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Chemical Precipitation

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

Improving performance of primary settling facilities


By chemical precipitation clear effluent devoid of suspended and colloidal solids can be obtained
Quantity of chemicals used and care of process control affect the degree of clarification obtained

Commonly used chemicals include


Alum - Al2(SO4)3.18H2O (or 14 H2O), Aluminum chloride AlCl3 Calcium hydroxide Ca(OH)2 Ferric chloride - FeCl3, Ferric sulfate - Fe2(SO4)3, Ferrous sulfate - FeSO4.7H2O Sodium aluminate - Na2Al2O4

Improving performance of primary settling facilities


Alum and aluminum chloride
Alum reacts with the calcium and magnesium bicarbonate alkalinity of water and forms aluminum hydroxide precipitate

3Ca ( HCO3 ) 2 Al 2 ( SO4 ) 3 .18 H 2 O 2 Al (OH ) 3 3CaSO4 6CO2 18 H 2 O


Aluminum chloride addition also forms similar precipitate Insoluble aluminum hydroxide forms gelatinous flocs that settle slowly, sweeping out suspended material Every 10 grams of alum added requires 4.5 grams of alkalinity (as CaCO3) If sufficient alkalinity is not available, lime is added to the wastewater

Improving performance of primary settling facilities


Lime (calcium hydroxide)
When sufficient lime is added then carbonic acid and calcium bicarbonate will precipitate as calcium carbonate
H 2CO3 Ca (OH ) 2 CaCO3 2 H 2O Ca ( HCO3 ) 2 Ca (OH ) 2 2CaCO3 2 H 2 O

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)

FeSO 4 .7 H 2 O Ca ( HCO3 ) 2 Fe ( HCO3 ) 2 CaSO4 7 H 2 O

Improving performance of primary settling facilities


Ferrous sulfate Ferrous bicarbonate in turn dissociates into ferrous hydroxide and carbon dioxide

Fe ( HCO3 ) 2 Fe (OH ) 2 CO2


100 grams of alkalinity may be needed for the precipitation of 278 grams of ferrous sulfate in case of low alkalinity, lime is added

Ferrous bicarbonate combines with lime and form ferrous hydroxide and calcium carbonate

Fe ( HCO3 ) 2 2Ca (OH ) 2 Fe (OH ) 2 2CaCO3 2 H 2 O

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

Ferrous sulfate is not commonly used in wastewater treatment

Improving performance of primary settling facilities


Ferric chloride
Combines with calcium bicarbonate and forms ferric hydroxide (insoluble), calcium chloride (soluble) and carbon dioxide Each gram of ferric chloride requires 0.925 grams of alkalinity

2 FeCl 3 3Ca ( HCO3 ) 2 2 Fe (OH ) 3 3CaCl 2 6CO2

Ferric chloride and lime


Ferric chloride reacts with calcium hydroxide (lime) to form ferric hydroxide and soluble calcium chloride
Each gram of ferric chloride may require 0.518 grams of lime

2 FeCl 3 3Ca (OH ) 2 2 Fe (OH ) 3 3CaCl 2

Ferric sulfate and lime


Ferric sulfate reacts with calcium hydroxide to form ferric hydroxide and soluble calcium sulfate

Fe 2 ( SO4 ) 3 3Ca (OH ) 2 2 Fe (OH ) 3 3CaSO4

Each gram of ferric sulfate requires 0.42 grams of lime

Improving performance of primary settling facilities


Degree of clarification achieved depends on
quantity of chemicals used mixing time care taken for process monitoring and control

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)

Improving performance of primary settling facilities


Physico-chemical treatment can be alternative to biological treatment for municipal wastewater, but suffers from
Lack of consistency in meeting the discharge requirements High costs of chemicals Handling and disposal of greater volumes sludge Numerous operational problems

Precipitated wastewater after clarification in settling tank may require


Recarbonation (specially if lime is used) Filtration for removing the residual flocs Activated carbon column for removing dissolved organic compounds

Output from the activated carbon column is usually chlorinated prior to discharge into receiving waters

Improving performance of primary settling facilities


Estimation of sludge volume from the chemical precipitation of untreated wastewater Estimation may involve the following:
Mass of TSS removed Mass of precipitating chemical added Mass of lime added to facilitate floc formation Mass of chemical sludge formed Mass of the total sludge generated Consistency of the sludge generated Volume of the total sludge generated

Removal of Heavy Metals and Dissolved Inorganic Salts


Metals of interest are arsenic, barium, cadmium, copper, mercury, nickel, selenium and zinc Chemical precipitation, adsorption, ion exchange and reverse osmosis can be used for metal removal Removed as hydroxide and/or sulfide and sometimes as carbonate precipitates
Can be removed separately or co-precipitated with phosphate

