A Report of In-Plant Traning

at

Gujarat Alkalies & Chemical Limited

Baroda Complex

Submitted by

Sahil Dabir

in partial fulfillment for the award of the degree

of

Bachelor of Engineering

In

Chemical Engineering Department

Faculty of Technology & Engineering

Maharaja Sayajirao University of Baroda
 CERTIFICATE
This is to certify that Mr. Sahil Dabir, a third-year undergraduate of Bachelor of Engineering in Chemical
Engineering from MSU, Baroda has completed his 6 week period (1/06/22 to 10/07/22) industrial
training at Gujarat Alkalies and Chemicals Limited, Baroda Complex.

This report is submitted for this training at the same time.

TRAINING MENTOR

DATE:
 ACKNOWLEDGEMENT
It has been my upmost privilege to work with Gujarat Alkalies and Chemicals Limited. The opportunity
of training here has given me an enriching learning experience & practical knowledge which is necessity
in modern growing world today. I have been quite fortunate enough to have trained under knowledgeable
people and extremely hardworking staff.
I would like to thank MSU, Baroda for providing me such a great opportunity & let myself adopt this
kind of environment at a very early stage.
I would like to thank Mr. Y.K. Shishode as well as the H.R. department for helping me out the orientation
of my vocational training and the efforts to make whole process of my training at GACL smooth. I would
like to extend my thanks to M. Upadhyay for guiding and helping me to solve all kind of queries
regarding the project and providing additional knowledge.
 OBJECTIVE OF INTERNSHIP
The objective of the internship is to acquire practical knowledge and on-field experience along with the
theoretical experience gained by us. Training of the students in the field of the engineering is necessary
as it provides them with required knowledge of the industry and equips them to prepared for work.

The technology is evolving day by day and the students in this field of engineering should be well versed
with the latest technology being used in the industries today. So, to build a better tomorrow, it is
imperative that student youth must be trained in the respective fields of education. This fact was literally
reflected in the internship experience incorporated by me at GACL
 INDEX

TABLE OF CONTENTS
CHAPTER -1 INTRODUCTION ......................................................................... 6
1.1 ABOUT GACL .................................................................................................................................................................................................. 6
1.2 HISTORY OF GACL .................................................................................................................................................................................... 7
1.3 PRODUCTS OF GACL ................................................................................................................................................................................ 8
1.4 PRODUCT SPECIFICATIONS ............................................................................................................................................................... 9
1.5 TECHNOLOGY PROVIDERS ................................................................................................................................................................. 9

CHAPTER-2 CAUSTIC SODA PLANT ......................................................... 10

2.1 PROPERTIES OF CAUSTIC SODA (NAOH) ................................................................................................................................10
2.2 OVERVIEW OF CAUSTIC SODA PLANT .....................................................................................................................................11
2.3 SECTIONS OF CAUSTIC SODA PLANT (NAOH).....................................................................................................................11
2.3.1 BRINE HOUSE ................................................................................................................................. 11
2.3.2 CELL HOUSE ................................................................................................................................... 17
2.3.3 COMPRESSOR HOUSE: ................................................................................................................ 20
2.3.4 CAUSTIC EVAPORATION UNIT (CEU): .................................................................................... 27
2.3.6 HCL UNIT ......................................................................................................................................... 31
2.3.7 HYPO UNIT ...................................................................................................................................... 32
CHAPTER 3 HYDROGEN PEROXIDE (𝑯𝟐𝑶𝟐) PLANT .............................. 33
3.1 ABOUT HYDROGEN PEROXIDE: ....................................................................................................................................................33
3.2 PROPERTIES .................................................................................................................................................................................................33
3.3 CHEMICAL REACTION FOR SYNTHESIS OF 𝐇𝟐𝐎𝟐 ..........................................................................................................34
3.4 PROCESS DESCRIPTION ...........................................................................................................................................................................35

CHAPTER 4 CHLOROMETHANE (CLM) PLANT ....................................... 40

4.1 METHANOL PLANT (MEOH)..............................................................................................................................................................40
4.1.1 INTRODUCTION TO METHANOL PLANT: ...............................................................40
4.1.2 PROCESS DESCRIPTION: ..............................................................................................41
4.2 CLM-1 ..................................................................................................................................................................................................................44
4.2.1 INTRODUCTION ..............................................................................................................44
4.2.2 DESCRIPTION OF SECTIONS .......................................................................................44
PRESSURE SWING ADSORPTION (PSA) UNIT ...............................................................................................................................49

CHAPTER-5 MATERIAL BALANCE .............................................................. 51

5.1 INTRODUCTION ............................................................................................................................................................................................51
5.2 MASS BALANCE OVER PRECIPITATORS IN CS PLANT .................................................................................................51
5.3 MATERIAL BALANCE OVER ELECTROLYTIC CELL: ....................................................................................................54

CHAPTER 6 ENERGY BALANCE.................................................................... 56

6.1 INTRODUCTION .........................................................................................................................................................................................56
6.1 ENERGY BALANCE ON ELECTROLYZERS .............................................................................................................................56

CHAPTER- 7 CONCLUSION: .......................................................................... 59

CHAPTER-8 REFERENCES: ............................................................................. 60
 CHAPTER -1 INTRODUCTION

1.1 ABOUT GACL

GACL is one of the largest producers of Caustic Soda in India, with a production capacity of 1087 TPD.
GACL is accredited with ISO 9001:2015, ISO 14001:2015, ISO 45001:2018, ISO 50001:2018
Popularly known as GACL is situated 15 kms north of Vadodara near Ranoli on the main railway track
between Ahmedabad and Vadodara near huge IPCL Complex.
The Second Plant has been set up in 1995 in Dahej in Bharuch District 450 kms north of Mumbai and
then and hours train journey from location on the seashore of Gujarat port trust Ltd.
1.2 HISTORY OF GACL
Gujarat Alkalies and Chemicals Limited (GACL) was incorporated on 29th March, 1973 in the State of
Gujarat-by-Gujarat Industrial Investment Corporation Limited (GIIC), a wholly owned company of
Govt. of Gujarat, as a Core Promoter.
The Company commenced its operations in 1976 with 37,425 MTPA Caustic Soda Plant based on the
then, state-of-the-art Mercury Cell process at its Plant which is situated 16 km North of Vadodara near
Village Ranoli on the main Railway track route between Ahmedabad and Mumbai.
GACL has two units located at Vadodara and Dahej, both in the State of Gujarat. It has integrated
manufact. facilities for Caustic Soda, Chlorine, Hydro. Gas, Hydrochloric Acid, Chloromethanes,
Hydro. Peroxide, Phosphoric Acid, Potassium Hydroxide, Potassium Carbonate, Sodium Cyanide,
Sodium Ferrocyanide. The Dahej unit also has 90 MW Captive Power Plant (CPP) for regular and
economical power supply.
Right from the inception, GACL has been following the strategy of continuous capacity expansion in
core areas. The first stage expansion of the Caustic Soda Plant raising the capacity to 70,425 MTPA was
undertaken in October, 1981 followed by a diversification programme to produce 2000 MTPA of
Sodium Cyanide in December, 1982.
In 1995, as a part of diversification programme and to meet the growing demand of its products in the
State of Gujarat and nearby areas, the Company had set up a plant for the manufacture of Technical
Grade Phosphoric Acid with a capacity of 26400 MTA (85% Phosphoric Acid) at a new location at
Dahej, District Bharuch. GACL-NALCO Chemicals Limited (GNAL) is a Joint Venture with NALCO,
that is setting up a Membrane Cell-based grass root Caustic-Chlorine Unit with a capacity of 100000
MTA at Dahej. Along with this, a captive 130 MW co-generation Power Plant is also being set up so as
to ensure uninterrupted and low-cost power for its captive operations.
In 1984, the second stage expansion to increase the capacity of Caustic Soda Plant to 103,425 MTPA
was undertaken. Simultaneously, the Company undertook the diversification project for manufacture of
10,560 MTPA of Chloromethanes using Chlorine, a co-product of the Company and in 1991, the
capacity of Chloromethanes production was doubled.

Since production of Caustic Soda is highly power intensive, in order to reduce power cost and to
eliminate mercury pollution, the Company during the year 1989 converted one of its Cell Houses
producing Caustic Soda from Mercury Cell Technology to environment friendly Membrane Cell
Technology, thereby eliminating the use of mercury. The Capacity of Caustic Soda was also increased
to 132000 MTA.
The conversion of second Mercury Cell to Membrane Cell was carried out during March, 1994, thereby
eliminating the total use of mercury from the Complex for production of Caustic Soda and increasing
the capacity of plant along with this conversion to 170000 MTA including Potassium Hydroxide facility.
As part of this Membrane Cell Conversion Project, a new facility for manufacture of 16500 MTA of
Potassium Hydroxide Lye based on Membrane Cell was also set up. The Company has further set up
facility for converting part of this Caustic Potash Lye into Potassium Carbonate with a capacity of 13200
MTA.
As power is the major input for production of Caustic Soda and constitutes about 65% - 70% of the cost
of production, the Company alongwith other Corporations like M/s. GSFC, Petrofils Co-operative Ltd.
and Gujarat Electricity Board promoted a gas-based power unit in Vadodara under the name of Gujarat
Industrial Power Company Ltd. (GIPCL) during the year 1985. As a promoter of GIPCL, the Company
gets low-cost power, as the plant is gas based and is depreciated.
In order to add further value to its products, the company had set up manufacturing facility for production
of 11000 MTA Hydrogen Peroxide (100%) at Vadodara Complex during the year 1996 to utilize
Hydrogen gas, which is a co-product from Caustic Soda Process
1.3 PRODUCTS OF GACL
Caustic Soda Group
 Caustic Soda Lye
 Caustic Soda Flakes
 Caustic Soda Prills (Not in Baroda Complex)
 Hydrochloric Acid
 Compressed Hydrogen Gas
 Chlorine
Caustic Potash Group
 Caustic Potash Lye
 Caustic Potash Flakes
 Potassium Carbonate
Chloromethane Group
 Methyl Chloride
 Chloroform
 Carbon Tetrachloride
 Methyl Chloride
Hydrogen Peroxide Group
 Hydrogen Peroxide
Special Chlorine Derivative Group
 Anhydrous Aluminum Chloride
 Chlorinated Paraffin
 Benzyl Alcohol
 Benzyl Chloride
 Benzaldehyde
Sodium Chlorate Group
Sodium Chlorate
1.4 PRODUCT SPECIFICATIONS
Production (Vadodara Caustic
Product Complex)
MT/Day Concentration
(Min.)
Caustic Soda Lye 485 47.0%
Caustic Soda Flakes 165 99.5%
Chlorine (Gas/liquids) 410 99.8%
Hydrogen (Gas) 89.88 99.5%
Hydrochloric Acid 500 30.0%
Caustic Potash lye 45 47.0%
Caustic Potash Flakes 44 87.0%
Potassium Carbonate 44 99.0%
(Powder and Granules)
Hydrogen Peroxide 38 100.0%
Methyl Chloride 3 99.0%
Methylene Chloride 115 99.0%
Chloroform 36 99.9%
Carbon Tetrachloride 18 99.9%

1.5 TECHNOLOGY PROVIDERS

 ThyssenKrupp UHDE Chlorine Engineers, Germany
 Shin-Etsu Chemical Co. Ltd, Germany

1.6 Block Diagram of Products (Vadodara Complex)

 CHAPTER-2 CAUSTIC SODA PLANT
2.1 PROPERTIES OF CAUSTIC SODA (NAOH)
2.1.1 P HYSICAL PROPERTIES
IUPAC Name Sodium Hydroxide
Chemical Formula NaOH
Molar Mass 39.9971 g/mole
Appearance White, waxy, opaque crystals
Odour Odourless
Density 2.15 g/𝑐𝑚
Melting point 318 °C
Boiling point 1388 °C
418 g/1 at 0°C
Solubility in water 1110 g/l at 20°C
3370 g/l at 100°C
Solubility Soluble in glycerol, Negligible in Ammonia,
Insoluble in Ether, slowly soluble in propylene glycol.
Solubility in methanol 238 g/l
Solubility in ethanol <139 g/l
Vapor pressure <2.4 kPa at 20°C
pH Highly alkaline
Refractive Index 1.3576
Flammability Not flammable
Flashpoint Not applicable
Stability Stable and doesn't decompose

2.1.2 CHEMICAL PROPERTIES

1) Reaction with Acids: Sodium hydroxide reacts with acids to form salt and water.
NaOH + HCl NaCl + H O
2NaOH + H SO Na SO + H O

2) Reaction with Acidic oxides: Sodium hydroxide reacts with carbon/sulfur dioxide to form sodium
carbonate/sulfite and water.
2NaOH + CO Na CO + H O
3) Reaction with Fats: Sodium hydroxide reacts with fats to form soap, and the reaction is known as
saponification.
NaOH + Fat Soap + Glycerine
2.2 OVERVIEW OF CAUSTIC SODA PLANT

2.3 SECTIONS OF CAUSTIC SODA PLANT (NAOH)

In Caustic Soda Plant, Caustic Soda and Caustic Potash lye is Manufactured. During this process chlorine,
hydrogen and chlorates are obtained as by-products.
Caustic soda Plant comprises of following sections:

1. Brine House
2. Cell House
3. Compressor Unit
4. Caustic Evaporation Unit
5. Caustic Concentration Unit
6. HCl Unit
7. Hypo Unit

2.3.1 BRINE HOUSE

So, raw salt is unloading for Salt Washery plant. And if Salt Washery is not working then raw salt is fed
to Saturator via Conveyor. For Caustic production, ultra-pure brine is must. It is done by membrane cell
electrolytic cell. Before that Sulphate, Calcium & Magnesium impurities have to remove. Following step
is included in brine system.

