TY - CONF A1 - Meyer, Klas A1 - Paul, Andrea A1 - Bräuer, Bastian A1 - Bremser, Wolfram A1 - Maiwald, Michael T1 - Quantitative determination of methanol in FAME by Near-Infrared (NIRS) and qNMR spektroskopy T2 - 7th International Gas Analysis Symposium T2 - 7th International Gas Analysis Symposium CY - Rotterdam, Netherlands DA - 2013-06-05 PY - 2013 AN - OPUS4-29205 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kipphardt, Heinrich A1 - Maiwald, Michael T1 - Quantitative NMR spectroscopy for gas analysis T2 - 7th International Gas Analysis Symposium T2 - 7th International Gas Analysis Symposium CY - Rotterdam, Netherlands DA - 2013-06-05 PY - 2013 AN - OPUS4-29203 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Maiwald, Michael T1 - NMR Spectroscopy of fluids and gases from moderate to high pressure T2 - 9. AK PAT T2 - 9. AK PAT CY - Ludwigshafen am Rhein, Germany DA - 2013-11-28 PY - 2013 AN - OPUS4-29613 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Zientek, Nicolai A1 - Meyer, Klas A1 - Panne, Ulrich A1 - Kraume, M. A1 - Maiwald, Michael T1 - Untersuchung der Auflösungskinetik von pharmazeutischen Cokristallen mittels Onlilne-NMR-Spektroskopie T2 - 7. Interdisziplinäres Doktorandenseminar N2 - Bei der Entwicklung pharmazeutischer Wirkstoffe werfen Substanzen mit einer geringen Löslichkeit, Auflösungsrate und damit einhergehend schlechten Bioverfügbarkeit immer größere Probleme auf. Diese Eigenschaften und nicht etwa toxikologische Eigenschaften oder schlechte Wirksamkeit sorgen dafür, dass es weniger als 1 % aller Wirkstoffe bis in die Markteinführung schaffen. Eine Reihe von Ansätzen zur Verbesserung der schlechten Wasserlöslichkeit konnten bereits etabliert werden. Hierunter zählen die gezielte Salzbildung bzw. Salzscreening, Solubilisierung mit Cosolventien oder die Nutzung von Polymeren als mögliche Transportwege. Eine weitere Möglichkeit bietet die Bildung verschiedener polymorpher Formen, sowohl der Einzelkomponente als auch von den verschiedenen Mehrkomponentenverbindungen. T2 - 7. Interdisziplinäres Doktorandenseminar CY - Berlin, Germany DA - 24.02.2013 KW - Quantitative Online-NMR-Spektroskopie KW - Pharmazeutische Cokristalle PY - 2013 SN - 978-3-9815360-9-6 SP - 9 EP - 11 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) AN - OPUS4-28266 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Maiwald, Michael A1 - Panne, Ulrich T1 - Quantitative NMR-Spektroskopie für die Gasanalytik T2 - Anakon 2013 T2 - Anakon 2013 CY - Essen, Germany DA - 2013-03-04 PY - 2013 AN - OPUS4-29202 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Maiwald, Michael A1 - Panne, Ulrich T1 - Quantitative NMR-Spektroskopie für die Gasanalytik T2 - Adlershofer Forschungsform T2 - Adlershofer Forschungsform CY - Berlin, Germany DA - 2013-11-12 PY - 2013 AN - OPUS4-30205 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Esche, E. A1 - Kraemer, B. A1 - Müller, D. A1 - Meyer, Klas A1 - Zientek, Nicolai A1 - Maiwald, Michael A1 - Wozny, G. T1 - Improved desorption control via Raman spectroscopy T2 - 20th International Conference of Process Engineering and Chemical Plant Design - Conference Proceedings N2 - In this contribution a Raman spectrometer based control structure for the heating of a desorption column is proposed. For this purpose calibration experiments for the absorption of carbon dioxide using monoethanolamine solutions are carried out and calibration models are developed to measure both carbon dioxide liquid loads and monoethanolamine mass fractions. The calibration experiments are supported by online NMR spectroscopy to accurately measure the appearance of all species in the electrolyte system. Both models are tested during the plant operation of a mini-plant for the oxidative coupling of methane and the proof of concept for the control structure is given. The Raman spectroscopy implemented in the ATEX conform mini-plant shows a reliable and robust performance being even indifferent to impurities hindering the GC analysis. T2 - 20th International Conference of Process Engineering and Chemical Plant Design CY - Berlin, Germany DA - 15.10.2014 KW - Absorption KW - Carbon capture KW - Raman spectroscopy KW - desorption control KW - Prozessanalytik KW - Process analytical technology PY - 2014 UR - https://www.verfahrenstechnik.tu-berlin.de/fileadmin/fg158/Dokumente/Manuskripte/2014/20th-ICPEPD-Proceedings.pdf SN - 978-3-00-047364-7 SP - 223 EP - 233 PB - Technische Universität Berlin CY - Berlin AN - OPUS4-37399 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Zientek, Nicolai A1 - Laurain, Clement A1 - Meyer, Klas A1 - Paul, Andrea A1 - Engel, D. A1 - Guthausen, G. A1 - Kraume, M. A1 - Maiwald, Michael T1 - Automated data evaluation and modeling of simultaneous 19F-1H medium resolution NMR spectra for online reaction monitoring T2 - Tagungsband - 10. Kolloquium Arbeitskreis Prozessanalytik N2 - Medium resolution nuclear magnetic resonance spectroscopy (MR-NMR) currently develops to an important analytical tool for both quality control and process monitoring. One of the fundamental acceptance criteria for online MR-MNR spectroscopy is a robust data treatment and evaluation strategy with the potential for automation. The MR-NMR spectra were treated by an automated baseline and phase correction using the minimum entropy method. The evaluation strategies comprised direct integration, automated line fitting, indirect hard modeling, and partial least squares regression. T2 - 10. Kolloquium Arbeitskreis Prozessanalytik CY - Gerlingen, Germany DA - 25.11.2014 KW - Online NMR spectroscopy KW - Data evaluation KW - Reaction monitoring KW - Indirect hard modeling PY - 2014 UR - http://arbeitskreis-prozessanalytik.de/images/stories/Veranstaltungen/Kolloquien/10_kolloquium_2014/tagungsband_10_kolloquium_ak_prozessanalytik_2014_hq-druck_f.pdf SP - P04, 24 EP - 25 PB - BAM Bundesanstalt für Materialforschung und -prüfung CY - Berlin AN - OPUS4-38360 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Zientek, Nicolai A1 - Esche, E. A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Eine robuste Protessnalytik für die Reaktivabsorption von CO2 aus industriellen Gasströmen basierend auf Online- NMR- und Rama-Spektroskopie T2 - 10. Kolloqium des Arbeitskreises Prozessanalytik T2 - 10. Kolloqium des Arbeitskreises Prozessanalytik CY - Gerlingen DA - 2014-11-25 PY - 2014 AN - OPUS4-33136 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kraemer, B. A1 - Zientek, Nicolai A1 - Esche, E. A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Eine robuste Prozessanalytik für die Reaktivabsorption von CO2 aus industriellen Gasströmen basierend auf Online-NMR- und -Raman-Spektroskopie T2 - Tagungsband - 10. Kolloquium Arbeitskreis Prozessanalytik N2 - Die Abtrennung von CO2 aus industriellen Gasströmen