SITARA CHEMICAL INDUSTRIES LTD.

STANDARD OPERATION INSTRUCTIONS

FOR

MEMBRANE CHLOR-ALKALI PROCESS

SECTION I

ELECTROLYSIS PLANT

June 2002

ASAHI KASEI CORPORATION

 ML-190
- TABLE OF CONTENTS -

I. Electrolysis Plant

I-A General description

I-A-1 Electrolysis process

I-A-2 Anolyte part

I-A-3 Catholyte circulation part

I-A-4 Electrolysis part

I-B Principles on ion-exchange membrane process

I-B-1 Reaction
(1)Main reaction
(2)Selective permeation of sodium ion
(3)Transfer of water through membrane
(4)Precipitation of metal hydroxides

I-B-2 Operating variables

(1)Current application
(2)Concentration of anolyte
(3)Concentration of catholyte
(4)Flow rate of electrolyte
(5)Acidity of anolyte
(6)Pressure difference across membrane
(7)Gas pressure
(8)Temperature of electrolyte
(9)Hydraulic press

- 1 -
I-C Electrolyzer Operation

I-C-1 Alarm signal list

I-C-2 Safety devices

I-C-2.1 Automatic shut down of rectifier
I-C-2.2 Other interlocking systems
I-C-2.3 Details
I-C-2.4 Emergency power
I-C-2.5 Interlock diagram

I-C-3 Membrane leakage test

(1)Outline
(2)Preparation
(3)Pressurization of catholyte compartments with N2
(4)Membrane leakage test
(5)Necessity of membrane leakage test
(6)Occasion membrane leakage test have to be done

I-C-4 Electrolyzer leakage test and air purge

(1)Outline
(2)Preparation
(3)Filling with D. M. water
(4)Electrolyzer leakage test
(5)Draining

- 2 -
I-D Start-up of electrolysis

I-D-1 Preparatory Operation

I-D-1.1 Air purge in catholyte system
I-D-1.2 Brine circulation
I-D-1.3 Caustic soda circulation

I-D-2 Electrolyzer start up

I-D-2.1 Electrolytes filling
I-D-2.2 Connection to gas headers, electrolyte circulation and turn-on
I-D-2.3 Steps to normal state

I-D-3 Rectifier control for cut-in

I-E Shut down of electrolyzer

I-E-1 Outline
(1)Standard procedure
(2)Treatment of electrolyzer after shut down

I-E-2 Scheduled shut-down of electrolyzer

I-E-3 Electrolytes draining

I-E-4 Cell and membrane washing

I-E-5 Membrane wetting

I-E-6 Emergency shut-down

I-E-7 Rectifier control for cut-off

- 3 -
I-F Normal operation of electrolyzer(s)

I-F-1 Electrolysis load adjustment

I-F-2 Electrolyte flow-rate adjustment

I-F-3 HCl flow-rate adjustment

I-F-4 Pressure difference adjustment

I-F-5 Temperature adjustment

I-F-6 Electrolyte concentration adjustment

I-F-7 Locking electrolyzer

I-G Operation of hydraulic press

(1) Start of oil pump and adjustment of main line pressure
(2) Adjusting relief valve of manifold block
(3) Operation of hydraulic press
(4) Direction of oil supply
(5) Maintenance instruction for hydraulic system

I-H Standard operating conditions for electrolysis process Tables and correlation figures

I-I Trouble shooting

I-J Step diagrams for electrolyzer operation

- 4 -
I Electrolysis plant
I-A General description
I-A-1 Electrolysis process
The electrolysis process consists of three electrolyzers and their associated equipments.
The electrolyzer structure is Fig. I-1.
The electrolyzer consists of a filter press with hydraulic cylinder and it is equipped by 109 bipolar
cell frames and an anode terminal cell frame and a cathode terminal cell frame. One set of cell
consists of one ion exchange membrane placed between anode and cathode with gaskets.
Therefore one electrolyzer is consisted by 110 membranes.

Fig. I-1

- 1 - I-A-1
A bipolar cell is separated by a partition wall into two compartments, namely Anolyte Compartment, and
Catholyte Compartment.

The Anolyte Compartment is made of all titanium to give resistance against chlorine, and the Catholyte
Compartment is made of all nickel to give resistance against caustic soda with high concentration and
high temperature.
Anode is welded on titanium ribs of the Anolyte Compartment and Cathode is welded on nickel ribs of the
Catholyte
Compartment. Anolyte Compartment has one inlet nozzle and one outlet nozzle and gas separation chamber
on top of cell frame. It is same for Catholyte Compartment but the material is all nickel. Internal
view of cell unit are shown Fig. I-2.

Fig. I-2

- 2 - I-A-1
Process flow diagram is shown in Fig. I-3

Fig. I-3

The electrolysis process can be divided into three parts as follows:

Anolyte part

Catholyte circulation part

Electrolysis part
- 3 - I-A-1
Descriptions of these three parts are as follows:

- 4 - I-A-1
I-A-2 Anolyte part

The purified brine is fed to the anolyte inlet sub-header of each electrolyzer through Brine Head
Tank(D-200), and then supplied to each Anolyte compartment through hoses which connect the sub-header
with each cell compartment.

The hydrochloric acid flow is controlled by FIC-231A/B/C. The amount of purified brine flow rate is
controlled by FICZ-230A-C. FIC-231A/B/C and FICZ-230A/B/C are cascade-controlled by DC-electric current
supplied to each electrolyzer.

During electrolysis, OH-anion migrates from Catholyte Compartment to Anolyte Compartment through the
membrane. Hydrochloric acid is continuously supplied to Anolyte Compartment to neutralize the migrated
OH-anion.
The amount of this hydrochloric acid is adjusted by FIC-231A/B/C in order to keep acidity in anolyte
outlet within the specified range. FIC-231A/B/C is shut automatically when DC current supply for each
electrolyzer is stopped.

The purified brine is then electrolyzed in Anolyte Compartments, while chlorine gas is generated and
sodium chloride concentration is reduced.

Mixture of chlorine gas and depleted brine comes out through hoses and flows into the outlet sub-
header. The mixture is sent to Anolyte Separator(D-231A/B/C) where it is separated into gas and
solution.

Chlorine gas discharged from each electrolyzer is collected into main chlorine gas header and sent to
chlorine gas treatment section. PICZ-231 equipped on the main chlorine gas line controls chlorine gas
pressure.

While, depleted brine discharged from each electrolyzer is collected Depleted Brine Tank(D-240).
Depleted brine collected in Depleted Brine Tank(D-240) is fed to next section by Depleted Brine Pump(P-
244A/B).

A part of depleted brine is fed to the purified brine by FICA-240 to prevent the corrosion of anolyte
inlet sub-header. The discharged amount of depleted brine is controlled by level controller LICZ-240
of Depleted Brine Tank(D-240).

- 1 - I-A-2
A small amount of depleted brine is sent to DIA-240 in order to monitor the concentration of depleted
brine and return to Depleted Brine Tank(D-240).

- 2 - I-A-2
I-A-3 Catholyte circulation part

Catholyte is fed to the inlet sub-header of the electrolyzer through Caustic Soda Tank(D-250) by
Caustic Soda Pump(P-254A/B), and then supplied to each Catholyte Compartment through hoses which
connect the sub-header with each cell compartment.
In order to keep caustic coda concentration of catholyte at the specified value, demineralized(D.M.)
water is fed catholyte inlet main-header. The flow rate of D.M. water is controlled by FIC-205. FIC-
205 is cascade-controlled by DC-electric current and density meter DIA-250 which is installed on
Caustic Soda Tank(D-250).

Catholyte Cooler(E-223) is installed between Caustic Soda Pump(P-254A/B) and electrolyzers in order to
control the temperature of outlet catholyte of the electrolyzers with TICA-223.
The amount of catholyte fed to each electrolyzer is monitored by FI-223.

Hydrogen gas and caustic soda are produced by electrolysis in the Catholyte Compartments. Mixture of
hydrogen gas and catholyte comes out from the cells through hoses into the outlet sub-header. The
mixture is sent to Catholyte Separator(D-232A/B/C) where it is separated into gas and solution.

Hydrogen gas separated in Catholyte Separator(D-232A/B/C) is collected into main hydrogen gas header
and sent to hydrogen gas treatment section.

Hydrogen gas pressure is controlled by PICZ-233 equipped on the main hydrogen gas line. PICZ-233 is
cascade-controlled by chlorine gas pressure controller(PICZ-231) to keep the pressure difference
between hydrogen and chlorine gas at the specified value.

While, the catholyte separated Catholyte Separator(D-232A/B/C) is collected into Caustic Soda Tank(D-
250) as product. The amount of product caustic soda sent to the next section by Caustic Soda Pump(P-
254A/B) is controlled by LICZ-250 of D-250 and measured by Caustic Soda Flow Totalizer(FIQ-250).

Concentration of outlet catholyte from electrolyzers is measured by DIA-250 on D-250.

A part of outlet catholyte from electrolyzers is recycled back to catholyte inlet sub-header by Caustic
Soda Pump (P-254A/B).

- 1 - I-A-3
I-A-4 Electrolysis part

One electrolyzer is composed of the following parts:

(1) 109 bipolar cell frames, anode terminal cell frame and cathode terminal cell frame
(2) 110 sheets of ion exchange membrane
(3) 110 sets of gasket
(4) one press unit to press mounted cell frames
(5) inlet sub-headers for feeding anolyte and catholyte
(6) outlet sub-headers for collecting electrolysis products
(7) 110 X 4 flexible hoses for connecting cells with sub-headers
(8) one hydraulic manifold block which control oil pressure to hydraulic cylinders
(9) one oil pressure unit for 3 electrolyzers

Electrical cables are connected to each terminal cell mounted on both ends of the electrolyzer.
Current supply is adjusted from the control room.

Anolyte and catholyte are supplied to the electrolyzer in the manner described in I-A-2 and I-A-3.

The gas pressure difference is controlled within a certain range to obtain good performance and to
avoid membrane damage and electrode damage. During electrolysis the differential pressure is kept by
PICZ-231 and PICZ-233 within a certain range.

In order to observe the pressure of Anolyte and Catholyte inlet headers for the electrolyzer, PI-231A/B
and PI-232A/B are installed.

For maintenance of electrolyzer, water is filled and drained. For liquid filling, transparent tubes
are installed on Anolyte and Catholyte compartments to observe liquid level.

When electrolyzers are disassembled or shut down for more than 4 hours, both anolyte and catholyte must
be drained from the electrolyzer to Anolyte Blow Down Tank(D-260) and Catholyte Blow Down Tank(D-270).
The procedures are as follows; After electrolysis stop, brine and caustic is kept supplied to the
electrolyzer for certain time to get rid of gas zone in the cell, then both chlorine and hydrogen gas
are purged from the electrolyzer, and anolyte and catholyte are started draining.

Chlorine gas is purged to chlorine gas absorber, and hydrogen gas is purged to vent stack with nitrogen
gas.
- 2 - I-A-3
Anolyte remaining in the electrolyzer is blown down to Anolyte Blow Down Tank(D-260) and catholyte to
Catholyte Blow Down Tank(D-270), respectively.
Recovered blow down anolyte in the tank is sent to (De-chlorination Tower) by Anolyte Blow Down Pump(P-
264A/B). Recovered blow down catholyte in the tank is supplied to the next section by Catholyte Blow
Down Pump(P-274).
Both Anolyte and Catholyte Blow Down Tanks have enough capacity for drained electrolyte from all
electrolyzers.

Inside of the electrolyzer must be washed with demineralized water after draining electrolyte.
For washing the electrolyzer, Anolyte and Catholyte Compartments are filled with demineralized water.
And washed water of anolyte is drained to anolyte Blow Down Tank(D-260) and that of catholyte is
drained to Wash Water Tank(D-51500).

