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Vocational Training Report

ON
Manufacturing of Caustic Soda Flakes

Heavy Chemicals Division,


Tamilnadu Petroproducts Ltd, Manali

By:
Hemant Gaule (U04CH115)
B.Tech-IV, Chemical Engineering
Acknowledgements

The period of my vocational training at the Heavy Chemicals Division of Tamilnadu


Petroproducts Limited was a great learning experience for me. It helped me relate the theoretical
aspects of Chemical engineering to the practical working and functioning of various phases of
production of caustic soda flakes. This, however, could not have been without the efforts and co-
operations of the employees and mentors at TPL. This report is credit to the contributions and
generous aids provided by the members of TPL, and hence I am obliged to say a word of thanks to
everyone who helped me with their guidance throughout the training program.

I am thankful to Dr. R. Krishnan, Technical Head, Heavy chemicals division for his generous help
throughout the training.

I would like to thank Mr. R. Joseph Premkumar, Executive (Training) for giving me the
opportunity to undergo this training program.

I would like to thank Mr. M. Yerumalai, Technical Head, Brine House for his help and support.

I am thankful to Mr. V. Malayan, Operator, Brine House for all his help and co-operation.

I express my thanks to Mr. M, Vijayamohan, Chief of safety, HCD, for his generous guidance.

I would also like to thank all the employees at HCD, TPL for all their support and co-operation.

HEMANT GAULE
Contents

Chapter 1 General Outline

Chapter 2 Process Description


2.1 Primary Brine Treatment
2.1.1 Anthracite Filters
2.1.2 Precoat Filters
2.2 Secondary Brine Treatment
2.2.1 Polishing Filters
2.2.2 Depleted Brine Dechlorination
2.3 Electrolyzers
2.4 Caustic Concentration
2.4.1 Caustic Evaporation Plant
2.4.2 Fusion Plant

Chapter 3 Demand, supply and manufacturers in India

Chapter 4 Line Sizing

Chapter 5 Instrumentation

Chapter 6 Pumps and valves

Chapter 7 Motors, RPM, make types;

Chapter 8 Environmental Issues

Summary
1.General Outline

The plant is designed to produce close to 100 TDP of caustic soda by Ion Exchange Membrane electrolysis
process. This process has replaced the Mercury Cell process as it produced huge amounts of mercury as waste,
which was highly toxic to the environment. Chlorine and Hydrogen gases are liberated as side products.

The raw materials are raw salt, water and power. The final products are
a) 32.5 wt% caustic soda (concentrated to 48% in existing mercury cell)
b) liquid chlorine
c) hydrogen gas

The plant consists of sections for raw material treatment, electrolysis, product treatment and utility supply. The
chemical process, however, may be broadly classified into three sections:

Table 1General Outline


Section No. Section name
I Brine treatment section
a) Primary brine precipitation and chemical preparation
b) Primary brine filtration
c) Sludge treatment
d) Secondary brine purification
e) Brine dechlorination
II Electrolysis (32% caustic, H2, Cl2 as products)
III Caustic concentration
a) Caustic Evaporation Plant (32% caustic to 48% caustic lye)
b) Fusion Plant (48% caustic lye to 98% caustic flakes)
2. Process description
2.1 Primary brine purification

The depleted brine after vacuum dechlorination and sodium sulfite treatment is sent to, the saturators. Two
saturators are provided; one working and one stand by. However, when one is in service, a small quantity of
depleted brine is sent through the other saturators to prevent clogging of dip pipe as well as to remove the
impurities by leaching.

During the electrolysis, some amount of water from brine will be transported to the cathode compartment along
with the sodium ions. This water loss from brine is made up by adding DM water tom the depleted brine before
tit enters the saturators. The concentration of crude brine is controlled by mixing some amount of lean brine
with saturated brine from the saturators inside a strainer tank.

Raw salt contains many insoluble matters, which get settled at the bottom of the saturators. These insolubles are
removed periodically from the bottom of saturator. The bottom discharge is collected in a saturator recovery pit.
When the insolubles are settled, the clean brine is recovered back to the saturator by the raw salt sludge pump.

The crude brine contains impurities like calcium, magnesium, sulphates, heavy metals etc. the calcium,
magnesium and sulphates are eliminated by treating the crude brine with the sodium carbonate, sodium
hydroxide and barium carbonate respectively. The reactions are carried out in two reactors. The sodium
carbonate and barium carbonate are added to the first reactor and sodium hydroxide in the second rector. To
speed up the reaction and to prevent settling of precipitators, both reactors are provided with agitation. The first
reactor is agitated with air and the second one with mechanical agitator (since any air bubble trapped in the
brine affects the settling efficiency of clarifier, in the second reactor air agitation is not used.).

Following reaction occur in the reactors:

Na2SO4 + BaCo3  BaSO4 + Na2CO3


CaSO4 + BaCO3  BaSO4 + CaCO3
MgCl2 + 2NaOH  Mg(OH)2 + 2NaCl
Ca+ + + Na2CO3  CaCO3 + 2 Na+

The flow rate of 10 % Na2CO3 and 20 % NaOH supplied to the reactor are controlled to get an excess sodium
hydroxide content of 150 – 200 mgpl and excess carbonate content of 250 – 300 mgpl in the brine at the outlet
of second reactor. Barium carbonate slurry concentration is kept at around 16 wt%. The brine recovered from
various operations are collected in a pit and supplied to the first reactor at constant flow rate. For the stable
operation of the clarifier, it is advisable not to allow major variations in the flow rate of recovered brine.

Crude brine overflowing from the second reactor enters a flocculants mixing tank where 0.05 wt% flocculants
solution so that the concentration of flocculants in brine is maintained at around 5 ppm. (This quantity may
further be reduced as per the actual performance of the clarifier).

The brine then overflows into the clarifier where the residence time is long. In the clarifier, all the reactions are
completed and the precipitates get settled at the bottom. The precipitates are periodically removed from the
bottom and sent to the vacuum drum filter using clarifier sludge pump.

The clarifier is a water seal type, where a layer of water is always maintained on the surface of brine to prevent
heat loss from brine due to radiation and to prevent convection current (thereby settling is improved). If the
water layer decreases, the sealing water temperature increases. Then the clarifier is to be supplied with
additional sealing water supply at the top. DM water is used as the sealing water.

The clarifier brine overflows into the CB tank. The suspended solid of this brine is about 20 ppm or less.

SLUDGE FILTRATION AND BRINE RECOVERY

1. Clarifier underflows, precipitates underflow and the backwash from polishing filter are collected in the
sludge pit.

2. The polishing filter backwash, clarifier underflow are filtered using vacuum filter and the filtrate is collected
in recovered brine pits.

3. The backwash brine from Anthracite filters, various tank overflows and the filtrate from vacuum drum filter
are collected in the recovered brine pits.

4. From the pit recovered brine is continuously fed to the brine circuit at a constant flow rate using recovered
brine pumps.
DM
Water 10%
FIC Na2CO3 20%
NaOH Floxin
Depleted 16%
Brine BaCO3

pH
Mixing
Strainer Mixing Tank
Mixing
Reactor Reactor
I II
Saturator

Clarifier
LIC

FIC

Filtered Brine
Tank
Clarified
Filtered Brine Backwash Brine Tank
Pump pump
Clarified
Brine Pump
Body Na2SO3
Polishing LIC
Feed FIC
Filter Tank Prep
Tank
AIC
To Secondary
Brine System
Polished Brine
Tank
Polished Brine
Pump Filter
Backwash

Fig 1 Primary Brine Treatment


Table 2(a) Parameters

PRIMARY BRINE PURIFICATION

NO. ITEM STANDARD UPPER LOWER LIMIT


LIMIT
1 Saturator brine 305 gpl 315 gpl 270 gpl
concentration
2 Agitation air flow 500 NM3/HR
rate to reactor I
3 Flocculant solution 1-2 mg/l 5 mg/l 1 mg/l
flow rate
4 Crude brine pH 9.5 10.5 9
5 Water seal layer Ambient Ambient + -
temperature of 15 Deg.C
clarifier (V.112)

CHEMICAL PREPARATION

6 Agitation air flow 50 NM3/hr 100 NM3/hr -


to V.114 A/B
7 Agitation air flow 50 NM3/hr 100 NM3/hr -
to V.116 A/B
8 Agitation air flow 50 NM3/hr 100 NM3/hr -
to V.117 A/B

PRIMARY BRINE FILTRATION

9 Clarified brine tank 70% 80% 40%


level
10 Filtered brine tank 70% 80% 40%
level
11 Clarified brine 74 M3/hr 80 M3/hr -
flow rate to
anthracite filters
12 Brine flow rate to 37 M3/hr 45 M3/hr -
individual
anthracite filters
13 Differential 0.5 ksc 1.5 ksc -
pressure across the
anthracite filters
14 Turbidity of Less than 10 10 ppm -
filtered brine ppm
2.1.1 ANTHRACITE FILTERS

The clarified brine from is fed to the primary brine filters to reduce suspended solids
content in brine to les than 10 ppm. Out of three filters, two will be working in parallel
and one will remain as stand by.

Anthracite is used as filtering medium. The filtered brine is collected in a filtered brine
tank. During the operation, when one filter becomes saturated, the pressure drop across it
increases. The differential pressure across the anthracite filters is monitored by individual
differential pressure indicators. when the pressure drop across the filter increases then the
stand by filter is taken in line and the saturated filter undergoes backwashing. Filtered
brine sent from using the backwash pump is used for backwashing.

Backwashing carried out in 3 steps:

1) Surface washing
2) Backwashing
3) Resetting (preparation )

Step -1: SURFACE WASHING:

This is provided to loosen the sludge cake at the surface of filter medium.

Step -2: BACKWASHING:

During backwashing, the filtered brine is introduced from the bottom of the filter and all
the precipitators trapped in the filter medium are removed and sent to the recovered brine
pit.

Step -3: RESETTING: (Preparation)

After the backwashing step, the clarity of filter outlet is established by passing the filtered
brine from top to bottom of filter (resetting) for a small duration.

All the steps are carried out either automatically from the DCS or manually from local
control station. The selection of the operation shall be through a local/auto selection from
DCS. This local/auto selection shall be done by the engineers on the DCS panel.

During each stage of regeneration steps, step break provision is provided to stop the
operation. Unless the step break step is activated, the operation goes to the next step
automatically, by pass provision also provided for each step of operation. In case of
malfunctioning of any value, mishap alarm appears, indicating valve malfunctioning.
Table 2 (b) Valve Opening Time

STEP VALVE OPENING TIME FLOW RATE

1. SURFACE WASHING XC 123 5 MIN 40 M3/HR


XC 125
2. BACKWASHING XC 121 15 MIN 80 M3/HR
XC 125
3. RESETTING XC 126 5 MIN 40 M3/HR
XC 124
4. NORMAL RUNNING XC 127 --- 37 m3/hr
XC 122 (MAX 40 m3/hr /filter)

VALUE DETAILS

1) XC 121  Backwash inlet (6”)


2) XC 122  Running outlet (4”)
3) XC 123  Surface wash inlet (4”)
4) XC 124  Preparation outlet (4”)
5) XC 125  Backwash outlet (6”)
6) XC 126  Preapration inlet (4”)
7) XC 127  Running inlet (4”)

Table 2 (c) Quantity of Anhtracite in each filter and size distribution

Size (mm) Height (cm) Cu.m

Top 0.6 - 1.2 600 4.6


3.0 – 4.0 75 0.55
5.0 – 10.0 100 0.73
11.0 – 15.0 100 0.73
16.0 – 30.0 130 0.94
Bottom 4.0 – 50.0 630 2.70
2.1.2 PRECOAT FILTERS

The filtered brine from is fed to the polishing filters to reduce suspended solids to less
than 0.5 ppm. This is a candle type precoat filter. Two such filters are provided – one
operating and while the remaining one stays in stand by mode after backwashing.

