Hydrogen Sulfide in PetroleumHydrogen Sulfide in PetroleumHydrogen Sulfide in Petroleum
Mike Nicholson/Tim OMike Nicholson/Tim O’’BrienBrienBaker Petrolite CorporationBaker Petrolite Corporation
Hydrogen SulfideHydrogen SulfideHydrogen Sulfide
Toxic, Colorless GasToxic, Colorless GasRotten Egg OdorRotten Egg Odor
Detectable at >10Detectable at >10 ppbppbParalyzes olfactory systemParalyzes olfactory systemLC50 = 713 ppmLC50 = 713 ppm
Weak Acid, Air Oxidized, Absorbs On Weak Acid, Air Oxidized, Absorbs On MetalsMetalsSolubility Depends On Temperature, Solubility Depends On Temperature, Fuel, & HenryFuel, & Henry’’s Laws Law
Hydrogen Sulfide ToxicityHydrogen Sulfide ToxicityHydrogen Sulfide Toxicity
Concentration (ppm) Health Effect
< 0.02 Olfactory Detection Limit
10 8 Hr Exposure Limit
15 15 Min. STEL
100 Common Ship Headspace Spec.
300 Considered Immediately Hazardous
713 LC50 Concentration
1000 Common Tank, Ship Headspace Concentration
Hydrogen Sulfide ConcernsHydrogen Sulfide ConcernsHydrogen Sulfide Concerns
HH22SS
ToxicToxicEmployee exposureEmployee exposure
Storage tanksStorage tanksBarges, shipsBarges, ships
CorrosiveCorrosiveFuel specs.Fuel specs.Tank roofTank roofPipelinesPipelines
Odor ControlOdor ControlStorage tank ventsStorage tank ventsSewersSewers
Odor IssuesOdor IssuesOdor Issues
Detection Limits for CommonOdorants
ODORANT DETEC TION LIM IT (PPM V/V)ETHYL M ERCAPTAN 0.0003M ETHYL M ERC APTAN 0.0008HYDROGEN SULFIDE 0.002DIM ETHY L SULFIDE 0.002PHENOL 0.05P-XYLENE 0.05TOLUENE 2.0BENZENE 5.0AM M ONIA 50
Hydrogen SulfideHydrogen SulfideHydrogen Sulfide
Crude OilCrude OilAsphaltAsphaltResidual Fuel & ComponentsResidual Fuel & ComponentsMidMid--Distillates & Blend ComponentsDistillates & Blend ComponentsGasoline & Blend ComponentsGasoline & Blend ComponentsNatural Gas, Propane, LPGNatural Gas, Propane, LPG
Petroleum Streams Where HPetroleum Streams Where H22S FoundS Found
Crude OilCrude OilCrude Oil
High Sulfur CrudesHigh Sulfur CrudesMexicoMexico
MayaMaya 100ppm liquid100ppm liquidOlmecaOlmeca 116ppm liquid116ppm liquid
Middle EastMiddle EastEoceneEocene 90ppm liquid90ppm liquidRatawiRatawi 80ppm liquid80ppm liquid
AfricaAfricaSoyoSoyo 16ppm liquid16ppm liquid
H2S PartitioningH2S PartitioningH2S Partitioning
200
800
0100200300400500600700800
ppm
Hea
dspa
ce H
2S Fuel AFuel B
2 ppm liquid phase H2S content2 ppm liquid phase H2S content60 F with sample mixing60 F with sample mixing
Partition CoefficientsPartition CoefficientsPartition Coefficients
Crude OilCrude Oil8080--300 300 vppm vppm per 1lppmper 1lppm
Residual OilResidual Oil8080--400 400 vppm vppm per 1lppmper 1lppm
Gas OilGas Oil3030--150 150 vppm vppm per 1lppmper 1lppm
GasolineGasoline5050--200 200 vppm vppm per 1lppmper 1lppm
Partitioning of H2SPartitioning of HPartitioning of H22SS
1 ppm in liquid can equate to > 50 1 ppm in liquid can equate to > 50 ppm in vapor spaceppm in vapor space100 ppm in liquid can equate to 100 ppm in liquid can equate to 20,000 ppm in vapor space20,000 ppm in vapor space
Hydrogen Sulfide ConcentrationsHydrogen Sulfide ConcentrationsHydrogen Sulfide Concentrations