Before the electrolyzer is started, Anolyte and Catholyte Compartments, inlet and outlet sub-headers,
must be filled with purified brine and caustic soda, respectively.

- 3 - I-A-3
I-B Principles on Ion-Exchange Membrane process

The following describes the major principles of Asahi Kasei's ion exchange
membrane chlor-alkali process.

(1) Main reaction

In the ion-exchange membrane process for producing caustic soda,
permselective cation exchange membranes are installed between
cathodes and anodes. Electrolysis is carried out while brine is
supplied in Anolyte Compartment, and caustic soda circulated through
Catholyte Compartment. Chlorine is produced in the Anolyte
Compartment, hydrogen and caustic soda are produced in the Catholyte
Compartment according to the following reaction; Fig. I-4

Ｈ 2 Gas
Anode: NaOH
Cl2 Gas

Cathode:

Total:
Ｈ+
Cl-
NaCl is ionized into Na+ ion and Cl- ion. Electric charges of chlor Ｎ a+
ion are discharged at the anode to change into chlorine gas.
Meanwhile, sodium ions are transferred through the ion-exchange
membrane into the Catholyte Compartment.
In the Catholyte Compartment, water changes to hydrogen gas and
hydroxyl ions. Caustic soda is formed by the reaction of sodium OH―
ions with hydroxyl ions. (Refer to Fig. I-4)
The above main reaction is essentially the same as that of the
conventional diaphragm process. But in the membrane process, pure NaCl H2O
caustic soda can be obtained due to complete separation of
- 4 - I-A-3
 electrolyte and selective permeation of sodium ions.

(2) Selective permeation of sodium ion Fig. I-5

membrane
Selective permeation of sodium ions through the membrane will be
explained by the simplified diagram in Fig. I-5. anolyte catholyt
Sodium ions in the Anolyte Compartment are able to pass to e
Catholyte Compartment through the membrane because of their
Cl OH
affinity to the membrane.
As chlor ions and hydroxyl ions have negative electric charges
similar to the membrane, they are repulsed by the membrane and
cannot pass through it.
Na Na
Na Na
(3) Transfer of water through membrane

By applying electric potential across the membrane, not only

cations but also water can be transferred from the Anolyte
Compartment to the Catholyte Compartment.
Although the amount of water transfer depends on membrane and
electrolysis conditions, it is estimated to be about 3.1 ton/hr at
current load of 10.8 KA. Therefore the decomposition ratio of
sodium chloride can not be calculated simply on the basis of the * Water transfer:
concentration of sodium chloride in feed-brine and return-anolyte. 4.1 mole/faraday

* : 4.1 X 10.8 X 0.0373 X 18 X 110 X 0.95 = 3107

mol/eq-Na KA F/AH g/mole cells C.E.
Kg/Hr
(4) Precipitation of metal hydroxides

During electrolysis, some amount of OH- ions can exist in the

membrane because the transport number of Na+ ions in the membrane is
not strictly 1.0. If there is metal cations such as Ca ++, Mg++, Fe++
+
, Al+++, Ni++ , Ba++ in the anolyte, they will precipitate on or in
the membrane as hydroxides, causing increase of operating voltage
and decrease of current efficiency.
Therefore it is necessary to remove these kinds of metal cations
- 5 - I-A-3
 and to keep the anolyte free from them at all times.
SiO2 and I2 promote effect of Ca++ and Ba++ for membrane

I-B-2 Operating variables

Allowable range of each operating variable is described in each Fig. I-6

section of operation instructions. This section describes the
effects of major operating variables qualitatively.

(1) Current application

1) Upper limit of current

The upper limit of applied current to one electrolyzer is 12.15

KA
(4.5 KA/m2). If the current is applied more than the upper
limit.

2) Relation between cell voltage and current

The relation between cell voltage and current can be expressed

as follows, if other variables are kept constant:

Cell voltage
Fig. I-7

E1 : Cell voltage at current I1

E2 : Cell voltage at current I2 (10.8 KA) E0
E0 : Constant (2.42 V)
t1 : Operation temperature
t2 : Standard temperature (90 oC)

- 6 - I-A-3 Electric current

 Usually 10.8 KA is taken as a standard current (I 2 =10.8 KA:
AKC standard point), and 90 oC is taken as a standard
temperature (t2 = 90 oC). E0 is about 2.42 volts at 32%
catholyte concentration.
The gradient of the line in Fig. I-7 depends on other variables
such as the performance of the membrane, the electrode, etc.
(2) Concentration of anolyte

In electrolysis using the ion-exchange membrane, transport number Critical concentration of

of Na+ ions in the membrane is greater than that in the anolyte. anolyte : 117 g/l
Therefore Na+ ion content on/near the surface of the membrane is
smaller than that in the bulk anolyte, and the necessary amount of
Na+ ions must be supplied by diffusion.

When anolyte concentration decreases, the content of Na+ ions

on/near the membrane finally reduces to zero. If the
concentration of anolyte decreases below such a critical level at
certain current, operating voltage will increase sharply and
purity of chlorine gas will decrease, and some blisters will be
generated on the membrane, these phenomena may be caused by the
electrolysis of water itself.

On the other hand, if the concentration of anolyte increases over

the specified level, operating voltage will increase due to
membrane shrinkage. Therefore, it is necessary to keep the
anolyte concentration within the specified range.

(3) Concentration of catholyte

If the concentration of catholyte increases over 33%, operating

cell voltage will become high. The membrane is so designed that
the current efficiency should be optimum at the concentration
between 31.5% and 32.5%.

- 7 - I-A-3
(4) Flow rate of electrolyte

Depending on the good design of cell frame, electrolyte is Anolyte

circulating in the cell compartment by distributor in it as self- Inner circulation rate:
controlled state. 600-900l/hr.cell
The flow rate of electrolyte has the following purpose. Feed rate:
63-185 l/hr.cell
1) Homogenize electrolyte Catholyte
Inner circulation rate:
It is necessary to homogenize electrolyte concentration at not measured
membrane surface to avoid blister generation. Feed rate:
300 l/hr.cell
2) Release gas

Hydrogen gas and chlorine gas are generated in the cells

during electrolysis. The cells and the electrodes are
designed to release generated gas effectively from the
electrode and membrane surface. If electrolyte flow rate
decreases, cell voltage will increase because of high
gas/liquid ratio.
Therefore a sufficient amount of electrolyte flow rate must be
maintained.