A) Brine Saturation
B) Brine Precipitation
C) Brine Clarification
D) Brine Filtration
E) Brine Polishing
F) Ion Exchange
A) BRINE SATURATION:
 The Saturation unit consists of 2 existing saturators, one in operation and other standby.
 The saturators are charged with salt with the help of bucket elevator via Conveyor Belt. The lean brine
(210-220 g. NaCl) coming from the cell house is dechlorinated and as its temperature is high it is cooled
in plate type heat exchanger with polished brine and then it is fed into the existing saturator.

 Through dip pipes the brine enters the saturator. The dip pipes are
facilitating the lean brine to rise from bottom to top and through
this passage lean brine is almost saturated.

 Insoluble material will get settled down. And it is removed

periodically in a form of sludge.

 The Concentration required is 310 gpl of brine which is maintained

by adjusting valve located on the bypass line near the lean brine
line (dip pipe)

 DM water is added to the lean brine line to make up the water loss due
to water migration to catholyte and evaporation.

 The pH in saturator must be kept below 9 as the silica in salt may get
dissolved at higher pH values. Hence recovery of alkaline waste brine may be done only under careful
supervision.

 Crude brine leaves as an overflow content from the top of saturator flows to new precipitation tank by gravity

B) BRINE PRECIPITATION:
 Impurities present in the saturated brine coming from saturator in the form of precipitates as Ba SO ,
CaCO and Mg(OH)
 There are 3 precipitation tanks by which 2 is in operation and one on standby. BaCO and Na CO are
added in first tank and Caustic soda is added in second tank. Reactions occurring in tanks are:

Ba CO + Na SO BaSO + Na CO

Na CO + CaCl CaCO + 2NaCl

2NaOH + Mg(Cl) Mg(OH) + 2NaCl

 In precipitation tank, air nozzles are provided at the bottom to spurge compressed air coming from
water in compressor, so that the precipitates remain in suspension.

 From the above given reactions it is clear that Barium Carbonate Sodium Carbonate and caustic soda are
reacted with impurities and form of Ba SO , CaCO and Mg(OH)
CHEMICAL PREPARATION FOR BRINE PRECIPITATION
 10% solution of BaCO and Na CO are prepared separately either in brine or DM water.

 There are two tanks and two pumps. One tank is under preparation and other tank is under feeding to
the chemical tank. Feeding is by centrifugal pumps and flow is measured by rotameter.

 The recirculation with high velocity is maintained to prevent the settling of chemicals in the pipes.
Barium Carbonate tank and Sodium Carbonate tanks is used for chemical preparation and feeding.
Chemical bags are charged manually to the hopper of respected tanks. Amount of Barium Carbonate
tank and Sodium Carbonate is decided on the basis of amount of sulphate and calcium respectively
present in salt. Amount of NaOH decides on basis of amount of magnesium present in salt. Chemical
tanks are connected with agitation air blower to facilitate agitation of the solution during the
preparation as well as feeding.
C)BRINE CLARIFICATION:

The crude brine containing Ba SO , CaCO and Mg(OH) precipitates which is settled down in clarifier.
In the clarifier more than 90% of solids will settled at the bottom of the clarifier and drawn off and pumped
out directly to the sludge tank with the help of pumps.
The clarifier underflow contains about 10% solids. The clarifier brine passes from the overflow launders to the
existing clarified brine tanks. clarified brine is collected in tank from these tanks is fed to Anthracite filters for
further separation of solids.

 For better settling of solids Flocculant is

added to the inlet of clarifier. This Flocculant
is sticky if it becomes wetted. So, impurities
will be stick with this Flocculant. And this
impurity becomes heavy and settled down
easily. This Flocculant is prepared in a tank
and pumped by metering pump to NaOH
Clarifier.

D)BRINE FILTRATION:

 The Clarified brine containing about l00ppm solids will be further filtered in the Anthracite filters.

 There are total nine filters of which are connected in parallel.

 In each anthracite filters there are total

3 fixed beds of anthracite(charcoal).
First bed from top having small size of
anthracite and as we move down the
size of anthracite becomes larger.
These fixed beds are rested on the
perforated plate. These plates having
filter nozzles of polypropylene which
prevents passing anthracite towards the
filter.

 Clarified Brine enters the filter housing

from top by means of pump pressure.
  So, when the clarified brine passes through these beds the charcoal adsorb the impurities and the
filtered brine is obtained.

 The filtered brine coming from the anthracite filters is collected in a filtered brine tank. This tank level
is controlled with the help of a level controller by controlling the brine flow at the outlet of polishing
filters.

 Each Anthracite filters is backwashed once a day by polished brine flow from bottom to top.
E) BRINE POLISHING:

 Solid is further separated in the polishing filters.

 Filtered brine goes to 2 types if filters:

1) Dr. M Filter
2) Scheibler Filter
1) Dr. M Filter

 This is the new generation filter which is used to polish the filtered brine.

 In this filter, the candles are there inside and the cloth are wrapped around these candles.

 When the Filtered brine passes through these clothes the impurities are adsorbed on the cloth and
Polished brine is obtained.

 To achieve good polishing and to avoid plugging of

micropores of filter candles by very fine suspended solids
present in brine, a pre-coat of 𝛼-cellulose is applied on
the outside of the candles before filtration is started.

 The application of 𝛼-cellulose is to bind the filter cake of

candle filters. During filtration, a small amount of 𝛼-
cellulose is added to brine as body feed is prepared in body
feed tank with agitator and fed in to brine thus porosity of
filtered medium increases.

2) Scheibler Filter

 This is the filter used to polish the filtered brine coming

from Anthracite filter.

 In this cloth supported on rods. Each filter contains 42

cloth bags as filter element.
In both filters the solid face builds on surface of filter medium
where it forms uniform cake. The filter cake gets stuck to gaps of
cloth. Since the brine throughout is constant, the pressure drop
across the filter increases with the increase in thickness of filter
cake, the pressure drop across the filter is monitored and it must not exceed to 2 bars.
In Dr M Filter, when pressure exceeds 2 bars the it goes to backwash but in Scheibler filter, when pressure
exceeds 2 bars the cakes are remove manually.
Now the Polished brine which is obtained from both these filters are collected in Polished Brine storage tank.
Now we know that the polished brine which is used in Ion exchange column should having high temperature.
So first this brine goes to chlorine recuperator (Shell and tube type heat exchanger) where it heat exchange
with chlorine gas coming from cell house which is having high temperature. These above polished brine goes
to Ion Exchange Column.
F) ION EXCHANGE COLUMN

Brine coming from the polished brine contains 𝐶𝑎 and 𝑀𝑔 impurities which are supposed to be
removed to concentration of less than 20 ppb (parts per billion) to make the brine suitable for membrane
cell.
This is done in ion exchange column. There are 2 columns. Both are in series.
One column acts as a main operating column and other is under regeneration
Column is filled with ion exchanger resin, with a very high selectivity for Calcium, magnesium
and strontium ion.
Ion exchange reaction can be written as follows:

𝐶𝑎 + 𝑁𝑎 Ca (Resin) + 2N𝑎
This reaction continues until equilibrium’s achieved and the break through point is reached then the resin must
be regenerated to its original state by another ion exchange reaction using consecutively 7% HCl and 5%
NaOH solution. The resin is then ready for further service. The reaction during regeneration can be represented
as:

Ca (Resin) + 2HCl H + Ca Cl
During this reason a volume concentration of approximate 40% from the initial volume of the sodium present
in resin takes place. After removing the calcium from the resin, the conversion to Sodium takes place by
treating with Caustic Soda solution.

𝐻   (Resin) + 2NaOH N𝑎 + 2H   O
The conversion to sodium ion is followed by expansion to its original volume.
This above three reactions is one regeneration. During such regenerations, a small position of resin beds will
be fractured due to repeated and excessive and contraction. It may be expanded about 5% to 10% of resin will
be fractured after 200 regeneration cycles.
These fines along with impurities which bind with the resin increase the pressure drop across the column which
causes further fracturing. Hence this removed from the bed by backwashing. During Backwash, DM Water
flow is from bottom to top.
The facilities removal of fines is done by
fluidization. The solution for regeneration (30%
HCl) and conditioning (32% NaOH) are stored
in their respective tanks. The Ultra-Pure Brine
from the ion exchange column then goes to pure
brine head tank via brine heat exchanger.
According to the load of the Electrolyser and
heat loss in Brine system, the feed brine to the
cell must be heated or cooled down. Therefore,
the pure brine cooling Heat-exchanger is
designed operated with either cooling water or
steam. The steam pressure is 0.5 bar g. The
purpose of reducing the pressure is to limit the
Temperature inside the Heat-exchanger in order to avoid corrosion, damage of the gasket
 Table: Recharge cycle for Resins

Sr. No. Steps Time (mins)

1 Isolation of column 2

2 Brine displacement (By DMW) 80

3 Backwash (DMW) 20

4 Regeneration 60

5 Acid rinsing (7% HCl) 80

6 NaOH conditioning 60

7 Caustic rinsing (with DMW) 20

8 Water displacement 15

9 Preparation 20
2.3.2 CELL HOUSE
Ultrapure Brine prepared in Brine System has to undergo Electrolysis process.
Electrolysis Process
Electrolysis is defined as a process of decomposing ionic compounds into their elements by passing a direct
electric current through the compound in a fluid form. The cations are reduced at cathode and anions are
oxidized at the anode. The main components that are required for conducting electrolysis are an electrolyte,
electrodes, and some form of external power source is also needed. Additionally, a partition such as an ion-
exchange membrane or a salt bridge is also used but this is optional. These are used mainly to keep the products
from diffusing near the opposite electrode.
This Process is usually done in a vessel named ‘electrolytic cell’ or ‘electrolyser’ containing two electrodes
(cathode and anode) connected to a direct current source and an electrolyte which is an ionic compound
undergoing decomposition, in either molten form or in a dissolves state in a suitable solvent. Generally,
electrodes that are made from metal, graphite and semiconductor materials are used. However, the choice of
a suitable electrode is done based on chemical reactivity between the electrode and electrolyte as well as the
manufacturing cost.
Types of Electrolyzer
There are three types of Electrolyzer used in this process.
a. Mercury cell
b. Diaphragm cell
c. Membrane cell

 Previously Mercury cell is used. But Mercury is very toxic in nature. So, it has to be banned.

 Then Diaphragm cell is used. But during that operation NaOH is obtained in Anode and Cathode both.
And separation of NaOH at the end is difficult. So, now this cell is not used.

 Now, Membrane cell is most widely used. Disadvantages of Diaphragm cell is come over in this cell.

 So nowadays in GACL, Membrane cell is used.

 GACL has been a pioneer in adopting the environment friendly and energy efficient technologies. It
converted to Membrane Cell Technology from Mercury Cell Technology way back in 1989 and since
1994 all the plants are running on Mercury free Membrane Cell Technology.
Advantages
The advantages of membrane cell over mercury cell and diaphragm cell are:
▪ Reduction in energy consumption in the membrane chlor-alkali process through the utilization of
perchloro-carbonic membrane suitable for production of 33-35% NaOH.
▪ Lower investment cost due to simplicity of electrolysis cell and less space requirement for electrolytic
cell
▪ Lower operation cost due to high expectancy for electrolytic cell and minimum 2 years of service life of
membrane and also due to less personal requirement for cell operation and maintenance.
▪ Operation of and high operation flexibility. And high product purity.
▪ No environment pollution due to mercury or asbestos or any other substance.
Cell Design
This Electrolysis of ultra-pure brine takes place in unit called cell house.
There are 2 cell house - MC-1 and MC-2.
Cell elements of electrolytic cell are suspended in steel frame and many of them are stacked together to form an
electrolytic cell. Each electrolytic cell contains approximate 64 elements.MC-1 contains 16 electrolytic cell and
total of 1024 elements. On other hand MC-2 has 20 electrolytic cell and total 1280 elements. MC-2 house was
made after MC-1 during the plant expansion. Element means set of anode, cathode and membrane. All
electrolytic cells are connected in parallel and the elements in cell are connected in series. As electricity passing
through cells are of high voltage the bus bar are use on negative terminal and positive terminal of the cell as the
normal cable wires cannot resist such a high voltage.
Cell Structure

Electrodes Anode -Titanium (Ti)

(MOC) Cathode – Nickel (Ni)

Anode Side Electrolyte In- Ultrapure Brine (300-310gpl)

Out- Lean Brine (220-230gpl) and C𝑙 gas

Cathode Side Electrolyte In- Dilute Caustic Soda (30%)

Out-Concentrated Caustic Soda (32%) and 𝐻 gas

Membrane Cation permeable membrane made of certain polymer (UHDE

Germany) allows only Na ion to pass through. It’s coated with
carboxylic acid on anode and with sulfonic acid on cathode side
of the membrane.

Surface area of Membrane 272 m

The Cell
The cell has 2 inlet and 2 outlets, both positioned on each
side of the cell. Inlet pipe on the anode side carries
ultrapure brine (300gpl NaCl) in the cell and the outlet
carries out depleted brine (220gpl NaCl) also called
anolyte of the cell.
While the inlet to cathode side carries 30% NaOH to it
and outlet one carries out 32% NaOH called Catholyte
out of it.
The membrane is heart of cell. It should be saved and damaged should not be done to make sure the cell runs
efficiently. Membrane (made by UHDE Technology) also called cation permeable membrane permits only
Na ion to pass through.
Anolyte and Catholyte solution from every cell enter a common header and separated. Gases go to different
section for their respective treatment. Gasket is used for leakage protection.
Gore-Tex is also used as membrane in sealed battery products, to allow pressure relief from outgassing, but
preventing ingress of moisture
Working of Cell
The most common process in GACL involves electrolysis of aqueous sodium chloride in membrane cell.
Saturated brine is passed in first chamber of cell where the chloride ion oxidized at anode, losing electrons to
become chlorine gas.
 2Cl Cl + 2e (at anode)
At cathode, water molecules is snapped by the electrons due to electric current giving hydrogen gas and
releasing hydroxide ions in the solutions.

