PREFACE

Industrial training is a part and parcel of every technical course and gives a face or foam to all
theoretical knowledge we gain in our classroom. We get to have a virtual experience of the
processes, methods, objects and phenomenon which used to be just an imaginary picture in
our minds. It also gives us an exposure to the environment of the industries and workshop
which are virtual components of our professional life.

I am thankful to my college administration that handed this invaluable chance

to me and at the same time I pay my regards to the administration of CA plant, Gujrat
Fluorochemicals Limited that proved to be a great supporting force for the fulfillment of the
purpose. The officials and the workers of the firm provided us with the best f their attention
and share ample of knowledge of their concered field with me.

1
 ACKNOWLEDEMENT

We would like to express our special thanks to the administration of Gujarat Fluorochemicals
Limited for providing us such an amazing opportunity to undergo training at their Dahej site.
We are thankful to the members of the plants for guiding us throughout our training period
and sharing their valuable time and knowledge with us.
We would like to express our gratitude to our college administration for providing
us such an amazing opportunity to undergo this training. I am really thankful to Vijay
kosambia sir, Mahesh sir, Shashank Tyagi sir and Gaurav Kumar sir for his valuable
guidance , keen interest and encouragement at various stages of my training period.

I acknowledge with thanks the kind of patronage, owing inspiration and

timely guidance, which I have received from each and every member of the workshop
whose guidance, encouragement, suggestion and very constructive criticism have
contributed immensely to the evolution of my ideas during the training period.

2
 INTRODUCTION

The group Gujarat Fluorochemicals Limited (GFL) is a part of the $3 billions INOX group of
companies.

INOX group is a family owned, professionally managed business group, with market
leadership in diverse businesses including industrial gases, refrigerant, chemicals, cryogenic
engineering, renewable energy and entertainment. The INOX group employs more than 9000
people at more than 150 business units across the country, and has a distribution network that
is spread across more than 50 countries around the globe. Each INOX group company is
characterized by three distinct characteristics early identification of a winning business idea,
building it to a size of market leadership in that segment, and attaining profit leadership
position through cutting-edge efficiency in operations.

Major INOX group companies other than GFL include:

INOX Air Products Limited
INOX India Limited
INOX Wind Limited
INOX Renewable Limited
Gujarat Fluorochemicals Americas LLC
Gujarat Fluorochemicals GmbH
INOX Wind Infrastructure Services Limited
INOX Renewable Limited

3
 COMPANY PROFILE

Gujarat Fluorochemicals Limited is India’s largest producer (by volume) of chloromethanes,

refrigerants and Polytetrafluoro-ethylene (PTFE).The firm which was incorporated in 1987, is
a subsidiary of INOX Leasing and Finance Limited. GFL has two manufacturing facilities in
Gujarat, a refrigerant plan at Ranjitnagar, and a PTFE facility at Dahej. It has two subsidiaries
Gujarat Fluorochmeicals Americas LLC and Gujarat Fluorochmeicals Gmbh.

In this company manufacturing plants established are:

Chemical Plants:
Calcium Chloride
Methylene Chloride
Sulfuric Acid
Hyrdochloric Acid etc.
Fluoropolymers:
TFE
D-P TFE
AQ-PTFE
PT-PTFE

The company GFL is a public limited company listed on both the leading stock exchanges of
India-BSE Limited and the National Stock Exchange of India Limited. It was incorporated in
1987 and commenced commercial operations in 1989 GFL has gross fixed assets of US $ 49
Million as on 31st March 2013. GFL has been accredited AA rating for long term credit and
A1+ rating for short term credit by CRISIL India’s largest rating agency.
Driven by the principle of “conservative aggression”, GFL’s dynamic corporate team very
meticulously identifies and plans new projects and growth opportunities, which, once
selected, are aggressively implemented by a professional management team. As result of this
approach GFL has attained leadership position in virtually all segment of its operations. GFL
attained a key milestone in 2007, when it commissioned India’s largest PTFE plant. PTFE is
an extremely specialized engineering plastic, and only a select few firms the world over have
the technology for PTFE manufacture. GFL also operates India’s largest refrigerant plant, and
at one time, exported refrigerants to more than 75 countries across the globe.

4
Chemicals Business

GFL’s Chemical Division combines chemistry and innovation with the principle of
sustainability to address diverse needs of industry. GFL has a well-established diverse
portfolio of chemicals catering to a broad range of industries.

GFL’s chemical complex commenced operations in the year 2007 at Dahej, Gujarat. which
has become as integrated and technologically advanced chemical complex which comprises
of a 1,34,500 MT Caustic Soda / Chlorine plant, a 1,08,500 MT Chloromethane plant, and
combined coal and gas based captive power plant with a capacity of around 90 MW.

These facilities have significantly enhanced GFL’s cost competitiveness due to the
advantages of backward integration, besides adding to GFL’s product portfolio. GFL will
always look to strengthen its chemicals business further primarily on the basis of upstream
investments in resources and raw materials.

Fluoropolymers Business

GFL is India’s largest PTFE producer with hi-tech state of the art technology plants at Dahej,
Gujarat. With its backward integration right up to caustic soda, hydrofluoric acid and captive
power, GFL is one of the world’s most integrated PTFE producers. GFL has an installed
capacity of 16,200 MT PTFE, covering a broad product portfolio of granular virgin and
modified PTFE resins, fine powder virgin and modified PTFE resins, PTFE based aqueous
dispersions and PTFE micro powders. The Dahej complex is ISO 9001:2008, ISO
14001:2004 and OHSAS 18001:2007 certified by Intertek.
To strengthen its physical presence in the strategic markets GFL has incorporated subdiaries:

 GFL Americas

 Gujarat Fluorochemicals GmbH

GFL Americas operates its own blending facility & warehouse at Rockdale, USA and caters
to PTFE and PTFE compounds customers in USA and Latin American countries. Gujarat
Fluorochemicals GmbH operates from Hamburg, Germany and has tie up with a well known
international warehousing company to service PTFE customers in European territory.

5
 SAFETY MANAGEMENT

There are three types of safety programs in GFL

 Fire extinguisher

 Safety induction

 O.H.C (Occupational Help Center)

Fire extinguisher

 Fires are classified by types of fuel they burnt.

1. Class A :- Class A fire consist of ordinary combustibles such as wood,

paper, trash or anything else that leaves an ash. Water works best to
extinguish a Class A fire.

2. Class B :- Class B fires are fueled by flammable or combustible liquids,

which includes oil, gasoline, and other similar materials. Something effects
which deplete the oxygen supply work best to extinguish Class B fires.

3. Class C :- Class C fires energized electrical fires are known as Class C fires.
Always de-energize the circuit then use a non-conductive extinguishing
agent such as Carbon dioxide.

4. Class D: Class D fires are combustible metal fires. Magnesium and

Titanium are the most common types of metal fires. Once a metal ignites do
not use water in an attempt to extinguish it. Only use a dry powder
extinguishing agent. Dry powder agents work by something and heat
absorption.

6
 Types of Fire Extinguishers :-

1. Water and Foam :-

Water and foam fire extinguishers extinguish the fire by taking away the heat
element of the fire triangle. Foam agents also separate the oxygen element from
the other elements. Water extinguishers are for Class A fires only – they should
not be used on Class B fire or could create a shock hazard on a Class C fire.
2.
3. Carbon dioxide :-

Carbon dioxide fire extinguishers extinguish fire by taking away the oxygen
element of the fire triangle and also be removing the heat with a very cold
discharge. Carbon dioxide can be used on Class B & C fires. They ineffective
on Class A fire.

4. Dry Chemical Powder (D.C.P) :-

Dry chemical extinguishers extinguish the fire primarily by interrupting the

chemical reaction of the fire triangle. Today’s most widely used type of fire
extinguisher is the multipurpose dry chemical that is effective on Class A, B
and C fires. This agent also works by creating a barrier between the oxygen
element and the fuel element on Class A fires.
Ordinary dry chemical is for Class B & C fires only. It is important to use the
correct extinguisher for the type of fuel. Using the incorrect agent can allow the
fire to re-ignite after apparently being extinguished successfully.

