Pretreatment and regeneration of oxides of manganese

• US 7,041,270 B2
• Filed: 12/23/2002
• Issued: 05/09/2006
• Est. Priority Date: 12/21/2001
• Status: Expired due to Fees

• Current Assignee: Enviroscrub Technologies Corp.
• Original Assignee: Enviroscrub Technologies Corp.
• Inventors: Hammel, Charles F., Boren, Richard M., Tuzinski, Patrick A.
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US10/328,490
• Publication Number:
  US 20030219368A1
• Time in Patent Office: 1,233 Days
• Field of Search: 423/605
• US Class Current: 423/605
• CPC Class Codes: B01D 2253/1124 Metal oxides
• CPC Class Codes: B01D 2257/30 Sulfur compounds
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/502 Carbon monoxide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• 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 53/565 by treating the gases with solids
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01D 53/83 with moving reactants
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3475 in the liquid phase
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 23/92 of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: C22B 43/00 Obtaining mercury
• CPC Class Codes: C22B 47/0081 Treatment or purification of solutions, e.g. obtained by leaching C22B47/0054 takes precedence
• CPC Class Codes: C22B 47/009 : refining, e.g. separation of metals obtained by the above methods
• CPC Class Codes: C22B 7/006 : Wet processes
• CPC Class Codes: C22B 7/02 : Working-up flue dust
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02P 10/146 : Perfluorocarbons [PFC]; Hydrofluorocarbons [HFC]; Sulfur hexafluoride [SF6]
• CPC Class Codes: Y02P 10/20 : Recycling

Abstract

The invention relates to systems and processes for treating particulate oxides of manganese useful as oxidizing sorbents for capturing or removing target pollutants from industrial gas streams, including, but not limited to, nitrogen oxides (NO_x), sulfur oxide (SO_x), mercury (Hg), hydrogen sulfide (H₂S), other totally reduced sulfides (TRS), and oxides of carbon (CO and CO₂) gases. Oxides of manganese are washed an aqueous oxidizing solution, which may be adjusted as necessary to maintain the oxidizing solution a desired range of pH (acidity) and Eh (oxidizing potential) within the MnO₂ stability area for aqueous solutions. The resulting treated oxides of manganese are equally or more efficient as sorbents as the oxides of manganese processed with the invention.

Claims

1. A process for pretreatment of virgin oxides of manganese for use as a sorbent to remove target pollutants from a gas stream, comprising the steps of:

a. washing virgin oxides of manganese in wash unit with an aqueous oxidizing solution, the solution having Eh and pH values within the MnO₂ stability area; and

b. filtering the washed oxides of manganese to form a filtrate and a pretreated oxides of manganese filter cake, the oxides of manganese of the filter cake having a pollutant loading capacity greater than the pollutant loading capacity of the virgin oxides of manganese.

6. The process of any one of claims 1 to 5, further comprising the steps of:

drying the filter cake; and

comminuting and sizing the dried filter cake to provide oxides of manganese particles.

7. The process of any one of claims 1 to 5, further comprising the steps of:

drying the filter cake;

comminuting and sizing the dried filter cake to provide oxides of manganese particles for introduction into a feeder or reaction chamber of a dry pollution removal system.

8. The process of any one of claims 1 to 5, further comprising the steps of:

drying the filter cake;

comminuting and sizing the dried filter cake to provide oxides of manganese particles for introduction into a feeder or reaction chamber of a dry pollution removal system; and

introducing the comminuted and sized oxides of manganese particles into the feeder or reaction chamber.

9. The process of any one of claims 1–

5, further comprising the step of;

conveying the filter cake to a dryer configured to inject a wet filter cake or a slurry of oxides of manganese sorbent into a flow of a gas stream prior to introduction into a reaction chamber of a pollutant removal system.

10. The process of any one of claims 1–

5, further comprising the steps of;

conveying the filter cake to a dryer configured to inject a wet filter cake or a slurry of oxides of manganese sorbent into a flow of a gas stream prior to introduction into a reaction chamber of a pollutant removal system; and

injecting the wet filter cake or the slurry into the reaction chamber.

12. The process of anyone of claims 1–

5, wherein the aqueous oxidizing solution contains an oxidizer selected from the group consisting of hypochlorites, chlorates, perchlorates, permanganates, oxygen (O₂), air, ozone, peroxides, persulfates, and combinations thereof.

2. A process for pretreatment of virgin oxides of manganese for use as a sorbent to remove target pollutants from a gas stream, comprising the steps of:

a. washing virgin oxides of manganese in a wash unit with an aqueous oxidizing solution, the solution having Eh and pH values within the MnO₂ stability area;

b. monitoring and adjusting the pH and/or the Eh values of the solution so as to maintain the Eh and pH values of the solution within the MnO₂ stability area; and

c. filtering the washed oxides of manganese to form a filtrate and a pretreated oxides of manganese filter cake, the oxides of manganese of the filter cake having a pollutant loading capacity greater than the pollutant loading capacity of the virgin oxides of manganese.

11. The process of claim 2, wherein the monitoring and adjusting step is carried out by a controller capable of individually or simultaneously monitoring and adjusting system operational parameters, the controller providing integrated control within the wash unit of the temperature, Eh values, and pH values in order to maintain conditions of the aqueous oxidizing solution within the MnO₂ stability area.

3. A process for pretreatment of virgin oxides of manganese for use as a sorbent to remove target pollutants from a gas stream, comprising the steps of:

a. washing virgin oxides of manganese in a rapid filtration wash unit with an aqueous oxidizing solution to form a filtrate and a pretreated oxides of manganese filter cake, the solution having Eh and pH values within the MnO₂ stability area; and

b. removing the pretreated oxides of manganese filter cake from the rapid filtration unit, the oxides of manganese of the filter cake having a pollutant loading capacity greater that the pollutant loading capacity of the virgin oxides of manganese.

4. A process for regeneration of loaded oxides of manganese formed through reaction between unreacted oxides of a manganese and target pollutants in a gas stream, comprising the steps of:

a. washing loaded oxides of manganese in a rapid filtration wash unit with an aqueous oxidizing solution having Eh and pH values within the MnO₂ stability area to form a filtrate and a regenerated oxides of manganese filter cake; and

b. removing the regenerated oxides of manganese filter cake from the rapid filtration unit, the oxides of manganese of the filter cake having a pollutant loading capacity equal to or greater than the pollutant loading capacity of the unreacted oxides of manganese from which the loaded oxides of manganese are formed.

5. A process for regeneration of loaded oxides of manganese sorbent particles bearing a reaction product layer of the surface thereof formed during reaction between unreacted oxides of manganese sorbent particles and target pollutants in a gas stream in a pollution removal system, comprising the steps of:

a. rapidly washing and filtering the loaded oxides of manganese sorbent particles in a rapid filtration wash unit with an aqueous oxidizing solution to dissolve the reaction product layer from the surface of the loaded oxides of manganese sorbent particles into the solution to form a filtrate and a regenerated oxides of manganese filter cake, the solution having Eh and pH values within the MnO₂ stability area; and

b. removing the regenerated oxides of manganese filter cake from the rapid filtration unit, the oxides of manganese of the filter cake having a pollutant loading capacity equal to or greater than the pollutant loading capacity of the unreacted oxides of manganese sorbent particles from which the loaded oxides of manganese sorbent particles are formed.