2H O + 2e H + 2OH (at cathode)

When 33000 V AC voltage passes through step down transformer and then passes through rectifier. This
rectifier converts AC to DC voltage. This 150 V cathode and anode bushers of each element of electrolytic
cell. Due to the applied voltage the electrochemical reaction occurs.

The non – permeable ion exchange, membrane at the center of the cell allows the sodium ions Na ion to pass
to the second chamber where they react with the hydroxide ions to produce caustic soda (NaOH). The overall
reaction for the electrolysis of brine is

2NaCl + 2H O Cl + H + 2NaOH (Overall)

During this process brine concentration is reduced from 310gpl to 220gpl. This 220gpl brine called as lean
brine which contains chlorine so called anolyte brine. This chlorine is extracted from anolyte in anolyte de-
chlorination.
A membrane cell is used to prevent reaction between the chlorine and hydroxide ion. If this reaction were to
occur, the chlorine would be disproportionate to form chlorine and hypo-chloride ions.

Cl + 2OH Cl + ClO + H O

Above at chlorate 60 C chlorate is formed;

3Cl + 6OH 5Cl + ClO + 3H O

Because of corrosive nature of chlorine production, the anode must be made from non-reactive metal such as
titanium, whereas the cathode can be made from more easily oxidized metal such as nickel.
In the membrane cell the cathode surface being rough and membrane being sensitive and expensive it’s
necessary that the membrane must always stick to anode surface. For this purpose, the 𝐻 pressure is kept
higher than that of Cl as well as the flowrate of 30% NaOH entering cathode is kept at high.
Anolyte De-chlorination:

The lean brine coming from the cell house is saturated with chlorine. Before the brine is re-saturated and
purified, it shall be completely de-chlorinated. The brine is leaving the cell at 4 to 4.5pH. For de-chlorination,
the pH must be reduced to 2.0. This is done by adding HCl from tank to anolyte. This addition is through a
nozzle which ensures the proper mixing.
The chlorine saturated anolyte flows by gravity from cell to anolyte tank via anolyte header. From there,
chlorine is sucked into vacuum tank, where most of the dissolved chlorine is removed. Sufficient surface area
is provided in the tank to remove chlorine gas from anolyte. After vacuum de-chlorination, the lean brine
contains approx. 20 ppm free chlorine. As the brine in ion exchange must not contain any free chlorine,10%
sodium bisulphite is added to lean brine to remove the remaining free chlorine. This reaction takes place as
follows:

𝑁𝑎𝐻𝑆𝑂 + 𝐻 O + 𝐶𝑙 2NaHS𝑂 + 2HCl

The lean brine is transferred to saturators via a brine recuperator with help of a lean brine pump. To increase
its pH from 2.0 to 10.0, 32% NaOH is added from MC-1 NaOH overhead tank
Chlorate Destruction

There are some side reactions occurring in the electrolysis cell. One of the side reactions is the productions of
chlorate in brine circuit. The chlorate formation is not useful in brine circuit. In order to maintain chlorate
concentration less than 7 gpl measured as NaClO , a chlorate destruction unit will have to be provided to
remove chlorate from the brine. To remove chlorate which is formed due to side reactions the hydrochloric
acid having concentration of 30% is added. The reaction is given by
NaClO + 6HCl NaCl + 3Cl + 3H O

The reaction efficiency is achieved above 80% at temperature 80 C and at HCl concentration not less than
20gpl in brine. The chlorate destruction unit consists of one pair of chlorate feed pump which will feed from
anolyte tank to chlorate destruction unit via level control valve. 30% HCl is fed to tank through flow meter.
The anolyte pH controller will control the anolyte pH regulating the acidified anolyte from the chlorate
destruction tank. Steam ejector is used to heat the acidified brine up to 90-92 C.
Replacement of membrane
We know that as the time goes on the efficiency of membrane decreases as the size of pores in membrane get
decreases due to deposition of impurities and membrane require more electricity for electrolysis. One new
membrane requires 2.6 V electricity for electrolysis. If this value exceeds to 3.2 V than the membrane is
washed with caustic soda or it is being replaced.

Catholyte Circulation system

Catholyte circulation is necessary to continuous production of 32% NaOH. The 32% NaOH caustic soda
from the catholyte head tank is sent to day tank and then it is diluted to 30% by adding DM water. This 30%
NaOH solution is sent to electrolytic cell where 32% NaOH solution is made. The major portion of this 32%
NaOH solution is sent to catholyte tank.
The temperature of 32% NaOH solution
around 90 C. The minor portion of 32%
NaOH solution is sent to day tank where
certain level of NaOH is always maintain
and from that, NaOH sent to CEU
(caustic evaporation unit) where 48%
NaOH is produced. After shutdown of
plant at time of restarting the plant, this
32% NaOH solution stored in day tank is
used.

2.3.3 COMPRESSOR HOUSE:

In compressor house, the treatments of the chlorine gas and hydrogen gas which are generated in
cell house are done.
2.3.1 Chlorine Treatment
Why Chlorine Treatment is done?
Chlorine that is coming from cell house is about 98% in which impurities like lean brine and also some amount
of moisture is present. So, to remove impurities and to increase the concentration of chlorine as per requirement
and demand the chlorine treatment is done.
Equipment used for chlorine treatment:
1. Chlorine Recuperator
2. UPSV
3. 1st Cooler
4. 2nd Cooler
5. Mist filter
6. Condensate Separator
7. Drying Tower
8. Acid Separator
9. GAB (Compressor)
10. Primary and Secondary Filter
11. Liquefier
12. Buffer vessel
13. Bullet Tank
14. Evaporator
15. Bottling
 1) Chlorine Recuperator:
Chlorine heat recuperation is carried out in recuperator which is nothing but shell & tube heat
exchanger. The recuperator is kept in a vertical positioned. Chlorine gas coming from cell
house is having the temperature around 85°C. This 85°C temperature of chlorine is reduced
around to 50°C by heat transfer with polished brine coming from the brine house.
Shell Side Inlet Polished Brine at
Shell Side Outlet Polished Brine at
Tube Side Inlet Chlorine gas at around 85 C
Tube Side Outlet Chlorine Gas at around 65 C
Shell Side MOC CS
Tube Side MOC Titanium
Pressure at tube inlet 1900mmWC
Pressure at tube outlet 1760mmWC
Pressure Drop (∆P) 140mmWC

2) UPSV
Chlorine enters a very important part after the storage tank chlorine called Under Pressure Safety Vessel
(UPSV). On the top of UPSV, NRV (non-return valve) is fitted which connected to the control valve before
acid separator. Certain level of DM water is maintained in the UPSV. The purpose of UPSV is to maintain
1900mmWC pressure in the system. Chlorine passes through this vessel. In case chlorine pressure would be
less than 1900mmWC compressor cannot run dry therefore, this vessel takes atmosphere air in and balances
the pressure inside. This prevents damage of the membrane cell.

3) 1st Cooler:
Chlorine coming from heat recuperator is sent to the 1* cooler where its temperature is reduced
from 50°C to 40°C by the shell and tube heat exchanger. In this heat exchanger cooling water is
used as a cooling media.
Shell Side Inlet Cooling Water at
Shell Side Outlet Cooling Water at
Tube Side Inlet Chlorine gas at around 65 C
Tube Side Outlet Chlorine Gas at around 30 C
Shell Side MOC CS
Tube Side MOC Titanium
Pressure at tube inlet 1760mmWC
Pressure at tube outlet 1600mmWC
Pressure Drop (∆P) 160mmWC

4) 2nd Cooler
Chlorine is sent to 2" cooler where its temperature is reduced to 15°C. In 2 nd cooer, the chilled
water is used as a cooing media.

Shell Side Inlet Chilled Water at

Shell Side Outlet Chilled Water at
Tube Side Inlet Chlorine gas at around 30 C
Tube Side Outlet Chlorine Gas at around 15 C
Shell Side MOC CS
Tube Side MOC Titanium
Pressure at tube inlet 1600mmWC
Pressure at tube outlet 1400mmWC
Pressure outlet (∆P) 200mmWC
5)Mist Filter
Chlorine then enters ‘Brink Mist filter’ which contains candles
packed with glass wool. In mist filters, 4 glass-wool candles are
used to remove NaCl impurities that may come along with
chlorine gas.

No. of candles 4

MOC of candles Glass wool

Gas under Chlorine gas

Treatment

Pressure at inlet 1400mmWC

6) Condensate Separator
From the top, chlorine gas goes to the condensate separator.
Condensate separator packed with polypropylene (PP) rings
which removes the remaining moisture and decreases moisture
content by few ppm. To even further decrease the moisture
content to ppb, it is sent to drying tower in drying section.
7)Drying Tower
Chlorine from the Mist filter is dried using 98% sulfuric acid in a vertical column. Upper part of the column consists
of 6 tunnel trays and the lower part is a packed tower with packing of polypropylene rings. 98%
concentrated 𝐻 𝑆𝑂 is fed to the top of the tower and it flows down by gravity. Countercurrent heat exchange takes
place as chlorine enters from the bottom. Acid percolates down and absorbs moisture from upcoming chlorine
gas and gets collected in the sump which is than recirculated back to the 78% conc. sulfuric acid tank.
As absorption reaction is exothermic, 78% conc. sulfuric acid passes through plate type heat exchanger, where it is
cooled by cooling water and again sprayed to the top of the bottom half of tower. 98% cone. sulfuric acid from the
overhead tank is sprayed from top of the tower
where it meets with already most of moisture removed chlorine gas and reduces its moisture
content to 5-6 ppb. Diluted acid goes to the storage tank and recirculated. Only make-up of 98% conc. Sulfuric acid
is recharged.

It is important to keep chlorine temperature in a range of 15-20°C only as at lower temperatures chlorine hydrate
will begin to crystallize out in the cooler and obstruct the gas passage and corrosion of titanium due to relatively
dry chlorine may occur. At temperatures above 20°C, too much water vapor enters the drying tower and sulfuric
acid consumption would be accordingly high.
8)Acid Separator

The chlorine gas leaving the tower is 𝐻 𝑆𝑂 droplets and fumes with it. These are separated in an 𝐻 𝑆𝑂 separated
in an 𝐻 𝑆𝑂 separator and acid filter. Acid separated is returned to drying tower circulation by gravity.
9)GAB (Compressor)

The chlorine gas leaving the tower is having 𝐻 𝑆𝑂 droplets and

fumes with it. These are separated
Several methods of compression may be used: liquid ring,
reciprocating, or centrifugal.
In Compressor House, chlorine compression for its subsequent
liquefaction is done by Liquid Ring Rotary Type Compressor
which works on centrifugal action. Liquid used in the
compressor is 98% H SO .Sulphuric acid enters the compressor,
forming ring due to centrifugal force, compresses the liquid,
passes through heat exchanger and enters the compressor.
The acid concentration must be kept high to prevent corrosion.
The compression system in effect acts as an additional stage of
chlorine drying and continues to pick up traces of moisture. The system should be charged with acid of the
highest concentration available (minimum 96%). The strength of the circulating acid should be checked
regularly, and the acid should be changed when its concentration has fallen by about 2%. There should be a
provision for transferring this spent acid to the drying system.
Why wet chlorine is dried and moisture is removed before compression?
Chlorine is extremely toxic and corrosive. Releases of the gas will have serious consequences. Wet chlorine
is extremely corrosive to ferrous metals, which are the standard for fabrication of compressors and downstream
equipment. Moisture must be effectively excluded from the process. Chlorine reacts with many metals at
sufficiently high temperatures. That’s why chlorine is treated before compression.
Why liquid ring Compressor is used in GAB?
Chlorine reacts with many of the common types of lubricant and can destroy their lubricating power or even
cause fires. Contact between the gas and these lubricants must be avoided. That’s why we don’t use screw
compressor.
The dry chlorine present in the compression process will react combustively with titanium even at low
temperatures. When a compressor shuts down, backflow of the gas into a titanium-based cooling system must
be rigorously prevented.
Also, we have to create isothermal compression which is only possible in liquid ring compressors.
Why Compression is required to be done before liquefaction?

At atmospheric pressure, the boiling point of chorine is -34.6 C. So, to liquify the chlorine gas its temperature
should be higher than that.

According to ideal gas law, P ∝ T. So, if we increase pressure of chlorine gas the boiling point also increases.
Also, during the treatment of chlorine pressure is dropped. So, it’s difficult to liquify the chlorine and load will
increase on screw compressor of liquefier section of chlorine. That’s why we compress the chlorine gas before
liquefaction

After compression of chlorine, its pressure increases to 3.5 kg/cm before being liquefied by Freon in the
liquefaction unit.

10) Primary and Secondary Filtration

The chlorine gas that is being compressed from liquid ring compressor contains fumes of Sulfuric acid. So, the
chlorine gas passes through the primary and secondary filtration in which these fumes get removed.
11)Liquefier

The liquefier is simply a shell and tube heat exchanger in which chlorine is cooled by using freon-22
(dichloro-difluoro ethane).
Freon with a temperature of 20-21°C is on shell side. The level of 55% is maintained on shell side.
Chlorine gas enters tube side of liquefier with a pressure of 2.8 kg/cm , temperature around 15°C and flow
rate of 2100-2300 m /h. When chlorine gas moves from tube inlet to tube outlet it get cooled form liquid by
exchanging heat with freon. As, liquefier is tilted, the liquid chlorine gets collected on the other side of it.
During the process of heat exchange when chlorine gas converted to liquid chlorine the sniff gas is produced
which contains impurities of chlorine gas. This sniff gas is separated from pure liquid chlorine. This sniff gas
is used to the waste air de-chlorination unit in case of HCI unit failure or operating troubles.

