BRINE

PURIFICATION
PLANT

Submitted To Submitted By
Mr. Muhammad Khurshid Sheikh Muhammad Abdullah Irshad
(Head of Planning Department) Waqar sheikh
Mr. Malik Masnsoob

(Training Incharge & Planning Specialist)

Mr. Atta Hussein

(Incharge of Brine Purification Plant)

 ACKNOWLEDGEMENTS

Training is a basic necessity and requirement of Chemical Engineering. With blessing of

Allah, we got a chance to complete our Training in Brine Purification Plant at Ittehad Chemical
Limited

The people at ICL are very kind, friendly and corporative. We have gained a lot of
professional experience, skills and knowledge under the assistance of Mr.Atta Hussain

First of all we would like to thank Mr. Muhammad Khurshid Sheikh (Head of Planning
Department) and Mr. Malik Masnsoob (Training Incharge & Planning Specialist) who gave us
opportunity to do Training in ICL. We are also very thankful to all the management and staff of
Ittehad Chemical Limited especially unit managers, staff engineers, learning & development
center , supervisors, operators and others for all their utmost help, guidance and time.
Table of Contents

Introduction 3
Steps for Caustic Soda Production 3

Brine Purification 3
Raw Material 3
Why we purify Brine 4

Brine purification process 4

Saturator 4
Primary Pits 5
Secondary Pits 5
Purifier 5
Purifier-1 5
Purifier-2 6
Settler 7
Primary Filter 8
Secondary Filter 9
Ion Exchange Feed Tank 10
Ion Exchange Unit 11
Regenerations Steps 13
Introduction

Sodium hydroxide (NaOH), also known as lye and caustic soda, is an inorganic compound.
Sodium hydroxide is used in many industries, mostly as a strong chemical base in the
manufacture of pulp and paper, textiles, drinking water, soaps and detergents and as a drain
cleaner. Sodium hydroxide is industrially produced as a 50% solution by variations of the
electrolytic chloralkali process. Chlorine gas is also produced in this process. Solid sodium
hydroxide is obtained from this solution by the evaporation of water. Solid sodium hydroxide is
most commonly sold as flakes, prills, and cast blocks

Steps for Caustic Soda Production

Process of Caustic Soda is divided in following plants:

Brine Purification
Production Cell
Evaporation Unit
Flacks Formation
Packing Unit.

Brine Purification

Raw Material

Brine is a solution of NaCl (sodium chloride) salt in water. Brine is generally produced by the
dissolving of fresh (rock) salt in water or depleted brine from mercury and membrane processes.
Rock salt composition is given below as:

Components Weight % age

NaCl 93
Na2so4 2.2
Ca++ 0.4
Mg++ 0.4
Insoluble 3-4
Why we purify Brine

For membrane process, essentially high purity brine is required as the unwanted impurities
(Ca+2, Mg+2 and SO4-2) deteriorate ion exchange membrane (IEM) performance, therefore,
purification of brine, settling, filtration, acidification, de-chlorination are auxiliary processes for
the quality and efficient production of such alkalis.

Brine purification process

The main sections of brine purification process are:

Saturator
Primary Pits
Secondary Pits
Purifier-1
Purifier-2
Settler
Primary Filter
Secondary Purifier
Ion Exchange Method

Saturator

Brine is generally produced by the dissolving of fresh (rock) salt in water or depleted brine from
mercury and membrane processes. The low concentrated sodium chloride solution (brine) i.e.
220 g/l, which is coming from the cell room where it lost its sodium ions concentration due to
electrolysis to form caustic soda, so it is recycled back to saturator to gain its concentration level
up to 300 g/l. Saturator of 275 m3 is used to saturate the brine by showering de-chlorinated brine
on bed of NaCl rock salt with temperature 65-70 0C and flow rate 160 m3/hr. Industrial water
pipe of 2 inches is also used to shower water on salt bed for brine make up purposes. Low
concentration of sodium ion de-chlorinated brine passes through 13 ft height of rock salt bed and
then it enters into primary pits through Channel Lines. Saturated brine is collected in pits. There
are three primary pits and two secondary pits
Primary Pits