5. A .B.C fire extinguishers :-

A.B.C fire extinguisher is used in therr of fire i.e. solid, liquid and gaseous.

 In GFL plant, if fire occurred on large scale then GFL plant has the Fire
Hydran system using Hodge system.

7
 Safety Induction

In company all safety rules must be obeyed. Failure to do so will result in strict
disciplinary action

 All injuries must be reported as soon as possible.

 No alcohol or drugs allowed in company.

 No alcohol and smoking allowed in company.

 PPE must be worn as prescribed by management.

 All tools/equipments must be maintained in good condition.

 Only appropriate tools shall be used for specific jobs.

 All grades must be kept in place.

Occupational health center

GFL company believes that no job or task is more important than worker’s
health and safety. Health goals the following goals have been established in GFL
companies-

 Provide workers with safe work environments

 Conduct routine

 Provide personal protective equipment

8
 Preparation of chloralkalies by membrane electrolysis
The chlorine-alkali electrolysis is an important procedure in the chemical industry. Here the
products chlorine, hydrogen, hydrochloric acid and caustic soda are generated from sodium
chloride. There are three manufacturing methods:
The diaphragm

The membrane

The amalgam process

INTRODUCTION:-

The LiquiSonic analyzer provides an advantageous utilization in the varied

process steps of the three methods. Foremost, the customer gains the advantages of a
reduction in raw material and energy consumption, as well as an increase in the yield.

Dissolving Station and Brine Solution:-

The raw material sodium chloride (NaCl) is gained by either the vaporizing of sea water,
mechanical or solution mining of salt deposits. The raw brine contains contaminants and
calcium or magnesium salts, that clog the fine pores of the diaphragm or the
membrane during the electrolysis and can thereby visibly reduce their lifespan. It is for this
purpose that the contaminants are precipitated in the agitation plant containers (dissolving
vessels), through the addition of caustic soda. After the precipitating, the contaminants are
separated with the aid of a pressure filter. the diaphragm cell, mercury cell and present
membrane cell. In a diaphragm cell, a porous asbestos mat is used to separate the anodic
CER and cathodic HER, and NaOH is simultaneously formed in the cathodic
compartment. In the mercury cell, the CER on the anode is coupled with the formation
reaction of sodium amalgam (2Hg + 2Na+ + 2e− → 2NaHg) on the liquid mercury
cathode (Supplementary . Then, the sodium amalgam is separated and used in the second
cell to produce NaOH via the anodic reaction of Na-ion release (NaHg → Na+ + Hg + e−)

9
ADVANTAGES:

 Avoiding of quality failures during the brine purification

 Extending of the membrane‘s lifespan

 Incoming goods inspection (in cavern mining)

 Reduction in water and/or steam consumption (during the salt dissolving)

 Reduction in electrical energy consumption

Preparation by membrane process:-

Existing chloralkali processes generally use asbestos, mercury or fluorine-containing ion-

exchange membranes to separate the simultaneous chlorine production on the anode and
hydrogen production on the cathode, and form sodium hydroxide in the electrolyte. Here,
using the Na+ de-intercalation/intercalation of a Na0.44MnO2 electrode as a redox mediator,
we decouple the chlor-alkali process into two independent steps: a H2 production step with
the NaOH formation in the electrolyte and a Cl2 production step. The first step involves a
cathodic H2 evolution reaction (H2O → H2) and an anodic Na+ de-intercalation reaction
(Na0.44MnO2 → Na0.44−xMnO2), during which NaOH is produced in the electrolyte
solution.
The second step depends on a cathodic Na+ intercalation reaction
(Na0.44−xMnO2 →Na0.44MnO2) and an anodic Cl2 production (Cl → Cl2). The cycle of
the two steps provides a membrane-free process, which is potentially a promising direction
for developing clean chloralkali technology.The chloralkali process plays a predominant and
irreplaceable role in the chemical industry because its products are used in over 50% of all
industrial chemical processes. However, the chlor-alkali industry is among the highest
energy-consuming processes with pollutant emissions that have a serious effect on the
environment and human life Accordingly, it is desirable to develop a more efficient and
cleaner chloralkali process.
Typical chloralkali electrolysis (i.e. brine electrolysis) consists of two half
reactions: the hydrogen evolution reaction (HER) on the cathode and the chlorine evolution
reaction (CER) on the anode, which is accompanied by sodium hydroxide (NaOH) formation
in the electrolyte. From 1888 till now, three processes emerged in the chlor-alkali industry:

10
The operation of the present membrane cell is very similar to the diaphragm cell, but the
difference is to use a polymer ion-exchange membrane instead of the porous asbestos mat
(Supplementary. Because of the separated formation of Cl2 and NaOH, the mercury cell
generally produces a purer product than do the diaphragm and membrane cells but with
higher energy consumption because of the increased cell voltage for
electrolysis .

Over the past decades, many studies have been conducted to reduce the pollution
related to chlor-alkali processes. The environmental measures implemented over the past
several years have successfully alleviated the issue of huge mercury emissions. In the
diaphragm and membrane process, the use of asbestos or fluorine-containing materials only
causes indirect emissions. Because of the limited lifetime (approximately several years) of
these materials, the diaphragm and membrane process only result in moderate environmental
risks. Furthermore, the membrane cell has dominated the current chlor-alkali industry. The
application of oxygen-depolarised cathodes in the membrane cell also reduces the electric
energy consumption in the chloralkali process. However, the general applications of this
membrane based chlor-alkali process remain challenging. Although this method can facilitate
the separation of the products because of its chemical resistance, the expensive ion exchange
membrane generally exhibits limited useful life. In particular, this membrane is susceptible to
contaminant ions such as Mg2+ and Ca2+ in the brine, which shorten the useful lifetime of
the membranes. The precipitated calcium and magnesium will decrease the efficiency and
increase the power consumption. Inaddition, the high-pressure gases in the electrolytic cell
aggrevate the membrane degradation. Accordingly, unstable sustainable energy sources such
as wind and solar energy are difficult to use to directly power the membrane cell, because the
gas pressures in the anode and cathode compartments must remain in balance with a stable
power input. Therefore, it is highly desired to develop an environmentally friendly, high-
efficiency, membrane- free chlor-alkali process. In fact, the old mercury cell can be
considered as a typical membrane-free chlor-alkali technology,where the redox

11
mediator of amalgam/sodium amalgam (Hg/ NaHg) decouples the H2 (and NaOH)
production and Cl2 pro-duction. Unfortunately, because of the high toxicity, the mercury-
cell-based chlor-alkali technology must be stopped step by step.

MAIN REACTION:-

Step : 1
Anode : Na0:44 MnO2 ! Na0:44Àx MnO2 þ xNaþ þ xeÀ
Cathode : 2H2 O þ 2eÀ ! H2 þ 2OHÀ

Step : 2

Anode : 2ClÀ ! Cl2 þ 2eÀ

12
Cathode : Na0:44Àx MnO2 þ xNaþ þ xeÀ ! Na0:44 MnO2 This approach creates a chlor-
alkali electrolysis process with several important advantages. First, because of the
environmentally friendly nature of Na0.44MnO2, this technology is cleaner than diaphragm
cells, mercury cells and even the current membrane cells. Second, this architecture can
separately produce H2 (+NaOH) and Cl2 without using a membrane. Finally, the
separate generation of Cl2 and H2 prevents the mixing of product gases over a range of
current densities and also simplifies the gas handling, which significantly increases the
operational flexibility of chlor-alkali electrolysis cells and potentially make them
suitable to be driven by sustainable energy sources (such as solar or wind energy).
Na0.44MnO2 with a three-dimensional (3D) S-shaped tunnel structure was prepared
via a simple solid reaction according to previous reports The X-ray diffraction (XRD)
pattern, scanning electron microscopy (SEM) image and transmission electron microscopy
(TEM) image of the prepared sample Prior to the fabrication of this chlor-alkali electrolytic
cell, the intercalation/de-intercalation behaviours of the Na0.44MnO2
electrode in an alkaline electrolyte (1 M NaOH) and a brine electrolyte (saturated NaCl) were
investigated using cyclic voltammetry (CV) measurements with a typical three-electrode
system , the prepared Na0.44MnO2 exhibits identical electrochemical profiles in both
electrolytes, which indicates a possibility of the reversible cycle between the desodiation (i.e.
Na+ de-intercalation) in the alkaline electrolyte and the sodiation (i.e.Na+ intercalation) in
the brine electrolyte of one Na0.44MnO2 electrode. To further clarify this point, the
desodiation of a Na0.44MnO2 electrode in an alkaline electrolyte and consequent
sodiation of the resulting electrode in a brine electrolyte were investigated using linear sweep
voltammetry (LSV) measurements with a three-electrode system at a sweep rate of 2 mV s−1
The HER on a Pt-coated titanium mesh electrode in an NaOH solution and CER on a
RuO2/IrO2-coated titanium mesh electrode in a brine electrolyte were also investigated by
LSV measurements for comparison (the red line), five desodiation peaks at −0.04, 0.08, 0.28,
0.34 and 0.49 V (vs. Hg/HgO) appear in the positive sweep process (from −0.2 to 0.55 V vs.
Hg/HgO) in an alkaline electrolyte, and they indicate a desodiation reaction of Na0.44MnO2
→ Na0.44−xMnO2 + xNa+ + xe−. Then, the resulting Na0.44−xMnO2 electrode was put

