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Chemical Clarification

Precipitation Methods

Prepared By
Michigan Department of Environmental Quality
Operator Training and Certification Unit

Some things (chemists use term


compounds) dissolve in water
these are said to be soluble.

Some things (compounds) dont dissolve


in water these are said to be insoluble.

A precipitation reaction is a
reaction in which soluble ions in
separate solutions are mixed
together to form an insoluble
compound that settles out of
solution as a solid. That insoluble
compound is called a precipitate.

Precipitate Formation

soluble

insoluble

Precipitation of Metals from Wastewater


Metals Precipitation
Transforms dissolved contaminants into an insoluble
solid, facilitating the contaminant's subsequent
removal from the liquid phase by sedimentation and /
or filtration.
Usually accomplished by:
pH Adjustment
Chemical Coagulation
Flocculation
Separation

Hydroxide Precipitation
Most Soluble Heavy Metals Will Precipitate
When pH is Raised to a Given Point
pH is Raised by Addition of Hydroxide

Cu(NO3)2(aq)

2 NaOH(aq)

Cu(OH) 2(s)
+ 2 NaNO3(aq)

Hydroxide Precipitation
Sodium Hydroxide,
NaOH
Caustic Soda
Calcium Hydroxide,
Ca(OH)2
Hydrated Lime

Sodium Hydroxide
Caustic Soda, Soda Lye
Available in Liquid or Dry Form
Liquid:
Commercial Strength
50 % , 73 % NaOH
Often Stored at 20 %
50 % Crystallizes at 53 Deg. F
Dry:
99.9 % NaOH
Safety
Bag, Drum, or Bulk
Caustic Poison
Dangerous to Handle, Corrosive
Prevent All Body Contact
Protect Eyes

Calcium Hydroxide
Ca(OH)2
Hydrated Lime, Slaked Lime
Available in Dry or Liquid Form

Dry Form Available in Bags or Bulk


Commercial Strength 82 - 95 %
Safety
Caustic, Irritant, Dusty
Avoid Contact with Eyes, Nose,
Respiratory System

Hydroxide Precipitation
Sodium Hydroxide

VS
Hydrated Lime
Less Expensive
Solids Settle Faster
Higher Sludge Solids Conc
Sludge Easier to Dewater
Takes Longer to Neutralize
More Complicated Feed System
A Lot More Sludge

Process Water

Chemical
Treatment
..

Equalization Tank

Treatment Tank
Treated Water

Back To
Equalization Tank

Clarifier

Filter Press

Sludge Tank
Sludge Bin

Cu(NO3)2(aq) + 2 NaOH(aq) --> Cu(OH)2(s) + 2 NaNO3(aq)

Ni(NO3)2(aq) + 2 NaOH(aq) --> Ni(OH)2(s) + 2 NaNO3(aq)

2 AgNO3(aq) + 2 NaOH(aq) --> Ag2O(s) + 2 NaNO3(aq) + H2O(l)

Precipitation of Metals from Wastewater

The Solubility of Metals is Dependent on pH

Hydroxide Precipitation
From Chart (Book Value)
Minimum Solubility (Best Removal) Value for Some Metals
Cadmium
pH 11.0
Copper
pH 8.1
Chromium
pH 7.5
Nickel
pH 10.8
Zinc
pH 10.1

Hydroxide Precipitation
Need to Determine Optimum pH for Waste
May or May Not be Close to Book Value
Metals Precipitate at Various pH Levels
Depending On:
The Metal Being Precipitated
The Chemistry of the Wastewater
Other Metals Present
Presence of Chelates

Metal Precipitation
Precipitation of more than one metal from the
same solution:
Adjust for Optimum pH for One Metal
(With Lowest Discharge Permit Limit)
Adjust for Compromise pH
Operate in Stages
Adjust pH for Each Metal in Stages
Draw Off Sludge, or Transfer
Supernatant Between Stages

Hydroxide Precipitation
Expected Effluent Quality (mg/L) for Total Metals

Precip +
Settling
Cr
Cu
Ni
Cd
Zn

0.1 to 1.0
0.2 to 1.5
0.5 to 2.5
0.2 to 1.5
0.2 to 1.5

Precip +
Settling +
Filtration
0.05 to 0.5
0.05 to 0.5
0.25 to 1.5
0.05 to 1.0
0.05 to 1.0

NaOH

Mix Tank

Clarifier

Filter

Hydroxide Precipitation of Soluble Metals


Things that Make Life More Difficult
Many Metals are
Amphoteric
Metal hydroxides that
re-solubilize if the pH
increases or decreases
from the optimum
precipitation value

Hydroxide Precipitation of Soluble Metals


Things that Make Life More Difficult
Many Metals are
Amphoteric
Double Solubility Curve
pH Must be
Carefully Controlled

Hydroxide Precipitation of Soluble Metals


Things that Make Life More Difficult
Many Metals are Amphoteric
Double Solubility Curve
pH Must be Carefully Controlled
Presence of Chelating Agents will Interfere
with Ability to Precipitate Metals

Chelates
Cant Live With em, Cant Do Without em

An agent that will form a compound with a heavy


metal ion, with the intended purpose of keeping
the metal in solution.

