The Heavy Oil Storage Tank (HOST) Project

1. The Heavy Oil Storage Tank (HOST) Project Donald Lucas David Littlejohn Ernest Orlando Lawrence Berkeley National Laboratory

2. The Problem: Do Heavy Oil Storage Tanks Need Air Pollution Controls? • Regulatory agencies are tightening allowed emissions of VOCs and ROCs to meet ozone requirements • Existing regulations require action based on vapor pressure of liquid • It is recognized and accepted that current measuring protocols do not work for heavy crudes • There are thousands of tanks in California that do not have vapor recovery

3. Vapor Composition of Various Organic Liquids CO2 WATER VAPOR METHANE ROC ROC CO2 METHANE ROC Gasoline Light Crude Heavy Crude

4. HOST Working Group Members • California Air Resources Board (CARB) • Ernest Orlando Lawrence Berkeley National Laboratory (LBNL) • Monterey Unified Air Pollution Control District • San Joaquin Valley Unified Air Pollution Control District • Santa Barbara Unified Air Pollution Control District • U.S. Department of Energy (DOE) • U.S. Environmental Protection Agency (EPA) • Western States Petroleum Association (WSPA) and Oil Industries

5. HOST Working Group • Voluntary organization • Headed by Richard McVeigh (SJVUAPCD) • Meeting sites rotate • Meetings held every month or two • Meetings depend on work schedule • Teleconference and videoconferences possible • Decision by consensus • Trained facilitator provided by Chevron • Varied viewpoints, deadlines, and concerns

6. Host Project Goals • Compare various organic liquid vapor pressure measurement methods for tank emission estimation and regulatory decision making • Study existing vapor pressure methods • Modified RVP (high T, GC analysis) • EPA 25E • CARB 150 • Develop new, scientifically valid procedures for heavy crudes

7. Money and Contracts • Work co-funded by DOE and WSPA • Same work statement used for both proposals • Funding: 1996 - $75K by DOE, $50 K by WSPA 1997 (Expected)- $30 K by DOE, $30 K by WSPA • Legal problems numerous, time-consuming • Work done on industry sites by UC employees funded by WSPA and DOE • Liability issue most onerous • Individual oil companies have different requirements

8. New Methods Developed and Tested at LBNL • “LBNL” liquid sampler • High temperature RVP/GC analysis • Modified EPA 25E headspace vial protocol • CARB 150 • Gas Sampling in Vapor Space • “Minivap” automated vapor pressure

9. 20 43.8 Gas Flow in Texaco Shipping Tank 8000 6000 4000 Cubic Feet 2000 0 -2000 0 Time (hours)

10. Carbon Dioxide and Methane in Texaco Shipping Tank 4% CO2 Methane 3% 2% Fraction of Gas 1% 0% 0.0 21.1 38.7 Time (hours)

11. Selected Tank Results

12. What Produces ROC Emissions? • Three driving mechanisms • Breathing • Working • Flashing • Equilibrium? • High molecular weight components probably are (C6 and above) • Low molecular weight components may not be (air, methane, CO2)

13. 1 2 4 5 6 7 8 9 3 Composition of Vapor in Selected Tanks Values are #ROC/day .79 .13 Vapor Pressure (atm.) .005 .048 .0 .03 10

14. Why Work with a National Lab? Pluses: • Impartial • Scientific understanding of difficult problems • Flexibility • Access to lab capabilities • Co-funding possible Drawbacks: • Contracting and intellectual property • Time needed to build confidence • “Ivory Tower”

15. Future Plans • 20 - 50 additional tank measurements • Liquid and vapor methods • Representative samples from different fields and locations • Attempt to validate relationships among various methods and actual emissions • Develop scientifically sound protocol acceptable to regulatory agencies and industry • Report and publish results • SPE/EPA Exploration and Production Environmental Conference (March, 1997) • Air and Waste Management Section Meeting (March, 1997)

16. Acknowledgments Tim Stoner, Texaco David Todd, CARB Art Hartstein and Rhonda Lindsey, DOE Steve Arita, WSPA This work was funded by the Office of Fossil Energy, DOE, and WSPA