Levels of H2S Can be Extremely High Levels of H2S Can be Extremely High if Cargoes Are Over Heatedif Cargoes Are Over HeatedEocene Crude H2S Production After Eocene Crude H2S Production After Heating 1 Hour @ Specified Heating 1 Hour @ Specified TemperatureTemperature
100 Deg. F100 Deg. F 400 ppm400 ppm200 Deg F200 Deg F 16,000 ppm16,000 ppm300 Deg F300 Deg F >80,000 ppm>80,000 ppm
Factors Affecting PartitioningFactors Affecting PartitioningFactors Affecting Partitioning
TemperatureTemperatureViscosityViscosityPressurePressureAgitationAgitationBasic compound in oilBasic compound in oil
HEAD SPACE H2S VARIATION WITH TIMEHEAD SPACE H2S VARIATION WITH TIMEHEAD SPACE H2S VARIATION WITH TIME
0200400600800
100012001400
0 0.5 1 1.5 2 2.5
TIME (HOURS)
VAPO
R S
PAC
E H
2S (P
PM)
H2S SpecificationsHH22S SpecificationsS Specifications
Regulatory BodiesRegulatory BodiesLA harbor, < 70 ppm in liquid LA harbor, < 70 ppm in liquid
TerminalsTerminalsVariableVariableNone to 0 ppmNone to 0 ppm5050--200 ppm in vapor typical200 ppm in vapor typical
Processing FacilitiesProcessing FacilitiesVariableVariable< 50 ppm in Can Test to None< 50 ppm in Can Test to None
PipelinesPipelinesOnly one encountered, < 50 ppm in can testOnly one encountered, < 50 ppm in can test
Hydrogen Sulfide Test MethodsHydrogen Sulfide Test MethodsHydrogen Sulfide Test Methods
Vapor SpaceVapor SpaceGas detection tubesGas detection tubesMonitor ElectronicallyMonitor Electronically
Fuel SampleFuel SampleASTM DASTM D--5705 5705 ““Can TestCan Test””
LiquidLiquidSpargeSparge test, test, ASTM DASTM D--3227, UOP3227, UOP--163163New ASTM methodNew ASTM method
“Can Test” Method““Can TestCan Test”” MethodMethod
AdvantagesAdvantagesQuick & easyQuick & easy1 1 -- 80,000 ppm80,000 ppmIndustry standardIndustry standard
DisadvantagesDisadvantagesLoss of HLoss of H22SSPoor repeatability & Poor repeatability & reproducibilityreproducibilityResults influenced Results influenced by temp. & shakingby temp. & shaking
Step 1Step 1
Add 500 ml Add 500 ml Sample to Sample to cancan
Step 2Step 2EquilibrateEquilibrate
Temp. AgitateTemp. Agitate
Step 3Step 3Measure HMeasure H22SS
With Gas With Gas Detection TubeDetection Tube
Hydrogen Sulfide ScavengersD-5705 Test ConditionsHydrogen Sulfide ScavengersHydrogen Sulfide ScavengersDD--5705 Test Conditions5705 Test Conditions
140 F Test Temp140 F Test Temp1/2 Full Liter Bottle1/2 Full Liter Bottle3 Minutes @ 150 RPM on 3 Minutes @ 150 RPM on Orbital ShakerOrbital ShakerDragerDrager Tube DetectionTube Detection
Liquid Phase Sparge TestLiquid PhaseLiquid Phase SpargeSparge TestTest
MultiMulti--step Procedurestep ProcedureAdvantagesAdvantages
Results not dependent on Results not dependent on temp.,temp., volvol., etc...., etc...Field method Field method Works with a variety of Works with a variety of hydrocarbonshydrocarbons
DisadvantagesDisadvantagesWet chemistry analysisWet chemistry analysis
150150°°F Water F Water BathBath
HH22 SSHH22SS
HH 22SS HH22 SS
HH22SS
HH 22SS
GTD* TubeGTD* TubeNitrogen (150 ml/min.)Nitrogen (150 ml/min.)
Glass JarGlass JarStopperStopper
Total HTotal H22S = (GDT* Reading x 1.42) / Sample wt.S = (GDT* Reading x 1.42) / Sample wt.
*Gas Detection Tube with n=10 scale*Gas Detection Tube with n=10 scale
Hydrogen Sulfide ScavengersAdditional Test MethodsHydrogen Sulfide ScavengersHydrogen Sulfide ScavengersAdditional Test MethodsAdditional Test Methods
Vapor Space MethodsVapor Space MethodsEssoEsso Can TestCan TestShell Can TestShell Can TestBaker Petrolite Can TestBaker Petrolite Can Test
Liquid Test MethodsLiquid Test MethodsUOP 163UOP 163ASTM DASTM D--32273227ASTM DASTM D--6021 (New Method)6021 (New Method)
H2S AnalysisH2S AnalysisH2S Analysis
Good sampling critical for good resultsGood sampling critical for good resultsCommon mistakesCommon mistakes
cooling of samples before analysiscooling of samples before analysisexcessive pouring, transfer of samplesexcessive pouring, transfer of samplesstorage of oil before analysisstorage of oil before analysis
Test influencesTest influencesVapor phase testVapor phase test
agitation, temperature, vapor/liquid ratioagitation, temperature, vapor/liquid ratioLiquid phase testLiquid phase test
coating of electrodes,coating of electrodes, interferencesinterferences
Hydrogen Sulfide ScavengersHydrogen Sulfide ScavengersHydrogen Sulfide Scavengers
©©1999 Baker Petrolite1999 Baker Petrolite
Hydrogen Sulfide ScavengersAdditive TreatmentsHydrogen Sulfide ScavengersHydrogen Sulfide ScavengersAdditive TreatmentsAdditive Treatments
ChemistryChemistryOxidizersOxidizersNeutralizersNeutralizersReactantsReactants
Process ConsiderationsProcess ConsiderationsTemperature gradientsTemperature gradientsWeatheringWeatheringAdditive mixingAdditive mixing
Hydrogen Sulfide ScavengersOrganic BasesHydrogen Sulfide ScavengersHydrogen Sulfide ScavengersOrganic BasesOrganic Bases
Advantages:Advantages:Fast reactionFast reactionNo sodiumNo sodiumOil soluble/dispersibleOil soluble/dispersible
DISADVANTAGES:DISADVANTAGES:Reaction is ReversibleReaction is ReversibleWeak acid/base equilibriumWeak acid/base equilibriumNot specific for HNot specific for H22SS
Typically Amines (e.g. MEA)Typically Amines (e.g. MEA)HH22S + Neutralizer SaltS + Neutralizer Salt
Hydrogen Sulfide ScavengersInorganic NeutralizersHydrogen Sulfide ScavengersHydrogen Sulfide ScavengersInorganic NeutralizersInorganic Neutralizers
AdvantagesAdvantagesFast reaction, cheapFast reaction, cheapUse alone or in combinationUse alone or in combinationThermally stable products (Thermally stable products (NaHSNaHS))
DisadvantagesDisadvantagesNonNon--selective for Hselective for H22SS
Ash forming Ash forming Increases fuelIncreases fuel NaNa contentcontent . Reversible. ReversibleLimited Safe Injection TemperatureLimited Safe Injection Temperature
Inorganic Bases:Inorganic Bases: NaOHNaOH, KOH Or Blends, KOH Or BlendsHH22S +S + NaOHNaOH SaltSalt
H2S REDUCTION WITH CAUSTIC,50 PPM NaOHH2S REDUCTION WITH CAUSTIC,H2S REDUCTION WITH CAUSTIC,50 PPM50 PPM NaOHNaOH
60 MIN REACTION TIME
0200400600800
100012001400
FUEL A FUEL B FUEL C FUEL D
VAPO
R S
PAC
E H
2S
INITIAL FINAL
EFFECT OF TEMPERATURE AND CONCENTRATION ONCAUSTIC SODA SERVICE APPLICATIONEFFECT OF TEMPERATURE AND CONCENTRATION ONEFFECT OF TEMPERATURE AND CONCENTRATION ONCAUSTIC SODA SERVICE APPLICATIONCAUSTIC SODA SERVICE APPLICATION
CORROSION DATA SURVEY; NACE, 1968, p 4
050
100150200250300
0 10 20 30 40 50
CONCENTRATION OF NaOH %
TEM
PER
ATU
RE
F
AREA "C"AREA "C"NICKEL ALLOYS TO BE CONSIDERED NICKEL ALLOYS TO BE CONSIDERED IN THIS AREAIN THIS AREA
AREA "A" CARBON STEEL AREA "A" CARBON STEEL NO STRESS RELIEF NECESSARYNO STRESS RELIEF NECESSARY
AREA "B"AREA "B"CARBON STEELCARBON STEELSTRESS RELIEVE WELDS & BENDSSTRESS RELIEVE WELDS & BENDS
H2S ScavengersReactive/Conversion AdditivesHH22S ScavengersS ScavengersReactive/Conversion AdditivesReactive/Conversion Additives
Advantages:Advantages:NonNon--reversiblereversible Rapid reactionRapid reactionSelective for HSelective for H22S S Wide range of fuelsWide range of fuelsOil Soluble Additives &Oil Soluble Additives & RxnRxn. Products. ProductsMay be used at high temperature & with May be used at high temperature & with causticcaustic
Organic CompoundsOrganic CompoundsHH22S + Sulfix product alkyl sulfides S + Sulfix product alkyl sulfides
(RSR)(RSR)
H2S Scavenger ApplicationH2S Scavenger ApplicationH2S Scavenger Application
Scavenger/hydrocarbon mixing importantScavenger/hydrocarbon mixing importantInjection quillInjection quillInjection upInjection up--stream of sample pointstream of sample pointContinuous injectionContinuous injectionStorage tank mixing, blendingStorage tank mixing, blending
Transportation vessel effectsTransportation vessel effectsSteam coils, temperatureSteam coils, temperatureCompartment sealsCompartment seals““Soda bottleSoda bottle”” effecteffect