1 december 2015 - empir workshop environment call 2016 inrim, torino, italy ideas in gas chemistry...
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1 December 2015 - EMPIR Workshop Environment Call 2016 INRiM, Torino, Italy
Ideas in gas chemistry and gas flow for the EMPIR Environment Call 2016
Annarita Baldan, VSL
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Ideas
1. Sampling-free/ fast measurements in Air Quality
2. CCS
3. Mercuric Chloride
4. Follow-up on-going projects Environment Call 2013
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Sampling-free / fast measurements in Air Quality
Background info
CEN Reference methods available or under development (CEN/TC264)
Problems are :SamplingLengthy measurementCostly
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Problems associated with sampling in Air Quality
Reference methods both in ambient and stationary source emissions measurements need sampling.Sampling lines/filters/pumps can cause problems:
1 -Adsorption/reactions of the analyte (such as
ammonia, hydrogen chloride, nitrogen dioxide)
2-Condensation of moisture
3-Mold / Insects / Particles
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Problems in fugitive emissions
Concawe (ad-hoc group OGI) and US EPA are looking for alternatives for the LDAR* sniffing standard method as it is:
1) Time consuming & Costly: in a major petrochemical facility > 10.000 LDAR testing points to assess leaks
2) Quality issue: Occurrence of false positive (small leak, high concentration) and false negatives (large leak, low concentration)
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Sniffing device (TVA- FID)
*LDAR: Leak Detection and Repair (US EPA method 21)
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Role of NMIs
There are several techniques that can be applied in the field and that are in “advanced research stage”. These techniques should fulfill the metrological requirements of accuracy and traceability.
Metrological validation of sampling-free/fast measurement methods for air quality applications thanks to a multi-disciplinary approach
Examples:Optical Gas imaging (OGI)(low-cost) gas sensors
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Impact
Quantitative and reliable data for industry and policy makers thanks to development of calibration approaches for ‘sampling free instruments’ (e.g. gas sensors and OGI camera)
Faster route to the market for new emerging technologies (speed up of the acceptance process) thanks to the metrological validation
Fast, effective and less expensive measurement techniques for users working in Air Quality monitoring and LDAR measurements
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Carbon Capture and Storage
Background infoCarbon Capture and Storage (CCS) could be used to
(temporarily) lower CO2 emissions
CCS has a significant power consumptionThere are several EU pilot plants (being) realised that
aim at investigating/ demonstrating more efficient sequestration methods
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Project Proposal: COOPeRaTeCO2 Pilot Ratification for Transport
Directly using CO2 produced by the pilots of new technology being demonstrated across Europe for transport related testing, e.g. corrosionThese capture technologies will produce different CO2 streams (composition) that will also require metering
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STEPWISE Pilot – Luleå, SE NORCEM CO2 capture pilot, NO Capture Pilot Maasvlakte, NL La Pereda Capture Pilot, ES
Iron and Steel Cement Power Power & Waste
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Need
The pilot plants result in CO2 streams of ~96% purity, other components are NOx, SOx, N2
Current transport and storage strategies may not work for (all) different CO2 streams
Some CO2 streams are quite aggressive (e.g. corrosion)
Need for gas composition and gas flow measurements of CO2 streams: to achieve uncertainty 1.5% on mass for Safety in CC Storage (fugitive losses)
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EDGaR Project: Detection of H2S, SO2 andNO2 in CO2 by using broadband absorption spectroscopy in the UV/VIS range
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Role of NMIsFrom an earlier CCS proposal(s)
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1. Develop improved metering of flow and (on-line) composition for high pressure and supercritical/ dense CO2 streams
2. Measure and assess the challenges related to CO2 transport by pipeline as a result of internal corrosion
3. Develop field proven measuring instruments and open-path wide area screening of fugitive losses of CO2 from CCS-facilities
4. Improve equations of state
5. Experimental determination of the enhancement factors for water removal
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Impact
Facilitate the discussion on the safety of CCS
Facilitate ETS (emission trading schemes, EU ETS Directive 2003/87/EC)
Facilitate the implementation of CCS
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Mercuric Chloride
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Background infoMercury and its various compounds have a range of serious
health impacts including brain and neurological damage, especially among the young.
Ratification of the Minamata Convention is currently in operation. At the end of September 2015, 128 countries and the European Union have signed. The Minamata Convention on Mercury provides controls and reductions across a range of products, processes and industries where mercury is used, released or emitted.
The Global Mercury Partnership of the Minamata Convention is supporting the development of Hg measurement/
monitoring capabilities which require Hg reference materials and standards.
