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