15.03.2018PrabodhkumarMaiti
thyssenkruppIndustrialSolutionsIndiaPrivateLimited,Mumbai
IdentificationandMitigationofhighhazardprocessesinIdentificationandMitigationofhighhazardprocessesinIdentificationandMitigationofhighhazardprocessesinIdentificationandMitigationofhighhazardprocessesin
ChlorChlorChlorChlor----AlkaliAlkaliAlkaliAlkaliindustryindustryindustryindustry
AMAISEMINARAMAISEMINARAMAISEMINARAMAISEMINAR----2018,2018,2018,2018,BharuchBharuchBharuchBharuch
thyssenkruppIndustrialSolutions-India.PrivateLimited2 15.03.2018AMAISEMINARPrabodhkumarMaiti
IdentificationandMitigationofhighhazardprocessesinChlorIdentificationandMitigationofhighhazardprocessesinChlorIdentificationandMitigationofhighhazardprocessesinChlorIdentificationandMitigationofhighhazardprocessesinChlor----AlkaliindustryAlkaliindustryAlkaliindustryAlkaliindustry
Agenda:Agenda:Agenda:Agenda:
oHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasures
oChlorChlorChlorChlor----AlkaliMembraneplantprocessAlkaliMembraneplantprocessAlkaliMembraneplantprocessAlkaliMembraneplantprocessooooverviewverviewverviewverview
oHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
oSafetyfeaturesintkyssenkruppUhdemembranecellplantSafetyfeaturesintkyssenkruppUhdemembranecellplantSafetyfeaturesintkyssenkruppUhdemembranecellplantSafetyfeaturesintkyssenkruppUhdemembranecellplant
oSummarySummarySummarySummary
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•Hazardous Chemical
Occupational Safety & Health Act (OSHA) term that denotes any chemical that would be a risk to employees if exposed in the work place
•Highly Hazardous Chemical
OSHA term that denotes any chemical that would posses toxic, reactive, flammable or explosive properties
HazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasures
thyssenkruppIndustrialSolutions-India.PrivateLimited4 15.03.2018AMAISEMINARPrabodhkumarMaiti
Explosive
Oxidizing
Flammable
Toxic
Harmful to health
Corrosive
Irritant
Sensitizing
Carcinogen (cancer-causing)
Toxic for reproduction
Mutagen
Hazardous to the environment
HazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasures
thyssenkruppIndustrialSolutions-India.PrivateLimited5 15.03.2018AMAISEMINARPrabodhkumarMaiti
HazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasures
HazardousSubstancesHazardousSubstancesHazardousSubstancesHazardousSubstances
PhysicalState
Generalral
Liquid
Solid
Gas
Special
Vapor
Dust
Fume
Mist
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HazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasures
AcuteEffects
- Imminent-highconcentrationinshorttime.
- Indirect-highconcentrationinshorttime,
evennontoxicgases.
ChronicEffects
-lowconcentrationoverlongperiodoftime.
LatencyPeriodofDisease
Sensitizers
Actionoftoxins
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HazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasuresHazardoussubstancesandPreventivemeasures
PreventiveMeasures
Elimination Substitution Local exhaust ventilation General ventilation Isolation Preventive maintenance
Administrative controls
Limitation of time, shiftwork, change of workplaces Handling procedures Spill and Leak Prevention Procedures Storage requirements Special shipping Information
Engineering controls
Personal protective equipment
Respirators, Gloves, Eye Protection, etc. The Human Factor Training Essential
thyssenkruppIndustrialSolutions-India.PrivateLimited8 15.03.2018AMAISEMINARPrabodhkumarMaiti
Transformer/
Rectifier
Transformer/
Rectifier
Membrane
Electrolysis
Membrane
Electrolysis
Catholyte
Circulation
Catholyte
Circulation
Caustic
Concentration
Caustic
Concentration
Chlorine
Compression
Chlorine
Compression
WasteGas
Dechlorination
WasteGas
Dechlorination
HClSynthesisHClSynthesis
Chlorine
Treatment
Chlorine
Treatment
Cl2
98%
H2SO4ConcentrationH2SO4Concentration
Hydrogen
Treatment
Hydrogen
Treatment
H2
NaOH
H2O
H2O
78%
Clarification
Precipitation
Clarification
Precipitation
Brine
Filtration
Brine
Filtration
Brine
Purification
Brine
Purification
Brine
Saturation
Brine
SaturationSalt
a-Cellulose
Sludge
AnolyteAnolyteDechlorination
NaHSO3
Purge
Flocculant
NaOH
Na2CO3
BaCO3
NaOH
ChlorChlorChlorChlor----AlkaliMembraneplant-ProcessOverview.AlkaliMembraneplant-ProcessOverview.AlkaliMembraneplant-ProcessOverview.AlkaliMembraneplant-ProcessOverview.
