TY - CONF A1 - Meyer, Klas A1 - Rademann, K. A1 - Maiwald, Michael T1 - qNMR under pressure - applications on compressed and liquefied gases N2 - During the last years quantitative NMR spectroscopy has become a general method for solving complex problems in science and industry. The opportunity of a calibration-free quantification, related to a simple counting of the nuclear spins in the active volume of the spectrometer represents a key advantage comparing to other analytical techniques. With modern NMR systems detection limits in the lower ppm range on a molar basis are accessible in a reasonable time period, which makes it a promising method for purity assessment, as well as applications in metrological research. First experiments showed that qNMR is suitable for gas analysis with respect to components used for production of primary reference gas mixtures. For this a laboratory setup for high-pressure NMR experiments up to 20 MPa (2900 psi) in fluid and gas phase was built and tested. In this work we show the determination of the composition of high precision mixtures, consisting of liquid and liquefied hydrocarbons commonly supplied in floating piston cylinders. Therefore an experimental setup was developed allowing sampling, as well as circulation of the mixture within a high-pressure NMR tube by using a concentric tubing assembly. Additionally, a piston-cylinder pressure cell was designed and manufactured allowing wide-range volume displacement. Mainly intended for density variation within supercritical fluid experiments, it can also function as a compression element for further increasing of gas-pressure in the system. Equipped with liquid thermostat and a motor-powered screw drive unit it is designed to operate at pressure levels up to 60 MPa (8700 psi) and temperatures up to 130 °C. T2 - 4th Annual practical applications of NMR in industry conference (PANIC) CY - Houston, TX, USA DA - 15.02.2016 KW - Gas-phase NMR KW - High-pressure NMR KW - Liquefied gases PY - 2016 AN - OPUS4-35435 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kipphardt, Heinrich A1 - Maiwald, Michael T1 - High-pressure qNMR spectroscopy in condensed- and gas-phase towards determination of impurities and compositions of gas mixtures N2 - Recent technical developments of NMR instruments such as in acquisition electronics and probe design allow detection limits of components in liquid mixtures in the lower ppm range (approx.. 5–10 ppm amount of substance). The major advantage of quantitative NMR spectroscopy (qNMR) is that it is a direct ratio method of analysis without the need of calibration. This means that the signal for a specific NMR-active nucleus (e.g., a proton) in an analyte can be compared and quantified by reference to a different nucleus of a separate compound, comparable to a counting of spins in the active volume of the spectrometer. A special application of qNMR in technical mixtures is the observation in the gas phase, which is rarely applied compared to liquid and solid NMR studies. Because of the low density it results in a reduced sensitivity, which can be improved by applying pressure. Therefore a high-pressure NMR setup was developed based on a commercially available NMR tube made of zirconia. This is currently tested up to 20 MPa, but can be extended up to 100 MPa with regard to pressure rating of its components. This work shows results of gas-phase application on natural-gas like reference gas mixtures produced at BAM, as well as investigations on liquefied petroleum gas mixtures (LPG) with high accuracy provided in constant-pressure piston cylinders. T2 - 35th Meeting of the CCQM-Gas Analysis Working Group, Workshop "Cutting edge research for gas metrology" CY - Caparica, Portugal DA - 13.10.2016 KW - Quantitative NMR spectroscopy KW - Gas-phase NMR KW - Reference gas mixtures KW - Liquefied petroleum gas PY - 2016 AN - OPUS4-37803 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Kraemer, B. A1 - Illner, M. A1 - Müller, D. A1 - Esche, E. A1 - Paul, Andrea A1 - Wozny, G. A1 - Maiwald, Michael T1 - Quantitative NMR spectroscopy of technical mixtures and gases from elevated to high-pressure N2 - Recent technical developments of NMR instruments such as in acquisition electronics and probe design allow detection limits of components in liquid mixtures in the lower ppm range (approx.. 5–10 ppm amount of substance). The major advantage of quantitative NMR spectroscopy (qNMR) is that it is a direct ratio method of analysis without the need of calibration. This means that the signal for a specific NMR-active nucleus (e.g., a proton) in an analyte can be compared and quantified by reference to a different nucleus of a separate compound, comparable to a counting of spins in the active volume of the spectrometer. Technical mixtures can be investigated online directly next to a process setup by using flow probes. This makes it a promising method for process analytical applications, especially during process development in laboratory and pilot plant scale. With the growing market of Benchtop devices based on permanent magnets nowadays an integration of NMR spectroscopy in an industrial environment becomes reasonable. A special application of qNMR in technical mixtures is the observation in the gas phase, which is rarely applied compared to liquid and solid NMR studies. Because of the low density it results in a reduced sensitivity, which can be improved by applying pressure. Therefore a high-pressure NMR setup was developed based on a commercially available NMR tube made of zirconia. This is currently tested up to 20 MPa, but can be extended up to 100 MPa with regard to pressure rating of its components. This work shows results of gas-phase application on natural-gas like reference gas mixtures produced at BAM, as well as investigations on liquefied gas mixtures with high accuracy provided in piston cylinders. Besides that amine gas treatment and hydroformylation in a microemulsion represent two other examples of applications in process analytical technology. These show the potential of combination of online NMR spectroscopy with other spectroscopic methods, especially during model development for data evaluation. T2 - Presentation at Statoil Research Center CY - Trondheim, Norway DA - 27.05.2016 KW - Quantitative NMR spectroscopy KW - Process analytical technology KW - Gas-phase NMR PY - 2016 AN - OPUS4-36330 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas T1 - High-pressure qNMR spectroscopy in condensed- and gas-phase towards determination of impurities and compositions of gas mixtures N2 - Recent technical developments of NMR instruments such as in acquisition electronics and probe design allow detection limits of components in liquid mixtures in the lower ppm range (approx.. 5–10ppm amount of substance). The major advantage of quantitative NMR spectroscopy (qNMR) is that it is a direct ratio method of analysis without the need of calibration. This means that the signal for a specific NMR-active nucleus (e.g., a proton) in an analyte can be compared and quantified by reference to a different nucleus of a separate compound, comparable to a counting of spins in the active volume of the spectrometer. A special application of qNMR in technical mixtures is the observation in the gas phase, which is rarely applied compared to liquid and solid NMR studies. Because of the low density it results in a reduced sensitivity, which can be improved by applying pressure. Therefore a high-pressure NMR setup was developed based on a commercially available NMR tube made of zirconia. This is currently tested up to 20 MPa, but can be extended up to 100 MPa with regard to pressure rating of its components. This work shows results of gas-phase application on natural-gas like reference gas mixtures produced at BAM, as well as investigations on liquefied petroleum gas mixtures (LPG) with high accuracy provided in constant pressure piston cylinders. T2 - qNMR Summit 2017 CY - Berlin, Germany DA - 16.03.2017 KW - Quantitative NMR spectroscopy KW - Gas-phase NMR KW - Reference gas mixtures KW - Liquefied petroleum gas PY - 2017 AN - OPUS4-39425 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -