline earth metals is less than or equal to 0.06 mass % is used in at least one of the acid treatment and the water washing treatment after the gelation of the silica sol.

16. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 14 wherein the gelation is performed by spraying the silica sol into a gas medium or a liquid medium to mold the silica sol into a spherical shape.

17. The method for producing a catalyst for producing a hydrocarbon from a syngas according to claim 12 , wherein the cobalt compounds and the zirconium compounds are supported by the catalyst support mainly composed of silica after the concentration of th

Assignees

• Nippon Steel & Sumikin Eng Co

Inventors

• Fujimoto Kenichiro
• Yamane Noriyuki

Classifications

• B01J23/8913 Primary

  Cobalt and noble metals · CPC title

• B01J23/96

  of catalysts comprising metals, oxides or hydroxides of the noble metals · CPC title

• C10G2/333

  of the platinum-group · CPC title

• B01J38/10

  using elemental hydrogen · CPC title

• B01J37/0201

  Impregnation · CPC title