Process Synthesis Term Project:

Chloroalkali process: Membrane cell

Synthesis of sodium hydroxide through electrolysis of sodium chloride (brine)
Madhumita
Aneesh
Richa

Acknowledgement
 We would like to show our appreciation to Mr. Abhishek Sharma for
giving us the opportunity to pursue this project ’Chloroalkali process’. It
was a valuable exploration of knowledge and information and has helped
us form a deep and thorough understanding of the material industry.

Table of contents
 The Chloro alkali process and the membrane cell
 The membrane cell mechanism
 Uses of Caustic soda
 Process flow diagram
 Material Balance
 Energy Balance
 Atom and process economy
 Bibliography
The chloro alkali process and membrane cell
 Electrolysis of aqueous sodium chloride solution (brine) to produce
chlorine and sodium hydroxide (lye/caustic soda)
 Most common chloroalkali process system is a membrane cell
 Overall Reaction:
 2NaCl + 2H2O  Cl2 + H2 + 2NaOH
 2 moles of Sodium Chloride reacts with 2 moles of water to produce
one mole of chlorine, one mole of hydrogen and 2 moles of sodium
hydroxide
Membrane cell mechanism

Uses of Caustic Soda

 Sodium hydroxide is an organic compound (NaOH). It is used in many
industries: in the manufacture of pulp and paper, textiles, drinking water,
soaps and detergents and as a drain cleaner
 Saturated brine is passed into the first chamber of the cell.
 Here, oxidation of chloride ions happens at the anode. The chloride ions
lose electrons to become chlorine gas:

2Cl-  Cl2 + 2e-

 The membrane at the center of the cell is ion permeable and allow for
ion exchange. It allows the sodium ions (Na+) from the brine solution to
pass to the second chamber of the cell.

 In the second chamber of the cell, positive hydrogen ions are pulled from
the water molecules of the brine solution and are reduced by the
electrons provided by the electrolytic current (and the oxidation of
chloride ions) to form hydrogen gas and release hydroxide ions back into
the solution:
 2H2O + 2e-  H2 + 2OH-
 The sodium ions that have permeated into the second chamber of the
cell react with the hydroxide ions released from the reaction at the
cathode to produce caustic soda (sodium hydroxide NaOH).
 The overall reaction, as mentioned previously:
 2NaCl + 2H2O  Cl2 + H2 + 2NaOH

 Membrane: prevents reaction between chlorine and hydroxide ions.

Otherwise, chlorine disproportionates to form chloride and hypochlorite
ions.

 Anode: Titanium (non reactive because of corrosive nature of chlorine)

 Cathode: Nickel (more easily oxidized)

Process flow diagram

Material Balance across system
Basis: We want to produce 1000 kg/hr of NaOH
In order to achieve this, we will be working backwards, from the last process
to the first process as sodium hydroxide is our final product.

Process 3: Single stage Evaporator

Calculations:
 We know that there is 1000 kg/hr of NaOH in the product 1, which is a
solution of aqueous NaOH (50% conc NaOH).
1000/0.5= 2000 kg/hr of aqueous NaOH (50% conc NaOH)
 Water content in product 1: 0.5 x 2000= 1000 kg/hr
 The amount of NaOH in the feed and the amount of NaOH in the product
1 is equal. The feed has aqueous NaOH (35% conc NaOH). Therefore, the
total feed is: 1000/0.35= 2857.14 kg/hr
 The water content in the feed is: 0.65 x 2875.14 = 1857.14 kg/hr
 Applying a water balance, we can find the amount of water vapor in
product 2: Water (Feed) = Water (Product 1) + Water (Product 2)
 1857.14 = 1000 + 1.0(Water vapor)
 Therefore, the amount of water vapor in product 2 is 857.14 kg/hr

Process 2: Membrane cell

Calculations:
 Overall Reaction of membrane cell is:
2NaCl + 2H2O  Cl2 + H2 + 2NaOH
 Extent of reaction is 55%

2NaCl 2H2O  2NaOH H2 Cl2

Mass flow
(kg/hr) (actual)
2658.83 818.1 1000 25 875
(moles x
mol.wt)

Molecular
weight
58.5 18 40 2 70
(kg/mol)
(from periodic
table)