Three primary pits of 400 m3 each are used to sediment the 4% remaining impurities like mud,
silicate, granules and other settle down impurities, it takes 4 hour of retention time to settle down
impurities. And it takes almost four hours to fill one pit. Out of three pits, second pit is used as
standby pit. When one pit become full of sludge then it is cut off from the circuit and the other
pit ready for use is put into circuit. Pits are made inclined for the removal of sludge.

Secondary Pits

Two secondary pits of 35 m3 each are used to remove the further impurities which are not
removed by primary pits. One pit is used as standby for removal of remaining settle down
impurities. A titanium coated or fiber pipe with number of holes of half centimeter size is used as
filter media attached at end side of secondary pit from where pump suction start. At the end two
centrifugal pump of 60 HP (one as standby) are used to transfer brine to purifier 1.

Purifier

Purifier is a reactor or vessel in which chemical reaction occur. Two open tank CSTR
(continuous stirred tank reactor) purifier of 70 m3 each are used to produce adequate particles
size that can be easily agglomerate with flocculent in settler. Paddle agitator is used to provide
mixing energy in such way that particles do not disintegrate. Four reactant chemicals are added
in purifier to achieve large particle size of the impurities so that they are bound by flocculants
and are easily settled down and hence removed.

Barium carbonate
Sodium carbonate
Sodium Hydroxide 31%
Accofloc

Purifier-1

Saturated brine from secondary pits enters into purifier#1 from bottom side and emit from top
side after retention time of 45 minute. A bypass line is attached with inlet of brine to purifier
which is used for distribution of additive chemical to purifier. Two type of reactant chemicals are
used to remove sulfate and calcium ions from brine as fellow:
 1. Barium carbonate
2. Sodium carbonate

Chemical Reaction

3 + 2 4 4 + 2 3

2 + 2 3 3 + 2

Solution tank of barium carbonate

Barium carbonate has ability to remove sulfate ions present in brine in form of barium sulfate.
Amount of BaCo3 required removing impurities depend on sulfate ions. Barium carbonate
solution of 8 % w/w is prepared in 7 m3 of fiber or mild steel with rubber lining tank. Brine from
primary filter is used as solvent for BaC03 solution to maintain sodium ions in purifier 1. A
motor driven mixer of 70 rpm (revolution per minute) is used to provide mixing energy for
solution formation. A batch for two hours of BaC03 is prepared and then it transferred to purifier
from top side position with the help of two centrifugal pumps (one as standby) to purifier.

Solution tank of sodium carbonate

Sodium carbonate solution of 8% w/w is prepared in 7 m3 of fiber or mild steel with rubber
lining tank. Brine is used as solvent for solution formation. A peddle type motor driven mixer
with 30 rpm is used to provide mixing energy. One batch of 2 hours is added to purifier in bypass
line of brine to distribute the solution partially from top and bottom.

Purifier-2

Brine enters from bottom side into purifier 2 after emitting from top side of purifier 1. In this
purifier caustic soda 31% solution is added by gravity from overhead tank and its flow can be
adjusted through rotameter. A stand by tank can also be used in case of NaOH solution shortage.
Sodium hydroxide is used to precipitate the magnesium ion impurity in form of magnesium
hydroxide. NaOH is added into purifier 2 because reaction of caustic soda with magnesium is
fast as compared to reaction of barium and sodium carbonate with sulfate or calcium ions.