3) Release heat

Generated heat during electrolysis is transferred across the

membrane from anolyte to catholyte by Na ion and water
transferred.
The heat is removed by electrolyte cooling.
Therefore, sufficient flow of electrolyte is necessary to remove
excess heat and to maintain the membrane temperature
- 8 - I-A-3
 homogeneous.

4) Control acidity
Anolyte flow rate is also decided to keep acidity lower than
a certain level in feed anolyte, even when sufficient amount
of hydrochloric acid is supplied to the Anolyte Compartments.

(5) Acidity of anolyte

OH- ion equivalent to (1-CE) back migrates from the Catholyte CE: current efficiency
Compartment to the Anolyte Compartment. To neutralize this OH- ion,
appropriate amount of hydrochloric acid shall be added to the
anolyte.

Fig. I-8
η： Current efficiency

- 9 - I-A-3
- 10 - I-A-3
1) Acidity and pH
The relation between anolyte acidity and pH depends on the
composition of anolyte, especially the content of SO42-.
Therefore, actual relation between acidity and pH shall be
obtained by using customer's brine. One example is shown
below in Fig. I-9.

Fig. I-9

- 11 - I-A-3
2) Acidity of anolyte and performance of membrane

The Asahi Kasei's membrane (ACIPLEX F-4401) is the perfluoro- High limit of acidity in feed
carboxylic acid type and shows its superior performance when it anolyte: 0.15 N
-
is in the state of -COO Na . +
If the carboxylic group is
changed into -COOH type, it can not work as an ion-exchange High limit of acidity in every
membrane. Therefore, it is max. 0.01 N extremely important to anolyte outlet: max. 0.01N
maintain the acidity of anolyte below a certain level or to
maintain pH of anolyte above a certain level.

At very low current density, which tends to occur at start up

or shut down, the control of acidity must be severer than in Fig. I-10
normal conditions because the amount of OH- ion transferred
through membrane is very small.
Therefore, on this occasion, it is necessary to decrease the
acidity (or to increase pH level) by reducing the addition of
hydrochloric acid.
In actual operation, flow rate of hydrochloric acid is adjusted
to maintain the acidity of return anolyte within a certain
range.

3) Acidity of anolyte and oxygen content in chlorine gas

The reaction on the anode is a competitive reaction of Cl - ion

and OH- ion, producing Cl2 and O2 respectively. If the acidity
of anolyte decreases, oxygen content in product chlorine gas
will increase as shown in Fig. I-10.

- 12 - I-A-3
4) Estimation of CE (current efficiency) based on acidity of
anolyte

As reduce the acidity of anolyte migration of OH- ion

equivalent to (l-CE) during electrolysis, current efficiency
can be calculated based on the difference of acidity between
feed anolyte and return anolyte.

This calculation is not precise enough but is convenient for

quick estimation of current efficiency.

CE : Current efficiency (%)

Ci : Acidity of inlet anolyte (N)
Co : Acidity of outlet anolyte (N)
Qi : Flow rate of inlet anolyte (= FICZ-230)(m3/hr)
Qo : Flow rate of outlet anolyte (= 0.77 x Qi)
0.77 :Depleted brine flow rate is 0.77 times feed
brine flow rate because H2O migrates from
anolyte compartment to catholyte compartment
I : Electric current applied to the electrolyzer (KA)
N : Number of cells installed in electrolyzer
Lc : Leak current ratio (%)0.36% at 110 cells/EL
O2/Cl2 : Oxygen content in chlorine gas (%):
0.5% at pH = 2 of anolyte outlet

- 13 - I-A-3
(6) Pressure difference across Membrane Fig. I-11

Fig. I-11 shows the effect of pressure difference on cell

voltage. The "positive" pressure difference effectively
reduces cell voltage. On the contrary, the "negative"
pressure difference increases cell voltage by 0.4 to 0.5
volt/cell. In actual operation of the electrolyzers, 0.4
mH2O of pressure difference at the top of cells is applied
between Catholyte and Anolyte Compartments.
If the pressure difference is excessive, the anode will be
deformed. On the contrary, if the pressure difference is
too low or negative, the membrane will be pin-holed by hard
rubbing on the both anode and cathode in a short period
operation. Therefore, it is necessary to maintain the
pressure difference within a certain range. The pressure
difference at the top of cells depends on the pressure pressure difference (cmH2O)
difference between hydrogen and chlorine gas pressure in the
outlet sub-header.

(7) Gas pressure

By increasing pressure in the cell, the gas volume in

electrolyte is reduced then the cell voltage decreases.
The increase in pressure, however, requires a stronger design Cl2 : 0.40 kg/cm2G (4.0 mH2O)
for cells and other related equipments, especially in view of H2 : 0.44 kg/cm2G (4.4 mH2O)
leakage of gas or liquid. To meet these requirements, the Gas dP : 0.04 kg/cm2G (0.4 mH2O)
product gas pressure is controlled at a specified level.

(8) Temperature of electrolyte Fig. I-12

- 14 - I-A-3
 Cell Voltage
Electric resistance of the electrolyte and the membrane decrease as
their temperature increase. In actual electrolysis, however, the
lowest cell voltage has been observed at about 90oC.

This is because the vaporization of water increases at temperature

higher than 90oC, causing large gas/liquid ratio. As is shown in
Fig. I-12,
a linear relation between cell voltage and operating temperature can

Cell voltage
be observed up to 88oC.

Since most of the heat is transferred to the Catholyte Compartment Temperature 88 90 92 ℃

across the membrane from anolyte during electrolysis, the
temperature of catholyte is controlled by catholyte cooler.

