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CHEMICAL TREATMENT:

CHEMICAL PRECIPITATION

ASTRI FADHILAH BINTI ABDUL RAHIM (2010163445)


MARCELLE MARTIN (2011193821)
MUHAMMAD FADHLI BIN SAMSUDIN (2010744793)

CHEMICAL PRECIPITATION
Transforms dissolved contaminants into an insoluble
solid, facilitating the contaminants subsequent
removal from the liquid phase by sedimentation
and/or filtration.
Chemical precipitation in wastewater treatment
involves the addition of chemicals to alter the
physical state of dissolved and suspended solids and
facilitate their removal by sedimentation.

TYPE OF CHEMICAL PRECIPITATION

HYDROXIDE

SODIUM
BOROHYDRIDE

CARBONATE

SULFIDE

What is Hydroxide
Precipitation?
Soluble heavy metal ions are converted to relatively
insoluble metal-hydroxide precipitates by adding an
alkali-precipitating agent
Treated and Removed by adjusting the pH of
wastewater to reduce the solubility of dissolved
metals

Metal precipitation is primarily dependent upon two


factors:
a.

The concentration of the metal,

b.

The pH of the water.

.Heavy metals are usually present in wastewaters in dilute


quantities and at neutral or acidic pH values (< 7.0). .

Above is a metal hydroxide solubility curve showing the


solubility of the common heavy metal ions and their
respective solubility versus pH

Precipitating Agent
The most commonly use agent for hydroxide precipitation
are:
i.

Sodium Hydroxide (NaOH)

ii.

Lime (CaO @ Ca(OH)2)

iii. Magnesium Hydroxide (Mg(OH)2)

How does Hydroxide Precipitation


Occurs?
Adding and thoroughly mixing the precipitating
agent with the influent waste stream to form
hydroxide particles

Coagulants is also added where it will attach to


the metal solid particles increasing the particle
size to promotes settling
Sedimentation: The particle become entangled
and heavier than water: they are then allowed
to settle down
Then in a filtration unit: Particles that did not
settle in the sedimentation basin @ did not have
sufficient time to settle and were carried out of
the basin are trapped
The solids produced in the sedimentation stage
(and possibly solids from filtration) are denoted
as a sludge and periodically removed

Hydroxide Precipitation Reaction

Advantages & Disadvantages


Some metals
require reduction
before they can be
precipitated as a
hydroxide.
Precipitates tend
to resolubilize if
the solution pH is
changed
Not effective in a
mixed metal
solution due to
solubilities of
different metals

Disadvantages

Advantages

Well proven and


accepted in
industry
NaOH available
as liq. & easily
delivered into the
system.
Calcium-based
Reagents As
source of hardness
into the
environment &
reduce toxicity of
the residual

Sulfide Precipitation
An effective alternative to hydroxide precipitation
Works under the same basic principle as does hydroxide
precipitation
Converts soluble metal compounds
insoluble sulfide compounds

into

relatively

Precipitated by adding sulfides (S-2, HS), extremely


reactive with heavy metal ions
The precipitation reaction is generally induced under
near neutral conditions (pH 7.0 to 8.0)
Similar to hydroxide precipitation, metal sulfide
precipitates most often must be physically removed from
solution
through
coagulation,
flocculation
and
clarification or filtration
Effective for metals

Precipitating Agent
Sulfide reagents used to cause precipitation of
contaminants:
a) Ferrous Sulfide (FeS)
b) Sodium Hydrosulfide (NaHS)
c) Sodium Sulfide (Na2S)
d) Calcium Sulfide (CaS)

Sulfide Precipitation Reaction


Example of sulfide precipitation reaction on soluble
nickel using sodium sulfide (Na2S)

Nickel sulfide (NiS) is the solid precipitate formed


from this reaction

Soluble Sulfide Precipitation (SSP)

Insoluble Sulfide Precipitation (ISP)

Precipitating agents
Sodium Sulfide (Na2S)
Sodium Hydrosulfide (NaHS)

Ferrous Sulfide (FeS)


(other alternative: Calcium sulfide (CaS))

Advantages
High effective removal of metals from
complex wastewater

Large volume of sludge

Disadvantages
Excess soluble sulfide in the treated
effluent may result in taste and odor
problems, present health or biotoxic
hazards

Poor settling due to the high sulfide


concentration which causes rapid
precipitation of metal sulfides in small
particulate fines and hydrated colloidal
particles