Moles flow
(theoretical)
45.45 45.45 25/0.4= 22.72 22.72
(mass/mol wt) 45.45
Moles flow
(Actual)
45.45 45.45 25 12.5 12.5
(mass/mol wt) (25 (25
x 0.55
used) used)
  We calculated that the NaCl required to produce 1000 kg/hr of NaOH is
2658.83 kg/hr. We also know that this is 28% of the total aqueous
solution of NaCl coming as feed. Therefore, the total feed is:
2658.83/0.28=9495.82 kg/hr
 The water content in the feel is: 0.72 x 9495.82 = 6836.99 kg/hr
 To find the slurry composition: We know that only 25 moles of the NaCl
that was fed was used, the rest (45.45-25=20.45 moles) is excess that
goes into the slurry. Therefore the amount of NaCl in the slurry is 20.45 x
58.5 = 1196.33kg/hr
 The excess water from the reaction is 20.45 x 18 = 368.1 kg/hr
 The total amount of water present in the slurry is: 368.1 +6836.99 =
7205.09 kg/hr
 The slurry is recycled back into the original feed stream to be used again.
It will be brought to the required concentration first by adding more
water and then it will be recycled as feed.

Process 1: Brine purification

Calculations:
  We know that P2 has a total product of 9495.92 kg/hr and has 28% NaCl.
We also know the assumed amount of sodium carbonate is 20 kg/hr.
 We can apply an overall balance and a salt balance to give the following
equations:
 1. 0.28(9495.82) + 0.10 S = 0.15 F
 2. F + 20 = S + 9195.82
 Solving equation 1 and 2 simultaneously, we get the value of S to be
24749.2 kg/hr and F to be 34225.02 kg/hr.
 The constituents of F1 (34225.02 kg/hr) are: 0.28 x 34225.02=5133.75
kg/hr of NaCl and 0.72 x 34225.02= 29091.27 kg/hr of water
 The constituents of the slurry S (24749.2 kg/hr) are: 0.10 x 24749.2=
2474.92 kg/hr of NaCl and 22274.28 kg/hr of water
 The slurry is recycled
 We now know that to produce 1000 kg/hr of Sodium hydroxide in
aqueous solution, we need to feed 5133.75 kg/hr of sodium chloride
Process 4: Dryer

Calculations:
 We know that the feed of wet chlorine is 875 kg/hr. We have assumed
the amount of H2SO4 (98% conc.) to be 25 kg/hr.
 By applying a mass balance, we have the following equation 1: Wet Cl2 +
H2SO4 (98% conc.) = dry Cl2 + H2SO4 (70% conc.)
 The amount of inlet hydrochloric acid is equivalent to the amount of
outlet hydrochloric acid because there is no reaction taking place.
Therefore, we get the following:
 0.98 x 25 = 0.70 x H2SO4 (70% conc.)
 Thus, we find the amount of H2SO4 (70% conc.) is 35 kg/ hr
 Substituting this in equation 1, we get the amount of dry Cl2 to be 865
kg/hr

Energy Balance across

system
Important concept:
 m = mass flow rate of substance
 Cp= specific heat capacity of a substance at a specific temperature
 ∆T=change in temperature
 Lv= Latent heat
 Sensible heat: Q= mCp∆T
 When phase changes, Q=mL
 ∆HR= Heat of reaction= ∆HF (products) - ∆HF (reactants)
 ∆HF= Heat of formation
 NOTE: IN THE FOLLOWING CALCULATIONS, DATUM TEMPERATURE IS
ASSUMED TO BE 25˚C

Membrane Cell:
Material name Specific heat at 60˚C (kJ/kgK) Flow rates (kg/hr)

H2O 4.185 818.1 (only 450 used)

Aqueous NaCl solution 3.247 2658.83 ((only 1450

(28% wt) used)

Material name Specific heat at 80˚C (kJ/kgK) Flow rates (kg/hr)

Hydrogen (g) 14.43 25

Chlorine (l) 0.48 875

NaOH (35% by wt) 3.594 2857.14

Slurry 3.247 8401.42

Calculation:
 Heat of reaction ∆HR=

Material Heat of Number of Total heat of

name formation moles formation (kJ)
∆HF (kJ/mol)
Water -285.96 25 -7149
NaCl -411.14 25 -10275
Hydrogen 0 12.5 0
Chlorine 0 12.5 0
NaOH -425.9 25 -10647.4

 ∆HR= Heat of reaction= ∆HF (products) - ∆HF (reactants)

 ∆HR= 10647.4 – (7149 + 10275)= -6776.6 kJ
 Total Heat Input= ∆HR+ Heat required to raise temperature of reactants
from 25˚C to 60˚C (Qin)
 Qin= mwater Cp(water)∆T + mNaCl Cp(NaCl)∆T
 Qin= (818 x 4.185 x (60˚-25˚)) + (2658.83 x 3.247 x (60˚-25˚))
 Qin= 3140841.6 + 6776.6 = 3147618.19 kJ