in the brine electrolyte for the LSV measurement with a negative sweep from 0.55 to −0.2 V
vs. Hg/HgO (the blue line), the sodiation peaks in the brine electrolyte appear at 0.38, 0.25,
0.16, −0.08 and −0.16 V vs. Hg/HgO in the negative sweep process. The potential gap

13
between the main peaks of desodiation in the alkaline electrolyte and those of sodiation in the
brine electrolyte is ~0.11 V, which indicates a good reversibility. Furthermore, the special
potential window for the Na0.44MnO2/Na0.44−xMnO2 redox couple is between the onset
potentials for the HER and CER (the green and black lines in respectively). The result
indicates that Na0.44MnO2 can be used as a redox mediator to decouple the conventional
chlor-alkali process into two steps,. The galvanostatic charge–discharge curve of the
Na0.44MnO2 electrode at a current density of 0.1 A g−1 to clarify the specific capacity of
Na0.44MnO2. Performance of the two-step chlor-alkali electrolysis. The chlor-
alkali electrolytic process was constructed with a commercial Pt-coated Ti-mesh electrode for
the HER (2.5 × 4 cm2,, a commercial RuO2/IrO2-coated Ti- mesh electrode for the CER (2.5
× 4 cm2 and an Na0.44MnO2 electrode (2.5 × 4 cm2, Step 1 (NaOH/H2 production) and
Step 2 (Cl2 production) were conducted in two separated cells with the alkaline electrolyte
and brine electrolyte, respectively.
The electrolysis of the cells was investigated by chronopotentiometry with an applied current
of 100 mA and a step time of 600 s, and the corresponding chronopotentiometry curves
(cell voltage vs. time) . The chronopotentiometry data of the anode (anodic potential vs. time)
and cathode (cathodic potential vs. time) were also investigated during the electrolysis
process, Step 1 (i.e. the NaOH/H2 production process) exhibits an average cell voltage of
~1.3 V, which arises from the difference between the average anodic potential of 0.3 V (vs.
Hg/HgO) of the desodiation (Na0.44MnO2 → Na0.44−xMnO2 + xNa+ + xe−) and the
cathodic potential of approximately −1.0 V (vs. Hg/HgO) of the H2O reduction (2H2O → H2
+ 2OH−). Then, after the washing with NaCl solution, the resulting Na0.44−xMnO2 formed
in Step 1 was moved to another cell for Step 2 (the Cl2 production process).
The average cell voltage in Step 2 was ~1.07 V, which is equal to the average potential
difference between the anodic CER (2Cl− + 2e− → Cl2, ~1.24 V vs. Hg/HgO) and cathodic
sodiation (Na0.44−x MnO2 + xNa+ + xe− → Na0.44MnO2, ~0.17 V vs. Hg/HgO). The
photo profiles of the H2 generation in Step 1 and Cl2 generation to characterise
the decoupled steps. Furthermore, video evidence is shown to further clarify the separated H2
generation in Step 1 and Cl2 generation in Step 2 (see Supplementary materials, Supplemen-
tary Movies 1 and 2). The electrolysis of the cells with a longer step time of 1 h (3600 s) was
investigated by chronopotentiometry at an applied current of 100 mA . The chlor-alkali
electrolytic process with the decoupled H2 (+NaOH) production and Cl2 production was
further characterised by the chronopotentiometry measurements at the higher applied cur-
rents of 200, 500 and 1000 mA, respectively. The corresponding video proofs for the

14
electrolysis at 1000 mA are shown in Supplementary Movies 3 and 4. When tested at a high
current of 1000 mA ( = current density of 100 mA cm−2), the overall cell voltage (average
voltages on Step 1 + Step 2) is ~3.65 V. Obviously, the applied current density (100 mA
cm−2) is still much lower than the typical current densities in modern membrane cells (150–
700 mA cm−2)8. For this case, the electrolysis rate in the cell is limited by the Na+
intercalation/ de-intercalation in the crystalline framework of solid electrode material
(Na0.44MnO2). An efficient solution for this issue is to reduce the current density (mA
cm−2) applied on the Na0.44MnO2 electrode, which can be achieved by increasing the area
(cm2) ratio between the Na0.44MnO2 electrode and the CER (or HER) electrode. For
example, a higher applied current density of 500 mA cm−2 on the CER or HER electrode has
been successfully achieved using this method The kinetics of the Na+ or Li+
intercalation/de-intercalation also controls the power performance of current rechargeable
Na-ion or Li-ion batteries. Various approaches such as nanosizing and nanostructuring
electrode materials have been developed to improve the power of these rechargeable
batteries41, which can also be used to improve the electrolysis rate of the new chlor-alkali
process, the H2/NaOH gen-eration (Step 1) and Cl2 generation (Step 2) are performed in two
separated cells: Cell 1 and Cell 2. In theory, both steps can be conducted in a single cell with
the brine electrolyte. However, the generated NaOH is dissolved in the brine electrolyte
solution, which indicates that no pure NaOH stream is produced. Furthermore, with the
increase of generated NaOH in the brine solution, the oxygen evolution reaction (OER)
occurs on the CER electrode. The separated cells can efficiently prevent the undesired issues,
which is one of the purposes of the design . A conceptual design of the continuous production
of the decoupled process , and the technology challenges are briefly analysed in the
corresponding discussion. According to recent reports about decoupled water electrolysis42–
45, we can assume that the decoupled chlor-alkali process can be driven by an unstable
renewable energy, which may improve the cost and efficiency of electrolysers.
As a typical electrode material for sodium-ion batteries, Na0.44MnO2 exhibits the
high efficiency and long cycle capability, which were demonstrated in a previous report on a
Na0.44MnO2- based aqueous battery39. To further clarify this point, the cycle performance
of Na0.44MnO2 was investigated using a galvanostatic charge (in the 1 M NaOH
solution)/discharge (in the saturated NaCl solution) test (Supplementary Fig. 15). Obviously,
the highly reversible Na+ intercalation/de-intercalation behaviour of Na0.44MnO2 facilitates
the cycle of NaOH/H2 production (Step1) and Cl2 production (Step 2). Accordingly, the
cycle profile of NaOH/H2 production and Cl2 production was investigated with an applied

