Operation Manual for Perfluorinated ion-exchange membrane

which used in Chlor-alkali industry

Our Perfluorinated ion-exchange membrane is cation exchange membrane which can be the
Separation membrane in NaCl and KCl Electrolysis. Cation ion, Na+ ion or K+ ion can pass the
membrane in the electric field, Cl- or OH- will be obstructed by this kind of membrane.

This Manual provide right operating method focus on membrane which used in Chlor-alkali industry,
Perfluorinated ion-exchange membrane can be used in 15-32 ％ NaOH production.
Thinkre company and our cooperate factory summarize rules in years, which can extend the lifetime of the
membrane and get the best performance. If Customers use the membrane without accordance these
instructions, our company will not be responsible for the production.
Prepared with Mercury method, Use the Perfluorinated ion-exchange membrane Can save 25% electricity
and steam.

Security
This product does not cause skin disease without protective clothing. Somebody’s skin may be allergy, if
they touch it in a long time. If you operate with the Operation Manual, it will be security.
Oral Toxicity Testing Laboratory to mouse, it is Low toxicity. LD > 20000mg/kg.
The membrane will not fire in the air but will be fire in the Oxygen-rich environment.
The membrane will decompose when the environment temperature is above 150 ℃. If film fire, the Firefighters should wear
insulated air respirator and protective clothing to prevent mist and suspended micro particles.

Waste
This membrane rubbish can’t be decomposing naturally, we always manage the membrane rubbish through bury them in
land. It can be burned with other rubbish, but you need to get the exhaust gas to lye to Remove acidic fluorides.

Security to chlor-alkali industry

Perfluorinated ion-exchange membrane is a kind of Polymer film which can separate the NaCl solution、Cl2、H2、NaOH
solution continuousIF the H2 mix with Cl2, or Cl2 mix with H2、air, the electrolyzer maybe explode. So, you must keep the
membrane complete, and operate with the regulations.22

Please keep the membrane intact.

Membrane must be installed in strict accordance with instructions and technical procedures for the
supplier's recommendations, beware of pinholes or membrane tearing.
Pretreatment and membrane installation is required in accordance with this specification and technical
proposals from vendors operating procedures, to prevent wear and tear due to membrane wrinkling caused
by the generation of pinholes. Membrane installed, before the test technology suppliers must follow the
recommended steps to check whether the entire cell leakage. Stand the film under the conditions required
to maintain its moisture, to prevent tear film. Electrolyzer also need to maintain a certain humidity.
Operate in strict accordance with procedures to ensure that the membrane differential pressure (DP) stable,
pressure will lead to abnormal membrane damage. If there is a sudden stop or severely abnormal
phenomenon, should be checked again before driving each cell for leaks.

