Naphtha Product Spill and Leak Detection in Shared Process Cooling Water

David J. Veltkamp - Presenter CPAC, University of WA John Crandall Analytical Specialists, Inc. Brian Rohrback Infometrix, Inc.

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

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

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?

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

microFAST GCtm with EZChrom Used for On Site Validation

System Operation

Typical Results, Solvesso 200 ULN in Wastewater Headspace Gas

Simultaneous, 2 Channel FID results in 75 seconds Column 1, DB5

Column 2, DB1701

Typical Naphtha Product Range (in Wastewater) Results

Typical Naphtha Product Range (in Wastewater) Results

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?

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

Cyan sample from sample system Blue sample manually collected with a syringe

Cyan sample from sample system

Red sample manually collected with a syringe

Two Wastewater Sewer Background Chromatograms, at Solvesso 200 ULN scale

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

Cyan sample is Solvesso 200 ULN Red 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

Chemometric Modeling Approach

It is clear from the analyses that the four different naphtha products can be differentiated (visually) by GC We want to demonstrate that the chemometrics can reliably differentiate products Lump all chromatograms into a single data file Apply Principal Component Analysis (PCA) to identify and model chromatographic characteristics that distinguish different possible products that could potentially leak into waste water New chromatograms projected into PCA model to identify Has waste stream composition changed? Can we identify what changed (products in the waste stream)? Can we determine severity of leak?

Pattern Recognition (PCA Modeling)

2 Clusters of Wastewater Air Because these 2 are mislabeled blanks. Solvesso 200 ULN

PCA scores differentiate products

Aligned

The scores trend is explained by concentration differences

Unaligned

The scores trend is explained by concentration differences

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