BROMINE HANDLING activity in reactor .pptx

Solvent handling

1. BROMINE HANDLING SYSTEM SOLARIS CHEMTECH INDUSTRIES LIMITED

2. Topics About Bromine- MSDS ISO Tanker Unloading Procedure Neutralization of Bromine Material compatibility Work Safety – Practices SOLARIS CHEMTECH INDUSTRIES LIMITED

3. Bromine is a member of the halogen group of elements along with chlorine, iodine and fluorine. It is a heavy, reddish-brown liquid that gives off a red vapor at room temperature. It is the only non-metallic element that is liquid at room temperature. Bromine serves as a starting material for a variety of products that are the building blocks for highly complex organic molecules that meet specific performance, environmental, and quality requirements. Bromine is utilized in many applications including flame retardants, agrochemicals, pharmaceuticals, fine chemicals, high performance rubber, polymers, biocides and energy storage, as well as in chemicals used by the oil and gas industries in completion fluids, and inorganic bromides for mercury control. Bromine as a liquid or as a vapour is highly irritating to skin, mucous membranes, eyes and respiratory tract. Being a powerful oxidizing agent, it also constitutes a Exposure event at low concentrations may result in inflammatory reactions in the eyes and respiratory passages. About Bromine SOLARIS CHEMTECH INDUSTRIES LIMITED

4. Identification of the substance Chemical Name : Bromine Chemical formula : Br2 Chemical family :Halogens Molecular weight : 159.81 Type of product and use : For manufacturing of pharmaceuticals, flame retardants, dyes, fumigants, sanitizers, petrol antiknock compounds and other organic derivative . An analytical reagent UN number :1744 CAS Number :7726 - 95 - 6 EINECS Number :231-778-1 MSDS Sheets - SOLARIS CHEMTECH INDUSTRIES LIMITED OSHA:- Occupational Safety and Health Administration of the United. States NIOSH:- National Institute for Occupational Safety and Health  ACGIH:- American Conference of Governmental Industrial Hygienists

5. Bromine ISO tanker unloading and storage   SCIL is dispatching Liquid Bromine in 6 KL ISO tankers. These tanks are exclusively made for Bromine and are imported from Germany. The ISO tanks are made of Mild steel with Lead lining inside . One tanker can carry 18 MT of Bromine. These ISO tanks are mounted on dedicated road trailers.   SCIL produces Bromine with water content less than 50 ppm and Lead lined ISO tanks can easily handle Bromine containing moisture up to 50 ppm. It may please be noted here that Bromine is highly Hygroscopic and if not handled properly the water content can quickly increase to 300 ppm making Bromine Highly corrosive to the lead lining of the ISO tank. There fore it is essential that Customers use Compressed Nitrogen Cylinders for emptying out Bromine from the ISO tanks .   SOLARIS CHEMTECH INDUSTRIES LIMITED

6. The following figure gives the schematic arrangement necessary for unloading an ISO tank SOLARIS CHEMTECH INDUSTRIES LIMITED

7. Pre check before unloading of ISO tank 1. Ensure that the bromine vent scrubber is working and scrubbing media solution concentration and pH are as specified and capable of handling vented bromine vapors. 2. Ensure personnel responsible for unloading wear personal protective equipments like face shield, full body suit, helmet, goggle, and rubber hand glove and safety shoes. 3. Ensure availability of 10% sodium thiosulphate solution for neutralization , decontamination in case of spillages. 4. Ensure that adequate numbers of filled nitrogen cylinders are available. 5. Ensure ISO tanker is weighed and its initial weight recorded. 6. Ensure that the tanker is positioned at required location for unloading, hand brake applied, wheel chokes placed behind and ahead of front and rear wheels 7. Check that all ISO tanker valves are closed and blind flanges are in place. 8. Ensure availability of chilled water supply. 9. Establish circulation of chilled water in bromine vent scrubber, jacket of the bromine storage tank and vent condenser. SOLARIS CHEMTECH INDUSTRIES LIMITED

