Manufacturing of

Caustic
Soda
Harshal Marathe
2017A1PS0635G

Ritvik Hegde
2017A1PS0743G

Siddesh Patil
2017A1PS0849G

Siddhant Waikar
2017A1P0852G

Piyush Agarwal
2017A1PS0898G
About Caustic Soda

▸ Caustic soda, is an inorganic compound with the formula

NaOH.
▸ It is a white solid ionic compound consisting of sodium
cations Na+ and hydroxide anions OH−.
▸ Sodium hydroxide may be an extremely caustic base and
alkali that decomposes proteins at normal ambient
temperatures and may cause severe chemical burns.
▸ It is extremely soluble in water, and readily absorbs
moisture and carbon dioxide from the air.
▸ It forms a series of hydrates NaOH·nH2O.
▸ The hydrate NaOH·H2O crystallizes from water solutions
between 12.3°C and 61.8 °C.
▸ The commercially obtainable "sodium hydroxide" is usually
this monohydrate

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In the Industry
Caustic Soda is used in many industries:
▸ In the manufacture of wood pulp and paper, textiles,
drinking water, soaps and detergents, and as a drain
cleaner.
▸ Poor quality crude oil can be treated with sodium
hydroxide to remove sulphurous impurities in a
process known as caustic washing.
Current Market:
▸ There are more than two hundreds manufacturers in
the world, and high-end products are mainly from
America and Western Europe.
▸ Worldwide, giant manufactures are mainly
distributed in America, Europe and China.
▸ Caustic soda industry mainly concentrate in several
manufacturers like Dow (now Olin), Axiall, OxyChem
etc.
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Market of Caustic Soda in India:
▸ The Installed Capacity as on 31 March 2018 was
38.80 Lakh MTPA.
▸ The Production during the year 2017-18 was 32.42
Lakh MT.

SECTOR WISE CAUSTIC SODA

CONSUMPTION IN INDIA DURING 2017-18:

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Existing Production
Process
● Electrolysis of brine is one of the most common
process used for the production of Caustic Soda in
the industry

● Called the ‘Chlor Alkali process’ it gives chlorine and

sodium hydroxide.

● Industrial Scale production began in 1892.

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● The electrolysis process has three different
alternatives which each have their advantages and
shortcomings.

● Namely:
a) Castner-Kellner Cell (Mercury Process)
b) Nelson Diaphragm Cell
c) Membrane Cell

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1. Castner Kellner Cell
● Apparatus divided into two cells. Sodium metal
formed on one side of the cell dissolves as an
amalgam, which in the other part gives Na+. The net
effect of the cell is increase in concentration of NaOh
which is removed as product from the bottom.
● A by-product of this process is Chlorine gas.

Left - Right of Cell Center of Cell

● Electrolyte: sodium chloride ● Electrolyte: sodium hydroxide
solution solution
● Anode: Graphite ● Anode: Mercury
● Cathode: Mercury ● Cathode: Iron
● Rxn at Cathode: Na+ + e− → Na ● Rxn at Cathode: 2H2O + 2e− →
(amalgam) 2OH− + H2
● Rxn at Anode: Cl− →1/2 Cl2 + e− ● Rxn at Anode: 2Na (amalgam)
→ 2Na+ + 2e−
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2. Nelson Diaphragm Cell

● Uses Sodium chloride as an electrolyte with

a titanium anode and steel cathode.
Separated by a diaphragm made of a porous
substance like asbestos or metal oxide.

● It prevents the hydroxide ions entering anode

compartment and prevents chloride ions entering
cathode compartment.

● Na+ migrates across diaphragm to cathode

compartment combining with OH- to form NaOH.

● The NaOH formed can be crystallised out of the cell.

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3. Membrane Cell
● Favored method for producing very pure
NaOH
● Has the lowest power requirements and leaves
no harmful waste
● A selective ion exchange membrane separates
the cathode and anode side.
● Saturated brine enters the anode side which is
made of titanium.
● Na+ migrates across the membrane to cathode
compartment combining with OHto form NaOH.

Anode: Titanium
Reaction: 2H2O(l) + 2e H2(g) + 2OH- (aq)

Cathode: Nickel
Reaction: 2Cl- (aq) Cl2(g) + 2e

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Flow sheet of the selected method:

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 KEY SHORTCOMINGS OF
THE PROCESS

● Chlorine is evolved as a by-product and is not advisable to

do so, keeping in mind the harm it causes to the
environment,

● Chlorine containing oxygen must be purified by

liquefaction and evaporation introducing further operation
costs.

● Mercuric poisoning may also be involved when one of the

electrodes has mercury

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● High capital cost is involved because of titanium
electrodes and ion selective membranes

● Efficiency of reactions involved is 80-85% and some

NaOH also goes in the form of a slurry and is very
difficult to recover.

● Requires pretreatment of raw material (brine)

● Electrolysis produces heat and thus additional cooling

is required than necessary.

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Process Intensification

Unit Operation Necessity

Brine Saturation Help to bring the undersaturated brine up to

saturation conditions

Brine Purification Purifying raw brines which containing impurities

Electrolysis Building the atmosphere to occur chemical reactions

Cooling and Remove the brine mist

Filtration Reduce the heat of the gas

Concentration Increase the NaOH concentration of the brine.

Drying Removing the moisture

Compression Decrease the volume of the gasses.

