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INTRODUCTION

Chloroalkali technology is one of the largest electrochemical industries in the world. Main products being Caustic, Chlorine and Hydrogen is generated by the electrolysis of Sodium Chloride, which is energy intensive. Chloroalkali industries is the 2nd largest consumer of electricity next to aluminum. Chloroalkali plants are notable for wide variety of hazards inherent in their operation.

These include: To hazards chlorine is a notoriously toxic gas. Explosive hazards Hydrogen forms explosive mixtures with Air or Chlorine. Corrosive hazards These results from stray electric currents as well as wet chlorine hypo chlorite and strong acids. Electrical hazards High direct current are used in the electrolytic process
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Chlorine is a very useful but Hazardous Chemical

Chlorine finds versatile application in our daily life starting from drinking water chlorination to sanitation, insecticides, pesticide, agriculture, drugs, pharmaceuticals, automobiles, paper, textiles, plastic and many more. Chlorine is a very useful & indispensable chemical. Chlorine is also very hazardous & toxic because of its properties.

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Properties of Chlorine
Chlorine is a gas because its boiling points is -340 C which is less than ambient temperature. Due to low boiling point (-340 C) It rapidly volatilizes when released from storage tanks and Tonners to the atmosphere. Chlorine is liquefiable under pressure, because its critical temperature is1440 C Vapour Pressure of chlorine at 550 C: About 16 Bars (absolute) and increases to about 20 Bars (absolute) at 650 C. Toxic and Corrosive when water / moisture is present due to formation of Hypochlorous acid which further dissociates to Hydrochloric acid and nascent oxygen. Yellow chlorine Hydrate (Cl2..8 H2O) may crystallize below 9.40 C at atmospheric Pressure and therefore chlorine pipe lines may choke in cold weather. Chlorine has ill effect on the human health.
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HAZARDS ASSOCIATED WITH CHLORINE

Chlorine is very reactive gas, hardly found in free state. 0.15% is available in combined state only. Threshold value are as under Odor threshold 0.31 ppm PEL (OSHA) 1 ppm TLV-STEL (ACGIH) 3 ppm IDLH (NIOSH,MSHA) 10 ppm Chlorine was used during world war 1 as a choking (pulmonary) agent. Recently in 2007 about 30 tons chlorine was used in Iraq war. Extent of poisoning depends on amount of chlorine, how exposure take place and length of time. Exposure signs Coughing Chest tightness burning sensation in hose, throat, eyes watery eyes blurred vision Nausea & vomiting Burning pain, redness, blisters on skin, frost bite in case of liquid chlorine. Difficulty in breathing Fluid in the lungs with 2-4 hrs.

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Contd..
Long terms effects are not found in people who survive sudden exposure. High potential for terrorist use, as readily available. Natural element extremely oxidizing. Combine with water forms hydrochlorous and hydrochloric acid and oxygen free radicals. All cause major tissue damages. Possibility of public exposure during transportation and water treatment use. Corrosion due to leakage. Contamination with other liquid chlorine in storage can cause explosion. Formation of NCl3 in liquid chlorine in storage can cause explosion. Chlorine toner valve leakage. Exposure of chlorine toner to high temperature or fire. Immediate reaction of dry chlorine with titanium. Over chlorination is absorption and water chlorination. Explosive with hydrogen in presence of moisture. Iron fire at 251 o C. Exothermic reaction with organic/oil/grease. Cl2 gas liquefies in pipeline under external temp condition. Liq Cl2 expands with rise in temp Also pressure rises with temp.
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Physiological effects of various concentrations of Chlorine Gas on Human Beings.

S.no. (1) i) (2) Least amount required to produce slight symptoms after several hours of exposure Effects Chlorine Concentration by Volume (ppm) (3)
1.0

ii)
iii) iv)

Least detectable odour

Maximum amount that may be inhaled for 1 hour without serious disturbances Noxiousness, impossible to breathe for several minutes

3.5
4.0 5.0

v)
vi)

Least amount required to cause irritation of throat

Least amount required to cause coughing

15.1
30.2

vii)
viii)

Amount dangerous in 30 minutes to 1 hour

Amount likely to be fatal after few deep breaths

40 to 60
1000.0
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Hazards Associated with Chlorine usage (contd)

Release of chlorine is usually a flashing (two-phase) jet with small liquid aerosols drops embedded since when liquid chlorine is released, it flashes off more and more and simultaneously expand to vapour creating a turbulence, which causes the remaining liquid to be broken up into an aerosols (small drops) and is carried along with the flashed vapour. The aerosol usually evaporates within a short period, leaving a cold dense cloud of chlorine gas. Usually no significant liquid pool is formed under the Chlorine container.

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Hazards Associated with Chlorine usage (contd)

A liquid pool may form if ambient temperatures are cold and/or the chlorine is semi refrigerated. For holes with diameters larger than a few mm, the contents of a Tonner are released very fast and thus very less time is available for emergency response. Develops high hydraulic pressure in overfilled tonners or overfilled bullets or in liquid full pipelines. This hydraulic pressure is sufficient to cause bursting of tonners or bullets or pipelines with 1 to 3 degree C temperature rise.