8. Procedure for unloading: 1. ISO tanker for Bromine is provided with 3 valves at the top colored RED,YELLOW and GREEN. The function of these valves is • YELLOW VALVE IS FOR BROMINE UNLOADING • GREEN VALVE IS FOR PRESSURISING THE ISOTANK WITH DRY NITROGEN GAS • RED VALVE IS FOE VENTING THE ISO TANK 2. Record initial weight of bromine in bromine storage tank. 3. Remove the blind flange above the Green valve on the ISO container. 4. Connect the nitrogen pressure supply line to the Green valve . Ensure the PTFE envelope gasket used is in good condition. 5. Remove the blind flange above the yellow valve. 6. Connect the unloading line to the YELLOW valve outlet. Ensure the PTFE envelope gasket used is in good condition. 7. Open the YELLOW valve and all the valves in the liquid unloading line (pump suction and discharge lines). SOLARIS CHEMTECH INDUSTRIES LIMITED

9. 8. Open the pressurizing valve (Green Valve) slowly (to check for bromine leaks), then fully, to start bromine flow into the pump suction line. Restrict Nitrogen pressure inside the ISO tanker to 1-1.5 kg/cm2 (g), to lift bromine for priming the pump. NEVER EXCEED 2 kg/cm2 (g). 9. Start bromine transfer pump and adjust the pump discharge valve to get desired flow. Continue pumping until all the bromine from ISO tanker is transferred. This will be known when the nitrogen blows through the unloading line. 10. After unloading stop the pump, close the pressurizing valve and cut off nitrogen supply. 11. Close the YELLOW valve and then all the other valves in the liquid unloading line. 12. Slowly open the depressurizing valve (Red valve) to release the nitrogen pressure on the ISO tanker to the scrubber unit. Weight for at least 15-20 min. Once the tanker is depressurized disconnect all the lines to the ISO tanker, close the red, yellow and green valves. Put blinds with proper gaskets on these valves. 13. If there are spillages of Bromine on the tank surface wash them with sufficient water other wise the outer layer (Mild steel)of the tank would get corroded very fast. MOST IMPORTANT •NEVER EVER USE COMPRESSED AIR TO UNLOAD THE ISO TANKER AS THE MOISTURE CONTENT OF THIS AIR WOULD BE ABSORBED BY BROMINE MAKING IT HIGHLY CORROSIVE TO THE LEAD LININGG OF THE ISO TANK.THIS IS HIGHLY DETRIMENTAL TO THE LIFE OF THE LEAD LINING. •WATER IN ANY FORM SHOULD NEVER EVER BE ALLOWED TO ENTER INTO THE ISO TANK. SOLARIS CHEMTECH INDUSTRIES LIMITED

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12. NEUTRALIZATION OF BROMINE Liquid phase Alternative neutralizers Solid: Slaked lime, Soda ash. Dissolved: Soda ash, Sodium hydroxide, Sodium thiosulphate, Sodium sulphite, Sodium bisulfite. Sodium thiosulphate must only be used for small spills (high heat of reaction). Do not directly put powder of Sodium thiosulphate as it is highly reactive & will generate fumes. Soda Ash: 3Na2CO3 + 3Br2 = NaBrO3 + 5NaBr + 3CO2 Slaked Lime: 6Ca (OH)2 + 6Br2 = Ca (BrO3)2 + 5 CaBr2 + 6H2O Caustic Soda: 6NaOH + 3Br2 = NaBrO3 + 5NaBr + 3H2O Sodium sulphite: Br2 + Na2SO3 + 2NaOH = 2NaBr + Na2SO4 + H2O Sodium bisulphate: Br2 + NaHSO3 + 3NaOH = 2NaBr + Na2SO4 + 2H2O We recommend the use of solid slaked lime to neutralize liquid bromine. Absorb the bromine into the material and mix. Add water and continue to mix slowly until all material has reacted. SOLARIS CHEMTECH INDUSTRIES LIMITED

13. Note : The information summarized below provides guidance on the selection of materials of construction. The user should consult a reputable materials supplier and the bromine supplier to satisfy himself that it will give the required performance under the actual conditions of use including temperature, pressure and presence of moisture. SOLARIS CHEMTECH INDUSTRIES LIMITED