ist eine großtechnisch wichtige Trennaufgabe. Neben der Aufarbeitung von Erdgas werden diese Verfahren zur Verminderung der CO2-Emission durch industrielle Rauchgase, insbesondere für alternativlose Prozesse wie die Stahl- und Zementproduktion diskutiert. T2 - 10. Kolloquium Arbeitskreis Prozessanalytik CY - Gerlingen, Germany DA - 25.11.2014 KW - Prozessanalytik KW - Quantitative NMR-Spektroskopie KW - Raman spectroscopy KW - CO2-Absorption KW - CCS PY - 2014 UR - http://arbeitskreis-prozessanalytik.de/images/stories/Veranstaltungen/Kolloquien/10_kolloquium_2014/tagungsband_10_kolloquium_ak_prozessanalytik_2014_hq-druck_f.pdf SP - P03, 23 EP - 23 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-38359 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zientek, Nicolai A1 - Laurain, Clement A1 - Meyer, Klas A1 - Kraume, M. A1 - Guthausen, G. A1 - Maiwald, Michael T1 - Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring JF - Journal of magnetic resonance N2 - Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16'' fluorinated ethylene propylene (FEP) tube with an ID of 0.04'' (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16'' FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in D2O (single scan)) and maximum quantitative flow rates up to 0.3 mL min-1. Thus, a series of single scan 19F and 1H NMR spectra acquired with this simple set-up already presents a valuable basis for quantitative reaction monitoring. KW - NMR KW - 1H KW - 19F KW - Medium-resolution NMR KW - Online NMR KW - Quantitative NMR KW - Reaction monitoring KW - Data processing KW - Process analytical technology PY - 2014 DO - https://doi.org/10.1016/j.jmr.2014.10.007 SN - 1090-7807 SN - 0022-2364 VL - 249 SP - 53 EP - 62 PB - Elsevier CY - San Diego, Calif. AN - OPUS4-32008 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Zientek, Nicolai A1 - Maiwald, Michael A1 - Kraemer, B. A1 - Esche, E. A1 - Müller, D. A1 - Wozny, G. T1 - Eine robuste Prozessanalytik für die CO2-Abtrennung industrieller Gasströme basierend auf Online-NMR- und Raman-Spektroskopie T2 - ProcessNET Jahrestagung 2014 T2 - ProcessNET Jahrestagung 2014 CY - Aachen DA - 2014-09-30 PY - 2014 AN - OPUS4-31883 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Zientek, Nicolai A1 - Kraemer, B. A1 - Maiwald, Michael T1 - Quantitative Online NMR Spectroscopy of Technical Mixtures and Gases T2 - Agilent NMR-Seminar T2 - Agilent NMR-Seminar CY - Waldbronn DA - 2014-05-20 PY - 2014 AN - OPUS4-31888 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zientek, Nicolai A1 - Meyer, Klas A1 - Dalitz, F. A1 - Kraume, M. A1 - Guthausen, G. A1 - Maiwald, Michael T1 - Neue Möglichkeiten für die Prozessanalytik mit gekoppelter 1H- und 19F-Medium-Resolution-NMR-Spektroskopie JF - Chemie - Ingenieur - Technik N2 - Die Entwicklung innovativer Medium-Resolution-NMR-Spektrometer eröffnet eine Reihe bemerkenswerter Applikationen für die Qualitätskontrolle, die akademische Ausbildung und die Prozessanalytik. Die Verwendung von Permanentmagneten erlaubt den Einsatz der NMR-Spektroskopie in industriellen Prozessumgebungen. KW - NMR KW - 1H KW - 19F KW - Medium-resolution NMR KW - Online NMR KW - Quantitative NMR KW - Reaction monitoring KW - Data processing KW - Process analytical technology KW - IHM KW - PLS PY - 2014 DO - https://doi.org/10.1002/cite.201450687 SN - 0009-286X SN - 1522-2640 VL - 86 IS - 9 SP - 1575 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-32560 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Panne, Ulrich A1 - Rademann, K. A1 - Maiwald, Michael T1 - Quantitative NMR Spektroskopie unter Druck - Anwendungen an fluiden und gasförmigen technischen Mischungen T2 - 8. Interdisziplinäres Doktorandenseminar N2 - Die quantitative NMR-Spektroskopie (qNMR) gewinnt in den letzten Jahren immer mehr an Bedeutung, speziell hinsichtlich der Anwendung auf komplexe Fragestellungen der analytischen Chemie. Ein großer Vorteil dieser Methode ist die Möglichkeit der Relativquantifizierung durch das „Zählen von Kernspins" in der Probe. Unter der Voraussetzung eines korrekt ausgeführten NMR-Experiments ist so der direkte Vergleich von Signalflächen im Spektrum möglich, ohne dass zuvor zwingend eine Kalibrierung notwendig ist. T2 - 8. Interdisziplinäres Doktorandenseminar CY - Berlin, Germany DA - 23.02.2014 PY - 2014 SN - 978-3-9816380-1-1 SP - 20 AN - OPUS4-32090 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Maiwald, Michael A1 - Panne, Ulrich A1 - Rademann, K. T1 - Quantitative NMR Spectroscopy in the Gas Phase - Applications for Gas Industry and Metrology T2 - EuroPACT 2014 T2 - EuroPACT 2014 CY - Barcelona, Spanien DA - 2014-05-06 PY - 2014 AN - OPUS4-31880 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Panne, Ulrich A1 - Maiwald, Michael A1 - Rademann, K. T1 - Quantitative NMR Spektroskopie unter Druck - Anwendungen an fluiden und gasförmigen technischen Mischungen T2 - 8. Interdisziplinäres Doktorandenseminar T2 - 8. Interdisziplinäres Doktorandenseminar CY - Berlin, Germany DA - 2014-02-23 PY - 2014 AN - OPUS4-30204 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Maiwald, Michael A1 - Panne, Ulrich A1 - Rademann, K. T1 - NMR Spectroscopy at elevated pressure - Applications on fluids and gases T2 - Practical Applications of NMR in Indutry Conference (PANIC) T2 - Practical Applications of NMR in Indutry Conference (PANIC) CY - Charlotte, NC, USA DA - 2014-02-03 PY - 2014 AN - OPUS4-30203 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kraemer, B. A1 - Zientek, Nicolai A1 - Esche, E. A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - A robust method for process monitoring of reactive absorption of CO2 in industrial gas streams based on Online-NMR- and Raman spectroscopy T2 - 1. Symposium NMRPM "Quantitative NMR Methods for Reaction and Process Minitorig" T2 - 1. Symposium NMRPM "Quantitative NMR Methods for Reaction and Process Minitorig" CY - Kaiserslautern DA - 2015-01-15 PY - 2015 AN - OPUS4-33135 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas T1 - Online Spectroscopy in Microemulsions- A Process Analytical approach for Hydroformylation Miniplant I- Experimental setup and NMR Reaction Monitoring T2 - Pro2NMR Autum School 2015 T2 - Pro2NMR Autum School 2015 CY - Aachen, Germany DA - 2015-12-08 PY - 2015 AN - OPUS4-35110 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Rademann, K. A1 - Maiwald, Michael T1 - High-pressure NMR spectroscopy in condensed- and gas- phase T2 - 8th Internatiomal Gas Analysis Symposium T2 - 8th Internatiomal Gas Analysis Symposium CY - Rotterdam, Netherlands DA - 2015-06-10 PY - 2015 AN - OPUS4-35056 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael A1 - Meyer, Klas A1 - Zientek, Nicolai T1 - Towards online reaction monitoring with fully automated NMR data evaluation and modelling - Current results from simultaneous 19F-1H medium resolution NMR experiments N2 - NMR Process Monitoring Towards an automated field integration T2 - 3rd Practical Applications of NMR in Industry Conference (PANIC) - Mestrelab users' meeting CY - La Jolla, CA, USA DA - 08.02.2015 KW - Online NMR spectroscopy KW - Reaction monitoring KW - Prozessanalytik KW - Process analytical technology PY - 2015 AN - OPUS4-36145 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Paul, Andrea A1 - Ruiken, J.