4135 Bluebonnet Dr.4135 Bluebonnet Dr.Stafford, TX 77477Stafford, TX 77477

1-877-864-77101-877-864-7710www.factorydirectsafety.com

Photoionization Detectors for

Industrial Hygiene in the Oil & Gas Industry

Werner Haag, Ph.D.Werner Haag, Ph.D.

Brent YaschukBrent Yaschuk

Factory Direct Safety & Environmental, Inc.Factory Direct Safety & Environmental, Inc.

PID Standard Features:PID Standard Features:

• Measure many organic vaporsMeasure many organic vapors& some inorganics& some inorganics

• 10.0 eV, 10.6 eV, & 11.7 eV Lamps10.0 eV, 10.6 eV, & 11.7 eV Lamps• Non-specific: Need to know gas Non-specific: Need to know gas being being measured to quantifymeasured to quantify• DataloggingDatalogging• TWA & STEL RecordingTWA & STEL Recording• Fast response (<3 seconds)Fast response (<3 seconds)• Continuous read-outContinuous read-out

PID Chemical ResponsePID Chemical ResponseCompound Class Relative

SensitivityAromatics (e.g., Benzene, Pyridine)

++++

Alkyl Iodides, Bromides, Chlorides ++++ , +++ , +Double Bonded Compounds +++Organic Amines +++Sulfides & Mercaptans +++Ketones, Ethers & Silicates +++Alkanes, Esters, Alcohols, Aldehydes

++

H2S, NH3 & PH3 + to ++

H2, CO, CO2, O2, N2, HCN, SO2, Acids

-

PID Applications: PID Applications: Oil RefineriesOil Refineries HydrocarbonsHydrocarbons

PID Applications: PID Applications: Oil/Chemical Oil/Chemical TankersTankersDiesel Fuel, HCs, Solvents, NHDiesel Fuel, HCs, Solvents, NH33, , etc. Confined Space Entryetc. Confined Space Entry

PID Applications: PID Applications: Heat Heat ExchangersExchangersDowtherm: Diphenyl oxide / Dowtherm: Diphenyl oxide / BiphenylBiphenylOSHA OSHA PEL for PEL for mix = mix = 0.5 ppm0.5 ppm

PID Applications: PID Applications: Fugitive Fugitive Emissions Emissions Testing - EPA Testing - EPA Method 21Method 21

PID Applications: PID Applications: Hazmat Hazmat ResponseResponse

Various ChemicalsVarious Chemicals

PID Applications: PID Applications: Soil Soil Remediation Screening & Leaking Remediation Screening & Leaking Underground Storage TanksUnderground Storage Tanks

Various ChemicalsVarious Chemicals

PID PID ApplicationApplications: s:

Natural Natural Gas Gas Dehydrator Dehydrator Re-boilersRe-boilers & & CompressoCompressorrCondensatCondensatee(Benzene)(Benzene)

PID PID ApplicationApplications: s:

Fenceline Fenceline MonitoringMonitoring

PID Applications: PID Applications: Indoor Air Indoor Air Quality Quality ppb Level TVOC & Locating Odor ppb Level TVOC & Locating Odor SourcesSources

PID Applications: PID Applications: Space Shuttle Space Shuttle TanksTanks

Hydrazine Fuel Hydrazine Fuel DecontaminationDecontamination

Modern PIDs Recent Modern PIDs Recent Improvements:Improvements:• Sensitivity to low ppb levelsSensitivity to low ppb levels

• 450 Chemical Response Factors450 Chemical Response Factors• Improved Linearity: ppb to 10,000 Improved Linearity: ppb to 10,000 ppmppm• Humidity Effects Almost EliminatedHumidity Effects Almost Eliminated• Reduced Methane InterferenceReduced Methane Interference• 30-hour Li-Ion Battery30-hour Li-Ion Battery

Improvements Accomplished Improvements Accomplished by:by:

• Shorter cell path length to improve Shorter cell path length to improve linearity & reduce interference, linearity & reduce interference,

requires requires precise manufacturing & precise manufacturing & strong lampsstrong lamps• “ “Fence” Electrode removes Leak Fence” Electrode removes Leak CurrentCurrent• Proprietary Anti-contamination Proprietary Anti-contamination TechnologyTechnology

Water Vapor Effects1) Reduced response of Organic Vapors

due to competitive light absorption & chemical quenching

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

Relative humidity, R.H., %

per

cen

tag

e o

f re

spo

nse

at

RH

= 0

20 oC

10 oC

30 oC

40 oC

Water Vapor EffectsWater Vapor Effects2) “Leak” Current at high humidities when

sensor is not ultra-clean

“Fence”