Chemical Reaction

2NaOH + MgCl2 Mg (OH) 2 + 2NaCl

Solution Tank of Accofloc

Accofloc solution of 1% (w/w) is prepared in 7 m3 of fiber or mild steel with rubber lining tank.
First of all, 700-gram cationic polymer Accofloc is added into 1/2 m3 tank with de-ionized water
as solvent mixed by using tee mixer at 42 rpm. Then this solution is transferred into 7 m3 tank
filled with industrial water as solvent for further dilution. Sodium sulfite tank is also present for
addition into Accofloc tank if chlorine present in settler. When all these additives are mixed with
peddle mixer at 50 rpm to form uniform mixture then it is transferred to small tank place
between purifier and settler by using two centrifugal pumps (one as standby).

Settler

Settler is a clarifier used to remove solid particulates or suspended solids from brine by
sedimentation process.

Construction

The brine settler is a solid contact type clarifier like a huge bowl which is broad from the top and
narrows at the bottom. A big high efficiency marine propeller type agitator is fitted at the center
of the settler which completes its one revolution in 9 minute and 6.6 revolutions per hour keeps
on fluid in slight motion. It is made up from mild steel material with titanium coating from
interior side and has capacity of 1000 m3 which takes 10 hours of retention time for settling.

Working

First of all, brine enters into settler from the center with Accofloc into primary mixing zone of
settler, here flocculation, with suspended particles present in brine, occur. After this it enters into
secondary mixing zone of settler, here charge reduction and agitation increase the particles
collision and then particles move down (or settle) by gravity due to its weight and size increased
by flocculating medium. The impurity particles bound with each other to form bigger size
particles called as Sludge which settles down at the bottom of the settler and send to sludge pits.
Brine recovered from sludge pits send to purifier 1 and sludge dumped to drain well. An
automatic instrument air control pneumatic valve is attached with bottom end for de-slugging
which open after every 45 minutes for 30 second valve opening. At the top section clarified brine
overflow and move toward clarifier tank by gravity and overflow from tank again move toward
settler top side. After every two hours, down take sample analyze the excess carbonate and
hydroxyl ions. Test result tells us how much amount of reactant chemicals are needed in
purifiers. Brine is send towards primary filter from clarifier by using two centrifugal pumps (one
as stand by) of 60hp.

Sample Test Unit Limit

Settler Overflow T.S.S NTU <10
Primary Filter

Brine primary filters are required to remove the suspended solids overflowing with the brine
from the settler/clarifier. There are five number of flowing gravity sand filters operated in
parallel.

Construction

Primary filters are made up of mild steel of total volume of 13 m3 consists of a multilayered
pebbles and stone filtering bed and one upper layer of anthracite coal. The bed of these
multilayered pebbles and stones are formed according to their size increase from top bed to
bottom and anthracite coal at upper most bed of filter.

Working

Brine enters into primary filter from top side and out from bottom. After passes through bed of
anthracite coal and multilayered bed of pebbles, impurities like excess carbonate and hydroxide
ions stuck with porous part of pebbles and brine out with impurities reduce up to 10 ppm (parts
per million). Pressure gauge (not in working at present) is attached with top of filter which tells
us about backwashing indication. If pressure increases from 1 bar, then it means filtering media
become full of suspended particles. By using backwashing, we can reuse our filtering media
again

Sample Test Unit Limit

Primary Filter T.S.S NTU <10
Free Cl2 mg/l Nill
PH mg/l 9.5-10.5
Ca , Mg++
++
-- <5

Backwashing steps

To backwash a primary filter for 45 minutes the following steps should be followed:

Close inlet and outlet valves of brine simultaneously

Open the vent valve for air removal
Open the drain valve for 5-10min and let the drain into recovery pit
Close the drain and recovery pit valve after draining all brine
Open the industrial water valve for backwashing
Backwashing water enter from bottom and coming out of the backwash pipe at the top
When water becomes clear then close the water inlet valve and open the drain valve to
drain the water into drain channel
 Now close the drain valve and backwash valve
Open the inlet and outlet valve of brine and at the end close the vent valvressure increases
from 1 bar, then it means filtering media become full of suspended particles. By using
backwashing, we can reuse our filtering media again

Secondary Filter

The brine from the primary filter is stored in the storage tanks, from it is pumped to the four
secondary filters, arranged in parallel operation to remove the further impurities that are not
removed from primary filters. The secondary brine filters reduce the concentration of suspended
solids (mostly CaCO3 and Mg (OH) 2) to < 1 ppm with particle size < 0.5 micron.