15
current of 100 mA. The achieved result where the new chlor-alkali electrolytic process stably
produced H2 (+NaOH) and Cl2 in over 50 consecutive cycles. For practical application, it is
also necessary to clarify the durability of the Na0.44MnO2 electrode and its electrochemical
stability in NaOH solution with higher concentrations. Therefore, the Na+ intercalation/de-
intercalation behaviour of the Na0.44MnO2 electrode in the 10 M NaOH (30 wt %) solution
was investigated by CV measurement at a scan rate of 2 mV s−1 , where the achieved
electrochemical profile is identical to that in 1 M NaOH. This result demonstrates the high
stability of Na0.44MnO2 in high-concentration alkaline solutions. Then, the 10 M NaOH
solution was used to perform Step 1 for NaOH and H2 production (Supplementary Fig. 17).
The electrochemical profile of Step 1 in 10 M NaOH is identical to that in 1 M NaOH. Gas
analysis of the H2 evolution and Cl2 evolution. As shown above, the new chlor-alkali
electrolytic process involves the decoupled H2 (and NaOH) production step and Cl2
production step. To further confirm this point, in situ differential electrochemical mass
spectrometry (DEMS) was used to measure the H2 evolution in Step 1 and Cl2 evolution in
Step 2 with a constant applied current of 100 mA. In this experiment, a quadrupole mass
spectrometer with a leak inlet was connected to the chlor-alkali electrolytic cell (the cell for
Step 1 or Step 2) with two tubes as the purge/carrier gas inlet and outlet . A pure Ar gas
stream was used as the purge gas before the electrolysis and the carrier gas during the
electrolysis process. Prior to the gas analysis, the system was purged with a pure Ar stream
for 1.5 h. Then, the system was purged with a pure Ar stream for an additional hour, and an
online analysis record shows that H2 eached a stable background line , when the H2-
production step (Step 1) begins, the H2 evolution is clearly observed in the online analysis
record. In parallel with the H2 production, the NaOH is produced in the electrolyte solution
because of the OH− generation in the HER at the cathode (Eq. 2) and Na+ de-intercalation
from the Na0.44MnO2 anode (Eq. 1). After Step 1, a rest step of 130 min was performed
with a pure Ar stream to eliminate the remnant H2 in the system, and a hysteresis of H2 was
observed in the online analysis record Then, the resulting Na0.44−xMnO2 electrode that was
formed in Step 1 was washed with NaCl solution to remove the surface adsorbed NaOH. The
washed Na0.44−xMnO2 electrode was moved to another cell for the Cl2 production (Step 2)
and the corresponding DEMS analysis.,the Cl2 evo-lution is clearly observed in the online
analysis record of DEMS during Step 2. However, it should be noted that the DEMS result
cannot demonstrate the pure Cl2 production. It is almost impossible to fully avoid the
parasitic OER reaction during the CER process8. This point will be further clarified by the
yield analysis for H2 and Cl2. Furthermore, the Cl2 gas, which is generated at the anode,

16
experiences immediate hydrolysis as follows: Cl2 + H2O → HClO + HCl46. As a result, only
a part of the generated Cl2 gas is recorded by DEMS, which will be later confirmed. Step 1 is
performed in an alkaline electrolyte (NaOH solution). Therefore, in theory, the NaOH
generated in Step 1 is not mixed with other salts. However, the Na0.44MnO2 electrode is
moved between the NaOH electrolyte in Step 1 and the brine electrolyte in Step 2, which can
result in the presence of OH− (or Cl−) in the brine electrolyte (or NaOH electrolyte).
Therefore, additional washing is necessary to remove the surface-adsorbed OH− (when
moving from Step 1 to Step 2) or Cl− (when moving from Step 2 to Step 1), which is one of
the disadvantages of the new chlor-alkali electrolytic process. This disadvantage is further
clarified by the continuous production design shown in the discussion
A typical drainage method was used to quantify the H2 or Cl2 generation over a
specific time length. In this experiment, the produced H2 gas volume (mL) was measured
with an applied current of 200 mA for 500 s The Faradaic efficiency was calculated from the
ratio between the measured and theoretical H2 gas volumes. the H2 production data obtained
from five repeated experiments, where the Faradaic efficiency of the H2 production is
~100%. With the identical measurement condition, the obtained Cl2 gas volume is lower than
that of H2 gas because some Cl2 that was generated at the anode undergoes hydrolysis (Cl2 +
H2O → HClO + HCl). The HClO and Cl2 in the electrolyte were determined using the
iodometric titration method (see Methods)47. The total chlorine that evolved because
of the electrolysis of NaCl solution was determined by adding the chlorine in gas phase to the
'available chlorine' in liquid phase

Discussion:-

In summary, the Na+ intercalation/de-intercalation reaction has been successfully used to

decouple the H2 (+NaOH) and Cl2 production in the conventional chlor-alkali electrolysis
technology. The separated H2 (+NaOH) and Cl2 production in different compartments
facilitates the membrane-free chlor-alkali process. This technology should be cleaner than the
previous chlor-alkali electrolytic process because Na0.44MnO2 is environmentally friendly.
Finally, as a typical Na-storage electrode material with low cost, Na0.44MnO2 can be easily
produced on a large scale when using the conventional solid-state method. This work may
open the door to build a cleaner chlor-alkali electrolysis tech- nology, where the reversible
Na+ storage in the electrode plays the role of a redox mediator to decouple the H2 (+NaOH)
and Cl2 production. For example, the reversible Na+ adsorption/desorption in the porous

17
carbon electrode of electrochemical double- layered capacitors can be used to decouple the
conventionalchlor-alkali Furthermore, the recent chlorine technology with oxygen-
depolarised cathode can be decoupled by the reversible Na+ storage in an Na0.44MnO4
electrode . However, in the current state, the decoupled chlor-alkali process is still some way
away from practical application. The movement of the battery electrode between Steps 1
and 2 and the corresponding washing processes requires a complex automation operation and
advanced industrial design. The kinetics of the battery electrode reaction is still lower than
that of the HER and the CER, so the advanced electrode is required to reduce the difference
in kinetics. Other issues, such as the reachable concentrations, purity of products, required
amount of Na0.44MnO2, parasitic OER reaction etc, also need to be solved
in future research endeavours. However, the old mercury cell gives us the inspiration that the
reversible Na+-storage reaction can decouple the chlor-alkali technology. In recent years,
sodium-ion batteries (SIBs) are attracting extensive attention as a promising alternative
candidate to lithium-ion batteries (LIBs) because of the abundant natural reserve and low cost
of sodium. The reversible Na+ intercalation/de-intercalation of the electrode is also expected
to be used as a redox mediator to decouple the chlor-alkali technology. Here we report a
membrane-free chlor-alkali electrolysis process, where the Cl2 evolution and H2/NaOH
production are decoupled by the reversible Na-ion intercalation/de-intercalation reaction of
the Na0.44MnO2 electrode. This decoupled strategy shows promise in developing a clean
chlor-alkali technology.

ELECTROLYSIS:-

With the help of electrical power, the salt (NaCl) is broken down into chlorine (Cl2), caustic
soda (NaOH) and hydrogen (H2). For this purpose, two methods are primarily utilized:the
diaphragm and the membrane method. With both methods, the same electrochemical
reactionoccurs: The NaCl flows into the anode chamber of the cell, where the CI2 separates
as chlorine gas. Subsequently, the solution reaches the cathode chamber, where H2 and
NaOH are formed.
The deciding difference in both methods, lies in the technical execution of the
anode and cathode separation, which is crucial for the purity and concentration of generated
caustic soda.

18
 The membrane and the diaphragm constitute a high cost factor within both
methods .The LiquiSonic® analyzer is utilized for a precise determination of the catholyte
concentration, in order to identify possible electrolyzer inefficiencies and to counteract them.
This way, an optimum membrane lifespan can be achieved.
Depending on which method is utilized, the catholyte involves either a NaOH-
solution (membrane method) or a NaOH-NaCl-solution (diaphragm method). The concent-
ration measurement of the 3-component mixture is accomplished with the use of a Liqui-
sonic® 40 analyzer, whereby the ultrasonic sensor is combined with a conductivity probe.

ADVANTAGES:-

 Maximizing of the electrolyzer‘s effectiveness

 Degree, through the continuous concentration

 Measurement directly in the process

 Energy saving and consumption optimizing

 Reduction in labor intensive comparison analyses

 Extending of the membrane‘s lifespan.

Preparation of end products:-

Caustic Soda Concentration:-

The market ready caustic soda (NaOH) typically has a concentration between 45 wt% and 50wt%.
Due to the fact that NaOH gained from electrolyzer cells only yields a concentration range between 12
wt% and 33 wt%, it is concentrated in cascade evaporators. If next to NaOH the solution contains
NaCl (diaphragm method), the excess salt in the caustic soda precipitates in a crystal form during the
evaporation.This way, the NaOH concentration is elevated to 45 wt% and 50 wt%. The LiquiSonic®
analyzer continuously determines the concentration of caustic soda at any time after the evaporator. A
subsequent dilution of the caustic soda to a customer specific product concentration, can also be
monitored.