(9) Hydraulic press

A hydraulic press is composed of a fixed head, two rear heads, two

loose heads, two hydraulic cylinder and side bars.
The role of the hydraulic press is very important in the
electrolyzer system. If the pressure of the hydraulic press is
insufficient, cell liquid will leak out; if excessive, the membrane
will be damaged. Meanwhile, the hydraulic cylinder has lock nut
mechanism in order to lock the loose head. The purpose of locking
the loose head during electrolysis is to prevent from an excessive
seal pressure on the membranes between cells, which may be caused by
power failure or other troubles.
In case of power failure or other troubles for oil unit pump, it is
necessary to lock the loose head as soon as possible if it is not
locked yet.

- 15 - I-A-3
It is necessary to re-press the cells after start up until the loose
head stays at a constant position, since new gaskets tend to creep
and it takes more than 3 months for the loose head to settle on a
constant position (See Fig. I-13).

When the electrolyzer is energized, the loose head moves according

to heat expansion of cells and creep of gaskets. One example of
this movement is shown in Fig. I-14.

In order to seal liquid and gas without damaging membranes, proper

pressure must be applied by hydraulic cylinder. The relationship
between internal pressure and sealing pressure of electrolyzer is
shown in Fig. I-15.
In pressurized operation, hydraulic pressure is partially
compensated by internal pressure. So, sealing pressure is not so
high. (Point-A)
When internal pressure decreases, sealing pressure rises to point-B.
High sealing pressure at high temperature can cause deformation of
gaskets and membrane damage. Therefore, it is necessary to reduce
hydraulic pressure to point-C after locking loose head, in order to
get adequate sealing pressure even when internal pressure is
suddenly lost.

- 16 - I-A-3
- 17 - I-A-3
Fig. Ⅰ-15 Sealing Pressure vs Inner Pressure

Ps: Sealing Pressure (kg/cm2G)

Pi: Inner Pressure of Electrolyzer
2
(kg/cm G)

Poil: Oil Pressure (kg/cm2G)

Start-up: D→C→B→A
Shut-down
Unlocked: A→B
Locked: A→E→C

- 1 - I-B-2
 HYDRAULIC OIL PRESSURE AND LOCK NUTS POSITION

Hydraulic oil pressure (Kg/cm2G)

gas pressure
Operation stage of electrolyzer Lock nuts position
Atmospheric Raised

1) Electrolyzer maintenance 10 - Release

2) Pressure after membrane installation 70 - Release

3) membrane leakage test 70 - Release

4) Electrolyzer leakage test 90 - Release

5) Electrolytes filling 70 - 25 mm away

Connection to main lines
6) 90 90 25 mm away
(H2, Cl2 gas valve open)
7) Electrolytes circulation 90 90 25 mm away

8) Turn on DC-current 90 90 25mm away

9) H2, Cl2 gas pressure raising - 90 10-2 mm away

10) Reached to a stable temperature - 90 1-2 mm away

11) 2 hours passed at a stable temperature - 90 -> Lock -> 70 Lock the nuts

12) Shut down of unlocked electrolyzer 90 -> Lock -> 70 90 -> Lock -> 70

13) Shut down of locked electrolyzer Locked (70) Locked (70) Locked

14) Electrolytes draining and membrane washing 70 - Locked

- 2 - I-B-2
I-C Electrolyzer Operation
I-C-1 Alarm Signal List
Fig. No. Normal(at H L HH LL Remark
12.15KA/El)
FICZ-230 A-C 20.4 m3/H +20 % -20 % - -30 % Brine Feed :
Depending on KA
FICA-231 A-C (η=95%) 182 l/h +20 % -20 % max. KA x 24.2 - HCl : Depending
l/h on KA & η
FIZ-233 A-C 33 m3/H +20 % -20 % - -30 % Catholyte:
Independing on KA
FICA-205 5.2 m3/H +20 % -20 % DM water :
Depending on KA
TIA-232 A-C 88-90 oC 92 oC - - - Catholyte out temp

PHIA-231 A-C 2.2 3.0 2.0 - - Anolyte outlet PH

Rev in Oct
02
EdIZ-230 A-C 0 V + 1.0 V - 1.0 V + 2.0 V - 2.0 V Differential
voltage
PICZ-231 4.0 mH2O 5.0 mH2O 3.0 mH2O 7.0 mH2O - Cl2 gas

PICZ-233 4.4 mH2O 5.4 mH2O 3.4 mH2O 7.4 mH2O - H2 gas

PIZ-230 4.0 mH2O 5.0 mH2O - 7.0 mH2O - Cl2 gas

PIZ-232 4.4 mH2O 5.4 mH2O - 7.4 mH2O - H2 gas

PdIZ-234 0.4 mH2O 0.6 mH2O 0.2 mH2O 0.9 mH2O -0.1 mH2O Gas pressure
difference
TIA-231 A-C 40 - 60 oC 65 oC 35 oC - - Temp for PH meter

PA-230 110 kg/cm2G - 95 kg/cm2G - - Stand-by pump

start
automatically when
- 3 - I-B-2
 oil pressure down.
DC Current (5) – 12.15 KA 17.0 KA - 17.5 KA (15 sec) 0 KA
18.9 KA (instant)
Fig. No. Normal(at H L HH LL Remark
12.15KA/El)
LICA-200 90 % 100 % 80 % - - Brine Head Tank

TIA-230 60 oC 65 oC 55 oC - - Feed Brine Temp

LICZ-240 50 % 65 % 30 % 80 %(as HHH) 20 % Depleted Brine

70%(Both pump Tank
start)
FICA-240 7.4 m3/h +10 % -10 % - - Depleted Brine
Return Depending
on KA
TIA-240 88-90 oC 92 oC - - -