Principle

The Secondary brine polishing filters are vertical tubular backwash filters that utilize a cellulose
fiber pre-coat to achieve such level of filtration that protect the ion exchange system from
suspended solids which would otherwise plug the column.

Construction

The secondary brine filters contain 142 tubes suspended vertically from a tube sheet. The filter
tubes are constructed of C-PVC (chlorinated polyvinyl chloride) with a polypropylene sleeve and
are covered with a seamless polypropylene sock type covering. The conical shaped bottom
facilitates the backwash by directing the filtered solids cake to the dump (drain) connection
during the backwash. All other internal hardware (fasteners etc.) is constructed of titanium or
plastic and gaskets are constructed of EPDM (ethylene propylene diene monomer) to minimize
metals contamination of the brine.

Working

Brine enters the filter through the bottom conical section and is evenly distributed throughout the
filter chamber. Brine cross exchanger is located upstream of the secondary filter. The brine cross
exchanger is designed to exchange thermal energy between the brine primary storage tank to the
secondary filters. Filtration is from the outside of the tubes to the inside. As the brine passes
through the cake and tubes, suspended solids are deposited on the outside diameter of the tubes.
The collection of these suspended solids forms a cake layer on the tubes. The formation of this
cake layer results in increased pressure drop from 2.5 kg/cm2 to above and eventually
necessitates backwashing of the filtered brine. Filtered brine flows up through the inside
diameter of the tubes and enters the top head of the filter through the openings in the tube sheet.
Filtered brine is then discharged from the top head through the main filtered brine outlet and
stored in 70 m3 storage tanks.
 Sample Test Unit Limit
Secondary Filter T.S.S NTU <1
Free Cl2 mg/l Nill

Pre-coat Solution Tank

The pre-coating solution tank is used for mixing pre-coat material and brine. The 7 m3 tank is an
open top FRP vessel with peddle type agitator 32 rpm provided to ensure a homogenous mixture.
Industrial and DI water can be use as solvent but mostly brine is used as solvent to form 20 %
w/w of Alfa cellulose by adding pre coating material i.e. Arbocel of 17.5 kg (one bag) in the
tank.

Backwashing and pre-coating steps

To backwash a primary filter for 35 minutes the following steps should be followed:
Close the inlet and outlet valves of brine simultaneously
Open the drain pneumatic valve and drain all the filter cake solution into the pit
Brine will drain at a high rate because of the compressed air entrap inside the filter doom
Close the drain valve after complete draining of brine and filter cake
Turn on the Arbocel pump for circulation
Open the inlet and outlet pre-coat valve to circulate a brine solution containing the pre-
coat material through the filter until a uniform layer of pre-coat is applied
Watch glass will show milky liquid coming out of the filter when it becomes clear
(coating will complete) then close the Arbocel coating
Close the inlet pre-coat valve
Open the inlet and outlet valve of brine
At the end close the outlet of pre-coat valve and turn off the pump of Arbocel

If the brine feed stream contains a large percentage of fines (small) or slimy solids, then the
pressure drop across the filter may rise rapidly, giving short cycle times. This is often the case
when the brine has a poor Ca to Mg ratio (less than 2:1).

Ion Exchange Feed Tank

Filtered brine from the secondary brine filters flows into the FRP made Ion Exchange Feed Tank.
Brine exiting the ion exchange feed tank is pumped through the brine cross exchanger which is
located upstream of the ion exchange system. The brine cross exchanger is designed to exchange
thermal energy between the brine feed stream to the ion exchange system. The brine cross
exchanger is a plate and frame heat exchanger constructed of titanium plates used to steam heat
the brine feed to the brine ion exchange system as required to maintain the temperature in the
range of 55 to 60C.

