NaOH Production Process

1 . RAW MATERIALS FOR CAUSTIC SODA PRODUCTION

Brine (salt water), sodium and chlorine are the major raw materials for
the industrial manufacture of caustic soda. These are obtained by dissolving
rock salt or naturally occurring brines. The salt solution contains some
impurities, these salts are salts of sodium, and magnesium. A critical parameter
in the chlor-alkali process is determining the purity of the feed brine. In the
membrane cell production process of caustic soda, trace levels of alkaline earth
metals (such as calcium and magnesium) and iodide can shorten the membrane
life. To ensure production efficiencies, the sum of calcium and magnesium must
be less than 20 ppb in 30% sodium chloride (NaCI).

2 . RAW MATERIAL PURIFICATION

The presence of trace metalssuch as magnesium, calcium, and

manganesein the brine feedstock can poison the ion-exchange membrane cell
and halt the chlor-alkali process. Iodide, present at ppb concentrations, is
another critical analyte to measure as it can interact with trace levels of alkaline
earth metals at the membrane surface and compromise the membranes useful
life. Soda and milk slake lime of a lime solution, are used to purify the brine.
Treatment with soda
MgSO4 + Na2CO3 MgCO3 + Na2SO4

CaSO4 + Na2CO3 CaCO3 + Na2SO4

Treatment with slake lime
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Mg(HCO3)2 + 2 Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O
Thickening and filtration are the main methods of removing all
suspended solids and precipitates.

3. Brine Purifier

3.1 primary brine purification

The PTFE membrane has many advantages compared to the present
system. It can filter up to submicron level. The PTFE membrane is applied at
many of the recent technologies where filtration is an essential part. The
conventional filtration is done through multiple steps before reaching to the

electrolyser but the PTFE membrane does not require clarifier and precoat
systems which reduces much of the operation and maintenance cost. A
bundle of tube inserted with PTFE membrane will be placed inside a dome
like structure will be used for the brine filtration. The brine enters the bottom
part of the vessel and passes through the tube during which much of the
suspended solids gets absorbed and crystal clear brine will reach at the top
surface. The solid sludge is removed by back wash process. It is also seen
that economic life of the PTFE membrane is high compared to the
traditional systems.
3.2 Secondary Brine Purification Unit
The secondary brine unit consists of two chelate resin towers.
The tower is a cylindrical MSrubber lined vessel having a perforated
plate in the lower portion of the vessel. Around 264 nos.of strainers are fitted
in the perforated plate. The strainers are made up of PPO (Poly
phenyleneoxide). Four cubic meter of DIOION-r-II is kept filled over the
strainers. The height of the resinwill be around 1.43 mts from the
perforated plate. Brine inlet distribution consists of four
poly p r o p y l e n e p i p e s f i t t e d a t t h e t o p d i s h e n d . H C L
i n j e c t i o n d i s t r i b u t i o n p i p e m a d e u p o f p o l y propylene wrapped
by poly propylene cloth is fitted just above the resin surface. There
are 3sight glasses fitted in the resin tower vessel. This will indicate the resin
level during the variousstages of regeneration. The resin level during HCL
injection will be in the lower most level dueto shrinkage of resin. After the
second backwash step, the resin level will be in the top sight glasslevel, due
to expansion of the resin particles.
The polished brine after adjusting the temperature to 60
Deg.C is sent to the CHELATE resincolumns. Temperature of polished
brine to Chelate resin columns is controlled by regulating LPsteam flow
rate to polished brine heater (E.151). in the chelate resin columns,
the hardness of brine is reduced to less than 20 ppb by absorption with
chelate resin. Two columns are providedin series and are operated in a merry
go round mode.
The two ion exchange vessels are normally operated in series while in
service. The brine solution passes from one ion exchange vessel (primary) to
the second ion exchange vessel (secondary).When the ion exchange resin in
the primary vessel is exhausted the primary vessel is passed andtotal brine