-P. A1 - Meyer, Klas A1 - Westad, Frank A1 - Illner, M. A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Online spectroscopy in microemulsions – A process analytical approach for hydroformylation miniplant II - Calibration and prediction by Raman spectra T2 - Tagungsband - 11. Kolloquium Arbeitskreis Prozessanalytik N2 - The Collaborative Research Center InPROMPT aims to establish a novel process concept for the hydroformylation of long-chained olefins, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro-emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the temperature and concentration sensitive multi-phase system demands a continuous observation of the reaction to achieve an operational and economically feasible plant operation. For that purpose, we tested the potential of both NMR and Raman spectroscopy for process control assistance. The lab-scale experiments were supported by sampling for off-line GC-analysis as reference analytics. The results of the NMR experiments will be part of another contribution. T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Wien, Austria DA - 30.11.2015 KW - Prozessanalytik KW - Process analytical technology KW - Prozess-Spektroskopie KW - Emulsions KW - Hydroformylation KW - Reaction monitoring KW - Raman spectroscopy PY - 2015 SP - 66 EP - 67 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-38846 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Illner, M. A1 - Müller, D. A1 - Esche, E. A1 - Paul, Andrea A1 - Wozny, G. A1 - Maiwald, Michael T1 - Online spectroscopy in microemulsions – A process analytical approach for hydroformylation miniplant I – Experimental setup and NMR reaction monitoring T2 - Tagungsband - 11. Kolloquium Arbeitskreis Prozessanalytik N2 - Hydroformylation represents an important homogeneous catalyzed process, which is widely used within chemical industry. Usually applied with simple alkenes like Propene and Butene aldehydes obtained from alkenes >C6 are relevant intermediates in production of plasticizers, surfactants and polymers. Today the active catalyst species is often based on valuable Rhodium complexes in aqueous solution. This implies the problem of limited water solubility of the reactands, which is acceptable for short chain lengths, but states a problem in case of higher alkenes. Along with that efficient separation and recycling of the catalyst becomes more complicated. There are different approaches tackling this problem, e.g., by using of salt formation in the BASF process or downstream distillation within the Shell process T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Wien, Austria DA - 30.11.2015 KW - Prozessanalytik KW - Process analytical technology KW - Emuslions KW - Hydroformylation KW - Online NMR spectroscopy KW - Reaction monitoring PY - 2015 SP - 51 EP - 51 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-38845 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kraemer, B. A1 - Zientek, Nicolai A1 - Esche, E. A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Vom Labor zum Prozess- Eine robuste Prozessanalytik für die Reaktivabsorption von CO2 aus in industriellen Gasströmen basierend auf Onlin-NMR- und Raman-Spektroskopie T2 - Anakon 2015 T2 - Anakon 2015 CY - Graz, Östereich DA - 2015-03-23 PY - 2015 AN - OPUS4-33132 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kraemer, B. A1 - Zientek, Nicolai A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Eine robuste Prozessanalytik für die Reaktivabsorption von CO2 aus in industriellen Gasströmen basierend auf Onlin-NMR- und Raman-Spektroskopie T2 - 9. Interdisziplinäres Doktorandenseminar T2 - 9. Interdisziplinäres Doktorandenseminar CY - Berlin DA - 2015-02-22 PY - 2015 AN - OPUS4-33131 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Kraemer, B. A1 - Esche, E. A1 - Müller, D. A1 - Wozny, G. A1 - Maiwald, Michael T1 - High-pressure qNMR studies of fluids and gases T2 - 3rd Annual Practical Applications of NMR in Industry Conference (PANIC) T2 - 3rd Annual Practical Applications of NMR in Industry Conference (PANIC) CY - San Diego, USA DA - 2015-02-09 PY - 2015 AN - OPUS4-33134 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, Jan-Paul A1 - Illner, M. A1 - Müller, B. A1 - Paul, Andrea A1 - Wozny, G. A1 - Maiwald, Michael T1 - Online Spectroscopy in Microemulsions- A Process Analytical approach for a Hydroformylation Miniplant I- Experimental setup and NMR Reaction Montoring T2 - 11. Kolloquium Prozessanalytik T2 - 11. Kolloquium Prozessanalytik CY - Wien, Austria DA - 2015-11-30 PY - 2015 AN - OPUS4-35156 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Illner, M. A1 - Paul, Andrea A1 - Müller, D. A1 - Esche, E. A1 - Repke, J.-U. A1 - Maiwald, Michael T1 - Prozessanalytik für die moderne Verfahrenstechnik – Online-NMR- und -Raman-Spektroskopie im mizellaren Stoffsystem N2 - Homogen katalysierte Reaktionen sind wichtige Werkzeuge der chemischen Industrie. Milde Reaktionsbedingungen und hohe Selektivitäten führen zu einer energie- und ressourcenschonenden Produktion. Ein bedeutender Prozessschritt ist die Hydroformylierung. Hier kommen Kobalt- und Rhodiumkomplexe mit mehrzähnigen Liganden zum Einsatz, die zumeist in wässriger Lösung vorliegen. Die Anwendbarkeit beschränkt sich demnach auf kurzkettige Edukte mit hinreichender Wasserlöslichkeit. T2 - ProcessNet-Jahrestagung und 32. DECHEMA-Jahrestagung der Biotechnologen 2016 CY - Aachen, Germany DA - 12.09.2016 KW - Hydroformylierung KW - Mizellen KW - NMR-Spektroskopie KW - Raman-Spektroskopie KW - Chemometrie KW - Prozesssensoren KW - Prozessanalytik KW - Industrie PY - 2016 AN - OPUS4-37388 LA - deu 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 - JOUR A1 - Kern, Simon A1 - Meyer, Klas A1 - Maiwald, Michael T1 - NMR-Spektroskopie im Feld - Eine neue Online-Methode für die Prozesskontrolle JF - ATP-Edition (Automatisierungstechnische Praxis) N2 - Flexible, modulare Produktionsanlagen auf der Basis von verfahrenstechnischen Teilmodulen stellen einen vielversprechenden Ansatz für die kontinuierliche Produktion von Fein- und Spezialchemikalien dar. Der Schwerpunkt des Horizont-2020-Projekts der Europäischen Kommission CONSENS (Integrated Control and Sensing) liegt in der Implementierung von innovativen Sensorkonzepten zur Prozessüberwachung und -regelung innerhalb