 Qout = Heat required to raise temperature of products from 60˚C to 80˚C

(Qin)
 Qout= mhydrogen Cp(hydrogen)∆T + mchlorine Cp(chlorine)∆T + mNaOH Cp(naOH)∆T +
mslurryCp(slurry)∆T
 Qout= (25 x 14.43 x (80˚-60˚)) + (875 x 0.48x (80˚-60˚)) + (2857.14 x
3.594 x (80˚-60˚)) + (8401.42 x 3.247 x (80˚-60˚)) = 766574.438

 Total energy investment = 3147618.19-766574.438= 2381043.752 kJ/hr

to produce 1000 kg of NaOH in membrane cell.
Single stage Evaporator
 Inlet stream
Material name Specific heat at 80˚C (kJ/kgK) Flow rates (kg/hr)

Aqueous NaOH (35% by 3.594 2857.14

weight)

 Outlet stream
Material name Specific heat at 60˚C (kJ/kgK) Flow rates (kg/hr)

Aqueous NaOH (50% by 3.564 2000

weight)
Steam 2231.86 857.14

Calculations:
 Total heat input
 Qin= mNaOH Cp(NaOH)∆T
 Qin=2857.14 x 3.594 x (80-25)= 564770.84 kJ

 Total heat output

 Qout= mNaOH Cp(NaOH)∆T + msteam Cp(steam)∆T
  Qout= (2000 x 3.564 x (110-80)) +(857.14 x 2231.86 x
(110-80))=57604334.41 kJ

 Total heat generated: 57604334.41 - 564770.84 = 57039661.57 kJ/hr

Dryer (heat exchange)

 Inlet stream:
Material name Specific heat at 80˚C (kJ/kgK) Flow rates (kg/hr)

Wet Chlorine 0.48 875

H2SO4 (98% conc) 1.465 25

 Outlet stream
Material name Specific heat at 70˚C (kJ/kgK) Flow rates (kg/hr)

Dry Chlorine 0.48 865

H2SO4 (70% conc) 2.177 35

Calculations:
 Qin= mwet chlorine Cp(wet chlorine)∆T
 There is no temperature change in sulfuric acid as it is entering system at
25˚C therefore, the term gets cancelled out
 Qin= 875 x 0.48 x (80-25)= 23100 kJ

 Qout= mdry chlorine Cp(dry chlorine)∆T + msulfuric acid Cp(sulfuric acid)∆T

 Qout= (875 x 0.48 x (70-25)) + (35 x 2.177 x (30-25)) =19280.975 kJ

 Heat investment= 23100 - 19280.975 = 3819.025 kJ/hr

Atom economy and process economy

 Compound Vi (number Mi ViMi Mass flow ($/kg) ($/day)
of moles) Molecular (kg/hr) rate
(mol) weight (kg/day)
(kg/mol) (SF= 24)
NaCl -45.45 58 2658.83 -63811.92 0.42 -26801

Water -45.45 18 818.1 -19634.4 0.04 -785.38

Chlorine 12.5 70 875 21000 0.50 10500

Hydrogen 12.5 2 25 600 14.00 8400

NaOH 25 40 1000 24000 0.50 12000

Total profit/day ($) 3313.62

Bibliography:
1. Subrata Basu , Swapan Kumar Mukhopadhyay , Amitava Gangopadhyay
and Sujata G. Dastidar “International Research Journal of Environment
Sciences Characteristic Change of Effluent from a Chlor-alkali Industry of
India due to Process Modification” 2013
2. S.Koter.A.Warszawski “Polish Journal of Environmental Studies Electro-
membrane Processes in Environment Protection”
3. Yohannes Kiros and Martin Bursell “International Journal
Electrochemistry Science Low Energy Consumption in Chlor-alkali Cells
Using Oxygen Reduction Electrodes (2008)”
4. Rezaee, J. Derayat, S.B. Mortazavi,Y. Yamini and M.T. Jafarzadeh
“American Journal of Environmental Sciences Removal of Mercury from
Chlor-alkali Industry Wastewater using Acetobacter xylinum
Cellulose(2005)” Dryden’s outlines of chemical technology (2012)
5. Murphy, M. Regina “Chemical processes: Principles, Analysis and
Synthesis” 2007