Highly Desired in Plating Solutions


A Big Problem in Wastewater Treatment

Commonly Used Chelating Agents


Ammonia, NH3
Phosphate
EDTA
Citrate
Cyanide

Chelates

Methods of Addressing the Problem


1. Precipitate at high pH
pH > 10 (may also add CaCl2)
2. Add a material which the chelate prefers
over the metal to be precipitated.
Ferrous Sulfate
3. Use a reducing agent to convert the
heavy metal from the ion back to the
metal
Sodium Borohydride
4. Use a precipitating chemical that steals
the metal from the chelate
Sulfide
Sodium Dimethyldithiocarbamate (DTC)

Sulfide Precipitation of Soluble Metals


Extremely Low Metal Solubilities
Often Preferred for Wastewaters
Containing Chelating Agents
More Negative Environmental Impacts
More Costly (About Twice $ as for OH)
May Produce H2S in Lethal Concentrations

Sulfide Precipitation of Soluble Metals

Cu(NO3)2(aq) + Na2S(aq) --> CuS(s) + 2 NaNO3(aq)

CdCl2(aq) + Na2S(aq) --> CdS(s) + 2 NaCl(aq)

Ni(NO3)2(aq) + Na2S(aq) --> NiS(s) + 2 NaNO3(aq)

Ca(OH)2

Mix Tank

Cr
Cu
Ni
Cd
Zn

FeS

Mix Tank

OH
Precip +
Settling +
Filtration
0.05 to 0.5
0.05 to 0.5
0.25 to 1.5
0.05 to 1.0
0.05 to 1.0

Clarifier

Filter

OH + S
Precip +
Settling +
Filtration
0.01 to 0.20
0.01 to 0.25
0.05 to 0.50
0.01 to 0.25
0.01 to 0.25

Sodium Dimethyldithiocarbamate
(DTC or SDDC)
Organic sulfur compound
Controls chelated waste streams
Not pH sensitive
any pH above 3
Non amphoteric
Very toxic
Agricultural insecticide
Industrial biocide

Sodium polythiocarbonate (PTC)


Thio-Red
Much less toxic than DTC
50% less sludge than DTC, lime or iron chemistries;
Requires lower dosing of flocculent chemistry
for liquid/solid separation
Treated waters pass toxicity tests for National
Pollutant Discharge Elimination System (NPDES)
discharges

Hydroxide Precipitation of Soluble Metals


Things that Make Life More Difficult
Metals are Amphoteric
Double Solubility Curve
pH Must be Carefully Controlled
Presence of Chelating Agents will Interfere
with Ability to Precipitate Metals
Hydroxide Sludges May be Difficult to Dewater
Metal Finishing Sludge is Classified as a
Hazardous Waste by Federal & State Law (RCRA)

Batch Treatment
Usually Preferred for Small Flows
Either a Holding Tank and Reaction Tank,
or Two Reaction Tanks
Reaction Tanks Serve Also as Clarifiers
Allows for Maximum Control of Effluent Quality
Influent Wastewater

Sludge

NaOH

NaOH
Effluent

Effluent

Sludge

Continuous (Flow-Through) Treatment


Usually Used For Larger Flows
Addition of OH Controlled by pH Meter / Controller
NaOH

Storage

Clarifier

React

Flocculation

pH

Sludge Recirculation
Precipitated Solids Act as Seed Structure for
Forming Precipitate

Batch Treatment
Portion of Settled Sludge Left on Tank Bottom that
Re-suspends When Mixing For New Batch Begins

Sludge Recirculation
Continuous Treatment
Sludge is Recirculated from Sludge Hopper of
Clarifier to the Influent or Reaction Tank

Review Metal Precipitation


1 Sodium Hydroxide is hazardous to handle in that
it is both _____________
and ______________.
toxic
corrosive
2. List three options for precipitating two metals
with different optimum pH.
a. Optimize for One Metal
b. Find a Compromise pH
c. Operate as a Two-Stage System

3. Metal hydroxides that resolubilize if the pH


increases or decreases from the optimum
precipitation value are said to be
amphoteric
__________________.
4. Ammonia, phosphates, and EDTA are
chelating
_______________agents
used in plating
solutions.
5. Describe the problem that may occur when
precipitating metals from wastewater where the
materials described in #4 are present.
Chelates hold metals in solution, not allowing
them to precipitate.

6. List 3 ways a wastewater treatment plant


operator may be able to overcome the
problem in #5 that is caused by the materials
listed in #4.
a.

Precipitate at high pH

b.

Add a metal to tie up chelate

c.

Add a chemical that steals metal


from the chelate (Sulfide)

7. Recirculation of _________________
precipitated sludge may be
beneficial in that it provides seed material
for the precipitation process.

Chemical Clarification
Precipitation Methods

Prepared By
Michigan Department of Environmental Quality
Operator Training and Certification Unit