Perovskite metal oxide catalyst, in which metal ion is substituted, for reducing carbon deposition, preparation method therefor, and methane reforming reaction method using same

Patent metadata

Field	Value
Publication number	US-2020269217-A1
Application number	US-201716648190-A
Country	US
Kind code	A1
Filing date	Nov 6, 2017
Priority date	Sep 18, 2017
Publication date	Aug 27, 2020
Grant date	—

Abstract

The present invention relates to a perovskite metal oxide catalyst substituted with metal ions for reducing carbon deposition, a method for producing the same, and a process for performing a methane reforming reaction using this catalyst. According to the present invention, a novel type of catalyst is produced in which Ni, iron or cobalt in ionic form is substituted at a portion of the Ti site (B-site) of SrTiO 3 , MgTiO 3 , CaTiO 3 or BaTiO 3 , which is a multicomponent metal oxide having a perovskite (ABO 3 ) structure. Then, various methane reforming reactions (e.g., steam-methane reforming (SMR), dry reforming of methane (DRM), catalytic partial oxidation of methane (CPOM), etc.) may be efficiently and economically performed using this catalyst. The nickel-substituted perovskite metal oxide catalyst according to the present invention has a structure in which Ni 2+ , Co 2+ , Fe 2+ , Co 3+ or Fe 3+ is substituted in the perovskite lattice structure. Thus, the metal oxide catalyst has advantages in that carbon deposition thereon does not occur, and thus the catalyst has a high catalytic stability and may be used for a long time.

First claim

1 . A multicomponent metal oxide catalyst in which Ni, Co or Fe in ionic form is substituted in the lattice structure of the catalyst and which has a perovskite lattice structure.

2 . The multicomponent metal oxide catalyst of claim 1 , wherein the multicomponent metal oxide having the perovskite structure is selected from the group consisting of MgTiO 3 , CaTiO 3 , BaTiO 3 and SrTiO 3 .

3 . The multicomponent metal oxide catalyst of claim 2 , wherein the multicomponent metal oxide having the perovskite structure is SrTiO 3 .

4 . The multicomponent metal oxide catalyst of claim 1 , wherein the multicomponent metal oxide having the perovskite (ABO 3 ) structure is MgTiO 3 , CaTiO 3 , BaTiO 3 or SrTiO 3 , and Ni, Co or Fe in ionic form is substituted at the Ti site (B-site) of the MgTiO 3 , CaTiO 3 , BaTiO 3 or SrTiO 3 .

5 . The multicomponent metal oxide catalyst of claim 4 , wherein the multicomponent metal oxide having the perovskite (ABO 3 ) structure is SrTiO 3 , and Ni in ionic form is substituted at the Ti site (B-site) of the SrTiO 3 .

6 . The multicomponent metal oxide catalyst of claim 1 , wherein the catalyst is represented by the following formula (1):
MTi 1-x Ni x O 3-δ (wherein x is 0<x<0.05, δ is 0<δ<0.10, M is Sr, Mg, Ca or Ba)   Formula (1)

7 . The multicomponent metal oxide catalyst of claim 6 , wherein the catalyst is represented by the following formula (2):
MTi 0.97 Ni 0.03 O 3-δ (wherein δ is 0.06, and M is Sr, Mg, Ca or Ba)   Formula (2)

8 . A method for producing a multicomponent metal oxide catalyst having a perovskite lattice structure, the method comprising:
a step of mixing and stirring a first metal precursor, citric acid, and ethylene glycol at a molar ratio of 0.1:0.4:0.9 in distilled water in a temperature range of 50 to 90° C., thereby preparing a first mixture solution; a step of mixing and stirring a titanium precursor and a second metal precursor in anhydrous ethanol in a temperature range of 50 to 90° C., thereby preparing a second mixture solution; a reaction step of mixing the first mixture solution and the second mixture solution, followed by stirring in a temperature range of 50 to 90° C. for about 24 hours; a step of removing the solvent through a drying step after the reaction step; a first calcination step of calcining a solid-state material, obtained through the drying step, in a temperature range of about 300 to 400° C. under an oxygen atmosphere; and a second calcination step of calcining the solid-state material in a temperature range of about 800 to 1,000° C. under an oxygen atmosphere after the first calcination step, wherein the ratio of the sum of the moles of Ti and the second metal, which are contained in the titanium precursor and the second metal precursor, respectively, to the moles of the first metal contained in the first metal precursors, is maintained at 1:1, so that the second metal in ionic form is substituted in the perovskite lattice structure, the first metal precursor is a strontium precursor, a magnesium precursor, a calcium precursor or a barium precursor, and the second metal precursor is a nickel precursor, a cobalt precursor or an iron precursor.

9 . The method of claim 8 , wherein the first metal precursor is strontium nitrate, magnesium nitrate, calcium nitrate or barium nitrate.

10 . The method of claim 8 , wherein the titanium precursor is titanium(IV) isopropoxide.

11 . The method of claim 8 , wherein the second metal precursor is nickel(II) nitrate hexahydrate, cobalt nitrate hexahydrate or iron nitrate nonahydrate.

12 . The method of claim 8 , wherein the first calcination is performed under calcination conditions of temperature rising time of 1 hour and 10 minute and highest temperature-keeping time of 5 hours, and the second calcination is performed under calcination conditions of temperature rising time of 4 hours and highest temperature-keeping time of 5 hours.

13 . A methane reforming process comprising performing a methane reforming reaction using the multicomponent metal oxide catalyst of claim 1 .

14 . A methane reforming process comprising performing a methane reforming reaction using the multicomponent metal oxide catalyst produced by the production method of claim 8 .

15 . The methane reforming process of claim 13 , wherein the methane reforming reaction is any one of a steam methane reforming (SMR) reaction, a dry reforming of methane (DRM) reaction, and a catalytic partial oxidation of methane (CPOM) reaction.

16 . The methane reforming process of claim 14 , wherein the methane reforming reaction is any one of a steam methane reforming (SMR) reaction, a dry reforming of methane (DRM) reaction, and a catalytic partial oxidation of methane (CPOM) reaction.

Assignees

• Univ Nat Chonnam Ind Found

Inventors

• Ko Chang Hyun
• Jeon Ji Yoon
• Yun Jeong Woo
• Park Eun Gyong

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/733

  Perovskite-type · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title

• B01J37/088

  Decomposition of a metal salt · CPC title

• B01J37/031

  Precipitation · CPC title