Caustic
Flaking
Caustic
Flaking
Chlorine
Liquefaction
Chlorine
Liquefaction
Hydrogen
Compression
Hydrogen
Compression
Power
Hypo
Solution
Hypo
Solution
thyssenkruppIndustrialSolutions-India.PrivateLimited9 15.03.2018AMAISEMINARPrabodhkumarMaiti
HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
Chlorine:Chlorine:Chlorine:Chlorine:
Chlorine:Chlorine:Chlorine:Chlorine:
Cell House
Chlorinesystem-wet&dry.
HClsynthesis
ChlorineCompression&liquefaction
Chlorinestorage&filling
Waste gas/hypo system
thyssenkruppIndustrialSolutions-India.PrivateLimited10 15.03.2018AMAISEMINARPrabodhkumarMaiti
HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
Caustic:Caustic:Caustic:Caustic:
Caustic:Caustic:Caustic:Caustic:
CellHouse-32%w/w.
Catholytesystem-32%w/w.
Concentration-32%- 50%w/w.
Flaking-50%- 100%w/w.
Causticstorage
IOXregenerationsystem-4-20%w/w.
thyssenkruppIndustrialSolutions-India.PrivateLimited11 15.03.2018AMAISEMINARPrabodhkumarMaiti
HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
Hydrogen:Hydrogen:Hydrogen:Hydrogen:
HydrogenHydrogenHydrogenHydrogen::::
Cell House
Hydrogensystem
HCl-synthesisunit
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Hydrochloricacid:Hydrochloricacid:Hydrochloricacid:Hydrochloricacid:
HydrochloricHydrochloricHydrochloricHydrochloric acidacidacidacid::::
HCl-synthesisunit
HClstorage
Anolyte system
IOXregeneration unit
Cell room -acidification.
HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
thyssenkruppIndustrialSolutions-India.PrivateLimited13 15.03.2018AMAISEMINARPrabodhkumarMaiti
SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:
SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:
Absorbtionsystem
Bleaching lye production
Anolyte system
HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
thyssenkruppIndustrialSolutions-India.PrivateLimited14 15.03.2018AMAISEMINARPrabodhkumarMaiti
Sulphuricacid:Sulphuricacid:Sulphuricacid:Sulphuricacid:
SulfuricSulfuricSulfuricSulfuric acidacidacidacid::::
Chlorinedryingtower
Sulphuricacidstorage
Sulfuric acid concentration unit
HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant
thyssenkruppIndustrialSolutions-India.PrivateLimited15 15.03.2018AMAISEMINARPrabodhkumarMaiti
SAFETYSAFETYSAFETYSAFETYFEATURESOFthyssenkruppUHDEMEMBRANEPLANTFEATURESOFthyssenkruppUHDEMEMBRANEPLANTFEATURESOFthyssenkruppUHDEMEMBRANEPLANTFEATURESOFthyssenkruppUHDEMEMBRANEPLANT
• Safety aspect of cell design
−Configuration of thyseenkrupp Uhde electrolysers into cell room layout
−Electrical circuit
− Instrumentation and interlocking system
−Double insulating system against ground
−Automatic Nitrogen Purging of anolyte & catholyte headers
−Uhde Evaluator
thyssenkruppIndustrialSolutions-India.PrivateLimited16 15.03.2018AMAISEMINARPrabodhkumarMaiti
SafetyofUHDEMembraneElectrolysersSafetyofUHDEMembraneElectrolysersSafetyofUHDEMembraneElectrolysersSafetyofUHDEMembraneElectrolysers---- InstrumentationInstrumentationInstrumentationInstrumentation
PICPICPICPIC
PICPICPICPIC
N2
N2
PICPICPICPIC
N2
Cl2 tocompressor
CoolersCoolersCoolersCoolers
2000mmWC
ClClClCl2222
PICPICPICPIC
AnolyteAnolyteAnolyteAnolyte CatholyteCatholyteCatholyteCatholyte
ElectrolyzerElectrolyzerElectrolyzerElectrolyzerHHHH2222 2200mmWC
PDICPDICPDICPDIC
H2 toconsumer
CoolersCoolersCoolersCoolers
Wastegas
PICPICPICPIC
PDICPDICPDICPDIC
TITITITI
thyssenkruppIndustrialSolutions-India.PrivateLimited17 15.03.2018AMAISEMINARPrabodhkumarMaiti
SafetyofthyssenkruppUHDEMembraneElectrolysersSafetyofthyssenkruppUHDEMembraneElectrolysersSafetyofthyssenkruppUHDEMembraneElectrolysersSafetyofthyssenkruppUHDEMembraneElectrolysers
Pinholescanbecausedby:Pinholescanbecausedby:Pinholescanbecausedby:Pinholescanbecausedby:
o Membranehandlingduringinstallation
o Electrodeirregularities
