Clay composites for the removal of SO.sub.x from flue gas streams

• US 5,126,300 A
• Filed: 06/24/1991
• Issued: 06/30/1992
• Est. Priority Date: 07/16/1990
• Status: Expired due to Term

• Current Assignee: Board of Trustees
• Original Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Pinnavaia, Thomas J., Amarasekera, Jayantha, Polansky, Christine A.
• Primary Examiner(s): DEES, CARL
• Application Number:
  US07/719,987
• Time in Patent Office: 372 Days
• Field of Search: 502/84
• US Class Current: 502/84
• CPC Class Codes: B01D 53/508 by treating the gases with solids
• CPC Class Codes: B01J 20/12 Naturally occurring clays or bleaching earth
• CPC Class Codes: B01J 21/16 Clays or other mineral silicates
• CPC Class Codes: B01J 37/0207 Pretreatment of the support
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: C01B 33/44 Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material

Abstract

A method for preparing smectite clay alkaline earth metal hydroxide and carbonate composite materials is described. The method uses low amounts of the clay added to water to which is added calcium oxide or calcium hydroxide. Optionally the calcium carbonate is formed in situ by exposure to air or to carbon dioxide in the solution. The product is dried to form the composite material which is used to remove SO_x from flue gases.

Claims

1. A method for preparing a composite material useful for SO_x removal from the flue gas of a coal-burning power plant and other gas streams which comprises:

(a) providing a suspension of a smectite clay containing 0.1 to 5% by weight of clay in water;

(b) adding a basic material selected from the group consisting of alkaline earth metal oxides and hydroxides to the clay suspension to provide a resulting suspension;

(c) mixing the resulting suspension;

(d) recovering a precipitate from the resulting suspension; and

(e) drying the precipitate at a temperature between 100°

-120°

C. to provide the composite material, wherein when the composite material is heated to a temperature of 500°

C. or above, the SO_x components from a gas stream are removed by the composite material upon contacting with the said gas stream at that temperature.

2. The method of claim 1 wherein the weight ratio of the basic material to clay in the composite material is between 1:

1 and 10;

1.

3. A method in accordance with claim 1 wherein the composite material is dried as a cake, crushed, and then sieved to separate desired mesh size ranges.

4. A method in accordance with claim 1 wherein the smectite clay is selected from the group consisting of montmorillonite, fluorohectorite, bentonite, nontronite, hectorite, saponite, and beidellite, preferably in Na⁺ exchanged form.

5. A method in accordance with claim 1 wherein the alkaline earth metal is selected from the group consisting of magnesium and calcium.

6. A method in accordance with claim 1 wherein the composite material is substantially in Ca(OH)₂ with minor amounts of CaCO₃ as the basic material.

7. A method for preparing a composite material useful for SO_x removal from the flue gas of a coal-burning power plant and other gas streams which comprises:

(a) providing a suspension of a smectite clay containing 0.1 to 5% by weight of clay in water;

(b) adding a basic material selected from the group consisting of alkaline earth metal oxides and hydroxides to the clay suspension to provide a resulting suspension;

(c) mixing the resulting suspension by stirring with CO₂ gas present in water to convert at least some of the basic material to alkaline metal carbonate;

(d) recovering a precipitate from the resulting suspension; and

(e) drying the precipitate in air at ambient temperatures to provide the composite material, wherein when the composite material is heated to a temperature of 500°

C. or above, the SO_x components from a gas stream are removed by the composite material upon contacting with the said gas stream at that temperature.

8. The method of claim 7 wherein basic weight ratio of the basic material to clay in the composite material is between 1:

1 and 10;

1.

9. A method in accordance with claim 7 wherein the composite mateiral is dried in a cake, crushed, and then sieved to separate desired mesh size ranges.

10. A method in accordance with claim 7 wherein the smectite clay is selected from the group consisting of montmorillonite, fluorohectorite, bentonite, nontronite, hectorite, saponite, and beidellite, preferably Na⁺ exchange form.

11. A method in accordance with claim 7 wherein the alkaline earth metal is selected from the group consisting of magnesium and calcium.

12. A method in accordance with claim 7 wherein the composite material is substantially CaCO₃ with minor amounts of Ca(OH)₂ as the basic material.

13. A method for preparing a composite material useful for SO_x removal from the flue gas of a coal-burning power plant and other gas streams which comprises:

(a) providing a suspension of a smectite clay containing 0.1 to 5% by weight of clay in water;

(b) adding a basic material seelcted from the group consisting of alkaline earth metal oxides and hydroxides to the clay suspension as a resulting suspension;

(c) mixing the resulting suspension by stirring while bubbling CO₂ gas through the suspension to convert at least some of the basic material to alkaline metal carbonate in the resulting suspension;

(d) recovering a precipitate from the water by filtration or by centrifugation; and

(e) drying the precipitate in air at ambient temperatures or in an oven at 110°

C. to prvoide the composite material, wherein when the composite material is heated to a temperature of 500°

C. or above, the SO_x components from a gas stream are removed by the composite material upon contacting with the said gas stream at that temperature.

14. The method of claim 13 wherein the basic compound weight ratio of basic material to clay in the composite is between 1:

1 and 10;

1.

15. A method in accordance with claim 13 wherein the composite material is dried in a cake, crushed, and then sieved to separate the desired mesh sizes.

16. A method in accordance with claim 13 wherein the smectite clay is selected from the group consisting of montmorillonite, fluorohectorite, bentonite, nontronite, hectorite, saponite, and beidellite, preferably in Na⁺ exchange form.

17. A method in accordance with claim 13 wherein the alkaline earth metal is selected from the group consisting of magnesium and calcium.

18. A method in accordance with claim 13 wherein the composite is substantially in calcium carbonate with minor amounts of calcium hydroxide as the basic material.