Disassociation processing of metal oxides

Abstract

The invention relates to systems and processes for recovery and/or extraction of metal values from ore or other raw material containing oxides of the metal and to precipitation of oxides of metals that have oxidation states and/or pollutant loading capacities equal to or greater than that of the metal oxides in the ore or other raw material which are suitable, amongst other uses, as a sorbent for capture and removal of target pollutants from industrial and other gas streams. Further, the invention relates to oxides of metals so recovered and precipitated.

What is claimed is:  
     
         1 . A method for rapid and adaptive recovery of metal values as precipitates of oxides of metals having loading capacities and/or oxidation states equal to or greater than that of the metal oxides in the ore or other raw material, comprising: 
 leaching metal values from ore or other metal oxide containing material to form a solution containing cations and anions of disassociated metal salts;    heating the solution containing cations and anions of disassociated metal salts;    mixing the heated solution containing cations and anions of disassociated metal salts and a heated aqueous oxidizing solution in a precipitation vessel to form a solution mixture, the heated aqueous oxidizing solution being prepared so as to have Eh and pH values within the metal oxide stability area of an aqueous solution heated to a temperature at or near boiling temperature at atmospheric pressure and being heated to a temperature at or near the boiling temperature;    monitoring and adjusting the temperature, Eh value and pH value of the solution mixture so as to rapidly move mixture conditions into and to maintain them within the metal oxide stability area; and    maintaining the solution conditions within the metal oxide stability area so as to precipitate the metal cations out of solution as precipitated oxides of metal having loading capacities and/or average oxidation states equal to or greater than that of the metal oxides in the ore or other raw material.    
     
     
         2 . A method for rapid and adaptive recovery of manganese values as precipitates of oxides of manganese having loading capacities and/or oxidation states equal to or greater than that of the oxides of manganese in the ore or other raw material, comprising: 
 leaching manganese values from ore or other metal oxide containing material to form a solution containing cations and anions of disassociated manganese salts;    heating the solution containing cations and anions of disassociated manganese salts;    mixing the heated solution containing cations and anions of disassociated manganese salts and a heated aqueous oxidizing solution in a precipitation vessel to form a solution mixture, the heated aqueous oxidizing solution being prepared so as to have Eh and pH values within the MnO2 stability area of an aqueous solution heated to a temperature at or near boiling temperature at atmospheric pressure and being heated to a temperature at or near the boiling temperature;    monitoring and adjusting the temperature, Eh value and pH value of the solution mixture so as to rapidly move mixture conditions into and to maintain them within the MnO2 stability area; and    maintaining the solution conditions within the MnO2 stability area so as to precipitate the manganese cations out of solution as precipitated oxides of manganese having loading capacities and/or average oxidation states equal to or greater than that of the oxides of manganese in the ore or other raw material.    
     
     
         3 . The method of any one of claims  1 - 2 , further comprising the step: 
 maintaining solution or solution mixture pH constant throughout the processing cycle.    
     
     
         4 . The method of  claim 1  further comprising the steps of: 
 separating the oxides of metal from the aqueous oxidizing solution to provide separated oxides of metal and a oxidation filtrate, the oxidation filtrate being routed for further processing and handling;  
 rinsing and filtering the separated oxides of metal to provide rinsed oxides of metal and a rinse filtrate, the rinse filtrate being directed for further handling and processing;  
 optionally, drying and/or comminuting the rinsed oxides of metal.  
 
     
     
         5 . The method of  claim 2  further comprising the steps of: 
 separating the oxides of manganese from the aqueous oxidizing 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 directed further handling and processing;  
 optionally, drying and/or comminuting the rinsed oxides of manganese.  
 
     
     
         6 . The method of any one of claims  1 - 2 , wherein the aqueous oxidizing solution contains an oxidant or oxidizer compatible with chemicals used to adjust the pH.  
     
     
         7 . The method of any one of claims  1 - 2 , wherein the aqueous oxidizing solution contains an oxidant or oxidizer selected from the group consisting of persulfates, chlorates, perchlorates, permanganates, peroxides, hypochlorites, oxygen, air, and ozone (O3).  
     
     
         8 . The method of  claim 1 , wherein temperature, Eh and pH are maintained within the metal oxide stability area for a period ranging from about 20 to about 70 minutes.  
     
     
         9 . The method  claim 2 , wherein temperature, Eh and pH are maintained within the MnO2 stability area for a period ranging from about 20 to about 70 minutes.  
     