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Hazards Associated with Chlorine usage (contd)

Chlorine reacts violently with substance such as oils, greases, paints, some solvents etc. it will also react with steel wool, oil filings or pipe cuttings. It is, therefore, essential that foreign material be removed from chlorine lines and containers before allowing chlorine to enter them. Wet chlorine gas may be handled in Titanium equipment. However, dry chlorine reacts violently with titanium. Dry Chlorine will react violently with hot steel. For this reason, welding should only be done on Chlorine lines that have been isolated, depressurized and made free from chlorine gas. Welding leads should not be attached to such lines.
Contd..

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Hazards Associated with Chlorine usage (contd)

Dry chlorine does not react with steel at normal temperatures. Under these conditions, steel is suitable for handling and storing Cl2. Chlorine and hydrogen mixture can react violently in equivalent mixture and the rate of reaction increase in presence of oxygen. Ultra violet light can start this reaction. Methyl Chloroform and other organic solvents should not be used to clean equipment where large amounts of Chlorine and its residues are present.

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Hazards Associated with Chlorine usage (contd)

We must remember that Chlorine dissipates more rapidly on a warm, windy day than on a cold, calm one. Causes inhalation health effects at relatively low concentrations. Vapour pressure increases considerably with increase in Temperature. Liquid chlorine inside tonner and bullet expands more and more with considerable increase in storage pressure with rise in Temperature.

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Chlorine is also explosive with Hydrogen

Hydrogen is a Co- product in the manufacture of chlorine. Mixture of Hydrogen becomes explosive as per the properties of mixtures of Hydrogen with chlorine, Hydrogen with air and Hydrogen with oxygen as tabulated.

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The properties of mixtures of Hydrogen with chlorine, Hydrogen with air and Hydrogen with oxygen
Properties of Hydrogen/oxygen mixture
Lower Flammability Limit (LFL) P=1 bar a, T=20. C

Hydrogen/ Air

Hydrogen / Chlorine
3.0% V/V

Hydrogen / Oxygen
4.0% V/V

4.0% V/V

Lower detonation Limit (LDL) (atmospheric condition) Ignition (Auto ignition) temperature

18.2% V/V

17.5% V/V

9.0% V/V

5600 C

2070 C

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Chlorine Production & Use in India

Chlorine is a Co-Product in the manufacture of Caustic Soda. The production facilities are spread through out India. 8 Plants in East Zone, 15 Plants in West Zone, 4 Plants in North Zone & 9 Plants in South Zone.

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Chlorine Production & Use in India (contd)

In India, most of the total installed capacities of Caustic Soda/ Chlorine are based on Membrane Cell Technology which is environmental friendly & energy efficient No production is based on Diaphragm Cell Technology Out of 19 Lakh MT of Chlorine Produced approximately 8.5 lakh MT Chlorine was captively used Approximately 10.5 lakh MT of Chlorine was transported from manufactures to end users. Chlorine is filled in small containers (900 kgs) & transported through trucks.

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Chlorine Production & Use in India (contd)

Sector wise use of Chlorine in IndiaVinyls (including PVC) Organic Chemicals Inorganic Chemicals Pulp & Paper CPW Water Treatment Pesticides/ Insecticides/ Weedicides Pharmaceuticals Dye & Inks Textiles Exports Other Uses -

18% 20%, 23%, 8%, 11%, 2.0%, 5%, 0.53%, 0.40%, 0.60%, 0.4% 11%.
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KEY TO ACCIDENT FREE PRODUCTION & HANDLING OF CHLORINE

There is a potential danger during manufacture, storage, filling, transportation and use of chlorine (as discussed) and therefore necessary control & safety measures needs to be adopted.

Key Factors
Technical Up-gradation and Innovation. Inclusion of all safety & control measures at the plant stage Following safe operating procedures, safe handling and transport procedures. Training of operating personnel. Training of Drivers and Transporters Learning from Past incidents

deign

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KEY TO ACCIDENT FREE PRODUCTION & HANDLING OF

CHLORINE
Compliacence to regulation, such as: Gas cylinders Rule, 2004 Static & Mobile Pressure Vessels (Unfired) Rules, 1981 [SMPV (U) Rules, 1981] Factories Act, 1984 Manufacture, storage and import of hazardous chemical Rules, 1989. The Chemical Accidents (Emergency Planning, Preparedness and Response) Rules, 1996 The Environment (Protection) Act, 1986 The Public Liability Insurance Act, 1991, amended in 1992 Central Motor Vehicles Rules 1989 (amended 95)
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Caustic Soda/ Chlorine Production Process

(Common to all Technologies)

Chlorine is a by product in the manufacture of caustic soda Technologies used for manufacture of caustic soda / chlorine
Mercury Cell Technology Diaphragm Cell Technology Membrane Cell Technology

The Caustic Soda Chlorine production & process can be sub grouped as:
brine treatment Electrolysis sodium hydroxide production, storage and handling chlorine production, storage and handling waste chlorine gas neutralization and production, storage and handling of sodium hypochlorite hydrogen production, storage and handling (chlorine filling)
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Chlorine Manufacture process and the bullet

CL2 from

cell

90 st 1 stage cooling 40 o C

40 o

H2SO4

filtration

2nd stage cooling 15 o C

Drying

Consumption

3.0 Kgcm2 Storage

liquification

compressor

00C

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Control & Safety Measures in production of Chlorine (Contd)

Control & Safety Measures in Operation of Electrolysers

Hydrogen content in chlorine in the cell gas is monitored to avoid formation of explosive mixture of Hydrogen & Chlorine. Electrolysers are shut off in case of high hydrogen concentration in the cell gas of the electrolysers. In case of high chorine pressure on the electrolysers, control is provided to switch off and shut down.

