identificationa ndm itigationo fh ighh azardp roces sesin chlor-chlor ... · 2020. 5. 20. ·...

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


•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


Explosive

Oxidizing

Flammable

Toxic

Harmful to health

Corrosive

Irritant

Sensitizing

Carcinogen (cancer-causing)

Toxic for reproduction

Mutagen

Hazardous to the environment




HazardousSubstancesHazardousSubstancesHazardousSubstancesHazardousSubstances

PhysicalState

Generalral

Liquid

Solid

Gas

Special

Vapor

Dust

Fume

Mist



AcuteEffects

- Imminent-highconcentrationinshorttime.

- Indirect-highconcentrationinshorttime,

evennontoxicgases.

ChronicEffects

-lowconcentrationoverlongperiodoftime.

LatencyPeriodofDisease

Sensitizers

Actionoftoxins



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


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


HazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlorHazardousoperationsandchemicalsinChlor----AlkalimembraneplantAlkalimembraneplantAlkalimembraneplantAlkalimembraneplant

Chlorine:Chlorine:Chlorine:Chlorine:

Chlorine:Chlorine:Chlorine:Chlorine:

Cell House

Chlorinesystem-wet&dry.

HClsynthesis

ChlorineCompression&liquefaction

Chlorinestorage&filling

Waste gas/hypo system



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.



Hydrogen:Hydrogen:Hydrogen:Hydrogen:

HydrogenHydrogenHydrogenHydrogen::::

Cell House

Hydrogensystem

HCl-synthesisunit


Hydrochloricacid:Hydrochloricacid:Hydrochloricacid:Hydrochloricacid:

HydrochloricHydrochloricHydrochloricHydrochloric acidacidacidacid::::

HCl-synthesisunit

HClstorage

Anolyte system

IOXregeneration unit

Cell room -acidification.



SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:

SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:SodiumHypochlorite:

Absorbtionsystem

Bleaching lye production

Anolyte system



Sulphuricacid:Sulphuricacid:Sulphuricacid:Sulphuricacid:

SulfuricSulfuricSulfuricSulfuric acidacidacidacid::::

Chlorinedryingtower

Sulphuricacidstorage

Sulfuric acid concentration unit



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


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


SafetyofthyssenkruppUHDEMembraneElectrolysersSafetyofthyssenkruppUHDEMembraneElectrolysersSafetyofthyssenkruppUHDEMembraneElectrolysersSafetyofthyssenkruppUHDEMembraneElectrolysers

Pinholescanbecausedby:Pinholescanbecausedby:Pinholescanbecausedby:Pinholescanbecausedby:

o Membranehandlingduringinstallation

o Electrodeirregularities

o PressureFluctuation

o SaltCrystaldeposition

o HydrogenflowintothechlorineAnodehalf-shellduetomechanicalfailure-pinhole.of

membraneinGaszone

Conditionsmaytheoreticallyleadformationofexplosivemixtureswithinthechlorinesystemwith

hydrogenastheflammablecomponent

o Qualityofmembrane


Polarization rectifier operation

On load Pinhole Detection /

Voltage test

H2 in Cl2 analyses at start-up

BubbleTestI&II MembraneTearTest PolarizationTest

Testsduring

start-up

FallowoperatingguidelinesFallowoperatingguidelinesFallowoperatingguidelinesFallowoperatingguidelines


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


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


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


CHLORINESAFETYCHLORINESAFETYCHLORINESAFETYCHLORINESAFETY

o Possible hazards of chlorine

o Designing a safe chlorine plant

o Chlorine storage installation

o Chlorine filling and handling


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


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


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.


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.


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


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.


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.


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.


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.


SafetyincausticsystemSafetyincausticsystemSafetyincausticsystemSafetyincausticsystem

oCaustic soda is a hazardous chemical

oOperation and maintenance by properly instructed personnel under experienced

supervision.

oPersonal protection.

oFirst aid.


DesignofasafecausticsystemDesignofasafecausticsystemDesignofasafecausticsystemDesignofasafecausticsystem

oChoosing the right materials of construction

oCovering of flanges

oSafety showers and eye-wash systems


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.


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.


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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identificationa ndm itigationo fh ighh azardp roces sesin chlor-chlor ... · 2020. 5. 20. ·...

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