von containerbasierten modularen Produktionsan lagen. In diesem Artikel wird die Feldintegration eines Online-NMR-Sensors als smartes Modul für die Prozesskontrolle beschrieben. Dieses Modul basiert auf einem kommerziell erhältlichen Niederfeld-NMRSpektrometer, das zurzeit für die Anwendung im Laborbereich erhältlich ist. Für die Feldintegration wurde ein ATEX-zertifiziertes, explosionsgeschütztes Gehäuse entwickelt sowie Automationsschemen für den unbeaufsichtigten Betrieb und für die spektrale Datenauswertung erstellt. Nachdem die Machbarkeit und Leistungsfähigkeit des Sensorkonzeptes in Laborexperimente an einer aromatischen Substitutionsreaktion bereits erfolgreich demonstriert wurde, ist die Inbetriebnahme des NMR-Sensormoduls in industrieller Umgebung für 2017 geplant. KW - Prozessanalytik KW - Reaction monitoring KW - Industrie 4.0 KW - Online-NMR-Spektroskopie KW - CONSENS KW - Prozess-Sensoren PY - 2016 SN - 2190-4111 VL - 58 IS - 12 SP - 21 EP - 25 PB - DIV Deutscher Industrieverlag GmbH CY - München AN - OPUS4-38675 LA - deu 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 A1 - Gräßer, Patrick A1 - Zientek, Nicolai A1 - Maiwald, Michael A1 - Paul, Andrea A1 - Kern, Simon T1 - Field integration of benchtop NMR instruments for online monitoring and process control of a modular industrial reaction step N2 - Online monitoring and process control requires fast and noninvasive analytical methods, which are able to monitor the concentration of reactants in multicomponent mixtures with parts-per-million resolution. Online NMR spectroscopy can meet these demands when flow probes are directly coupled to reactors, since this method features a high linearity between absolute signal area and sample concentration, which makes it an absolute analytical comparison method being independent on the matrix. Due to improved magnet design and field shimming strategies portable and robust instruments have been introduced to the market by several manufacturers during the last few years. First studies with this technology showed promising results to monitor chemical reaction in the laboratory. Within the project CONSENS, the continuous production of high-value products in small production scale is advanced by introducing benchtop NMR spectroscopy. CONSENS is a research and innovation project on integrated control and sensing for sustainable operation of flexible intensified processes. This poster will present the first steps of the process integration of a benchtop NMR instrument for a lithiation process and outlines further fields of activity and potential challenges. Hereby, the following issues are going to be addressed: explosion-proof housing for the spectrometer, automation of signal processing (data pretreatment, evaluation and communication to the control system), flow cells and measuring conditions. Furthermore, first online spectra of the lithiation reaction in batch mode were acquired in lab scale. The reaction was performed in a 25 mL glass reactor with thermal jackets for temperature control of the reaction mixture. The Li-HMDS was dosed stepwise by using a glass syringe. First spectra in the proton and fluorine domain were recorded online using a flowrate of 3.5 mL min–1 and a simple 5 mm polytetrafluoroethylene tube (PTFE) as a flow cell. T2 - 4th Practical Applications of NMR in Industry Conference (PANIC) CY - Houston, Texas, USA DA - 15.02.2016 KW - Reaction monitoring KW - Online NMR spectroscopy PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-354427 AN - OPUS4-35442 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meyer, Klas A1 - Kern, Simon A1 - Zientek, Nicolai A1 - Guthausen, G. A1 - Maiwald, Michael T1 - Process control with compact NMR JF - Trends in Analytical Chemistry N2 - Compact nuclear magnetic resonance (NMR) instruments make NMR spectroscopy and relaxometry accessible in industrial and harsh environments for reaction and process control. An increasing number of applications are reported. To build an interdisciplinary bridge between “process control” and “compact NMR”,we give a short overviewon current developments in the field of process Engineering such as modern process design, integrated processes, intensified processes along with requirements to process control, model based control, or soft sensing. Finally, robust field integration of NMR systems into processes environments, facing explosion protection or Integration into process control systems, are briefly discussed. KW - Prozessanalytik KW - Quantitative NMR-Spektroskopie KW - Industrie 4.0 KW - Reaction monitoring KW - Process control KW - Online NMR spectroscopy KW - Compact NMR PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-373562 UR - http://www.sciencedirect.com/science/article/pii/S0165993616300073 DO - https://doi.org/10.1016/j.trac.2016.03.016 SN - 0165-9936 VL - 83 IS - Part A / SI SP - 39 EP - 52 PB - Elsevier AN - OPUS4-37356 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Guhl, Svetlana A1 - Meyer, Klas A1 - Kern, Simon A1 - Gräßer, Patrick A1 - Maiwald, Michael T1 - Process monitoring of an intensified continuous production unit with compact NMR spectroscopy N2 - Monitoring chemical reactions is the key to chemical process control. Today, mainly optical online methods are applied. NMR spectroscopy has a high potential for direct loop process control. Compact NMR instruments based on permanent magnets are robust and relatively inexpensive analyzers, which feature advantages like low cost, low maintenance, ease of use, and cryogen-free operation. Instruments for online NMR measurements equipped with a flow-through cell, possessing a good signal-to-noise-ratio, sufficient robustness, and meeting the requirements for integration into industrial plants (i.e., explosion safety and fully automated data analysis) are currently not available off the rack. Recently, promising benchtop NMR instruments with acceptable performance came to market and process integrated sensors developed on basis of such laboratory instruments are on their way. Intensified continuous processes are in focus of current research. Compared to traditional batch processes, these are giving admittance to new and difficult to produce compounds, leading to better product uniformity, and dras-tically reducing the consumption of raw materials and energy. Flexible (modular) chemical plants can produce different products using the same equipment with short down-times between campaigns, and quick introduction of new products to the market. Typically, such plants have smaller scale than big size facilities for production of basic chemicals but are still capable to produce kilograms to tons of specialty products each day. Such flexible (modular) plants can be provided in the size of 20 ft freight containers and represent a promising