TY - JOUR A1 - Meyer, Klas A1 - Ruiken, J.-P. A1 - Illner, M. A1 - Paul, Andrea A1 - Müller, D. A1 - Esche, E. A1 - Wozny, G. A1 - Maiwald, Michael T1 - Process spectroscopy in microemulsions - setup and multi-spectral approach for reaction monitoring of a homogeneous hydroformylation process N2 - Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed. KW - Online-spectroscopy KW - Quantitative NMR spectroscopy KW - Process analytical technology KW - Microemulsions PY - 2017 DO - https://doi.org/10.1088/1361-6501/aa54f3 SN - 0957-0233 SN - 1361-6501 VL - 28 IS - 3 SP - 035501-1 EP - 035501-11 PB - IOP Publishing Ltd. AN - OPUS4-39091 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - Man proposes, God disposes – The Way from Reaction Monitoring to Industrial Automation 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. The talk presents current research activities towards process control with compact NMR and reflects “cultural differences” between the interdisciplinary parties involved. T2 - Symposium NMRPM - Quantitative NMR Methods for Reaction and Process Monitoring CY - Kaiserslautern, Germany DA - 19.01.2017 KW - Reaction Monitoring KW - Process Analytical Technology KW - Smart Sensors KW - Process Control KW - Industrie 4.0 KW - Online NMR Spectroscopy PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-389940 AN - OPUS4-38994 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krämer, D. A1 - Violet, N. A1 - Paul, Andrea A1 - Maiwald, Michael A1 - King, R. T1 - Robustification of partial least squares predictions based on near infrared spectroscopy trough nonlinear state estimation N2 - The Cultivation of “Saccharomyces cerevisiae” for enzyme production was monitored using Near-infrared spectroscopy. An inline NIR optrode was therefore immersed in a 15 L vessel. The calibration was done using a Partial Least Squares (PLS) model with reference measurements of glucose, ammonium, phosphate, ethanol, and optical density. A nonlinear biological process model based on an extended Kalman Filter (EKF) was used to describe the fermentation behavior. It was found that EKF corrects inaccurate PLS predictions. T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Wien, Austria DA - 30.11.2015 KW - PLS-R KW - Near infrared spectroscopy KW - Prozess-Spektroskopie KW - Process analytical technology KW - Fermentation PY - 2015 SP - 77 EP - 77 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-38844 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 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 - 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 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 - Paul, Andrea A1 - Heilmann, M. T. A1 - Schmid, Thomas A1 - Maiwald, Michael T1 - Multivariate classification of Raman spectra from synthetic polymers – an approach for the improved detection of microplastics N2 - The increasing pollution of terrestrial and aquatic ecosystems with plastic debris, which leads to the accumulation of microscopic plastic particles of still unknown fate, is an upcoming problem of our time. In order to monitor the degree of contamination and to understand the underlying processes of degradation and internalization of plastic debris, analytical methods are urgently needed, which help to identify and quantify microplastics. Currently, expensive collected and purified materials enriched on filters are investigated by (micro) infrared spectroscopy (FTIR). Few studies using micro-Raman spectroscopy have been published as well. In contrast to FTIR, Raman spectroscopy can handle wet samples, but it suffers from interference of fluorescent materials. Both micro-FTIR- and micro-Raman, always include time consuming scanning and mapping procedures followed by the manual inspection and measurement of selected particles. T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Wien, Austria DA - 30.11.2015 KW - Prozessanalytik KW - Microplastics KW - Mikroplastik KW - Raman-Spektroskopie KW - Polymers KW - Multivariate classification PY - 2015 SP - 80 EP - 81 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-38847 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Maiwald, Michael A1 - Guthausen, G. T1 - Abschlussbericht „Prozesskontrolle mittels Niederfeld-NMR-Spektroskopie“ N2 - Die Online-medium-resolution-NMR-Spektroskopie wurde als neue Technik zur Überwachung verfahrenstechnischer Prozesse weiterentwickelt. Entlang der Prozesskette wurden an den verschiedenen Elementen der Online-Spektroskopie gearbeitet. Ein temperierbarer und druckfester Bypass erlaubt, die reagierende Mischung bei Reaktionsbedingungen über eine Pumpe in die NMR-Messzelle zu fördern, für die verschiedene Versionen von temperatur-isolierten