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CE 370 Iron and Manganese Removal Fe++ and Mn++ Ferrous iron Fe++ and manganous manganese Mn++ are soluble invisible When exposed to air, they are oxidized to ferric iron Fe+++ and manganic manganese Mn++++, which are: insoluble visible Oxidation The oxidation rate depends on: pH alkalinity organic content presence of oxidizing agents If not removed from water, iron and manganese oxides create problem of brown color formation. Oxidation Reduced iron in water promotes the growth of autotrophic bacteria in distribution mains. Elimination of iron bacteria is difficult and expensive. When decays, iron bacteria release foul taste and odor. Heavy chlorination followed by flushing proved to be successful in some case. Removal of iron and manganese from water is the best solution to that problem. Oxidation of Iron and Manganese with Oxygen, Chlorine, and Chlorine Dioxide 4 Fe 2 O2 10 H 2O 4 Fe(OH ) 3 8 H 2 Fe 2 Cl2 6 H 2O 2 Fe(OH ) 3 6 H 2Cl Fe 2 ClO2 3H 2O Fe(OH ) 3 ClO2 3H 2 Mn 2 O2 2 H 2O 2 MnO2 4 H Mn 2 Cl2 2 H 2O MnO2 4 H 2Cl Mn 2 2ClO2 2 H 2O MnO2 2ClO2 4 H Treatment Alternatives Aeration, Sedimentation, and Filtration Aeration (air oxidation) is the simplest treatment in removing iron. The reaction that takes place is in the form of: Fe++(ferrous) + oxygen FeOx (ferric oxide) Soluble iron Insoluble iron Air oxidation can not remove manganese effectively. Increasing the pH to 8.5 can enhance the oxidation process. If manganese was not effectively removed from the water, it can cause problems with postchlorination. When oxidized: it can clog the solution-feed chlorinator it cause a staining water Aeration, Chemical Oxidation, Sedimentation, and Filtration This is a common method for removing iron and manganese from well water without softening treatment. Preliminary aeration strips out dissolved gases and adds oxygen. Iron and manganese are oxidized by free chlorine residual: Fe++ + Mn++ + Oxygen FeOx + MnO2 Soluble ions Insoluble metal oxides or by potassium permanganate Fe(HCO3)2 + KMnO4 Fe(OH)3 + MnO2 Ferrous bic. Potas. Perm. Ferric Hydrx. Mang. Diox. Mn(HCO3)2 + KMnO4 MnO2 Manganous bic Potas Perm Mang. Diox. Potassium permanganate oxidizes iron and manganese at rates faster than dissolved oxygen and its reaction is relatively pH independent. Since iron and manganese can not be completely removed by sedimentation, effective filtration is required. Manganese Zeolite Process Manganese zeolite is a natural greensand coated with manganese dioxide. It has the capability to remove iron and manganese from solution. When manganese zeolite becomes saturated with metal ions, it can be generated using potassium permanganate. A continuos flow diagram is shown in the following Figure. Reaction Equations Oxidation Z MnO2 Fe2 Z Mn2O3 Fe3 Z MnO2 Mn 2 Z Mn2O3 Mn 3 Re generation Z Mn2O3 KMnO4 Z MnO2 Manganese Zeolite Process KMnO4 is applied prior to filtration. The filter is a dual-media filter with anthracite is placed on top of the manganese zeolite. Iron and manganese are oxidized by KMnO4. The upper layer will remove the insoluble metal ions. Any iron and manganese ions not oxidized, it will be captured by the lower layer of manganese zeolite. Any surplus KMnO4 will regenerate the greensand. When the bed becomes saturated, it is backwashed by KMnO4 to remove particles from the upper layer and regenerate the greensand. Water Softening Lime and soda ash, which are used in water softening, can remove iron and manganese from water. Biological Treatment New process In the form of filters that support: Two separate filters are used pH and dissolved oxygen of the feed are critical Filtration rates are: Iron-oxidizing bacteria Manganese-oxidizing bacteria 25 to 40 m/h for iron 10 to 40 m/h for manganese Coarse sand is used Sequestering Sequestering agents are used Agents are added: Sodium silicates Phosphates polyphosphates In the form of colloidal complexes to bind iron and manganese and prevent them from forming color and turbidity In distribution system Chlorine is added simultaneously to oxidize iron and manganese Normal doses of silicates are 5 to 25 mg/l as SiO2 Iron is sequestered more with silicates than manganese