approach by their ability of easy transfer to production sites as well as the possibility of increasing production capacity by a simple numbering-up-approach. However, full automation is a prerequisite to realize such benefits of intensified continuous production. In continu-ous flow processes steady automated measurements and tight closed-loop control of the product quality are mandatory. If these are not available, there is a huge risk of producing large amounts of out-of-spec (OOS) prod-ucts. This is addressed in the European Union’s Research Project CONSENS (Integrated Control and Sensing) by development and integration of smart sensor modules for process monitoring and control within such modular plant setups. T2 - 12. Kolloquium des Arbeitskreises Prozessanalytik CY - Berlin, Germany DA - 28.11.2016 KW - Low field NMR spectroscopy KW - Modular production units KW - Online NMR spectroscopy PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-385628 AN - OPUS4-38562 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Guhl, Svetlana A1 - Meyer, Klas A1 - Kern, Simon A1 - Gräßer, Patrick A1 - Maiwald, Michael ED - Maiwald, Michael T1 - Process monitoring of an intensified continuous production unit with compact NMR spectroscopy T2 - Tagungsband – 12. Kolloquium Prozessanalytik N2 - Monitoring chemical reactions is the key to chemical process control. Today, mainly optical online methods are applied. NMR spectroscopy has a high potential for direct loop process control. Compact NMR instruments based on permanent magnets are robust and relatively inexpensive analyzers, which feature advantages like low cost, low maintenance, ease of use, and cryogen-free operation. Instruments for online NMR measurements equipped with a flow-through cell, possessing a good signal-to-noise-ratio, sufficient robustness, and meeting the requirements for integration into industrial plants (i.e., explosion safety and fully automated data analysis) are cur-rently not available off the rack. Recently, promising benchtop NMR instruments with acceptable performance came to market and process integrated sensors developed on basis of such laboratory instruments are on their way. T2 - 12. Kolloquium des Arbeitskreises Prozessanalytik CY - Berlin, Germany DA - 28.11.2016 KW - Online NMR spectroscopy KW - Modular production units KW - Low field NMR spectroscopy PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-383646 SP - P17, 75 EP - 77 AN - OPUS4-38364 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 - Zientek, Nicolai A1 - Paul, Andrea A1 - Kern, Simon A1 - Müller, D. A1 - Esche, E. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Online NMR spectroscopy as a reference tool for model developments - Successful approaches in process analytical technology N2 - Quantitative Online NMR spectroscopy as a direct ratio method of analysis represents a perfect reference for calibration of further process analytical techniques, e.g., optical spectroscopic techniques. In this work we present a combined approach including Online NMR and Raman spectroscopy on a laboratory setup for development of suitable models for process monitoring. Therefore we investigated the absorption process of carbon dioxide in solutions of monoethanolamine, as well as the homogeneous catalyzed hydroformylation reaction of 1-dodecene taking place in an emulsion stabilized by a technical surfactant. The models for Raman spectroscopy were tested and approved during several days of operational studies of miniplant-scale setups for both mentioned applications. T2 - 4th Annual Practical Applications of NMR in Industry Conference (PANIC) CY - Houston, Texas, USA DA - 15.02.2016 KW - Online-NMR spectroscopy KW - Online-Raman spectroscopy KW - Process Analytical Technology PY - 2016 AN - OPUS4-35423 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 - JOUR A1 - Zientek, Nicolai A1 - Laurain, C. A1 - Meyer, Klas A1 - Paul, Andrea A1 - Engel, D. A1 - Guthausen, G. A1 - Kraume, M. A1 - Maiwald, Michael T1 - Automated data evaluation and modelling of simultaneous F-19-H-1 medium-resolution NMR spectra for online reaction monitoring JF - Magnetic Resonance in Chemistry N2 - Medium-resolution nuclear magnetic resonance spectroscopy (MR-NMR) currently develops to an important analytical tool for both quality control and processmonitoring. In contrast to high-resolution onlineNMR (HR-NMR),MR-NMRcan be operated under rough environmental conditions. A continuous re-circulating stream of reaction mixture fromthe reaction vessel to the NMR spectrometer enables a non-invasive, volume integrating online analysis of reactants and products. Here, we investigate the esterification of 2,2,2-trifluoroethanol with acetic acid to 2,2,2-trifluoroethyl acetate both by 1H HR-NMR (500MHz) and 1H and 19F MRNMR (43MHz) as amodel system. The parallel online measurement is realised by splitting the flow,which allows the adjustment of quantitative and independent flow rates, both in the HR-NMR probe as well as in the MR-NMR probe, in addition to a fast bypass line back to the reactor. One of the fundamental acceptance criteria for online MR-MNR spectroscopy is a robust data treatment and evaluation strategy with the potential for automation. The MR-NMR spectra are treated by an automated baseline and phase correction using the minimum entropy method. The evaluation strategies comprise (i) direct integration, (ii) automated line fitting, (iii) indirect hard modelling (IHM) and (iv) partial least squares regression (PLS-R). To assess the potential of these evaluation strategies for MR-NMR, prediction results are compared with the line fitting data derived from the quantitative HR-NMR spectroscopy. Although, superior results are obtained from both IHM and PLS-R for 1H MR-NMR, especially the latter demands for elaborate data pretreatment, whereas IHM models needed no previous alignment. KW - NMR KW - 1H-NMR KW - 19F-NMR KW - Medium-resolution NMR KW - Online NMR KW - Quantitative NMR KW - Reaction monitoring KW - Data processing KW - Automation KW - Process analytical technology KW - IHM KW - Indirect hard modeling KW - Chemometrics KW - PLS-R KW - Partial least squares regression PY - 2016 UR - http://onlinelibrary.wiley.com/doi/10.1002/mrc.4216/abstract DO - https://doi.org/doi:10.1002/mrc.4216 VL - 54 SP - 513 EP - 520 PB - John Wiley & Sons, Ltd CY - Hoboken, New Jersey, USA AN - OPUS4-36135 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zientek, Nicolai A1 - Meyer, Klas A1 - Kern, Simon A1 - Maiwald, Michael T1 - Quantitative online NMR spectroscopy in a nutshell JF - Chemie Ingenieur Technik N2 - Online NMR spectroscopy is an excellent tool to study complex reacting multicomponent mixtures and gain process insight and understanding. For online studies under process conditions, flow