Additional safety measures

The amount of hydrogen for chlorine analysis of monitoring, the proposal must install continuous
analyzer. Before driving or parking period shall be aggregated using nitrogen purge tube of hydrogen.
Overall the tube during parking shall remove chlorine to protect the electrodes and membrane from the
reverse current effects and remove any materials react with hydrogen. Mixture of hydrogen and air can
cause an explosion, it is also
To use a nitrogen purge tube summarized in chlorine, cannot be used to clear the air. During the stop,
they must immediately clear summary of all the major gas pressure within the tube DP, until all the gas is
summarized tube blow. Otherwise, when the membrane is damaged, the pressure difference DP will cause
a mixture of substances within the cell.
Membrane handling and installation
Caustic treatment to be careful to avoid pinholes, creases or scratches. All surfaces in contact with the
membrane should be smooth and not have the slightest uneven. What is involved here is the surface of
receipt, inspection, storage, pretreatment, cut and install the device surface and the cell membrane surface
of the member.
Membrane transport, to film rolled up on a diameter of at least 100 mm cylinder. If the above
method cann ot be used, then the film transport fixed flat to avoid wrinkling the film, folded or
curled. Unnecessary multiple handling will increase the likelihood of membrane suffer physical damage.
Shipping instructions
Membrane will be shipping by dry, Packing with PVC pipe, and the PVC pipe will
be packed in wooden box. You should keep the environment temperature is in 5℃ to 45℃。And keep the
environment humidity is in 30% to 60%.
Storage Conditions
By the following method, the membrane can be stored for a long time:
Best storage method is to store the original sealed cylindrical flat membrane. If the original shipping
seal cartridge cannot be used, then the requirements:
The film flat, fixed.
May not be membrane folds, folded, or stretched.
- To prevent mechanical damage, dust, sand, and other friction materials for membrane damage.
Membrane suitable storage temperature is between 2 ℃ and 50 ℃ between. To avoid temperature
extremes, such as cold to freezing temperatures or direct sunlight induced surge.
Membrane unpacking and handling is required before:
- The temperature of the film is greater than 15 ℃. (Eg, the packaging film is placed in a treatment
plant before unpacking within 24 hours).
- Ensure the relative humidity greater than 40% and less than 85%, to prevent curl or dimensional
change film.
Cut processing
Membrane can be directly used knives, blades or scissors for cutting.
To prevent an operator from injury and prevent damage to the membrane cut should establish a set of
Safety rules
- Operator protective facilities.
- Choice of appropriate tools, utility knife sharpening regularly.
- The selected operators and equipment when trimming the best location. Film cutting table
should be clean and smooth.
 - Bolts, screws should be installed in place.
- Table to be rounded corners.
Need to be careful when installing the membrane:
- Move to avoid membrane folding, wrinkling.
- The whole film is placed flat on the table.
The size will vary membrane humidity changes. For example, the membrane from a relatively dry environment
(humidity 20%) moved to wetter conditions (humidity 90%), and its size will increase by 1 - 2%.
Pretreatment
Membrane before installation should be pre-expansion under operating conditions to prevent wrinkling.
Commercially available dry soaked in lye needed expansion.
Some cell operating conditions require further expansion of the membrane to prevent membrane wrinkling
during operation. In this case, the hot water treatment of the film can be further expanded (water not more
than 60 degrees)
Subjected to alkali operation, please follow the safety precautions.
Solution for membrane expansion deionized water or water to soft water, the final solution hardness than
5ppm. (Calcium and magnesium levels were converted into calcium content)
Technology provider to determine alkaline ph. Generally, by adding sodium hydroxide to adjust the pH to
11-12 (no pH indicating time, the preparation of the sodium hydroxide solution of 0.1% concentration can be).
Per square meter of film processing needs at least five liters lye. In addition, the depth of lye to fully cover
film (about 3-5 cm) is appropriate.
Immersion time of 4-12 hours at a temperature of 18-40 ℃.
The membrane can be hanged or horizontally to evenly impregnated into the pool.
The film cannot be folded or crumpled. If possible, remove the film from the packaging tube directly into
the dipping pool.

The membranes were flat type alkaline treatment, membrane separation between the need to screen,
but should pay attention to:
Installation
Film handling
When the membrane from the storage (or pre-) when removing the container must not be folded,
crumpled or abrasions.
Film after removing the container from the pre-installed immediately in order to prevent the membrane
from drying out.
Take into account the weight of the film and its softness, wet film fetch at least two people to operate.
Sealed and lubricated
For best performance, you need gasket sealant coating / release agent: To prevent membrane
electrolyzer repair gasket stuck in the groove. Shims between the anolyte and membrane
leakage.
Lubricated gasket surfaces to prevent tearing of the membrane fastening gasket.
Sealant / release agent is selected according to the type of membrane and its mounting techniques may
be used.
Note: Regardless of what kind of sealant use / release agent, are not able to use it for membrane
reactor surfaces. Otherwise, the film would work in cell damage.
Installed into the cell membrane

