TY - JOUR A1 - Guthausen, G. A1 - Dalitz, F. A1 - Zientek, Nicolai A1 - Nirschl, H. A1 - Kraume, M. A1 - Maiwald, Michael T1 - Applikationen der Medium-Resolution-NMR-Spektroskopie in der Prozessanalytik: Potenzial und Herausforderungen N2 - Die kernmagnetische Resonanz (NMR) erlaubt über die zeitaufgelöste Messung der chemischen Verschiebung und der Kopplungskonstanten eine andere Blickweise auf Moleküle, die an Reaktionen und anderen dynamischen Prozessen beteiligt sind und ermöglicht somit die Charakterisierung von Prozessen, die über optische Eigenschaften funktioneller Gruppen oft nicht zugänglich sind, z. B. Hydrierungen oder Isomerisierungen KW - Medium-Resolution-NMR-Spektroskopie KW - Prozessanalytik PY - 2012 SN - 0009-286X SN - 1522-2640 VL - 84 IS - 8 SP - 1364 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-28269 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - Quantitative - Online- NMR Spectroscopy: Three good arguments for a comprensive processes understanding T2 - 1. Symposium NMRPM " Quantiative NMR Methods for Reaction and Process Monitoring" CY - Kaiserslautern DA - 2015-01-15 PY - 2015 AN - OPUS4-33133 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 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 - 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 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 - CHAP A1 - Maiwald, Michael A1 - Gornushkin, Igor B. A1 - Ostermann, Markus ED - Gauglitz, G. ED - Moore, D.S. T1 - Trends in spectroscopic techniques for process control N2 - New developments in spectroscopic techniques for process control are, in general, driven by shortcomings of existing technology, for example, when sensitivity, selectivity, robustness, and so forth do not meet the demands. The perfect process analytical method would be based on a robust and easy to handle customized technique operating in real time, come without any need for calibration, that is, be an absolute method, have a professional support, and be compliant to increasing regulatory requirements. However, there are at least trends toward such an all-in-one device suitable for every purpose. Small, low-field NMR systems equipped with permanent magnet technology have been developed and allow for quantitative analysis as on-line instruments in a production environment. Quantitative high-resolution on-line NMR spectroscopy contributes to process understanding in pilot plant and research environments. Laser spectroscopy is a promising field in process analysis owing to its sensitivity and selectivity. Laser-induced breakdown spectroscopy LIBS is a promising field for direct in situ analysis and remote sensing. Applications of quantum-cascade lasers for process analytical applications are a promising technique. Techniques such as cavity ring-down spectroscopy (CRDS), tunable diode laser absorption spectroscopy (TDLAS), and photothermal techniques are briefly introduced. Recent developments of new detectors have improved X-ray fluorescence analysis (XRF) for qualitative and quantitative on-line evaluation of the elementary composition of liquid or solid samples, regardless of whether compact or bulk material. The chapter also introduces miscellaneous techniques such as ion mobility spectroscopy (IMS), microwave and dielectric spectroscopy, terahertz spectroscopy, ultrasonic acoustic spectroscopy, and other methods. KW - Process analytical technology (PAT) KW - NMR spectroscopy KW - IMS KW - CRDS KW - TDLAS KW - LIBS KW - Prozessanalytik KW - X-ray fluorescence KW - Terahertz spectroscopy PY - 2014 SN - 978-3-527-32150-6 DO - https://doi.org/10.1002/9783527654703.ch41 VL - 3 SP - Chapter 41, 1419 EP - 1438 PB - Wiley-VCH AN - OPUS4-31859 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - Multi-spectroscopic approach for the analysis of dissolution profiles of pharmaceuticals T2 - EuroPACT 2014, 3rd European Conference on Process Analytics and Control Technology CY - Barcelona, Spanien DA - 2014-05-06 PY - 2014 AN - OPUS4-31889 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - "Particle size monitoring using various techniques" T2 - EuroPACT 2014, 3rd European Conference on Process Analytics and Control Technology CY - Barcelona, Spanien DA - 2014-05-06 PY - 2014 AN - OPUS4-31890 