3 chemical precipitation
DESCRIPTION
Chemical PrecipitationTRANSCRIPT
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Chemical Precipitation
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Similar but NOT a Coagulation
Process
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Removal of dissolved metal ions from solution by changing the solution composition, causing the metal ions to form insoluble metal complexes
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Removal of dissolved metal ions from solution by changing the solution composition , causingthe metal ions to form insolublemetal complexes
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Solu.on with soluble ions
+
Chemical precipitant
Insoluble complex
+
Treated water
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Applications
Treatment of “hard” water – removal of Mg2+ and Ca2+
Phosphorus removal
Removal of metals from industrial wastewater
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TheoriticalBackground
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Solubility of Compounds
Compound Solubility, mg/L
CaCO3 18
CaCl2 745000
Ca(OH)2 770
CaSO4 1620
Mg(OH)2 40
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Equilibrium Considera t i on
Precipitate will form when two solutionsare mixed if and only if the
concentrations of the metal ions is greater than the solubility limits of the
ions in solution for the particular solution composition
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Applications
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Basic Procedures
A. Chemical additionB. MixingC. FlocculationD. Sedimentation
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How it WorksProcess Tank
Process Tank
S t i r r e r Unit 1. Ferric Addition 2. Lime addition
3. Alum addition4. Polymer addition5. After coagulation6. After sedimentation
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Industrial Equipment
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ApplicationsWater Softening
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Hardness
Caused by Ca2+, Mg2+, Fe2+, Mn2+, Sr2+
and Al3+
Carbonate hardness – caused by anion CO -‐2, HCO -‐
3 3
Non-‐carbonate hardness – caused by anion SO4
-‐2, Cl-‐
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Level of Acceptance Soft : < 60 mg/L as CaCO3
Moderately hard : 60 – 120 mg/L asCaCO3
Hard : 120 – 180 mg/L as CaCO3
Very hard : > 180 mg/L as CaCO3
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Problems
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Interfere with laundering –excessive soap consumption
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Scale productionin hot-water heaters and pipes
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Hair problem
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SolutionWater Softening
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Water Softening
To remove hardness by removing Ca2+ and Mg2+ via chemical percipitation
Use lime (CaO) or lime slurry (Ca(OH)2) and soda ash (Na2CO3)
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Chemical Reactions(Carbonate Hardness)
Reaction of lime with existing CO2 in water
CO2 + Ca(OH)2 = CaCO3 + H2O (3.6-‐1)
Reaction of lime with bicarbonate
Ca(HCO3)2 + Ca(OH)2 = 2CaCO3 + 2H2O(3.6-‐2)
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Chemical Reactions(Carbonate Hardness)
Conversion of Mg(HCO3)2 to MgCO3
Mg(HCO3)2 + Ca(OH)2 = CaCO3 + MgCO3
+ 2H2O
(3.6-‐3)
Precipitation of Mg2+
MgCO3 + Ca(OH)2 = Mg(OH)2 + CaCO3(3.6-‐4)
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Chemical Reactions(Non-‐carbonate Hardness)
Precipitation of Mg2+
MgSO4 + Ca(OH)2 = Mg(OH)2 + CaSO4
MgCl2 + Ca(OH)2 = Mg(OH)2 + CaCl2
(3.6-‐5)
(3.6-‐6)
Precipitation of Ca2+ by soda ash (Na2CO3)
CaSO4 + Na2CO3 = CaCO3 + Na2SO4
CaCl2 + Na2CO3 = CaCO3 + 2NaCl
(3.6-‐7)
(3.6-‐8)
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Lime-‐soda Ash Softening(Process Variations)
1. Excess lime softening
2. Selective calciumcarbonate removal
3. Split-treatment sof t ening
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Excess Lime Softening
Removal of Ca2+ and Mg2+ hardness to practical limit of CaCO3 solubility by
stoichiometric addition of lime
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Total hardness reduced to
40mg/L as CaCO3
30 mg/L of Ca2+
and
10 mg/L of Mg2+
3(as CaCO )
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Precipitation of Mg2+ requires a
surplus of 35 mg/L of CaO above stoichiometric
requirement for
pH adjustment
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After excess-‐lime treatment, water is highly alkaline and must be
neutralised.
This is carried out using CO2
(recarbonation)
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How it Works
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Example 1Water defined by the following analysis is to be sof t ened by excess lime treatment. Assume that the practical limit of hardness removal for CaCO3 is 30 mg/L and that of Mg(OH)2 is 10 mg/L as CaCO3.