Shell Side Inlet Freon at 21°C

Shell Side Outlet Freon at 3°C
Tube Side Inlet Chlorine gas at around 15 C
Tube Side Outlet Liquid Chlorine at around −3 C
Shell Side MOC CS
Tube Side MOC LTCS

Freon Cycle
The freon used in the liquefier to liquefy chlorine gas is in liquid form. But at room temperature
and atmospheric pressure it is in a form of gas.
At atmospheric pressure, the boiling point of freon is about -8°C. To liquefy it easily pressure is increased so
that boiling point increases. That’s why Freon-22 (dichloro-difluoro ethane) is compressed in a Screw
Compressor, which compresses the Freon from 14 to 25 kg/c𝑚 which elevates boiling point from-8°C to
60°C.
This compressed freon gas passes through two oil separators which removes oil from it which gets carried
over from the compressor. Next it enters Freon Condenser which is cooled by cooling water, where it liquefies
and gets in a by ‘Freon Receiver’.

Freon from receiver enters economizer which is just a shell and tube heat exchanger. Freon from receiver
enters economizer on shell side and one small line branched from which enters economists on tube side. Freon
from the small line passes through a Solenoid controlled expansion valve (SCEV). Freon pressure reduces
which produces a cooling effect
(Joule Thomson effect) and cools the
Freon on the shell side. In short, in
economizer we cool the Freon by
itself. Thus, Freon which is cool and
is in liquid form enters a liquefier
12) Buffer Vessel
Liquid chlorine from liquefier then passes through a 10-ft U-seal and enters a Buffer vessel. There is a
mechanism by which level in the buffer vessel is maintained at 50%.

13) Bullet Tank

Level of liquid chlorine when exceeds 50% enters into 5 large bullet tanks which are used as storage and the
bottling of chlorine is done from it.

14) Evaporator
Liquid chlorine which form lower 50% level in buffer vessel is pumped by liquid chlorine pumps to chlorine
evaporator. Evaporator is also a shell and tube heat exchanger. In evaporator chlorine exchanges heat with
ethylene glycol brine (EG Brine) which is warmer than chlorine and chlorine evaporates to gas phase.
EG brine is pumped from a brine storage tank to shell side of the evaporator. Liquefying and then evaporating
the chlorine removes impurities from it like oxygen, hydrogen and moisture from it.
After heat exchanged brine gets cooled, it is again heated up in a heat exchanger by water from super-hot well
which needs to be cooled before going to chilling unit. After heating, brine is again sent to the storage tank
and is recirculated.

Chlorine after evaporation is sent other consumers like IPCL, Reliance, Jayant Agro. or used in GACL
itself in plants like CLM, HCI unit, or hypochlorite plant.

15) Bottling
After coming from liquefier to bullet tank the pressure of chlorine is reduced. And it is very
Dangerous to fill the chlorine in bottle at a low pressure.
So first the atmospheric air is cleaned and then its pressure is increases to 11 kg/c𝑚 by air compressor and
this pressurized air is filled in bullet tank.
Then the chlorine gas is filled in bottles. As chlorine and air are unreactive and insoluble at these conditions
so it will not mix with each other and the air can be easily separated.
2.3.2 Hydrogen treatment
The equipment used in in Hydrogen Treatment are:
1) Hydrogen Recuperator
2) Mist filter
3) Safety seal
4) Hydrogen Holder
5) Compressor
6) Blower
7) Treatment of hydrogen gas for H O

1)Hydrogen Recuperator
The hydrogen is produced in cell house at operating pressure of 2200mmWC and temperature is approximately
90 𝐶 .The hydrogen is first cooled in hydrogen recuperator. It is a shell and tube heat exchanger. Here the
hydrogen is cooled down to 35 C by means of cooling water.

Shell Side Inlet Cooling water at °C

Shell Side Outlet Cooling water at 3°C
Tube Side Inlet Hydrogen gas at around 90 C
Tube Side Outlet Hydrogen gas at around 35 C
Shell Side MOC SS
Tube Side MOC SS

2)Mist Filter
After that hydrogen is sent to hydrogen filters to remove any impurities in it. In hydrogen filters the DM water
is added. In this filer there are glass wool candles which absorb impurities from hydrogen gas. This gas goes
to gas holder.

3)Safety Seal
In this safety seal water is stored. If pressure if hydrogen is increased then some amount of gas is releases in
safety seal. This gas passes though water to get bubble out. So, the pressure of gas get reduced.

4)Hydrogen Gas Holder

The function of hydrogen is to maintain suction
pressure of hydrogen gas in system. We know that
hydrogen gas cannot be stored. Hydrogen gas
holder is not storage tank but it works as a buffer,
removing the need for continuous gas production.
The weight of the gas holder lift (cap) controlled
the pressure of the gas in the mains and provided
back pressure for the gas-making plant. They are
the only storage method that keeps gas at district
pressure. This gas goes to compressor and blower
as per requirement.

5)Compressor
There are total 3 lines of compressors.
1) For CCU - 3 compressors in parallel (Single stage)
2) For Hydrogen Peroxide- 2 compressors connected in series (Double stage)
3) For Jayant agro. – 2 compressors in parallel (Single stage)
6)Treatment of hydrogen for 𝐇𝟐 𝐎𝟐
The hydrogen required in peroxide plant should be free from oxygen. The hydrogen from mist filter first goes
to de-oxo reactor where the oxygen is removed by using adsorption on silica bed. Then it is heated in heat
exchanger by using steam as a electric heater. This treated hydrogen goes to peroxide plant through compressor
at 2.3 kg/𝑐𝑚 .

2.3.4 CAUSTIC EVAPORATION UNIT (CEU):

In this unit concentration of caustic from 32% coming out from the membrane cell is increased to 47% using a
multi-effect evaporator. The evaporation unit consists of three falling film evaporators arranged in series forming
a triple effect backward feed evaporation system.
The 32% caustic solution having temperature 80-85 C enters the first caustic evaporator which gets evaporated
using vapors coming out from the second evaporator. The first evaporator is connected to the vacuum pump which
creates 600 mm Hg of vacuum. The concentration rises to 37% then it is sent to the second evaporator at 110 𝐶,
where its concentration and temperature rise to 42% and 120 𝐶 respectively.
The concentration rises to 48% in the third effect where evaporation is done by steam which is fed in at a pressure
of 8 kg/cm2 and product lye at 165’C temperature. The condensate produced in the second and third evaporators
is combined and collected in a condensate tank.
From this section, it can be sent to storage tanks and caustic concentration. 47% concentrated caustic soda from
the storage tank is sold in the market as caustic soda lye in the tankers and the rest lye is processed for the production
of caustic soda flakes in the caustic concentration unit.
2.3.5 CAUSTIC CONCENTRATION UNIT (CCU):
The Caustic Concentration Unit has total 4 parts:
1) COMBO
2) CCU-1
3) CCU-3

4) 𝐾 𝐶𝑂
1)COMBO PLANT
32% NaOH solution is stored in NaOH storage tank with the help of pump. Then, this 32% NaOH is sent to
1st evaporator and in this 1st evaporator heating media is vapour coming from 2nd evaporator and vapour
coming from the salt chest. Vapour coming from the 1st evaporator is condense in a surface condenser and
stored in vapour condensate tank. Temperature of 1st evaporator is around 86 C. After that NaOH coming
from the 1st evaporator having concentration of 48% is sent to 2nd evaporator where a heating media steam is
used. From 2nd evaporator, concentration of NaOH is increased from 48% to 63%. This 63% NaOH sent to
salt chest from the top and as a heating media molten salt is used which fed to salt chest from bottom of it.

Molten salt is mixture of three salts having concentration of 40% sodium nitrite (NaNO ) , 7% sodium nitrate
(NaNO ) and 53% potassium nitrate (KNO ). Molten salt mixture is made up in furnace. Salt mixture is fed
to bottom of furnace by molten salt pump and molten salt is collected also from the bottom of the furnace. The
fire in the furnace, the natural gas and hydrogen gas is used. For air, there is provision of two preheater of air.
This preheated air is sent to furnace. NaOH coming from salt chest is sent to anhydrous separator where vapour
and moisture are removed by applying steam. Vapour generated in anhydrous separator is sent to 1 st evaporator
as a heating media. Anhydrous NaOH is then sent to seal pot and from seal pot, NaOH is sent to flaker drum
where the caustic soda flakes (98%) is made. Then, caustic soda flakes is sent to packaging section.
2) CCU-1 AND CCU-3

47% KOH lye is stored in the KOH storage tank. From storage tank with the help of pump,47% KOH lye is
sent to the evaporator. Sugar solution is also added in the KOH lye before going in evaporator to avoid
corrosion. The vapour coming from the evaporator is condense in the surface condenser and stored in the
vapour condensate tank. The concentration of the KOH is increased from 47% to 56%. This 56% KOH is sent
to the salt chest from the top of the salt chest and as a heating media molten salt is used which is fed to salt
chest from bottom of it.

Molten salt is a mixture of three salts having the concentration of 40% sodium nitrite (𝑁𝑎𝑁𝑂 ), 7% sodium
nitrate (𝑁𝑎𝑁𝑂 ), and 53% potassium nitrate (𝐾𝑁𝑂 ), Molten salt mixture is made up in furnace. Salt-mixture
is fed to bottom of the furnace by molten salt pump and molten salt is collected also from the bottom of the
furnace. The fire in the furnace, the natural gas and hydrogen gas is used. KOH coming from the salt chest
having concentration 85-87% is sent to anhydrous separator where vapour and moisture are removed by
applying steam. Vapour generated in anhydrous separator is sent to evaporator as a heating media. Anhydrous
KOH is then sent to the seal pot and from seal pot, KOH is sent to the flaker drum where the caustic potash
flakes (85-87%) is made. Then caustic potash flakes sent to the packing section.

3)𝐊 𝟐 𝐂𝐎𝟑

Boiler produced 𝐶𝑂 is fed to the furnace and excess of 𝐶𝑂 is removed from a chimney. The air is withdrawn
from the atmosphere with the help of blower and this also fed to the furnace from furnace air and 𝐶𝑂 is fed
from the bottom of the reactor.

For production of 𝐾 𝐶𝑂 here fluidized bed reactor is used. In this reactor there are 𝐾 𝐶𝑂 granules bed at
the lower section of the reactor. Air and 𝐶𝑂 is passed from the bottom of the reactor. The reactor is always
filled with the 7 ton of KOH and the reactor temperature of 270-285 °C maintained KOH is fed 47lpm at
temperature of 60 °C and sprayed from the top of the reactor. KOH is sprayed with the help of sprayer that are
set at an angle of 60 degree. At 𝐾 𝐶𝑂 bed KOH and 𝐶𝑂 react to form 𝐾 𝐶𝑂
Chemical Reaction:

2KOH + CO K CO + H O
Then K CO is sent to granulator cooler at a temperature of 24 °C and outlet at 6°C and with the help of screw
conveyer and packed bucket elevator K CO is sent to the upper screening machine where particles of 0.9 mm
are separated and sent the K CO product silo remaining passed to the lower screening machine here also 0.9
mm of particles are separated and it is also sent to the product silo. The material pass from screening and goes
to K CO milling machine (pre-crusher) and then K2CO3 milling machine (vibrator) and again fed to the
reactor with the help of screw conveyer.

The lighter particles that are removed from the top of the reactor are harmful for environment. So, it is sent to
the cyclone separator where heavy particles are fall at the bottom having temperature 15-18°C and fed to the
reactor with the help of screw conveyer.

The particles from the cyclone separator are sent to the scrubber tank where particles are wetted with the help
of DM water at temperature of 80-90 °C and this wetted water is also recirculated in the tank and at a period
of time sludge is removed.

The product that are stored in the silo are in granulated form that are divided into two sections in one section
it is directly packed and send to the storage section and in another, the granules are sent to the milling machine
to make it in powder form and this also packed and send to the storage section.

Color Code of Packing Bags:

K CO Granules - Green Bags
Powder - Red Bags
NaOH Flakes - Blue Bags
KOH Flakes - Black Bags
2.3.6 HCL UNIT
Here for production of Hydrochloric acid the hydrogen that is coming from hydrogen gas holder through HCl
Blower and chlorine which is required is coming from GAB or from liquefier in a form of sniff gas.

Hydrogen inlet pressure – 2300mm 𝐻 𝑂

Chlorine inlet pressure – 2300mm 𝐻
Before entering the HCl unit both gas pass through a device or equipment called flame arrester. The function
of flame arrester is to prevent flame to pass through it so heat required for gas to combust is not available. In
HCl unit, first the hydrogen is combusted in presence of air with the help of burner and with a spark then it
goes to HCl unit to react with chlorine gas.
Chemical Reaction:
H + O 2H O
H + Cl 2HCl
When Hydrogen and chlorine reacted with each other and form HCl fumes and water formed is mixes with
fumes. As, these reaction is exothermic the heat is produced so fumes get heated. So, these fumes is first
condensed. So, to condensed these fumes it is pass through graphite blocks which have holes. Holes are from
top to bottom and right to left side. The fumes produced coming from top to bottom side of holes and utility
used is cooling water.
There are total 10 block of graphite in HCl unit. After the fumes which are condensed are taken out from
outlet and those fumes which uncondensed are passed through tail tower. In tail tower, the Dm Water is
sprayed so it form weak acid which again goes with fumes in HCl unit for further reaction. In tail tower
there are packing of pall rings to increase residence time.
Total HCl units
6 (old): Capacity of 20 TPD
1 (new): Capacity of 50 TPD
2.3.7 HYPO UNIT
We know that chlorine is very toxic and hazards so it cannot be vent out to atmosphere is excess. So, chlorine
which is remaining after all the processes comes to hypo unit. This unit mainly contains 5 towers of which
first two are primary section other two are of secondary section and the remaining last of tertiary section.
Here mainly the reaction between 18% NaOH and chlorine gas takes place and product is sodium Hypochlorite
(𝑁𝑎𝑂𝐶𝑙).
Chemical reaction:

𝑁𝑎𝑂𝐻 + 𝐶𝑙 𝑁𝑎𝑂𝐶𝑙 + 𝑁𝑎𝑂𝐻 + 𝐻 𝑂 + 𝐻𝑒𝑎𝑡

As reaction as exothermic and tower temperature is limited to 60 C, we have provided plate type heat
exchanger to cool the product.
In each reaction tower, there is continuous circulation of 18% NaOH sprinkled from top of tower and chlorine
gas is fed below the pall rings bed. As the reaction occurs and time proceeds the GPL of NaOH get reduces
and GPL of 𝑁𝑎𝑂𝐶𝑙 get increases. Upon certain GPL of 𝑁𝑎𝑂𝐶𝑙 ,mixture is taken out as product. Unreacted
chlorine goes to other section for reaction where same reaction takes place. At tertiary section, chlorine get
consumed completely.
 CHAPTER 3 HYDROGEN PEROXIDE (𝑯𝟐 𝑶𝟐 ) PLANT

3.1 ABOUT HYDROGEN PEROXIDE:

The chemical formula for Hydrogen Peroxide is H O . Or simply a water molecule 𝐻 𝑂 combined with an
additional oxygen atom. It can be produced in any concentration. The product is water-like in appearance.

