Monitoring of hydrogen sulfide via substrate-integrated hollow waveguide mid-infrared sensors in real-time

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Hydrogen sulfide is a highly corrosive, harmful, and toxic gas produced under anaerobic conditions within industrial processes or in natural environments, and plays an important role in the sulfur cycle. According to the U.S. Occupational Safety and Health Administration (OSHA), the permissible exposure limit (during 8 hours) is 10 ppm. Concentrations of 20 ppm are the threshold for critical health issues. In workplace environments with human subjects frequently exposed to H2S, e. g., during petroleum extraction and refining, real-time monitoring of exposure levels is mandatory. Sensors based on electrochemical measurement principles, semiconducting metal-oxides, taking advantage of their optical properties, have been described for H2S monitoring. However, extended response times, limited selectivity, and bulkiness of the instrumentation are common disadvantages of the sensing techniques reported to date. Here, we describe for the first time usage of a new generation of compact gas cells, i.e., so-called substrate-integrated hollow waveguides (iHWGs), combined with a compact Fourier transform infrared (FTIR) spectrometer for advanced gas sensing of H2S. The principle of detection is based on the immediate UV-assisted conversion of the rather weak IR-absorber H2S into much more pronounced and distinctively responding SO2. A calibration was established in the range of 10-100 ppm with a limit of detection (LOD) at 3 ppm, which is suitable for occupational health monitoring purposes. The developed sensing scheme provides an analytical response time of less than 60 seconds. Considering the substantial potential for miniaturization using e. g., a dedicated quantum cascade laser (QCL) in lieu of the FTIR spectrometer, the developed sensing approach may be evolved into a hand-held instrument, which may be tailored to a variety of applications ranging from environmental monitoring to workplace safety surveillance, process analysis and clinical diagnostics, e. g., breath analysis.1391198203Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)U.S. Department of Energy by Lawrence Livermore National Laboratory (LLNL) [DE-AC52-07NA27344]LLNL [B598643, B603018]Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESP [2012/05573-6]U.S. Department of Energy by Lawrence Livermore National Laboratory (LLNL) [DE-AC52-07NA27344]LLNL [B598643, B603018

Real-time monitoring of ozone in air using substrate-integrated hollow waveguide mid-infrared sensors

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Ozone is a strong oxidant that is globally used as disinfection agent for many purposes including indoor building air cleaning, during food preparation procedures, and for control and killing of bacteria such as E. coli and S. aureus. However, it has been shown that effective ozone concentrations for controlling e. g., microbial growth need to be higher than 5 ppm, thereby exceeding the recommended U. S. EPA threshold more than 10 times. Consequently, real-time monitoring of such ozone concentration levels is essential. Here, we describe the first online gas sensing system combining a compact Fourier transform infrared (FTIR) spectrometer with a new generation of gas cells, a so-called substrate-integrated hollow waveguide (iHWG). The sensor was calibrated using anUVlamp for the controlled generation of ozone in synthetic air. Acalibration function was established in the concentration range of 0.3-5.4 mmolm23 enabling a calculated limit of detection (LOD) at 0.14 mmol m23 (3.5 ppm) of ozone. Given the adaptability of the developed IR sensing device toward a series of relevant air pollutants, and considering the potential for miniaturization e.g., in combination with tunable quantum cascade lasers in lieu of the FTIR spectrometer, a wide range of sensing and monitoring applications of beyond ozone analysis are anticipated.3Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)U.S. Department of Energy by Lawrence Livermore National Laboratory (LLNL)LLNL sub-contract [B598643, B603018]Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESP [2012/05573-6]LLNL sub-contract [B598643, B603018

Apparatus for the measurement of chemical activity coefficients of gas phase species in thermodynamic equilibrium with liquid phase

The invention relates to an apparatus comprising a fluidic part (10) intended to contain a sample; an analytical part (30) comprising a waveguide (32); and a permeable membrane (20) closing the fluidic part (10), so as to physically separate the fluidic part (10) from the analytical chamber (30)

Monitoring of hydrogen sulfide via substrate-integrated hollow waveguide mid-infrared sensors in real-time