Film Before installation, please check the electrode and remove bumps or burrs.
Attention relatively smooth side of the film, one side is rough, place the smooth side of the high-
pressure side of the face
Carefully place the wet membrane electrode side. Avoid dragging the edge of the metal membrane.
If wrinkling or asymmetric membrane installation, please pull the film from the metal, re- reset the
installation.
Hoisting hook membrane should be no glitches, smooth edges. Avoid pulling too tight membrane.
The installation process, the film should remain moist (including exposure to the periphery of the cell
membrane). If necessary, the membrane with the alkaline spray.
After installation , to be in the cathode chamber and the anode chamber add a small amount of solution ,
aggregate import and export of pipe should be sealed after installation , to be in the cathode chamber and
the anode chamber to add a small amount of solution , aggregate import and export of pipe should be
sealed to keep the electrolysis 100% humidity tank . Pretreatment solution or the solution chosen
deionized water should electrodes provider to ensure that the processing solution used will not damage
the electrodes.
If the cell membrane becomes dry before installation, then the pre-treatment process failure. If the
membrane in the electrolytic cell dry phenomenon generated after installation, during normal operation in
the film will shrink and produce excessive wrinkles. Thus, affecting the life of the membrane.

Electrolyzer operation
Cell operating procedures vary according to their design. The purpose of these rules is to get the best
performance and the longest film membrane life, and technology providers about the entire cell system
operating procedures to be added.
New film test
The anode chamber into the salt (sodium chloride concentration greater than 210g /L, PH greater
than 2); cathode chamber into the concentration of 15-20wt% of the lye, the maximum not more than 28%.
Adding electrolyte to the cell, the cathode chamber is slightly faster feed rate, the membrane close to
the anode.
Current is applied before the first cell was heated to a minimum 70℃ (max not more than 85 ℃).
Note: If test delay, the electrolyte will penetrate the membrane caused by concentration. Test occurred
after a delay, the need for alkaline and saline concentrations were analyzed and adjusted.

According to the proposed increase in technology suppliers electrolyzer current, but cell voltage shall
not exceed 4V. Description electrolyzer working voltage is too high a problem. If the voltage exceeds 4V
and high, you must stop and check and troubleshooting.
After driving the first 24 hours, the need to maintain the current strength of less than 4kA/m2. 24 hours
later, according to the technology supplier's recommendations to further improve the current rate of
increase.
Be sure to follow the recommendation of the data in Table 1, we must use a qualified continuous
monitoring instrumentation and alarm device. The instrument used to spend far less significant
membrane damage losses. Significant membrane damage caused by chlorine and hydrogen, air mixing
and may even cause an explosion hazard.

- Condition for the rapid and sudden occurrence of membrane damage caused by the instrument
monitoring is particularly important. (Such as the anolyte pH, the flow rate of the feed brine, the
concentration of the anolyte or abnormal)
- Alarm device can be used to indicate the cell voltage increase caused by the conditions (such as
the anolyte pH, electrolyte concentration or temperature anomalies), such as pay attention monitor may
cause membrane damage.
Electrobath
Electric current According to the need to control the current density Constantly

Current density1 1.5-6.0kA/m2 constantly

Voltage Less than 4.0V(High voltage means high alkali Constantly2
concentration, low PH and other situation, at this time,
the film is easy be hurt)

Current efficiency Decide the operating condition of the film If need

Anode chamber (saltwater)

Feed brine Sodium chloride concentration is > 210g/L Constantly6
concentration3.4.5

Feed brine flow rate According to the need to control the anolyte concentration Constantly2

Amount of added acid7 According to the need to control the anolyte concentration Constantly2

Anolyte concentration3.4 Sodium chloride concentration200±30g/L Constantly2.8.9

Anode liquid acidity3.6 PH > 2 Constantly2

Sodium chloride content Sodium chloride concentration<20g/L Once/Day

in anode fluid4

Anode fluid temperature 80-90℃ Constantly

Feed brine impurities

Calcium Once/8hours
/magnesium See Table 2
Strontium Once a week
Sodium sulfate (Impurity content limit for reference) Once per day
Iodine Once a week
Barium Once a week
Aluminum Once a week
Silicate Once a week
Specification Operate conditions Frequency of
monitorin
 200,000ohm-cm
Cathode chamber main monitoring water resistance, water resistance, more than 200000 ohm - cm