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Control & Safety Measures in production of Chlorine (Contd)

Control & Safety Measures in Operation of Electrolysers (contd..) In the event of emergency shut down, Chlorine is released to the chlorine absorption unit through emergency relief valves. Emission of chlorine to the atmosphere is prevented. Formation of combustible & explosive mixture of hydrogen & chlorine in the operation of electrolysers are prevented by suitable Instrument contorl and safe operation procedure. Air must be excluded from the hydrogen stream so that it can not combine with hydrogen to form an explosive mixture of hydrogen and oxygen.
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Safety and control measures in Sodium Hydroxide Production, Storage & Handling

Control & Safety Measures in production of Chlorine (Contd)

All the caustic tanks are provided with in built facilities to prevent overflow or spillage of caustic soda. Such facilities include containment and mitigation. It should be noted that hydrogen gas can be released into the vapour space above the liquid in storage tanks. Tanks are normally vented from the highest point. Testing for an explosive mixture of hydrogen in air normally precedes any maintenance activity in the area. Storage tanks may be lined to minimize iron contamination of the prouduct and to avoid stress corrosion cracking of the tank.
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COOLING AND DRYING

AMA I

The chlorine gas produced in the cell room is hot and saturated. The temp. of the gas as high as 90 o c. Aspects of safety are as under: As titanium is used as a tube material for heat exchanger, a careful review must be made to ensure, even in upset conditions that dry chlorine does not come into contact with the tubes. Dry chlorine reacts violently with titanium. Back flow preventor is provided to take care this problem Careful control with adequate failure warning, of the gas temperature from the second coolers is required to prevent the formation of solid chlorine hydrate (9.6 o C). The hydrate formation may completely plug the heat exchanger or gas piping creating a big hazard in cell room. Facilities for periodic or continuous washing of them demister must be provided to prevent excess salt crystallization due to carryover from the cell room. This can lead to high pressure drops and stoppage of gas flow. To take care high temp of Cl2 before cooling the FRP line should be of 24 Alpolite (797) resin instead of Atlac 382 (Bis-phenol resin)

Contd.
AMA I

The method used for chlorine drying is by contact with H2SO4. Dry Cl2 is defined the moisture less than 150 ppm by volume of water. Aspects for safe operation Conc. Of H2SO4 is a major factor when selecting materials of construction. Plastics or lined equipment and pipes must be considered. Outlet conc. to be maintained 78 80% by continuous dosing of 98% H2SO4 to ensure proper drying. The use of H2So4 requires specific attention. Velocities must be kept low 1 m/sec to prevent excessive erosive wear. Due to corrosive nature of dilute H2SO4 seals or rotating parts become rapidly worse. Flange guards to be provided on H2SO4 pipe lines to avoid splashing of H2SO4. Hot work permit to be issued on dilute H2SO4 after thoroughly washing/drying that system. H2 generates in dilute H2SO4 system during washing which can lead to explosion with hot work. During above mentioned cooling & demisting operation, chlorinated water is generated which is effectively utilized in vacuum De-chlorination system.
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Contd.

Continuous monitoring of moisture in Cl2 by analysis/ by online instrumentation is a must. Instrumentation to monitor acid flow conc., temperature, as well as gas temp is required. The capabilities of monitoring the pressure difference across the drying towers and cooling equipments is important for detection of restriction to flow with in the system. Significant hazards involved in handling and storing H2SO4. All personnel need to be adequately trained for every phase of drying operation with particular attention given to avoidance of contact with the H2SO4. Protective clothing & safety equipments should be mandatory. Chlorine outlet from the drying tower should be at the top or immediately in line with the top portion to avoid accumulation of hydrogen at the top & to avoid explosion due to electrostatic charge
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Control & Safety Measure in production of Chlorine (Contd)

Control & Safety aspects in Chlorine Compression (contd)
Concentration of the H2SO4 in compressor to be monitored by analysis on daily basis to avoid corrosion. Higher moisture content in chlorine gas (due to inadequate drying) will corrode the chlorine compressor Sulphuric acid mist is to be removed with glass wool candle filters to avoid chocking in liquefier & pipeline. Continuous PH monitoring of the chilled water of individual chlorine compressor coolers are to be done to detect any tube leakage. If the tube leakage of chlorine compressor cooler goes unnoticed, it will affect the entire chilled water cycle.