19
Chlorine Gas Drying:-

The chlorine gas must be freed of its water content before it is further processed, due to the
fact that its corrosiveness elevates at a moisture content of over 30 ppm. For the drying, the
chlorine gas is routed into the absorption towers, where the water content in the chlorine gas
is absorbed with highly concentrated sulphuric acid (80 - 99 wt% H2SO4).
The effectiveness of this drying process significantly influences the productivity
and quality of the gas.This is why a reliable measurement of the H2SO4-concentration is
especially important.The LiquiSonic® analyzer offers a continuous and safe monitoring of
the H2SO4-concentration, in opposition to conductivity and density measurement.

ADVANTAGES:-

Elimination of labor intensive sampling

Continuous monitoring of H2SO4-concentration

Clear concentration determination signal between 80 wt% and 100 wt% H2SO4

Ensuring the desired Cl2 dryness to avoid corrosions in the system

Hydrochloric acid production:-

The chlorine gas that is generated on the anode of the electrolyzer and the added hydrogen, form the
base materials for the synthesis of hydrochloric acid. For this, both gases are fed into a burner and
there they react to form hydrogen chloride. Subsequently, the formed HCI-gas streams from the
burning chamber into the integrated isothermic falling-film-absorber.Here, The gas is absorbed with
the help of water or diluted acid, whereby concentrated hydrochlo- ric acid (37 wt% HCI) is formed.
Using the LiquiSonic® analyzer, a continuous monitoring of the hydrochloric acid concentration is
possible. This affords the ability to recognize deviations from the target concentration and to react
accordingly.

20
 UTILITIES:-

Distilled Water:-

water from which impurities, as dissolved salts and colloidal particles, have been
removed by one or more processes of distillation; chemically pure water.

Cooling Water:-

Cooling water is used to cool and/or condense streams. Cooling water is usually
circulated between process heat exchangers and a cooling tower. Water is cooled during
downward motion by contact with air blown upwards, which can bring the water
temperature to come within ~ 5 ⁰ F of air’s wet-bulb temperature.Approximately 80% of the
temperature reduction is due to evaporation of the cooling water and heat transfer to the
surrounding air. Water can also be cooled in spray ponds and cooling ponds. Both work by
providing high area for water to exchange heat with air. Water in cooling towers is lost
through drift and blowdown, and makeup is usually 1.5 to 3% of the circulating rate. If a
large natural body of water is nearby, it can be used as a source of cooling water and
discharged downstream. This water is usually filtered to remove salts and impurities that
may lead to fouling, but it is not treated.

Steam:-
Steam is the most commonly used heat utility used in chemical plants, and as a result
understanding how it is used is essential in the study of Utility systems. Steam is used both as
a process fluid (feedstock, diluent to absorb heat of reaction, heating agent, and stripping
agent in absorbers and adsorbers ) and utility. It can be used to drive pumps and compressors,
ejectors (for producing a vacuum), and heat exchangers. As one can clearly see, steam is a
versatile, and useful utility.

21
 Here are a few advantages of using steam as opposed to other methods of process heating:

 By controlling the pressure of the steam, one can control the temperature at which
the heat is released. Having a strong control over the temperature is essential in
several processes.
 Steam is an efficient heat source because the heat of condensation of steam is very
high. Meaning that there is is high output per mass of utility at a constant
temperature.
 Heat exchangers that use steam are relatively cheap because condensing steam
has a high heat transfer coefficient.
 Steam is non flammable, nontoxic, and inert to several process fluids.

Process & Hot Water:-

Process water is water that will be directly used in the process. Boiler-feed water (BFW) is
used to produce steam. Both may need to be purified to prevent impurities from
contaminating a process or from foul equipment. It can be used as a cooling stream when the
temperature of the stream to be cooled is greater than ~300 ⁰ F. Cost of BFW can be partially
offset by the steam credit.

Process water that undergoes moderate pre treatment can cost ~ $0.75/1,000 gal.
Extensive treatment ~ $6.00/1,000 gal.
Sterilized for pharmaceutical processes ~ $550/1,000 gal.

Industrial Gases:-

All the 3 gases that are produced using world leading MVS Engineering On -Site gas
generators – Nitrogen, Ox ygen and Hydrogen, find use in the chemical industry. Let’s
break it down.

Electricity:- Electricity is used to power many different kinds of equipment. It has many
advantages: it is efficient (> 90%), reliable, available in a wide range of power, shaft speeds,
designs, lifetimes, convenience, costs, and maintenance. It is generally used up to 200 hp, and

22
sometimes over 10,000 Hp. In chemical process plants, the electricity demand is generally
determined by the work or energy required for compression, pumping, air cooling, lights, and
many other items. This electricity often times is purchased from local electricity providers,
but many plants generate their own electricity via sophisticated processes.

Electricity is rarely used as a primary heat utility in large-scale chemical plants for a variety
of reasons. The main disadvantages of using electricity as a heat utility are as follows (Towler
2012)

 Heat from electricity is two to three times more expensive than heat from fuels.
This is attributed to the lack of efficiency when creating heat from electricity.

 Electrical heating units are expensive, require high maintenance, and must comply
with strict safety regulations.

 Electrical heating units are unsafe compared to steam heating units. In steam
systems, the physically steam controls the temperature, whereas in electrical
heating units temperature is controlled by temperature controllers, which can fail
or burn out.

The use of electricity carries with it some hazards depending on the environment.
Extra care must be taken when using electrically-powered equipment in areas
which may have combustible fluids, vapors, or dust, and where liquids may be
present.

Refrigeration:-

The pharmaceutical industry, as already mentioned, the user refrigeration in freeze-drying

processes. Approach, which seems to be popular in the industry, which is also to cool the
liquid, and distribute this cold fluids (antifreeze, ethylene glycol or alcohol, for example) the
place where refrigeration is needed. Low alcohol can cool jacket vessel, or glycol can be sent
by air-cooling coils are located in the room where the powder filling occurs that must be
maintained at low humidity.
Chemical, petrochemical and oil-refining industry, often require large refrigeration plants.

23
 Some important operations frequently require cooling: 

the condensation of gases, such as the capture of removal of gas from liquid storage
tank

the splitting of a single gas other way liquefaction more than one gas
solidification of one substance in the mixture to separate it from the other

contents stored liquid at low temperatures to control the pressure in the vessel,
containing the
removing the heat of reaction

humidity control for hygroscopic substances

Two main concepts in the provision of refrigeration are direct and indirect.
Cooling Towers:-

A cooling tower water treatment system is an arrangement of technologies that remove

damaging impurities from your cooling tower feed water, circulation water, and/or
blowdown. The specific configuration of your system will depend on several things,
including:

What type of cooling tower you have (open circulating, once-through, or closed loop)

quality of your feed water

manufacture-recommended quality requirements for the cooling tower and equipment

chemistry/makeup of your circulatory water

regulatory requirements for discharge

whether or not blowdown will be treated for reuse in the cooling tower

type of heat exchanger

cycle of concentration

24
 Process Description Of Calcium Chloride Plant
Calcium Chloride is one of the most versatile of the basic chemicals. It has been produced
commercially for well over the years. The properties and characteristics of Calcium Chloride
make it useful in a large number of applications. Commercially Calcium Chloride is produced
in following forms.

Liquid Calcium Chloride is manufactured in concentrations of 20% to 45% and it is also

available as 32% food grade formulation.

The object of the plant is to utilise Hydrochloric (HCl) acid by neutralizing it with Calcium
Carbonate (CaCO3) . The Calcium Chloride is produced by the reaction of Calcium
Carbonate (CaCO3) with 32% Hydrochloric acid in the reactor. The resulting 35 % Calcium
Chloride solution is produced and further it is neutralized with lime to make it free from any
acidity. It is also clarified to remove all suspended impurities. The clear Calcium Chloride
solution is then can be transferred for further use in evaporation or granulation plant to make
anhydrous/solid material.

The Calcium Chloride in the form of powder and granules and flakes are easily transportable
and sellable in the market in India & abroad.