Liquefaction Removing the oxygen content 13

Process Intensification
Solid Salt + Water Brine Brine
Impurities
Saturation Purification
HCl H20
Cooling & Cl2 gas H2 Gas
Cooling Water Electrolysis Cooling
Filteration
Caustic Solution
H2SO4 Drying Concentration Liquid
Hydrogen
Caustic Solution
Compression Cooling

Liquefaction
NaOH

Liquid
Chlorine

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Material Balance
Ag Nacl
1 2
10% NaCO3
Nacl by
wt
Brine 3
Purifier Purified NaCl
(28% by wt)

4
Sludge(10% by NaCl by wt)

Assumptions: No material accumulation in the steady state.

Stream Flow Rate(kg/hr)

1- aq. NaCl 15%(w/w) X

2- Na2CO3 Y

3- Pure aq.NaCl 28%(w/w) Z

4- Sludge 10% NaCl (w/w) U 15

Material Balance
Feed NaCl:
15/100 x Feed (F) = X
NaCl = F kg/hr.
Balancing overall material:
Feed (F) + Na2CO3 = |Sludge|4 + |NaCl|3
F +Y = |Sludge|4+ |NaCl|3 ………………………………..(a)
Balancing NaCl:
X = 28%|NaCl|3 + 10%|Sludge|4
100X = 28|NaCl|3 + 10|Sludge|4…………………………..(b)

Solving Equations (a) and (b)

We get
|NaCl|3 = Z Kg/hr
|Sludge|4 = U Kg/hr

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Material Balance
Membrane Cell

Stream Flow Rate (kg/hr)

1- Pure aq.NaCl 28%(w/w) Z

2- H2 A

3- Cl2 B

4- aq. NaOH 35%(w/w) C

5- Slurry D 17
Material Balance
Assumptions
1. Amount of liquid in the cell is constant throughout the process
ie: Q1 = Q4 + Q5 (Q = Volume Flow rate)
2. Slurry doesn’t contain NaOH
3. The volume changes of liquid due to evolution of Cl2 and H2 are
negligible.

Finding |NaOH|4;
Amount of NaCl entering a membrane cell = 28%*|NaCl|3 = 28%*(Z) = x kg/hr
Molar flow rate = x / 58.5 = y kmol/hr
No of moles of NaOH produced = 55%*(y) = p kmol/hr
Amount of NaOH produced = p*40 = z kg/hr
|NaOH|4 = z / 35% = C kg/hr

Finding Water in;

Amount of Water entering a membrane cell = 72% * |NaCl|3 = 72% * (Z) = u kg/hr
Molar flow rate = u/18 = v kmol/hr
Taking water to be Excess. Hence NaCl as the limiting reagent

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 2NaCl + 2H2O → 2NaOH + H2 + Cl2

(Mass)in flow x u
(kg/hr)

Molecular 58.5 18 40 2 70
Weight (g/mol)

(Moles)in flow y v
(kmol/hr)

Production Rate - (0.55y) -(0.55y) +(0.55y) +(0.275y) +(0.275y)

at 55%
(kmol/hr)

(Mass)out flow x- u- (0.55y)*4 A= B=

(kg/hr) (0.55y)*58 (0.55y)*1 0 (0.275y)* (0.275y)*
.5 8 2 70

Balancing total mass;

|NaCl|1 = |H2|2 + |Cl2|3 + |NaOH|4 + |Slurry|5
X = (0.275y) + (0.275y) + C + |Slurry|5
|Slurry|5 = D 19
ENERGY BALANCE
In this process the chlorine and hydrogen are the byproducts and
shall hence not be considered in the balances in the steps involving
the energy balances.

Using Material Balance Data,

1 2
Ag Nacl Assumptions:
10%
Nacl by
wt
Brine 3 1) No material accumulation of material
Purifier in steady state
Purified NaCl
(28% by wt)
1) Energy Consumption in the saturator
4 unit is negligible
Sludge(10% by NaCl by wt)

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ENERGY BALANCE
Energy balance for the Membrane Cell would be as follows:

Assumptions :
1) Change in specific heat capacity values with temp are negligible
2) The No energy/ work loss in the cell.

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 ENERGY BALANCE

Stream Specific Heat 60 ०C Flow Rate Temperature

(KJ/Kg K) (kg/hr) Change (K)

Water(25 ०C) 4.185 W 35

1- Pure aq.NaCl 3.247 Z 35

28%(w/w)

2- H2 14.420 A 35

3- Cl2 0.480 B 35

4- aq. NaOH 3.594 C 35

35%(w/w)

5- Slurry 3.247 D 35

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ENERGY BALANCE

Stream Heat Content (KJ/hr)

Water 35*4.185*W = 146.475*W

1- Pure aq.NaCl 28%(w/w) 35*3.247*Z = 113.645*Z

2- H2 35*14.42*A = 504.7*A

3- Cl2 35*0.48*B = 16.8*B

4- aq. NaOH 35%(w/w) 35*3.594*C = 125.79*C

5- Slurry 35*3.247*D =113.645*D

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ENERGY BALANCE
Input Stream = Stream 1 + Water Stream =146.475*W +113.645*Z

Output Stream = Stream 2 + Stream 3 + Stream 4 + Stream 5

= 504.7*A + 16.8*B + 125.79*C + 113.645*D

Electric Power Needed = Output Stream - Input Stream

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