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Control & Safety Measure in production of Chlorine (Contd)

Control & Safety aspects in Chlorine Compression
Automatic control valves and check valves are to be provided to prevent the back flow of chlorine (in case of compressor tripping) in to the low pressure system. Chlorine Compressors are fitted with mechanical seal to prevent any leakage of CL2. Acid temp of the chlorine compressor is to be maintained below 400 C to avoid corrosion.

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Control & Safety Measure in production of Chlorine (Contd)

Control & Safety aspects in Chlorine Cooling, Drying &Liquification As titanium is used as a tube material for heat exchanger. Dry chlorine reacts violently with titanium. Back flow preventor is provided to prevent contact of Dry Chlorine with titaniunm. Contd

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Control & Safety Measure in production of Chlorine (Contd)

Control & Safety aspects in Chlorine Cooling, Drying &Liquification Facilities for periodic or continuous washing of the demisters provided to prevent excess salt crystallization due to carryover from the cell room. This can lead to high pressure drops and stoppage of gas flow. To take care of high temp of Cl2 before cooling, the FRP line between electrolysers to chlorine cooler should be of proper quality (Alpolite (797) resin instead of Atlac 382 (Bis-phenol resin) Hydrogen is continuously monitored in the sniff gas to maintain below the explosive limit. Make sure that refrigerant used for liquefaction does not react with Cl2 if there is a leak

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Control & Safety Measure in production of Chlorine (Contd)

Control & Safety aspects in Chlorine Cooling, Drying &Liquification (Contd..)
Under pressure safety seal is to be provided in the system. Alignment of the compressor & motor should be proper as vibration damages seals and results gas/ acid leakage. Provision to run the compressor with closed discharge valves in case of startup/ stoppage/ maintenance (local by pass valve). Centrifugal compressor leads to unstable operation at high pressure and low volume. It can also occurs at low chlorine density. This results surging. Speed control/ by pass control is required to ensure stable operation. Initiations for trips of the chlorine compressors are provide, In case of abnormal chlorine temperature, chlorine pressure, oil pressures shaft vibration & axial movements etc. since the chlorine is at the peak pressure level at the compression stage. Contd..
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Control & Safety Measure in Production of Chlorine (Contd) Control & Safety aspects in Chlorine Cooling, Drying
&Liquification (Contd..)
The chlorine gas having moisture less than 150 ppm by volume of water is considered to be dry chlorine. Concentrated sulphuric (98%) has to be dosed continuously to ensure proper drying. Maintain outlet concentration (of chlorine drying Tower ) at 78% (Min) The use of H2SO4 requires specific attention. Velocities must be kept low at 1 m/sec to prevent excessive erosive wear. Due to corrosive nature of dilute H2SO4, seals or rotating parts rapidly deteriorates.

Contd..
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Control & Safety Measure in Production of Chlorine (Contd)

Control & Safety aspects in Chlorine Cooling, Drying &Liquification (Contd..)
Flange guards to be provided on H2SO4 pipe lines to avoid splashing of H2SO4.( saturated with Chlorine) Hot work permit to be issued for maintenance work on dilute sulfuric acid containing vessels/ pipe lines etc. since H2 generates in dilute H2SO4 system can lead to explosion with hot work. Such systems containing dilute sulfuric acid are to be washed & dried before undertaking maintenance work Re use the chlorine condensate generated in 33 the chlorine cooling.

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Control & Safety Measure in Production of Chlorine (Contd)

Control & Safety aspects in Chlorine Cooling, Drying &Liquification (Contd..)
The moisture content in Cl2 gas after drying has to be detected by on line measurement Instrument/ or by Analysis to ensure chlorine gas dryness since wet chlorine is corrosive. Instrumentation to monitor acid flow, acid concentration, acid temperature, for detection of restriction of flow with in the drying system. Chlorine outlet from the drying tower should be at the top or immediately in line with the top portion to avoid accumulation of hydrogen at the top to avoid explosion due to electrostatic charge.
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Control & Safety Measure in Production of Chlorine (Contd)