3.2 PROPERTIES
Physical properties

IUPAC Name Hydrogen peroxide

Chemical Formula H O

Molar Mass 34.0128 gm/mol

Appearance Appear like water

Odour Odourless

Density 35%- 1.13 gm/𝑐𝑚

50%- 1.20 gm/𝑐𝑚

60%- 1.24 gm/𝑐𝑚

Melting point -0.43 C

Boiling Point 150 C

Solubility in water Miscible

Solubility Soluble in ether, alcohol

Insoluble in petroleum ether

Vapour pressure 5mmHg (30 C)

𝑝𝐻 Between 6 to 7

Stability Unstable and decomposing readily to oxygen and

water with release of heat

Chemical Properties
Uses
 Paper and Pulp Industries — Bleaching Agent
 Textile Industries — Bleaching Agent
 Food Industries — Bleaching Agent
 Mining Industries — Oxidizing Agent
 Pharmaceutical Industries — Antiseptic
 Electronic Industries (Semiconductor) — Oxidizing & Cleaning Agent

Types of Processes for Production of 𝐇𝟐 𝐎𝟐

Hydrogen Peroxide is being manufactured by one of two processes:
I. Electrolytic Method
Il. Organic (Air or auto Oxidation “AO”) Process

In GACL, AO process is used, which was developed by H. J. RiedIt and G.P. Fleideror in 1935. In the UHDE
AO process, 2-ethylanthraquinone is hydrogenated in presence of catalyst and the anthrahydroquinone thus
obtained is oxidized by oxygen from air to obtain hydrogen peroxide and the 2-ethylanthraquinone. The
hydrogen peroxide produced is then
extracted with de-ionized water to produce crude hydrogen peroxide of 35% - 40% w/w
concentration.
Raw Material
 Hydrogen(H2)
 Ambient Air
Auxiliary Material
 2- Ethyl Anthra Quinone (EAQ)
 Sextate (2- Methyl Cyclohexyl Acetate)
 SC-150
 Caustic Soda
 Nitric Acid
 Stabilizer (Ammonium Nitrate)
 Sodium Acid Pyrophosphate
Specification Of Catalyst
 Palladium Catalyst on Zeolite Carrier
Specification of Utilities
 Steam And Condensate

3.3 CHEMICAL REACTION FOR SYNTHESIS OF 𝐇𝟐 𝐎𝟐

3.4 PROCESS DESCRIPTION
Various Units involving in manufacturing Hydrogen Peroxide are as follow:
1. WSN Preparation & Treatment
2. Hydrogenation
3. Oxidation
4. Extraction and WSN Scrubbing
5. Vaporizer
6. Distillation

1)WSN Preparation & Treatment

The working solution is primary compose of sextate(2-methylcyclohexylacetate) SC-150 and 2-ethyl-
anthraquinone based products.
The EAQ is a yellow organic solid that is subjected to chemical reaction during operation. Sextate is clear,
Water like organic liquid and primarily serves as a solvent for the reduced EAQ.

SC-150 is also clear, water like organic liquid. It reduces the density, viscosity and water solubility of the
working solution in addition to its solvent properties.

In preparation of WSN, First of all these three compound is mixed in WSN Preparation tank with the help of
agitator and it is heated by using coil and then this WSN goes to WSN Acidification tank for treatment and
then goes to WSN storage tank.

Many byproducts of WSN are formed due to repeated hydrogenation and oxidation reactions. So, the WSN is
feed to treatment unit before it is recycled back in the cycle and stored in WSN storage tank. A unit called
Hydrogen Peroxide working solution treatment is responsible for purification and removal of by-product, after
which WSN is recycled back to hydrogenation tank.
2)Hydrogenation:

Before the Hydrogenation, temperature of WSN should be 50° C. So, first WSN is heated in economizer. Then
it goes to pre-heater where its temperature maintained at 48-49° C
The working solution containing the dissolved anthraquinone is hydrated using
hydrogen gas in slurry-type hydrogenator using alumina loaded with a small amount of
palladium catalyst. Here fluidized bed reactor is used for hydrogenation. In this reactor the catalyst is 2%
palladium with zeolite carrier which is maintain in fluidization by 𝐻 and 𝑁
mixture flow from backward.

In Hydrogenator, the WSN is sprayed through spargers from top and hydrogen is passes from bottom also the
catalyst is sprayed in hydrogenator.

Temperature is controlled to around 62-65° C with the help of 𝑁 and the reactor is agitated to ensure good
mixing of catalyst with working solution and hydrogen. During hydrogenation the alkyl-anthraquinone,
although production of the tetra form of the quinone is preferred because it’s can be more easily hydrogenated.
Here excess 𝐻 is required to maintain catalyst in the fluidized state.

But if more excess amount of 𝐻 cause explosion. So, to regulate the flow of 𝐻 here liquid 𝑁 is used. Flow
rate of 𝐻 is about 1600 𝑚 /hr and flow rate of liquid 𝑁 is 45 𝑚 /hr.

The working solution that now contains hydrogenated anthraquinone is filtered to

remove any trace level of catalyst. If the catalyst is not removed then it will decomposed the hydrogen peroxide
in later stage reducing yields and causing potential hazard. So, primary filters are used initially to remove the
catalyst from the intermediate solution. These filters have screens of sizes 35 microns and are made of stainless
steel. There are total 8 primary filters which are placed around the hydrogenator. They all are working parallel
in which at a time 7 are in forward and 1 in back wash.
After this, WSN flows to oxidizing feed tank where 𝑁 blanketing is done to ensure that there is no leakage of
oxygen into the system. Then it is passes through series of three secondary glass wools filters of screen size 2
micron. These are required to remove solid impurities from the intermediate solution.

Even small quantity of catalyst can lead to decomposition of hydrogen peroxide in later stages therefore a
safety filter is installed to provide safeguard against trace quantities of catalyst.

We know that after some time the catalyst losses its activity so old catalyst is removed and new catalyst is
added through catalyst addition chamber.

3)Oxidation:

The WSN intermediate is entered from the top of the reactor and is oxidized by blowing air through it from
the bottom. WSN intermediate is cool prior to oxidation as oxidation is an exothermic reaction and can lead
to formation of other undesirable products.

EAQ-𝐻 + 𝑂 𝐻 𝑂 + WSN

The ‘tetra-hydro-alkyl-anthraquinone’ is oxidized forming mixture of hydrogen peroxide and WSN no catalyst
is used and hence this step is often referred to as auto oxidation.

Oxidation takes place in oxidizer. It is actually an absorption tower which is packed with porcelain saddle
packing which provides intimate contact between WSN intermediate and air for oxidation reaction.

In Oxidizer, compressed air is injected from bottom and mixture of Hydrogenated WSN comes from top.
Saddle packing provides contact time and surface for oxidation of Hydrogenated WSN hence it forms again
WSN and 𝐻 𝑂 mixture.

The upper outlet gas known as off gas which contains WSN traces moves to solvent recovery unit and the
bottom WSN + 𝐻 𝑂 moves to oxidizer bottom filter and degasser to remove air and after this cooled at 40 𝐶
and fed in extractor
.
4)Extraction and WSN scrubbing
Since the mixture of hydrogen peroxide and WSN is formed, it has to be separated. This
is done by using liquid-liquid extraction technique. DM water with stabilizer is fed with in liquid-liquid
extraction column to about 70% level. The water flows down the column.

In extractor there are sieve

plates. The extractor design
and operation a maximum
contact of water with the
working solution. We know
that density of water high as
compared to WSN so water
reaches the bottom of the
extractor and WSC reaches
the top of extractor. When
WSN bubble which contain
𝐻 𝑂 comes near sieve tray
this tray only allows the
WSN to pass through it. So,
WSN is collected at top and
𝐻 𝑂 get dissolve with
water at bottom. Bottom
solution contains 40% w/w
crude hydrogen peroxide oil.
The working solution being lower in density leaves from the top of the extractor. This WSN solution
contains some traces of water so it goes to coaleser which contains hydrophobic and hydrophilic plates
which separate WSN from water. This working solution now contains the original alkyl-anthraquinone and
tetra- hydro-alkyl-anthraquinone. This WSN goes to WSN storage tank.

The 40% 𝐻 𝑂 discharge from the bottom is called crude 𝐻 𝑂 is passed through scrubbing towers attached
adjacent to LLE tower.
Scrubbers contain solution of SC-150 which absorbs the traces of WSN and product moves to separator and
then crude feed tank. This product contains almost 38% 𝐻 𝑂 . Some amount of this product is sell and some
amount of it goes to vaporizer for concentration as per requirement and demand.
5)Vaporizer

The solution of 38% 𝐻 𝑂 is concentrated in vaporizer unit. In vaporizer the 38% 𝐻 𝑂 is concentrated by
heat it with steam. Steam is added from top and 38% 𝐻 𝑂 collected in vaporizer feed tank goes to vaporizer
from bottom.
Heat exchange takes place in vaporizer.
The 38% 𝐻 𝑂 absorbs heat from steam
and due to this heat, water in 38% 𝐻 𝑂
converted to vapour and 38% 𝐻 𝑂 get
concentrated to 50-55%. Condensate get
comes out from bottom of vaporizer.
The vapour that forms during this process
contains some traces of 𝐻 𝑂 . These
vapours goes to still mist separator. In mist
separator there are glass wool candles
which absorb remaining traces of
condensate and passes only 𝐻 𝑂 +Water
vapours. This 𝐻 𝑂 +water vapours goes to
distillation column.
6)Distillation

In Peroxide unit, there is vacuum distillation column to separate 𝐻 𝑂 +Water. The vacuum is created by using
water jet ejector.
Why Vacuum distillation is required here?

1) 𝐻 𝑂 is heat sensitive material.

2) If normal distillation is used more steam consumption is required due to increase in load on condenser.
In distillation column, Feed is coming from center. The mixture of cooled DM Water and stabilizer
(Ammonium nitrate) is charged in distillation column from top. Now cooled DM Water absorb heat from feed
due to which water from feed get evaporated. This water vapour as top product comes out from column. These
vapour get vent out.

Now the feed that contains 𝐻 𝑂 +Water

releases heat and get cooled. So 𝐻 𝑂 get
condensed and comes out from bottom of
column. But we know that some amount of
water also get condensed out with 𝐻 𝑂 . So,
the bottom mixture again go to column
through reboiler. By this we enrich the
process of distillation. And concentrated
𝐻 𝑂 taken out from bottom of column. This
concentrated 𝐻 𝑂 then goes to condenser to
cool and then goes to product tank to sell.
If the temperature of column get increased it
can effect the purity and productivity of
concentrated 𝐻 𝑂 so for this deluge system
is there which charges the DM water in
column to maintain temperature of column.
 CHAPTER 4 CHLOROMETHANE (CLM) PLANT

Raw Materials:
 Methanol
 Methane
 Chlorine
 Hydrochloric Acid

Utililies:
 Natural gas
 Nitrogen
 Electricity
 Cooling water

Products:
 Cl- Methyl chloride
 C2- Methylene chloride
 C3- Chloroform
 C4- Carbon Tetrachloride

Applications of Products:

1. Methyl Chloride: Manufacture of butyl and silicon, rubber as a refrigerant, as drug etc.

2. Methylene Chloride: Firefighting agent, manufacture of phenolic, solvent carrier for day sand textile
industry, chemical reaction media, paints removing agents etc.

3. Chloroform: As flavouring agent, in water treatment and also as an anesthesia for surgery

4. Carbon Tetrachloride: Used in fluorocarbon refrigerants and propellants, as fire extinguisher, in

pharmaceutical preparations etc.

There are total 3 sub-plants in CLM Plant:

1) Methanol plant (MEOH)
2) CLM-1
3) CLM-2

4.1 METHANOL PLANT (MEOH)

When CLM Plant was started in GACL, they used to combust the natural gas to form methane. But by doing
these the natural gas is more used. So that’s why the methanol plant get installed in CLM.

4.1.1 INTRODUCTION TO METHANOL PLANT:

In methanol plant, the raw materials are methanol and hydrochloric acid. GACL
purchased methanol from the other industry. And hydrochloric acid is taken from the HCl
plant of the GACL. The product of methanol plant is methyl chloride (C1). There are
seven sections in methanol plant:

1) 2100: Storage section

2) 2200: Reaction section

3) 2300: ME gas heat recovery section

4) 2400: ME gas treatment section

5) 2600: Dilute hydrochloric acid (DHA) purification section

6) 2800: Waste sulphuric acid (WSA) storage section

7) 2900: Waste caustic soda (WCS) recovery section

Chemical reaction:

𝐶𝐻 𝑂𝐻 + 𝐻𝐶𝐿( %) 𝐶𝐻 𝐶𝑙 + 𝐻𝐶𝐿( %)

Side reaction: 2𝐶𝐻 𝑂𝐻 𝐶𝐻 𝑂𝐶𝐻 + 𝐻 𝑂

4.1.2 PROCESS DESCRIPTION:

GACL purchased methanol from the other industries and stored in big
methanol storage tank. From the MeOH storage tank, liquid MeOH is sent to two shell &
tube heat exchangers which are in series, In 1st heat exchanger, the temperature of MEOH
is increased from 30-32°C to 75°C by steam condensate. And in 2" heat exchanger, the
temperature of MeOH is increased from 75°C to 105°C by 𝐶𝐻 𝐶𝑙 (C1) product which is
coming from the 2nd reactor. From this 2nd heat exchanger some portion of the liquid
MeOH is sent to sump of the 1st reactor.

Now, concentrated hydrochloric acid (CHA-31-33%) is heated in series of

the two heat exchangers. In 1st heat exchanger, the temperature of CHA is increased from
40°C to 80°C by dilute hydrochloric acid (DHA-14-16%) coming from outlet of the one
reactor which is having temperature of 120°C. Then CHA having temperature 80°C is
sent to 2nd heat exchanger which is cubic type heat exchanger. In this 2nd heat exchanger
C1 coming from the reactor-1 is used as heating media.

In 1st reactor, MeOH and CHA react to form 𝐶𝐻 𝑂𝐻 (C1). This C1 gas
contains some unreacted MeOH. SO, C1 gas and unreacted MeOH vapour is sent to 2 nd
reactor. In 2nd reactor unreacted MeOH is converted into C1 by 20 % HCl coming from
the bottom of the 1st reactor. Before sending C1 to treatment columns, C1 is passed
through numbers of heat exchangers to reduce its temperature around 19°C.

From the vessel-4, C; gas is sent to de-acidifier, where C1 is deacidified by

DHA and the temperature of de-acidifier column is around 19°C. From the de-acidifier
column, C1 is sent to neutralizer column where C1 is neutralizing by NaOH coming from
the dehumidifier. Temperature of neutralizer column is around 21°C. From the
neutralizer column C1 is sent to dehumidifier column where dehumidification of C, is
done by NaOH. The temperature of dehumidifier column is around 21°C. After
dehumidification C1 gas is sent to three drying column operated in series. In drying
columns C1 is dried. The temperature of drying columns is around 21°C.
Main Equipment Used in this process:
1) Reactor
2) Absorption column
3) Heat exchangers

1) Reactor
The reactor which is used for the reaction of methanol and Concentrated hydrochloric acid is TR (tank
reactor). Unlike CSTR, it has no continuous stirring.
The reason why we use this reactor is:
1) HCL is in liquid and CSTR is more efficient for liquid-based reactants.
2) Here we have to provide more residence time for the maximum conversion that can be achieved by
CSTR.
Here in this CSTR agitation is done by the means of DHA that have been first heated in reboiler by
steam condensate and that goes to reactor. This reflux creates a turbulence in reaction mixture.
Why the DHA is heated in reboiler?

The reaction temperature in reactor is 120 C. To achieve this, we heat the DHA and send it to reactor.
By doing this electricity consumption decreases.
2) Absorption column
After the reaction in reactor the C1 get produced and concentrated HCl get diluted. Now during this
process in product there are some impurities that has to remove. This is done by absorption. In all
absorption column there are packing of pall rings of PP.
The impurities that are in product stream of C1 is:
a) HCl
b) Moisture
c) Ether (formed dur to side reaction)

There are 4 absorption columns:

1) De-acidifier
2) Neutralizer
3) De-humidifier
4) Dryer

1) De-acidifier

De-acidifier is simply an absorption tower in which C1 come from bottom and DHA comes from top. When
both comes in contact with each other absorption takes place. The DHA absorbs HCl from Cl and get
concentrated and comes from bottom. The acid free C1 goes to neutralizer.
As this process is exothermic, so to maintain the temperature the DHA coming from outlet goes to HE where
it get cooled by means of brine and again sent to absorption tower.

2) Neutralizer
If some traces of HCL is there in C1 it get removed in neutralizer. Neutralizer is also an absorption tower
in which C1 come from bottom and NaOH comes from top. When both comes in contact with each other
absorption takes place. The HCl remaining in C1 get reacted with NaOH and forms NaCl and water. NaCl
get settle down and vapour comes with Cl in outlet.
 3) De-humidifier
C1 coming from neutralizer that contain vapours which has to remove. This is done by
De-humidifier. Dehumidifier is also an absorption tower in which C1 come from bottom and NaOH comes
from top. The vapour in C1 get absorbed by NaOH due to which concentration of NaOH reduces and C1
get dehumidify. This Dehumidified Cl comes out from outlet and goes to dryer. This less concentrated
NaOH only goes to neutralizer.
4) Dryer
In dryer the remaining moisture in C1 get removed. Dryer is also an absorption tower in which C1 come
from bottom and 98% 𝐻 𝑆𝑂 comes from top. There are total 2 dryers connected in series.

Here the 98% 𝐻 𝑆𝑂 absorb the moisture from C1 and get diluted to 78% 𝐻 𝑆𝑂 . This 78% 𝐻 𝑆𝑂 is
cooled and then again goes to column. From outlet we get dry C1.
3) Heat exchangers
In CLM, the heat exchangers other than shell and tube and plate heat exchanger is cubic graphite block heat
exchanger.
Cubic block heat exchanger
Impervite cubic block heat exchangers offer the maximum heat transfer area in the smallest envelope size. In
high fouling applications, easy access to both process and service holes make cleaning convenient and
simple. Our cubic design is very well suited for inter-changer applications.

Impervite is a composite material consisting of a graphite substrate impregnated using a proprietary phenolic
impregnation process. It is ideally suited for processing mixed acids, sulfuric acid, hydrochloric acid,
phosphoric acid, nitric acid, waste acids, and chlorinated hydrocarbons. It has excellent machining, physical,
and thermal properties.
Cubic block heat exchangers offer many of the same features as our heavy duty cylindrical block heat
exchangers and are fabricated using the same high quality impervious graphite, but typically at a lower
investment cost.

Advantages:
 Maximum heat transfer area in minimum envelope size
 High thermal efficiency, even with low temperature approach and temperature cross
 Small Envelope Size
 Excellent for inter-changer service (corrosive both sides).
 Good for low temperature approach or temperature cross.
4.2 CLM-1

4.2.1 INTRODUCTION
The products of chloromethane plant are: 1) Methyl Chloride
2) Dichloromethane
3) Trichloromethane
4) Tetrachloromethane

The formation of chloromethane by thermal chlorination proceeds by free radical

chain mechanism. Thermal activation is necessary for the dissociation of chlorine
molecules into active chlorine atoms, and this is initiated by heating the reactants to 300-
350°C. Once the reaction has begun, the temperature rises by reason of the large amount
of heat evolved. The reaction is controlled at around 420°C and proceeds homogenously in
the gas phase.

Chloromethanes by photo-chlorination are formed in the liquid phase also by a

free radical chain mechanism. Activation of chlorine is occurred by the photo-energy of
2300A and the reaction begins. The reaction is controlled at the around 45°C in the liquid
phase.

The chain reaction is initiated by thermally or photo-chemically dissociating

chlorine molecules to form free chlorine atoms. These reactive atoms then react with
methane or a chloromethane to form an organic free radical plus hydrogen chloride. The
chain mechanism proceeds when an undissociated chlorine molecule reacts with the
organic free radical to produce a molecule of chloromethane while simultaneously
regenerating a reactive chlorine atom to perpetuate the chain. Many chlorine molecules
react as a result of an initial activation until practically all the chlorine is consumed in an
excess of methane, yielding the desired chloromethane products and a small amount of heavy ends. The
chain mechanism may be terminated by preferential reaction of inhibitors and impurities, such as oxygen
and nitric oxide, with the active chain carriers. Also contact with reactor wall tends to have a terminating
effect by reconverting active chlorine atoms to molecular form.

Chemical Reaction

𝐶𝐻 + 𝐶𝑙 𝐶𝐻 𝐶𝑙 + 𝐻𝐶𝑙

𝐶𝐻 𝐶𝑙 + 𝐶𝑙 𝐶𝐻 𝐶𝑙 + 2𝐻𝐶𝑙

𝐶𝐻 𝐶𝑙 + 𝐶𝑙 𝐶𝐻𝐶𝑙 + 3𝐻𝐶𝑙

𝐶𝐻𝐶𝑙 + 𝐶𝑙 𝐶𝐶𝑙 + 4𝐻𝐶𝑙

4.2.2 DESCRIPTION OF SECTIONS

In GACL, there are two chloromethane plant named CLM-1 and CLM-2. Chloromethane plant divided into
different sections.
1) Section 100 Thermal chlorination Section
2) Section 200 Photo-Chlorination Section
3) Section 300 Hydrogen Chlorine treatment Section
4) Section 400 Dehumidification Section
5) Section 500 Liquefaction Section
6) Section 600 Purge gas treatment Section
7) Section 700 Crude products treatment Section
8) Section 800 Distillation Section
 9) Section 900 Product Handling Section
10) Section 1000 Utilities Section

1) Section 100 Thermal chlorination Section

In this section two feed stocks, purified methane gas (MT) and dried chlorine gas (CL) thermally
react to produce chloromethane at 410-430°C under nearly atmospheric pressure and the hot reaction gases
are cooled to around 40°C in heat exchangers, In order to prevent MT and CL being in the inflammability
limits by mixing, the feed ratio of MT and CL is regulated about 4/1.

Purified MT gas received at minimum 2 𝑘𝑔/𝑐𝑚 𝐺 at battery limits, is strictly filtered in

filter to remove the rust, dust, etc. which may possibly be accompanied in the MT gas and may cause a
back fire in TG mixer-1 and TG mixer-2 or reactors. Chlorine gas coming from CSL plant is stored in
buffer vessel and then it is sent to filter to remove
any impurities present in it. 𝐶𝑙 from the filter is sent to TG mixture-1 and TG mixture-2 and some portion
of 𝐶𝑙 gas is sent to section-200 (PC reactor). In TG mixtures C1 from section-800, C1 from MeOH plant
and 𝐶𝐻 from PSA (Pressure Swing Adsorption) are added. Then this entire mixture is sent to four reactors
operated in parallel fashion.
These reactors are placed on the heating furnace and for fuel of furnace NG is
used. In reactors the reaction is complete and the mixture of C1, C2, C3 and C4 having
temperature around 450°C and pressure 1 atm, is sent to waste heat recovery boiler. In waste heat recovery
boiler DMW is fed to produce steam. In WHRB steam generation takes place without energy and
temperature of C1, C2, C3, C4 mixtures is reduced so less heat duty is required. From WHRB the mixture
is sent to tar separator to remove tar from mixture. From tar separator mixture is send to 4 heat exchangers
for cooling. As cooling media cooling water is used in these HE. From the HEs this mixture is send to
section-300.

2) Section 200 Photo-Chlorination Section

The main commercially viable products are C2 and C3 not C1 hence in excess formation of C1 and during
the demand of C2, C3 and C4 the feed C1 is subjected to photo chlorination section where chlorination in
presence of UV rays at 45 𝐶 is carried out.
Chloromethanes (CLMs) from section 800 is introduced into HE-1 to decrease the temperature of CLMs
by using Brine. The reactor is glass lined to minimize the corrosion by activated chlorine and generated
hydrogen chloride, mainly contains 4 sets of mercury lamps covered by jackets with provision of cooling
water. One part of product mixture goes to HCL stripper while the part is subjected to two phase cooler.
The outlet of this cooler is mixture of C3 and C4 which is sent to Section 700 for purification.

3) Section 300 Hydrogen Chlorine treatment Section

In this section hydrogen chloride in reaction gas mixture is absorbed in water to be recovered as 32% HCl
acid, co-product.
The product stream from section 100 is sent to common header of section 300.From the common header
reaction gas mixture is sent to six parallel operated HA absorber where hydrogen chloride is absorbed in
counter flowing dilute HCI acid. Absorber are falling film type having a function of heat exchanger made of
graphite. Heat of absorption is removed by cooling water.

4) Section 400 Dehumidification Section

In this section, the reaction gas mixture, after HCI is removed is deacidified, neutralized, dehumidified and
dried.
The gas mixture after removal of HCL is de acidified with dilute HCL solution and after this it neutralized
with circulating caustic soda solution.
The acid free gas id dehumidified with the help of cooed circulating caustic soda solution. The dehumidified
gas is further subjected to concentrated Hydrochloric Acid for drying purpose and after this operation, the
carry over acid is separated by acid separator and the pure product mixture is moved to section 500.
5) Section 500 Liquefaction Section

The dried product gas from section 400 is filtered in filter to remove the mist, dust, etc. and after this it is
cooled in Pre-cooler to minimize the gas decomposition after compression and sent to the first stage of
Compressor. The compressor is of two stage reciprocating with 2 sets of compressor having half load capacity
is applied in order to save the energy at the low load operation and to be able to continue the operation even
if the one should be under trouble. Outlet gas of the first stage of compressor is cooled in H.E. 1 (Inter cooler
1) and H.E.-2 (NO.2 Inter cooler) with cooling water and brine respectively to minimize the gas decomposition
after the second stage compression and fed to the second stage of Compressor.

After second stage, compressed gases are pre cooled in H.E and combined at the outlet and heat exchanged to
be cooled and partially condensed in H.E with the recycle gas for heat recovery. The cooled gas is condensed
in a brine cooler. Condensed CLMs mixture having temp around -10°C is received in day tank and fed to No.
1 Distillation Column in section 800 (Distillation section) through the pump. Incondensable gas in H.E is
mainly MT, impurities and Cl and small amount of C2 and C3 which is termed as recycle gas is fed again in
TG mixer.

6) Section 700 Crude products treatment Section

In this section, the crude products chloromethane contains small amounts of HCl and Cl; coming from section
200 as product solution from section 800 as split fluid and from section 300 as drains are neutralized by caustic
soda and dehydrated by distillation.
The crude CLM is pumped into a U column where NaOH and water are added which neutralizes the crude
and by means of specific gravity difference the crude is separated inot upper NaOH flow and lower flow.
The lower layer is sent for washing with water and after this the wet product is dehydrated by distillation.
After all these, the CLM is sent to Section 800 for distillation.