NMR probes can be used in a wide range of temperature and pressure. This paper compiles the most important aspects towards quantitative process NMR spectroscopy in complex multicomponent mixtures and provides examples. After NMR spectroscopy is introduced as an online method and for technical samples without sample preparation in deuterated solvents, influences of the residence time distribution, pre-magnetization, and cell design are discussed. NMR acquisition and processing parameters as well as data preparation methods are presented and the most practical data analysis strategies are introduced. KW - Prozessanalytik KW - Process analytical technology KW - Online NMR spectroscopy KW - Online monitoring PY - 2016 DO - https://doi.org/10.1002/cite.201500120 SN - 0009-286X VL - 88 IS - 6 SP - 698 EP - 709 PB - Wiley-VCH Verlag GmbH & Co. KGaA CY - Weinheim, Germany AN - OPUS4-36333 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kern, Simon A1 - Meyer, Klas A1 - Paul, Andrea A1 - Maiwald, Michael T1 - Ugly Spectra and Lousy interfaces – Challenges for Compact NMR Spectroscopy in Process Control T2 - Chemie Ingenieur Technik N2 - With the introduction of advanced process analytical technology, the closeness of key process variables to their limits can be directly controlled and the product can be classified or even released in real time. Compact NMR instruments can make NMR spectroscopy accessible in industrial and harsh environments for process control. T2 - ProcessNet-Jahrestagung und 32. DECHEMA-Jahrestagung der Biotechnologen 2016 CY - Aachen, Germany DA - 12.09.2016 KW - Online NMR Spectroscopy KW - Smart Sensors KW - Industrie 4.0 KW - Reaction Monitoring PY - 2016 UR - http://onlinelibrary.wiley.com/doi/10.1002/cite.201650243/full DO - https://doi.org/10.1002/cite.201650243 SN - 1522-2640 VL - 88 SP - 1304 EP - 1317 PB - Wiley-VCH Verlag GmbH & Co. KGaA CY - Weinheim AN - OPUS4-37317 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Illner, M. A1 - Müller, D. A1 - Esche, E. A1 - Paul, Andrea A1 - Repke, J.-U. A1 - Maiwald, Michael T1 - Prozessanalytik für die moderne Verfahrenstechnik – Online-NMR- und -Raman-Spektroskopie im mizellaren Stoffsystem N2 - Homogen katalysierte Reaktionsschritte sind ein wichtiges Werkzeug in der chemischen Industrie. Durch die milden Reaktionsbedingungen hinsichtlich Temperatur und Druck bei gleichzeitig hoher Selektivität bieten diese die Möglichkeit energieeffizienter und ressourcenschonender Produktionsschritte. Eine der wichtigsten industriellen Anwendungen bildet die Hydroformylierung. Hier besteht das Katalysatorsystem meist aus Übergangsmetallkomplexen, vorwiegend Kobalt und Rhodium, die zur Steuerung der Selektivität und Löslichkeit mit mehrzähnigen Liganden koordiniert sind. Diese Komplexe liegen für eine effiziente Katalysator-rückführung in wässriger Lösung vor, was jedoch die Anwendbarkeit auf kurzkettige Edukte mit hinreichender Wasserlöslichkeit beschränkt. Ein möglicher Lösungsansatz für die Verwendung langkettiger Alkene ist die Umsetzung der Reaktion in einer Mikroemulsion. Durch die gesteigerte Phasen-grenzfläche besteht ein effektiver Kontakt von Katalysator und Reaktanden bei gleichzeitiger Möglichkeit der Produktseparation durch Phasentrennung, während der Katalysator dem Reaktionsschritt zurückgeführt wird und das Verfahren damit wirtschaftlich macht.[1] Am Beispiel der Reaktion von 1-Dodecen zu Tridecanal wird der Einsatz von Online-NMR- und -Raman-Spektroskopie für die Prozessanalytik (sowie Applikation von komplexen Regelungskonzepten) innerhalb eines mizellaren Systems demonstriert. Ein speziell konzipierter Laboraufbau ermöglicht die Durchführung von Experimenten unter Prozessbedingungen für die in Mikroemulsionen äußerst anspruchsvolle Entwicklung und Kalibrierung von multivariaten Modellen für die Raman-Spektroskopie. Diese konnten anschließend im Rahmen einer mehrtägigen Betriebs-studie einer Miniplant am realen technischen System erprobt werden. T2 - ProcessNet-Jahrestagung CY - Aachen, Germany DA - 12.09.2016 KW - Hydroformylierung KW - Prozessanalytik KW - Online-NMR-Spektroskopie KW - Online-Raman-Spektroskopie PY - 2016 N1 - Deutscher Vortrag mit englischsprachigen Folien AN - OPUS4-37385 LA - mul AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Illner, M. A1 - Paul, Andrea A1 - Müller, D. A1 - Esche, E. A1 - Repke, J.-U. A1 - Maiwald, Michael T1 - Prozessanalytik für die moderne Verfahrenstechnik – Online-NMR- und -Raman-Spektroskopie im mizellaren Stoffsystem T2 - Chemie Ingenieur Technik N2 - Homogen katalysierte Reaktionen sind wichtige Werkzeuge der chemischen Industrie. Milde Reaktionsbedingungen und hohe Selektivitäten führen zu einer energie- und ressourcenschonenden Produktion. Ein bedeutender Prozessschritt ist die Hydroformylierung. Hier kommen Kobalt- und Rhodiumkomplexe mit mehrzähnigen Liganden zum Einsatz, die zumeist in wässriger Lösung vorliegen. Die Anwendbarkeit beschränkt sich demnach auf kurzkettige Edukte mit hinreichender Wasserlöslichkeit. T2 - ProcessNet-Jahrestagung und 32. DECHEMA-Jahrestagung der Biotechnologen 2016 CY - Aachen, Germany DA - 12.09.2016 KW - Hydroformylierung KW - Prozessanalytik KW - Prozess-Spektroskopie KW - NMR-Spektroskopie KW - Raman-Spektroskopie KW - Mizellen PY - 2016 UR - http://onlinelibrary.wiley.com/doi/10.1002/cite.201650219/epdf DO - https://doi.org/10.1002/cite.201650219 SN - 1522-2640 VL - 88 SP - 1304 EP - 1317 PB - Wiley-VCH Verlag GmbH & Co. KGaA CY - Weinheim AN - OPUS4-37316 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - THES A1 - Meyer, Klas T1 - Hochdruck NMR-Spektroskopie N2 - Der Einsatz der quantitativen Kernspinresonanzspektroskopie (NMR-Spektroskopie) in technischen Mischungen stellt einen vielversprechenden Ansatz für die Verfolgung und Kontrolle von Abläufen innerhalb chemischer Produktionsprozesse dar. Die Möglichkeit der direkten Relativquantifizierung ohne Notwendigkeit der Zugabe von Standards oder einer vorherigen Kalibrierung, vergleichbar mit einem simplen „Zählen“ von Kernspins im Messvolumen, macht die Methode darüber hinaus besonders interessant für metrologische Fragestellungen. Im ersten Teil dieser Dissertation wird die Entwicklung von Hochdruckmethoden für Anwendungen in der Gasmetrologie thematisiert. Als ergänzende Analysenmethode liefert die NMR-Spektroskopie hier wichtige Erkenntnisse zur Unterstützung der Herstellung hochgenauer Gas- und Flüssiggasgemische. Der zweite Teil beinhaltet Anwendungsbeispiele für die Prozessanalytik an technischen Systeme auf Basis von Online-NMR- und -Raman-Spektroskopie anhand der industriell relevanten Verfahren der CO2 Absorption in wässrigen Alkanolaminlösungen, sowie der Hydroformylierung langkettiger Alkene in einer Mikroemulsion. KW - Hochdruck NMR-Spektroskopie KW - Quantitative NMR-Spektroskopie KW - Gasphasen NMR-Spektroskopie KW - Prozessanalytik PY - 2017 SN - 9783736994621 SP - 1 EP - 180 PB - Cuvillier CY - Göttingen AN - OPUS4-39092 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Illner, M. A1 - Müller, D. A1 - Esche, E. A1 - Paul, Andrea A1 - Westad, Frank A1 - Repke, J.