Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 General Session / AD Performance of Environmental Monitor for Total Sulfur and High Heating Value of Refinery Flare Vent Gas Systems Timothy Davidson, Rodelio Limfueco, Tony Rodriguez, Nand Khidkikar, David Brewster, Maxine Sauer, and Chris Cornell BP West Coast Products LLC Andrew Pierce Mangan Inc.

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 2 OUTLINE California Regulatory Requirements –Rule 1118 “Control of Emissions from Refinery Flares” No Analyzer Existed for Continuous Measurement Measurement Constraints –Flare Gas Measurement Ranges for Total Sulfur and High Heating Value –Flare Gas Sample Composition Variability –Flare Gas Safety Analytical Measurement Selection –Criteria Installations System Performance

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 3 California Regulatory Requirements AQMD RULE CONTROL OF EMISSIONS FROM REFINERY FLARES (a) Purpose and Applicability “The purpose of Rule 1118 is to monitor and record data on refinery and related flaring operations, and to control and minimize flaring and flare related emissions. “

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 4 Monitoring of Flare Related Emissions Quantification of Oxide of Sulfur (SOx) and Oxides of Nitrogen (NOx) Released During a Flare Event Vent Gas Air PollutantEquationEmission Factor (EF) SOxE = V(MSCFH) x Cs (ppm S) x E=Calculated vent gas emissions (lbs) NOxE= V(MSCFH) x HHV (BTU/FT2) x EF0.068 lb/mmBTU

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 5 What is Refinery Flare Vent Gas? VENT GAS is any gas generated at a facility subject to rule 1118 that is routed to a flare, excluding assisting air or steam Flare Event –Vent gases are only routed to a flare under these conditions Emergency Conditions –is a condition beyond the reasonable control of the owner or operator of a flare requiring immediate corrective action to restore normal and safe operation, Unit Shut down Unit Startup

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 6 Flare Gas Measurement Ranges SULFUR MEASUREMENT RANGE –10ppm to ppm HHV MEASUREMENT RANGE –0 TO 3000 BTU/Ft2

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 7 Flare Gas Sampling HYDROGEN PLANT SULFUR PLANT CRUDE DISTILLATION MULTIPLE UNITS CONNECTED TO ONE FLARE LIQUID KNOCKOUT DRUM WATER SEAL NATURAL GAS PURGE FLARE TOTAL SULFUR / HHV ANALYZER SAMPLING POINT

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 8 Flare Gas Sample Composition Variability Flare Composition is Dependent on the Process Unit or Process –Process Unit Feed –Intermediate Process Distillation Tower Reactor FLARE GAS COMPOSTION –Methane To Pentane Hydrocarbon Distribution varies with unit –Hydrogen 0-100% –Water (STEAM) 0-100% –Sulfur Compounds 0-15% Hydrogen Sulfide, Mercaptans, Thiophenes, Sulfides, Disulfides Specific Gravity Variation –0.7 to 1.5

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 9 Flare Gas Safety Requirements when Exposure is Threat to Life –Hazardous Gases and Explosive Hydrocarbon Level Audible Alarm Visual Flashing Light Alarm to Manned Control Room Detection at or Below (PEL) Detection at or Below (LEL) Remote Alarm Reset Remote Shut Down System Isolation Procedures and Training Automation of System with Remote Monitoring –Minimize People in Hazardous Area

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 10 Analytical Measurement Target Requirements SULFUR MEASUREMENT RANGE –10ppm to ppm HHV MEASUREMENT RANGE –0 TO 3000 BTU/Ft2 RESPONSE TIME (99%) –< 15 MIN VALIDATION –LINEARITY 10% ACCURACY TO CERTIFIED STANDARD OVER THE MEASUREMENT RANGE –SAMPLE SYSTEM BIAS LESS THAN 5% –7 DAY STABILTIY FOR STANDARDS AT 20% AND 80% FULL SCALE < 5% DRIFT (FS) (Total Sulfur) < 2.5% DRIFT (FS) HHV OPERATIONAL CONDITIONS –MUST BE FUNCTIONAL UNDER ALL CONDITIONS –HYDROGEN TO PENTANE IN ANY COMPOSTITION –STEAM OUT TO FLARE –NITROGEN PURGE TO FLARE –HIGH TEMPERTURE 500F –HIGH GAS VELOCITIES

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 11 Sample Composition Variability Measurement Errors Due to Flare Gas Sample Composition Variability (>factor of 2 error) –Example 1 34% Hydrogen, 7% Nitrogen, 35% Methane, 10% Ethane 14% Propane Specific gravity = 0.7 –Example 2 8% Hydrogen, 26% Nitrogen, 7% Methane, 2% Ethane, 10% Propane, 47% Butane Specific gravity = 1.5 Methods to Remove / Reduce Density Error –Volumetric injection *** –Density measurement and correction –Normalization (must measure everything)

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 12 Flare Gas Sample Contaminates High Concentration of Water Vapor Possible in Flare Gas Stream –Process Unit Cleaning Steam is Directed to Flare to Burn Excess Hydrocarbons (150 psi stream) 100% Water Vapor to Analyzer –Water Seal adds Water Vapor to Flare Gas Stream Up 12% on Hot days Heated Sample to 285 F