After all the successful opeartions in Chloromethane plant the products C2 and C4 are packed in Barrels or
tankers ready for sale, while the C3 is stored in SS tonners at 3kg pressure along with purged Nitrogen.

7) Section 800 Distillation Section

In distillation section, C1, C2, C3 & C4 products are separated in distillation towers by boiling temperature
difference of CLMs mixture.
Here in total are 8 Bubble cap tray distillation columns for required operation. In first distillation column C1
is separated from feed mixture leaving C2 ,C3,C4 as bottoms product.
Same way all other products are separated in this section. For maintaining pressure in column and to provide
required heat duty all 7 columns have thermo-siphon type reboilers while the last one has kettle type reboiler.

8) Section 1000 Utilities Section

1) Steam
In a traditional context, a boiler is an enclosed container that provides a means for
heat from combustion to be transferred into the working media (usual water) until it becomes
heated or a gas (steam). One could simply say that a boiler is a heat exchanger between fire
and water. The boiler is the part of a steam power plant process that produces the steam and
thus provides the heat. The steam or hot water under pressure can then be used for
transferring the heat to a process that consumes the heat in the steam and turns it into work

A steam boiler fulfills the following statements:

 It is part of a type of heat engine or process.
 Heat is generated through combustion (burning).
 It has a working fluid, a.k.a. heat carrier that transfers the generated heat away from the boiler.
 The heating media and working fluid are separated by walls.

In an industrial/technical context, the concept “steam boiler” (also referred to as

“steam generator”) includes the whole complex system for producing steam for use ¢ g in a
turbine or industrial process. It includes all the different phases of heat transfer from flames
to water/steam mixture (economizer, boiler, superheater, reheater, and air preheater) [t also
includes different auxiliary systems (e. g. fuel feeding, water treatment, flue gas channels
including stack). The heat is generated in the furnace part of the boiler, where fuel is
combusted. The fuel used in a boiler contains either chemically bonded energy (like coal,
waste, and biofuels) or nuclear energy. Nuclear energy will not be covered in this material A
boiler must be designed to absorb the maximum amount of heat released. in the process of
combustion. This heat is transferred to the boiler water through radiation, conduction, and
convection. The relative percentage of each is dependent upon the type of boiler, the designed
heat transfer surface, and the fuels that power the combustion.

At GACL, the fuel for combustion in boiler used is natural gas bought from the
GAIL. The steam is generated using horizontal shell and tube boiler. 4 boilers are used in
parallel continuously. 2 of which are 4 passes and the other 2 are 3 passes. pH is maintained
using a dozing tank to prevent corrosion. Dissolved oxygen is removed using a de-aerator. 64
The pressure of steam generated is 10.203 kg/𝑐𝑚 . The generated steam is sent to various
departments of the plant, and pressure required at a particular location is maintained using
pressure reducing valves. The rate of steam generation is 40 tons/hr

2) Nitrogen:
Nitrogen is very important for the safety of the plant. Some industries buy pure
nitrogen from OSBL and some produce it here in GACL, nitrogen is produced within the
plant. Nitrogen is produced using pressure swing adsorption. It consists of two vessels filled
with material that adsorbs only nitrogen air mixture and both of them are operated
alternatively. Air is sent into one vessel at high pressure where nitrogen is adsorbed and after
some time air supply is transferred into a second vessel and pressure in Is vessel is reduced
which led to desorption of pure nitrogen and sent to buffer vessel. Where one adsorbs
nitrogen other releases adsorbed nitrogen gas. Nitrogen is stored in the vessel at medium
pressure which is sent to the plant where required. Nitrogen is used in the lants as an inert and
a pipeline of nitrogen is provided at various locations for safety purposes.

3) Instrument Air:
Air is used in the lants for various purposes like for opening arid closing of valves,
to keep tank under some positive air pressure, etc. Ordinary atmospheric air is not used for
instrumental purposes. The pressurized air which is used for valve operation and many other
operations of that kind must have a dew point of -35°C. If the dew point of instrument air is
lower than that it cannot be used for such operations.

Instrument air required of the caustic plant is generated at the instrument air section.
Atmospheric air is filtered through the spiral filter and fed to the first stage compressor. Two
compressors are operated alliteratively they are two-stage double-acting non-lubricating
compressors. After passing through the distributor air is taken to the heater where it is heated.
The heated stream is split into two parts one taken to the regeneration column and the other to
the online column, Exit stream from the online column is taken to cooler where the air is
cooled using water as a cooling media. Cooled air is passed through a moisture separator
where moisture gets removed and dry air leaves the chamber. One part of the air is taken back
to the distributor whereas the other part after passing through the filter is taken to the plant
for operational purposes.

4) Electricity:
Electricity plays important role in any chemical process industry not as primary
heat duty but as the fulfillment of required energy for air cooling, lights, pumping,
compression other items. Electricity requirements for any industry are provided by local
electricity providers (like torrent power, Gujarat Electricity Board (GEB), but in absence of it
as it may occur due to line failure or any other reason, the Chemical industry should be able
to operate the plan without any disturbance at least for a short period during which problem
of electricity Supply can solve, This can be done if the industry has its generator or any other
power plant. In GACL If the electric line fails then for some crucial pump and equipment
GACL has a diesel generator set which fulfills the emergency requirement of electricity For
the DCS system, GACL has a battery backup, in case of electric line fails.

5) Cooling Towers:

Introduction
Cooling towers are a very important part of many chemical plants. The primary task
of a cooling tower is to reject heat into the atmosphere. They represent a relatively
inexpensive and dependable means of removing low-grade heat from cooling water. The
make-up water source is used to replenish water lost to evaporation. Hot water from heat
exchangers is sent to the cooling tower, The water exits the cooling tower and is sent back to
the exchangers or other units for further cooling.

Construction of Induced draft cooling tower

Larger towers sometimes are made of concrete. Many tower-casings and basins are
constructed of galvanized steel or, where the corrosive atmosphere is a problem, the
galvanized tower has a stainless-steel basin. Glass fiber is also widely used for cooling tower
casings and basins, giving long life and protection from the harmful effects of many
chemicals. Plastics are widely used for fill, including PVC, polypropylene, and other
polymers. Treated wood splash fill is still specified for wood towers, but plastic splash fill is
also widely used when water conditions mandate the use of splash fill. Film fill, because it
offers greater heat transfer efficiency, is the fill of choice for applications where the
circulating water is generally free of debris that could plug the till passageways.

Cooing tower specification

There are a total of three cooling towers: one for KOH one for NaOH and one for
the power plant and off-site facility. Each cell is provided with an induced draft fan of 8
blades, 45 rpm speed, and handling around 350 𝑚 /sec of air. The blade is made of
fibreglass-reinforced polyester material for lesser energy consumption. The tower is capable
to cool 3000 m3 /hr. of water from 38°C to 30 °C, when wet-bulb temperature is 30°C that is
a range of 10°C and approach of 5°C.

Quality as
 pH: 7.5 to 8

 Turbidity: less than 1.4 NTU

 Total hardness: less than 670 ppm as CaCOs,

The above quality is achieved by chemical dosing continuous blowdown and side
streams filtration. The side stream filtration in sand filters keeps turbidity around 1 NTU by
separating solid residues. The microorganisms are controlled by dosing chlorine in the outlet
of cooling towers. Concentrated Sulfuric acid and Scalewin are added to control pH and
turbidity.
PRESSURE SWING ADSORPTION (PSA) UNIT
Pressure swing adsorption (PSA) is a technique used to separate some gas species from a mixture of gases
(typically air) under pressure according to the species' molecular characteristics and affinity for an
adsorbent material. It operates at near-ambient temperature and significantly differs from the cryogenic
distillation commonly used to separate gases. Selective adsorbent materials (e.g., zeolites, ( molecular
sieves), activated carbon, etc.) are used as trapping material, preferentially adsorbing the target gas species at
high pressure. The process then swings to low pressure to desorb the adsorbed gas.
In PSA, Methane is separated from natural gas (NG) by adsorption process by using the variation in pressure.

A PSA plant consists basically of the adsorber vessels containing the adsorbent material, tail gas drum(s),
valve skid(s) with interconnecting piping, control valves and instrumentation and a control system for control
of the unit. The pressure swing adsorption process has four basic process steps:
 Adsorption
 Depressurization
 Regeneration
 Re-pressurization

Adsorption
Adsorption of impurities is carried out at high pressure being determined by the pressure of the feed gas. The
feed gas flows through the adsorber vessels in an upward direction. Impurities such as nitrogen and small
amount of ethane in natural gas are selectively adsorbed on the surface of the adsorbent material. Highly pure
hydrogen exits the adsorber vessel at top. After a defined time, the adsorption phase of this vessel stops and
regeneration starts. Another adsorber takes over the task of adsorption to ensure continuous hydrogen supply.
Natural gas is passed in PSA with a pressure of 22.5 kg/𝑐𝑚
As according to adsorption isotherm, as pressure is high there is low adsorption bed loading.

Adsorption bed used are:

1) Ceramic bed
2) Aluminium ball
3) Carbon molecular sieves

Size of molecular sieves are about 0.3 microns so it will allow only methane molecules to pass through it.
Other gas get adsorb on surface of bed.
Regeneration
The regeneration phase consists of basically five consecutive steps:
 Pressure equalization
 Provide purge
 Dump
 Purging
 Re-pressurization
The steps are combined so as to minimize hydrogen losses and consequently to maximize the hydrogen
recovery rate of the PSA system.

Pressure equalization (step E1)

Depressurization starts in the co-current direction from bottom to top. The hydrogen still stored in the void
space of the adsorbent material is used to pressurize another adsorber having just terminated its regeneration.
Depending on the total number of adsorbers and the process conditions, one to four of these so-called pressure
equalization steps are performed. Each additional pressure equalization step minimizes hydrogen losses and
increases the hydrogen recovery rate.

Provide purge (step PP)

This is the final depressurization step in cocurrent direction providing pure hydrogen to purge or regenerate
another adsorber.

Dump (step D)
At a certain point of time, the remaining pressure must be released in counter-current direction to prevent
break-through of impurities at the top of the adsorber. This is the first step of the regeneration phase when
desorbed impurities leave the adsorber at the bottom and flow to the tail gas system of the PSA plant

Purging (regeneration)
Final desorption and regeneration is performed at the lowest pressure of the PSA sequence. Highly pure
hydrogen obtained from an adsorber in the provide purge step, is used to purge the desorbed impurities into
the tail gas system. The residual loading on the adsorbent material is reduced to a minimum to achieve high
efficiency of the PSA cycle.

Re-pressurization (steps R1/R0)

Before restarting adsorption, the regenerated adsorber must be pressurized again. This is accomplished in the
pressure equalization step by using pure hydrogen from adsorbers presently under depressurization. Since
final adsorption pressure cannot be reached with pressure equalization steps, re-pressurization to adsorption
pressure is carried out with a split stream from the methane product line. Having reached the required pressure
level again, this regenerated adsorber takes over the task of adsorption from another vessel having just
terminated its adsorption phase.
 CHAPTER-5 MATERIAL BALANCE
5.1 INTRODUCTION
A mass balance, also called a material balance, is an application of the conservation of mass to the analysis of
physical systems. Material balances are an important first step when designing a new process or analyzing an
existing one. Material balances are nothing more than the application of the law of conservation of mass, which
states that mass can neither be created nor destroyed. Mathematically the mass balance fora system is given by:
INPUT + GENERATION = OUTPUT + ACCUMULATION + CONSUMPTION

The proper way to monitor the performance of a cat cracker is by periodic material and heat balance surveys on the
unit. By carrying out these tests frequently, one can collect, trend, and evaluate the unit's operating data. Additionally,
meaningful technical service to optimize the unit's operation should be based on regular test runs.

Plant Capacity for caustic production: 485TPD

Basis: MT of NaOH production

5.2 MASS BALANCE OVER PRECIPITATORS IN CS PLANT

Overall raw material requirement and byproduct production calculations concerning 1 MT NaOH production.
1 1
𝑁𝑎𝐶𝑙 + 𝐻 𝑂 𝑁𝑎𝑂𝐻 + 𝐻 + 𝐶𝑙
2 2
According to stoichiometry of reaction,

For NaOH quantity produced 40 kg

NaCl required 58.5 kg
Water required 18 kg
Hydrogen produced 1 kg
Chlorine produced 35.5 kg

Impurities to be removed in precipitators: 𝐶𝑎 , 𝑀𝑔 𝑎𝑛𝑑 𝑆𝑂

Calcium ions 0.12% w/w

Magnesium ions 0.06% w/w
Sulphate ions 0.25% w/w
Total salt weight 1523.4375 kg
Calcium ions in feed 1.8281 kg
Magnesium ions in feed 0.914 kg
Sulphate ions in feed 3.8086kg

Reaction 1: Ba CO + Na SO BaSO + Na CO
Molecular Weight

Ba CO 197 kg/kmol
Na SO 142 kg/kmol
BaSO 233 kg/kmol
Na CO 106 kg/kmol
 For every SO42- quantity of: 96 kg
Ba2+ required 137 kg
Available SO42- quantity 3.8086 kg
Ba2+ required 5.435 kg

= 0.03967 kmol
Ba2+ in kmol
= moles of Ba CO , Na SO , BaSO & Na CO

Ba CO required 7.8149 kg
Na SO as an impurity from feed 5.6331 kg
BaSO produced 9.2431 kg
Na CO produced 4.2050 kg

Reaction 2 Na CO + CaCl CaCO + 2NaCl

Molecular Weight

Na CO 106 kg/kmol
CaCl 111 kg/kmol
CaCO 100 kg/kmol
2NaCl 58.5 kg/kmol

For every Ca2+ quantity of: 40 kg

CO3 required 60 kg
Available Ca2+ quantity 1.8281 kg
=2.7421 kg
CO32- required = 0.0457 kmol
= moles of Na CO , CaCl & CaCO
Na CO required 4.844 kg
Since some parts of Na CO requirements
=4.844 - 4.205
come from reaction 1 and
=0.639 kg
Externally added Na CO for reaction 2
CaCl as an impurity from feed 5.0716 kg
CaCO produced 4.5701 kg
NaCl produced 5.3471 kg
Reaction 3 2NaOH + Mg(Cl) Mg(OH) + 2NaCl
Molecular Weight