DIA-240 18.2 wt% 18.7 wt% 17.5 wt% - -

LICA-205 90 % 100 % 80 % Caustic Soda Head

Tank
LICZ-250 50 % 70 % 30 % 80 % 20 % Caustic Soda Tank

TIA-254 86 - 88 oC 89 oC - - - Caustic Soda Temp

TICA-223 83 oC 88 oC 78 oC - - Catholyte Inlet

Temp.
Depending on DC
current.
DIA-250 32.0 wt% 31.5 wt% 32.5 wt%

LIAS-260 15 - 20 % 90 % 20 % 100 % 15 % Anolyte Blow Down

[at AUTO] [Start] [Stop] Tank
LIAS-270 15 - 20 % 90 % 20 % 100 % 15 % Catholyte Blow
- 4 - I-B-2
 [at AUTO] [Start] [Stop] Down Tank
TIA-270 - 80 C o
20 oC - - Temp. of D-270

Revised in October 2002

Control Data Sheet for Tuning Parameter (for reference)

Control Parameter Control Parameter

Tag No. P I D Tag No. P I D
FICZ-230 A/B 400 16 0
FICA-231 A/B 250 20 0
FICA-205 350 20 0
PICZ-231 80 10 0
PICZ-233 70 9 0
LICZ-240 100 60 0
FICA-240 170 7 0
LICZ-205 100 70 0
TICA-260 200 100 0

- 5 - I-B-2
Note: Parameters are fixed after commissioning

I-C-2 Safety devices

In order to assure the safety of the Electrolysis plant the following devices are installed.

I-C-2.1 Automatic open circuit breaker of the rectifier

Electrolysis power for all electrolyzers is automatically shut down due to following signals.
(1) High level of Depleted Brine Tank or Caustic Soda Tank (LICZ-240 [HHH], LICZ-250 [HH])
(2) Excess high pressure of chlorine and/or hydrogen gas (PICZ-231, PIZ-230, PICZ-233, PIZ-232)
[HH]
(3) Abnormal gas pressure difference (PdIZ-234) [HH or LL]
(4) Emergency Stop button
(5) Stoppage of instrument air supply
(6) Process heavy failure signal (for example Cl2 compressor stop, H2 compressor stop & others)
(7) Grounding of Electrolyzer

*When all electrolyzers are shut down, the following signal is sent.
(1) All rectifiers are tripped and then all electrolyzer NLSW is opened.

Electrolysis power for each rectifier is automatically shut down due to following signals.
(1) Abnormal electrolysis voltage distribution in the electrolyzer (EdIZ-230A/B/C) [HH or LL]
(1) Abnormal flow rate of feed brine (FICZ-230A/B/C) [LL]
(2) Abnormal flow rate of feed catholyte (FIZ-233A/B/C) [LL]
(3) DC over current of Electrolyzer

*When each electrolyzer is shut down, the following signals are sent.
(1) Feed Brine (KV230A/B/C) close
(2) Purified Brine (KV231A/B/C) open
(3) Hydrochloric acid (FICA231A/B/C) close

- 6 - I-B-2
I-C-2.2 Other interlocking systems

(1) Brine supply for all electrolyzers is automatically stopped, when level of Depleted Brine Tank
shows abnormally high (LICZ-240) [HHH].
(2) Depleted Brine Pump are automatically stopped, when level of Depleted Brine Tank shows
abnormally low (LICZ-240) [LL].
(3) Caustic Soda Pump are automatically stopped, when level of Caustic Soda Tank of shows
abnormally low (LICZ-250) [LL]

- 7 - I-B-2
－ 1 － I-C-2
－ 2 － I-C-2
－ 3 － I-C-2
－ 4 － I-C-2
I-C-2.3 Details

(1) Abnormal electrolysis voltage distribution in the electrolyzer (EdIZ-230)

As electrolyzer has a potential distribution shown in Fig. I-16, I-17 the following bridge circuit
can be used as a detector for abnormal operation.
In the circuit, if the electrical potential at point B is adjusted to the same potential at point
A by changing variable resistance r, no voltage difference appears on voltage meter V.
If it is supposed that E1 is nearly equal to E2, a change of cell voltage in either half of the
electrolyzer can be detected in terms of the reading on V as + 1/2 (E1 - E2). A significant
change in the reading on V means unstable operating state of cell(s), such as increase in voltage,
short circuit, fluctuation in pressure etc. If it is extreme, the rectifier is automatically
tripped by EdIZ (high high or low low) and electrolysis power for the electrolyzer concerned is
stopped. Because EdIZ is the earliest alert for abnormal operation, close observation is required
especially at start up.

Fig. I-16 Fig. I-17

－ 5 － I-C-2
(2) PICZ-231, PIZ-230; PICZ-233, PIZ-232 and PdIZ-234 for Cl2/H2 gas pressure

If Cl2 and/or H2 gas pressure in Cl2 gas header and/or H2 gas header exceeds the set point of high
high alarm (H.H.A.) on PICZ-231 and/or PICZ-233, all rectifiers are automatically tripped and
electrolysis power supply for all electrolyzers is stopped. To ensure and back up this interlock
system,
PIZ-230/PIZ-232 are additionally installed for Cl2/H2 gas pressure respectively.
The pressure difference between Cl2 gas and H2 gas affects on the pressure difference between
Anolyte and Catholyte Compartments. Therefore, if the gas pressure difference exceeds the
specified value (high high or low low), the electrolysis power supply for all Electrolyzers is
stopped automatically by PdIZ-234 interlock system.

(3) Interlocking circuit for feeding system to each Electrolyzer

When a rectifier stops, corresponding Hydrochloric acid feed valve (FICA-231) is closed and brine
feed valve (KV-230) is closed and purified brine valve (KV-231) is opened, to purge Cl2 gas and
solved Cl2 in Anolyte.
Catholyte feed valve is manually closed at the same timing for closing of anolyte valve (KV231),
at least 15 min after the rectifiers stop. [Refer to I-E-1]

－ 6 － I-C-2
(4) Grounding relay

The point which has the same electrical potential as ground is the center of the electrolyzer.
In the circuit shown in Fig. I-18, volt meter can be adjusted to show 0 volt by changing variable
resistancer. If some position of electrolyzer happens to ground, volt meter shows some
fluctuation. The Rectifier stops when the range of fluctuation is wider than the specified range.

