SODIUM CARBONATE:
MANUFACTURING PROCESSES
2.
3.
4.
Leblanc process.
Solvays ammonia soda process.
Dual process (modified Solvays process)
Electrolytic process.
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1.
SODIUM CARBONATE:
Raw materials
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Basis:
SODIUM CARBONATE:
Reactions
NaCl + H2SO4 NaHSO4 + HCl
(a)
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(b)
(c)
(f)
(h)
SODIUM CARBONATE:
SODIUM CARBONATE:
(a)
(b)
(c,d)
CaS is
separated
SODIUM CARBONATE:
NaCl is mixed with the conc. H2SO4 in equivalent quantities and heated
in a cast iron salt cake furnace by flue gases from adjacent coal of fire.
NaHSO4 along with HCl gas is formed.
HCl is passed to tower packed with coke and is absorbed through a spray
of water comes down in the tower.
The paste of NaHSO4 is taken out and heated to a high temperature on
the hearth of a furnace along with some more common salt.
NaHSO4 is thus converted into sodium sulfate, known as salt cake.
The salt cake is broken or pulverized, mixed with coke and limestone
and charged into black ash rotary furnace consisting of refractory lined
steel shells.
The mass is heated by hot combustion gases entering at one end and
leaving at the others.
The molten porous gray mass thus formed known as black ash is
separated from the calcium sludge and then crushed and leached with
water in absence of air in a series of iron tank.
SODIUM CARBONATE:
SODIUM CARBONATE:
(g)
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SODIUM CARBONATE:
Raw materials
Basis:
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SODIUM CARBONATE:
Reactions
CaCO3 CaO + CO2
H = +43.4kcals
H = 96.5kcals
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Overall reaction
CaCO3 + 2NaCl Na2CO3 + CaCl2
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
Filtration
NaHCO3
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SODIUM CARBONATE:
Calcination
NaHCO3
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SODIUM CARBONATE:
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liquor from the bottom of the lime still is free from ammonia and contains
unreacted NaCl and largely CaCI2, which is disposed off.
The liquor is, therefore allowed to settle in settling ponds and the clear liquid is
evaporated till the salt separates out and is sold as such for calcium chloride or 22
further evaporated.
SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
Above data indicate that precipitation fortunately tends to take place preferentially
with satisfactory yields.
On the basis of data and common ion effect on precipitation of salts, physicochemical
conditions most suitable for the forward step of reaction (b) which causes
precipitation of NaHCO3 are as under:
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To
maintain lowest possible temperature in order to lower the solubility off sodium bicarbonate
To maintain the greatest possible concentration of one or both the salts appearing on the
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product side of reaction (b) with the aim of lowering still further solubility of sodium
bicarbonate.
SODIUM CARBONATE:
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SODIUM CARBONATE:
units
Making tower
Development of suitable calcining equipment
Filtration unit
Ammonia recovery
Waste disposal
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SODIUM CARBONATE:
Raw materials
Basis:
1 t Sodium carbonate
Crystalline Salt
1260kg
Ammonia
325kg (HaberBosch Process)
High pressure steam 1350kg
Low pressure steam 100kg
Cooling water
5000080000kg
Electric power
450KWH
Co-product (NH4Cl)
620kg
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SODIUM CARBONATE:
Reactions
C + O2 CO2
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
purification
Corrosion
Refrigeration Cost
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SODIUM CARBONATE:
Advantage of Solvay
process
Less
electric power
Less corrosion
problem
Use of low grade brine
Not a problem of
disposal of co-product
Does not require
ammonia plant
Higher
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salt consumption
Waste disposal of CaCl2
brine stream
Higher investment in NH3
recovery units than
crystallization unit of NH4Cl
More steam consumption
Higher capacity plant set up
require for economic break
even operation (100 v/s
55tons/day)
NH4Cl can be used as mixed
fertilizer ingredient which 34
minimizes the disposal
problem of Duel process.
SODIUM CARBONATE:
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water)
Reactions
NaCl Na+ + Cl 2H2O + 2e H2 + OH
At
cathode
2H2O + 2e H+ + 2OH
Na+ + OH NaOH
2NaOH + CO2 Na2CO3 + H2O
At
Anode
Cl e Cl
Cl + Cl Cl2
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
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SODIUM CARBONATE:
PROPERTIES
Molecular formula :
Na2CO3
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SODIUM CARBONATE:
APPLICATIONS
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SODIUM HYDROXIDE
(NAOH)
CHLORINE (CL)
cell
Mercury cathode cell
Membrane cell
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Diaphragm
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Cells
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Dry
Diaphragm Cells
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Hooker cells are cubic in shape with capacity from 10000 amp to 55000
amp.
It has concrete cover at the base from which flat blades of the graphite
projects upward and act as anodes which is supported vertically by a layer
of lead cast concrete base.
90 graphite anodes, each has dimension of 46163 cm are used.
The cathode consisting of flat steel fingers are supported horizontally from
the side steel frame extending inwards, from two sides so as to fit between
the rows of anode blades.
Concrete cover has inlet for brine and exit pipe for chlorine gas.
This concrete cover also projects the cast lead forming the condenser to the
anodes from attack by cell liquor.
The cathode assembly has hydrogen and caustic off takes and the cathode
connection.
The cathode is directly covered with asbestos and forms the diaphragm,
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which is completely submerged.
Diaphragm
is applied by dipping the cathode into a bath of asbestos slurry and the
asbestos is drawn into the screen by applying a vacuum to the hydrogen outlet.
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H = + 97.2kcals
2H2O + 2e H2 + 2OH
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H = + 68.3kcals
At cathode
2H2O + 2e 2H+ + 2OH
Na+ + OH NaOH
H = + 112.0kcals
At Anode
Cl e Cl
Cl + Cl Cl2
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It
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Membrane is porous chemically active plastic sheet that allow Na+ ion
to pass but rejects the OH ions.
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Disadvantages
Readily
clogged of membrane
Pretreatment of brine is required to remove calcium
and magnesium salts
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Reaction
NaCl Na+ + Cl
H = + 97.2kcals
2H2O + 2e H2 + OH H = + 68.3kcals
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At cathode
2H2O + 2e H+ + 2OH
Na+ + OH NaOH
At Anode
Cl e Cl
Cl + Cl Cl2
H = + 112.0kcals
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Purification of Brine
Brine purification is essential for getting pure caustic soda and to
decrease clogging of the cell diaphragm by insoluble hydroxides formed
during electrolysis.
Brine contains impurities such as calcium, magnesium and iron
compounds.
These impurities are removed by adding lime and soda ash, when insoluble
carbonates and hydroxides are precipitated.
Sometimes sulfate are removed with BaCl 2 or the hot brine is treated with OH
and CO32 ions.
After the treatment brine is allow for settling to separate the impurities
and then neutralized with hydrochloric acid.
The saturated brine containing 324gms/liter of NaCl is fed to the cell at
600C.
The electrolysis is carried out in diaphragm cells; each cell usually
required 3.0-4.5 volts.
A number of them are put in series to increase the voltage of a given
group.
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fire.
Approximately 99% water is removed and molten caustic soda is
formed at 5000C to 6000C.
Now a days these pots are replaced by dowtherm heated evaporators
for caustic evaporation about 50%.
Another method of dehydrating 50% caustic soda is the precipitation
of NaOH.H2O by adding ammonia which also purify the caustic soda.
If 50% caustic soda is treated with anhydrous ammonia in pressure
vessels in a counter current manner, free flowing anhydrous crystals
of NaOH separate out from the resulting aqua ammonia.
The hot anhydrous caustic is treated with sulfur to precipitate iron
and then allowed to settle.
Then a centrifugal pump is lowered by crane in the molten NaOH
and the liquid is pumped out in to thin steel drums.
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Sodium
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Rotary
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Hydrogen
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Raw materials
Basis: 1 ton Sodium hydroxide
Sodium carbonate
1360kg (Solvays process, dual process or
electrolytic process)
Lime
75kg
(from mineral calcite or aragonite,
which can be used after removal of
clay,
slit and sand (silica).)
Water
1000kg
Steam
1225kg
Fuel
13000000 Btu
Electricity
19KWH
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Reaction
Na2CO3 + Ca(OH)2 NaOH + CaCO3
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The over flow liquid from the first thickener is filtered and filtrate
containing 10-11% NaOH is evaporated to 50 % solution in a triple effect
vacuum evaporator.
The solid CaCO3 is gradually settles to the bottom.
The lime sludge from the bottom of the first thickener is washed with the
water.
The filtrate from the next operation is also added to the second thickener,
where the liquor is treated with excess of weak soda solution.
The overflow from the second thickener is used as a weak liquor to make
soda ash solution.
The lye suspension from the thickener is filtered through rotary drum
vacuum filter and passed to a third thickener where it is finally washed
with fresh water to remove any traces of NaOH.
The slug of the filter cake (CaCO 3) is return in the lime kiln to from lime.
The caustic soda (11 % strength) contains small amount of NaCl and
Na2CO3.
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of temperature
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CaCO3 NaOH
Kc
OH 2
Na2CO---3 Ca
(1)
Since calcium carbonate and calcium hydroxide are only slightly soluble, their
solutions are always saturated and concentration of two components in the solution
is therefore constant.
Equation (1) can be written as
NaOH
k'c ---- (2)
Na2CO3
2
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NaOH
1
Na2CO3
NaOH 2 Na2---CO3 (3)
2
NaOH
1
1
NaOH
---- (4)
1 K"c NaOH
1 2
k'c
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CHLORINE (CL)
Using diaphragm cells
Deacons method
Other methods
All
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In 1630, Jan Baptist van Helmont was the first who obtained
the Chlorine gas.
The synthesis and characterization of elemental chlorine
occurred in 1774 by Carl Wilhelm Scheele, who called it
"dephlogisticated muriatic acid air," having thought he
synthesized the oxide obtained from the hydrochloric acid.
Because acids were thought at the time to necessarily contain
oxygen, a number of chemists, including Claude Berthollet,
suggested that Scheele's dephlogisticated muriatic acid air
must be a combination of oxygen and the yet undiscovered
element, and Scheele named this new element within this oxide
as muriaticum.
In 1809, Joseph Louis Gay-Lussac and Louis-Jacques proved
that this newly discovered gas was the simple element which
was reconfirmed by Sir Humphry Davy in 1810, who named it
chlorine, from the Greek word chlros meaning "green-yellow."
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Deacons method
HCl
mixed with unconverted HCI and system is washed with cold water and
dried with conc. H2SO4. This is an old method for manufacture of chlorine and
is not in used now.
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175 oC
190 oC
2AuCl3 2AuCl + 2Cl2 Au + 3Cl2
375 oC
600 oC
PtCl4 PtCl2 + Cl2 Pt + 2Cl2
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Cl2
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ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin
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