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

Laboratory bench scale or pilot scale testing is needed

Removal of Heavy Metals and Dissolved Inorganic Salts


Pre-treatment to remove interfering substances (cyanide and ammonia) is often necessary for efficiency Form complexes with many metals and limit removal
Cyanide can be removed by alkaline chlorination, catalytic oxidation of carbon - not effective for wastewater with nickel or silver Ferrocyanide is oxidized to ferricyanide (resists further oxidation)

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

Precipitation: technologies and achievable effluent concentrations


Metal Arsenic Barium Cadmium Achievable effluent concentration 0.05 mg/l 0.005 mg/l 0.5 mg/l 0.05 mg/l 0.05 mg/l 0.008 mg/l 0.02-0.07 mg/l 0.01-0.02 mg/l 0.01-0.02 mg/l 0.001-0.01 mg/l 0.0005-0.005 mg/l 0.12 mg/l 0.05 mg/l 0.1 mg/l Technology Sulfide ppt. With filtration Ferric hydroxide co-ppt. Sulfate ppt Hydroxide ppt. Co-ppt. with ferric hydroxide Sulfide ppt. Hydroxide ppt. Sulfide ppt. Sulfide ppt. Alum co-ppt. Ferric hydroxide co-ppt. Hydroxide ppt. at 10 pH Sulfide ppt. Hydroxide ppt. at 11 pH

Copper Mercury

Nickel Selenium Zinc

Removal of Heavy Metals and Dissolved Inorganic Salts


Arsenic
Removed by precipitation as arsenate, than as arsenite, arsenite may require oxidation into arsenate prior to precipitation Precipitation as sulfide can reduce concentration to <0.05 mg/l

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Copper
0.02 to 0.07 mg/l of copper can be achieved - precipitation as sulfide at 8.5 pH can reduce copper to 0.01 to 0.02 mg/l Complexing agents such as cyanide and ammonia introduce difficulties in the precipitation removal Copper can be recovered from the precipitate High sulfate levels can precipitate calcium sulfate and affect recovery from the sludge use of caustic can avoid this

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Lead
Removed by precipitation as carbonate or hydroxide With soda reduction to 0.01-0.03 mg/l at 9-9.5 pH is possible With lime reduction to 0.019-0.2 mg/l at 11.5 pH is possible With sodium sulfide reduction to 0.01 mg/l at 7.5-8.5 pH is possible

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Mercury
Mercury ions can be reduced upon contact with other metals like copper, zinc or aluminum For precipitation removal mercury compounds must be oxidized to mercuric ions Sulfide precipitation removes mercury to 10-20 g/l level Alum co-precipitation removes to 1-10 g/l level Iron co-precipitation removes to 0.5-5 g/l level

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Selenium
Selenious ion and selenide are most common in wastewater Sulfide precipitation can remove to 0.01-0.05 mg/l level at 6.6pH Iron co-precipitation can remove to 0.01-0.05 mg/l level

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Zinc
Can be removed by precipitation as zinc hydroxide with either lime or caustic effluent with 0.1 mg/l of zinc can be achieved at 11 pH Lime addition is associated with concurrent precipitation of calcium sulfate in the presence of high sulfate levels

Chromium
Ferrous sulfate, sodium meta-bisulfite or sulfur dioxide are used as reducing agents for reducing chromium from hexavalent to trivalent forms

2 Cr 6 Fe 2 or SO2 or Na2 S 2O5 H Cr 3 Fe3 or SO4

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Chromium
Since wastewater generation rate is low, batch treatment is economical Continuous treatment may require
tank for acidification and reduction (HRT 4 times to theoretical reaction time) mixing tank for lime addition settling tank with overflow rate <20 m/day Variable chrome concentration may require equalization

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

Removal of Heavy Metals and Dissolved Inorganic Salts


Chromium
Ferrous sulfate is reducing agent
Ferrous iron reacts with hexavalent chromium reducing it to trivalent state while getting itself oxidized to ferric state Occurs rapidly at 3.0 pH for pH adjustment acid is added For complete reduction excess dose of 2.5 times to theoretical dose of ferrous sulfate is added

Removal of Heavy Metals and Dissolved Inorganic Salts


Sodium meta bisulfite or SO2 as reducing agents Reduction occurs by reaction with H2SO3
Above 4 pH only 1% of the sulfite is present as H2SO3 and reaction is very slow at pH <2 the reaction is instantaneous and almost complete At pH >3 basic chrome sulfate is formed this reduces the lime required for subsequent neutralization Reaction involves formation of NaOH acid is required to neutralize it

Theoretical chemical requirement per ppm of hexavalent chromium is


2.81 ppm of Na2S2O3 or 1.85 ppm of SO2 1.52 ppm of H2SO4

Presence of DO which transforms sulfite to sulfate necessitates 35 ppm excess SO2 dosing