Ion Exchange Unit

Brine passes through secondary filter still has enough particles of size less the 0.5 microns may
damage the membrane of electrolysis cell. So the special unit called ion exchange resin applied
to remove unwanted impurities of calcium and magnesium ions.

There are two ion exchange units

Ion Exchange unit 1

Ion Exchange unit 2

Ion exchange unit 1 provides feed to IEM 1 and the ion exchange unit 2 provides feed to IEM 2.
Working of both units is same

Principle

Ion Exchange resins are insoluble granular substances which have in their molecular structure
acidic radicals that can be exchanged. The positive ions fixed on these radicals are replaced by
ions of the same sign in brine solution in contact with them.

Construction

The ion exchange vessels are typically constructed of rubber lined steel to minimize impurities
pick up by the passing brine. Internal piping is typically constructed of Titanium, Hastelloy C-
276, or C-PVC (plastic only for the top inlet distributor). External piping is typically constructed
of C-PVC or FRP. The vessel under-drain system must be constructed of metal (Titanium and/or
Hastelloy C-276), and must be spiral wound wedge (well screen) design. Plastic is not allowed to
be used for the bottom under-drain system, and cloth wrapped laterals are forbidden. An ion-
exchange resin or ion-exchange polymer is an insoluble matrix normally in the form of small
(0.5-1 mm diameter) beads, usually white or yellowish, fabricated from an organic polymer
substrate. The beads are typically porous, providing a high surface area. Ion exchange resin type
is a chelating resin of micro porous structure with polystyrene matrix cross-linked with di-vinyl
benzene substituted with weakly acidic amino-phosphonic active groups.

The characteristics reactions are shown below:

2RCH2NHCH2PO3Na2 + Ca+2 (RCH2NHCH2PO3)2CaNa2 + 2Na+

Regeneration to Hydrogen Form:

(RCH2NHCH2PO3)2CaNa2+4HCl 2RCH2NHCH2PO3H2+CaCl2+2NaCl
Conversion to Sodium Form

RCH2NHCH2PO3H2 + 2NaOH RCH2NHCH2PO3Na2 + 2H2O

The chemical structure of this resin facilitates the formation of complexes with metallic ions
such as calcium and magnesium. The relative affinities for metals in an alkaline brine
environment are as follows; Mg+2 > Ca+2 > Sr+2 > Ba+2.

Working

There are three ion exchange resin units operate in series, one unit use as ionizer (primary
column), second as polisher (secondary column) and the third one as standby for regeneration.
Alkaline brine enters the top of the column and flows downward through the resin bed. As the
brine contacts the resin, calcium ions in solution are exchanged for sodium ions in the resin.
Two sodium ions are exchanged for each calcium ion. The resin bed becomes exhausted where
there is too few sodium ions left to exchange with the calcium ions, resulting in the
breakthrough of calcium ions in concentrations exceeding 20 ppb in the exiting brine. Lab
analysis of the brine downstream of the ionizer (primary calcium) every 8 hours is used to
determine when break-through has occurred indicating the need to regenerate the ionizer
(primary column).

Merry-go-round Fashion

After regeneration, the regenerated column is placed in stand-by mode. When the primary
column (ionizer) is taken offline for regeneration, the stand-by column is put into service as the
secondary (polishing) column and the secondary column becomes the primary column (ionizer).
This cyclic operation has been described as merry-go-round fashion.

Safety Precaution for Resin

Four important safety precautions for resin are as given below:

The brine ion exchanges system must be free from mercury because it is not stripped
from the resin during regeneration and it will permanently reduce the capacity of the
resin, thereby shortening cycle time (i.e. shortening the length of time between
regenerations)
Brine feed to the ion exchange system must not have any free chlorine present. Free
chlorine will oxidize the resin which destroys the resins ion exchange capacity
The feed brine temperature should be maintained in the range of 55 to 60C and the pH
should be maintained in the range of 9-10.

