SODA INDUSTRY

Soda Ash dan Caustic Soda

 Sodium carbonate or SODA ASH (Na2CO3)

Soda ash usually found in the form of hidrate: Sodium

carbonat mohonidrat, sodium carbonat heptahidrat,
sodium carbonat decahidrat
Monohidrate : Na2CO3.H2O 85.48 % Na2CO3 +14,52 % water
Heptahidrate : Na2CO3.7H2O 45.7 Na2CO3 + 45.3% water
Decahidrate : Na2CO3.10H2O(sal soda or washing soda) 37,06 Na2CO3
+ 62,94 % water
 SODA ASH MANUFACTURE

Le Blanc Process
Trona Purification Process
Dual Process
SOLVAY Process atau Ammonia-Soda Process
 Soda Ash : Le Blanc Process

Le Blanc roasting salt cake + carbon + limestone

dalam rotary furnace, leaching the product with water
SODA ASH (Na2CO3)
 Le Blanc Process

Reaction of Soda Ash production in the Le Blanc Process :

2NaCl+H2SO4 Na2SO4+2HCL
4C+Na2SO4 Na2S+4CO
Na2S+CaCO3 Na2CO3+CaS
Treatment of CaS :
CaS + H2S Ca(SH)2
Ca(SH)2 + CO2 + H2O CaCO3 + 2 H2S
H2S + O2 H2O + S
 SODA ASH : Trona Purification Process

TRONA : Carbonate mineral: Na3(CO3)(HCO3)2H2O

Two type of process in Trona Purification:
1. Trona calcination impure soda ash purification pure soda
ash (MONOHIDRATE PROCESS)
2. Calcination of purified sesquicarbonat from trona
(SODIUM SESQUICARBONATE PROCESS)
Trona Purification Process : Monohidrate
Process
The trona ore is cursed and then calcined in a rotary kiln
150-300 deg C sodium sesquicarbonat decomposition
(Na2CO3.NaHCO3.2H2O) Na2CO3, H2O, CO2

The calcined material, which is impure soda ash, is agitated

in tanks with water or weak soda ash liquors to dissolve the
soda ash and soluble impurities, such as sodium chloride
and sodium sulphate.
Trona Purification Process : Monohidrate
Process
Insoluble material, consisting of shale, clay, and complex
salts containing calcium carbonate, is separated from the
hot, near-saturated soda ash solution.
Crystallization is carried out in multiple effect evaporators at
a maximum temperature of about 100 deg C, which is below
the transition temperature of monohydrate to anhydrous
soda ash
 Trona Purification Process : Sodium
Sesquicarbonate process

Crushed trona dissolve saturated mother liquor.

Saturated mother liqour evaporated in vaccum
crystrallizers, cooled to 40 deg C sodium sesquicarbonate
crystal centrifuge sesquicarbonate crystals
Sesquicarbonate crystal calciner 200 deg C soda ash
 SOLVAY or Ammonia Soda Process

Raw Materials:
- Brine (NaCl), composition of 28% w/w
- Lime stone(CaCO3)
- Ammonia
Reaksi overall :
Principal of Solvay Process :
Ammonia is dissolved in a salt solution and then ammoniate brine solution
is allowed to react with CO2 obtain by calcining lime stone with coke. A
precipitate of NaHCO3, thus obtain is then calcined to produce high purity
Na2CO3.
Reactions
BLOCK DIAGRAM of Solvay Process
 Processing Stage

1. Preparation and purification of brine

2. Ammoniation of Brine (AMMONIA TOWER)
3. Lime kiln
4. Carbonation of ammonium brine (CARBONATION
TOWER or SOLVAY TOWER)
5. Filtration
6. Calcination
7. Ammonia Recovery
 AMMONIA ABSORBER

The purified brine is allowed to percolate down the strong

ammonia tower in which ammonia gas is passed through the
bottom. The brine and ammonia thus meet in a counter current
fashion. The brine solution thus takes up the necessary amount of
ammonia
Reactions :
2 NH3 + H2O + CO2 (NH4)2 CO3
If Ca and Mg were found in Brine solution :
CaCI2 + (NH4)2 CO3 CaCO3 + 2NH4CI
MgCI2 + (NH4)2 CO3 MgCO3 + 2NH4CI
NH4OH + CO2 NH4HCO3
NH3 + H2O NH4OH
 Carbonation Tower (SOLVAY TOWER)

Carbon dioxide obtained from the lime kiln is first compressed and
then passed through the bottom of carbonating tower down which
ammoniated brine percolates.
The sodium bicarbonate with ammoniated brine formed a solution of
ammonium carbonate. This ammonium carbonate solution with some
unconverted NaHCO3 is allowed to fall down a second tower, called
making tower, along with ammoniated brine (which was previously
washed) and rich carbon dioxide (90-95%) gas from the bicarbonate
calciner is recompressed and pumped to the bottom of the making
tower. The ammonium carbonate first reacts with CO2 to form
ammonium bicarbonate and the latter reacting with salt, forms sodium
bicarbonate.
 Carbonation Tower (SOLVAY TOWER)

Carbonating towers are about 22-25 m height, 1.6-2.5 m in

diameter and constructed of cast iron.
Reactions:

