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

2. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division Vapor Composition of Various Organic Liquids ROC METHANE ROC METHANE CO2 WATER VAPOR GasolineLight CrudeHeavy Crude

4. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division Gas Flow in Texaco Shipping Tank -2000 0 2000 4000 6000 8000 2043.8 Time (hours) Cubic Feet 0

10. Environmental Energy Technologies Division Carbon Dioxide and Methane in Texaco Shipping Tank 0% 1% 2% 3% 4% 0.021.138.7 Time (hours) Fraction of Gas CO2 Methane

11. Environmental Energy Technologies Division Selected Tank Results

12. Environmental Energy Technologies Division What Produces ROC Emissions? Three driving mechanisms –Breathing –Working –Flashing Equilibrium? –High molecular weight components probably are (C 6 and above) –Low molecular weight components may not be (air, methane, CO 2 )

13. Environmental Energy Technologies Division Composition of Vapor in Selected Tanks Vapor Pressure (atm.) 10 12 3 457896.005.0.79.048.03.13 Values are #ROC/day

14. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division 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. Environmental Energy Technologies Division 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