NaOH 40 kg/kmol
Mg(Cl) 95 kg/kmol
Mg(OH) 58 kg/kmol
NaCl 58.5 kg/kmol

For every Mg2+ quantity of: 24 kg

OH- required: 34 kg
Available Mg2+ ions from feed 0.914 kg
OH- required =1.2948 kg
= 0.07616 kmol
OH- in moles
= moles of NaOH and NaCl
Moles of Mg(OH) and Mg(Cl) =0.03808 kmol
Mg(Cl) as an impurity from feed 3.6176 kg
NaOH required 3.0464 kg
Mg(OH) produced 2.2086 kg
NaCl produced 4.4553 kg

Overall Mass Balance Over Precipitator:

Input Output
Sr No. Stream Kg/MT Kg/MT
NaOH NaOH
1 Na SO 5.6331 -
2 Ba CO 7.8149 -
3 BaSO - 9.2431
4 Na CO 0.6391 -
5 CaCl 5.0730 -
6 CaCO - 4.5701
7 NaCl - 5.3471
8 Mg(Cl) 3.6176 -
9 NaOH 3.0464 -
10 Mg(OH) - 2.2086
11 NaCl - 4.4553
TOTAL 25.824 25.824
5.3 MATERIAL BALANCE OVER ELECTROLYTIC CELL:

NaCl + H2O → NaOH + ½ H2+ ½ Cl2

58.5 18 40 2 71
kg/k kg/k kg/k kg/k kg/k
mol mol mol mol mol

For NaOH Quantity required 40 Kg

NaCl required 58.5 kg
Water required 18 kg
Hydrogen produced 1 kg
Chlorine produced 35.5 kg
=1000kg
Basis NaOH production quantity
=25 kmol
=1462.5 kg
NaCl required
=25 kmol
=450 kg
Water required
=25 kmol
=25 kg
Hydrogen gas produced
=12.5 kmol
=887.5 kg
Chlorine gas produced
=12.5 kmol

Mass inflow/Outflow at Anode:

 NaCl in = 300gpl or 0.3kg/l. Density= 1.2 kg/l.
 NaCl out = 230gpl or 0.23 kg/l. Density= 1.11 kg/l.
 Concentration difference = 0.07kg/l.
 The volume of NaCl solution providing 1462.5 kg NaCl required for 1MT NaOH
= 1462.5/0.07
= 20892.857 ltr
 Mass= Volume*ρ
 Inlet brine (300gpl) mass= 20892.857*1.2 = 25071.428 kg/MT NaOH
 Outlet brine (230gpl) mass= 20892.857*1.11 = 23191.071 kg/MT NaOH
 Chlorine gas produced per MT NaOH. = 12.5kmol = 887.5 kg
 Mass Inflow/Outflow at Anode:
 Water electrolyzed per MT NaOH= 25kmol or 450kg.
 Cathode inlet= 30% NaOH w/w = 0.3kg NaOH/ kg soln. Density = 1.3023 kg soln./ ltr.
 Cathode outlet= 32% NaOH w/w = 0.32kg NaOH/ kg soln. Density = 1.30628 kg soln./ ltr.
 NaOH inlet = 0.3*1.3023 = 0.39069 kg NaOH/ltr.
 NaOH outlet= 0.32*1.30628= 0.4180 kg NaOH/ltr.
 Water inlet = 1.3023 – 0.39069 = 0.91161 kg water/ ltr soln.
 Water outlet = 1.30628 – 0.418 = 0.88828 kg water/ ltr soln.
 Let x and y be the volume of inlet and outlet streams in liters respectively.
Framing equations in x and y, we have,
1. For Water
0.91161x – 0.88828y = 450 kg/MT NaOH
2. For NaOH,
0.418y – 0.39069x = 1000 kg/MT NaOH.

 Solving for x and y, we have x = 31648.120 ltr/MT NaOH y = 31972.737 ltr/MT NaOH.
 Total NaOH inlet = 0.39069*31648.12= 12364.604 kg NaOH/ MT NaOH Produced.
 Total cathode in (30% NaOH) = 12364.604/0.3 = 41215.346 kg soln./MT NaOH.
 Total NaOH out = 0.4180*31972.737 = 13364.604 kg NaOH/ MT NaOH Produced.
 Total cathode out (32% NaOH) = 13364.604/0.32 = 41764.387 kg soln./MT NaOH.
 Hydrogen gas produced per MT NaOH = 12.5 kmol = 25 kg.

 Overall Material Balance over electrolytic cell:

Cell Input (kg/MT NaOH Output (kg/MT

Stream
Side produced) NaOH produced)

300gpl conc. Brine 25071.428 -

230gpl Depleted Brine - 23191.071

Anode
Chlorine gas - 887.5

30% Caustic lye feed 41215.346 -

32% caustic lye product - 41764.387

Cathode
Hydrogen gas - 25.0

TOTAL 66286.774 65867.958

Accumulation Output – Input = 418.816

 CHAPTER 6 ENERGY BALANCE
6.1 INTRODUCTION

Energy balances are also done based on heats of reaction, heat capacities, expected temperatures, and
pressures at various points to calculate the amounts of heating and cooling needed in various places and to
size heat exchangers.

The general equation for the conservation energy can be written as:

ENERGY IN + GENERATION - CONSUMPTION = ENERGY OUT

Kinetic energy and potential energy are generally very small compared to the enthalpy, except in Cases of
very rapid flow or when no significant temperature changes are occurring in the system. Therefore, they
are often neglected in performing energy balances. Heat capacity of all components found at 60 C and
85 C as inlet and outlet streams have ta temperatures of 60 C and 85 C respectively. Taking reference
temperature 25 C

Cp (KJ/kmol K)
Component 60’C 85’C

NaCl 51.2326 51.6908

NaOH 61.5414 62.6692

Water 75.3415 75.6824

Chlorine gas 34.5095 34.8399

Hydrogen gas 29.0181 29.0994

6.1 ENERGY BALANCE ON ELECTROLYZERS

INLET STREAMS AT 600 C:

1. Pure Brine (300gpl):

 Flow in = 25071.428 kg soln.

 NaCl inlet = (0.3/1.2) *25071.428 = 6267.857 kg NaCl = 107.142 kmol NaCl.
 Amount of water = 25071.428 – 6267.857 = 18803.571 kg water = 1044.642 kmol.
 Enthalpy contained by NaCl= m*Cp*∆T = (107.142) (51.23265) (60-25)
= 192121.797 kJ
 Enthalpy contained by water= m*Cp*∆T = (1044.642) (75.3415) (35)
= 2754671.334 kJ.

2. 30% Caustic soda lye input at 600 C:

 Mass flow = 41215.346 kg soln.

 NaOH input = 12364.604 kg NaOH = 309.115 kmol.
 Water input = 28850.742 kg water=1602.819 kmol.
 Enthalpy contained by NaOH= m*Cp*∆T = (309.115) (61.5414) (35)
= 665818.16 kJ.
  Enthalpy contained by water= m*Cp*∆T = (1602.819) (75.3415) (35)
= 4226557.569 kJ.
OUTLET STREAMS AT 850 C:

1. Lean Brine (230gpl)

 Mass flow = 23191.071 kg soln.

 NaCl mass flow = (0.23/1.11) * 23191.071 = 4805.357 kg NaCl
= 82.142 kmol
 Water mass flow = 18385.713 kg water = 1021.428 kmol.
 Enthalpy with NaOH= m*Cp*∆T = (82.142) (51.6908) (85-25)
= 254759.1416 kJ.
 Enthalpy with water= m*Cp*∆T = (1021.428) (75.6824) (60)
= 4638247.348 kJ

2. 32% Caustic Soda Lye:

 Mass flow = 41764.387 kg soln.

 NaOH in outlet = 13364.604 kg NaOH = 334.1151 kmol NaOH.
 Water in outlet = 28399.783 kg water= 1577.765 kmol water.
 Enthalpy with NaOH= m*Cp*∆T = (334.1151) (62.6692) (60)
= 1256323.561 kJ
 Enthalpy with water= m*Cp*∆T = (1577.765) (75.6824) (60)
= 7164542.51 kJ.
3. Hydrogen Gas:

o Flowrate = 12.5 kmol

o Enthalpy = (12.5) (29.0994) (60) = 21824.55 kJ.

4. Chlorine Gas:

 Flowrate = 12.5 kmol

 Enthalpy = (12.5) (34.8399) (60) = 26129.925 kJ.
TOTAL HEAT AT INLET STREAMS:

Stream Component Mass flow Molar flow Cp Enthalpy

(kg/MT NaOH) (kmol/ (kJ/kmol K) (kJ/MT NaOH)

MT NaOH)

Pure NaCl 6267.857 107.142 51.232 192121.797

Brine
(300 gpl) H O 18803.571 1044.642 75.3415 2754671.334

Caustic lye NaOH 12364.604 309.115 61.5414 665818.160

30%
H O 28850.742 1602.819 75.3415 4226557.569

Total 66286.774 Total 7839168.860

TOTAL HEAT AT OUTLET STREAMS:

Stream Component Mass flow Molar flow 𝑪𝒑 Enthalpy

(kg/MT (kmol/MT (kJ/kmol K) (kJ/MT
NaOH) NaOH) NaOH)
Lean Brine NaCl 4805.357 82.142 51.6908 254759.141
𝐻 𝑂 18385.713 1021.428 75.6824 4638247.348
Caustic Soda NaOH 13364.604 334.115 62.6692 1256323.561
Lye (32%) 𝐻 𝑂 29399.783 1577.765 75.2864 7164542.510
Gases 𝐶𝑙 887.500 12.500 34.8399 26126.925
H 25.000 12.500 29.0994 21824.550
Total 65867.957 Total 13361827.040

HEAT OF REACTION:

Component The heat of Formation (kJ/mol)

NaCl -410.90
H2O -285.82
NaOH -426.70
H2 0
Cl2 0

OVERALL REACTION:
1 1
𝑁𝑎𝐶𝑙 + 𝐻 𝑂 𝑁𝑎𝑂𝐻 + 𝐻 + 𝐶𝑙
2 2

H = ∑H + ∑H
∆H = -426.7 + 410.9 + 285.82
= 270.02 kJ/mol
Total moles of product formed = 25 kmol

∆H Total = 270.02 * 25 * 1000

= 6750500 kJ/MT NaOH.
Now Based on total enthalpies at reactant side and product side the electricity requirement is
provided below:

Heat (in) + electrical power = Heat (Out) + ∆H (Total)

Electrical power required = 13361827.04 + 6750500 – 7839168.86

= 12273158.18 kJ/MT NaOH

= 12273.16 MJ/MT NaOH

= 3409 Units. (1 Unit = 3.6 MJ)

 CHAPTER- 7 CONCLUSION:
After completing this six week industrial training at GACL, I came on conclusion that such a type of training
connects theoretical aspects of technical knowledge and how that is implemented in practical world. Also,
this training helped me a lot in terms of technical aspects along with social wellbeing.
This project work is based on the Chlor-Alkali industry and membrane cell process for the manufacturing
of NaOH. I have learned that NaOH is a crucial compound and the core of multi- billion-dollar businesses
around the globe. It is mainly used to manufacture detergents, soaps, bleaches etc. It is an essential chemical
used in the municipal water treatment facility. Various details of equipment are provided for easy
understanding. Material and energy balances are important part of any chemical industry and through
which a process is selected and the plant is operated. Plant economics and efficiency are determined by
these balances.
Utilities are also very important in a chemical industry. An engineer must have the knowledge about steam
and cooling tower. In every industry, the equipments are labeled with specific codes. These codes must be
known before actually going in the plant. Designing of equipment is one of the main roles of a chemical
engineer. Safety in any industry is given the utmost importance. This includes not just the safety and
welfare of employees and workers but also that of the environment. A lot of human energy and finances
go into ensuring no stone is left unturned when it comes to safety, especially in a chemical process industry.
But apart from the technical aspects, I also experienced the working atmosphere, how everyone is trying
continuously to upgrade and maintaining the quality, etc. The work ethic and discipline that this company
portrays is commendable. The basic fundamentals, how all the departments are integrated with one another
and how all the departments are working together towards a single vision is what I tried to imbibe through
the course of my internship. I am very glad that I had such a good organization to learn from.
 CHAPTER-8 REFERENCES:

 GACL Training Manual

 Bhatt B.I. & Vora S.M.; Stoichiometry, 4th edition; McGraw Hill: 2006.
 Robert H. Perry & Howe Grant; PERRY'S CHEMICAL ENGINEERS HAND BOOK, 7th edition; McGraw
Hill: 1998.
 Peters M.S. & Timmer Haus K.D.; Plant Design & Economics for Chemical Engineering, 4th edition;
McGraw Hill: 1991.
 Sinnott R.K., Coulson & Richardson’s; Chemical Engineering, Vol.6, 5th edition; Butterworth
Heinemann: 2002.
 Warren L. Mc-Cabe, Julian C. Smith, Peer Harriot; UNIT OPERATION OF CHEMICAL ENGINEERING,
5th edition; McGraw Hill: 1993.
 Kirk-Othmer Encyclopedia of Chemical Technology; Volume 01 (of 27) A to Alkaloids (4th Ed.) -
Wiley.
 D. Q. Kern; Process Heat Transfer; International Student edition; McGraw Hill: 1983.
 Thomas F. O’Brien, Tilak V. Bommaraju, Fumio Hine (auth.) – Hand book of Chlor- Alkali
Technology_ Volume I_ Fundamentals-Springer US (2005).
 Ullmann's Encyclopedia of Industrial Chemistry part 1 A-M (2005).
 Hydrogen PSA by LINDA
 www.wikipedia.org
 www.google.com