     
         10 . The method of  claim 1 , wherein temperature, Eh and pH are maintained within the metal oxide stability area for a period ranging from about 35 to about 55 minutes.  
     
     
         11 . The method of  claim 2 , wherein temperature, Eh and pH are maintained within the MnO2 stability area for a period ranging from about 35 to about 55 minutes.  
     
     
         12 . The method of  claim 1 , wherein temperature, Eh and pH are maintained within the metal oxide stability area for a period ranging from about 40 to about 50 minutes.  
     
     
         13 . The method of  claim 2 , wherein temperature, Eh and pH are maintained within the MnO2 stability area for a period ranging from about 40 to about 50 minutes.  
     
     
         14 . Oxides of metal produced by a method of rapid and adaptive recovery of metal values as precipitates of oxides of metals having loading capacities and/or oxidation states equal to or greater than that of the metal oxides in the ore or other raw material, the method comprising the steps of: 
 leaching metal values from ore or other metal oxide containing material to form a solution containing cations and anions of disassociated metal salts;    heating the solution containing cations and anions of disassociated metal salts;    mixing the heated solution containing cations and anions of disassociated metal salts and a heated aqueous oxidizing solution in a precipitation vessel to form a solution mixture, the heated aqueous oxidizing solution being prepared so as to have Eh and pH values within the metal oxide stability area of an aqueous solution heated to a temperature at or near boiling temperature at atmospheric pressure and being heated to a temperature at or near the boiling temperature;    monitoring and adjusting the temperature, Eh value and pH value of the solution mixture so as to rapidly-move mixture conditions into and to maintain them within the metal oxide stability area; and    maintaining the solution conditions within the metal oxide stability area so as to precipitate the metal cations out of solution as precipitated oxides of metal having loading capacities and/or oxidation states equal to or greater than that of the metal oxides in the ore or other raw material.    
     
     
         15 . Oxides of manganese produced by a method of rapid and adaptive recovery of manganese values as precipitates of oxides of manganese having loading capacities and/or oxidation states equal to or greater than that of the metal oxides in the ore or other raw material, the method comprising: 
 leaching manganese values from ore or other raw material to form a solution containing cations and anions of disassociated manganese salts;    heating the solution containing cations and anions of disassociated manganese salts;    mixing the heated solution containing cations and anions of disassociated manganese salts and a heated aqueous oxidizing solution in a precipitation vessel to form a solution mixture, the heated aqueous oxidizing solution being prepared so as to have Eh and pH values within the MnO2 stability area of an aqueous solution heated to a temperature at or near boiling temperature at atmospheric pressure and being heated to a temperature at or near the boiling temperature;    monitoring and adjusting the temperature, Eh value and pH value of the solution mixture so as to rapidly move mixture conditions into and to maintain them within the MnO2 stability area; and    maintaining the solution conditions within the MnO2 stability area so as to precipitate the manganese cations out of solution as precipitated oxides of manganese having loading capacities and/or oxidation states equal to or greater than that of the oxides of manganese in the ore or other raw material.    
     
     
         16 . The oxides of metal of  claim 14 , wherein the method further comprises the step of maintaining solution or solution mixture pH constant throughout the processing cycle.  
     
     
         17 . The oxides of manganese of  claim 15 , wherein the method further comprises the step of maintaining solution or solution mixture pH constant throughout the processing cycle.  
     
     
         18 . The oxides of metal of  claim 14 , wherein the method further comprises the steps of: 
 separating the oxides of metal from the aqueous oxidizing solution to provide separated oxides of metal and a oxidation filtrate, the oxidation filtrate being routed for further processing and handling;    rinsing and filtering the separated oxides of metal to provide rinsed oxides of metal and a rinse filtrate, the rinse filtrate being directed for further handling and processing; and    optionally, drying and/or comminuting the rinsed oxides of metal.    
     
     
         19 . The oxides of manganese of  claim 15 , wherein the method further comprises the steps of: 
 separating the oxides of manganese from the aqueous oxidizing 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 directed further handling and processing; and    optionally, drying and/or comminuting the rinsed oxides of manganese.    
     
     
         20 . The oxides of metal of  claim 14 , wherein the aqueous oxidizing solution contains as oxidant or oxidizer selected from the group consisting of persulfates, chlorates, perchlorates, permanganates, peroxides, hypochlorites, oxygen, air, and ozone (O3).  
     