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 13 Sample Pressure and Flow Sample Pressure – psig –Typical Atmospheric pressure Sample Flow –0 to 250 ft/sec Sample Temperature –Ambient to 500 F

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 14 Sulfur Adsorption Adsorption of Sulfur Compounds on Metal Surfaces –Slow Response Time 99% Response Required in < 15 min Daily Validation Error < 5% Sample System Bias < 5% Special Silicon Coatings (Sulfinert) are Required to Reduce Adsorption –All sample system components

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 15 Sample System

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 16 Sample System Probe

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 17 Flare Analyzer Sample System Installation Heated Pump Box

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 18 Sample Composition CompoundMinimum Volume %Maximum VolumeMedian Volume % Hydrogen09832 Methane09720 Ethane Ethylene Propane Propylene C4’s C Nitrogen Oxygen0210 CO0100 CO Water

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 19 Sulfur Composition in Sample Based on one Flare 2 years of Data Analyzed by AQMD method Sulfur Compound Min (ppm)Max (ppm)Average (ppm) Hydrogen Sulfide Mercaptan’s Thiophene’s Sulfides0201 Disulfides020020

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 20 Analytical Sulfur Measurement Thermal Fisher Scientific Sola II TWO (Sola II) ANALYZERS TO COVER THE RANGE FROM –10 ppm to ppm or 1 ppm to ppm HIGH RANGE INSTRUMENT –IN CONTROL –2000 ppm TO ppm or 100 ppm to ppm LOW RANGE INSTRUMENT –10ppm TO 2500ppm or 1 ppm to 200 ppm –SWTICHES FROM N2 TO PROCESS WHEN HIGH RANGE INSTRUMENT MEASUREMENT EXCEEDS 2500ppm USE GAS SAMPLE INJECTION –SAMPLE LOOP WITH KNOWN VOLUME WILL INJECT SAME NUMBER OF MOLES INDEPENDENT OF GAS COMPOSTION Two Different Flare Systems –Red Flare Group I ( ppm Sulfur) –Blue Flare Group II ( ppm Sulfur)

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 21 Sulfur Measurement: Zero Drift Test

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 22 Sulfur Measurement: Linearity Test

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 23 Analytical Measurement Selection Hamilton Sundstrand MGA 1200EC Magnetic Mass Spectrometry –Permanente Magnet –Non-Scanning –Faraday Collector for Each Mass or compound Detected Direct Reader –Chemical Composition Based on Least Squares Analysis

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 24 HHV Measurement: Linearity

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 25 HHV Analyzer Composition Measurement

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 26 System Performance Calibration Error –Measurement Period 1 year –Definition {ABS[ Expected Response – Actual Response] / FSR} *100 Calibration Drift –Measurement Period 1 year –Definition {(ABS[d] + ABS[CC] ) / FSR } * 100 –D is the average Difference Between Expected and Actual –CC is the Correlation Coefficient at 95% Confidence –FSR is Full Scale Response

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 27 Low Range Sulfur Calibration Error

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 28 High Range Sulfur Calibration Error

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 29 HHV Calibration Error

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 30 Calibration Drift Total Sulfur & HHV Flare SystemLow Range Sulfur High Range Sulfur HHV 1- Group I Group I Group II Group II Group II Group I ppm Sulfur Group II 0 – ppm Sulfur

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 31 Linearity Error Total Sulfur & HHV Flare SystemAnalyzer TypeLinearity Error Percent (<10%) 10-30% FSR40-60% FSR80-100% FSR 1.) Group IHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IIHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IIHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IIHigh Range Sulfur Low Range Sulfur High Heating Value

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 32 Sample System Bias Total Sulfur & HHV Flare SystemAnalyzer TypeSample System Bias 0-20% FSR80-100% FSR 1.) Group IHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IIHigh Range Sulfur Low Range Sulfur High Heating Value ) Group IIHigh Range Sulfur Low Range Sulfur01.5 High Heating Value ) Group IIHigh Range Sulfur Low Range Sulfur0.5 High Heating Value

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 33 Zero Drift Total Sulfur & HHV Flare SystemLow Range SulfurHigh Range SulfurHHV 1.) Group I ) Group I ) Group II ) Group II ) Group II

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 34 Conclusion Analyzer Systems Meet Regulatory Requirements –< 5% Daily Calibration Drift Total Sulfur –< 2.5% Daily Calibration Drift HHV –< 10% Linearity Error (Total Sulfur & HHV) –< 5% Bias Error –< 5% Zero Drift Factors to meet requirement –Stable Instrumentation –Heated Sample System –SulfInert Coated Sample System

Set Your Sails For South Shore Harbor The 56th Annual Symposium of the Analysis Division League City, Texas, USA; April 2011 Slide 35 Acknowledgements SCAQMD –Eugene Teszler –Dr. Raul Dominguez BP Project Engineering –Blake Thompson Jacobs Engineering Mangan Inc