The polished brine after adjusting the pH to 9 after adding 32 wt% HCl is sent to the
polished brine storage tank. DM water is added to the 32 % HCl in small quantities to
prevent crystallization of brine at the point of entry of HCl.

The pH is adjusted to 9 to facilitate converting all the suspended impurities to their ionic
forms (chelate resins can absorb only the ionic impurities).

Each operating filter is a cylindrical vessel MS rubber lined. Inside this vessel, a
perforated plate having 73 holes is provided in the upper portion of the vessel. Carbon
filter candles are suspended from the holes of the perforated plate. Each candle has 3
carbo elements. Total no. of elements present is 219 in each filter.

The filter elements used in this unit are porous cylinders SCHUMACHER “CARBO 40”.
This material is composed of pure carbon with an average pore size of 110 micron.

The filter aid used is - Alpha cellulose (BWW 40)

FILTERATION

Filtration cycle : Pressure drop : 2 Kg/cm2 (max.)


Operating time: 48 Hrs

Whatever expires first i.e., pressure drop exceeds 2 kg/cm2 or operating time 48 hrs filter
is isolated.

Filtration area  41 m2
Design temp.  80 Deg.C
Design pressure  5 kg/cm2
Capacity  80 m3/hr (normal)

SPECIFICATION OF INLET BRINE

Fluid : Saturated NaCl Brine


Flow rate : 80 m3/hr (normal)
COMPOSITION OF BRINE

NaCl -- 300 – 310 g/l


NaClO3 -- 20 g/l (max.)
Na2SO4 -- 5 g/l (max.)
Na2CO3 -- 300 mg/l (max.)
NaOH -- 300 mg/l (max.)
CaCO3 and Mg(OH)2 -- 5 mg/l (max.)
Cl2 (free chlorine) -- 0

BaSO4 has to be prevented as it can lead to the clogging of the carbo-cylinders.

Density - 1.190 kg/m3


pH – value - 9.5 – 11
Temperature - (max.) 70 Deg.C
Suspended solids - normal 5.0 mg/l
(max.) 10.0 mg/l

QUALTIY OF POLISHED BRINE

Suspended solids: Less than 1 mg/l suspended solids in the treated brine.
SUMMARY OF OPERATION

The operation can be divided into 4 steps.

I Preparation of precoat/body feed


II Precoat
III Filtration
IV Washing

I PREPARATION OF PRECOAT

The precoat tank (V.142) is filled with polished brine up to 80%. The required alpha
cellulose (41 kgs) is added. Start the agitator (A.142) and run it for 10 min.

MIXING BY CIRCULATION

The mixing aims to make a uniform alpha cellulose concentration in the precoat tank and
filter vessel. The precoat suspension from the precoat tank (V.142) is sent to the filter
vessel using precoat pump (P.142), through three air vent valves (V.9, V.10, V.11) at the
upstream side of the filter. The brine liquid is circulated back to the precoat tank. Precoat
pump (P.142) discharge flow rate is kept 103 m3/hr.

II PRECOATING

In precoating the precoat layer is formed on the surface of the filter elements. In order to
do this, the precoat outlet valve (V.15) is opened (after completion of precoat mixing by
circulation) and then the upstream air vent valves V.9, V.10, V.11 are closed. Precoat tank
level is monitored. The precoat suspension is pushed from the outside to the inside
through the filter elements and is returned to the precoat tank.

The filter aid (alpha cellulose) deposits on the surface of the filter elements. Precoat layer
formed. The precoat layer contributes to achieve a fine filtration quality by preventing
filter elements from blinding.

A FLOW STOP OR A SUDDEN FLOW CHANGE AFTER THIS STEP CAN CAUSE
BLINDING OF THE FILTER ELEMENTS

Flow rate changed from precoat (103 m3/hr) to filtration (80 m3/hr) in acceptable time.

III FILTRATION

a) PREFILTRATION: The filtrate recycle valve is opened (V.16). the polished brine
which is coming out of the filter is pumped into filtered brine inlet valve V.1 and
V.2 (P.121 A/B discharge) opened and V.3 – precoat inlet valve is closed.
The valves V.1, V.2 should be opened and V.3 should be closed slowly and
simultaneously. The prefiltration starts when the above mentioned steps are carried out.
The prefiltration i.e., the circulation of brine between filter and filtered brine tank, is
intended to secure full and fine filtration efficiency.

Flow rate of brine is changed by control valve (V.5). Setting of flow: 80 m3/hr.

Once the above steps are over, polished brine is sent to polished brine tank (V.143). When
the filtered brine has passed through the precoat layer formed on the surface of the filter
elements from the upstream side to downstream side, the fine impurities are trapped and
removed.
The control of filtration process made by
- filtration time (48 hrs)
- The differential pressure inlet and outlet of filter vessel (2 kg/cm2)
whichever is earlier.
Once a filter is isolated, the next filter should be lined up. Accordingly the stand
by filter should be precoated and kept ready for lining up.

b) DOSING BODY FEED SUSPENSION


When process has entered precoating, start body feed.

BODY FEED METHOD

Body feed method is one for mixing filtered brine feed with alpha cellulose by body feed
pump. The body feed suspension is filtered together with filtered brine. This method
gives advantages to prevent filter elements from blinding and to extend the filteration
time.

IV WASHING

Normally the washing process is carried out four times. The washing steps to be made
each time are as follows:

The upstream air vent valves V.9, V.10, V.11 are mounted below the perforated plate at
120 Deg. gap around the vessel. During the over flow through sight glass, open the
upstream air vent valves V.9, V.10, V.11 one by one in turn, in order to wash evenly the
surface under the perforated plate.
Table 3 VALVE DETAILS

V1 Filtered brine inlet isolation (Manual)

V2 Filtered brine inlet actuated type (ON/OFF)

V3 Precoat inlet

V4 Mud discharge (Backwash outlet)

V5 Inlet flow control valve

V6 Downstream air vent valve

V7 Plant air inlet isolation valve

V8 NRV Plant air

V9 Upstream air vent valve

V 10 Upstream air vent valve

V 11 Upstream air vent valve

V 12 Filter outlet to V.143 polished brine tank


(ON/OFF)

V 13 Outlet isolation valve (manual)

V 14 Backwash inlet (or) washing brine inlet

V 15 Precoat outlet

V 16 Recycle to V.121

V 17 Precoat outlet, air vent overflow to sludge

V 18 Filtered brine to Body feed tank filling

V 19 Precoat recycle to V.142 isolation

V 20 Precoat recycle to V.142 (ON/OFF)

V 21 Backwash pump discharge to V.142 filling


Table 4 location and operating range of filters and accessories
No. Item Location Standard Upper limit Lower limit

PARAMETERS

SECONDARY BRINE FILTRATION

1. Brine flow FIC-140 A/B 74 m3/hr 80 m3/hr


rate to
polishing
Filter
2. Differential PDI-140 A/B Less than 2 2 kg/cm2
pressure kg/cm2
across
polishing filter
3. Polished brine LIA-143 70% 80% 40
tank level

4. Polished brine AICA-141 9 10 8


pH

5. SS in polished Less than 0.5 Less


brine ppm Than
ppm 0.5 ppm

6. Body feed P-141 A/B


flow rate

SECONDARY BRINE PURIFICATION


7. Polished brine TICA-151 60 Deg.C 65 Deg.C 55
temperature

8. Polished brine FIA-151 74 m3/hr 80 m3/hr


flow rate to
Chelate resin
tower
9. Super purified AIC-151 4 5
brine pH

10. Super purified AI-152 Less than 20 ppb as Ca


brine hardness 20 ppb as
(Ca & Mg) Ca

11. Super purified Sample Less than 100 ppb as Sr


brine hardness Analysis 100 ppb as
(Sr) Sr
2.2 Secondary Brine Purification Unit

The secondary brine unit consists of two chelate resin towers. The tower is a cylindrical MS
rubber lined vessel having a perforated plate in the lower portion of the vessel. Around 264 nos.
of strainers are fitted in the perforated plate. The strainers are made up of PPO (Poly phenylene
oxide). Four cubic meter of DIOION-r-II is kept filled over the strainers. The height of the resin
will be around 1.43 mts from the perforated plate. Brine inlet distribution consists of four poly
propylene pipes fitted at the top dish end. HCL injection distribution pipe made up of poly
propylene wrapped by poly propylene cloth is fitted just above the resin surface. There are 3
sight glasses fitted in the resin tower vessel. This will indicate the resin level during the various
stages of regeneration. The resin level during HCL injection will be in the lower most level due
to shrinkage of resin. After the second backwash step, the resin level will be in the top sight glass
level, due to expansion of the resin particles.

The polished brine after adjusting the temperature to 60 Deg.C is sent to the CHELATE resin
columns. Temperature of polished brine to Chelate resin columns is controlled by regulating LP
steam flow rate to polished brine heater (E.151). in the chelate resin columns, the hardness of
brine is reduced to less than 20 ppb by absorption with chelate resin. Two columns are provided
in series and are operated in a merry go round mode.

The two ion exchange vessels are normally operated in series while in service. The brine solution
passes from one ion exchange vessel (primary) to the second ion exchange vessel (secondary).
When the ion exchange resin in the primary vessel is exhausted the primary vessel is passed and
total brine flow diverted to the secondary vessel. The primary vessel is then regenerated. After
regeneration, the brine flow is again diverted to pass through the regenerated vessel, which is
taken back in service as secondary ion exchanger.

When the hardness at the outlet of the first resin column in the series reaches more than 100 ppb
or 24 hrs service (whichever is earlier) it is isolated for regeneration.

REGENERATION INVLOVES FOLLOWING MAJOR STEPS:

1 BACKWASH: DM water is introduced from the bottom of the chelate resin column to
make the resin loose and remove any suspended solids or broken resin to outside the column.

2 ELIMINATION BY HCL: HCl diluted to about 4 wt% is fed to the column at its top
exposure of the entire resin to the acid causes exchange of all the hardness and heavy metals with
H+ ions. After the elimination any excess of HCl in the column is washed out with DM water.

3 REPLACEMENT OF H+ WITH Na+ BY NaOH: Sodium hydroxide diluted to about 5


wt% is introduced from the bottom of the resin column. Exposure of the entire resin to NaOH
causes exchange of H+ ion with Na+ ions. After the replacement, any excess NaOH is washed out
with DM water.

4 BRINE REPLACEMENT: Before the chelate resin column (T.151 A/B) is put into
operation the fluid in the column is replaced with secondary brine.

The regenerated resin is put into service as secondary column in the series. All the secondary
brine purification plant operations are carried out automatically by a PLC. However, it is
interfaced with a DCS for indications.

