Highly attrition resistant and dry regenerable sorbents for carbon dioxide capture

• US 8,110,523 B2
• Filed: 11/27/2007
• Issued: 02/07/2012
• Est. Priority Date: 01/04/2005
• Status: Active Grant

• Current Assignee: Korea East-West Power Co., Ltd. (Government of South Korea), Korea Electric Power Corporation (Government of South Korea), Korea Midland Power Company Limited (Government of South Korea), Korea South-East Power Co., Ltd. (Government of South Korea), Korea Western Power Company Limited (Government of South Korea), Korea South Power Company Limited
• Original Assignee: Korea East-West Power Co., Ltd. (Government of South Korea), Korea Electric Power Corporation (Government of South Korea), Korea Midland Power Company Limited (Government of South Korea), Korea South-East Power Co., Ltd. (Government of South Korea), Korea Western Power Company Limited (Government of South Korea), Korea South Power Company Limited
• Inventors: Ryu, Chong-Kul, Lee, Joong-Beom, Eom, Tae-Hyoung, Oh, Je-Myung
• Primary Examiner(s): Silverman, Stanley
• Assistant Examiner(s): Liao, Diana J
• Application Number:
  US11/945,504
• Publication Number:
  US 20080119356A1
• Time in Patent Office: 1,533 Days
• Field of Search: 502/84, 502/400, 502/427, 502/514, 951/39
• US Class Current: 502/400
• CPC Class Codes: B01D 2253/10 Inorganic adsorbents
• CPC Class Codes: B01D 2253/304 Linear dimensions, e.g. particle shape, diameter
• CPC Class Codes: B01D 2253/306 Surface area, e.g. BET-specific surface
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2259/40088 by heating
• CPC Class Codes: B01D 53/12 according to the "fluidised technique"
• CPC Class Codes: B01J 20/043 Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
• 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 20/14 Diatomaceous earth
• CPC Class Codes: B01J 20/18 Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28011 Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/28014 characterised by their form
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/2803 Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/28045 Honeycomb or cellular structures; Solid foams or sponges
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28059 : being less than 100 m2/g
• CPC Class Codes: B01J 20/28069 : Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/3021 : Milling, crushing or grinding
• CPC Class Codes: B01J 20/3042 : Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• CPC Class Codes: B01J 20/3078 : Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3433 : of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3483 : by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• CPC Class Codes: B01J 2220/56 : Use in the form of a bed
• CPC Class Codes: B82Y 30/00 : Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y10S 502/514 : Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent

Abstract

Disclosed herein is a method for preparing a dry regenerable sorbent which comprises the steps of obtaining a slurry through formulation, mixing, comminuting and dispersion of the sorbent raw materials, forming the slurry by spray drying to produce sorbent particles, and calcining the sorbent particles. In the step of obtaining a slurry, there is used organic additives (dispersant, a flow control agent, and an organic binder) necessary to obtain a well-dispersed, stable and free-flowing slurry in which the raw materials are present below a sub-micron level (nanosize). The organic additives are removed and decomposed through the calcining. The use of the hydrophilic and high specific surface area support allows the dry regenerable sorbent to have a high reactivity. The solid active component is used instead of a liquid amine used in a conventional wet carbon dioxide capture technology. In addition, the sorbent can be re-used through continuous sorption and regeneration processes.

Claims

1. A method for preparing a dry regenerable sorbent for carbon dioxide capture from flue gas produced by fossil fuel-fired power plants including industrial boilers before being released to atmosphere or from fuel gas stream produced by conversion of fossil fuel, by dry regenerable sorbent technology,

wherein the method comprises the steps of:

1) sequentially or simultaneously adding solid raw materials of the sorbent to water with stirring using a mixer or homogenizer to form a mixture;

2) adding a dispersant to the mixture such that the solid raw materials are well mixed with and dispersed in the water without agglomeration and adding a defoamer to the mixture to remove bubbles or prevent the formulation of bubbles during the stirring and homogenization;

3) wet-comminuting using at least one mill selected from roller mills, ball mills, attrition mills, vibratory mills, planetary mills and bead mills and homogenizing to obtain a well-dispersed colloidal slurry;

4) controlling a concentration of the slurry within the range of 15˜

50 wt %;

5) sieving an impurity impeding the dispersion and stability of the slurry and obstructing or plugging the spray of slurry from a nozzle or an atomizer;

6) forming the slurry to produce sorbent particles using a spray dryer; and

7) pre-drying and calcining the sorbent particles to prepare the final sorbent, wherein the sorbent comprises;

solid raw materials comprising;

10˜

60 wt % of an active component selected from carbonates or bicarbonates of sodium or potassium;

15˜

40 wt % of a support selected from solid porous non-metallic materials hydrophilic and capable of imparting a required specific surface area to the sorbent; and

10˜

60 wt % of an inorganic binder selected from cement-like, clay-like, and ceramic-like binders capable of imparting mechanical strength to the sorbent, wherein the total weight of the solid raw materials is 100 wt %, and wherein the purity of active component is 98% or higher, and wherein the sorbent has a spherical shape, a specific surface area of 20 m²/g or more, and a porosity of 30% or more, bulk density of 0.4 g/ml or more, a carbon dioxide sorption capacity of 3% or more, a utilization efficiency of 7% or more, an attrition index (Al) of 90% or less, an average particle size of 60˜

160 μ

m, and a particle size distribution of 40˜

300 μ

m, and wherein the sorbent is used to capture and separate carbon dioxide in a fluidized-bed or transport absorber and a fluidized-bed or transport regenerator at a temperature range of 40˜

200°

C.

2. The method according to claim 1, wherein the mixer or homogenizer has a speed of 50 rpm˜

30,000 rpm, and is at least one machine selected from mechanical stirrers, double-helix mixers, modular homogenizers, blenders, and ultrasonic homogenizers.

3. The method according to claim 1, wherein the dispersant contains a flow control agent;

is at least one surfactant selected from nonionic and anionic surfactants compatible with water; and

is added in an amount of 0.01˜

10 wt %, based on the total weight of the solid raw materials.

4. The method according to claim 1, wherein the defoamer is at least one material selected from silicon, metallic soaps, polyethers, polyesters, polyglycols, organic phosphates, higher alcohols, and sulfuric acid;

and is added in an amount of 0.001˜

1 wt %, based on the total weight of the solid raw materials of the sorbent, in order to inhibit the formation of bubbles by the use of the dispersant or by stirring or to break the bubbles.

5. The method according to claim 1, wherein the mixed slurry is wet-comminuted using a high-energy bead mill so as to allow the solid raw materials to have an average particle size of 1 μ

m or less, and dispersed to obtain a well-dispersed and uniform colloidal slurry.

6. The method according to claim 1, further comprising the step of adding 0.5˜

5 wt % of an organic binder to the colloidal slurry, based on the total weight of the solid raw materials of the sorbent.

7. The method according to claim 6, wherein the organic binder is at least one binder selected from polyvinyl alcohols, polyethyleneglycols, and methylcelluloses.

8. The method according to claim 1, further comprising the step of aging the slurry for better dispersion, homogeneity and stability of the slurry, before or after the sieving step.

9. The method according to claim 1, wherein the slurry free of impurity is transferred to a spray drier and spray-dried through a nozzle or an atomizer to form the sorbent particles.

10. The method according to claim 1, wherein the pre-drying is carried out at 110˜

150°

C. and the calcination is carried out at 350˜

900°

C.

11. The method according to claim 1, wherein the spray-dried or pre-dried green body is used as a raw material to prepare a sorbent in the shape of granule, extruding, pellet or honeycomb.