Chemistry of the Process:-

The Calcium Chloride is mainly produced commercially by Lime stone and Hydrochloric
acid reaction. The other production process such as recovery from by the product or naturally
available forms are not covered here.

Lime stone-Hydrochloric acid Process:-

Limestone can be treated with HCl to form Calcium Chloride and Carbon Oxide.

CaCO3 + 2HCl CaCl2 + CO2 + H2O

If concentrated 32% HCl is utilized the concentration of CaCl2 in the produced solution will
be approximately 32% and the further evaporation is only needed when flakes/granules are
produced. The purification of the product is mainly accomplished by adding Ca(OH)2 as
described in the natural brine process.

Ca(OH)2 + Mg2+ Mg(OH)2 + Ca2+

25
The high purity of the produced CO2 makes it suitable for applications within the food and
pharmaceuticals industries. Extremely pure Calcium Chloride products can be obtained using
this process if the purity of the Hydrochloric acid is sufficient.

Design Basis:-

The design of the process is based upon the following steps :

Neutralization of HCl with lime stone to produce 35% Calcium Chloride solution.The
neutralization of HCl with limes stone is carried out as explained above to produce CaCl 2
and CO2 as by product. The CaCl2 solution which contains unreacted solids settled down in
the bottom of the reactors which can be removed by drain Valves/Man Holes periodically to
settling pits.

The CaCl2 solution which contains un-reacted solids free acid and Chlorides of other
undesirable metals like Magnesium etc. (impurities from the lime stone) flows by gravity to
Clarifier through retention tank. Milk of Lime solution is dozed in reaction tank wherein the
Milk of the Lime react with free acid and other metallic chlorides. The Calcium Chloride
solution becomes neutral and other metallic Chlorides converted into metallic hydro-oxides
which are insoluble in water.

Clarification:-

The neutralized Calcium Chloride solution impurities gets settled down in clarifier which is
continuously containing insoluble impurities. The Flocculent (alum) is added in the solution
overflowing from the retention tank to the clarifier. The un-dissolved solids get settled down
at the bottom of the clarifier which are intermittently discharged into settling pit. The

overflow from the clarifier is discharged into Calcium Chloride solution storage tank. The
neutralized clean solution Calcium Chloride can be filtered by inner line polished filter and
transferred for further process of concentration and granulation. The sludge is filtered in a
separated filter press where the cake builds upon the filter cloth. The filtrate is collected in a
filtrate tank and the solids are discharged.

26
 Process Overview Of TFE Plant

R 22
Steam Heating React Cooling,ca Compressi
Furnace or ustic ng,
Steam washing Dehydrati
ng

Rectification Recovery

TFE Product R 22, C3F6

Process Block Diagram

Production of TFE consists of following steps:

TFE productions by Steam dilute Pyrolysis of R22.

Cooling of cracking gas

Separation of Impurities, Water washing & Caustic washing to remove HCL.

Cracking gas Compressing, Dehydrating and deoxidizing;

Cracking gas rectification to produce TFE monomer & Recover Unreacted R22.

The Quality of Cracking gas Directly Effects Rectification and the Final Product.
The temperature for cracking reaction is kept between 760 °C to 900°C.

760~900oC
2CF2HCL CF2=CF2 + 2HCL
Overheated steam

27
Main reaction :-

CF2HCL CF2 + HCL

2CF2. C2F4
Main Side Reaction:-

CF2. + C2F4 CF2=CF-CF2

C2F4 + HCl H (CF2)2CL

CF2HCL + C2F4 H (CF2)3CL

R22 Steam Dilute Pyrolysis:-

The reaction is a homogeneous endothermic reaction. It is a Volume Increasing Process, so

low pressure preferred. Steam used is a kind of dilution solvent & heat carrier.Steam hampers
the formation of High boiling Components.

Cracking Process:-

Fresh R22 is unloaded in R22 storage tank. Tank is provided with condenser and jacket for
steam heating. Fresh R22 is unloaded to R22 storage tank through metering pump.
Depressurization line for depressurization of pump discharge line is given directly to buffer
tank.

Fresh R22 transfer to R22 metering tank by heating Fresh R22 storage tank up to 8 kg/cm 2.
Metering tank is provided with two jackets, upper jacket for -15 oC chilling medium and
bottom jacket for steam heating (3 kg/cm2).Fresh R22 is passed through R22 Vaporizer to
heat up to 30 oC and collected into R22 buffer tank. Recycled R22 & Fresh R22 are mixed in
R22 Buffer tank. Mixed R22 enter R22 Heater and heated to certain temperature. R22 enters
into upper convection section of steam heating furnace, and goes into Reactor where
temperature is around 400~450 °C. Along with that steam comes from steam drum and
outside battery limit goes into steam buffer tank after depressurization, and then flows into
the convection section of steam heating furnace. Where the temperature is rise from 150 oC to
around 900 °C. The steam goes into the mixer in reactor to mix with the Pre-heated R22.

28
The heat supply for Steam heating furnace is by Heavy fuel oil combustion. It is transported
to through pipeline (oil pressure 10 kg/cm2) and then to burner of steam heating furnace by
ball valve. Heavy fuel oil burn with natural circulated air and the flue gas, after combustion
passes through radiant and convection sections of furnace to vent through stacks.

R22 cracking reaction is carried out within reactor. The inlet and outlet of Reactor are direct
welded with steam heat furnace and Quencher. Reaction is carried out at 760~900 oC with
resident time of ~ 0.02seconds. Cracking gas is composed of C2F4, HCL, traces of other
cracking product, unreacted R22 and excess steam.

They enter Graphite Condenser after Quenching in Quencher. Heat from cracking reaction is
recovered by Quencher, generating Steam with pressure of 4 kg/cm2 through steam drum.
The feed water of steam drum comes from De-ionized water storage tank through De-ionized
water pump.

Cracking gas treatment:-

In Graphite Condenser, steam and HCL are condensed into hydrochloric acid of 12.5%.It
passes through water sealing drum to HCL receiving tank. This tank is open to atmosphere.
This HCL will be transported to HCL tank through pump depending on the level in the
Receiving Tank. Uncondensed cracking gas enters Caustic washing tower through Gas-
Liquid Separator. Cracking Gas is brought into contact with 15% caustic from caustic tank
and caustic recycle pump. Alkali is discharged to Liquid waste pit when its concentration
falls down to 5%. One spare caustic tank of 15% is provided while changeover of caustic
solution. After the acidic components being neutralized Cracking gas enters Gas Hooder and
then to First stage compressor through 1-Buffer tank. After pressurization up to 3 kg/cm2 and
temperature up to 70 oC in first stage compressor. Then cracking gas enters into Freezing
Dehydrator to cool down the temperature from 25 oC to 2 °C so as remove most of the
moisture before entering the Second stage compression. The Cooling Dehydrator and
Freezing Dehydrator are provided with shell side -15 oC chilling circulation. The moisture
content of cracking gas is less than 150 ppm. The inlet temperature and pressure of second
stage compressor is 2 °C and 3 Kg/cm2 respectively. After second stage, compression the
cracking gas enters into secondary cooler through oil separator then enter into Silica gel
Dryer. Remaining Traces of Moisture are removed in Silica gel Dryer. Silica gel dryer is used
to remove the final traces of moisture. The moisture content of crackling gas coming out of
silica gel dryer is less than 100 ppm. Silica gel dryer is provided with cooling water jacket.
29
Cracking gas coming from silica gel dryer enter into intermediate condenser. Five number of
intermediate condenser are operated in parallel flow. Intermediate condensers are provided
with -35 oC chilling medium circulation. Cracking gas converted from gas phase to liquid
phase is stored into intermediate storage tank after passing through tail gas condenser.
Uncondensable gases are sending to tail gas tower. .

Rectification:-

Cracking gas coming from top of intermediate storage tank is at 15 kg/cm2 pressure and 22 oC
temperature. Enters in to # 1 Rough separation tower. Distillate from the bottom of condenser
of #1 tower, which content traces of R22, TFE, and other light components, are sent to # 2
Light fraction removal tower. Traces of TFE, R22 and other heavy component left at the
bottom of # 1 tower are sent to # 5 R22 Recovery tower. The uncondensed component in gas
phase are sent to # 10 Absorption tower.

Light component (including CO and traces of oxygen) with boiling point lower than that of
TFE are rectified from top of # 2 Light fraction removal tower and mixed with uncondensed
gas from top of # 1 Tower and condenser of # 2 Tower. The mixture are sent to # 10
Absorption tower. TFE at the bottom of # 2 Tower goes into # 3 Rectification tower.

The side cut gases TFE monomer from top of # 3 Rectifications tower is sent to PTFE plant
after metering. There are pipeline on the top of tower to vent traces of light component to # 3
Buffer tank and then sent to Gas hooder. Material left at the bottom goes back to Gas hooder
for recycle.

Traces of TFE, R22 and other heavy component left at the bottom of # 1 tower are collected
in feed tank. Feed tank is provided with steam heating coil. Feed tank pressure is maintained
at 3 kg/cm2 and temperature is at 30~40 oC . The pressurized gas enters at bottom of # 5 R22
Recovery tower. In # 5 Tower Deionised water is kept in circulation and gas is counter
currently contacted with DI water. DI water removes all Triethylamine from cracking gas.

30
 Process Overview Of PTFE Plant

INTRODUCTION:-

Polytetrafluoroethylene is a synthetic fluoropolymer of tertrafluoroethylene that has

numerous applications. The best known brand name of PTFE based formula is Teflon.

General:-
 Product name : Teflon

 IUPAC name : Poly tetra fluoro ethylene

 Chemcal formula : (𝐶2𝐶2)n

Physical & chemical features:-

 Thermo plastic polymer

 The product has very good features such as thermal and chemical resistance,
electrically and insulativity, self lubrication ability, non sticky, non
flammability.

Chemical properties:-
 Molecular formula: C𝐶2-C𝐶2

 Molecular weight: 100

 Boiling point: -76.3⁰ C

 Melting point: 327⁰ C

 Igniting point: 620⁰ C

 Critical Temperature: 33.3⁰ C

 Critical pressure: 39.2kg/cm²

 Polymerization heat: 412 kcal/kg

 Explosion limit: 11-60%

31
FLOW-SHEET OF PTFE:-

Main reaction:-

nCF2=nCF2 (CF2-CF2)n + 412 cal/Kg

Process description:-
 Monomer storage and metering

 TFE monomer in gas phase goes into PTFE plant continuously and is fed
into TFE monomer storage tank after being condensed into liquid phase by
condenser. The liquid TFE monomer from the storage tank flows into TFE
monomer-metering tank on level differentials. Both monomer storage tank
and metering tank are equipped with -35⁰ C cooling medium jacket. The
jacket is cold insulated. The steam jacket at the bottom of monomer storage
tank can raise the polymerization reactor.

32
 Suspend polymerization reaction:

 After entering the de-ionized water tank, the de-ionized water is fed into
polymerization reactor, crushing & washing kettle, and caustic storage tank
by feed water pump.
 The de-ionized water is fed into the polymerization reactor following
specific ratios, along with which some disodium hydrogen phosphate is also
added into it through hand hole.
 The air in the reactor is extracted for air freeing after sealing off. It includes
three times of evacuating and two times high purity nitrogen replacement.
Then TFE monomer is fed into the reactor after air freeing to the pressure of
0.5kg/cm². Sampling is taken and analysed. It is considered qualified when
the oxygen content in the reactor is below or equal to 30ppm. Start the
polymerization agitator. Ammonium perasulfate, sodium hydrogen
bisulphate, and ferrous sulphate are dosed into the reactor by diaphragm
dosing pump from the initiator cup. While the temperature is kept at 15⁰ C.
TFE monomer is added till the pressure in the reactor reaches 8kg/cm².
 In the process reaction, TFE feeding is adjusted according to the pressure at
8kg/cm². The polymerization heat generated during the reaction is absorbed
by the -15⁰ C brine that passes through jacket of the reactor. The brine
volume is adjusted according to the temperature in the reactor to keep the
temperature 45⁰ C. The reaction stops when certain volume of TFE
monomer is consumed. The residual TFE monomer in the reactor is
recovered to TFE plant after passing through caustic washing tank, gas-
liquid separator, trace of TFE in the system is vented to the atmosphere from
vacuum buffer tank by vacuum pump.
 Resin crushing, washing and drying:

 When the polymerization reaction stops, the reactor is emptied and purged.
The PTFE resin is discharge into crushing & washing kettle along with
mother liquid and de-ionized water used for washing. Resin is crushed and
washed through agitation, after which, the resin is screwed out from the top
of the crushing and washing kettle and transferred to the hot air mixer and
pneumatic dryer for drying after mixing with hot air.

33
  Polymerization mother liquid from the bottom of crushing and washing
kettle passes through filter tank and is collected in the collecting pit.
 After some periods of operation, each polymerization reactor needs to be
cleaned by high pressure filch gun. The cleaning materials are collected in
stainless steel cylinder.
 After being filtered by primary air filter, the air used for drying the resin
enters air blower. After being further purified by secondary air filter and
high efficiency air filter, the air, which is heated by electric heater to the
temperature 200-220⁰ C, is mixed with aqueous resin by hot air mixer.
 The moisture in the resin, which is brought by hot air, is vent to the
atmosphere by ID fan. Dried resin gravity distributor from bottom of
cyclone separator.
 After being purified by primary air filter, cooling air, which is used for
cooling the resin, passes through blower and air cooler. After being further
purified by the secondary and high efficiency air filters, it is mixed with hot
resin by cold air mixer. The mixture of cooling air and resin, after being
cooled down by pneumatic cooler, enters cyclone separator.
 After being separated from bottom of cyclone separator contains a small
quantity of resin, goes to filter bag to further collect resin. The air
discharged from top of filter bag is vent to the atmosphere through ID fan.

 Packing and storing of PTFE resin:

 After being weighted, the middle and fine grain PTFE resin are separately
packed in packaging barrels with two layers of low density polyethylene
plastic bags. Then they are sent to the storehouse and become finished
products if they are tested qualified.
 Transportation and storage

The product can be transported as unhazardous goods. Humidity and severe shaking
should be avoid during transportation. Long term storage is allowed in clean, cool and
dry place

34
 Preparatiom of chloro-methanes by distillation method

Introduction:-
Methyl Chloride:-
Methyl chloride (CH3Cl) which is also known as chloromethane, R-40 or HCC 40, is achemical
compound of the group of organic compoundscalled haloalkane. It was widely used as a refrigerant. It
is a colourless andextremely flammable gas with a mild sweet odour.
However, the odour isdetected at possibly toxic levels.

Methyl chloride is a naturally occurring ozone-depleting gas. CH3Clmeasurements in air

extracted from the ice core from South Pole, Antarcticacovers the time period from 160 BC
to 1860 AD.
CH3CL levels

were elevated from 900 – 1300 AD by about 50 ppt relative to the previous 1000 years,
coincident with the warm Medieval Climate Anomaly. CH3Cl levels decreased to a minimum
during the Little Ice Age cooling (1650 – 1800 AD),before rising again to the modern
atmospheric level of 550 ppt. These variations most likely reflect changes in tropical and
subtropical conditions and raise the possibility that a warmer future climate may result in
higher trophospheric CH3Cl levels
Chloromethane was first synthesized by Jean-Baptiste Dumas and Eugene Peligot in
1835. They prepared it by boiling a mixture of methanol, sulphuric acid and sodium chloride.
This method is similar which is used today .The higher toxicity restrict its use in the
consumer products.

Dichloromethane:-

Dichloromethane (DCM) is an organic compound with the formula CH2Cl2.

Dichloromethane is also known as methylene chloride, methane dichloride, methylene
bichloride, ethylene dichloride. It is a colourless and volatile liquid with a moderately sweet
aroma. It is miscible with many organic solvents but not miscible with water. It is widely
used as a solvent.