EFFLUENT:
The effluent generated during the backwashing which is acidic in nature are collected in a waste
water pit (V.152) neutralized with NaOH and pumped to the main effluent treatment plant using
waste water pumps (P.152 A/B0. the total quantity of effluents generated per regeneration is
approx. 65 cu.m.

Table 5 Parameters of Secondary Brine (Resin Tower Outlet)

NaCl 300-310 gpl


Ca & Mg Less than 20 gpl
Sr 0.06 ppm
SiO2 4ppm
pH 9.0
Temperature Around 60 deg. C
Suspended solids 1 ppm
Ba 0.4 5 gpl
NaClO3 20 gpl
Na2SO4 5 gpl
I 0.2 ppm
Al 0.1 ppm
Fe 0.2 ppm
Mn 0.2 ppm
Ni 0.01 ppm
Total organic content (TOC) 10 ppm
AIC

LIC

TIC SuperPurified
Polished Brine Secondary
Brine Head
Heater Brine Tank
Chelate Resin
Tower
Polished Brine Pump Feed Brine
Pump
To Cl2 First Cooler
AIC
PIC

To Chlorine
Section HC

TIC
Depleted Electrolyzer
Brine Brine Tank By Pass
Dechlorination LIC
Tower
Vacuum Pump Depleted
Drain Separator Recovered Cl Brine Pump
2
10% Na2CO3
Cooler

Saturator
Dechlorinated LIC
Brine Tank pH

Dechlorinised
Brine Pump 20% NaOH
AIC
Fig 2 Secondary Brine Treatment & Dechlorination
2.2.2 Depleted Brine Dechlorination Section

To carry out effective dechlorination, chlorinated brine of which the pH is 4-5 under normal
operating conditions is acidified to a pH of about 2 by adding 32 wt% HCl in the line before
entering the depleted tank. The acid addition under automatic pH control drives the hydrolysis
reaction to the left.

Cl2 + H2O ---------- HOCl +HCl

Most of the free chlorine exceeding the equilibrium solubility under acidic brine conditions
escapes to the main chlorine gas header.
The brine is then sent to the dechlorination tower. In the dechlorination tower, operated at about
230 torr vacuum by a dechlorination vacuum pump, free chlorine is stripped from the chlorinated
brine by lowering the chlorine gas equilibrium partial pressure. At the tower outlet, the active
chlorine content in the brine will be as low as 20 ppm. This dechlorinated brine after the tower
outlet is called “lean brine”.
The dechlorinated brine is collected in a dechlorinated brine tank. The condensate collected from
the hydrogen gas cooler is also added in this tank.
The lean brine is neutralized with 209 wt% NaOH to a pH of 8. The 10wt% Na 2SO3 solution is
added to the lean brine to eliminate the active chlorine content completely according to the
following reaction.

NaClO + Na2SO3 ---------- NaCl + Na2SO4

The élan brine with no active chlorine is then sent to the saturators for further saturation with the
raw salt. A part of the lean brine is purged out to maintain the chlorate level (NaClO 3) less than
27 gpl.
The 10 wt% Na2SO3 solution is prepared by dissolving Na2SO3 powder in DM water. Two tanks
are provided for preparation and supply of Na2SO3 solution. The solution is supplied to the lean
brine using metering pumps.
The HCl required for acidification of brine is collected in the HCl day tank and supplied to
various users by HCl feed pump. To ensure the availability of HCl to all users, one pressure
control system is provided in the HCl supply ring.
The free chlorine removed from the depleted brine at the dechlorination tower is sucked by a
vacuum pump through recovered chlorine coolers. In recovered chlorine coolers, the chlorine gas
is cooled to about 50 deg C to reduce its volume. The condensate is returned to depleted brine
tank.
The vacuum system consists of two liquid ring vacuum pumps (one working and the other
standby) one gas separator and one cooler. The cooled chlorine gas from the recovered chlorine
gas cooler is sucked by vacuum pump under a controlled pressure of about 230 torr and then sent
at a slightly negative pressure to wet chlorine gas main header for further treatment.

NOTE: If alkaline brine comes in contact with ceramic packing inside the vacuum tower, it will
pick up silica from it which is not desirable for membrane cell operation.
Na2SO3 Addition.
It is recommended to add 10 wt% Na2SO3 solution in the line two times the quantity required for
treating the chlorine in dechlorinated brine.
Flow rate of 10 wt% Na2SO3 solution is calculated as follows.

Vss = 0.0346 X CNaClO X Vdb

Vss : actual flow rate of 10 wt % Na2SO3 solution (l/h)


CNaClO : NaClO concentration in dechlorinated brine after vacuum dechlorination (ppm)
Vdb : dechlorinated brine flow rate

Depleted brine composition

NaCl -- 200-220 gpl


Na2SO4 -- less than 10 gpl
NaClO3 -- less than 27 gpl
Temperature -- 80-90 deg C
Flow rate -- 58 m3/hr

Chlorate removal system

Chlorate is an undesirable by-product in the electrolyzers; the production rate is subjected to the
current efficiency level of the electrolyzers in the operation.
A build up of NaClO3 level in the brine loop towers the NaCl saturation limit because the
solubility of NaClO3 is higher than that of NaCl and can increase the NaClO3 content in the
product caustic. Therefore the NaClO3 level in the feed brine is generally maintained at 10 ± 5
g/l. in order to maintain this level, periodically brine will be purged from dechlorinated brine
pump discharge to sea disposal.
2.3 Electrolyzer
BASIC PRINCIPLE

NaOH is produced by the following principle.

Electrochemical reaction in an Ion-Exchange-Membrane Electrolyzer by utilization of super


purified brine.

Sodium chloride is dissolved in the brine solution in the anode compartment according to the
following equation.

NaCl  Na+ + Cl-

The principal anodic reaction involves oxidation of the anion Cl- to produce gaseous chlorine

2Cl-  Cl2 + 2e-

The cation Na+ in the anode compartment is transferred with water to the cathode compartment
through the ion-exchange – membrane. Water is electrolyzed in the cathode compartment
according to the following equation.

2H2O + 2e-  2H+ + 2OH-  H2 + 2OH-

The primary cathodic reaction is the reduction of the cation H+ to produce gaseous H2 and to
regenerate hydroxyl ions.
The sodium cation Na+ combines with OH- to form NaOH

Na+ + OH-  NaOH

Overall electrochemical reaction

2NaCl + 2H2O  2NaOH + Cl2 + H2

Demineralised water is fed in recycle NaOH line in order to regulate the NaOH strength in
cathode compartment. Depleted brine is discharged with chlorine from the anode compartment.
Caustic soda produced in the cathode compartment is discharged with hydrogen from cathode
compartment.

Recycled caustic diluted with DM water is fed into the cathode compartment.
REACTIONS AND SIDE REACTIONS

Reaction in the cathode chamber


The main reaction on the cathode surface is H2O reduction.

H2O + e-  ½ H2 (g) + OH- --- (1)

1/F mol of OH- is generated in the cathode side and (1/EK) mol of OH - is back migrated to the
anode side through the ion exchange membrane where EK is a current efficiency in the cathode
side.

Reaction in the anode chamber

The main reaction on the anode surface is Cl- oxidation i.e.

Cl- ½ Cl2 (g) + e- --- (2)

The electrochemical side reaction is O2 (g) generation by H2O oxidation i.e.

H2O ½ O2 (g) + 2H+ +2e- --- (30

The first chemical side reaction in chlorine dissolution without dissociation according to the
equation 4

Cl2 (g) Cl2 (aq) --- (4)

The second chemical side reaction is free chlorine dissolution in water according to equation 5

Cl2 (aq) + H2O HOCl (aq) + H+ + Cl- --- (5)

The third chemical side reaction is dissociation with the hypochlorus acid, HOCl according to
the equation 6

HOCl (aq) + OCl- OCl- + H+ --- (6)

The fourth chemical side reaction is CLO3- generation according to the equation 7

2HOCl (aq) + OCl- ClO3 + 2H+ + 2Cl- --- (7)

The fifth chemical side reaction is neutralization between H+ ions generated by the side reactions
(eq. 3, 5, 6 & 7) and OH- ions back migrated from the cathode side i.e.

H+ + OH- H2O --- (8)

The sixth chemical side reaction is neutralization between H+ ions and Na2CO3 and NaHCO3 in
the feed brine according to the following reactions.
Na2CO3 + 2HCl 2NaCl + H2O + CO2
NaHCO3 + HCl NaCl + H2O + CO2

SPECIFICATION

1 Type: DCM 405 x 2


2 No. of unit cells: 5 x 2
3 Anode effective area : 15.15 M2 x 2
4 Anode : DSA
5 Cathode : Activated cathode
6 Rated current : 54.24 KA
7 Current density : 3.29 KA/m2 (rated : 3.59)
8 Cell voltage : 3.18 V
9 Dimensions : 2560 W x 1360 H x 1058 L
10 Weight (empty) -- 4.9 mt
11 Weight (operating) -- 7.4 mt
12 Cathode current efficiency : 95.5 %
13 Power consumption at rectifier terminal : 2250
(DC KWH/metric ton of NaOH)
14 Caustic conc. : 32.5 %
15 Cell operation temp: 90 °C (Max.)
16 Life of anode coating: 8 yrs (min)
17 Life of cathode coating : 8 yrs (min)
18 Membrane and gasket life ; 4 yrs (min)

STRUCTURE

The DCM 405 x 2 consists of DAM – 405 monopolar electrolyzers, i.e., two DCM – 405 are
combined with one set of tie rods structurally and connected electrically in series with one set of
under cell bus bars. An insulation element is positioned between DCM – 405 electrolyzers.

Each DCM – 405 is electrochemically divided into 5 unit cells and structurally consists of 2
anode elements, 1 half anode element, 2 cathode elements, one half cathode elements and
between the elements membranes are positioned.

CIRCUIT OF ELECTRIC CURRENT

The electric current flow for each electrolyzer is as under.

The Electric current from the positive side of the rectifier flows through 8 under cell bus bars and
enters into each anode element of the first set of DCM 405 x 2 twin electrolyzer.

Then it flows to the cathode element through ion exchange membrane and to the under cell bus
bars.
From the under cell bus bars, the current, flows to the anode element, of the second half of DCM
405 x 2. There it follows similar current path as in the case of first half and goes to the next
electrolyzer through inter cell bus bars.

Finally from the cathode side of the last electrolyzer, current flows back to the negative terminal
of rectifier.

PROCESS DESCRIPTION

1 Electrolyzer circuit
The electrolyzer circuit has 44 no.s of DCM 405 x 2 electrolyzers and a rectifier unit.
The circuit is arranged in two rows. Both rows are connected to the rectifier unit with power
supply bars and one row is connected to the other with cross over bus bars at the opposite side of
the rectifier unit. Each electrolyzer in a row is connected with each other through inter cell bus
bars.

2 Fluid stream (Super purified brine)


Super purified brine from the brine treatment section is fed into the feed brine manifold of each
DCM 405 X 2 electrolyzer through a header pipe and each branch pipe. Brine is distributed to
each anode chamber. A restriction orifice is provided at the inlet of each anode chamber
respectively. Brine flow rate to each DCM 405 X 2 electrolyzer is adjusted by a brine flow gauge
mounted on each branch pipe.

3 Anode chamber
Super purified brine fed into anode chamber is decomposed electrically into Cl- and Na+ by direct
current in the anode chamber.

The Cl- ions are oxidized at the anode surface and from chlorine gas. Depleted brine and wet
chlorine gas at 80 – 90 ° C form a two phase system and overflow out of the anode chamber.

The two phase flows from each anode chamber and are collected into the manifold of each
electrolyzer and flows by gravity into depleted brine tank (V.201) from the depleted brine tank
chlorine gas goes to chlorine gas treatment section and depleted brine pumped to brine treatment
section.

Reaction:
Sodium chloride is dissociated in brine solution in the anode compartment according to the
following equation:

NaCl Na+ + Cl-

Principle of anodic reaction involves oxidation of the anion Cl-

2Cl- Cl2 + 2e-


The sodium ions in the anode chamber pass through the membrane and enter into the cathode
chamber together with water.

Cathode chamber

In the cathode chamber water is decomposed electrolytically into H+ and OH- by direct current.
The H+ ions are reduced on the cathode surface and form Hydrogen gas. The OH- ions combine
with Na+ ions and form caustic soda. The two phase stream of NaOH + H2 at 80-90 Deg.C
overflows out of each cathode chamber and are collected into the manifold; they flow by gravity
to NaOH circulation tank (V.202).

From the NaOH circulation tank, Hydrogen gas and NaOH separated. Hydrogen gas goes to the
Hydrogen circulation pump (P.202 A/B). This caustic soda is separated into two streams.

a) 32.5 wt% caustic head tank for conc. In Mercury cell up to 48%.
b) Recycle NaOH to the electrolyzer.

Recycled caustic is fed to the recycle caustic manifold of each DCM 405 X 2 electrolyzer
through a header pipe and each branch pipe and distributed to each cathode chamber. Caustic
flow gauge mounted on each branch pipe is used for adjusting the caustic flow rate to each
electrolyzer.
The caustic strength is generally kept about 32.5 wt% at the outlet of the electrolyzer by
controlling feed quantity of DM water which is added into the recycle caustic stream.

CAUSTIC SODA HEAT EXCHANGER


A caustic soda heat exchanger is installed in the recycled caustic steam to control electrolysis
temperature by cooling down or by heating up. This heat exchanger functions as a heater to
warm up the electrolyte in the electrolyzer during the plant startup. As the membranes become
colder and the electrolyzers become less energy efficient due to increase in cell voltage, this heat
exchanger functions as a cooler.
The gas pressure control in the anode and the cathode chambers are very important for stable
electrolyzer operation. The hydrogen gas pressure is controlled to avoid membrane rubbing with
the rough cathode surface leading to membrane damage. A differential pressure indicator is
provided in the main header to monitor the differential pressure between both chambers. In case
of large surge in gas pressure, the interlock system will work to protect the electrolyzers.
Moreover a hydrogen gas vent stack is installed top protect the circuit against extremely high
pressures of the hydrogen gas and two chlorine gas seal pots against extremely high/low
pressures of chlorine gas respectively. The hydrogen vent stack is also used to vent hydrogen gas
to atmosphere during startup.
Operating conditions for electrolyzer

1. Current increase and decrease.


Sudden current load change will abruptly affect the bubbling ratio in electrolyte and could cause
the overflow stream to sprout or stop.
Also membrane vibration due to gas pressure fluctuation and the membrane exposure to pressure
zone will shorten the membrane life. Therefore the current load should be increased or decreased
only gradually at the rate of 1 KA/min.

2. Feed brine flow rate


a) Current load increase. Before increasing the current load, the feed brine flow rate is
increased to the value corresponding to the projected current load.
b) Current load decrease. The current load is decreased before decreasing the feed brine
flow rate to the projected current load.

In either case of increase/decrease in current load, the NaCl strength in depleted brine is analyzed
and checked if it is more than 180 gpl in order to prevent membrane damage.

3. DM Water supply rate.

The DM water supply rate to the recycled caustic soda will be controlled to maintain the caustic
soda strength in the catholytic constant.
a) Current feed increase. Before increasing the current, the DM water flow rate to the valve
corresponding to the projected current load is increased.
b) Current load decrease. The current load is decreased before decreasing the DM water
flow rate corresponding to the projected current load.
2.4.1 Caustic Evaporation Plant
The purpose of the plant is to concentrate the 32% caustic coming out of the electrolyzers
to 48% caustic lye. This concentration is achieved by three multi effect evaporators.
These evaporators concentrate the 32% caustic to 36%, 41% and eventually 48% caustic
lye. Multi effect evaporators are usually fed by 3 possible feed systems:
1. Forward feed system: where feed and the heating medium both enter the first
evaporator, in other words, co-currently.
2. Backward feed system: In this system the feed enters counter-currently with
respect to the heating medium.
3. Mixed feed system: In this feed system the feed enters from the first evaporator,
and the fresh heating medium may be introduced anywhere between the
evaporators.

The caustic evaporation plant at TPL employs the backward feed system. The
evaporators are shell and tube type. The caustic flows in the tube side and steam
circulates on the shell side. Glass wool insulated steel lines are used for circulation of
steam. The caustic is carried in stainless steel lines up to a concentration of 36%, after
which glass wool insulated Titanium lines are used for it. Steam is used as the heating
medium. 32% caustic from the electrolyzers is preheated to 90° C by the 48% caustic
coming out of the CEP plant. Steam coming from 2nd evaporator is fed into the 1st one,
and caustic is concentrated to 36%. It is sent to a vapor separator, which is connected to a
steam ejector, which separates the vapors from the caustic which are cooled and sent for
recovery.
The vapors separated from the 3rd evaporator are used to pre-heat the 36% caustic
before it enters the 2nd evaporator; it is heated up to 110° C. Out coming steam from the
3rd evaporator is circulated inside the 2nd one and the caustic is concentrated to 41%, and
the temperature to 120° C. The vapor is separated and the used up steam is re-used in the
1st evaporator.
The steam and caustic from the 3rd evaporator pre-heat the 41% caustic to 160° C for
more efficient concentration. Fresh steam enters the evaporator and concentrates the
caustic to 48% caustic lye. The out coming caustic is cooled down by using its heat to pre
heat the caustic feeds to the other evaporators. It is finally cooled by cooling water lines
to 45° C caustic lye. This is either sold as a product or sent for further concentration in
the fusion plant.
Cold water In

32% NaOH, 90°C


Water Out
Steam 36% NaOH, 110° C 41% NaOH, 160° C
Ejector

Steam
Inlet
EV EV EV
I II III Vapor
Vapor Vapor
Separator Separator Separator
Condensate
32%
to BH Fresh Caustic
36%
41%
NaOH
NaOH
100° C
Heat 120° C
Exchangers Heat Heat
Exchangers Exchangers

Pump Pump Pump

48% NaOH, 180° C


To 41%
Int Recovery NaOH,
Water 45° C
Tank 48% NaOH, 100° C
(Product)
Pump

Fig 3 Caustic Evaporation Plant (CEP)


2.4.2 Fusion Plant

The purpose of this plant is to concentrate the 48% caustic from the CEP plant to 98%
Caustic flakes.
The plant consists of three different multi effect evaporators. The temperature of the
caustic goes as high as 420° C in this plant. Normal steel apparatus may get corroded in
such a highly alkaline and hot environment. Hence all lines and inner lining of the
equipments are made up of Nickel. The plant consists of:
1. Pre-Concentrator (PC)
2. Rising Film Evaporator (RFE)
3. Falling Film/Final Evaporator (FFE)

48% caustic liquor is fed by pump to the PC from top, operating on the product side
under a pressure of approximately 65 torr (87 mbar). During a single pass through the
PC, the caustic is concentrated up to approximately 55.4-55% caustic.
The PC is heated by the vapors coming out of FFE.
Before entering PC, a 5% sugar solution is added to the caustic. Sugar acts as a
corrosion inhibitor. This forms a layer of Nickel oxide on the lines. This layer prevents
further oxidation of Ni. The quantity of sugar to be added will be adjusted to the plant
capacity each time. The NaOH 55% pump conveys the dilute acid to the pre heater at
about 90 ° C.

The pre-concentrated caustic liquor is passed through a double tube type heat
exchanger heated by condensed steam off the RFE. The outlet NaOH temperature is
about 140-145 ° C. when passing the steam heated RFE, caustic soda is concentrated
under a pressure of approximately 200 torr (267 mbar) up to 76% NaOH.
The 76% caustic leaving the RFE is dipped into barometric seal pot. The PC and the
RFE work under vacuum, which in both cases is produced by the vacuum ejector pump.

The vacuum of 65 torr is required for the PC is produced by the 3 step injection
group. The vapors from the PC are condensed in the mixing condenser via a barometric
dipping tube. The condensed vapors and he cooling water are carried in to the waste
water pit. For the RFE, a vacuum of 200 torr is produced by the 2 step injection group.

The 76% NaOH pump carried the caustic soda to the molten salt heated FC, where it
is evaporated under normal pressure up to a min of 98.5%Naoh. The distributing device
is fixed to the lower part of the separator and by this device; the caustic soda can be
switched to either placer or drum filling station.

In order to exclude atmospheric oxygen from penetrating into the system and to avoid
corrosion the distributing system is superposed with nitrogen. The filling tubes to the
flaker and to the drum filling station have been provided with a molten salt heating and
the tube for NaOH 55-76% with steam heating.
The well cooled flakes are then filled into 50 kg bags by means of the bagging scale.
The balance to the nominal capacity of 100 tpd (37-20, maximum 50 tpd) of caustic melt
can be fed via existing distributing devices to the drum filling unit.

Control High Pressure Steam and Condensate System.


RFE is heated with high pressure steam concentration of the leaving NaOH solution
is determined by it outlet temperature, therefore a thermometer is installed in the outlet
tube. Above the temperature controller TIC, the temperature of 160 ° C is adjusted which
corresponds to the concentration of NaOH to 76% at 200 torr.
From there corresponding command variable is given to the steam pressure control
valve TCV in the steam tube, thus increasing or diminishing the steam throughput. The
steam leaves RFE at the lower end. A level transmitter LT built in keeps the condensate
which is under pressure constantly on a certain level. Control valve LCV is arranged in
the flow direction after following caustic pre heater and receives its command variable
from level control LIC.
This arrangement guarantees an effective heat transfer in rising film evaporator and
exploitation of the condensate cooling in the caustic pre heater.

Design Description
The dehydration line consists of the following three stages:

1. Preconcentrator.
It is designed as a tube bundle FFE. In the concentration head, the caustic solution is
distributed as follows.
Above the tube plate, concentration tubes are provided with vertical slits through
which caustic solution flows evenly through the tubes and down the inside surface of the
tubes forming an unbroken film along the inside wall. The PC works at 65 torr vacuum
on product side.
The vacuum is produced by steam ejector vacuum pump. The PC caustic leaves the
PC at 55% concentration and reaches the vapor separator installed beneath the PC. The
vapors produced in the PC are removed by the vacuum pumps and leave the PC through a
demister consisting of very fine nickel wire meshing which permits the separation of
even the smallest caustic droplets carried along by the vapor. In the subsequent mixing
condenser the vapors are condensed.
The PC is heated with vapors from the FC.