o PressureFluctuation
o SaltCrystaldeposition
o HydrogenflowintothechlorineAnodehalf-shellduetomechanicalfailure-pinhole.of
membraneinGaszone
Conditionsmaytheoreticallyleadformationofexplosivemixtureswithinthechlorinesystemwith
hydrogenastheflammablecomponent
o Qualityofmembrane
thyssenkruppIndustrialSolutions-India.PrivateLimited18 15.03.2018AMAISEMINARPrabodhkumarMaiti
Polarization rectifier operation
On load Pinhole Detection /
Voltage test
H2 in Cl2 analyses at start-up
BubbleTestI&II MembraneTearTest PolarizationTest
Testsduring
start-up
FallowoperatingguidelinesFallowoperatingguidelinesFallowoperatingguidelinesFallowoperatingguidelines
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HydrogeninchlorineanalysisatstartHydrogeninchlorineanalysisatstartHydrogeninchlorineanalysisatstartHydrogeninchlorineanalysisatstart----upupupup
Gen.6experience:H2 inCl2 higheratstart-upcomparedwithearliergeneration
1.TakesamplestomeasureH2 inCl2
a.byORSATorOnlineinstrumentfor1st indication
b.byGC
2.IfH2 inCl2 islessthan0.25%v/vrampupDCloadfurther
Note:Note:Note:Note: Residencetimeatlowloadmustbeasshortaspossible!
3.Iflimitisexceeded,shutdownelectrolyserandcontinuewithMembraneTearTest
thyssenkruppIndustrialSolutions-India.PrivateLimited20 15.03.2018AMAISEMINARPrabodhkumarMaiti
Electricshockbydangerousvoltages-Potentialdifference.
Burningsbyelectricarcs-alsobylowvoltageshort-cutsbuthighdischargeenergy.
Secondaryinjuriesbyshockreactions-lossofbalance,falling,droppingtoolsetc..
RHuman ≈ 1300Ω
Cardiacfibrillationlimit≈ 40mAAC
HazardHazardHazardHazard limitsfortouching/bridgingpotentialsare120VDC-50VAC.
1000V1000V1000V1000VNoPotentialdifference
→→→→ notdangerousnotdangerousnotdangerousnotdangerous
Potentialdifference,
electriccircuitclosed
→→→→ dangerousdangerousdangerousdangerous
1000V1000V1000V1000V
ElectricalSafetyElectricalSafetyElectricalSafetyElectricalSafety–––– HazardPrincipleHazardPrincipleHazardPrincipleHazardPrinciple
thyssenkruppIndustrialSolutions-India.PrivateLimited21 15.03.2018AMAISEMINARPrabodhkumarMaiti
o On line analyzers: H2 in Chlorine
o Off line analyzers: ICP, Gas chromatograph, TOC
o 24 hours sampler
o Uhde Evaluator™
o Regular audit of plant performance
o Regular training of Plant Operators
FurtherFurtherFurtherFurther improvementsinoperationimprovementsinoperationimprovementsinoperationimprovementsinoperation
thyssenkruppIndustrialSolutions-India.PrivateLimited22 15.03.2018AMAISEMINARPrabodhkumarMaiti
CHLORINESAFETYCHLORINESAFETYCHLORINESAFETYCHLORINESAFETY
o Possible hazards of chlorine
o Designing a safe chlorine plant
o Chlorine storage installation
o Chlorine filling and handling
thyssenkruppIndustrialSolutions-India.PrivateLimited23 15.03.2018AMAISEMINARPrabodhkumarMaiti
CHLORINE CONC. IN AIR, PPM
DEGREE OF HAZARD
0.2 – 0.5 No noxious long term effect
0.5 Slight odour
1.0 – 3.0 Definite odour, irritation of eyes and nose
6.0 Irritation of the throat
30 Intense cough fits
40 – 60 Exposure without effective respirator for 30-60 minutes or more may cause serious damage
100 May cause lethal damage
1000 Danger to life even after few deep inhalations
HazardsofchlorineatdifferentatmosphericconcentrationsHazardsofchlorineatdifferentatmosphericconcentrationsHazardsofchlorineatdifferentatmosphericconcentrationsHazardsofchlorineatdifferentatmosphericconcentrations
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Fire&ExplosionhazardsofchlorineFire&ExplosionhazardsofchlorineFire&ExplosionhazardsofchlorineFire&Explosionhazardsofchlorine
oNeither liquid nor gaseous chlorine is explosive or flammable by itself
oChlorine reacts to cause fire or explosions upon contact with turpentine, ether,
ammonia gas, hydrocarbons, hydrogen, powdered metals, sawdust and
phosphorus.
