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APPLICATION NOTE

PROCESS OVERVIEW

MEMBRANE INTERFACE MASS SPECTROMETRYCONTAMINATION IS A POSSIBILITY

The ProLine process mass spectrometer provides fast online analysis of volatile organic compounds (VOCs) in fracking site waste water and ambient environments. With multiple sampling points and easy operation, the ProLine is the choice as the front-line tool for EPA environmental compliance.

The hydraulic fracturing process (fracking) has proven itself to be invaluable in the releasing of trillions of BTUs of formerly inaccessible energy. The process requires millions of gallons of chemically treated water to be pumped into a well under high pressure. This chemically treated water creates micro-fractures in the rock strata, which allows the natural gas (NG) and natural gas liquids (NGL) to flow from the rock strata into the well, where it is brought to the surface for processing and transportation.

While every effort is made to contain the water used for the process after it is brought to the surface – either for disposal or treatment for re-use – the sheer amount used will result in some spillage or tank overflow that can lead to above and below-ground contamination.

The United States government has conducted a targeted campaign to reduce methane emissions and, as a result, fracking sites have come under scrutiny. The amount of gaseous methane escaping the site will also become of interest to the operator because of the same regulatory concerns.

As a greenhouse gas, methane has 21 times the potency of carbon dioxide in increasing the temperature of the Earth. While methane, at present, comprises only 8% of the current greenhouse gas load, any activity that has the potential to increase the emissions of this gas will come under ever-increasing regulatory pressure.

Mass spectrometry has been used online for more than 30 years to control and monitor industrial processes. Membrane interface mass spectrometry (also called membrane inlet mass spectrometry or MIMS) is a specific technique that allows direct measurement of liquid streams and is ideally suited for the analysis of VOCs in water.

At the heart of the MIMS technique are the various membrane materials which block certain components (including water and bulk materials) while allowing the analytes of interest to migrate through the membrane. Usually the membrane is a thin sheet or tube of polydimethylsiloxane, which works well with VOCs.

This selective extraction of the analyte from the bulk matrix concentrates the components of interest and delivers a highly enriched sample directly to the ion source. Since the mass spectrometer is already very sensitive, this technique provides very low limits of detection.

PROLINE PROCESS MASS SPECTROMETER

MEASURING VOLATILE ORGANICS AT FRACKING SITES

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PROLINE FOR MIMS

Equipped for MIMS operation, the ProLine process mass spectrometer uses a polydimethylsiloxane membrane inlet coupled directly to its ion source, with a small pump to ensure constant sample flow across the membrane. Additional sample inlets are available as options.

While the speed of the ProLine facilitates the analysis of multiple streams, a typical configuration dedicates one instrument per holding tank inlet. This provides the earliest notice of stream contamination and significantly reduces the cost of heated sample lines and their associated maintenance.

The multi-point, high-speed sampling capability of the ProLine process analyzer allows up to 32 locations to be assayed for gas leakage and reported back to a central data repository.

Hydraulic fracturing drilling rig

The software provides easy set-up, operation, and calibration, along with advanced alarm and automation capabilities. Self-diagnostics and modular design ensure ease of maintenance on site, by your own personnel. Remote support is available for additional factory diagnosis and troubleshooting.

Data can be exported using all common industrial protocols, as well as dedicated analog lines to bring the data to a common point for collection. Alarms are available for every stream, along with an “on the fly” mathematical package allowing data to be presented in any number of ways (mole, %, mg/M3, lb/hr, etc.).

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© 2019, by AMETEK, Inc. All rights reserved. Printed in the U.S.A. A-0436 Rev 5 (0219)One of a family of innovative process analyzer solutions from AMETEK Process Instruments. Specifications subject to change without notice.

Ability to scan for unknownsIn addition to monitoring specific ions, the analyzer can periodically scan for mass intensities across the operating range. This will detect the presence of components other than those specifically monitored and can provide advanced warning of leaks or other problems.

Direct analysis of the sample streamUnlike sparging techniques, which must consider the flow rates into and out of the sparger to establish accurate volumes for correct concentration determination, MIMS simply requires an appropriate standard for calibration. These standards are readily available and are introduced to the instrument in the same way as the sample stream itself. In this way, a very high correlation develops between the calibration method and the actual sampling event – an absolute necessity for generating consistent, meaningful data. For ambient air analysis, the instrument is calibrated using NIST-traceable gas standards. All calibrations are automatic and are programmed according to a schedule set by the customer.

Traditionally, monitoring process water required either sending grab samples to the laboratory for analysis, or using process gas chromatography. MIMS provides significant advantages over these traditional analytical methods.

Speed of analysisMass spectrometry is a very rapid analytical method. Even when taking into consideration delays for stream switching, a MIMS-equipped ProLine provides data in virtual real-time. This is generally 10 to 50 times faster than gas chromatography, where separation must be performed prior to analysis.

Specific component informationUnlike instruments that provide a “total” reading of VOC levels, mass spectrometry offers direct quantification of the species of interest. A single mass ion can be chosen specific to each compound and then these masses can be continuously monitored. This level of specificity allows the continuous speciation of the targeted VOCs and may reduce, or eliminate, the need for off-site lab analysis. If a total VOC number is required, the mass spectrometer can survey all VOCs, total them within the software and output a real-time concentration.

MASS SPECTROMETRY AND VOCS