2. Rising Film Evaporator.


The caustic enters the lower part of the RFE with concentration of NAOH at 55% fills
it up and distributes into the individual tubes of the tube bundle. The rising film
evaporator is on the product side under a vacuum of 200 torr.
Heating is done with steam in reverse direction, i.e. the steam entrance is located at
the upper part of the tube bundle and the condensate leaves the lower part.The NaOH
solution to be evaporated thus enters the tubes at the bottom surrounded by steam.
Due to condensation enthalpy of the steam set free, the evaporation process in the
tubes is initiated and the liquid rises to the top according to the air lift pump principle, or
is driven through the tubes by the existing vapor respectively. The liquid/steam mixture
reaches the vapor chamber which is located directly above the tube bundle.
Immediately above the upper plate, a buffer plate is mounted acting as a liquid
separator. By exploitation of the different densities of both the phases, here an intense
liquid separation is achieved. The remaining liquid evaporated to the desired
concentration is collected in the area around the upper tube bottom and leaves through a
nozzle.
The vapors deviated at the baffle plate reach the demister made of fine nickel wire
meshing. Caustic droplets carried along are separated by this knitmesh and drop back into
the liquid collecting chamber. The vapors leave the vapor room and reach the mixing
condenser via a duct, where they’re condensed. The non condensable gases are sucked off
by the vacuum pump. The heating or blanketing room of the tube bundle is equipped with
a venting nozzle at its upper end. At the lower end there are 2 level control nozzles for the
level transmitter.

3. Final Concentrator.
It consists of individual tube elements, concentrator tubes and the vapor separator.
The caustic is evaporator in the falling film concentrator at atmospheric pressure by
means of heat supplied from outside. The PC caustic is fed to the caustic collector by
means of the caustic transfer pump. Causes even distribution to the individual
concentrator elements where the caustic forms an unbroken film over the whole inside
surface flows from top to bottom. Propeller inserts built into the center of each
concentrator tube prevent the caustic film from being blown off the inside wall surface
due to rapid evaporation taking place. The water contained in the caustic is evaporated
while flowing down the concentrator tube. The caustic film, now with a concentration of
98.5% leaves the concentrator element and is fed by a collecting element to the seal pot.
Each element is provided with an individual heating jacket in which the heat transfer
medium flows in the reverse direction to the caustic to be concentrated. The heat transfer
medium is fed through these jackets and led off through collection. Each heating jacket is
provided with throttle valves on the outlet side which permit even distribution of the heat
transfer medium to all concentrated elements.
The collectors of the heating jackets of the individual concentrator elements are
provided with steam trace heating, to prevent the heat transfer medium from freezing
during start-up. Shortly before heat transfer medium reaches operating temperature steam
tracing is turned off and vented. Thus formation of inadmissibly high temperature in the
steam tracing system is prevented.
The vapors resulting from evaporation stream, together with the caustic, flow form
top to bottom of the concentrator tube. Then flow velocity, together with the effect of the
above mentioned propeller inerts, cause the caustic film to adhere to the inside wall
surface of the concentrator tube. At the bottom of the concentrator tubes, the vapors flow
into the horizontal collection channel which leads them to the separator. Caustic droplets
possibly carried along by the vapors are separated by the gravitation at considerably
reduced flow velocity.
The vapors roughly clean, then leave the separator through a mattress type demister
made of fine nickel wire meshing. This demister offers largest possible surface contacts,
greatest number of deflection and still causes the least possible pressure drops. The fine
mist is transformed into large caustic droplets which due to gravity fall back into the
collector and are led together with the concentrated caustic to the caustic outlet nozzle.
The vapors now almost completely cleaned are led to the PC which removes their heat.

Sucrose System

All equipment components and piping coming in contact with the concentrated
caustic are made up of pure Nickel (low carbon Nickel) because of its corrosion
resistance. Oxygen acts highly corrosively, particularly combined with high temperature.
Therefore, oxygen must be kept out of the equipment components by all means. If
corrosion occurs, oxidized nickel would be there in the caustic melt.
Penetration of atmospheric oxygen into the equipment is prevented by designing the
plant as air tight as possible and by additionally blanketing the distributing device of the
final concentrator with nitrogen. However, the caustic solution itself brings down the
oxygen into the equipment in the form of Sodium Chlorate (NaClO3). This type of
oxygen is eliminated by adding sugar solution to the feed caustic as corrosion inhibitor.
The sugar solution reacts with NaClO3 to form Na2CO3 which is harmless from the point
of view of Ni corrosion.
Depending on the chlorate content of feed caustic and feed quality, granulated sugar
is added to the feed as an aqueous solution prior to its entry into the NaOH piping. 0.05
kg of sugar per ton of 100% NaOH is added, whereby the nickel pickup of caustic melt is
reduced to about 1 ppm. Food quality granulated sugar is use and pumped into the feed
liquor as a 5% aqueous solution before being led to the concentrator. At startups, restarts
or during any interruptions in the operation, the nickel pickup drops within 24 hours from
startup value (approximately 20-30 ppm) to the operating value.
The sugar solution is prepared in the dissolving vessel together with the condensate
coming off the condensate tank resulting in a 5% sugar solution. The complete sugar
solution is led into the NaOH piping before the PC by means of a dosing pump.

Molten Salt Heating System

The heating system using molten salt as a heating medium mainly consists of a
salt tank and an immersion pump, forced circulation heater with a built in burner, the sir
preheater with incorporated fuel gas stack and salt piping system.

Concept of the Heat Transfer Circuit.

The heat transfer salt is molten in the salt tank i.e. kept hot and in liquid phase
during interruption of operation. During operation salt is circulated by means of an
immersion pump from bottom to top by heating coils of the heaters.
The heat produced by the burner is transferred to the salt circulation in the heater
coil. From the heater the molten salt goes to the FC. There it heats up and concentrates
the caustic, and is circulated back to the salt tank. A by-pass valve regulates the quantity
of molten salt in circulation through FC, permitting a part of salt quantity to be returned
directly into the salt tank if required.
The whole salt piping system is arranged such that in case of interruption of
operation of salt pump (as in case of power failure) the whole salt contents can freely
flow back into the salt tank installed at the lowest point of the plant.
Heat Transfer Salt.
The salt used for final concentration is a mixture of three salts :
1. KNO3 (53%)
2. NaNO2 (40%)
3. NaNO3 (7%)
The advantages of using this mixture are:
• It has excellent heat transfer properties
• Pressureless operation to 500° C
• Non-flammable
• Non-corrosive

The disadvantages of this salt mixture are:


• It has a high crystallization point.
This is countered by making sure that whole system is heatable and can be easily
emptied.

Behavior of heat transfer medium.


• Provided normal operating conditions, the heat transfer salt can be used for many
years.
• A certain oxidation of NaNO2 occurs in presence of atmospheric oxygen, causing
a rise in point of crystallization. This is prevented by blanketing the salt tanker
with Nitrogen.
• In case molten salt is heated over a larger period, (for instance quantity of salt
circulating through the heater is insufficient due to faulty operation), the
component NaNO2 may decompose to Na2O, O2 and N2, which also lead to
higher point of crystallization of the salt mixture. Such conditions are, however,
prevented by temperature control of the wall of temperature of the salt heater.

Despite above mentioned precautionary measures, the heat transfer salt has to be
regenerated after several years of operation.
Steam, 330°C

48% NaOH, 50°C 76% NaOH, 160°C

PIC
TIC
5% Steam 76%
Sugar
55% NaOH,
Soln Seal Pot
55% LIC NaOH, 160°C Flaker Drum
Molten
NaOH, 150°C Oil
Salt,
90°C
420°C H2 Air
Int
Tank Used 98%
55% Salt, Caustic
48%
Pump 390°C Flakes,
Pump
76% Salt 45°C
Mixing Pump
Pump
Condenser
Cold
Water
Cold Pit
Water
Pit
Salt Tank

Fig 4 Fusion PLant


Chapter 3

Demand, supply and manufacturers in India


In India the chloralkali industry is over 100 years old. Its products, chlorine and
caustic soda are two basic chemicals. Chlorine is used for disinfecting drinking water
bleaching of textiles and pulp, manufacture of insecticides, pesticides, weedicides,
pharmaceuticals, pyro/plastics and refrigerants, industrial solvents, rocket fuels and
treatment of cooling water for electricity generation etc. chlorine production in our
country in 1995-96 was 1.61 Mn tons. Though it is highly toxic and hazardous, it has
become indispensable for mankind.
Caustic soda is used for manufacture of paper and pulp, textiles, soap and detergents,
aluminium, rayon /viscoelastic fibre, inorganic chemicals, dyestuffs petroleum refining
and pharmaceuticals etc caustic production in our country was 1.308 Mn tons.
There are three basic processes for caustic soda production:
1. Diaphragm cell process (1865)
2. Mercury cell process (1892)
3. Membrane cell process (1970)

Each method represents a different method of keeping the chlorine produced at the
anode separate form the hydrogen produces, directly or indirectly at the cathode.
Membrane process has the following advantages over the diaphragm and mercury cell
process.
1. 25% lower energy consumption
2. Pollution free operation
3. Higher production purity
4. Easier and more flexible operation
5. Lower operation temperature

India is self-sufficient in caustic soda. The present installed capacity is distributed


amongst different processes as under.
Table 6 membrane cell capacity as 31.3.2002

Sr. No. Companies Capacity


(1000 MTPY)
1. Gujarat Alkalies, Vadodara 170
2. Grasim Inds, Nagoda 85.5
3. Standard Alkalis, Kumool 53
4. Modi Alkali, Alwar 19.8
5. Chemfab alkalis, pondicherry 16.5
6. Century chemicals, kalyan 55.7
7. Hukumchand jute mills, amlai 15.6
8. Atul products, valsad 11.2
9. Shree gopal, yamunanagar 13.2
10. B&T, balarshah 13.2
11. Punjab alkalis, naya mangal 33
12. Tata chemicals 26.4
13 Kadakja alkalis, ankleshwar 18.5
14. Search chemical Indus., Jhagada 16.5
15. DCM Con solidated, Bharuch 49.5

Indian chloralkali products expect to see caustic soda exports to increase from 90,000
tonne in 2001-02 to 210,000 tonnes onwards to close to 3.5 Mn tonnes/year of new
capacity and incremental expansions will be added in 2003-04 will almost double the
Indian chloralkali capacity. Live growth in domestic alumina production is one factor that
could prompt even higher exports long-term. India has no option but to export 20-25% of
the total caustic soda production.
A number of new alumina units are at the planning stage, but it will take some time
before they can be counted as secure caustic soda consumers. Another factor pushing up
Indian exports of caustic soda stems from the duties charged on the imported
technologies. Indian caustic soda manufacturers face power from 95 cent/KWhr,
compared with 10-15 cents/KWhr in Saudi Arabia, and 20-25 cents/KWhr in the US.
To compete internationally, Indian producers have switched to membrane cell
technology and invested in captive power plant generation to ensure reliable low cost
supply. However, the current import of 25% on both membrane cell plant and captive
power plant in India made it a little uneconomical to implement both options together.
Chapter 4

Line sizing
The chloralkali plant at TPL uses mainly five types of lines in the process; namely
1. Mild Steel Rubber Lined (MSRL)