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16. Recommendation/Suggestion to Customers 1.Bromine transfer from ISO tanker to Storage tank by Nitrogen . 2.Ensure the availability of 10% Sodium thiosulphate- 5 KL HDPE Tank to be provided near Bromine handling system for neutralization in case of leakages & spillages. 3. NRV to be required to nitrogen line 4. Recommended to unload ISO tanker – by N2 pressure with Maximum 2 Kg/cm2 pressure 5. No water should be enter in ISO tanker as more than 50 PPM highly corrosive to lead lining to ISO tanker 6. MSDS , SOP : Should be display near bromine unloading & transferring system – hazard , emergency plan 7. Preferred MOC for Piping : PVDF for ISO tanker unloading line. 8. Check list to be maintained during the Bromine ISO tanker unloading 9. Ensure the personnel responsible Unload – Wear PPE – Face shield, Hand gloves, full body suit, goggles & Nitrile hand gloves, safety shoes. 10.Ensure that the Bromine vent scrubber & scrubber media solution – concentration & PH are as specified & capable of Vent load bromine vapors. SOLARIS CHEMTECH INDUSTRIES LIMITED

17. SAFETY PRECAUTIONS SOLARIS CHEMTECH INDUSTRIES LIMITED

18. SOLARIS CHEMTECH INDUSTRIES LIMITED Installed Safety Measures 1. Cl 2 / Br 2 sensors 2. Sodium thio-sulfate solution available @ 24 hrs. 3. Provision of PPE cupboards 4. Interlocking in production plant 5. Flange guards in pipe works 6. Dyke wall 7. Safety shower 8. On site emergency plan 9. ISO leak arrestor tourniquet 10. ISO tankers with GPS tracking system.

19. Safe handling and storage of bromine Avoid contact with bromine or bromine fumes. Never drink water from glass bottle. Never inhale bromine or other chemical fume. Required PPEs must be warn. Pipe work and tanks should be checked regularly for leaks. Before transferring bromine between containers, a check should be made that the receiving container has space for it. SOLARIS CHEMTECH INDUSTRIES LIMITED

20. Store in a dry, well-ventilated area. Containers should be stored upright and all be clearly labeled. Glass or lead containers are suitable for bromine. Lead-lined steel tanks can be used. A free space of 8-10% by volume should be left in the container. All bromine containers (glass bottle, sample bottle etc) should be kept closed. Open glass or sample bottles must be handle under fume extraction hood. SOLARIS CHEMTECH INDUSTRIES LIMITED

21. Safe handling of spilled bromine 1. Ho w to approach? site condition wind direction Use necessary PPE without fail Spilled chemical Wind direction Your position Is this right? SOLARIS CHEMTECH INDUSTRIES LIMITED

22. SOLARIS CHEMTECH INDUSTRIES LIMITED ISO LEAK ARRESTING TOURNIQUET

23. SOLARIS CHEMTECH INDUSTRIES LIMITED PROBABLE EMERGENCY SITUATION Minor leak Major leak Vehicle accident Combination of two or more scenarios as mentioned earlier

24. SOLARIS CHEMTECH INDUSTRIES LIMITED PROBABLE EMERGENCY SITUATION – MINOR LEAKAGE continue… Toxic vapor release Bromine Breakage of two – three filled bottle Leakage from Valve of ISO tanker, rupture disc, man hole cover joint when atm pressure in tanker

25. SOLARIS CHEMTECH INDUSTRIES LIMITED PROBABLE EMERGENCY SITUATION – MAJOR LEAKAGE continue… Toxic liquid release Bromine Breakage of multiple filled bottle Pin hole in body of ISO tank Failure of ISO taker valve, man hole joint or activation of rupture disc when tank is pressurized above atm pressure Major damage to valve, it’s nozzle, rupture disc

26. SOLARIS CHEMTECH INDUSTRIES LIMITED QUICK RESPONSE ACTION MINOR LEAK Isolate the area and shift people away falls in radius of at least 50 meter . Try to prevent leak safely if safe to do so. Transfer the remaining material to other safe container. Contain a spilled liquid by forming bund wall of suitable absorbent around the spillage. Try to reduce the evaporation of chemical by spreading absorbing/neutralizing media. Use PPEs of level at least C to perform above activities. Do not allow to enter chemical or contaminated neutralizing/absorbing media in to near by water body.