Impurity Restriction Restriction physical effects Performance Treatment

＜4kA/m2 4-6kA/m 2
impact

Calcium Calcium magnesium Calcium Deposition on Reduced to 80% of Cation exchange process
hybrid magnesium the membrane current efficiency
＜30ppb hybrid＜20ppb
Magnesium As above As above As above Boosted voltage flocculation process in
saltwater first, filter after quietly
keep. Then cation exchange
process

Strontium ＜500ppb ＜400ppb As above Less than Ca cation exchange process

(Strontium into the resin
bed is faster than
calcium and magnesium)

Barium ＜1ppm ＜500ppb As above Less than Flocculation process and

Ca, Strontium cation exchange barium
part will be removed

Sodium In sodium sulfate In sodium diffusion through Concentration of Precipitation or form of

sulfate ＜10g/L sulfate the membrane, more than 10 g/L calcium, barium or use
(1)
＜8g/L so me will cause current saltwater to clean
Deposition on efficiency
the membrane decreased

Iodine ＜1ppm ＜200ppb Extremely easily reduced current There is no way to

in the fluid of efficiency to the remove the iodine in the
the anode original 80-85%, saltwater and saltwater
oxidation into affects on the washing will reduce
iodate, after current efficiency some of its content
entering is not big
membrane, is
oxidized to
 When high
concentration,
sodium periodate
can deposit on
the ion
membrane,
membrane
damage. Low
concentration,
and alkaline
earth metal
cations with
precipitation

Aluminum ＜ 100ppb, In ＜ 100ppb, In In acidic May reduce the Carefully and quietly
Silicate SiO , ＜10ppm
2
SiO , ＜6ppm
2
condition, current efficiency keep the original salt
aluminum, for the original water, then the filter
dissolve, type 90-93% will control the
I square impurity content
aluminum
silicate
Deposition in
ionic
membrane
TOC ＜7ppm ＜7ppm Ause the Increased Control TOC of water,
t
Organic anolyte blister voltage, reduce salt or TOC in the
matter

Or ionic the electric effect pipeline system

membrane and ionic
expansion membrane
permanently
damaged

Sodium ＜20g/L ＜20g/L Affect the Increase content Cleaning or filter in the
chlorate Content of of sodium loop
Sodium chlorate in
th
chloride alkali
 Membrane possibility of mechanical damage

Operating conditions
Operating conditions on membrane performance
Users should understand the different operating conditions have what effect on the
membrane. This will extend the life of the membrane and to analyze the cause operational failure
occurs.
Electrolyzer conditions
Current density
Recommended current density range 1.5-6.0kA/m2
Current density exceeds 6 kA/m2, depending on operating conditions and other factors, it
may exceed the maximum capacity of the membrane. At this point film may be subject to
physical damage, the current efficiency decreases.
Current density is less than 1.5 kA/m2, the film will not be damaged, but the current
efficiency drops, the current density is normal can be restored.
Cyclical changes in the current density can effectively save electricity. At the same time to
adjust the anolyte and the catholyte concentration, to ensure that the current density is changed
during the constant concentration of electrolyte.

Cell temperature
Recommended temperature range: 80-95 ℃.
Temperature less than 80 ℃ , the film conductivity decreased, the current efficiency. Higher current
density, the greater the risk of damage to the membrane.
When the temperature exceeds 95 ℃, the gas mass produced. Membranes swell and produce wrinkles.
 Electrode spacing
The distance between the cathode and the membrane is narrowed, fluid resistance of the
cathode voltage decreases. 2-3mm spacing is less than occurs when the "gas blocking" and cause
a voltage rise.

Membrane Pressure
Cathode- side fluid pressure is standard. Proper pressure is achieved by specific
cell experiments may be, pressure to maintain the membrane toward the anode and
minimizes vibration, or vibration can cause prolonged wear or other membrane
damage.
Due to an increase or decrease in electrolyte interior piping or obstruction due to a
sudden change in pressure generated will result in membrane electrode breakage or
tearing.?
Pressure is too high:
- Film will be pressed into the anode and deformation. Electrode shape shadow
Rang it.
Film is too close to the anode will be blocked and the anode outlet
Bubbling.
Resulting voltage is increased, the chamber salt depletion, the membrane will be affected by
Loss.