Fig. I-18

－ 7 － I-C-2
I-C-2.4 Emergency power

The following pumps are connected to the emergency power.

(1) Hydraulic Oil Pump for Electrolyzer press
(2) Caustic Soda Pump for filling caustic soda to the Electrolyzer (P-254A/B)
(3) Depleted Brine Pump (P-244A/B)
(4) Anolyte Blow Down Pump (P-260)

(5) Wash Water Pump (located at out of battery limit)

(6) De-Chlorination Tower Pump (located at out of battery limit)
(7) Sodium Sulfite Pump (located at out of battery limit)
(8) Demineralized Water Pump (located at out of battery limit)
(9) Cl2 Gas Absorber Blowers and Absorber Pumps (located at out of battery limit)

－ 8 － I-C-2
－ 1 － I-C-3
－ 2 － I-C-3
Ⅰ-C-3 Membrane leakage test

(1) Outline

This section describes the leakage test of membrane to check whether there is pin hole or
breakage on membrane or not.
This leakage test is carried out by pressurizing catholyte compartments with N2 gas while
anolyte compartments are kept empty and check gas leaking rate through membrane.
If certain membrane shows a leakage rate of over limit, it must be replaced to a new or
repaired membrane.

Membrane leakage test is carried out in the following cases [refer to Page 5 (5) in I-C-3].

(a) When membrane is installed (initial installation, membrane replacement, gasket replacement)
(b) Before start up after the long period shut-down of electrolyzer more than 4 weeks.
(c) When membrane leakage is suspected.
(d) Before dismounting of all the membranes from an electrolyzer.
(This information of each membrane leakage is useful in checking for anode and/or cathode
damage of each cell unit.)

－ 1 － I-C-3
 (2) Preparation

1) Disconnect EdI-230 cables

2) Open following valves: Anolyte; 7, 19, 41
Catholyte; 8, 20, 10, 42
3) Confirm N2 gas bubbling in D-237 and pressure at 500 mmH2O on PCV-237.
Note: If excess pressure will be applied, it leads excess pressure difference, and then it
may be generate some damages for membrane.
4) Confirm hydraulic pressure at 70 kg/cm2G
5) Prepare soap solution, rotameter, torque wrench and recording sheet for leakage test.
6) Disconnect anolyte outlet hoses from cell nozzles only.
7) Open 17 and 11 to fill water to the half height of anolyte inlet hoses, and then close 17 and
11.
8) Connect a hose to 26 and the coupler of N2 gas line from D-237. However, keep closing 26.

(3) Pressurization of Catholyte compartments with N2

1) Close 8, then open 26 and the block valve of N2 gas line from D-237 to introduce N2, and
confirm
N2 gas pressure at 500 mmH2O on PCV-237. Adjust the N2 flow rate around 5 Nm3/hr at FI-236 at
the beginning of pressurization. N 2 flow rate goes down and reach to 0 Nm 3/hr with
pressurization．
2) Keep Catholyte Compartments at around 0.05 kg/cm2G (0.5mH2O) on water level gauge.
It is also confirmed on PI-232A/B/C.

－ 2 － I-C-3
(4) Membrane leakage test

1) After N2 flow rate becomes 0 Nm3/hr and pressure in catholyte compartment at 0.05 kg/cm2G
(0.5mH2O)
on water level gauge (or PI-232A/B/c), carry out 'Soap check' on each anolyte outlet nozzle
waiting
10 seconds per each cell.
2) If some leakage is detected by 'Soap check', set a rotameter on the anolyte outlet nozzle
of
the membrane, then measure and record the N2 flow rate on the rotameter.
3) Repeat step – 2) for the all membranes.
4) After finish membrane leakage test, close 26 and the block valve of N2 gas line for D-237,
and open 8 to depressurize.
5) Open 13 to drain water in anolyte inlet header, and then close 13.
6) If there are the membranes which leakage has over 10 l/hr on N2 flow, replace them and carry
out membrane leakage test again for all membranes.
7) Connect EdIZ-230 cables.
8) Connect anolyte outlet hoses.

－ 3 － I-C-3
(5) Necessity of membrane leakage test

If pin-holed membrane is operated, it might cause following troubles.

1) Concentration increase of H2 gas in Cl2 gas

excess ・Explosion in Cl2 Drying Tower or in the Electrolyzer by mixture of H 2 gas and Cl2
gas

2) Anode damage by back migrated NaOH passed through Membrane pinholes

excess ・Anode destruction (Falling down due to alkali attack)

・membrane tear due to anode destruction
・Cell frame damage (Leakage of NaOH to Anolyte Compartment)
・Short service life of anode and cell frame

3) Cathode damage by Cl2 gas passed through membrane pinholes

excess ・Cathode destruction (corrosion)

・Short service life of cathode

4) NaCl concentration increase in caustic soda

excess ・Production of off-spec. NaOH

5) Cell gasket eating at membrane pinhole parts by hypo (NaClO)

excess ・Electrolyte blow-out

・Short service life of cell gasket

－ 4 － I-C-3
(6) Occasion membrane leakage test have to be done

To avoid above trouble, membrane leakage test has to be done in the following cases.
Note: membrane is made of thin plastic film.

1) When membrane is installed

(a) Initial installation of membrane
(b) membrane replacement
(c) Cell gasket or cell frame replacement

2) Before electrolyzer start up after shut down for a long time

(a) Shut down for a long time (about four weeks)
(b) Annual shut down

3) When membrane leakage is suspected during shut down and start up procedure which include
draining,
filling and Electrolyzer leakage test
(a) Excess high differential pressure across membrane: more than 2.0 mH2O
(b) Excess low differential pressure across membrane: less than -0.2 mH2O
i.e. reverse pressure
difference
(c) In the case of continuous liquid flow in particular anolyte outlet hose when
electrolyzer outlet valves are opened before the electrolyte circulation step in the
electrolyzer start up procedure.