Similarities
Generates sulfide sludge that difficult to dispose properly due to potential sulfide
reactivity

Advantage
s

Effective for
many metals
including zinc
and cadmium

Disadvanta
ges

Less effective
for some
contaminants
such as
manganese

Metal sulfide
sludge exhibit
better
thickening and
dewatering
characteristics

High cost
disposal of
metallic sulfide
sludge

Yield more
complete metal
removal than
hydroxide
precipitation

Safety concern
where easily
leave toxic
sulfides in
solution

Attainment of
high degree of
metal removal,
even with pH
values (pH 2 to
3)

Potential for
toxic hydrogen
sulfide gas
emissions

Heath effect
Sodium sulfide owning to its corrosive nature
Cause severe burns to eyes or skin
Can form toxic hydrogen sulfide(H2S) gas when in contact
with acid

Carbonate Precipitation

Carbon
dioxide

Sodium
carbonate

Calcium
carbonate

General equation
+
metal

M
carbonate ion

metal carbonate

Precipitation can only happen in present of carbonate ions

Examples

Examples of precipitation

Carbonate precipitation
Solubility's of most
hydroxide and sulfide

metal

carbonates

fall

between

Effective in removal cadmium, nickel and lead at a slightly


lower pH than either hydroxide or
sulfide precipitation
Also effective in removal copper and zinc
Optimum treatment in removal cadmium at neutral pH
High pH and low carbonate level lower the effectiveness of
carbonate precipitation

Cadmium removal
pH required is 7.5 to 8.5 to form carbonate
precipitation in removal cadmium
Compare remove as hydroxide precipitation at pH
range 8 (solubility: 1ppm) to 11 (solubility: 0.05ppm)
Sources of cadmium
Metallurgical products
Ceramics
Synthetic chemical

Lead removal
Lead can be removed by precipitation as sulfide and
carbonate at pH 7.5 to 8.5
Lead can be removed by precipitation as hydroxide
at pH 11.5
Sources of lead
Batteries
Printing products

Nickel removal
Nickel can be removed by precipitation as hydroxide
at pH range 10 to 11
Nickel can be removed by precipitation as carbonate
or sulfate

Calcium carbonate (limestone)


Has widespread availability
High reaction rate
Less sludge is produced during precipitation
Limited to treat wastewater outside pH range 5-7
Efficiency decrease if waste stream
concentration greater than 5000mg/L

has

acid

Sodium carbonate (soda ash)


Used for treating acidic aqueous metal waste stream
Generating less sludge
carbonate precipitation
But do not filter well

compare

to

calcium

Carbon dioxide
Mostly used in treating metal-bearing waste streams
Carbon dioxide generates
introduced into the reactor

carbonic

acid

after

Then react with the available hydroxide ions to form


less soluble carbonates.
Required slow moving influent being fed
Required neutralization prior to final discharge

Advantages

Improved settle ability

Reduce sludge volume/yield lower metal residue

Easier to filter precipitate

Availability of chemical

Potential recover the metal

Disadvantages

Longer retention time, greater than 45 minutes

Lower solubility (20% by weight)

Difficulty of mixing

Sodium Borohydride Precipitation


NaBH4 is a mild reducing agent that will result in the
precipitation of certain soluble metal ions by
converting them into their insoluble metal form
Works well for removing nickel, lead and mercury
Can use for extract several precious metals (gold and
platinum groups) thus providing a good method for
their recovery
React with water to generate hydrogen gas
Unstable in acidic alcohol (phenol) and low molecular
weight primary alcohols (methanol, ethanol)
Stable in secondary and tertiary alcohols
Stable thermally
pH range 8 to 11 which is good for lead, mercury,
nickel, copper and gold.

Sodium Borohydride Reaction


Conversion of a soluble metal cation (or complexed
metal cation) to the insoluble elemental metal:

Since one equivalent of sodium borohydride can


reduce eight equivalents of metal ion, low level
borohydride usage results in substantial reduction of
the dissolved metal

Advantages

Nonflammable

By-product
NaBO2 can be
recycled back
to NaBH4

High yields of
reduced metal

Disadvanta
ges
Catalyst
required to
generate
hydrogen in
this reaction

Health Effects
The health effect that cause by sodium borohydride
are as follow:
Can cause cancer
Reproductive hazards