NMR-Durchflusszellen berechnet, realisiert und mittels MRI hinsichtlich ihrer strömungsdynamischen und NMR-Eigenschaften charakterisiert wurden. Austauschbare Polymerleitungen für robuste, industrielle Anwendungen kamen ebenso zum Einsatz wie maßgeschneiderte Flusszellen zur Reduktion der Verweilzeitverteilung und des Stoffdurchsatzes. Bewertungsverfahren für MR-NMR-Spektrometer und Durchflusszellen auf Basis leicht verfügbarer Flüssigkeiten (wie z. B. Aceton, Ethanol, Wasser) wurden abgeleitet, Mindestspezifikationen für die Anwendbarkeit der MR-NMR im Prozessmonitoring wurden erarbeitet. Auf der Basis des Bypasssystems konnten einige verschiedene chemische Reaktionen im Bereich einiger 10 s zeitaufgelöst gemessen und ihre Kinetik auch im Fall von Nichtgleichgewichtsmagnetisierung und schneller Strömung analysiert werden. Voraussetzung ist eine stabile und automatisierte Datenbearbeitung, die sich nahtlos in den Workflow von der Datenakquisition bis zur Datenanalyse einbindet. Daher war ein weiteres Augenmerk auf die Datenvorbehandlung gelegt. Bekannte Algorithmen wie die automatisierte Phasenkorrektur entlang der „Minimum Entropy“ Methode und der Maximierung des Realteilspektrums wurden zusammen mit neuen Methoden wie dem Softewarelock implementiert und angewandt. Zur Bestimmung der Konzentrationen wurden verschiedene Verfahren wie die direkte Integration, die Spektrenmodellierung mit und ohne Vorkenntnisse sowie statistische Methoden der Chemometrie angewandt und verglichen. Ebenso ließen sich erstmalig quasiparallel akquirierte 1H- und 19F-MR-NMR-Spektren für die Prozesskontrolle mit gutem Ergebnis analysieren. Die erarbeiteten Konzepte und Verfahren sind unabhängig von der Hard- und -Software des MR-NMR Geräts und damit allgemein einsetzbar. Während des Projektverlaufs kamen Benchtop-Laborgeräte von einer wachsenden Zahl an Herstellern auf den Markt, die immer besser den Anforderungen der Spektroskopie gerecht werden. Online-MR-NMR-Spektroskopie erweitert die Prozessanalytik um eine bislang nur im Labor bekannte chemische Sensitivität gegenwärtig mit der Fähigkeit zur Unterscheidung von beispielsweise Aliphaten, Olefinen oder Aromaten (z. B. Hydrierung) oder Strukturänderungen (z. B. Isomerisierung), bei denen klassische Techniken an ihre Grenzen stoßen. Sie stellt nun eine Alternative für die Prozessanalyse dar, insbesondere wenn schnelle, zerstörungsfreie und integral arbeitende Methoden erforderlich sind. KW - Prozess-Sensoren KW - DFG KW - NMR-Spektroskopie PY - 2015 SP - 1 EP - 15 AN - OPUS4-38852 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kern, Simon A1 - Gräßer, Patrick A1 - Zientek, Nicolai A1 - Maiwald, Michael T1 - First steps towards field integration of benchtop NMR spectroscopy for online monitoring and process control 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 spectros-copy 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 com-parison 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. T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Wien, Austria DA - 30.11.2015 KW - Online NMR Spectroscopy KW - Smart Sensors KW - Prozess-Spektroskopie KW - Process Analytical Technology KW - Process control PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-388411 SP - 43 EP - 44 AN - OPUS4-38841 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael T1 - Die neue Technologie-Roadmap „Prozess-Sensoren 4.0“ N2 - Derzeit finden gravierende Veränderungen im Umfeld der Informations- und Kommunikationstechnik statt, die eine große Chance für die optimierte Prozessführung und Wertschöpfung mit darauf abgestimmten vernetzt kommunizierenden Sensoren bieten. Diese Art „smarter“ Sensoren stellen Dienste innerhalb eines Netzwerks bereit und nutzen Informationen daraus. Dadurch ergibt sich aktuell die Notwendigkeit, die Anforderungen an Prozess-Sensoren sowie an deren Kommunikationsfähigkeiten detaillierter zu beschreiben – vom einfachen Temperatursensor bis über heute in Entwicklung befindlichen Mess-Systemen hinaus – da diese Technologieentwicklungen rasant voranschreiten. Vernetzte Sensoren sind die Voraussetzung für die Realisierung von Cyber-physischen Produktionssystemen (CPPS) und zukünftiger Automatisierungskonzepte für die Prozessindustrie, wie sie auch durch das Zukunftsprojekt „Industrie 4.0“ adressiert werden. T2 - 11. Kolloquium Arbeitskreis Prozessanalytik CY - Wien, Austria DA - 30.11.2015 KW - Roadmap KW - Prozess-Sensoren 4.0 KW - Smart Sensors KW - Smarte Sensoren KW - Prozessanalytik KW - Prozessindustrie PY - 2015 SP - 26 EP - 27 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-38842 LA - deu 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 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 -