BROMINE HANDLING activity in reactor .pptx

BROMINE HANDLING SYSTEM
SOLARIS CHEMTECH
INDUSTRIES LIMITED

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

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

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 -
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

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.

Fig1- Side View of Recommended Unloading Hook-up
Customer's scope
Vent to absorber
Vent Line
Liquid unloading line sight glass
Dry air or N2
R Y G
Pressure relief valve
set at 3 ATM
Bromine
Iso tanker
Customer's scope
Customer's
Storage tank
Fig2- Plan View of Valves on the ISO -Container
(with the dome cover open)
Safety relief valve
Pressure release valve
Bromine Unloading Valve
Dry air or Nitrogen Valve
Fusible thermal
relief element
PI
Dip
pipe
The following figure gives the schematic arrangement
necessary for unloading an ISO tank

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.

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).

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.

Example : Bromine Storage arrangement required at the customers end.
Nitrogen Liquid Bromine
Bromine Vapor Line
PG Nitrogen / Dry Air
Instrument Air To caustic scrubber system
PRV CHWS - Chilled water Supply
CHWR CHWR - Chilled Water return
CHWR
Nitrogen CHWS CHWS
To ISO tanker
Liquid bromine
from ISO tank
CHWR CHWR
Bromine to
Day tanks
CHWS CHWS
Dyke wall
P1
Bromine unloading/transfer Pump
( cap-5M3/Hr,Head-25 m,MOC-PVDF) `
BROMINE STORAGE SYSTEM
T1
8 KL (MSGL)
T2
8 KL (MSGL)

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.

MATERIALS OF CONSTRUCTION FOR USE IN CONTACT WITH BROMINE
Gas Liquid Gas Liquid
Metals Lead (2) (3) (4) S at 25°C G up to 50°C
Tantalum (3) G up to 200°C G up to 200°C
Mild Steel, Cast Iron U U U U
Aluminum/Aluminum Alloys U U U U
Stainless Steels (Austenitic) U U S S
Nickel, Monel U U G G
Inconel U U S S
Hastelloy "C" U U G G
Copper, Brass U U U U
Bronze U U S S
Silver U U S S
Titanium [S(5)] U U U
Niobium and Niobium/Tantalum Alloy S S S S
Ceramics
Stoneware, Porcelain, Glass (6) G G G G
Plastics
PTFE, PCTFE, PVDF, FEP (7) G G G G
Ebonite U U U U
CPVC, PVC U U U U
Polyethylene, Polypropylene U U U U
S = Satisfactory under carefully controlled conditions
U = Unsatisfactory
CONDITION OF BROMINE
Wet (1) Dry (Below 30 mg/kg)
G = Good
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.

Safety Practices in The Work Area
General instructions
• Maintain and clean uncontaminated equipment, floors, and work areas.
• Immediately contain and clean up all bromine spills.
• Wear approved respiratory equipment and protective clothing.
• If bromine spill or leakage to be used sodiaum thiosulphate soln ,soda ash solution or hypo solution on the liquid bromine to neutralize.
• Using cold water, wash neutralized bromine to a sump for disposal.
• Open doors and windows to ventilate.
Ventilation
• Transfer or repackage bromine only in a controlled, closed environment.
• Positive exhaust ventilating systems must be used in enclosed areas where bromine is handled.
Containers and storage
• Empty shipping containers completely.
• Do not return used or recycled bromine or other bromine containing liquids in containers as this could lead to catastrophic container failure.
• Store bromine containers in dry, well-ventilated areas, protected from moisture and excessive heat or cold.
• Store only in approved bromine containers. Never store in containers that resemble food or beverage packaging.
• Protect bromine-handling equipment from strong alkalis, reducing agents, other metals, wood, fabric, paper, grease, and oils.
• Check all equipment used for bromine handling or processing for deterioration, as well as leaky valves and couplings. Proper maintenance requires
periodic cleaning and drying with nitrogen.
• Restrict bromine vapor concentration in the work area to less than 0.1 ppm with adequate exhaust hoods, ventilation systems, and scrubbers.
Analyze the air for bromine concentrations to ensure proper control.
• Read and follow all directions and warning labels carefully.
• Inform all personnel of the potential hazards of contact with bromine and train them in appropriate first-aid procedures.
• Store and handle bromine over drip pans drained by a sump that is vented to a scrubber system.
• Bromine handling areas should be clearly marked and restricted to qualified and trained personnel only.
• Avoid contact of bromine with strong reducing agents, strong alkalis, metals, wood, paper products, fabric, grease, and oil or other
combustible materials.

Operator Health Monitoring
There are no regulations or standards indicating a medical test, which would show an overexposure to bromine.
It is recommended that complete medical records be kept for each person working in a facility where there is potential exposure to bromine vapors.
Medical Record for Employee Exposed
Periodic health checks have to be done on employees, aligned to Indian legal requirements
Operator/Driver Safety Training
Some of the subjects to be covered should be:
• The main types of hazards
• Packaging details
• Labeling and marking to indicate hazards
• Precautions during loading and unloading
• Environmental protection
• First aid
• Firefighting
• Selection and use of personal protection equipment
• Respiratory protection
• Emergency procedures
The management should be aware of the potential dangers of bromine. Management personnel should undergo training in bromine specific safety
inspections and safety auditing.
Workers regularly exposed to possible bromine vapors should be given routine medical check-ups. This applies to personnel of operations where
bromine is used, stored, filled, or unloaded.
Workers involved with bromine must have special safety training regarding the precautions to observe in accordance with local regulations. This
applies to personnel of operations where bromine is used, stored, filled or unloaded.
The safety training for handling bromine has to include both theoretical classroom courses and practical hands-on and observation exercises,
appropriate to the level of likely exposure of the individual worker to bromine. Records should be kept of each person’s participation in initial
training and refresher courses.

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.

SAFETY PRECAUTIONS

Installed Safety Measures
1. Cl2 / Br2 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.

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.

 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.

Safe handling of spilled bromine
1. How to approach? - site condition
- wind direction
Use necessary PPE without fail
Spilled
chemical
Wind
direction
Your
position
Is this
right?

ISO LEAK ARRESTING
TOURNIQUET

PROBABLE EMERGENCY SITUATION
• Minor leak
• Major leak
• Vehicle accident
• Combination of two or more scenarios as mentioned earlier

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

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

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.

QUICK RESPONSE KIT
• Traffic cone / barricading tape
• Public warning system
• Earth excavating, collecting and shifting equipment
/ gadgets
• PPEs at least level B

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

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

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

 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 [Na2(CO3)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.

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

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. EEBA Can be use up to 10 min max
Contact to SAFETY department immediately

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

 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.

 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.

 Ingestion:
 Do not induce vomiting.
 Rinse mouth with water
 Never give anything by mouth to an
unconscious person.
 Obtain immediate medical
attention.

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