oOne volume of liquid chlorine when vaporized yields about 460 volumes of gas
oHydrogen and chlorine can form explosive mixtures
thyssenkruppIndustrialSolutions-India.PrivateLimited25 15.03.2018AMAISEMINARPrabodhkumarMaiti
AccidentsrelatedtochlorineAccidentsrelatedtochlorineAccidentsrelatedtochlorineAccidentsrelatedtochlorine-Source:Eurochlor.-Source:Eurochlor.-Source:Eurochlor.-Source:Eurochlor.
o70% of accidents due to human errors and rest due to failure of various plant
components.
oDue to wrong management
oSome 20% of recorded incidents happened in handling chlorine cylinders
osome 35% of incidents happened in water treatment plants as a result of chlorine
emission from acidic water.
thyssenkruppIndustrialSolutions-India.PrivateLimited26 15.03.2018AMAISEMINARPrabodhkumarMaiti
DesigningasafechlorineplantDesigningasafechlorineplantDesigningasafechlorineplantDesigningasafechlorineplant
oChoosing the right materials of construction
− Dry Cl2 : pH2O < 1 mbar (-20°C < T < 120°C) : CS is safe material for construction.
− Wet Cl2 : pH2O > 14 mbar (15°C < T < 70°C) and exponentially more at higher temperatures:Titanium is safe material for construction.
oBellow sealed valves.
oNo pockets in pipelines.
thyssenkruppIndustrialSolutions-India.PrivateLimited27 15.03.2018AMAISEMINARPrabodhkumarMaiti
LIPI PI
100
WI
AI
CHLORINE DETECTOR
HSE
EMERGENCY TRIP
HSE
From Liquefier
Unloading air
To Cl2 compressor discharge
To waste gas dechlorination unit
To filling station
PCC Flooring
Emergency
waste air
blower
1. SMPV/PESO rules
2. Emergency spare tank
3. Filling of one tank at a time
TI
CHLORINESTORAGEINSTALLATIONCHLORINESTORAGEINSTALLATIONCHLORINESTORAGEINSTALLATIONCHLORINESTORAGEINSTALLATION24
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ChlorinecylinderfillingandhandlingChlorinecylinderfillingandhandlingChlorinecylinderfillingandhandlingChlorinecylinderfillingandhandling
oStorage area should be cool, dry, well-ventilated, clean of trash and protected
from external heat sources.
oKeep them away from sun or sources of heat.
oUse cylinders in the order of receipt.
oTon containers should be stored on their sides. They should not be stacked or
racked more than one high.
oWhen being emptied, the key should be opened fully, it should not be allowed to
regulate the flow of chlorine.
oThe tonners should be handled with a hoist or a crane.
thyssenkruppIndustrialSolutions-India.PrivateLimited29 15.03.2018AMAISEMINARPrabodhkumarMaiti
ChlorineabsorptionsystemChlorineabsorptionsystemChlorineabsorptionsystemChlorineabsorptionsystem
oThe waste air dechlorination unit is designed for the following cases:
− Normal operation
− During start-up of the electrolysers.