Hydrogen sulfide is a highly corrosive, harmful, and toxic gas produced under anaerobic conditions within industrial processes or in natural environments, and plays an important role in the sulfur cycle. According to the U.S. Occupational Safety and Health Administration (OSHA), the permissible exposure limit (during 8 hours) is 10 ppm. Concentrations of 20 ppm are the threshold for critical health issues. In workplace environments with human subjects frequently exposed to H2S, e. g., during petroleum extraction and refining, real-time monitoring of exposure levels is mandatory. Sensors based on electrochemical measurement principles, semiconducting metal-oxides, taking advantage of their optical properties, have been described for H2S monitoring. However, extended response times, limited selectivity, and bulkiness of the instrumentation are common disadvantages of the sensing techniques reported to date. Here, we describe for the first time usage of a new generation of compact gas cells, i.e., so-called substrate-integrated hollow waveguides (iHWGs), combined with a compact Fourier transform infrared (FTIR) spectrometer for advanced gas sensing of H2S. The principle of detection is based on the immediate UV-assisted conversion of the rather weak IR-absorber H2S into much more pronounced and distinctively responding SO2. A calibration was established in the range of 10-100 ppm with a limit of detection (LOD) at 3 ppm, which is suitable for occupational health monitoring purposes. The developed sensing scheme provides an analytical response time of less than 60 seconds. Considering the substantial potential for miniaturization using e. g., a dedicated quantum cascade laser (QCL) in lieu of the FTIR spectrometer, the developed sensing approach may be evolved into a hand-held instrument, which may be tailored to a variety of applications ranging from environmental monitoring to workplace safety surveillance, process analysis and clinical diagnostics, e. g., breath analysis1391198203CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPUnited States Department of Energy (DOE); LLN

Monitoring Of Hydrogen Sulfide Via Substrate-integrated Hollow Waveguide Mid-infrared Sensors In Real-time

Hydrogen sulfide is a highly corrosive, harmful, and toxic gas produced under anaerobic conditions within industrial processes or in natural environments, and plays an important role in the sulfur cycle. According to the U.S. Occupational Safety and Health Administration (OSHA), the permissible exposure limit (during 8 hours) is 10 ppm. Concentrations of 20 ppm are the threshold for critical health issues. In workplace environments with human subjects frequently exposed to H2S, e.g., during petroleum extraction and refining, real-time monitoring of exposure levels is mandatory. Sensors based on electrochemical measurement principles, semiconducting metal-oxides, taking advantage of their optical properties, have been described for H 2S monitoring. However, extended response times, limited selectivity, and bulkiness of the instrumentation are common disadvantages of the sensing techniques reported to date. Here, we describe for the first time usage of a new generation of compact gas cells, i.e., so-called substrate-integrated hollow waveguides (iHWGs), combined with a compact Fourier transform infrared (FTIR) spectrometer for advanced gas sensing of H2S. The principle of detection is based on the immediate UV-assisted conversion of the rather weak IR-absorber H2S into much more pronounced and distinctively responding SO2. A calibration was established in the range of 10-100 ppm with a limit of detection (LOD) at 3 ppm, which is suitable for occupational health monitoring purposes. The developed sensing scheme provides an analytical response time of less than 60 seconds. 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An instrumented microfluidic tool for complex fluid phase diagram determination: Inline and real-time exploration of solvent extraction

International audienceLiquid-liquid extraction, i.e. control of the reversible transfer of cations between phases, is a core chemical process for metal purification and recycling. The objective of the “REE-CYCLE” project (Rare Earth Element reCYCling with Low harmful Emissions) is to develop the fundamental understanding of complex fluid processing in order to innovate environmentally friendly, economically competitive processes. The presented work on micro-solvent-extraction takes this approach beyond the state-of-the-art: An instrumented and computer-controlled microfluidic device is described, enabling the first steps towards fast measurement of the free energy of ion transfer between complex fluids. Continuous screening of a manifold parameter set, including e.g. multi-component phase composition, pH, temperature, will be enabled by integra-ting inline, real-time measurements into a robotized lab-on-a-chip. Miniaturized spectro-scopic and sensing methods will allow automated characterization of kinetics/thermody-namics, partition coefficients, chemical potential differences and constituent’s activity coefficients. First results of the microfluidic device, compared to batch mode assays, are presented concerning temperature and pH variation. Examples are shown on N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) reverse micelles diluted in dodecane for lanthanide extraction in the presence of iron. Partition coefficients and kinetics data for different parameters are addressed and resulting pathways explored to enhance separation and selectivity. First data on solvent activity coefficient measurements will also be presented, giving insight on molecule aggregation, constituents’ chemical potentials and solvent vapour pressure

An instrumented microfluidic tool for complex fluid phase diagram determination: Enabling in-line and real-time screening of solvent extraction processes

