Oxides of Manganese Processed in Continuous Flow Reactors

Abstract

Methods and systems for regenerating and pretreating oxides of manganese and precipitation of oxides of manganese from manganese salt solutions. Oxides of manganese, a slurry containing oxides of manganese or manganese salt solutions are mixed with heated aqueous oxidizing solutions and processed in a continuous process reactor. Temperature, pressure, Eh value, and pH value of the mixed solution are monitored and adjusted so as to maintain solution conditions within the MnO 2 stability area during processing. This results in regenerated, pretreated and precipitated oxides of manganese having high or increased pollutant loading capacities and/or oxidation states. Oxides of manganese thus produced are, amongst other uses; suitable for use as a sorbent for capturing or removing target pollutants from industrial gas streams. Filtrate process streams containing useful and recoverable value present as spectator ions may be further processed to produce useful and marketable by-products.

1 . A method for rapid and adaptive processing of oxides of manganese, comprising the steps of:
 a. providing a manganese containing solution selected from the group consisting of a slurry of virgin oxides of manganese, a regeneration slurry containing rinsed reacted oxides of manganese, a slurry of loaded oxides of manganese containing disassociated manganese cations, a manganese salt solution containing disassociated manganese cations;   b. providing a aqueous oxidizing solution, the oxidizing solution being prepared to have Eh and pH values within a permanganate stability area or an MnO 2  stability area or to move solution conditions initially into the permanganate stability area or an MnO 2  stability area when contacted with the manganese containing solution;   c. feeding the manganese containing solution and the aqueous oxidizing solution into at least one continuous flow reactor, the solutions being fed either separately into the continuous flow reactor where they mix to form a combined mixed processing solution or being premixed and fed as a combined mixed processing solution;   d. heating the combined mixed processing solution to process temperature;   e. monitoring and adjusting combined mixed processing solution temperature, Eh value, pH value, molarity, and pressure within the continuous flow reactor so as to rapidly and adaptively move combined mixed processing solution conditions into and maintain processing solution conditions within the MnO 2  stability area; and   f. maintaining combined mixed processing solution conditions within the MnO 2  stability area as the combined mixed processing solution travels through the continuous flow reactor so as to produce oxides of manganese selected from the group comprising regenerated oxides of manganese, pretreated oxides of manganese, precipitated oxides, and regenerated and precipitated oxides of manganese.   
     
     
         2 . A method for rapid and adaptive processing of oxides of manganese, comprising the steps of:
 a. providing a heated manganese containing solution selected from the group consisting of a slurry of virgin oxides of manganese, a regeneration slurry containing rinsed reacted oxides of manganese, a slurry of loaded oxides of manganese containing disassociated manganese cations, a manganese salt solution containing disassociated manganese cations;   b. providing a heated aqueous oxidizing solution, the oxidizing solution being prepared to have Eh and pH values within a permanganate stability area or an MnO 2  stability area or to move solution conditions initially into the permanganate stability area or an MnO 2  stability area when contacted with the manganese containing solution;   c. feeding the manganese containing solution and the aqueous oxidizing solution into at least one continuous flow reactor, the solutions being fed either separately into the continuous flow reactor where they mix to form a combined mixed processing solution or being premixed and fed as a combined mixed processing solution;   d. monitoring and adjusting combined mixed processing solution temperature, Eh value, pH value, molarity, and pressure within the continuous flow reactor so as to rapidly and adaptively move combined mixed processing solution conditions into and maintain processing solution conditions within the MnO 2  stability area; and   e. maintaining combined mixed processing solution conditions within the MnO 2  stability area as the combined mixed processing solution travels through the continuous flow reactor so as to produce oxides of manganese selected from the group comprising regenerated oxides of manganese, pretreated oxides of manganese, precipitated oxides, and regenerated and precipitated oxides of manganese.   
     
     
         3 . The method of  claim 1  or  claim 2 , further comprising the step of heating the combined mixed processing solution within the continuous flow reactor to a temperature at or above 100° C. 
     
     
         4 . The method of  claim 1  or  claim 2 , further comprising the step of heating the combined mixed processing solution within the continuous flow reactor to a temperature above 100° C. after, wherein the manganese containing solution and the aqueous oxidizing solution are heated to a temperature of about 100° C. prior to being fed into the continuous flow reactor. 
     
     
         5 . The methods of  claim 1  or  claim 2 ; further comprising the steps of:
 separating the oxides of manganese from the processing solution to provide separated oxides of manganese and a oxidation filtrate, the oxidation filtrate being routed for further processing and handling; and   rinsing and filtering the separated oxides of manganese to provide rinsed oxides of manganese and a rinse filtrate, the rinse filtrate being directed further handling and processing.   
     
     
         6 . The methods of  claim 1  or  claim 2 ; further comprising the steps of:
 separating the oxides of manganese from the processing solution to provide separated oxides of manganese and a oxidation filtrate, the oxidation filtrate being routed for further processing and handling;   rinsing and filtering the separated oxides of manganese to provide rinsed oxides of manganese and a rinse filtrate, the rinse filtrate being directed further handling and processing; and   drying and/or comminuting the rinsed oxides of manganese.   
     
     
         7 . The methods of  claim 1  or  claim 2 ; further comprising the steps of:
 separating the oxides of manganese from the processing solution to provide separated oxides of manganese and a oxidation filtrate, the oxidation filtrate being routed for further processing and handling;   rinsing and filtering the separated oxides of manganese to provide a rinsed oxides of manganese filter cake or and a rinse filtrate, the rinse filtrate being directed further handling and processing; and   directing the filter cake to a filter cake feed for introduction into a reaction chamber of a pollutant removal system.   
     
     
         8 . The methods of  claim 1  or  claim 2 ; further comprising the steps of:
 separating the oxides of manganese from the processing solution to provide separated oxides of manganese and a oxidation filtrate, the oxidation filtrate being routed for further processing and handling;   rinsing and filtering the separated oxides of manganese to provide a rinsed oxides of manganese filter cake or and a rinse filtrate, the rinse filtrate being directed further handling and processing;   adding water to the rinsed oxides of manganese to form a oxides of manganese slurry; and   directing the oxides of manganese slurry to a feeder selected from the group consisting of slurry feeders, spray feeders, spray injection feeders for introduction into a reaction chamber of a pollutant removal system.   
     
     
         9 . The method  claim 1  or  claim 2 , wherein the aqueous oxidizing solution contains an oxidant or oxidizer selected from the group consisting of persulfates, chlorates, perchlorates, permanganates, peroxides, hypochlorites, organic oxidizers, oxygen, air, and ozone.