-U. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Online spectroscopy in micellar systems – A process analytical approach for a hydroformylation mini-plant N2 - Within the Collaborative Research Center InPROMPT a novel process concept for the hydroformylation of long-chained olefins is studied in a mini-plant, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro¬emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the high sensitivity of this multi-phase system with regard to changes in temperature and composition demands a continuous observation of the reaction to achieve a reliable and economic plant operation. For that purpose, we tested the potential of both online NMR and Raman spectroscopy for process control. The lab-scale experiments were supported by off-line GC-analysis as a reference method. A fiber optic coupled probe of a process Raman spectrometer was directly integrated into the reactor. 25 mixtures with varying concentrations of olefin (1-dodecene), product (n-tridecanal), water, n-dodecane, and technical surfactant (Marlipal 24/70) were prepared according to a D-optimal design. Online NMR spectroscopy was implemented by using a flow probe equipped with 1/16” PFA tubing serving as a flow cell. This was hyphenated to the reactor within a thermostated bypass to maintain process conditions in the transfer lines. Partial least squares regression (PLSR) models were established based on the initial spectra after activation of the reaction with syngas for the prediction of unknown concentrations of 1-dodecene and n-tridecanal over the course of the reaction in the lab-scale system. The obtained Raman spectra do not only contain information on the chemical composition but are further affected by the emulsion properties of the mixtures, which depend on the phase state and the type of micelles. Based on the spectral signature of both Raman and NMR spectra, it could be deduced that especially in reaction mixtures with high 1-dodecene content the formation of isomers as a competitive reaction was dominating. Similar trends were also observed during some of the process runs in the mini-plant. The multivariate calibration allowed for the estimation of reactants and products of the hydroformylation reaction in both laboratory setup and mini-plant. T2 - Quantitative NMR Methods for Reaction and Process Monitoring (NMRPM) CY - Kaiserslautern, Germany DA - 19.01.2017 KW - Online reaction monitoring PY - 2017 AN - OPUS4-39012 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Rademann, K. A1 - Maiwald, Michael T1 - Quantitative NMR spectroscopy for gas metrology – applications in liquefied petroleum gases N2 - The field of gas metrology is dealing with the development and improvement of gas analytical methods, as well as production of highly accurate primary reference standards. These are prepared at national metrological institutes (NMI) and represent the highest national level of traceability. Used for certification of secondary standards provided by specialty gas distributors these are very important for a high number of industrial sectors, which have to proof traceability due to legal or regulatory affairs, e.g., natural gas suppliers. Thus, improvements in the production and certification of these mixtures will have a direct influence on gas industry. Due to its direct correlation to the number of spins within active sample volume quantitative NMR spectroscopy (qNMR) is a highly promising method with absolute comparison abilities in complex systems. Especially for liquefied petroleum gases (LPG) it has the ability of studying the unmodified sample at same conditions like in the cylinder. In contrast to gas chromatography no preparation steps and no changes like evaporation of the sample are necessary. In this work we show the most recent results of our investigations on highly accurate LPG mixtures provided in constant-pressure piston cylinders. A dynamic pressure-resistant setup allows for sampling and circulation of the samples to ensure a homogeneous withdrawal from the cylinder. This is presented on examples of a commercial multicomponent LPG mixture obtained from specialty gas distributor, as well as two cylinders from the key comparison CCQM-K119 at highest level of international metrology. T2 - 5th Panic - Practical Applications of NMR in Industry Conferece CY - Hilton Head Island, SC 29928, USA DA - 20.02.2017 KW - Quantitative NMR spectroscopy KW - Gas metrology KW - Liquefied petroleum gas PY - 2017 AN - OPUS4-39234 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Gräßer, Patrick A1 - Wander, Lukas A1 - Guhl, Svetlana A1 - Kern, Simon A1 - Maiwald, Michael T1 - Quantitative online NMR spectroscopy for industrial reaction and process monitoring N2 - Compact nuclear magnetic resonance (NMR) instruments make NMR spectroscopy and relaxometry accessible in industrial and harsh environments for reaction and process control. An increasing number of applications are reported. Robust field integration of NMR systems have to face explosion protection or integration into process control systems with short set-up times. Tis paves the way for industrial automation in real process environments. Automated data preparation and analysis are cornerstones for a breakthrough of NMR techniques for process control. Particularly, robust chemometrics as well as automated signal processing methods have to be (further) developed especially for NMR spectroscopy in process control. This becomes even more important for so called “smart sensors” providing the basis for the future project “Industrie 4.0”, and Industrial Internet of Things (IIoT), along with current requirements to process control, model based control, or soft sensing. Data analysis techniques are available but currently mostly used for off-line data analysis to detect the causes of variations in the product quality. T2 - Syngenta Face to Face Meeting Process Analytical Technology CY - Münchwilen, Switzerland DA - 12.09.2017 KW - Process monitoring KW - Online NMR spectroscopy KW - Reaction monitoring KW - Hydroformylation KW - Gas analysis KW - CONSENS KW - Indirect hard modeling PY - 2017 AN - OPUS4-41946 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Guhl, Svetlana A1 - Kern, Simon A1 - Meyer, Klas A1 - Gräßer, Patrick A1 - Wander, Lukas A1 - Maiwald, Michael T1 - Online NMR Spectroscopy for Process Monitoring in Intensified Continuous Production Plants T2 - Processdings of 4th European Conference on Process Analytics and