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David J. Veltkamp - Presenter CPAC, University of WA John Crandall Analytical Specialists, Inc. Brian Rohrback Infometrix, Inc.
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
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?
System Operation
Column 2, DB1701
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?
Solvesso 200 ULN at Detect & Divert Level Overlaid Wastewater Background
Blue is wastewater background. Red is Solvesso 200 ULN.
Solvesso 200 ULN at Detect & Divert Level Overlaid Wastewater Background
Cyan sample is Solvesso 200 ULN Blue sample is background
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
2 Clusters of Wastewater Air Because these 2 are mislabeled blanks. Solvesso 200 ULN
Aligned
Unaligned
Aligned
Discussion
Chemometrics Results Demonstrates the separation in the samples of concern and That it is unlikely that samples will be mis-identied even when mislabeled These techniques can be used not only for the analytical results but also as system diagnostics For example, sample system failures (like a sticking sample valve) would produce chromatograms and PCA plot positions that look like blanks. Flags could be set to notify personnel of a problem and what the likely problem and solution might be With only a little more work, should be possible to implement PCAbased control charts and /or on-line monitors for contaminate levels
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 differentiate the hydrocarbon products made in the plant and use this information to identify the source of any leak With more data, we can build a mixing model and quantitate the relative contributions of multiple sources All interpretations and quantitations are automated and can be fed into any control system Micro GC coupled with NeSSI is a good fit Eases implementation: feasibility deployment Feasibility is one thing; this system needs to go on-line