Thermally stable monolith catalyst for reforming reaction

Patent metadata

Field	Value
Publication number	US-10113119-B2
Application number	US-201715659261-A
Country	US
Kind code	B2
Filing date	Jul 25, 2017
Priority date	Jul 27, 2016
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

The present invention relates to a monolith catalyst for reforming reaction, and more particularly, to a thermally stable (i.e. thermal resistance-improved) monolith catalyst for reforming reaction having a novel construction such that any one of Group 1A to Group 5A metals are used as a barrier component in the existing catalyst particles to inhibit carbon deposition occurring during the reforming reaction in a process for formation of a reforming monolith catalyst while improving thermal durability as well as non-activation of the catalyst due to a degradation.

First claim

What is claimed is:

1. A thermally stable monolith catalyst for reforming reaction, comprising:
an active ingredient and Group 1A to 5A metal of barrier components represented by Formula 1 below on a monolith catalyst support, wherein the active ingredient of Formula 1 has 0.5 to 10 parts by weight based on 100 parts by weight of a monolith catalyst,
a (X)- b (Y)  Formula 1

wherein X is a catalytic active ingredient selected from Co, Ni, Ru, Rh and a mixture thereof, Y is a mixture of Zr as a promoter and Group 1A to 5A metals as a barrier component in a mixing ratio by weight of 1:0.1 to 1:10, and ‘a’ and ‘b’ denote the ratios by weight of X and Yin order, wherein ‘a’ is 1 and ‘b’ ranges from 0.2 to 1.5.

2. The thermally stable monolith catalyst according to claim 1 , wherein Y is a barrier component including Zr and the Group 1A to 5A metals mixed in a ratio by weight of 1:0.3 to 1:5.0.

3. The method according to claim 2 , wherein the Group 1A to 5A metals are present in a form of metal or metal oxide while being separated from the catalytic active ingredient.

4. The thermally stable monolith catalyst according to claim 1 , wherein the Group 1A to 5A metal barrier particles include at least one component selected from Li, Ca, Mg, Ba, Y, La, Er, Pr, Ce, Nd, Sn, B, Al, Ga, In, Si, Sb, Bi, Fe, W and Re.

5. The method according to claim 4 , wherein the Group 1A to 5A metals are present in a form of metal or metal oxide while being separated from the catalytic active ingredient.

6. The thermally stable monolith catalyst according to claim 1 , wherein the Group 1A to 5A metals are present in a form of metal or metal oxide while being separated from the catalytic active ingredient.

7. The thermally stable monolith catalyst according to claim 1 , wherein the monolith support consists of ceramic, silicon carbide or metal component having a specific surface area of 10 m 2 /g or less.

8. A method for manufacturing a thermally stable monolith catalyst for reforming reaction, comprising:
mixing a metal precursor solution so as to be coincident with a compositional ratio of Formula 1 below;
treating an active metal precursor and a barrier component precursor using at least one of surfactants, organic solvents and water so as to separate an active ingredient and a barrier component from each other;
coating a monolith support with the mixed metal precursor solution;
drying the monolith support coated with the metal precursor solution; and
calcining the dried monolith support at a high temperature,
a (X)- b (Y)  Formula 1

wherein X is a catalytic active ingredient selected from Co, Ni, Ru, Rh and a mixture thereof, Y is a mixture of Zr as a promoter and Group 1A to 5A metals as a barrier component in a mixing ratio by weight of 1:0.1 to 1:10, and ‘a’ and ‘b’ denote the ratios by weight of X and Yin order, wherein ‘a’ is 1 and ‘b’ ranges from 0.2 to 1.5.

9. The method according to claim 8 , wherein the Group 1A to 5A metal barrier precursor is a compound in a salt form.

10. The method according to claim 8 , wherein the high temperature calcination in the calcining process at a high temperature is executed at 300 to 900° C. for 4 to 12 hours.

11. A method for manufacturing a thermally stable monolith catalyst for reforming reaction, comprising:
mixing a metal precursor solution so as to be coincident with a compositional ratio of Formula 1 below;
treating an active metal precursor and a barrier component precursor using at least one of surfactants, organic solvents and water so as to separate an active ingredient and a barrier component from each other;
coating a monolith support with the mixed metal precursor solution;
drying the monolith support coated with the metal precursor solution;
calcining the dried monolith support at a high temperature; and
further adding the active metal ingredient and the barrier component while entirely or partially repeating the above processes, so as to carry the monolith catalyst corresponding to the compositional ratio of Formula 1,
a (X)- b (Y)  Formula 1

wherein X is a catalytic active ingredient selected from Co, Ni, Ru, Rh and a mixture thereof, Y is a mixture of Zr as a promoter and Group 1A to 5A metals as a barrier component in a mixing ratio by weight of 1:0.1 to 1:10, and ‘a’ and ‘b’ denote the ratios by weight of X and Yin order, wherein ‘a’ is 1 and ‘b’ ranges from 0.2 to 1.5.

12. The method according to claim 11 , wherein the active metal precursor and the barrier component precursor are treated using at least one substance selected from surfactants, organic solvents and water so as to separate the active ingredient and the barrier component from each other, and the follow-up processes include: coating the monolith support with a low concentration active metal precursor solution; drying and calcining the same; re-coating the catalyst-coated monolith with the barrier precursor solution; and drying and calcining the same, so as to coat and calcine the catalyst active ingredient and the barrier component in a separated form.

13. The method according to claim 11 , wherein the Group 1A to 5A metal barrier precursor is a compound in a salt form.

14. The method according to claim 11 , wherein the high temperature calcination in the calcining process at a high temperature is executed at 300 to 900° C. for 4 to 12 hours.

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Heo Il Jeong
• You Young Woo
• Park Ji Hoon
• Park Jung Hyun
• Chang Tae Sun
• Kim Beom Sik
• Suh Jeong Kwon

Classifications

• B01J23/38

  of noble metals · CPC title

• B01J23/70

  of the iron group metals or copper · CPC title

• C10G2/50

  from carbon dioxide with hydrogen · CPC title

• C01G25/04

  Halides · CPC title

• B01J33/00

  Protection of catalysts, e.g. by coating · CPC title