CO2
Mg2+
SO42-‐
Ca2+
Na+
Cl-‐
= 40.0 mg/L
= 13.7 mg/L
= 17.9 mg/L
Alk (HCO3-‐) =
= 8.8 mg/L
= 14.7 mg/L
= 29.0 mg/L
135 mg/L as CaCO3
1. Sketch a meq/L bar graph and list the hypothetical combinationsof chemical compounds in solution.
2. Calculate the sof t ening chemicals required expressing lime dosage asCaO and soda ash as Na2CO3.
3. Draw a bar graph for the sof t ened water before and afterrecarbonation. Assume that half the alkalinity in the sof t ened water is inthe bicarbonate form.
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Selective CaCO3 RemovalTo soften water low in Mg2+
hardness (< 40 mg/L as CaCO3)
i.e. NO Mg2+ removal
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No excess lime for Mg2+ removal
One step recarbonation
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How it Works
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Consider selective calcium carbonate removal sof t eningof a raw water with a bar graph as drawn in the figurebelow. Calculate the required lime dosage as CaO, and sketch the sof t ened water bar graph after recarbonation.
2.0 2.6 2.9
2.2 2.7 2.9
Example 2
Ca2+ Mg2+ Na+
HCO -3 SO4
2- Cl-
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Split Treatment Softening
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First Stage
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First Stage
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Mixing
Mixing point
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AdvantageExcess lime in the first stage is utilised
in second stage
Reduce cost of lime and recarbonation
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ApplicationsPhosphorus Removal
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Involve precipitation with calcium, iron or aluminium.
Reaction with Ca2+ produce hyroxypalite, Ca5OH(PO4)3:
5Ca2+ + 7OH-‐+ 3H2PO4-‐ Ca5OH(PO4)3 +
6H2O
Precipitation is subjected to pH
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ApplicationsHeavy Metal Removal
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Industrial wastewaters eg. plating and polishing operations, mining, steel manufacturing, electronics manufacturing
Arsenic (As), barium (Ba), chromium (Cr), cadmium (Cd), lead (Pb), mercury (Hg), silver (Ag)
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Types of Precipition
Hydroxide precipitation (OH-‐)
Sulphide precipitation (S-‐2)
Carbonate precipitation (CO32-‐)
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Hydroxide Precipitation (OH-‐)
Add lime (CaO) or sodium hydroxide (NaOH) to precipitate heavy metals in the form of metalhydroxides
Cd2+ + Ca(OH)2 Cd (OH)2 + Ca2+
Will form floc and sludge in clarifier
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Hydroxide Precipitation (OH-‐)
CaO in the form of slurry (Ca(OH)2) NaOH in the form of solution
NaOH is easier to handle but very corrosive.
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Sulphide Precipitation (S2-‐)
Use of sulphide in the form of FeS, Na2S or NaHS
Better metal removal as sulphide salt has low solubility limit
Cu2+ + FeS CuS + Fe2+
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Sulphide Precipitation (S2-‐)
Limitation: can produce H2S (gas) at low pH
2H+ + FeS H2S + Fe2+
At low pH, reaction to the right
pH > 8 for safe sulphide precipitation.
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Carbonate Precipitation (CO3)2-‐
Use of carbonate in the form ofNa2CO3
Ni2+ + Na2CO3 NiCO3 + 2Na+
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Equilibrium/ Solubility Limit
OH-‐/ S2-‐
precipitation
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CO32-‐
precipitation
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Example 3
One litre of an aqueous wastewater containing 10-‐4
moles/L Zn2+ is treated by hydroxide precipitation at pH=10 (Atomic weight of Zn = 65.4 g/mol)
Zn2+ + Ca(OH)2 Zn(OH)2 + Ca2+
1. Will a precipitate form?
2. What will the equilibrium composition of the solution be in the presence of the precipitate?
3. What is the % Zn removed from the solution?
4. What could be done to improve the treatment?
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1. 10-‐4 mol/L Zn2+ x 65.4 g/mol x 103
mg/g = 6.54 mg/L
Refer to HO-‐ solubility graph (Fig. 3.3).
It will precipitate as the value is
greater than the equilibrium
concentration (red dashed line)
2. At pH 10, the equilibrium concentration of Zn2+ would be ~1mg/L
3. %Removal = (1 – Ce/Ci) x 100
= (1 – 1/6.54) x 100
= 84.7 %
4. Adjust pH to 9.3 or use sulphideprecipitation
6.54 mg/L
pH = 10
Solution
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Read This!!Hammer and Hammer, Water and
Wastewater Technology, 2004, pg. 239 – 244