Removal of Heavy Metals and Dissolved Inorganic Salts


Fluoride
Removed by precipitation with lime as calcium fluoride Precipitation at pH >12 suffers from poor settling and cementation of the filters used Presence of magnesium is reported to enhance removal
Fluoride ions adsorb into the magnesium hydroxide floc Effluent fluoride concentration is <1.0 mg/l Alum co-precipitation can reduce concentration to 0.5-2 mg/l

Polishing units needed for residual fluoride removal


contact beds of activated alumina can be employed

Chemistry of phosphate precipitation


Phosphorus removal involves use of metal salts and polymers or lime Multivalent metal ions (calcium, aluminum and iron) form precipitates of sparingly soluble phosphates Polymers act as flocculant aids in the removal process Phosphate precipitation by lime
Lime, when added, reacts with bicarbonate alkalinity and form carbonate precipitation At pH >10, excess of calcium ions react with phosphate to form hydroxylapatite precipitate
3 10Ca 2 6PO4 2OH Ca10 ( PO4 ) 6 (OH ) 2

Amount of lime required is independent of the phosphate concentration


Depends primarily on the alkalinity of the wastewater Requirement may be 1.4 to 1.5 times to the total alkalinity

Chemistry of phosphate precipitation


Phosphate precipitation with alum and iron 3 Al 3 or Fe3 H n PO4 n AlPO4 or FePO4 nH
Many other reactions compete with phosphate precipitation
Alkalinity, pH, trace elements, and lygands found in water influence the precipitation process

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

Chemical precipitation for phosphorus removal


Choice chemical used for phosphate removal depend on
Influent phosphorus level Wastewater suspended solids and alkalinity levels Chemical cost and reliability of supply Sludge handling facilities and ultimate sludge disposal methods Compatibility of phosphate removal with other treatment process

Phosphorus removal can be a


Pre-precipitation process precipitation of raw wastewater and removal in the primary sedimentation tanks Co-precipitation process precipitation of phosphate for removal along with the waste biological sludge
Chemical is dosed to the primary effluent or to the mixed liquior of ASP or biological treatment effluent prior to secondary settling

Post-precipitation process chemical dosing to clarified secondary effluent and removal of precipitate by filtration/sedimentation

Removal by metal salts and polymers


Polyphosphates and organic phosphorus are less easily removed by metal salts (aluminum and iron)
For best results secondary effluents are treated

Dosing of metal salts to untreated wastewater


Precipitate mainly the orthophosphate Alum dose may be 1.4-2.5 moles of Al/mole of phosphorus (actual dose determination may require on-site testing Dosing of polymer can aid the settling In case of low alkalinity waters addition of alkali for maintaining pH in 5-7 may also be needed Can enhance the removal of TSS and BOD as primary sludge

Removal by metal salts and polymers


Metal salt dosing to the secondary treatment
Can be added to secondary treatment unit inlet, or to secondary treatment unit or to secondary clarifier inlet
Multipoint addition can also be practiced

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

Removal by metal salts and polymers


In case of trickling filters, extended aeration, etc, units clarification in the secondary clarifier may not be good

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

Removal of phosphorus by lime


Use of lime for phosphorus removal has the limitations
Substantial increase in the mass of sludge to be handled Operation and maintenance problems associated with the handling, storage and feeding of lime

Dose depends on removal level needed & wastewater alkalinity


Dosed either in the primary sedimentation tanks or following secondary treatment Dose required is found by on-site testing

Lime addition to the primary clarifier


Removal can be 65-80% Calcium and hydroxide react with orthophosphorus and form insoluble hydroxyapatite [Ca5(OH)(PO4)3] Residual phosphorus level of 1 mg/l can be achieved if filtration facility is also added High lime system: involves raising of pH to > 11 lime required is high - after precipitation recarbonation may be needed Low lime systems: lime dose is 5/1 molar ratio of Ca2+/Mg2+

Removal of phosphorus by lime


Lime addition following secondary treatment
Meant to reduce phosphorus and TSS level in the effluent

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

Recarbonation may be needed to remove excess of soluble calcium


Filtration aids and filtration can be used to remove the flocs

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

Removal from secondary effluent by chemical addition and filtration


Chemical addition to clarified secondary effluent and filtration is used to
improve the quality (in terms of TS levels) of treated effluent remove contaminants, such as, phosphorus, metals, etc.

2-stage up-flow continuous backwash filters can be used


First filter uses large size sand and the second one small size sand Compressed air is used for backwashing and about 5% of inflow is rejected as backwash water Backwash water of the second filter is recycled to the first filter

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

Advanced 1 or 2 stage filtration

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

Estimation of the Sludge Generated


With lime
The precipitate contains hydroxylapatite, CaCO3 and Mg(OH)2
3 10Ca 2 6PO4 2OH Ca10 ( PO4 ) 6 (OH ) 2

With Alum

2 CO3 Ca 2 CaCO3 Mg 2OH Mg (OH ) 2

The precipitate contains AlPO4 and Al(OH)3

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

Fe3 3OH Fe(OH ) 3

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