1. Remote Sensing Refinery Pollutants Alex Cuclis Houston Advanced Research Center Eyes in the Sky II Workshop June 24, 2010

2. TexAQS 2000 A comprehensive Air Quality Study in the Houston Area Over $20 million was spent. More than 200 scientists were involved. Main Finding: Emissions of Highly Reactive Volatile Organic Compounds (HRVOCs) were substantially higher than expected.

3. Differential Absorption LIDAR (DIAL) Houston Area Ozone Plume Airborne DIAL By NOAA - 500 - 1000 - 1500 Height in meters

4. Differential Absorption LIDAR (DIAL) Ozone on the Texas Coast

5. Air Quality Studies – TexAQS 2006 20002006 100 50 Reported 0 Measured HRVOC Emissions 2004 1. HRVOC Emissions dropped 40% between 2000 and 2006. 2. In 2006 HRVOCs were still 10-40 times higher than reported in 2004. HRVOCs = Highly Reactive Volatile Organic Compounds

6. Petrochemical Emissions Emissions include nitrogen oxides (NOx) and Volatile Organic Compounds (VOCs) which in the presence of sunlight form ozone. NOx appears anywhere there is a flame, and most can be measured from stacks with continuous analyzers. VOCs can literally come from millions of places in a plant and are not easily measured.

7. Petrochemical Emissions VOCs leaks are measured with hand-held analyzers that are typically calibrated with propone and use a flame ionization detector (FID).

8. Remote Sensing Tools Can Find and Reduce Emissions Future DIAL SOF Hawk

11. Remote Sensing: Old School Can count the number of molecules, but cannot calculate the concentration. Must be mounted in a specific location, typically ground level. Light Source Reflector

12. IR Camera (LSI or FLIR) Some companies report that they saved over $1 million/year by finding and fixing a single leak!

13. IR Camera (HAWK) Different Barge with IR Camera Barge with naked eye Barge with IR Camera

14. Detection By Reflection MethodMediumMeasures SONAR Sound Often Under Water Location, Speed RADAR Radio Waves High Energy EM Location, Speed LIDAR Light Waves Single Wavelength Wind Speed, Surveys DIAL Light Waves Dual Wavelength Concentration, Composition, Location, Flux Light Detection And Ranging DIfferential Absorption LIDAR Radio Detection And Ranging Sound Navigation And Ranging

15. Part 3

16. DIAL History 1.BP – 1979 - 1992 2.Spectrasyne – 1992 - Present 3.NPL – 1990 - Present 4.Shell Global Solutions – 1994-2002 5.Sweden 6. API/CONCAWE 7. Solar Occultation Flux (SOF) 8. Canada 9. U.S.

17. Lasers send dual-wavelength pulses towards a gaseous plume. Back-scattered light returns to a detector assembly. By Spectrasyne Differential Absorption LIDAR (DIAL)

18. By Spectrasyne

19. Solar Occultation Flux (SOF)

20. FTIR Sun Tracker Sunlight is the light source for the FTIR mounted inside the van. Solar Occultation Flux (SOF)

21. SOF Measurements at the Houston Ship Channel Solar Occultation Flux (SOF)

22. Radial Plume Mapping (RPM) Real-Time Software Like a CAT scan of the atmosphere.

23. ADVANTAGESDISADVANTAGES QuantificationVery Expensive SpeciationAnalysis Takes Time ComprehensiveComplex Concentration PlaneRequires Expertise No Thermal Gradient NeededDifficult to Set up Technology Comparison DIAL vs HAWK

24. ADVANTAGESDISADVANTAGES InexpensiveRequires Sunlight Relatively Easy Set-upDaytime Bias Obtains Full IR SpectrumNo Spatial Mapping Requires Less TimeSingle Vendor Similar Results to DIALLess History Available Technology Comparison SOF vs DIAL

26. Refinery Emissions Some refineries lose 2 or 3 wine glasses per barrel. The average refinery in Houston reports losing about 1 tablespoon of oil per barrel to air emissions. Of the 2.3 million barrels of oil processed each day in the Houston area, refineries report emissions of 250 barrels per day. Measurements at other refineries suggest that it could be closer to 2500 barrels per day. suggest that refineries in other locations emit about 1 wine glass (4 ounces) of oil per barrel. A variety of measuring techniques

27. Flares?

29. Tanks -Seals, Landings, “Splatterings”, Fittings Flares -Minimization, Steam/Air Assist, Flow, Wind Delayed Cokers -De-heading, Drilling, Fugitives (Alberta and the 2 ½ times factor) Water Treatment -Recovery, Aeration, Mixing Emission Sources

30. Refinery Cokers http://primis.phmsa.dot.gov/comm/images/RefineryProcess.jpg Coke drums can be 80 - 100 ft tall and up to 27 ft in diameter. Drilling derricks on top of the coke drums contain water jets that are used to cut the solid coke out of the drum.