35
Manufacture:-

1. From methane by chlorination (Methyl chloride and Dichloromethane)

Raw materials:-

Basis: 1000kg methyl chloride, dichloromethane, chloroform and carbon tetrachloride by

from methane by chlorination:
Chlorine1530kg
Methane305kg

Main Reaction:-

CH4 + Cl2 → CH3Cl + HCl

CH3Cl + HCl → CH2CL2 + HCl
CH2CL2 + Cl2 → CHCl3 + HCl
CHCl3 + HCl → CCl4 + HCl
Yield (chlorinated methane) - 99-100% (based on chlorine) 85-99% (based on methane)

Manufacture process:-

• Methane and Cl2 are mixed and sent to a furnace

• The furnace has a jacket or shell and tube system to accommodate feed pre-heating to
desired furnace inlet temperature (about 280 – 300°C).
• To control temperature, N2 is used as a diluent at times.
• Depending on the product distribution desired, the CH4/Cl2 ratio is chosen.

• The product gases enter an integrated heat exchanger that receives separated CH4 (or a
mixture of CH4 + N2) and gets cooled from the furnace exit temperature (about 400°C).

• Eventually, the mixture enters an absorber where water is used as an absorbent and water
absorbs the HCl to produce 32 % HCl.

• The trace amounts of HCl in the vapour phase are removed in a neutralizer fed with NaO

36
• The gas eventually is compressed and sent to a partial condenser followed with a phase
separator. The phase separator produces two streams namely a liquid stream consisting of the
chlorides and the unreacted CH4/N2.

• The gaseous product enters a dryer to remove H2O from the vapour stream using 98%
H2SO4 as the absorbent for water from the vapour.

• The chloromethanes enter a distillation sequence. The distillation sequence consists of

columns that sequentially separate CH3Cl, CH2Cl2, CHCl3 and CCl4.

Figure 14.2 Flowsheet of Chloromethane production

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The reaction between chlorine and methane in the presence of light or a catalyst yieldsmethyl
chloride with the formation of methylene dichloride, chloroform and carbon tetrachloride.
99% pure methane was mixed with chlorine in a mole ratio of 1.7:1. The preheated
reactants were fed to a reactor fitted with mercury arc lamps which promotes the reaction.

About 65% of the methane was reacted at 350 – 3700C and slightly above atmospheric
pressure with desired residence times. A typical range of products which leaves the reactor is
methyl chloride - 58.5%; methylene dichloride - 29.3%; chloroform - 9.7%; and carbon
tetrachloride - 2.3%. The effluent gases from the reactor also contain unreacted methane and
hydrogen chloride.
Unreacted methane and HCl were separated from the chloromethanes by
scrubbing the reacted gases with a mixture of liquid chloromethanes usually a refrigerated
mixture of chloroform and carbon tetrachloride. They were separated in water absorber while
methane was recycled. The chloromethane absorbent, enriched with the chlorinated products
removed from the reaction gases, was charged to a stripping column. Methyl chloride and
some methylene dichloride go over head and then sent for purification where first hot water
wash was given to remove residual hydrogen chloride, an alkali wash for a neutralization and
a strong sulfuric acid wash to dry the solvent mixture. The methyl chloride and methylene
dichloride were separated by series of fractional column.
The bottoms from the stripping column were recycled to the absorber while a
considerable portion of the liquid was fed to a secondary reactor.In the reactor more chlorine
was added and by photochemically. Hydrogen chloride vented from the reactor. The reaction
products were run into intermediate column where methylene dichloride was distilled and
recycled to reactor and desired quantities of chloroform was purified in the chloroforms
column. The remaining mass was passed to a third reactor where it was again chlorinated and
produce carbon tetrachloride which was then purified using carbon tetrachloride column.
Heavy ends were separated from the bottom of the column.

2. Other Methods:-

Another methane chlorination process was directed specifically to methyl chloride; it makes
use of a high methane chlorine ratio (10:1 by volume) and a catalyst such as partially reduced

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cupric chloride deposited on pumice. The gases were mixed and passed through a
chlorination furnace where reaction takes place at about 4500C. The contact time varies
in the range of 1 to 20sec.
To remove the hydrogen chloride, the reaction gases were passed through a water
scrubber and then led through a series of water-cooled and refrigerated condensers under
pressure. The mixture of chlorinated hydrocarbons condensed while unreacted methane was
recycled to the mixing chamber. As all the chlorine was reacted with the methane, so that
little or no chlorine remains in the reaction gases.
Crude methyl chloride was distilled under pressureto yield pure methyl chloride of
refrigerant grade. Approximately 85 – 90% of the condensate distills between -23 to -250C at
atmospheric pressure to give a yield of methyl chloride of about 80% based on the chlorine
charged.
Engineering Aspects:-

 Reaction Control:-

The highly exothermic reaction is a chain initiated and propagated one involving Cl.
radical and can be explosive if not controlled properly.Considerations to control the
reaction are:
 Use of a methane cycle where there is a considerable excess of CH4 – leads to large
amount of mono- and dichloromethane as product.
 Use a liquid as a co-solvent.

 Use a nitrogen gas or itself product as diluents.

 Chlorine has to be added stage wise along the reactor.

 Product ratio control:-

The methane cycle is the easiest to design and operate but gives largely CH3Cl.
However, the predominate demand for CCl4. This requires a CH4/Cl2 ratio of
between 0.5 and 0.8 with N2 diluent and operation with recycle, requiring one large
furnace or a separate set of furnaces. Another alternative is to strip out the light
chlorinated product from the methane cycle and add excess chlorine to produce CHCl
3 and CCl4. This also requires additional equipment.This reaction was carried out at
high temperature in gaseous phase.The reaction was initiated by heating the reactants.
Onces reaction was started, free radical process rapidly goes on completion with the

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 Utilisation of HCL to produce more CH3Cl

CH3OH + HCL → CH3CL + H2O

In plant where methanol is available, it is available to utilize the replacement reaction.
This can be carried out as a vapour phase reaction using alumina or other similar catalyst. In
liquid phase zinc or aluminium catalyst was employed.
The process is also used I plants when methanol and by-product HCl, not necessarily
from methane chlorination.

Properties:-

Methyl Chloride:-

 Molecular formula : CH3Cl

 Molecular weight : 50.49gm/mole

 Appearance : Colourless gas

 Odour : Faint, ethereal odour

 Boiling point : -23.80C

 Melting point : -97.40C

 Flash point : -20.00C

 Auto ignition temperature : 6250C

 Density : 1.003gm/cm3 (-23.80C, li quid)

2.306gm/cm3 (00C, gas)
 Solubility : Soluble in water

DiChloromethane:-

Molecular formula : : CH2Cl2

Molecular weight : 84.93gm/mole

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 Appearance : Colourless liquid

 Odour : Sweet

 Boiling point : 39.60C

 Melting point : -96.70C

 Flash point : None

 Auto ignition temperature : 5560C

 Density : 1.33gm/cm3 (liquid)

 Solubility :miscible in water

USES:-

Methyl Chloride:-

 Methyl chloride was widely used as refrigerant

 Used for producing lead-based gasoline additives (tetramethyllead)

 As a chemical intermediate in the production of silicon polymers

 As a solvent in petrol refining and butyl rubber manufacturing

 As a chlorinating and methylating agent

 As propellant and blowing agent in polystyrene foam production, as an extractant for

grease oils and resins
 As a local anesthetic and also as an intermediate in drug manufacturing

 As a catalyst in low-temperature polymerization

 As fluid for thermostatic and thermometric equipment and also used as herbicide

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 Dichloromethane:-

 Dichloromethane is useful solvent for many chemical processes as it having good

volatility and dissolves a wide range of organic compounds
 In food industry it has been used to decaffeinate coffee and tea as well as to prepare
extracts of hops and other flavourings
 As an aerosol spray propellant and as an blowing agent for polyurethane foams

 In garment Industry for removal of heat-sealed garment

 Used to seal the casing of electric meters

 Used by model building hobbyist for joining plastic component together

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 CONCLUSION

Various plants of GFL were studied. We compared the applicability of the theoretical knowledge
with the practical. We also studies various unit operations unit processes different types of
equipments, types of supports to the vessels and the safety devices. It was overall a good
experience to do our training from GFL. We got an exposure to how the actual process is being
performed for manufacturing of various chemicals. We also got a good chance to see various
equipments such as reboilers, separators condensers, distillation columns storage tanks pumps
and instrumentation. We also learned about the various management skills required in
chemical-industries

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