Control & Safety Measures during Production of Liquid Chlorine
An important control parameter is moisture content in dried chlorine in relation to the materials of construction as wet chlorine is highly corrosive. The moisture content is measured before liquefaction. Care needs to be taken about nitrogen trichloride (NCI3) as it is explosive. Procedures for maintaining levels of NCI3 below the explosive limit is available. In addition, care needs to be taken to avoid high temperatures which could lead to a chlorine / iron reaction.
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Safety & Control Measures in Chlorine Storage and chlorine filling (contd)
Design aspects and Material of Construction of chlorine storage Tanks. Liquid chlorine is generally stored in horizontal pressure vessels. Adequate distance between two storage tanks is to be maintained. Chlorine storage tanks to be located away from hazardous processes or storage with potential fire/explosion risk to minimize risk of damage. Dyke wall and impervious flooring with 1:100 slope are to be provided in the storage area. Tanks are to be designed as per IS 2825. Design pressure for chlorine storage tonner is 19.9 kg/ cm2 at 650 C.
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Safety & Control Measures in Chlorine Storage and chlorine filling (contd)
Corrosion allowance of 3 mm is to be provided. 100% stress relieved and X-rayed. Material of Construction (MOC) of chlorine storage Tanks is low temperature carbon steel SA 516 grade 60/70 (-350 C to 550 C). Valves are of forged carbon steel, spindle of monel metal or SS 316 and bellows are of hastalloy C 276. Pressure Gauges with Haste alloy C diaphragm, Haste alloy C/ SS316 dip pipe. Bolts, nuts & studs of proper MOC is used. Stud- 320 L7_, ( Nut A194 grade -4)
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Safety & Control Measures in Chlorine Storage and chlorine filling (contd..)
Control & Safety measures for storage of liquid chlorine (contd)
Provide Low and high level alarm, 20% low & 80% high. Provide High & low pressure alarm, 2.5 Kg/ cm2 low and 11.5 Kg/ cm2. Provide Temperature alarm -150 C low and 300 C high. Provide Double Rupture disc, 13.5 Kg/ cm2. Provide Double Safety valve which opens at 13.0 Kg /cm2 & closes at 12.7 Kg/ cm2.
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Safety & Control Measures in Chlorine Storage and chlorine filling (contd..)
Control & Safety measures for storage of liquid chlorine (contd)
Provide Double valve of international standards quality of each line. Provide Remote type valve in liquid chlorine line. Always one tank is to be kept empty for emergency transfer of liquid chlorine. Connection of the emergency release line with the neutralize system. Provide adequate number of CI2 detector in the storage area.
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Safety & Control Measures in Chlorine Storage and chlorine filling (contd..)
Control & Safety measures for storage of liquid chlorine (contd) Transfer of liquid CI2 to empty tank. Time for transfer 2 hrs by compressed dry air at 10.8 Kg cm2. Tank volume 100 NM3. Foam is used to contain chlorine, leakage. Chilled water below 100C can be used to control liquid CI2 spillage. Liquefied gas pool can also be controlled by covering with a large sheet of poly ethylene. Vapor evaporating from pool below the cover can be withdrawn by large bore hose to a neutralization system with on line connected vacuum hose. Provision for Neutralization of chlorine with caustic soda (3 40 stage system).

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Safety & Control Measures in Chlorine Storage and chlorine filling (contd..)
Prevent passage of liquid chlorine into drainage system/ effluent. Dyke wall kept dry during rainy season. To avoid percolation, a steep slope is provided leading to a sump with provision of small pumps or airlifts for recovery. Provision for prevention of free access of wind and airflows to pool area. The storage tanks may be fitted inside a close room with emergency exhaust blower. Which is connected to neutralization system. Provide high capacity blowers in the storage and bottling area connected to the neutralizing system.
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SAFETY MESAURES FOR CHLORINE STORAGE TANKS

REQUIREMETNT UNDER SMPV RULE 1981

License under SMPV Rules must be obtained by the producers. Level or weight, pressure and temperature indicator will be provided on each chlorine storage tank with proper alarm system. Provision for release of excess pressure with rupture disc will be provided at chlorine storage tanks. It will be provided with safety valve and safety valve will be connected to Hypo System. Pressure indication between rupture disc and safety valve will be given to detect any damage in rupture disc. Alternately, two Nos. Safety Relief Valves to be provided on each storage tank.
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SAFETY MESAURES FOR CHLORINE STORAGE TANKS

REQUIREMETNT UNDER SMPV RULE 1981 Provision of emergency suction hose for evacuation of chlorine leakage to hypo system will be provided. Provision of On line Breathing Apparatus and Self contained Breathing Apparatus at different locations for emergency operation will be available at storage site. Dew point of padding air will be monitored. Dew point should not be more than -450 C Emergency Response Plan for Chlorine leakage is to be developed as per statutory guide lines and to be made operational. The operation will be done by trained and experienced persons.
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Scrubbing of Waste Cl2

For the scrubbing of waste vented chlorine, a scrubbing tower system is used. Since in Cell gas is hot and wet and generally large volume and at low pressure, a low pressure drop system is required. Two/Three scrubber are provided in series so that is capable of absorbing all gases even during emergency. Bleach liquor in the circulation is regularly checked for excess caustic to effect changeover at proper time. Auto control valve is to be provided to maintain uniform vacuum in the system Full Overhead tank with 20% caustic should be available to meet any emergency it should be linked with ON/OFF control valves in order to dump caustic from control room also. Temp alarm for sodium hypo system is required to maintain temp below 35 o C Titanium pumps, MSRL pipeline & towers with titanium coolers are to be used for the service to give reliable emergency services
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EMERGENCIES: The most common emergency is Power failure. To avoid leakage of CL2 gas in the atmosphere, a number of critical equipments are connected to the generator set with automatic changeover. Equipments generally connected with DG set are 1) DC blower 2) Caustic circulation pumps 3) Emergency lights 4) Inst. Air, cooling water, chilled water & Nitrogen system Apart from this, regular inspection and changeover of pipelines, hydraulic testing of storage tanks and containers are done to minimize chance of any Cl2 leakage due to corrosion.
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INSTRUMENTATION
Instrumentation plays a very important role in chlorine manufacture. some of this important instruments are as under: Rectifier Tripping Interlocks High Current of electrolyzer Tripping of 2 or more electrolyzer One of Cl2 compressor running High level of anolyte tank Low level of overhead pure brine tank High temp of catholyte vent pot High Cl2 pressure Low Cl2 pressure Low H2/Cl2 differential pressure High H2/Cl2 differential pressure Liquid Cl2 pumps not running 46 Full opening of Hypo valves

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Contd.
In addition to this a multipoint chloro alarm sensors are provided at various places within the complex to detect Cl2 leakage easily at 3.00 ppm conc. These instruments are checked & calibrated regularly. Breathing apparatus and other emergency kits are available at different locations.