− To absorb the total chlorine production at 100% load for a period of 10 minutes in the
case of an emergency.
o In any eventuality chlorine will not be released into the atmosphere because each of the
two stage system is designed for 100% capacity.
oThe unit runs continuously on emergency power supply.
oThe unit consists of a two stage ejector system / two stage tower absorption system. This
is followed by a final absorber.
thyssenkruppIndustrialSolutions-India.PrivateLimited30 15.03.2018AMAISEMINARPrabodhkumarMaiti
Chlorineabsorptionsystem-contd..Chlorineabsorptionsystem-contd..Chlorineabsorptionsystem-contd..Chlorineabsorptionsystem-contd..
oPractically all the chlorine is absorbed in the first stage itself.
o In the second stage, any unabsorbed chlorine is absorbed in circulating bleach
lye with a high excess of NaOH.
oThe final absorber is provided for additional safety (for polishing)
oDuring normal operation, the required quantity of caustic depending on the
chlorine load, is fed to the final absorber by a redox controller.
oThe waste gas stream leaving the final absorber has a chlorine content of CPCB
norms / international standard.
oA chlorine detector is provided at the vent to atmosphere.
oNo pockets in pipelines.
thyssenkruppIndustrialSolutions-India.PrivateLimited31 15.03.2018AMAISEMINARPrabodhkumarMaiti
SafetyinHydrogensystemSafetyinHydrogensystemSafetyinHydrogensystemSafetyinHydrogensystem
oThe system is a completely sealed system under positive pressure.
oProtection against low pressures
oNo pockets.
oCondensate seals.
oStack safety: Safe location, Flame arrestor/N2 purging, steam quenching.
o The cell room and the hydrogen compressor house is designed for adequate
ventillation and air circulation to prevent accumulation of hydrogen.
oLightening arrestors.
thyssenkruppIndustrialSolutions-India.PrivateLimited32 15.03.2018AMAISEMINARPrabodhkumarMaiti
SafetyincausticsystemSafetyincausticsystemSafetyincausticsystemSafetyincausticsystem
oCaustic soda is a hazardous chemical
oOperation and maintenance by properly instructed personnel under experienced
supervision.
oPersonal protection.
oFirst aid.
thyssenkruppIndustrialSolutions-India.PrivateLimited33 15.03.2018AMAISEMINARPrabodhkumarMaiti
DesignofasafecausticsystemDesignofasafecausticsystemDesignofasafecausticsystemDesignofasafecausticsystem
oChoosing the right materials of construction
oCovering of flanges
oSafety showers and eye-wash systems
thyssenkruppIndustrialSolutions-India.PrivateLimited34 15.03.2018AMAISEMINARPrabodhkumarMaiti
HazopHazopHazopHazop studystudystudystudy-Hazardandoperabilitystudy.Hazardandoperabilitystudy.Hazardandoperabilitystudy.Hazardandoperabilitystudy.
oMost fundamental & valuable tool towards safety is experience, but not sufficient
because:
− Costly in terms of human suffering & financial losses
− Hazards identified as a consequence of experience, require changes, which
could result in new & unidentified hazards
oHAZOP study is an additional tool to supplement experience.
oApplying hypothetical guide words (deviations) based on P&ID. Relatively cheap at
implementation stage.
o99% of possible hazards can be identified & rectified.
thyssenkruppIndustrialSolutions-India.PrivateLimited35 15.03.2018AMAISEMINARPrabodhkumarMaiti
SILSILSILSIL -SafetyIntegrityLevel.studySafetyIntegrityLevel.studySafetyIntegrityLevel.studySafetyIntegrityLevel.study
SIL is an exercise in risk analysis associated with a specific hazard, that is
intended to be protected against by a SIF (Safety Instrumented Function):
There are several methods used to assign a SIL
oRisk matrices
oRisk graphs
oLayers of protection analysis (LOPA)
− LOPA is by far the most commonly used by large industrial facilities
oOut come of HAZOP is used to study SIL in order to eliminate risk for a specific
hazard.
thyssenkruppIndustrialSolutions-India.PrivateLimited36 15.03.2018AMAISEMINARPrabodhkumarMaiti
SummarySummarySummarySummary
oList down the hazardous operations and chemicals
oList mitigation and response strategies for each hazard
oPeriodically conduct HAZOP/SIL study and implement the outcome
oSelect the best and safe available process technology and engineering
o Improve existing plant performance and safety by audit from competent agencies
oUse automation wherever possible in order to avoid human error
oPreventive and predictive maintenance
oUse personal protection equipment
oPeriodical training of plant operating staff
oUpdate the standard operating procedure
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