International audience1 Scientific and technological background: Solvent extraction of metal ions and circular economy If Richard Feynman is often cited as a pioneer in Nanosciences, one should also cite Glenn Seaborg, 1951's Nobel prize in chemistry who stated in 1980 in a visionary conference that: « In the future, chemistry will be called upon to extend our natural resources of copper, lead, zinc, and other non-ferrous metals by making it possible to recover these metals more economically from low-grade ores or to recycle materials now discarded as waste » [1]. And indeed, rare earth elements as trivalent cations are absolutely irreplaceable for strong magnets, " energy-saving " light bulbs and high capacity batteries, amongst other applications. They are in fact not rare, just highly diluted in the earth crust. They are also chemically very similar. For these two reasons, their extraction and separation is a lengthy and very polluting process. Consequently, cost and environmental constraints led to the closure of most mining facilities in western countries over the past few decades, leading to today's quasi-monopoly of China which controls approximately 97% of the world's rare earth element market as per 2012 figures [2]. The same year, the first industrial recycling of rare earth elements by solvent extraction was started in Saint-Fons and La Rochelle, France, showing that supply autonomy, economical and ecological considerations are of importance in today's society. Following 2011 figures [3], Japan detains 300 kT of WEEE, corresponding to nearly three times the annual global production of rare earths. In order to recycle these ressources, solvent extraction processes need to be rendered ecologically friendly, and be rapidly adapted to each kind of urban mining material. Solvent extraction, i.e. control of the reversible transfer of cations between feed and extraction phases, is a core chemical process for metal purification and recycling in hydrometallurgy. These processes are very complex chemical two-phase systems, where slight changes in parameters may imply huge effects on the phase behavior of the involved complex fluids. This may lead to so-called " third-phase accidents " , representing huge financial losses for a production plant. The overall behavior of these complex fluids is analyzed in multi-dimensional phase diagrams, requiring several years of thorough analysis by techniques ranging from simple pH measurements to scattering techniques implying consequent instrumental and time efforts. Thus, solvent extraction process tweaking is frequently based on empirical data. The objective of the " REE-CYCLE " project (Rare Earth Element reCYCling with Low harmful Emissions) [4] is to develop the fundamental understanding involved in the process' complex fluids (both experimental and theoretical) in order to enable a quantum leap in process analysis and thereby rapidly innovating environmentally friendly and economically competitive processes. 2 Instrumented microfluidic device for complex fluid phase diagram exploration If extraction microfluidic devices have already been reported [5], the presented work takes this approach beyond the state of the art. Indeed, we will describe the instrumented and computer-controlled microfluidic device enabling the first steps towards simultaneous fast measurement of the free energy of mass transfer per ion pair between complex fluids. In the longer run, high-througput screening in this lab-on-a-chip tool, and complete automation and robotization of the experimental setup, will enable: 1) Rapid evaluation for innovative " green " processes issued of synthetic chemistry, 2) Benchmarking for numerical approaches and predictive theories, e.g. ienaics [6], 3) Process intensification and ecologilization regarding principles of green chemistry and circular economy. Screening of a manifold parameter set, including e.g. multi-component phase composition, pH, temperature, etc., will be enabled by integrating inline and real-time measurements into a fully robotized system. Ultimately, the Les Rencontres Scientifiques d'IFP Energies nouvelles Microfluidics: from laboratory tools to process development Rueil-Malmaison, France, 4-5 November 2015 device will be designed to deliver continuous, in-line and real-time exploration of phase diagrams by combining several miniaturized spectroscopy and sensing methods for characterization of kinetic & thermodynamic time scales, partition coefficents of extraction, chemical potential differences and constituent activities, without user intervention. Here, we show first results of the microfluidic device (cf. Figure 1) and compare these with batch mode assays concerning temperature and pH variation. Examples will be shown on TODGA reverse micelles diluted in dodec-ane as model system, and extraction of five rare earth elements: La, Nd, Eu, Dy and Yb; in the presence of iron. Partition coefficients and kinetics data for different parameters will be addressed as well as pathways explored to enhance separation and selectivity. First data on solvent activity coefficient measurements will also be presented, giving insight on molecule aggregation, solvent chemical potentials and constituents' vapor pressures. Fig. 1. Microfluidic chip for solvent extraction with in-line measurement sites. Conclusions The microfluidic device stands as a first pillar of the REE-CYCLE project, enabling benchmarking for meso-scale modelling and numerical analysis, testing of newly synthesized extraction agents, and paving the way to assisted pertraction devices. On the longer time range, a semi-industrial prototype device for solvent extraction will be conceived gathering the results of all working groups. Furthermore, the microchemistry and-analysis activity is meant to be developed and extended beyond solvent extraction, involving research as well as industrial partners