2. Stainless Steel (SS)

3. Fibre Reinforced Plastic

4. Titanium lines

5. Ni plated or entirely Ni lines.

The first three types can be generally used about anywhere in the process, except for
lines transporting high temperature or highly acidic/ corrosive media. The fourth type,
i.e., Nickel lines are used wherever the media being transported is highly alkaline caustic
or that at a high temperature. Nickel is used for this purpose because of its resistance
against high temperature and alkalinity. Titanium lines are used where high strength and
certain resistivity towards heat and alkalinity is desired.
The line size, however, varies according to the following factors:
1. Type of transported media

2. The driving force of the media

3. Flow rate of the media

This implies that, for instance, that a media of high viscosity or rich in suspended
impurities will require a line a larger diameter. Also, if the media is being transported by
a pump, a line of smaller diameter will be favorable. Based on such factors, the size of
lines connecting various parts across the plant can be tabulated as follows:

Table 7 (a) Line Sizing


Transported Line from Line to Line size, MOC
media
Primary Brine treatment

DM water DM water Saturator 16’‘, SS

Depleted Brine Depleted brine tank Saturator 16’‘, MSRL

Saturated Brine Saturator Mixing reactor-I 32’‘, SS


16% BaCO3 Barium chloride Mixing reactor -I 2’‘, MSRL
storage tank
10% Na2CO3 Sodium chloride Mixing reactor -I 2’‘ MSRL
storage tank
26% NaOH Caustic head tank Mixing reactor –II 2’‘ MSRL

Mixing tank outflow Mixing reactor -II Mixing tank 8’‘, MSRL

0.05% Floxin Floxin tanks- I&II Mixing tank 1’‘, MSRL

Mixing tank outflow Mixing tank 2 m to clarifier 16’‘, SS

Rest Open channel

Clarified brine clarifier Clarified brine tank 8’‘ SS

Clarified brine Clarified brine tank Anthracite filters 8’‘ FRP

Filtered brine Anthracite filters Filtered brine tank 8’‘FRP

Filtered brine Filtered brine tank Polishing filters 8’‘ FRP

Body feed (alpha Body feed tank Precoat filters 1’‘ FRP
cellulose)
Na2SO3 Na2SO3 preparation Precoat filters 1’‘ FRP
tank
HCl HCl storage tank Polished brine tank 1’‘ FRP

Polished brine Polished brine tank Secondary Brine 8’‘, FRP(/PVC)


treatment
Secondary Brine and Dechlorination

Polished brine Primary brine Polished brine heater 8’‘, FRP


treatment facility
Heated polished Polished brine heater Chelate resin tower 8’’, FRP
brine
Super purified brine Chelate resin tower Secondary brine tank 8’’, FRP

Super purified brine Secondary brine tank Super purified brine 8’’, FRP
head tank
Super purified brine Super purified brine Electrolyzer 8’’, FRP
head tank
Depleted brine Electrolyzer Depleted brine tank 8’’, FRP

Recycled caustic Caustic storage tank Electrolyzer 6’’, Ni plated SS


Feed brine Super purified brine Electrolyzer 8’’, MSRL
head tank
Depleted caustic Electrolyzer NaOH drain 18’’, MSRL

H2+32% Caustic Electrolyzer Caustic concentration 15’’, MSRL


plant
Depleted brine Depleted brine tank Brine dechlorination 8’’, FRP
tank
10% Na2SO3 Sod. Sulfite Head Dechlorinated brine 2’’, MSRL
tank tank

Table 7 (b) Line Sizing

Caustic Evaporation Plant


Upto 36% caustic 2’’, SS
Above 36% caustic 2’’, Ti
Steam lines 2’’, SS, Glass wool insulated
Cooling water lines 2’’, MSRL
Chapter 5

Instrumentation

The instruments used in the caustic soda plant work on the following principle.

• Flow Control: flow control is done with the help of the “I to P” apparatus. This
produces a pneumatic pressure in the tube in accordance with the current that it
receives, thereby controlling the amount of fluid that passes through. Other devices
used for this purpose are rotameter, control valves etc.

o Mass Flow Meter – Works on the “Caroli’s principle”


Caroli’s principle: When the flow of a liquid flowing in a tube varies, the
frequently with which it vibrates/shakes, the tube also changes. This change can
be used to calculate the mass flow/density of the fluid.
o Electromagnetic flow meter: (Anthracite filters)
Principle: electromagnetic plates are kept or either sides of the line, and
electromagnetic waves are transmitted. The consequent emf induced varies with
the flow rate of the fluid. Hence, the induced emf can be used to indicate the flow
rate.
o Oval Meter: This is used for flow metering the oil used as fuel in boilers. This
consists of oval leads inside the lines which rotates as the oil flows and their
rotations are used to detect the flow rate if oil.
o Rotameter: these are extensively used throughout the plant. A rotameter contains a
floating device which stays afloat due to the force of the flowing fluid. The
elevation gained by the float is used to predict the flow rate of the fluid. This is
used for metering the flow of HCl.
o Critical Control valve. This is a device used to control the flow of a fluid, if it
goes above a particular value.
o I to P (Current to Pressure) flow controller: if its current input changes, this device
produces a consequent change in pneumatic pressure over that liquid, thereby
controlling its flow. It is used in dechlorinised brine tank.
o

• Shut Off Valves: These are used to completely stop/restart the flow automatically can
be controlled directly from the control room, without manual involvement. It can’t be
used to control the flow rate, however, but only to stop/restart.
These are used in every line, to stop the flow automatically, say in case of
emergencies

o Hydrogen Shut Off Valve: This is used for the supply lines in the boiler. It is
equipped with a leak detector which measures pressure of hydrogen on either side
of valve. If the pressure is same on either side, it indicates no leak. But if the
pressure on either side differs, then this is an indication of leak. Similarly, there
are oil, and water control valves which work on the same principle.
o Solenoid Valve for Oil Control. It opens and lets the oil inside the burner when
relay is received.
o Positioner: used in the Electrolyzer unit and it displays the position of the control
valve after it has been operated on.
o Photocensor. This is a special type of control used in the salt heater. Since
hydrogen and oil are used as fuel in the heater, it checks the spark generated for
ignition. As soon as it’s sensor detects the spark created by the arc, it sends the
power in relay, cutting it off and putting it in standby mode.

• Level Measurement/Indication.

o Level Indicators: (Indicate the level of the liquid inside a vessel)


These work on the Bernoulli’s principle as well, and indicate the level of the fluid
inside the vessel under a given pressure.
o Ultrasonic Sensors: transmits ultrasonic waves towards the fluid level and the
time lag after which they are received can be used to calculate the level.
o Bubbler System: this simply indicates weather the fluid level is high or low, by
measuring the pressure of the gas above it. This is a form of approximate
measurement.
o Displacement Type Level Transmitter. This is primarily used in the whole of
fusion plant. It consists of a float inside the tube which on moving up/down
deflects a “torque-tube” and its consequent displacement displays the level.

• Calcium Analyzer: This is used to measure the quantity of Calcium and Magnesium
present in brine, right before it enters the membrane cells.
It uses three reagents:
1. Potassium Hydroxide
2. Ethylene Glycol
3. Phenolphthalein

These are mixed with a sample of brine. The mixer contains a magnetic stirrer and is
connected to a colorimeter via fiber optic lines. The color of the sample changes on
mixing the reagents and the intensity of the change is detected by the colorimeter, to
calculate the amounts of calcium and magnesium in ppm. It can be caliberated from time
to time using a standard reagent.
• Temperature Indication. This is done by the following instruments.
o Radiation Temperature Detectors: these are extensively used in the plant, also in
the membrane cells for indication of the temperature of vessel contents. This
works on the principle of thermal radiation, that every hot body emits some
thermal radiation proportional to the fourth power of its temperature, and this
instrument uses the intensity of the radiation to indicate the temperature of the
body.
o Flame Temperature Measurement: the device consists of a Ultra-violet sensor,
which compares the color of the flame with standard colors to determine the
temperature. For instance, a flame of higher temperature would be more reddish,
sometimes whitish in color, and so on. Naturally, this is used only wherever the
temperature of a flame is required to be measured. It has a relatively high range;
of up to 3000ºC. it is used in the burner of the fusion plant.

• Pressure Indication:
o Pressure transmitters: These are diaphragm type pressure transmitters and work
on Bernoulli’s principle, i.e. indicate pressure when height of the liquid in a
column is already known.
o Pressure Switch: these are used to measure the pressure of a flowing fluid.
Consists of a diaphragm or a metal sheet lodged inside the line. A switch is placed
in the direction opposite to the flow. As the fluid slows, it exerts some pressure on
the diaphragm or the metal sheet, which pushes the switch that it is in contact
with. The switch displays the pressure it has received.

Following table shows a list of the instruments, their range and accuracy for the primary
brine treatment section of the plant.

Table 8 Instrumentation
Sr No. Description Range Accuracy
1 POLISHED BRINE 0-14 pH ±0.2 pH
pH
2 FEED BRINE pH 0-14 pH ±0.2 pH
3 EFFLUENT pH 0-14 pH ±0.2 pH
4 DECHLORINATED 0-14 pH ±0.2 pH
BRINE pH
5 SATURATED 144-364 gpi ± 5%
BRINE DENSITY
6 D.P. IN 0-2500 mm ± 1%
ANTHRACITE WC
FIKTERS
7 BRINE FLOW TO 0-50 m3/hr ± 1%
ANTHRACITE
FILTERS
8 ANTHRACITE 0-100 m3/hr ± 1%
FILTER
BACKWASH
FLOW
9 RESIN TOWER 0-100m3/hr ± 1%
BRINE FLOW
10 Na2CO3 TANK-A 0-4200 mm ± 1%
LEVEL WC
111 Na2CO3 TANK-B 0-4200 mm ± 1%
LEVEL WC
12 FLOXIN TANK-A 0-1800 mm ± 1%
LEVEL WC
13 FLOXIN TANK-B 0-1800 mm ± 1%
LEVEL WC
14 CLARIFIED 0-4720 mm ± 1%
BRINE TANK WC
LEVEL
15 FILTERED BRINE 0-3900 mm ± 1%
TANK LEVEL WC
16 BODY FEED 0-2900 mm ± 1%
TANK LEVEL WC
17 PRE-COAT TANK 0-2900 mm ± 1%
LEVEL WC
18 POLISHED BRINE 0-4700 mm ± 1%
TANK LEVEL WC
19 SECONDARY 0-6250 mm ± 1%
BRINE TANK WC
LEVEL
20 FEED BRINE 0-3200 mm ± 1%
TANK LEVEL WC
21 DECHLORINATED 0-3400 mm ± 1%
BRINE TANK WC
LEVEL
22 SODIUM SULFATE 0-2000 mm ± 1%
TANK-A,B LEVEL WC
23 CLARIFY BRINE 0-80 DEG ± 2 DEG
TEMP
24 POLISHED BR 0-100 DEG ± 2 DEG
TEMP
25 VACUUM PUPM 0-100 DEG ± 1%
SUCTION TEMP
26 CAUSTIC 0-100 DEG ± 1%
STORAGE TANK
TEMP
27 20% NAOH TANK 0-2000 mm ± 1%
LVL WC
28 32%TANK FLOW 0-25 m3/hr ± 1%
29 STEAM INLET 0-16 KSC ± 1%
PRESSURE

Chapter 6

Pumps and Valves


The chlor-alkali plant employs the following types of pumps:

• Centrifugal pump
• Reciprocating pump
• Metering pump

The 4 wetting parts; front casing, impeller, stuffing box,/back casing and sleeve
usually differ in MOC according to the application of the pump. The rest of the parts are
made of the same MOC for almost every application. The following materials of
construction are used for pumping various materials:

• Pure brine: Stainless steel

• Pure brine + chlorine gas: titanium

• Acids

o H2SO4: Alloy 20

o HCl: polypropylene, Ceramic, Fibre reinforced plasic

• NaOH: 3% Nickel casting or just Nickel

• Molten salt: alloy of Cobalt and Molybdenum

• For any other non-corrosive medium at normal temperature: Cast iron, Mild
steel, Stainless steel may be used.

Up to clarified brine tank, no valves or pumps are used, the flow of the substances is
completely due to gravity. After clarified brine tank, the clarified brine is circulated using
butterfly valve; having MOCs of either Teflon or MSRL. A level indicating valve is also
used in the line from clarified brine tank. The backwater from clarified brine tank is
pumped out by backwater pump, having the MOC as Ti. The filtered brine from the brine
filters is pumped using filtered brine pump. More than 30 valves are used for polishing
filters. Pneumatic control valves are used to control the flow of brine in this region.
As16% slurry is pumped as slurry, for this purpose, ODS pumps are used (pneumatically
controlled).

For fusion plant, all the lines are Ni lines, and all the pumps used are centrifugal
pumps, except for the sugar pumps, which is a reciprocatory pump. For the molten salt
line, wetted parts of pumps are made up of an alloy of molybdenum and cobalt, as the
circulatory medium s highly corrosive, and also because this MOC is highly suitable for
high temperature. TPL uses VFD (variable frequency drive), which is a mode to save
energy. Using this, they are able to run all motors at about 2100 rpm, which can be varied
using VFD according to required flow rates.
Chapter 7

Motors RPM make types


Electric motors have a tremendous impact on overall energy use. Between 30 to 40
percent of all fossil fuels burned are used to generate electricity, and two-thirds of that
electricity is converted by motors into mechanical energy. The two basic parts of an
induction motor are the stationary stator located in the motor frame and the rotor that is
free to rotate with the motor shaft. The basic simplicity of this design ensures high
efficiency and makes them easily adaptable to a variety of shapes and enclosures. By
varying the design of the basic squirrel-cage motor, almost any characteristic of speed,
torque, and voltage can be controlled by the designer. The speed of an ac induction motor
depends on the frequency of the supply voltage and the number of poles for which the
motor is wound. The term pole refers to the manner in which the stator coils are
connected to the three incoming power leads to create the desired rotating magnetic field.
Motors are always wound with an even number of poles. The higher the input frequency,
the faster the motor runs. The more poles a motor has, the slower it runs at a given input
frequency. The synchronous speed of an ac induction motor is the speed at which the
stator magnetic flux rotates around the stator core at the air gap. At 60 Hz the following
synchronous speeds are obtained:

Table 9. RPM for No. of Poles


Number of poles RPM
2 3,600
4 1,800
6 1,200
8 900
10 720
12 600

Providing the motor is properly constructed, the output speed can be doubled for a
given number of poles by running an ASD supplying the motor at an output frequency of
120 Hz. Induction motors are made with slip ranging from less than 5% up to 20%. A
motor with a slip of 5% or less is known as a normal-slip motor. A normal-slip motor is
sometimes referred to as a 'constant speed' motor because the speed changes very little
from no-load to full-load conditions. A common four-pole motor with a synchronous
speed of 1,800 rpm may have a no-load speed of 1,795 rpm and a full-load speed of 1,750
rpm. The rate-of-change of slip is approximately linear from 10% to 110% load, when all
other factors such as temperature and voltage are held constant. Motors with slip over 5%
are used for hard to start applications.
Historically a variety of terms have been used to describe a system that permits a
mechanical load to be driven at user-selected speeds. These terms include, but are not
limited to:

Variable-Speed Drive
Variable-Frequency Drive
Adjustable-Frequency Drive
Adjustable-Speed Drive
The term variable implies a change that may or may not be under the control of the
user. Adjustable is the preferred term since this refers to a change directly under control
of the user. The term frequency can only be applied to drives with an ac output, while the
term speed is preferred since this includes both ac and dc drives. Thus, the term most
commonly accepted is Adjustable-Speed Drive (ASD).
Most ASD units consist of three basic parts. A rectifier that converts the fixed
frequency ac input voltage to dc. An inverter that switches the rectified dc voltage to an
adjustable frequency ac output voltage. (The inverter may also control output current
flow, if desired.) The dc link connects the rectifier to the inverter. A set of controls directs
the rectifier and inverter to produce the desired ac frequency and voltage to meet the
needs of the ASD system at any moment in time.
The advantages of ASDs do not stop with saving energy and improving control. ASD
technology can now be applied to manufacturing equipment previously considered too
expensive or uneconomical. Such applications are often unique to a particular industry
and its equipment, or even to a particular facility. Cost benefits, such as those obtained
from improved quality, may be desirable for each application.
The motors at the Heavy Chemicals Division of TPL are powered by a pair of
recently installed DG sets. These have greatly helped meet the power requirements of the
chlor-alkali plant and have also ensured un-interrupted power supply to the fragile
membrane cells which in turn avoided generation of effluents due to power shortages.
Chapter 8

Environmental Issues
I Impact Identification.

Introduction.

Environmental consequences which are generally known as impacts, is creation of a new


set of Environmental conditions, adverse or beneficial inducted by the action or the set of
actions under considerations.
The impact analysis of different factors of the operation of the plant is shown below.

The impacts during operational phase:

1. Socio Economic Impacts.


Replacement of the mercury cells by the membrane cells has helped abate the problem of
effluent disposal, which no more contains mercury.
The plant operation requires a total power of 4.5 lac units/day, which it gets from two
sources, partially from Tamilnadu Electricity Board, and the rest from its owned DG sets.
The installation of the DG sets helped meet the power requirement of the chlor-alkali
plant and also ensured un-interrupted source of power supply to the fragile membrane
cells which avoided the generation of effluents due to power shut-down.

And hence newer installations directly imply more number of job opportunities. This will
help improve the status of the peripheral local communities whose living standards will
go up considerably due to the higher income levels, better medical facilities and
communication advances and access to better education facilities. Due to marginal
increase in employment opportunities associated with the modernization, development is
bound to occur.
On the above scores, the impact will be marginally positive in this action.

2. Air Quality

a) Impact on air quality due to plant emission.


Ambient air ambient air quality levels wit respect to SPM, SO2, NOx are well
within the prescribed limit by CPCB and MOEF in the core and buffer zone. The outlet
compositions of the stacks existing within the premises of the plant are tabulated in table
Note: As H2 is used as fuel in boiler there’ll be no SO2 emissions.
The emissions of SPM, SO2, NOx, acid mist and Cl2 from utilities as well as
scrubbers are well within the limits. These stacks are monitored regularly enforce
preventive measures in case of any excess.
\

Table 10 Stack Data


No. Stack Fuel Stack Stack Dia Temperature Volume of
Attached To Type Height gas
m m °C Nm3/hr
1. Caustic H2 20 0.8 200 °C 3 MT/hr
Fusion Plant steam
(Concentrator
Stack)
2. Caustic H2 25 0.38 200 °C 2000
Fusion Plant
(Salt Heater)
3. Steam Boiler H2 35
4. DG Cell Set Fuel Oil 8 0.15 200 °C 500
5. WAD Plant 1 16 0.3 30 °C 1100
6. WAD Plant 2 16 0.3 15 °C 1100

The following control measures have been incorporated\ for controlling the emissions.
1. Each HCl unit is filled with a tail gas scrubber for removing traces of HCl (acid
mist) present.
2. Excess of NH3 from the NH4Cl plant is washed with DM water in mother liquor
scrubber packed with poly propylene packing to remove excess of NH3
3. Cl2 waste gases are removed by neutralization and absorption of caustic
soda/milk of lime towers.

Due to enforcement of various control measures, impact on air quality due to existing
plant operations are well within sustainable limits.

a) Impact on air quality due to DG sets.


Initially fuel oil was employed for the operation of DG sets which was later replaced by
environmentally friendly fuels like LSHS, LSWR, and LNG etc. as liquid fuels are used.
The impacts due to SPM are negligible. SO2 and NOx are major pollutants whose
impacts are to be contained during the operational phase of the plant.

The impacts on air quality due to the following fuels are considered.
(i) fuel oil with 4 % sulfur content
(ii) LHS with 1.9 % sulfur content
(iii) LNG with 0.001 % sulfur content

b) Impact on air quality due to heavy fuel oil.


In the hot flue gases let out in the stack, SO2 and NOx are the major pollutants. The
quantum of SO2 and NOx emission from the plant will be as below;
SO2 emission
(i) Total fuel (HFO) consumption = 3800 kg/hr
(ii) S content (max) in HFO = 4.0%
(iii) S load produced assuming 100% combustion = 4% of 3800 = 152 kg/hr
(iv) Quantity of SO2 gas produced = 152*2 = 304 kg/hr = 84.4 kg/sec

Considering that 3 DG sets (2 running and 1 standby) will give an output of 30 MW the
emission rate of SO2 from each stack is 42.2 g/sec

NOx emission
The NOx emission from the stack will be restricted to 1100 ppm which will lead to
emission rate of 61.6 g/sec

c) Impact on air quality due to LNG

LNG is the most environmentally friendly fuel with S content as low as 0.001 % which
will lead to almost negligible SO2 emission. The NOx emission will also be 61.6 g/sec

Air Quality Modeling


The emission rates calculated above have been subjected to the PTDIS model to asses the
impact on the air quality due to dispersion effects. Inputs to the model are given below:

Stack height : 65.5 m


Stack Diameter: 1.7 m
Stack temperature: 453 K
Exit Velocity : 12.22 m/sec
Emission rate
For SO2 : 42.2 g/sec

PTDIS Model
It is an interactive program that estimates the short term concentration directly down
wind of a point source at a distance specified by the user. The effect of estimation vertical
dispersion by mixing heat can be included.
The model uses Briggs-Phume residency method and Pasquilli-Grifford Dispersion
methods for this.
The various inputs required to run this model are:
• Number of sources
• Number of receptors
• Emission rate, physical stack height and diameter, stack gas temperature and stack
gas velocity for each value entered.
• Number of meteorological scenarios.
• For each scenario, the meteorological information required is wind velocity,
ambient temperature and mixing heights.
The PTDIS model was run for respective wind velocities (1.5 m/s, 2 m/s, 6.5 m/s and 8.0
m/s) and stability classes 2 and 4 taking into account the natural stability.