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MATERIAL OF CONSTRUCTION
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WET CHLORINE LOW PRESSURE 1) Stone ware 2) Porcelain 3) hard rubber 4) Unplasticised PVC 5) Glass fiber (FRP) HIGH PRESSURE 1) Titanium 2) Tantalum inert up to 150 deg.c 3) Haste alloy C 4) Monel metal B DRY CHLORINE GAS OR LIQUID 1) Seamless carbon steel 2) Corrosion allowance 1 mm 3) Service temp 35 to 650c 4) Pressure- 19.9 kg/cm2 5) Tounge and groove flanges 6) Gaskets-CAF/Lead 7) Nut Bolts-Alloy Steel.

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Contd..
VALVES 1) Drop forged steel 2) Monel spindle/haste alloy c 3) Cast steel seat 4) Teflon Gland packing. Carbon steel is suitable upto 120 o C. SS with 10% nickel is suitable upto 150 o C. SS with more than 10% nickel is suitable upto 250 o C. Monel is suitable upto 350 o C. Nickel, Inconel & Hastalloy C is suitable upto 400-500 o C. Nickel is used as lining material as it has poor mechanical properties.

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PIPING DESIGN/MAINTENANCE
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DESIGN: Piping arrangements simple with min. flange joints/ screwed joints Above ground layout Well supported and adequately sloped Expansion vessel in liqcl2(20% vol) Min 20 mm pipe diameter to be utilized Lines cleanly labeled and painted as per color code (yellow) Linseed oil and graphite,linseed oil and white lead ,litharge and glycerin can be used for permanent joint. Seamless schedule 80 pipeline upto 6 inches above that schedule 40 is acceptable Regular NDT testing of chlorine pipeline Velocity to be maintained 2 m/sec 100% stress relieving & radiography for liquid Cl2 service pipeline MAINTENANCE: All pipelines are to be cleaned. No oil/grease/hydrocarbon/alcohol is to be used for cleaning Cleaning can be done with trichlorethylene /carbontetrachloride Chlorine line can be washed, steam heated and dried before use Chlorine lines to be hydro tested before drying (Dry Air 400c Dew point) After drying lines to be tested with 1)Dry Air-/nitrogen - check for leak with soap solution 3)Dry Air + chlorine - check leakage with Ammonia solution 4)chlorine - DO Never attempt to repair leak by welding until all chlorine has been purged. The line to be retested after repair Contact of Ammonia with Brass is to be avoided 50 All old & unused pipelines must be identified and removed.

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SAFETY SYSTEMS
Neutralization system by caustic soda to form sodium hypochlorite products with emergency power supply (Three stage neutralization) Use of safety kit to stop release. On line detection sensors for chlorine gas. All PPEs provided. Training of employees at shop floor and at consumers premises. Training of drivers and conductors. Rescue team availability on effected site on call. Provision of high capacity blowers in tanks and liquid Cl2 filling area (Connected with neutralizing system) Minimum inventory in liquid Cl2 tank Public announcement facility and local phones
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Contd.

Central Control Room for Co-ordination Earthing Systems. Remote control valve with local control Double valve in each line Emergency release line Seamless piping with tongue and groves flanges. Expansion chamber in liquid CL2 line. 100% instrumentation control in CL2 system manufacture Competent persons to handle liquid Cl2 system approved by CCE Liquid Cl2 tank insulated with 75 MM thick thermocole insulation and cladded with Aluminum sheet Flame proof lights
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Other Safety Measures in complex

Adequate wind socks are provided to know wind direction. Tank replacement every 20-25 years irrespective of tank health/condition or after the report by third party or in case of physical damages. Assembly points identified and marked properly for emergency. Periodical mock drill exercise carried out. Availability of On site/Off site emergency plan

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STATUATORY REQUIREMENT
License for liquid Cl2 storage in tanks. License for liquid Cl2 storage in Tonners/Cylinders. Approved layout plan indicating surrounding area and Cl2 neutralizing facilities. Liquid Cl2 filling license. Recognition for hydraulic testing facilities of Cl2 Tonners/cylinders List of competent persons handling Cl2 operation Environment protection Act. The Factories Act ON site/ OFF site emergencies Plan. Mock drill (every Six month) Hydraulic testing of Tonners/storage tank every two year. Compliance of GAS CYLINDER RULES 2004 and STATIC AND MOBILE VESSEL RULES. Lloyd inspection report of every Tonner and CCE approval before filling. SAFETY MANUAL with MSDS and safety permit system. Central Motor Vehicle Transport Act. Storage and impact of Hazardous chemicals Rules. 54 The Public liabilities Insurance Act.