Membrane damage (de otro paper)

Membrane damage is frequently due to brine impurities. Other causes include upset in operating
conditions, particularly catholyte concentration above 36% NaOH, anolyte concentration below
170 g/l NaCl, anolyte pH below 2, and mechanical damage (Fig. 5.27). The damage evident in
Figure 5.27 is believed to be due to abrasion by the cathode, caused by wide variations in the pressure
differential between the two compartments. As the cations move through the membrane, they drag
along a certain amount of water of hydration. This is desirable because removal of water from the
anolyte reduces the amount of depleted anolyte that needs to be resaturated. Transport of about 5.5
mol of water per sodium ion would be optimum, because it is the amount necessary to form
32–34% sodium hydroxide in the cathode compartment without any additional water feed to that
compartment. Actual water transport is about 4 mol/Na+. The operating temperature of the cells is maintained
near 90°C. In the range of 75–90°C, the cell voltage drops about 8 mV for each degree of temperature
increase. Any further increase in operating temperature would result in a prohibitive increase in the volume of
the gas release, as the boiling point of the electrolyte is approached. Development of the BM 2.7 electrolyzer is
continuing. Version 5, planned for introduction in 2007, is designed for a power consumption of less than
2000 kWh/t of NaOH at a CD of 6 kA/m2. The NaCl content of the 32% NaOH will be less than 10 ppm. The
performance improvement of the BM 2.7 electrolyzer versions 3, 4, and 5 is shown in Table 5.6.

3.2. Influence of Temperature on the Conductivity

To demonstrate the effect of temperature on conductivity, different solutions were used: 0.5 g/L NaCl and 0.5
g/L
NaOH. Conductivity measurements were taken for each solution set at 23, 28, 33, 38, 43 and 50°C. The
experimental conductivity values for each solution are shown in figure 3.

Figure 3. Effect of temperature on the conductivity of 0.5 g/L NaCl and 0.5 g/L NaOH.
The temperature profile has a great impact on the electrolyte conductivity. For example, the brine conductivity
at 23°C is 973.8 µS/cm and by increasing the temperature at 28°C, its conductivity increases to 1077.54
µS/cm. This could be related to the mobility of ions. As the matter of fact, by increasing the temperature of
 solution, the mobility of ions (Na+, Cl- for NaCl and Na+, NaOH- for NaOH) in solution also increases, and
consequently this will lead to an increase in its conductivity. Additionally, different ionic species show
different effects with temperature which is due to the size of the ion and its charge density. This study shows
the conductivity response to temperature of 0.5 g/L NaCl compared to 0.5 g/L NaOH. The ion OH-, being
smaller than Cl-, has a higher charge density and hence the conductivity of a solution of the same
concentration is greater.
From figure 3 it can be concluded that the optimum electrolyte conductivity value was observed for higher
temperatures. The cell performance improved with electrolyte temperature [16]. This positive contribution
could be related to the internal kinetic processes, which are normally exponentially temperature dependent,
and to the NaCl and NaOH conductivity increase. Authors [17] reported that cell temperature was one of the
most striking parameters on the cell voltage with contribution percentage of 23%. However, the increase in the
temperature is limited by the behavior of electrolyzer materials and at temperatures higher than 90°C the
amount of water vapor increases tremendously, while the membrane stability decreases [20]. In addition, the
membrane stability may decrease due to decarboxylation for temperatures higher than 90°C [21]. At industrial
scale, physical damage to the membrane (blistering) becomes more likely to occur at temperatures lower than
75°C. It is usually recommended to operate in the range 80 - 90°C [16].
In these experiments, the value of 80°C was retained for chlor-alkali production. The anolyte and catholyte
temperatures must be similar (80°C) in both compartments. This value is in agreement which the value
previously reported [16, 21].