     
         21 . The oxides of manganese of  claim 15 , wherein the aqueous oxidizing solution contains as oxidant or oxidizer selected from the group consisting of persulfates, chlorates, perchlorates, permanganates, peroxides, hypochlorites, oxygen, air, and ozone (O3).  
     
     
         22 . The oxides of metal of  claim 14 , wherein temperature, Eh and pH are maintained within the metal oxide stability area for a period ranging from about 20 to about 70 minutes.  
     
     
         23 . The oxides of manganese of  claim 15 , wherein temperature, Eh and pH are maintained within the MnO2 stability area for a period ranging from about 20 to about 70 minutes.  
     
     
         24 . The oxides of metal of  claim 14 , wherein temperature, Eh and pH are maintained within the metal oxide stability area for a period ranging from about 35 to about 55 minutes.  
     
     
         25 . The oxides of manganese of  claim 15 , wherein temperature, Eh and pH are maintained within the MnO2 stability area for a period ranging from about 35 to about 55 minutes.  
     
     
         26 . The oxides of metal of  claim 14 , wherein temperature, Eh and pH are maintained within the metal oxide stability area for a period ranging from about 40 to about 50 minutes.  
     
     
         27 . The oxides of manganese of  claim 15 , wherein temperature, Eh and pH are maintained within the MnO2 stability area for a period ranging from about 40 to about 50 minutes.  
     
     
         28 . A system for rapid and adaptive recovery of metal values as precipitates of oxides of metal having loading capacities and/or oxidation states equal to or greater than that of the metal oxides in the ore or other raw material, the system comprising: 
 a well bore hole for injecting a leaching solution; a leaching solution injector;    a well bore hole for recovering a solution containing cations and anions of disassociated metal salts;    solution recovering equipment; a precipitation vessel equipped with probes for measuring temperature, Eh and pH values of aqueous solutions within the precipitation vessel, the precipitation vessel being configured for introduction of a solution containing cations and anions of disassociated metal salts;    a oxidant feeder containing a supply of aqueous oxidizing solution, the aqueous oxidizing solution being prepared so as to have Eh and pH values within the metal oxide stability area for an aqueous solution heated to a temperature at or near boiling temperature at atmospheric pressure;    a heater for providing heat to the precipitation vessel;    a base and/or acid feeder for feeding base or acid to the precipitation vessel;    at least one filtration and/or rinse unit, which optionally may be incorporated into and a part of the precipitation vessel; and    a controller for simultaneously monitoring and adjusting system operational parameters and regulating system components, the controller being in electronic communication with the probes of the precipitation vessel, the feeders, the at least one filtration and/or rinse unit and the heaters; the controller being capable of monitoring and adjusting system operational parameters selected from the group consisting of temperature, Eh, pH and feeder rates so as maintain conditions in the oxidation vessel within the metal oxide stability area through processing cycles.    
     
     
         29 . A system for rapid and adaptive recovery of manganese values as precipitates of oxides of manganese having loading capacities and/or oxidation states equal to or greater than that of the metal oxides in the ore or other raw material, the system comprising; 
 a well bore hole for injecting a leaching solution; a well bore hole for recovering a solution containing cations and anions of disassociated manganese salts; solution recovering equipment; a leaching solution injector; a precipitation vessel equipped with probes for measuring temperature, Eh and pH values of aqueous solutions within the precipitation vessel, the precipitation vessel being configured for introduction of a solution containing cations and anions of disassociated manganese salts;    a oxidant feeder containing a supply of aqueous oxidizing solution, the aqueous oxidizing solution being prepared so as to have Eh and pH values within the MnO2 stability area for an aqueous solution heated to a temperature at or near boiling temperature at atmospheric pressure;    a heater for providing heat to the precipitation vessel;    a base and/or acid feeder for feeding base or acid to the precipitation vessel;    at least one filtration and/or rinse unit, which optionally may be incorporated into and a part of the precipitation vessel; and    a controller for simultaneously monitoring and adjusting system operational parameters and regulating system components, the controller being in electronic communication with the probes of the precipitation vessel, the feeders, the at least one filtration and/or rinse unit and the heaters; the controller being capable of monitoring and adjusting system operational parameters selected from the group consisting of temperature, Eh, pH and feeder rates so as maintain conditions in the oxidation vessel within the MnO2 stability area through processing cycles.