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Dr. Akepati S. Reddy Associate Professor, Thapar University Dept. Biotechnology & Environmental Sciences Patiala (PUNJAB) -147 004 INDIA
Chemical Precipitation
Involves addition of chemicals to alter physical state of dissolved and suspended solids and removal by settling Used for
Improving the performance of primary settling facilities Removal of phosphorus and heavy metals
For the precipitation to occur mineral acids and acid salts must be first neutralized for the precipitation formation
Ferrous sulfate
In most cases, it should be added along with lime Reacts with calcium bicarbonate of wastewater and form ferrous bicarbonate and calcium sulfate (soluble)
Ferrous bicarbonate combines with lime and form ferrous hydroxide and calcium carbonate
Dissolved oxygen oxidizes the ferrous hydroxide into ferric hydroxide (which forms insoluble), bulky gelatinous floc
1 1 Fe(OH ) 2 O2 H 2 O Fe(OH ) 3 4 2
Every 10 grams of ferrous sulfate added may require 3.6 grams of alkalinity, 4 g of lime and and 0.29 grams of oxygen
Typically 80-90% of suspended solids (also some colloidal solids), 50-80% of BOD and 80-90% of bacteria are removed
Well operated primary settling tank gives about 50-70% TSS removal, 25-40% BOD removal, & 25-75% bacteria removal
For clarification of various chemical suspensions overflow rates in the settling tanks can be in the range of 30-70 m3/m2.day (80 m3/m2.day for peak flow)
for lime floc the overflow range can be 35-80 m3/m2.day (90 m3/m2.day for peak flow)
Output from the activated carbon column is usually chlorinated prior to discharge into receiving waters
For precipitation as hydroxides lime/caustic is added to adjust pH to minimum metal solubility (varies with metal)
Location of minimum solubility also vary with and depend on the constituents in the wastewater
Minimal concentration in effluent depends on concentration and nature of organic matter and temperature
Ammonia can be removed by stripping, break point chlorination Hexavalent chromium must be reduced to trivalent chromium prior to precipitation with lime Arsenic and cadmium can be better removed if coprecipitated with iron or aluminum (metal adsorbs to the alum or iron floc) Filtration can be used to remove the floc carried over from the precipitation process (can reduce metal level in the effluent from >1 to 2 mg/l to <0.5 mg/l Carbamate salts can be used as a polishing step after conventional precipitation for enhancing metal removal
Copper Mercury
Barium
Removed as barium sulfate Solubility of barium can be reduced to very low level (0.03 to 0.3 mg/l) in the presence of excess sulfate
Cadmium
Forms insoluble and stable hydroxide precipitate at alkaline pH (1 mg/l concentration at 8 pH and 0.05 at 10-11 pH) Sulfide and lime precipitation with filtration can reduce concentration to 0.002 to 0.03 mg/l at 8.5-10 pH Co-precipitation with iron hydroxide reduces concentration to 0.05 mg/l at 8.5 pH, and 0.008 mg/l at 6.5 pH Cyanide interference requires prior cyanide destruction hydrogen peroxide oxidation-precipitation system can be used for simultaneous cyanide oxidation and cadmium precipitation
Iron
Iron form depends on pH and DO of the wastewater At 7.5 pH in the presence of oxygen ferrous iron is converted to ferric iron and removed as ferric hydroxide At higher pH ferric hydroxide solubilizes through formation of Fe(OH)4- complex Ferrous and ferric iron are solubilized in the presence of cyanide by formation of ferro and ferricyanide complexes
Manganese
Only manganous salts and highly oxidized permanganate anions are appreciably soluble in wastewaters Being a strong oxidant, permanganate under normal circumstances is converted into insoluble manganese dioxide Removal involves conversion of the soluble manganous ion into insoluble oxide and hydroxide precipitate Air oxidation: significant at >9.4 pH Presence of copper enhances oxidation organic matter interferes with oxidation Oxidation by chemical oxidants: Chlorine dioxide, ozone in conjunction with lime or permanganate can be used
Nickel
