Naphtha Product Spill and Leak Detection in Shared Process Cooling Water

1. Naphtha Product Spill and Leak Detection in Shared Process Cooling Water

2. Define the Problem Hydrocarbon spills & leaks are costly events resulting in Loss of product to waste Manpower and other resources to correct the problem Damage to the environment Possibly regulatory and public relations issues All leading to lost productivity and profits Prevention of “spill & leak events” Is critical to process operation whether Into the air, process or waste water or on the ground Inevitably, spills and leaks will occur requiring A system for detection and Diversion of the material for correction and remediation

3. Focus of This Work, Naphtha Products in Water Naphtha range products including C6 to C10 hydrocarbons With varying volatility and solubility in water Production shares cooling towers Multiple naphtha product types use the same heat exchange system Once through cooling water shares the same discharge point Thus, simple leak detection using wastewater total organic carbon (TOC) is unsuitable No speciation for product type spilled or leaking Varying, temperature dependent solubility of the naphtha products lead to erroneous results

4. Measurement Possibilities Gas Chromatography with Flame Ionization Detection Should provide the speciation required for leak identification Direct liquid injection would simply duplicate TOC but with speciation May not be sensitive or fast enough for the requirements microGC and FID coupled with trapping technology Provides more sensitivity with the speciation & speed required Sensitivity enhancements enable headspace gas sampling Headspace gas sampling removes “particulates” from the sampling problem and Turbulent water effectively “sparges” hydrocarbons from the water enriching the headspace gas with naphtha sample minimizing temperature variability and erroneous measurements

5. Measurement Possibilities microGC FID with trapping coupled with chemometrics Provides fast sensitive product leak detection and information for initiating diversion to the remediation tank Provides faster, easier product leak identification Can lead process operations to the source of the leak quickly for repairs The possibilities needed validation Can the microGC detect naphatha components? Can the microGC chromatographic results identify the components? Can the microGC and chemometrics discriminate “background within a hydrocarbon processing facility” from “leaks?”

6. On Site Measurement Validation Project Definition Establish “normal background” Determine whether new microGC solution can work Demonstrate that the background is sufficiently low Demonstrate that the “detect & divert” measurement levels are sufficiently high enough to differentiate from background Demonstrate “leaked product identification” potential Demonstrate chemometric application efficacy Onsite work definition Measure background at “sump” and through a “sump sampling system” Measure prepared naphtha product samples at the “detect and divert” levels Follow up with data reduction and presentation

7. microFAST GCtm with EZChrom Used for On Site Validation

8. System Operation

9. Typical Results, Solvesso 200 ULN in Wastewater Headspace Gas

10. Typical Naphtha Product Range (in Wastewater) Results

11. Typical Naphtha Product Range (in Wastewater) Results

12. Discussion of Results Typical Naphtha Range products Were prepared in water at the detect and divert levels Solvesso 200 ULN was chosen for special attention Has the highest water solubility translating into the lowest wastewater headspace gas concentration Deemed to be the most difficult of the range to discern over normal background Chromatographic traces are distinctive for each naphtha product Boiling range distributions follow expected product compositions Sensitivity over noise is more than adequate But is it adequately higher than “background?”

13. Two Wastewater Sewer Background Chromatograms, original scale ~15,000 F.S.

14. Two Wastewater Sewer Background Chromatograms, at Solvesso 200 ULN scale

15. Solvesso 200 ULN at Detect & Divert Level Overlaid Wastewater Background

16. Solvesso 200 ULN at Detect & Divert Level Overlaid Wastewater Background

17. Discussion of Results Solvesso 200 ULN Has the lowest headspace gas concentration Is the most difficult to measure Yet is clearly distinctive and well above “normal background” at the detect and divert level Plenty of sensitivity is available over background for early warning All naphtha range samples Were prepared at the detect and divert levels for each product Headspace gas concentrations range from 0.4 to about 10 ppm All are clearly distinctive, one from the others and Well above background levels

18. 1st Step Chemometrics: Merge Data into a Single File

19. 2nd Step: Principal Component Analysis

21. Blank Run: notice the highlighted components in the blank

22. Solvesso 200 ULN Overlaid Wastewater Headspace Gas

23. Conclusions Micro GC coupled with trapping technology Is sufficiently sensitive for the job Can detect “worst case” leak situation for the high solubility product and Micro GC coupled with chemometrics Is sufficiently selective for the job Can discern which product has leaked into the cooling water Can identify multiple product leaks simultaneously On Site measurements provide significant value Scoping a measurement project is fortified with real data Potentially provides data enough to eliminate continuous measurement need Micro GC coupled with NeSSI is a good fit Future production implementation project is pending