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Need
According to US EPA:Gaseous Mercuric Chloride (HgCl2), the primary oxidized form of
mercury, is an environmental concern, primarily due to its high water solubility and ultimate role in the availability of organic mercury.
HgCl2 is released directly to the environment from combustion processes (e.g. coal-fired utilities, hazardous and municipal waste combustors) but is also formed atmospherically through the oxidation of atmospheric elemental mercury.
The direct measurement of gaseous HgCl2 has become a major focus of international continuous source emission and ambient measurement and monitoring programmes. These measurements are dependent on the availability of reliable HgCl2 gaseous reference standards and materials to assess and verify data quality.
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Role of NMIs
In many cases, HgCl2 must be reduced to the detectable, elemental form in order to be quantified. Reliable HgCl2 reference gases are needed to quantify this conversion as well as assess the ability to quantitatively transfer the reactive HgCl2 through the entire measurement system.
Reliable HgCl2 reference gases with known uncertainty do not yet exist. Research topics include:
Quantitative confirmation of the output of liquid evaporative HgCl2 generators.
Development real-time/on-site HgCl2 measurement technique or HgCl2 transfer standard.
Development of reliable, portable HgCl2 reference gas materials/sources.
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Impact
Quantitative confirmation of the output of liquid evaporative HgCl2 generators
A fundamental difference is found between the absolute output of Hg0 and HgCl2 reference gases of the same concentration. A measurement study to determine the output of liquid evaporative HgCl2 generators and agreement with Hg0 reference gases would enable an understanding of how liquid evaporative HgCl2 generators can be used as reference gases.
Development of a real-time direct HgCl2 measurement technique or HgCl2 transfer standard
To this point, all measurements are based on Hg0 measurements (analyzers) where the HgCl2 must first be reduced in order to be measured. This reduction or conversion step is of unknown efficiency and has to be investigated.
Development of reliable, portable HgCl2 reference gas materials/sources
Currently the liquid evaporative HgCl2 generators are the only technology available. However they are currently not accepted.
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Follow up of ENV56 KEY-VOCs
Background infoVOCs are a multitude of organic chemicals present in traces in the air. They include both anthropogenic and biogenic compounds. VOCs are relevant because: Involved in atmospheric processes (WMO-GAW) Air pollutants (regulation emission and ambient air) Indoor Air (Construction Products regulation)
KEY-VOCs project aims at building a metrological infrastructure (traceability and accuracy) for measuring a selected group of VOCs by conventional and gas sensing analytical techniques
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Role of NMIs
The work initiated in KEY-VOCs needs to be further addressed. Specifically: Focus on Toxic Organic Air Pollutants (US EPA TO-14 and TO-15)Evaluation of new high accurate real-time analytical techniques: PTR-MS/ SIFT-MSContinue the studies on the interaction of VOCs on surface materials for the preparation of stable Reference Materials
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Impact
Provide traceability and accuracy so that reliable data can be obtained
Facilitate the implementation of new analytical techniques
Support policy makers in preparation of regulation on VOCs
Protect environment and climate, health and safety
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Follow up of ENV52 HIGHGAS
Background infoThere is a direct link between climate change and
the increasing levels of greenhouse gases (GHG) in the atmosphere. The IPCC has established that man-made emissions of GHG’s have become dominant over the natural cycles of e.g. CO2, CH4 and N2O.
Good measurement of GHG’s is pivotal to understanding changes in the earth climate and are required to underpin legislation to reduce the emission of GHG.
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State-of-the-art
Accurate and reliable measurements require accurate instruments and metrologically traceable calibration standards (reference gases).
State of the art:Within the WMO-GAW, GHG’s in the atmosphere have been monitored with high quality for many yearsTo maintain, improve and expend the activities on GHG measurements, the WMO and the metrology institutes have joined their forces within the CCQMWithin the 2013 EMRP programme the ENV52 HIGHGAS project has started to improve the level of the NMI’s on the production of GHG calibration gases, field measurements and instrumentation
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Role of NMIs
One of the outcomes of HIGHGAS is that the current (and future) measurement techniques, especially spectroscopic, are biassed by the presence of different isotopologues in the sample or in the calibration gas
What can NMIs do: Work together on the investigation and quantification of
different isotopes in the reference materials Collaborate with universities and instrument manufacturers to
develop measurement techniques which can correct for the presence of different isotopic abundance or techniques that are not biassed by different isotopes
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Impact
Maintain stable values of Greenhouse Gas trend analysis
Underpin the quality of future data sets Transparent basis for developing and implementing policies for the control of anthropogenic emissions (based on e.g. the Kyoto protocol, Cancun agreement, or the COP21 Climate Conference meeting in Paris that is held right now (dec 2105))
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See you at the breakout session Gas pollutants and Aerosol !