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.

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Equipment for chlorine handling

Tonners
Net carrying capacity -900 Kg. It is a welded steel tank with a gross wt of 1500 Kg. Manufactured as per ASME SEC VIII DIV.1:2004. The provisions made under 1) Gas cylinder rules,1981, 2004 and 2) IS:4263-1967(code of safety for Chlorine). To be followed while handling these tonners and cylinders. Any party possessing more than 5 containers at any one time will have to take out a license under the gas cylinder rules; 1981, 2004.

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Chlorine tonner

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Various safety measures related to chlorine tonner design and usage

1. 2. 3. 4. 5. 6. 7. Concave ends. Hydrostatic stretch testing. Rejection when permanent stretch is more than 10%. Rejection when tonner weight loss exceeds 5%. Approx min.10% empty space after filling. Filling and emptying on weighing balance. Periodic checking of weighing balance calibration.

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8. Regular inspection for dents, pitting and any abnormal loss in weight after every trip. 9. Valve protection hood . 10. 24 hours storage after filling for observation. 11. 900kg liquid chlorine filling in the tonner quantity of liquid chlorine (kgs)= water capacity*1.19

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Cylinders
Cylindrical container of welded steel construction with one end closed and a valve at the other end. A valve protective hood is fitted on the threaded neck ring. Capacity 100 kg and 50 kg. Made as per IS:7681, IS:3196-Part-4:CL-1 1958

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Chlorine cylinders

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Accessories of tonner
2 nos of valves as per IS: 3224 2 nos of Brass plug for inspection Two number of 15 NB eduction pipe 1 no of valve protecting dom (hood) Our Container valve specification Type 1, size 2, 3/4 14NGT (cl)-2 with outlet No.5 as per IS 3224:2002. Type1 - Stem taper indication. Size2 - Total dimension indication. 14 NGT - Thread specification. NGT threads are based on the American standard taper pipe threads but are longer to provide fresh threads if further tightening is necessary. IS:3224:2002 is the Indian standard valve fittings for compressed gas cylinder excluding liquefied petroleum gas cylinders (L P G).

Chlorine cylinder valve

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Eduction pipe

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Material of construction of valve

Body---Aluminium Silicon Bronze alloy. Spindle---Monel (Nickel copper alloy). Gland nut, Neck ring---Brass. Gland packing---PTFE.

Valve suppliers
Kosan industries Pvt Ltd Surat Techno valves Kolkata. Vanaz engineers Ltd Pune

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CONCLUSION
BREADTH AND DEPTH OF DEFENCE FOR CHLORINE SAFETY PREDICTION PREVENTION DETECTION MANAGEMENT AUDITNG IMPROVEMENT Refresher training to operating personnel Thinking globally and working locally

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Recommended standard procedure for handling chlorine containers

1. 2. 3. The process area should be well ventilated with frequent air changes so as to minimize the impact of any sudden leakage. Carry out all operation under the supervision of a trained and competent person Under the provision of the gas rule 1981 any person possessing storing or using 5 containers or more at a time has to obtain an appropriate license from chief controller of explosives, Nagpur (PESO).

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5
6 7

Care should be taken that the surface over which container is moved is as smooth as possible and does not involve sudden drops and lumplings. Particular care has to be taken to ensure that the valve hoods are in place while the containers are moved. Ammonia torch should be located at near by places where chlorine containers are generally received stored or used in process, so as to facilitates easy detection of any leakage. In case of any leakage from the containers immediate and appropriate action is to be taken only to control the leak after controlling the leak the supplier should be immediately informed to take suitable action.

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Consumer should not make any effort to repair affected portion of the container. 9 Gas masks and emergency kits should be located in secured cabinets at strategic points. These are to be periodically inspected to ensure that they are properly maintained and in working condition.

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10 All chlorine consumer must establish and maintain appropriate facility for chlorine absorption through caustic soda/ lime/ soda ash/ solution to be of use in the event of major leakages 11 Valve hood should be removed from the container only during the time it remains connected to process. Care should be taken to ensure that the valve hood remain fitted to the container at all other times. 12 Even the slightest leak should not be neglected. A chlorine leak never get corrected by itself it can only get worse

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13 water should never be used directly on the container for controlling the leakage. 14 As chlorine is heavier than air it tends to accumulate near the ground. In case of any leakage it is advisable to move all personal to higher areas opposite to the windward side. 15 Tonners storage should be in cool, dry covered space and protected from direct sunlight / weather and extreme temperature changes. Proper handling facilities should also be provided.

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Despatch of empties
Abnormalities or defects, if any are noticed may be specifically pointed out in the dispatch Chelan. Containers may be loaded on to the truck with the help of a hoist or wooden ramp ensure that valve cap nuts are fully tightened and the hoods fixed in position. Containers should be properly secured with ropes, wooden blocks etc, and should not project outside the truck frame, also ensure that the valves of tonners are in vertical plane. Dispatch new cylinders for filling only with proper attested certificates such as Cylinder manufacturing certificate with annexure1, annexure2, annexure3, valve certificate and filling permission from PESO with a covering letter from concerned officer.