flow diverted to the secondary vessel. The primary vessel is then

regenerated. After regeneration, the brine flow is again diverted to
pass through the regenerated vessel, which istaken back in service as
secondary ion exchanger.
When the hardness at the outlet of the first resin column in the series
reaches more than 100 ppm or 24 hrs service (whichever is earlier) it is
isolated for regeneration.
REGENERATION INVLOVES FOLLOWING MAJOR STEPS:
1. B A C K W A S H : D M w a t e r i s i n t r o d u c e d f r o m t h e
b o t t o m o f t h e c h e l a t e r e s i n c o l u m n t o make the resin
loose and remove any suspended solids or broken resin to outside the
column.
2. E L I M I N A T I O N B Y H C L : H C l d i l u t e d t o
about 4 wt% is fed to the column at its
t o p exposure of the entire resin to the acid causes exchange of all the
hardness and heavy metals with H+ ions. After the elimination any
excess of HCl in the column is washed out with DM water.
3. R E P L A C E M E N T O F H + W I T H N a + B Y N a O H :
S o d i u m h y d r o x i d e d i l u t e d t o a b o u t 5 wt% is
introduced from the bottom of the resin column. Exposure of the
entire resin to NaOH causes exchange of H+ ion with Na+ ions. After
the replacement, any excess NaOH is washed out with DM water.
4. B R I N E R E P L A C E M E N T : B e f o r e t h e
chelate resin column (T.151 A/B) is put
i n t o operation the fluid in the column is replaced with secondary brine.
The regenerated resin is put into service as secondary column
in the series.

3 . Electrolyzer
BASIC PRINCIPLE
NaOH is produced by the following principle:
Electrochemical reaction in an Ion-Exchange
Membrane Electrolyzer by utilization of super purified brine.
Sodium chloride is dissolved in the brine solution in the
anode compartment according to thefollowing equation.
NaCl ======

Na+ +

Cl-

The principal anodic reaction involves oxidation of the anion Clto produce gaseous chlorine
2Cl- ====

Cl2

2e-

The cation Na+ in the anode compartment is transferred with water to

the cathode compartment t h r o u g h t h e i o n
exchange membrane. Water is electrolyzed in the cathode
c o m p a r t m e n t according to the following equation.
2H2O + 2e-

=====

2H+ + 2OH- ==== H2 + 2OH-

The primary cathodic reaction is the reduction of the cation

H+ to produce gaseous H2 a n d t o regenerate hydroxyl ions.
The sodium cation Na+ combines with OH- to form NaOH
Na+ + OH- ======

NaOH

The overall chemical reaction

2NaCl + 2H2O ===== 2NaOH + Cl2 + H2
DM w a t e r i s f e d i n r e c y c l e N a O H l i n e i n o r d e r t o
r e g u l a t e t h e N a O H s t r e n g t h i n cathode compartment. Depleted brine
is discharged with chlorine from the anode compartment. Caustic soda
produced in the cathode compartment is discharged with hydrogen

from cathode compartment. Recycled caustic diluted with DM water is fed

into the cathode compartment.

REACTIONS AND SIDE REACTIONS

Reaction in the cathode chamber
The main reaction on the cathode surface is H2O reduction.
H2O +

e-

======

H2 (g)

+ OH-

--- (1)

1/F mol of OH- is generated in the cathode side and (1/EK) mol of
OH- is back migrated to the anode side through the ion exchange
membrane where EK is a current efficiency in the cathode side.
Reaction in the anode chamber
The main reaction on the anode surface is Cl- oxidation i.e.
Cl- ===== Cl2(g) + e----(2)
The electrochemical side reaction is O2 (g) generation by H2O oxidation i.e.
H2O +
O2 + 2H+ + 2e- ----(3)
The first chemical side reaction
in chlorine dissolution without dissociation according to the
equation
Cl2(g) ======

Cl2(a q)

The second chemical side reaction is free chlorine dissolution in water

according to equation
Cl2(aq) + H2O ====== HOCl(aq) + H+ + ClThe third chemical side reaction is dissociation with the
hypochlorus acid, HOCl according to the equation
HOCl + OCl- ====== 2 OCL- + H+

--- (6)

The fourth chemical side reaction is CLO3- generation according to the

equation
2HOCl + OCl- ====== ClO3 + 2H+ + 2Cl-

--- (7)

The fifth chemical side reaction is neutralization between H+ ions generated

by the side reactions(eq. 3, 5, 6 & 7) and OH- ions back migrated from the
cathode side
H+ + OH- ======

H2O

-------(8)

The sixth chemical side reaction is neutralization between H+ ions and

Na2CO3 and NaHCO3 inthe feed brine according to the following reactions
Na2CO3 + 2HCl ====== 2NaCl + H2O + CO2
NaHCO3 + HCl ======= NaCl + H2O + CO2

6. Multiple effect evaporator

7. Centrifuge
8. Salt Saturator
9. Denuding Tower
10. Dryer