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zientek, Nicolai A1 - Maiwald, Michael A1 - Guthausen, G. T1 - NMR-Spektroskopie im Feld? Monitoring chemischer Reaktionen in der Prozesskontrolle N2 - In der Forschung wird die Kernspinresonanzspektroskopie (NMR-Spektroskopie von englisch: nuclear magnetic resonance) für die Strukturaufklärung und Quantifizierung genutzt. Eine Arbeitsgruppe an der Berliner Bundesanstalt für Materialforschung und -prüfung (BAM) und am Karlsruher Institut für Technologie (KIT) hat die Möglichkeiten untersucht, die NMR-Spektroskopie auch als Online-Methode für das Monitoring chemischer Reaktionen in der Prozesskontrolle einsetzbar zu machen. PY - 2014 SN - 1436-2597 VL - 17 IS - 12 SP - 25 EP - 26 PB - GIT-Verl. CY - Darmstadt AN - OPUS4-32434 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Maiwald, Michael T1 - Teil der Revolution - Prozessanalysentechnik: Kernstück von "Industrie 4.0"? N2 - Ohne die vielfältigen Messmethoden der Prozess­analysentechnik (PAT) sind viele moderne Anlagen der verfahrenstechnischen Industrie heute nicht mehr wirtschaftlich oder sicher zu betreiben. Dementsprechend ­erfährt die sich mittlerweile immer mehr als selbstständig etablierende Branche Prozessanalysentechnik einen großen Zuwachs und ­eine ­spannende Dynamik. Sie ermög­licht eine Produktion in der geforderten Produktqualität unter optimaler Ausnutzung von Rohstoffen, Anlagen und Energie. KW - Prozessanalytik KW - Industrie 4.0 KW - Pharmazeutische Produktion KW - Process analytical technology PY - 2014 SN - 2191-3803 VL - 5 IS - 04 SP - 10 EP - 12 PB - Succidia AG, Verl. und Kommunikation CY - Darmstadt AN - OPUS4-31435 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Paul, Andrea A1 - Meyer, Klas A1 - Ruiken, Jan-Paul A1 - Illner, M. A1 - Müller, D.-N. A1 - Esche, E. A1 - Wozny, G. A1 - Westad, Frank A1 - Maiwald, Michael T1 - Process spectroscopy in microemulsions — Raman spectroscopy for online monitoring of a homogeneous hydroformylation process N2 - A major industrial reaction based on homogeneous catalysis is hydroformylation for the production of aldehydes from alkenes and syngas. Hydroformylation in microemulsions, which is currently under investigation at Technische Universität Berlin on a mini-plant scale, was identified as a cost efficient approach which also enhances product selectivity. Herein, we present the application of online Raman spectroscopy on the reaction of 1-dodecene to 1-tridecanal within a microemulsion. To achieve a good representation of the operation range in the mini-plant with regard to concentrations of the reactants a design of experiments was used. Based on initial Raman spectra partial least squares regression (PLSR) models were calibrated for the prediction of 1-dodecene and 1-tridecanal. Limits of predictions arise from nonlinear correlations between Raman intensity and mass fractions of compounds in the microemulsion system. Furthermore, the prediction power of PLSR models becomes limited due to unexpected by-product formation. Application of the lab-scale derived calibration spectra and PLSR models on online spectra from a mini-plant operation yielded promising estimations of 1-tridecanal and acceptable predictions of 1-dodecene mass fractions suggesting Raman spectroscopy as a suitable technique for process analytics in microemulsions. KW - Raman KW - Online KW - Chemometrics KW - Hydroformylation KW - Mini-plant KW - Microemulsion PY - 2017 DO - https://doi.org/10.1088/1361-6501/aa54f0 SN - 1361-6501 SN - 0957-0233 VL - 28 IS - 3 SP - 035502-1 EP - 035502-11 PB - IOP Publishing Ltd CY - UK AN - OPUS4-39032 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Meyer, Klas A1 - Paul, Andrea A1 - Ruiken, J.-P. A1 - Westad, Frank A1 - Illner, M. A1 - Müller, D. A1 - Esche, E. A1 - Repke, J.-U. A1 - Maiwald, Michael T1 - Online Spectroscopy in Microemulsions – 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 - 4th European Conference on Process Analytics and Control Technology (EuroPACT 2017) CY - Potsdam, Germany DA - 10.05.2017 KW - Microemulsions KW - Process Analytical Technology KW - Reaction Monitoring KW - Online NMR Spectroscopy KW - Online Raman Spectroscopy PY - 2017 SP - 64 EP - 64 CY - Frankfurt a. M. AN - OPUS4-40228 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -