Treat yourself to better rental service. Thank You for Attending Today’s W ebinar: Benzene-Specific Monitoring Your Host Featured Speaker Werner Haag Matt DeLacluyse Sr Application Chemist Operations Mgr Ion Science RAECO Rents Werner.Hagg@ionscienceusa.com mattd@raecorents.com Follow the Conversation LI VE @RaecoRents # RentsW ebinar
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-Specific Benzene Monitoring 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 U.S. Steel Light Oil 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%
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 1 TWA total = ______________ f benzene f gasoline ______ ______ + TWA benz TWA gas.
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) Sensor type 10.0 eV PID with selective filtering Measuring gas Benzene specific Detection range Linear 0-40 ppm (up to 300 ppm) Resolution 0.01 ppm Accuracy ± 0.05 ppm or ± 10% ( whichever is greater) Measurement time About 2 minutes
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 Used New • Response will lag actual concentrations by a minute or two
Tiger Select Temperature Effect 9 30ºC 40ºC 20ºC 15ºC 5ºC 2ºC 8 7 Response 6 2°C 5°C 5 15°C 4 20°C 3 30°C 2 40°C 1 0 0 100 200 300 Time (Sec)
Linearity
Selectivity Compound Test Conc. 2-min. Max Conc. (ppm) Result 15 min. Toluene 400 0 100 Xylene 200 0 100 Ethylbenzene 200 0 100 n-Octane 300 0 200 n-Heptane 20 0 >20 n-Hexane 100* 0 20 Pentane 1500 0 Butane 100 0 Propane 1000 0 Methane 25000 0 10000* * Higher concentrations may decrease benzene response.
Selectivity Compound Test Conc. 2-min. Max Conc. (ppm) Result 15 min. Cyclohexane 50* 0 Isobutylene 100 0 Gasoline 50 No Effect 50 Acetone 400 0 200 Isopropanol 400 0 >400 Ethyl Acetate 400 0 400 H 2 S 25 0 >25 CO 100 0 >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) TVOC † by Tiger Select Sample by GAC (ppm) Initial* STEL Cooler: Refined 90 0.38 0.37 0.38 fuel samples Standard Mix: 20 ppm Hexane 19 ppm Heptane 65 0.45 0.44 0.44 26 ppm Toluene 0.3 ppm Benz. ‡ Cal. Gas Mix 212 4.8 4.2 4.4 (17 Compounds) † 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 3 Titan Reading (ppm) 100 ppm Gasoline No Gasoline 2 1 0 0 0.5 1 1.5 2 Benzene Added (ppm)
The Importance of Continual Monitoring Sample every minute Sample every hour Entire events Missed by GC Time (Hours:Minutes)
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 info@ionscience.com 1-408-599-9709 mobile +44 (0) 1760 208503 1-877-864-7710 headquarters
TAC Response w/10.0 eV Lamp In a typical gasoline, TAC reading is about 80% due to aromatics
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