Adsorbent for carbon dioxide, method of preparing the same, and capture module for carbon dioxide including the same

• US 9,248,395 B2
• Filed: 03/15/2013
• Issued: 02/02/2016
• Est. Priority Date: 03/26/2012
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Lee, Hyun Chul, Seo, Jeong Gil, Kwon, Soon Chul, Kwon, Hyuk Jae
• Primary Examiner(s): Jones, Christopher P
• Application Number:
  US13/837,036
• Publication Number:
  US 20130247757A1
• Time in Patent Office: 1,054 Days
• US Class Current: 1/1
• CPC Class Codes: B01D 2253/1124 Metal oxides
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2253/304 Linear dimensions, e.g. particle shape, diameter
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/04 with stationary adsorbents B01D53/025 takes precedence
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

An adsorbent for carbon dioxide may include a structure that includes composite metal oxide including a first metal (M¹) and a second metal (M²) linked through oxygen (O). The first metal (M¹) may be selected from an alkali metal, an alkaline-earth metal, and a combination thereof. The second metal (M²) may have a trivalent oxidation number or greater. The composite metal oxide may include mesopores inside or in the surface thereof. The adsorbent may be included in a capture module for carbon dioxide. A method of reducing emissions may include adsorbing carbon dioxide using the adsorbent for carbon dioxide.

Claims

1. An adsorbent for carbon dioxide, comprising:

a composite metal oxide including a first metal (M¹) and a second metal (M²) linked together by oxygen (O), the first metal (M¹) selected from at least one of an alkali metal and an alkaline-earth metal, the second metal (M²) having a trivalent oxidation number or greater, and the composite metal oxide being mesoporous, the first metal (M¹) and the second metal (M²) being present at an atomic ratio (M¹/M²) of about 1/1 to about 3/1,

wherein the composite metal oxide has a spinel structure, and wherein the composite metal oxide is a calcined wet gel.

2. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide is a crystalline oxide.

3. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide includes mesopores having an average pore size of about 2 nm to about 50 nm.

4. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide is in a form of a plurality of particles having an average particle size of about 0.01 μ

m to about 10 μ

m.

5. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide is represented by the following Chemical Formula 1,

a(M¹_xM²_yO_z)−

b(M²_pO_q)−

c(M¹_rO_s)  

 

[Chemical Formula 1]

wherein 0<

x≦

1, 0<

y≦

2, 0<

z≦

4, 0<

p≦

2, 0<

q≦

3, 0<

r≦

2, 0<

s≦

1, 0 <

a≦

1, 0≦

b≦

199, 0<

c≦

9, and 0<

a+b+c.

6. The adsorbent for carbon dioxide of claim 1, wherein the alkali metal is selected from at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), and the alkaline-earth metal is selected from at least one of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).

7. The adsorbent for carbon dioxide of claim 1, wherein the second metal (M²) is selected from at least one of a Group 13 element, a Group 14 element, and a transition element.

8. The adsorbent for carbon dioxide of claim 1, wherein the second metal (M²) is selected from at least one of aluminum (Al), silicon (Si), titanium (Ti), and zirconium (Zr).

9. The adsorbent for carbon dioxide of claim 1, further comprising:

an oxide of at least one of the alkali metal and the alkaline-earth metal on the surface of the composite metal oxide.

10. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide is selected from at least one of a silicate, an aluminate, a titanate, and a zirconate, the second metal (M²) is selected from at least one of Si, Al, Ti, and Zr, and the second metal (M²) is partially substituted with the first metal (M¹).

11. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide has a pore volume of about 0.01 to about 3.0 cm³/g.

12. The adsorbent for carbon dioxide of claim 1, wherein the composite metal oxide has a specific surface area of about 10 to about 500 m²/g.

13. A module for capturing carbon dioxide, comprising:

the adsorbent for carbon dioxide according to claim 1.

14. A method of capturing carbon dioxide, comprising:

adsorbing carbon dioxide using the adsorbent for carbon dioxide according to claim 1.

15. The method of claim 14, wherein the adsorbing carbon dioxide is performed at an adsorbing temperature that includes at least one of a middle temperature ranging from 200°

C. to 500°

C. and at a higher temperature of more than 500°

C.

16. A method of preparing an adsorbent for carbon dioxide, comprising:

preparing a first mixture by adding a precursor of a second metal (M²) to a polar solvent, the second metal (M²) having a trivalent oxidation number or greater,

adding water to the first mixture to prepare a partially-hydrated mixture,

preparing a second mixture by adding a precursor of a first metal (M¹) to the partially-hydrated mixture, the first metal (M¹) selected from at least one of an alkali metal and an alkaline-earth metal, adding water to the second mixture to induce hydrolysis and produce a wet gel, and

calcining the wet gel to provide a composite metal oxide, the composite metal oxide being mesoporous and having a spinel structure, the composite metal oxide including the first metal (M¹) and the second metal (M²) linked together by oxygen (O), the first metal (M¹) and the second metal (M²) being present at an atomic ratio (M¹/M²) of about 1/1 to about 3/1.

17. The method of claim 16, further comprising:

adding an acid or alkylene oxide to the first mixture to promote partial hydration of the first mixture.

18. The method of claim 16, wherein the preparing a first mixture includes the precursor of the second metal being an alkoxide or an inorganic salt of the second metal.

19. The method of claim 16, wherein the preparing a first mixture includes the precursor of the second metal being represented by the following Chemical Formula 2,

M²(R¹)_m(R²)_n-m  

 

[Chemical Formula 2]

wherein

R¹ and R² are the same or different and are each independently hydrogen, an acryloyl group, a methacryloyl group, a vinyl group, a C1 to C15 linear or branched alkoxy group, a halogen, or a nitrate group, provided that at least one of R¹ and R² is the C1 to C15 linear or branched alkoxy group, the halogen, or the nitrate group,

n denotes a valence of M², and

m is an integer in a range of about 0 to n.

20. The method of claim 16, wherein the preparing a first mixture includes the polar solvent being selected from at least one of water, alcohol, and ether.

21. The method of claim 16, wherein the preparing a second mixture includes the precursor of the first metal (M¹) being an alkoxide or a salt of the first metal (M¹).

22. The method of claim 16, wherein the preparing a second mixture includes the precursor of the first metal (M¹) including a cation of the first metal and an anion selected from an alkoxide anion (OR⁻

, wherein R is a linear or branched C1 to C15 alkyl group), a halide anion (X⁻

, wherein X is a halogen), a nitrate anion (NO₃₋

), a carbonate anion (CO₃²⁻

), a sulfate anion (SO₄²⁻

), a sulfonate anion (SO₃₋

), a phosphate anion (PO₄³⁻

), and an acetate anion (CH₃COO⁻

).

23. The method of claim 16, wherein the calcining is performed at a temperature ranging from 400°

C. to 800°

C.