4) When membrane leakage is suspected during electrolyzer running

(a) Color change of anolyte outlet hose: pink, purple or transparent
(b) Anolyte PH: abnormal HCl consumption or fluctuation in flow rate
(c) H2/Cl2: more than 0.3%
(d) Cell voltage: unstable or high, low (±0.1V) voltage
(e) Excess high differential pressure across membrane: more than 2.0 mH2O
(f) Excess low differential pressure across membrane: less than 0.0 mH2O
(g) EdIZ indication: shift more than ±0.1 voltage from the stable value.

5) When electrolyzer is operated without membrane leakage test more than 6 months, as occasion
offers such as annual shutdown.
－ 5 － I-C-3
－ 6 － I-C-3
I-C-4 Electrolyzer leakage test and air purge

(1) Outline

This section describes the Electrolyzer leakage test in order to check leakage of the assembling
of Electrolyzer after the membrane leakage test completed.
This Electrolyzer leakage test is carried out by pressurizing Anolyte and Catholyte Compartments
with D.M. water and checking the leakage outside.
After the leakage test, D.M. water is drained with introducing N2 gas into Catholyte Compartments
to avoid air suck.

* The liquid level in electrolyzer can be measured by transparent tubes connected to valve 41 and
42 at filling and draining procedure.

(2) Preparation

1) Connect a hose to 26 and coupler of N2 gas line for SP-236 or 237.

2) Ensure following valves are opened: Anolyte; 7, 19, 41
Catholyte; 8, 10, 20, 42
3) 2
Adjust hydraulic pressure at 70 kg/cm G.

(3) Filling with demineralized (D.M.) water

1) Open catholyte 18 and 12, and then anolyte 17 and 11 keeping a positive differential of 0.3
to 0.5mH2O on cathode side. Flow rates of D.M. water are about 15 m3/hr at FI-232 and FI-
235.
2) When water comes out from outlet nozzles, reduce water flow to 5 m3/hr by slightly closing
12 and 11.
3) When water overflows to the sight glass SG-231 of overflow line for catholyte, close 12.
4) When water overflows to the sight glass SG-230 of overflow line for anolyte, close 11.

-1- I–C-4
(4) Electrolyzer leakage test

1) Increase hydraulic press to 90 kg/cm2G.

2) Close 7, 8 and then close 41, 42.
3) Slowly open 12 then open 11 to increase inlet pressure to 0.6 kg/cm2G keeping Pressure
difference around 0.2 mH2O between PI-230 and PI-232, and then close 12 and 11.
4) Check leakage water from Electrolyzer (cell gaskets, hose gaskets, cells themselves and valves
around Electrolyzer).
5) Slowly and synchronously open 7 and 8 to release pressure (Open 7 a little bit earlier than 8)
after finishing Electrolyzer leakage test.
6) Reduce hydraulic press to 70 kg/cm2.

(5) 1st Draining (with N2 feed to catholyte in order to purge air)

1) Close 8 after confirming water not to overflow to the sight glass SG-231 and confirm 7 and 19
are opened.
2) Open 41 and 42.
3) Connect N2 gas line for draining (D-238 or D237).
4) Open 26 and the block valve to D-238, adjust N2 flow rate at around 30 Nm3/hr and confirm the
pressure of PI-238 or FI-237 about 0.05 kg/cm2G.
5) Open 15 then open 16 to drain water in outlet headers. (Keep positive pressure in the
catholyte outlet sub-header on PI-232)
6) Wait 10 minutes, after outlet flexible hoses are empty, then close 15 and 16.
7) Open 13 then open 28.
Maintain catholyte outlet sub-header pressure positive on PI-232 by throttling valve 18.
Use valve 13 or 28 to regulate drainage so that catholyte side remains between 0.3 and 0.5
mH2O higher than anolyte side on water level gauges from Z-type cell.
8) After finishing to drain water out of Anolyte and Catholyte Compartments, close 13, 28 and 26,
then close the block valve of N2 gas line for draining (D-238 or D237).

-2- I–C-4
Revised in October, 2002
(6) Filling with D.M. Water and 2nd Draining

This procedure is operated to purge air in Catholyte Compartments.

(1) Open 8 and confirm 7, 19, 41 and 20, 42 are opened.

(2) Open 12 then open 11, keeping a positive differential of 0.3 to 0.5 mH2O on catholyte side
on water level gauges from Z-type cell. Flow rates of D.M. water are about 15 m3/hr at FI-
235 and FI-232.
(3) When water comes out from outlet nozzles, reduce water flow to 5 m3/hr by slightly closing
12 and 11.
(4) When water fills the catholyte outlet sub-header and into the hoses, close 12.
(5) When water fills the anolyte to outlet sub-header and into the hoses, close 11.
(6) Close 8 and confirm 7 and 19 are opened.
(7) Open 26 and the block valve of N 2 gas line for draining (D-238 or D-237), adjust N2 flow
rate at around 30 Nm3/hr and confirm the pressure of PI-232 about 0.05 kg/cm2G.
(8) Open 15 then open 16 to drain water in outlet headers. (Keep positive pressure in the
catholyte outlet sub-header on PI-312)
(9) Wait 10 minutes, after outlet flexible hoses are empty, then close 15 and 16.

(10) Open 13 then open 28.

Maintain catholyte outlet sub-header pressure positive on PI-232 by using valve 28.
Use valve 13 or 28 to regulate drainage so that catholyte side remains between 0.3 and 0.5
mH2O higher than anolyte side on water level gauges from Z-type cell.
(11) After finishing to drain water out of Anolyte and Catholyte Compartments, close 13 and 28.
(12) Confirm N2 gas flow rate at 0 Nm3/hr on FI-236 and N2 gas pressure at 0.5 mH2O on PCV-238 or
PCV-237.

* If Start-up operation (Electrolyte filling operation) can't make immediately progress after
finishing this procedure, set the electrolyzer “waiting state” [refer to (4)] “Waiting” in
P2 of I-E-4].

-3- I–C-4