In the presence of cyanide like complexing agents nickel exists in the soluble form With lime at 10-11 pH through forming hydroxide solubility is reduced to 0.12 mg/l Nickel hydroxide has poor settling properties precipitation with lime at 11.5 pH and sedimentation and filtration removal of precipitate reduces nickel to 0.15 mg/l level Can also be precipitated as carbonate or sulfate
Silver
Removed to 1.4 mg/l level as silver chloride precipitate at 25C excess of chloride through forming silver chloride complexes increases solubility of silver Acid wash of silver chloride precipitate can remove other contaminant metal ions from it and facilitate silver recovery Silver cyanide interferes with the chloride precipitation the interference can be taken care off by cyanide oxidation with chlorine Hydroxide precipitation reduces silver to 0.02 mg/l level at 11 pH Silver sulfide is extremely insoluble Alum or iron co-precipitation can reduce silver to 0.025 mg/l
Chromium
Ferrous sulfate, sodium meta-bisulfite or sulfur dioxide are used as reducing agents for reducing chromium from hexavalent to trivalent forms
Cr 3 3OH Cr (OH ) 3
Reduction of chromium is most effective at acidic pH and hence a reducing agent with acidic properties is preferred
Acid requirement may be estimated through experimentation At pH 8-9.9 reduced chromium is virtually insoluble and forms 1-2% consistency sludge
Sludge formed can be dewatered and dried in sludge drying beds
Presence of DO which transforms sulfite to sulfate necessitates 35 ppm excess SO2 dosing
Hence dose of alum or iron can not be directly estimated dose estimation requires bench scale tests Polymers can be used as flocculation aids
Theoretically minimum solubility for AlPO4 is at about 6.3 pH, for FePO4 it is at about 5.3 pH
But good removals are achieved in 6.5 to 7.0 pH range
Post-precipitation process chemical dosing to clarified secondary effluent and removal of precipitate by filtration/sedimentation
Use of ferrous salts is limited because they require high pH values for producing low phosphorus levels Dosage may be 1-3 metal ion-phosphorus molar ratio Polymers can added to the inlet of secondary clarifier Adsorption, exchange and agglomeration may also assist in the removal process
Though minimum solubility of AlPO4 is at 6.3 pH and of FePO4 is at 5.3 pH, good phosphate removal is achieved at 6.5-7.0 pH Can result in improved settling and lower BOD in treated effluent
Dosing metal salts to the inlet of secondary clarifier can be very helpful both for phosphorus and TSS removal specially when phosphorus is >0.5 mg/l in the effluent
Dose is 1 to 3 metal ion/phosphorus on molar ratio basis Use of polymers can further enhance the removal process
Sufficient lime is dosed to raise pH above 11, to precipitate phosphorus as calcium phosphate (apatite) and to remove TSS by the calcium carbonate precipitate
Settling removes the precipitates
If precipitate formed from recarbonation is more for filtration, then two stage recarbonation is practiced
First stage recarbonation to bring pH to about 10 and remove flocs in a settling tank Second stage recarbonation to bring back the pH to normal level and remove flocs through filtration
Phosphorus levels < 0.02 mg/l can be achieved in the filtered effluent
Advantages and disadvantages of chemical addition in various sections of treatment plant for phosphorus removal
Section of treatment Primary Advantages Increased BOD and SS removal Lowest degree of metal leakage Lime recovery demonstrated Lowest cost because of lower chemical dose and polymer is not required Improved stability of the activated sludge Disadvantages Least efficient use of metal salt and polymer Sludge is more difficult to dewater than primary sludge Overdose of metal salt can cause low pH and toxicity Lime because of high pH needed can not be used Inert solids become part of activated sludge Highest capital cost Highest metal leakage
Secondary
Advanced precipitation
Lowest phosphorus in the effluent Most efficient use of metal Demonstrated lime recovery Low cost Length of filter run is reduced Improved removal of 2-stage filtration can increase residual suspended solids cost
With Alum
2 Al 3 3OH Al (OH ) 3
With Fe(III)
The precipitate contains FePO4 and Fe(OH)3
3 Fe3 PO4 FePO4
3 Al 3 PO4 AlPO4