FENCE ELECTRODE PREVENTS FENCE ELECTRODE PREVENTS LEAK CURRENT IN HIGH LEAK CURRENT IN HIGH HUMIDITYHUMIDITY

FENCE ELECTRODE PREVENTS FENCE ELECTRODE PREVENTS LEAK CURRENT IN HIGH LEAK CURRENT IN HIGH HUMIDITYHUMIDITY

FENCE ELECTRODE PREVENTS FENCE ELECTRODE PREVENTS LEAK CURRENT IN HIGH LEAK CURRENT IN HIGH HUMIDITYHUMIDITY

Benzene in GasolineBenzene in GasolineTypically 0.5-2%: Difficult to measure selectivelyTypically 0.5-2%: Difficult to measure selectively

Benzene in FuelsBenzene in FuelsExposure Limits for Various FuelsExposure Limits for Various Fuels

Chemical ACGIH TWABenzene 0.5 ppm

Diesel Fuel 12 ppm

Jet Fuel 30 ppm

Gasoline 300 ppm

Benzene in FuelsBenzene in FuelsMixture TWA CalculationMixture TWA Calculation

TWATWAtotaltotal = = ____________________________11

ffbenzenbenzen

ee

ffgasolingasolin

ee++

TWATWAbenzbenz

____________ ____________TWATWAgas.gas.

Benzene in GasolineBenzene in GasolineTypically 0.5-2%: Difficult to measure Typically 0.5-2%: Difficult to measure selectivelyselectively

Benzene in FuelsBenzene in FuelsExposure Limits for Various FuelsExposure Limits for Various Fuels

Chemical ACGIH TWABenzene 0.5 ppm

Diesel Fuel 12 ppm

Jet Fuel 30 ppm

Gasoline 300 ppm

Benzene Specific Benzene Specific Measurement Methods with Measurement Methods with DL near 0.5 ppmDL near 0.5 ppm

Method Time DL Cost OtherTubes 10-20 min 0.5 ppm ¢

Automated Tubes (Draeger CMS)

10 min 0.2 ppm ¢¢

PID w/Filter Tube

1-3 min 0.02 ppm

$

Portable GC 5-10 min 0.1 ppm $$ Bulky

Portable IR <1 min 2 ppm $$$ Heavy

GAC or Gas Bag + Lab Analysis

1 week 0.01 ppm

$$$$ Off-site

Tiger Select PID/Tube can measure

• Continuous ppb Levels Total Aromatic Compounds (TAC)

• Benzene Specific readings – Single Point and 15-minute STEL

Total Aromatic Compounds Mode • Uses 10.0 eV lamp

• Applies the Benzene response factor (0.5)

• Responds predominantly to aromatics

• Continuous readings with ~5 ppb resolution

• If a reading over 0.5 ppm is seen, insert a tube and make a Benzene specific measurment

Chemical I. E. R.F.

Benzene 9.25 eV 0.55

Toluene 8.82 eV 0.54

o-Xylene 8.56 eV 0.56

n-Hexane 10.13 eV -

n-Octane 9.82 eV 13

Benzene Tube Specificity

No Effect of:• 400 ppm Toluene

• 200 ppm o-Xylene

• 300 ppm Octane

• 25 ppm H2S ● 100% Methane

Benzene STEL measurements • Continuous benzene readings and/or STEL

measurements can be made until the color change proceeds up to the 3/4 length mark indicated on the tube

• Response will lag actual concentrations by a minute or two

Benzene Standard – Humidity Test(Filter Tube absorbs moisture)

Tube #Relative Humidity

PID/TubeResponse

1 Dry 5.0 ppm2 Dry 4.9 ppm

3 100 % 5.1 ppm

4 100 % 4.8 ppm

Benzene in Refinery Samples

SampleLab

GC/FID(mole %)

PID/Tube(mole %)

87 Octane Gasoline

0.86 % 0.63 %

Reformer Feed 1.2 % 1.0 %Reformer Product 6.3 % 7.2 %Benzene Light Ends

22 % 24 %

Benzene Field ComparisonAs % of Lab Value ± Standard Deviation± Standard Deviation

Sample PID/TubePortable GC/FID

Draeger CMS

Standards1)

101 ± 16%

116 ± 23%

120 ± 52%

Field Samples2) 97 ± 29% 84 ± 21%

103 ± 92%

1) Avg of 24 Standards, including BTEX mixtures

2) Avg of 18 different field measurements

Stafford, TexasStafford, Texas1-877-864-77101-877-864-7710

Thank youThank you