(NH4)2CO3 + CO2 + H2O 2 NH4HCO3

NH3 + H2O + CO2 NH4HCO3
 Filtration and Calcination

The slurry from carbonation tower filtered on a rotary vacuum

filter. The filtrate containing NaCl, NH4Cl, and NH4HCO3 is
treated with lime obtained from lime kiln to recover NH3 and
CO2. The solution containing crystals of NaHCO3 is drawn off
from the base of the carbonation tower and filtered to get
NaHCO3.
The NaHCO3 obtained from the above step is heated strongly
in kiln to covert it into sodium carbonate (Na2CO3)
2NaHCO3 Na2CO3 + CO2 + H2O
The carbon dioxide produced here is sent to carbonation
tower.
 AMMONIA RECOVERY TOWER

The ammonia is recovered in a distillation column. The filtrate of

rotary filter cocntaining NaCl, NH4Cl, and NH4HCO3 is fed into tower
where free ammonia and carbon dioxide are driven off by
distillation.
Dry lime or milk of lime (slaked lime) obtained from lime kiln is fed
through the lime inlet and mixed with the liquor from the upper
part or heater. As the liquor flows down the column, calcium
chloride and calcium sulfate are formed and NH3 gas is released.
Reaction :
NH4HCO3 NH3 + H2O + CO2
2NH4CI + Ca (OH)2 2NH3 + 2H2O + CaCI2
 Caustic Soda (NaOH)
Sodium hydroxide (NaOH), also known as lye and
caustic soda is a highly caustic metallic base which is
a white solid available in pellets, flakes, granules, and
as 50% saturated solution.ses
It is used in soap, rayon, dyes, paper, drugs, foods,
rubber, textiles, chemicals, bleaching, metallurgy and
petroleum industries.
Caustic soda and chlorine are produced as co-
products by the electrolysis of brine.
 Manufacture of Caustic Soda (NaOH)
Sodium Chloride solution (brine) is electrolytically decomposed to
elemental chlorine (in the anode compartment), and sodium
hydroxide solution and elemental hydrogen (in the cathode
compartment) in all the processes
Overall reaction :

Method of manufacture :
Lime-Soda Process
Electrochemical : Chloro Alkali Process
 Lime Soda Process
Sources of raw material :
Sodium carbonate (can be manufactured by Solvays process, dual
process or electrolytic process
Lime stone is obtained from mineral calcite or aragonite, which can
be used after removal of clay, slit and sand (silica).
Reaction :

Block diagram :
 Process Description

Series of causticizer tank or agitator are added with 20% solution of soda
ash and milk of lime or slaked lime. The causticizer tanks containing steam
line to heat the mixture to 8090 deg C are either fitted with mechanical
stirrer or compressed air as substitute of agitator.
After the equilibrium the liquid is allowed to settle for 2-3hour. The clear
liquid containing about 10% NaOH is drawn by a swing pipe. The sludge is
washed in counter current manner with the washing of the previous
operation. The causticising process is completed in the series of three
agitators.
The mixture of NaOH and CaCO3 from the last agitator is charged to the
first Door thickener, which consist of a large shallow cylindrical tank into
which the slurry is fed at the center. 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
 DIAGPRAHM CELL
Two types of diagprahm cell :
(1) Submerged Cells
Cathodes remain submerged in this type of cell. Graphite is
universally used as anode. The liquid in the cathode
compartment is at low-level in order to prevent the back flow
of OH ions by diffusion. E. g. Hooker and Townsend cells
(2) Dry Diaphragm Cells
The diaphragm cells contain a porous asbestos diaphragm
which permits a flow of brine from the anode to cathode and
prevents the mixing of anode product and cathode products.
Graphite is used as an anode. Electrolysis starts with dry or
empty cathode compartment. E. g. Nelson, Gibbs and Vorce
cells
 Sub Merged Cell
The cathode assembly has hydrogen and caustic off takes and the
cathode connection. The cathode is directly covered with asbestos and
forms the diaphragm, 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.
 Dry/Porous diaphragm cells
Sources of raw material :
- Common salt can be obtained from sea water, salt lake and sub soil
water
- Sodium carbonate
- Sulphuric Acid for Chlorine Drying
 Dry/Porous diaphragm cells
Manufacture :
1. Brine purification
2. Brine electrolysis:
10 to 15% caustic soda solution along with some unconverted NaCl is
obtained after electrolysis.
3. Evaporation and salt separation :
The liquid obtained from the salt separator is 50% caustic soda solution
containing 2% NaCl and 0.1 to 0.5% NaCl on a dry basis.
4. Final evaporation :
99% of water from caustic soda solution and molten caustic soda is formed
at 500 deg C to 600 deg C. Another method of dehydrating 50% caustic soda is
the precipitation of NaOH.H2O by adding ammonia which also succor to purify
the caustic soda.
 Dry/Porous diaphragm cells
5. Purification of caustic soda
Impurities of 50% caustic soda solution : colloidal iron, NaCl and NaClO.
Iron is removed by treating caustic with 1% by weight of 300mesh CaCO3 and
filtering the resulting mixture through a filter on CaCO3 per coat.
Sodium chloride and hypochlorite are removed by dropping the 50% caustic
solution through a column of 50% NH4OH.
6. Chlorine Drying