27. SOLARIS CHEMTECH INDUSTRIES LIMITED QUICK RESPONSE KIT Traffic cone / barricading tape Public warning system Earth excavating, collecting and shifting equipment / gadgets PPEs at least level B

28. SOLARIS CHEMTECH INDUSTRIES LIMITED QUICK RESPONSE KIT WITH CONSIGNMENT Safety helmet Safety googles PVC apron Gum Boot SCBA set / cartridge mask Rubber Hand gloves Barricading tape 1 kg / 5 kg sodium Thio -sulphate powder First Aid Kit TREM Card

29. 2. How to assess situation ? Quantum of leakage Requirement of additional sources and assistance 3. How to response ? Work in pair Large leakage / Small leakage Isolation mechanically / bund wall 4. How to apply neutralizing agent ? Solid / Liquid Jet / Spray Use qty of neutralizing agent as per requirement Wind direction Use necessary PPE without fail SOLARIS CHEMTECH INDUSTRIES LIMITED

30. Bromine neutralizers Slaked Lime [Ca(OH) 2 ] Slaked lime (solid) is recommended because it is usually readily available and it can be used to form a dike around a bromine spill will adsorb the bromine.  Slaked lime will only begin to react with bromine when water is added. A 20% - 40% slaked lime water slurry can be used. Procedure for use Form a dam of solid slaked lime around the bromine spill Adsorb the bromine in the slaked lime and mix with a shovel or other suitable device Slowly add water to a small amount of the mixed solids to activate neutralization SOLARIS CHEMTECH INDUSTRIES LIMITED

31. mix water/bromine/slaked lime mixture thoroughly using a shovel or other mixing aid repeating steps until all the bromine is neutralized. Collect the neutralized materials for further remediation at an approved site. Sodium thiosulfate (sodium hyposulfite) A solution of 40% sodium thiosulphate ( hyposulphite ) in water containing 1% soda ash [Na 2 (CO 3 ) 2 ] can also be used. Sodium thiosulphate has a very high heat of reaction and should only to be used for neutralizing small quantities Roughly 1 kg sodium thiosulfate will destroy 1 kg bromine. Solution of thiosulphate is always available at every floor or point of plant. Apply thiosulphate solution by spray ; not jet. SOLARIS CHEMTECH INDUSTRIES LIMITED

32. USE FULL PPE NON – RESPIRATORY EQUIPMENTS 1. Foot PVC gum boots 2. Hand gloves Neoprene or nitrile rubber hand gloves 3. Full body PVC / Neoprene rubber suit / apron 4. Eye & Face Air tight goggles / face shield SOLARIS CHEMTECH INDUSTRIES LIMITED

33. Training is required to use these PPEs RESPIRATORY EQUIPMENTS 1. Full face mask with filter cartridge Can be use for short time work (i.e. valve closing in emergency) 2. Air line Apparatus Can be use for continuous work 3. Breathing Apparatus set Can be use up to 45 min max 4. EE BA Can be use up to 10 min max Contact to SAFETY department immediately SOLARIS CHEMTECH INDUSTRIES LIMITED

34. 7. FIRST AID Contact with eyes: Immediately flush/wash out with plenty of water for at least 15 minutes. Seek medical attention. SOLARIS CHEMTECH INDUSTRIES LIMITED

35. Contact with skin: Immediately flush/wash affected area with plenty of water while removing all contaminated clothing and shoes for at least 15 minutes. Seek immediate medical attention. Contaminated clothing and footwear should be discarded. SOLARIS CHEMTECH INDUSTRIES LIMITED

36. Inhalation: Remove patient to fresh air. Keep them quiet and warm. Apply artificial respiration only if patient is not breathing. Avoid mouth to mouth resuscitation. Use alternate methods: bottled air, bottled oxygen or a compressed air driven apparatus. Pursue immediate medical attention. SOLARIS CHEMTECH INDUSTRIES LIMITED

37. Ingestion: Do not induce vomiting. Rinse mouth with water Never give anything by mouth to an unconscious person. Obtain immediate medical attention. SOLARIS CHEMTECH INDUSTRIES LIMITED

38. Thank You ! Think Safety Be Safe Work Safely SOLARIS CHEMTECH INDUSTRIES LIMITED