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Emergencies and emergency management

There are many hazards inherent in the manufacture, storage, handling and use of chlorine. Whenever chlorine is handled, a potential risk is involved and a serious emergency may suddenly crop up. The most common kind of emergency that arises during chlorine handling by consumer is through leakage and rarely is due to fire. A chlorine leak never gets corrects by it self. It only gets worse if not promptly attended to. Water should never be used on a chlorine leak.

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Measures in facing leakages Detect the exact location with the help of an ammonia torch Remove all the persons, not directly concerned from the area affected. If the leak is from process cut off the supply. If the leak is from the valve roll the cylinder make the leaking valve on top. Ensure that only chlorine gas escapes instead of liquid. One volume of liquid chlorine is equivalent to 457.6 volume of gaseous chlorine.

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Type of valve leak and remedies

Leak from valve packing Leak from valve seat or from spindle Leak due to defective inlet thread Broken valve Tighten the gland nut
Gently open and close the valve Tighten the valve carefully to the container Use the valve hood assembly

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Tonner shell leakage

Bring the leaking point on top by rolling the tonner. Insert a led peg or soft wooden wedge with a hammer inside the leaking hole. Use chain and yoke assembly made to arrest tonner/ cylinder wall leak. If leakage continues chlorine may be absorbed in caustic soda solution, hydrated lime solution or soda ash solution

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Chlorine emergency kit

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Leak arresting by using emergency kit

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The effect of chlorine exposure on eyes

Irritation associated with burning discomfort spasmodic blinking, redness, conjunctivitis and burning. Dos Hold the eyes open, flush with tepid water. Get medical attention. Donts Do not try to neutralize with chemicals.

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The effect of chlorine exposure on skin

Burning sensation and skin irritation typically at high concentration. Dos Flush with tepid water for 15 minutes. Don'ts Do not apply any ointment for 24 hrs as it may lead to irritation

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The effect of chlorine inhalation

Exposure to low concentration may cause nasal and respiratory tract irritation. At higher concentration coughing and difficult breathing possibly leading to respiratory distress. Any chlorine inhalation in an individual with compromised pulmonary function should be regarded as a severe inhalation and a respiratory emergency.

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Dos Remove the exposed person to fresh air and summon professional medical assistance immediately. If breathing has ceased, begin artificial respiration. Trained personnel should administer oxygen as soon as possible. If breathing has not ceased the person should be placed in a comfortable position either seated in a chair or in severe case laying down with the head and body trunk elevated at 450 to 600 angle. Encourage the person to take slow deep regular breath. Administer oxygen as soon as possible. Keep the person warm and at rest. Don'ts Sodium bicarbonate should not be given. No attempts should be made to induce vomiting or to use a stomach tube.

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The effect of chlorine ingestion

No adverse effects are anticipated by this route of exposure. Dos If a person is swallowed chlorine and is conscious he should be made to drink copious amount of lime water, milk of magnesia, curd or fresh water. The victim may be expected to vomit spontaneously. Get medical attention immediately Donts Alcoholic drinks shouldnt be given.

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Personal protective equipment

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Self contained breathing apparatus Emergency escape breathing apparatus Industrial canister type mask Helmet Hand gloves Face shield Protective clothing

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Protective clothing

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References for safe operation INDIAN EXPLOSIVE ACT 1884 Gas Cylinder Rules 2004 IS 8867 - Hydraulic Stretch Test test pressure IS 3710 - Values of saturated VP of different gases. (FILLING RATIO) IS 3224 - Specifications of Industrial gas cylinders. IS 5903 - Details of safety devices in cylinder valves fitted with safety devices. IS 4379 - Identification colours for industrial gases. IS 356 - (IS Standard Colour No. 356) Colour of gas Nonflammable but toxic. IS 5844 - Hydrostatic stretch test Procedure (welded cylinder) IS 3196 - Specification of low pressure liquefiable gas service. ASME - Specification of Cl2 tonners (SEC. VIII WITH LATEST AMENDMENT CHIMED ENDS SPECIFICATION NO. 179.300 OF CFR 49)

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Static & Mobile Pressure Vessel Rules 2004 IS 2825 - Design code of pressure vessels. IS 4263-1967 - Code of safety for chlorine IS 10553 - Withdrawal of Cl2 from ton container. PART:I, 1983 - (Requirements of chlorination equipments, general Guidelines for chlorination plant and safety of chlorine. IS 2379-1963 - Colour code for identification for pipelines. IS 10553 Part(2) Vacuum feed type chlorination. IS 10553 Part(4) Gravity feed gaseous chlorination. IS 646 - Chlorine purity. USA Chlorine Institute pamphlets. Eurochloro guidelines. World Chlorine Council guidelines

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Conclusion
Safety is the result of conscious, well-thought out, painstaking and sustained actions by the Entire Team involved. Brilliant but erratic actions cannot ensure Safety. Safety is inescapably linked to Total Quality Management..