The brine flow rate is typically controlled in the range of 10 to 30 BV per hour
Regeneration of resin

An exhausted column that has been taken off line must have the resin converted from the
calcium form back to the sodium form. This conversion procedure is called regeneration. It is not
possible to go directly from the calcium to the sodium form as with a classical water softener
resin. Sodium chloride is not used to place the resin in sodium form since the chelated
functionality of the cation resin is not able to split a neutral salt.
Auxiliary equipment required for the ion exchange system regeneration includes;

HCl Measuring Tank (for 31% HCl)

NaOH Measuring Tank (for 32% NaOH)
HCl Metering Pump
NaOH Metering Pump

Weak acid and weak caustic are made by diluting strong acid and strong caustic with de-ionized
water for regeneration of the ion exchange resin. The metering pumps are designed to provide the
proper flow rates of strong chemicals so that the final (diluted) concentrations are 4-5 wt.%
HCl/NaOH. Sodium sulfite must be added into the HCl Measuring Tank as required to eliminating
the chlorine otherwise free chlorine will damage the ion exchange resin permanently, causing
reduced capacity. Free chlorine can also be generated by the reaction of HCl with sodium chlorate. It
is therefore important to completely rinse the column of brine prior to the start of acid regeneration.
Lastly, the de-ionized water used for regeneration also must be free of chlorates and free chlorine.
A general outline of the sequence for this chemical addition is as follows;

Regenerations Steps

There are nine steps needed to regenerate an exhausted primary column (ionizer) as given below:

Brine drain
Brine displacement
Backwashing
Water drain
Acid injection
Acid displacement
Caustic injection
Caustic displacement
Brine rinse
Brine Drain

First step is to drain all the brine before regeneration. Close inlet and outlet of brine then open
manual and automatic drain valve with opening air vent valve that brine could drain easily.

Brine displacement

After the brine is completely drained, open DI water inlet valve as the drain valve is already
open. When brine is completely drain then close the water inlet valve and drain valve.

Back Washing

Backwashing is done from bottom to top. Open the backwash DI water inlet and outlet valve.
Adjust the water manual valve so that resin does come out of the vessel. Air vent valve should
close during backwash.

Water Drain

To drain water after backwash, open drain valve and vent valve so that water can be drained
easily and early.

HCl Injection

After the removal of free chlorine from HCL tank by suing sodium sulfite, open acid tank valve
and adjust the water manual valve to reduce 32% acid to 4%. Open the suction and delivery
valves of acid metering pump. Adjust the pump stroke to 78% and Check the concentration of
acid from sample point, it should be 4%. The concentration of acid 4% is used because it
provides roughly the same molarity as the brine solution which reduces the likelihood that the
resin will experience osmotic shock. After 1 hour, check the acid concentration from the drain
valve and if this concentration is equal to the inlet concentration, acid injection is complete. If
this concentration is not equal to 4% then continue acid injection.

Acid Displacement

After acid injection remove the excess acid from ion exchanger, open the DI water inlet valve
and check the pH of water coming out of drain valve. Continue this process until pH is normal
(7.0) and when the excess acid is completely removed then close the DI water inlet valve.
Caustic Injection

After complete water drain, start caustic injection. Open caustic tank valve and adjust the water
manual valve so that the concentration of caustic is 4%. Start the caustic injection pump and
open its suction and delivery valves by keeping the pump strokes to 66%. After 1 hour, check the
caustic concentration from the drain valve and if this concentration is equal to the inlet
concentration, caustic injection is complete. If this concentration is not equal to 4% then continue
acid injection.

Brine rinse

After caustic injection the primary column is regenerated with sodium ions and can be uses again
after rinsing the bed with brine at the end to continue to process. Now this regenerated column
becomes secondary column (polisher).