Control Technology (EuroPACT 2017) N2 - Process analytical techniques are extremely useful tools for chemical production and manufacture and are of particular interest to the pharmaceutical, food and (petro-) chemical industries. Today, mainly optical online methods are applied. NMR spectroscopy has a high potential for direct loop process control. Compact NMR instruments based on permanent magnets are robust and relatively inexpensive analysers, which feature advantages like low cost, low maintenance, ease of use, and cryogen-free operation. Instruments for online NMR measurements equipped with a flow-through cell, possessing a good signal-to-noise-ratio, sufficient robustness, and meeting the requirements for integration into industrial plants (i.e., explosion safety and fully automated data analysis) are currently not available off the rack. A major advantage of NMR spectroscopy is that the method features a high linearity between absolute signal area and sample concentration, which makes it an absolute analytical comparison method which is independent of the matrix. This is an important prerequisite for robust data evaluation strategies within a control concept and reduces the need for extensive maintenance of the evaluation model over the time of operation. Additionally, NMR spectroscopy provides orthogonal, but complimentary physical information to conventional, e.g., optical spectroscopy. It increases the accessible information for technical processes, where aromatic-toaliphatic conversions or isomerizations occur and conventional methods fail due to only minor changes in functional groups. As a technically relevant example, the catalytic hydrogenation of 2-butyne-1,4-diol and further pharmaceutical reactions were studied using an online NMR sensor based on a commercially available low-field NMR spectrometer within the framework of the EU project CONSENS (Integrated Control and Sensing). T2 - 4th European Conference on Process Analytics and Control Technology (EuroPACT 2017) CY - Potsdam, Germany DA - 10.05.2017 KW - Process Monitoring KW - CONSENS KW - Online NMR Spectroscopy KW - Process Analytical Technology KW - Process control KW - Hydration KW - EuroPACT PY - 2017 SP - 103 EP - 103 CY - Frankfurt a. M. AN - OPUS4-40231 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Illner, M. A1 - Meyer, Klas A1 - Paul, Andrea A1 - Esche, E. A1 - Maiwald, Michael A1 - Repke, J.-U. T1 - Operation and Optimal Control of Multiphase Systems – Hydroformylation in Microemulsions on the Mini-plant Scale T2 - Processdings of 4th European Conference on Process Analytics and Control Technology (EuroPACT 2017) N2 - Hydroformylation of short-chained olefins has been established as a standard industrial process for the production of C2 to C6 aldehydes. Using aqueous solutions of transition metal complexes these processes are carried out homogeneously catalyzed. A biphasic approach allows for highly efficient catalyst recovery. Regarding renewable feedstocks, the hydroformylation of long-chained alkenes (> C10) in a biphasic system, using highly selective rhodium catalysts has yet not been shown. Therefore, the Collaborative Research Center SFB/TR 63 InPROMPT develops new process concepts, involving innovative tuneable solvent systems to enable rather difficult or so far nonviable synthesis paths. One possible concept is the hydroformylation of long-chained alkenes in microemulsions. For this, a modular mixer-settler concept was proposed, combining high reaction rates and efficient catalyst recycling via the application of technical grade surfactants. The feasibility of such a concept is evaluated in a fully automated, modular mini-plant system within which the characteristics of such a multiphase system pose several obstacles for the operation. Maintaining a stable phase separation for efficient product separation and catalyst recycling is complicated by small and highly dynamic operation windows as well as poor measurability of component concentrations in the liquid phases. In this contribution, a model-based strategy is presented to enable concentration tracking and phase state control within dynamic mini-plant experiments. Raman spectroscopy is used as an advanced process analytical tool, which allows for online in-situ tracking of concentrations. Combined with optical and conductivity analysis optimal plant trajectories can be calculated via the solution of dynamic optimization problem under uncertainty. Applying these, a stable reaction yield of 40 % was achieved, combined with an oil phase purity of 99,8 % (total amount of oily components in the oil phase) and catalyst leaching below 0.1 ppm. T2 - 4th European Conference on Process Analytics and Control Technology (EuroPACT 2017) CY - Potsdam, Germany DA - 10.05.2017 KW - Hydroformylation KW - Micoemulsion KW - Dispersion KW - Process Analytical Technology KW - Mini-plant KW - EuroPACT PY - 2017 SP - 92 EP - 92 CY - Frankfurt a. M. AN - OPUS4-40230 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kern, Simon A1 - Guhl, Svetlana A1 - Meyer, Klas A1 - Wander, Lukas A1 - Paul, Andrea A1 - Maiwald, Michael T1 - Mathematical and statistical tools for online NMR spectroscopy in chemical processes T2 - Tagungsband 13. Dresdner Sensor-Symposium N2 - Monitoring chemical reactions is the key to chemical process control. Today, mainly optical online methods are applied, which require excessive calibration effort. NMR spectroscopy has a high potential for direct loop process control while exhibiting short set-up times. Compact NMR instruments make NMR spectroscopy accessible in industrial and harsh environments for advanced process Monitoring and control, as demonstrated within the European Union’s Horizon 2020 project CONSENS. We present a range of approaches for the automated spectra analysis moving from conventional multivariate statistical approach, (i.e., Partial Least Squares Regression) to physically motivated spectral models (i.e., Indirect Hard Modelling and Quantum Mechanical calculations). By using the benefits of traditional qNMR experiments data analysis models can meet the demands of the PAT community (Process Analytical Technology) regarding low calibration effort/calibration free methods, fast adaptions for new reactants or derivatives and robust automation schemes. T2 - 13. Dresdner Sensor Symposium CY - Dresden, Germany DA - 04.12.2017 KW - Online NMR spectroscopy KW - Process control KW - Partial least squares regression KW - Indirect hard modeling KW - Quantum mechanics KW - First principles PY - 2017 UR - https://www.ama-science.org/proceedings/details/2748 SN - 978-3-9816876-5-1 DO - https://doi.org/10.5162/13dss2017/P2.07 SP - P2, 209 EP - 212 PB - AMA Service GmbH CY - Berlin AN - OPUS4-43254 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -