Chemical Technology (CHE1004)

DR.S.KARTHIKA
ASSISTANT PROFESSOR (SENIOR)
 Chloro alkali industries

Three major chemicals Soda ash manufacture

 Soda ash/washing soda  Natural soda ash from
(sodium carbonate – deposits
Na2CO3)  Solvay/ammonia soda
 Caustic soda (sodium process
hydroxide- NaOH)  Dual process
 Chlorine (Cl2) Chlorine-caustic soda
Uses of soda ash  Electrolytic process
 Chlorine process without co
products
 NaOH process with no Cl2
coproduct
 Soda ash
manufacture
NH3 dissolved in NaCl solution and then treated with CO2
to give NaHCO3 which on calcination gives high purity soda
ash. (Solvay in 1869)
The following steps are involved
 Brine purification
 Ammoniation of brine

 Reactions in Solvay Tower

 Reactions in klin/Separation of solid sodium
hydrocarbonate formation of sodium carbonate
 Ammonia Recovery
 Production process

Brine purification Lime Kiln

 Brine solution is concentrated by evaporation to at least CaO is formed as a by-product of the thermal
30 per cent . decomposition of limestone in the lime kiln.
 Calcium, magnesium and iron are collected as
precipitants in this reaction.
CaCo3(s)- CaO(s)+CO2(g)
Ca2+(aq) + CO32-(aq) → CaCO3(s) C(s)+O2 (g) - CO2(g)
Mg2+(aq) + 2OH-(aq) → Mg(OH)2(s)
Fe3+(aq) + 3OH-(aq) → Fe(OH)3(s) This CaO enters a lime slaker to react with water
to form calcium hydroxide:
 Following the precipitation reaction, brine solution is
then filtered and passed through an ammoniation
tower to dissolve ammonia. CaO(s) + H2O (l) → Ca(OH)2(aq)

Ammoniation This milk of lime is used to recover ammonia in

combined NH3 still.
 Through this process energy is released because of its
exothermic nature, thereby, the ammonia tower will get
cooled by this energy. NH3(g)+H2O ⇌ NH4+ OH-
 Carbonation and NH3 recovery
 The Solvay Tower is tall and contains a set of Formation of sodium carbonate in calciner
mushroom-shaped baffles to slow down and break  Suspended sodium hydrogen carbonate is
up the brine flow so that the carbon dioxide can removed from the carbonating tower and
be efficiently absorbed by the solution. heated at 300oC to produce sodium carbonate
(carbonation)
CO2(g) + H2O(l)   ⇌ HCO3-(aq) + H+(aq)  2NaHCO3(s) → Na2CO3(s) + H2O (g) + CO2
(g)
NH3(aq) + H +
(aq)    ⇌ NH4 +
(aq)

Free & Combined NH3 still

HCO -
3 (aq)  + Na +
(aq)    ⇌ NaHCO3(s)  The filtrate from rotary filter is sent to free
NH3 is driven off in the free ammonia stills
 Overall reaction by distillation

 The calcium hydroxide produced is reacted

NH3(aq) + CO2(g) + NaCl(aq) + H2O(l) →
with the ammonium chloride separated out of
the carbonating tower by filtration
NaHCO3(s) + NH4Cl(aq)
 Ca (OH)2(aq) + 2NH4Cl(aq) → CaCl2(aq) +
 NaHCO3 precipitates as a solid in the lower part 2H2O(l) + 2NH3(g)
of the tower, which is cooled.
 Major Engineering Problems

 Caking of NaHCO3 inside the kiln

 Disposal of solid waste
 Ammonia recovery
 Economic tower design
 Thermal pollution

For more information

https://www.ausetute.com.au/solvay.html
https://www.essentialchemicalindustry.org/chemicals/
sodium-carbonate.html
M A N U F A C T U RE O F C H L O R IN E -
CAUSTIC SODA
 Electrolysis process

The Chlor-Alkali industry in India forms an

important component of basic chemicals industry
,comprising around 74% of the basic chemicals
production in India.

Three methods of electrolysis

The diaphragm cell process
The mercury cell process
The ion exchange membrane process
The mercury cell process, now phased out in Europe
and US (due to environmental concerns)

The diaphragm cell process (used as main route in

US)

The membrane cell process, used in Europe, US.

In India, mercury and diaphragm cells are used.

Mercury cell
 Mercury electrolytic cell

The salt from the centrifuge is added to salt saturator.

Depleted brine from mercury cell is also added to it to attain saturation

Cell description

Cathode – thin film of mercury running in a sloped, narrow trough modern rubber-lined or
PVC-lined steel cells
The anodes are a series of titanium plates (100 cells) suspended 2mm above mercury level
Brine flowing on mercury gets electrolyzed to form sodium amalgam

Amalgam flow s into down the decomposer (made of steel and contains graphite blocks). Water
flow counter currently, releases Na from amalgam as NaOH (50-70% NaOH) & H2 gas.
Pure grade is filtered, evaporated and solidified.
Wet Cl2 is cooled to remove moisture, dried in H2SO4 scrubber and compressed to liquid Cl2.
H2 evolved at cathode can be used as boiler fuel or hydrogen source for synthesis reactions.
 Diaphragm cell
Membrane cell

Membrane is (0.15-0.3 mm thick)

and is a co-polymer of  tetrafluoro
ethane

https://www.essentialchemicalindustry.org/chemicals/chlorine.html#membrane
_cell
http://www.oocities.org/tiger_dil3000/
https://www.essentialchemicalindustry.org/chemicals/sodium-hydroxide.html
 Diaphragm electrolytic cell

 Treatment of brine solution to remove calcium,

magnesium, iron salts
 Saturated brine solution (25-28% NaCl) is heated and
electrolyzed in diaphragm cell
Decomposition efficiency 45-55%
Discharges 10-12% caustic soda + NaCl [H2 and Cl2 are also released]
 Concentrate the cell liquor to 50% NaOH in multiple
effect evaporators. (commercial grade)
 This is further concentrated to saturated 73% NaOH or
fused to flake, granular or stick caustic.
 Major Engineering Problems

 Mercury is detrimental to the aquatic life. Therefore this

water should be passed through a special mercury trap
where the mercury could be recovered.

 Mercury vapour pollutes the air.

 Presence of wet chlorine and NaOH cause corrosion

problems.
 Production of calcium hypo chlorite

 Calcium Hypochlorite Ca(clo)2

Usage:
For bleaching purpose of wood pulp, silk, cloth and fibre.
Disinfection and water-treatment.
Disinfectant for chemical poisonous and radioactive
substance.
 It is manufactured using the calcium process or the sodium process.

Calcium Process

2 Ca(OH)2 + 2Cl2 → Ca(ClO)2 + CaCl2 + 2H2O

 Sodium Process

2 Ca(OH)2 + 3 Cl2 + 2NaOH → Ca(ClO) 2 + CaCl2 + 2H2O + 2 NaCl

 Bleaching powder is actually a mixture of calcium hypochlorite Ca(ClO)2 and

the basic chloride CaCl2 , Ca(OH) 2 , H2O with some slaked lime, Ca(OH)2 .
 Process description

Raw materials are hydrated lime and gaseous chlorine

 An aqueous suspension of milk lime is fed to the first reactor, where the chlorination takes place.
Temperature is kept constant and the reaction heat is taken away by cooling water circulation through
an external jacket.

The product discharged from the first reactor is centrifuged in order to separate mother waters, rich of
chlorides, from the solid which mainly contains dibasic hypochlorite (Ca(ClO)2.2Ca(OH)2 – an
intermediate)

The solid is suspended again in water. It is introduced too a small quantity of NaOH solution.
The new suspension is fed to a 2nd reactor where the final stage of chlorination takes place.

The product discharged from the reactor is filtered; the separated mother liquors, containing valuable
percentage of hypochlorite, are recycled to the preparation tank of 1st stage chlorination.
The filtered solid is washed and discharged into a re-slurry tank where water is added to prepare a
pumpable slurry to be fed into a spray-dryer.

The drying takes place at controlled temperature in order to avoid decomposition.
The dried product is finally stored, weighed and packed.
Thank you