Thank You for Attending Todays W ebinar: Benzene-Specific Monitoring - - PowerPoint PPT Presentation

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Thank You for Attending Today’s W ebinar:

Your Host Matt DeLacluyse Operations Mgr RAECO Rents mattd@raecorents.com Featured Speaker Werner Haag Sr Application Chemist Ion Science

Werner.Hagg@ionscienceusa.com

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Benzene-Specific Monitoring

Benze Benzene-Spec Specif ific M Monitoring ing

Werner erner R. Haag aag Io Ion Sc Scie ience U USA SA

RA RAECO ECO W Webi ebinar ar, 8 Mar arch, h, 201 2016

Benzene Monitoring

Benzene-Specific Monitoring

Werner Haag B.S. Chem., M.I.T. Ph.D. Chem., U. Tenn. Author of “The PID Handbook – Theory and Applications of Direct- Reading Photoionization Detectors”

Benzene Industrial Exposure

• Oil refineries, Petrochemical Plants
• Storage, distribution & use of gasoline or benzene
• Offshore installations, Fracking operations
• Coke works
• Natural Gas condensate
• ABS Plastics manufacturing

Benzene Applications

Compound Fraction

Benzene 60-85% Toluene 3-25% Napthalene 0-6% Xylenes 0-5% Styrene 0-3% Indene 0-3% Carbon Disulfide 0-3% Thiophene 0-1%

U.S. Steel Light Oil

Benzene Applications In Refineries, interest from

• Health & Safety
• Hazmat
• Environmental Compliance

Benzene EPA 2015 Final Rule

Requires Benzene Fence-Line Monitoring at 12 to 24 locations every 2 weeks

Benzene Fence-line Monitoring

Benzene Fence-line Monitoring

• If rolling avg. over 0.003 ppm, search for sources

within 5 days, implement correction in 45 days.

• Annual sampling and analysis costs have been

estimated at $40,000 to over $100,000 per year for biweekly sampling

• rule allows for less frequent carbon tube sampling

if the plant can demonstrate a history of staying under the 0.003 ppm annual limit, moving from bi-weekly to monthly, quarterly, semi-annually and finally annual sampling.

Benzene Toxicity

Exposure Limits for Various Aromatics

Chemical ACGIH TWA

Benzene 0.5 ppm

(Carcinogen)

Toluene 50 ppm Ethylbenzene 100 ppm Xylenes 100 ppm

Benzene Toxicity

Exposure Limits for Various Fuels

Chemical ACGIH TWA

Benzene 0.5 ppm

(Carcinogen)

Diesel Fuel 12 ppm Jet Fuel 30 ppm Gasoline 300 ppm

Benzene in Fuels

Mixture TWA Calculation

TWAtotal = ______________ 1

fgasoline fbenzene

+ TWAbenz ______ ______ TWAgas.

Benzene in Gasoline

Benzene in Gasoline

Typically 0.5 – 2% Difficult to measure selectively

Tiger Select PID/Tube can measure:

• No Tube: Continuous ppb levels of

VOCs for screening

• Insert Tube: Benzene-specific readings

– Single Point and 15-minute STEL

How the Tiger Select Works

Cub/Tiger Select Combination

• Personal TAC screening with Cub
• Benzene-specific readings if alarms

Cub 10.0 eV lamp for continuous screening for total aromatic compounds (TAC)

Benzene Monitoring

Specifications (Tiger Select)

Measurement time About 2 minutes Resolution 0.01 ppm Accuracy ± 0.05 ppm or ± 10% (whichever is greater) Sensor type 10.0 eV PID with selective filtering Measuring gas Benzene specific Detection range Linear 0-40 ppm (up to 300 ppm)

Benzene STEL Measurments

• 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

Used New

Tiger Select Temperature Effect

1 2 3 4 5 6 7 8 9 100 200 300

Response Time (Sec)

2°C 5°C 15°C 20°C 30°C 40°C 2ºC 40ºC 20ºC 15ºC 30ºC 5ºC

Linearity

Selectivity

Compound Test Conc. (ppm) 2-min. Result Max Conc. 15 min.

Toluene 400 100 Xylene 200 100 Ethylbenzene 200 100 n-Octane 300 200 n-Heptane 20 >20 n-Hexane 100* 20 Pentane 1500 Butane 100 Propane 1000 Methane 25000 10000* * Higher concentrations may decrease benzene response.

Selectivity

Compound Test Conc. (ppm) 2-min. Result Max Conc. 15 min.

Cyclohexane 50* Isobutylene 100 Gasoline 50 No Effect 50 Acetone 400 200 Isopropanol 400 >400 Ethyl Acetate 400 400 H2S 25 >25 CO 100 >100 Trichloroethylene 100 1.8 Perchloroethylene 50 >11 * Higher concentrations may decrease benzene response.

STEL: Benzene in Fuel Storage Cooler

Accuracy: Refinery Samples

Benzene Response (ppm) Sample TVOC† (ppm) by GAC by Tiger Select Initial* STEL Cooler: Refined fuel samples 90 0.38 0.37 0.38 Standard Mix: 20 ppm Hexane 19 ppm Heptane 26 ppm Toluene 0.3 ppm Benz.‡ 65 0.45 0.44 0.44

• Cal. Gas Mix

(17 Compounds) 212 4.8 4.2 4.4

† Total Volatile Organic Compounds

* Spot reading after the first two minutes of sampling

‡ Added benzene amount, plus unknown amounts present as a trace impurity in the other solvents

TITAN Continuous Benzene Monitor

• Sample every minute
• Detection Limit 0.1 ppm
• No gases or tubes
• Semi-annual maintenance
• Weight 15 kg
• 2 Years data storage

Titan Selectivity:

Benzene in Gasoline

1 2 3 0.5 1 1.5 2

Titan Reading (ppm) Benzene Added (ppm)

100 ppm Gasoline No Gasoline

The Importance of Continual Monitoring

Time (Hours:Minutes) Entire events Missed by GC

Sample every minute Sample every hour

Benzene Specific Measurement Methods with DL near 0.5 ppm Method Time DL Cost Other

Tubes: Manual 10-20 min 0.5 ppm ¢ Single Point Tubes: Draeger CMS 10 min 0.2 ppm ¢¢ Single Point PID w/Filter Tube 1-3 min 0.1 ppm $ Single Point Portable GC 5-10 min 0.1 ppm $$ Single Point Titan Separator 1 min 0.1 ppm $$$ Continuous Portable IR <1 min 2 ppm $$$ Continuous GC: On-Line 1 hour 0.01 ppm $$$$ Semi-Contin. GAC: Lab Analysis 1-10 days 0.001 ppm $$$$ Off-site Portable IMS 1 min 0.01 ppm $$$$ Not Intr. Safe.

The End

Thank you

werner.haag@ionscienceusa.com 1-408-599-9709 mobile 1-877-864-7710 headquarters info@ionscience.com +44 (0) 1760 208503

TAC Response w/10.0 eV Lamp

In a typical gasoline, TAC reading is about 80% due to aromatics

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