Analysis of dispersion model

The ground level concentrations have been worked out as mentioned earlier for each of
the gas from the stack and predicted in a consolidated form for each parameter namely
SO2, NOx in tables 2 for short term concentrations and corresponding 8 hourly and 24
hourly values. For SO2, the max short term concentration, 8 hourly and 24 hourly values
due to the use of HFO are 339.0, 99.0, and 66.0 respectively at a downwind distance of 1
km where LSHS is used.
The SO2 maximum 8 hourly and 24 hourly values will be 150.0, 45.0 and 30.0 at a
distance of 1 km.
For NOx the maximum short term concentration 8 hourly and 24 hourly values due to the
stack are 351.0, 105.3, and 10.20 mg/m3 respectively at a downwind distance of 1.0 km
for 3 stacks. In reality, GLC will be less due to changing wind direction, combined effects
of alternating sources and other Environmental factors. Even after addition of projected
ground level concentrations to the existing background loads when 2 GD sets are in
operation the ambient air quality will be maintained within prescribed limits both in core
and buffer zones.
With introduction of LSHS and LNG as fuels, levels of SO2, NOx are relatively reduced.

Table 2 Level Concentration For SO2 (HFO as fuel) in mg/m3


No. Distance Short Term 3 stacks 8 hourly 24 hourly
Concentration
(1 stack)
1. 0.50 34.00 102.00 30.60 1.21
2. 1.00 110 330.00 99 1.55
3. 2.00 48.40 145.2 43.56 2.2
4. 3.00 23.70 71.1 21.53 2.42
5. 4.00 13.90 41.7 12.51 2.72
6. 5.00 9.09 27.27 8.18 3.17
7. 6.00 6.61 19.83 5.95 3.97
8. 7.00 5.29 15.87 4.96 5.45
9. 8.00 4.53 13.59 4.08 8.34
10. 9.00 4.04 12.12 3.64 14.22
11. 10.00 3.67 11.01 3.3 29.04
12. 15.00 2.58 7.74 2.32 66.00
13. 20.00 2.02 6.06 1.82 20.40

3. Impact on water quality


The entire water requirement of 1980 m3/day will be met from the metro water supply or
from ground water sources located within the factory area. The auxiliary cooling water
will be recycled and only make up water will be supplied. The domestic waste water
generated which is about 80 m3/day will be treated with the existing sewage treatment
plan. As such no waste water will be discharged from the process. Occasionally waste
water containing oil and grease generated due to washing will also be treated in the ETP.
Due to various Environmental control measures environmental aged the impact on water
quality will be less.

Environmental Control Measures

General
The adverse affects of the various impacts due to the modernizations during the
operational phase of the plant. These can be ameliorated and brought to sustainable limits
by planning and adapting necessary measures.

1. Land Use
There was no agricultural land spoilage while setting up of the plant. As no forest land or
hutments exist in the core zone, the question of rehabilitation and corresponding
compensatory afforestation does not arise.

Socio Economic factors


The plant is amidst an industrial area. Hence it enjoys all the conveniences of being close
to other industries. The Manali industrial area is situated about 30 kms away from the
metro Chennai. Consequently, the plant provides employment opportunities to people of
many sections of society.

Air Quality.
Ambient air quality is well within the limits of CPCB and MOEP. Also, LNG is being
used as fuel instead of Heavy Fuel Oil, so less sulfur dioxide is released as pollutant gas.

Chlorine Neutralization of Vent Gases. (Wad Section)

Chlorine waste gases generated from chlorine storage and vent gases during start up are
neutralized in two absorption towers where caustic lye is circulated. This system has
additional caustic soda polishing column to ensure no chlorine escapes to the atmosphere.
The vent gases being released into the atmosphere are been continuously monitored by an
analyzer and being shown in the control room. Further, a sodium hypo system has also
been introduced where chlorine is completely removed as sodium hypochloride by
effective neutralization with caustic soda. The sodium hypochloride produced is saleable
and does not contribute to any solid or liquid waste.

Capacity of Sodium Hypo System : 1 MT/hr Chlorine


Around 10 KL/day of sodium hypochloride solution is produced per day in this section
and dispatched out as a by-product.

Water Quality

Water quality is maintained well within the prescribed limits as a result of treatment
procedures described below:
Waste water is treated using the principle of attraction while process waste water is
disposed into the sea after pH neutralization. The total quantity of waste water from
different sections is given below:

Process : 290 m3/day


Domestic : 80 m3/day

The treatment procedures for the two types of effluents are described below:

Method of Treatment of Sewage Effluent

Effluent waster from canteen contains oily matter and solid food particles that are bio
degradable. The water is treated biologically for recovery and reuse in the canteen waste
water treatment plant. Solids in the waste water are retained by a mesh screen and then
sent to the oil removal pit, where the mater is relieved of its oil content. From the oil
removal pit, the waste water flows from the collection tank by gravity. The water is then
pumped to the equalization tank, which serves to smooth the variation in quality of
effluent coming from the collection tank.
A feed pump delivers waste water from equalization tank to the aeration tan, which is
provided with two aerators. Reduction of Biological Oxygen Demand (BOD) takes place
in the aeration tank, where microorganisms are allowed to grow for this purpose. From
the aerator tank, water flows to the settling tank, where microbial sludge is separated.
Clean water overflows to the treated water tank, from where it is pumped for reuse. Part
of sludge is sent to sludge pits for disposal.

Effluent Treatment Process System

The process effluents come from the following sections:


1. IEM plant floor washing - 20m3/day
2. Brine section - 90 m3/day
3. Boiler blowdown - 5 m3/day
4. Caustic Soda Evaporation - 5 m3/day
5. DM water plant - 100 m3/day
6. Cooling water - 45 m3/day
7. Hydrogen Unit - 15 m3/day
8. Ammonium Chloride - 5 m3/day
9. DG set (floor washing) - 5 m3/day
_______________
290 m3/day
_______________

The non-mercury bearing effluent stream is collected in the main effluent pit. 12″ dia
HDPE pipes laid underground connects effluents generated from different sections to
collection pits/ main effluent pit.

Since cleaner technology is used, the effluents from the plant will not contain any
hazardous chemicals. pH correction, if required, will be done and pumped to final
disposal point along with the treated effluent from the canteen waste water treatment
plant.

The combined treated effluents will continue to be pumped into the sea.

Water Quality Monitoring:

It is required to carry out continuous monitoring of treaded effluent quality in and around
factory premises
The quality of treated effluents in and around factory premises is being continuously
monitored. The treated effluent quality is monitored at the outlet of individual in-plant
effluent treatment as well as from the outlet after neutralization. Automatic sampler
collectors are installed to collect samples continuously. From each point minimum eight
hours composite samples will be collected and analyzed for the relevant pollutants as
indicated in the respective treatment scheme. Regular sampling is conducted at the
discharge point of the diffuser system to detect any deterioration of the treated effluent
quality.

Environmental Management Plant


It is imperative to device in advance a proper management plant for Environmental
control during operation phase of the plant so these measures can be enforced promptly.
The HCD at TPL has a well lad out management plan and proper implementations of
various control measures have helped to keep the Environmental quality within
sustainable limits. The main environmental factors which are to be included have been
given due consideration in the management plan are the following.
1. Ambient air quality for the monitoring of SPM, SO2 and NOx emissions to asses
the efficiency of control measures incorporated.
2. Ecological factors
3. Ambient noise in the plant area and the surrounding buffer zone.
a. Water analysis due to discharge of treated effluents.
b. Safety and health measures.

Regular systematic and sustained program schedule for implementation and monitoring
of various control measures are to be devised in advance with clear cut guidelines for
various plants for keeping a continuous surveillance on the environmental quality of the
area. It is noteworthy to highlight here that a full fledged control scheme to minimize the
impacts on environmental factors has already been adapted.

Statutory Fulfillments

The monitoring schedules will be planned to aim at regular and systematic study of
various pollution levels with respect to air and water qualities, noise levels, etc., to ensure
that they conform to the standards laid down by the Central and State Pollution Control
Board limits. Stack emissions are and shall be monitored regularly to check the efficacy
of the control equipments.
All the stipulations in respect of methodologies and studies of various parameters by
MOEF and State Pollution Control Board should be followed.
Wherever excess levels are noticed, prompt control measures will have to be effected to
bring the quality parameters under control.
Socio-economic status with respect to health, education occupational health,
communication welfare measures etc are reviewed at least once in three years to bring
them on par with the population growth, social development etc.
HCD at TPL has adapted environmental control and management as a corporate policy to
ensure that all the parameters for various environmental components such as air, water,
noise, soil, etc conform strictly to standards of Central and State Pollution Control Board.
The general manager will over see the environmental management system directly, duly
supported by the concerned departmental executives.

Environmental Management Cell

This cell will oversee the measures to be taken under the Environmental Management
Plan to ensure the impacts arising from the pollutional parameters of the power plant are
within prescribed limits. For this purpose the cell will comprise of a monitoring group
and a pollution control equipment maintenance group.
The environmental management cell will oversee the following aspects.
a) Conducting environmental audits and reporting to TNPCB
b) Sending periodical monitoring reports as prescribed by TNPCB and other statutory
authorities.
c) Recommending in advance necessary measures to improve the environmental aspects.
d) Conducting safety audits and programs and safety awareness among workers/staff.
e) Conduct annual health audits to detect any health problems promptly in the
workers/staff.

Ambient Air Quality and Stack Monitoring.


For ambient air quality monitoring, necessary instruments such as high volume
samples are available. Stack monitoring is conducted regularly in the existing unit
available stack monitoring kits, SO2 Analyzer, Automatic Recording emitter, Weather
data etc. these will be adapted by respective instruments having high accuracy.

Water Quality Monitoring


It is required to carry out monitoring of treated effluent quality in and around factory
premises. The treated effluent quality should be monitored at the outlet of individual in-
plant effluent treatment units as well as from the outlet after neutralization. Automatic
sample collectors are installed to collect the samples continuously from each point.
Minimum 8 hours of composite samples shall be collected and analyzed for relevant
pollutants as indicated in the respective treatment schemes described. The effluent
samples are collected and analyzed daily. Regular sampling is conducted at the discharge
point of the diffuser system to detect any deterioration of the treated effluent quality. The
marine ecosystem will also be continuously monitored.

Soil Quality Monitoring.


Monitoring program for the soil will help in the improvement in physical and
chemical properties of the soil corresponding improvement in ground water quality and
water table levels. Thus, monitoring measures may provide useful guidelines and for
taking remedial measures in time for the result and any further development in the
activities in the area.

Environmental Control Cost


Towards pollution control, a capital investment of Rs. 287 lacs has been made of
which Rs. 207 lacs has been spent for pollution control schemes to control water
pollution. During the modernization program, Rs. 40 lacs were spent towards air
pollution control equipment and Rs. 30 lacs was spent on Green Belt Development.
Besides, the annual expenditure for operation and management is about Rs. 69 lacs for air
pollution and Rs. 10 lacs for ETP.
Summary

The heavy chemicals division of tamilnadu petroproducts limited produces about 100
MT/day of Caustic Soda Flakes (98%), along with hydrogen and chlorine as by-products.
the mere raw materials it uses are water, electricity and raw salt. The plant is powered by
a set of 3 Deisel generator Sets, 2 always operational and one on standby. The plant
makes the use of Membrane Cell technology in the electrolyzers, which relatively more
eco-friendly, cheap and efficient in terms of quality of the product. Despite of a few
power cuts due to heavy rains, it was observed during the training period that the plant
was operating at par with the demand of caustic soda flakes. It makes good use of the
gases it generates as by-products in generating power or other chemical substances. TPL
takes complete care of all the safety norms required to be followed to ensure the safety of
its employees, workers and the surrounding environment. The training was a healthy
learning experience.