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- Gefahrgutverpackungen (7)
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- Reaction monitoring (4)
- Überdruck (4)
- Bubble test (3)
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Organisationseinheit der BAM
Enhanced post-denitrification without addition of an external carbon source in membrane bioreactors
(2005)
This study investigates a post-denitrification process without the addition of an external carbon source combined with an enhanced biological phosphorus removal (EBPR) in a membrane bioreactor (MBR). Three trial plants, with two different process configurations, were operated on two different sites, and a variety of accompanying batch tests were conducted. It was shown that even without dosing of an external carbon source, denitrification rates (DNR) much above endogenous rates could be obtained in post-denitrification systems. Furthermore, the anaerobic reactor located ahead of the process had a positive impact on the DNR. Given these surprising results, the project team decided to identify the carbon source used by the microorganisms in the post-denitrification process. Batch tests could demonstrate that lysis products do not play a major role as a C-source for post-denitrification. The following hypothesis was proposed to explain the observations: the glycogen, internally stored by the substrate accumulating bacteria, if anaerobic conditions are followed by aerobic conditions could act as carbon source for denitrification in post-denitrification system. First exploratory batch tests, where the glycogen evolution was monitored, corroborate this assumption.
The International Dangerous Goods Regulations prescribe the immersion under water method (“bubble test”) as standard method for the leakproofness test of dangerous goods packagings. But this test procedure acts as a test method for leak localisation, not for quantitative leakage rates measurement. Additionally, the sensitivity in detecting leaks of small diameters is restricted, depending on the test liquid and the test pressure. The bubble test is not suitable for a comparison with quantitative limit leakage rates based on realistic transport conditions. This is especially important when estimating the risk of the formation of an explosive atmosphere during the intercontinental carriage of dangerous goods packagings in freight containers. To compare measured leakage rates with limit leakage rates, a quantitative leak testing procedure is required. Therefore a new approach for dangerous goods packagings is implemented: The pressure technique by accumulation using Helium as a tracer gas. This work presents the test equipment necessary for the quantitative measurement of Helium leakage rates through closures of different kinds of dangerous goods packagings. The essential steps to achieve good repeatable results are: A controlled Helium filling process to reach a defined test pressure in the test sample, a sufficient homogenisation of the Helium-air-mixture inside the test sample and the ensuring of a constant pressure level of the test sample during the test. The Helium loss rate of the accumulation chamber has to be measured separately to receive a correction factor for the measured leakage rates. Different constructional measures are introduced to prevent a disturbing influence of the Helium leakage rate of the filling valves on the measurement results. Methods to estimate the disturbing effect of Helium permeation through permeable parts of the test sample are also presented. As a supporting method for the experimental investigations the Helium sniffer test can be applied. This practical application-oriented advice can enable other users to establish a pressure technique by accumulation for their own technical field.
Ziel einer Dichtheitsprüfung ist es entweder, mit einem quantitativen Prüfverfahren integrale Leckageraten zu messen, oder mittels eines lokalisierenden Verfahrens den genauen Leckageort aufzuspüren.
In einigen Fällen kann das Betriebsmedium gleichzeitig das Prüfmedium sein, wenn geeignete Sensorik zu Verfügung steht. In anderen Fällen kann dies aus unterschiedlichen Gründen nicht möglich sein. Daher ersetzt man bei der Verwendung von Prüfgasverfahren das Betriebsmedium durch ein spezifisch nachweisbares Prüfgas.
Für die Interpretation eines quantitativen Messergebnisses ist es notwendig, die Ist-Leckagerate mit einer zuvor berechneten Grenzleckagerate (maximal zulässige Leckagerate) zu vergleichen. Entspricht das für die Dichtheitsprüfung verwendete Prüfgas nicht dem Betriebsmedium, so ist hierfür eine Umrechnung von Leckageraten notwendig.
Es wird ein Überblick über für die Dichtheitsprüfung gängige Prüfgase, deren Eigenschaften sowie Vor- und Nachteile gegeben. Die grundlegenden Prinzipien bei der Umrechnung von Leckageraten (Druckumrechnung; Temperaturumrechnung; Umrechnung der Gasart bzw. des Mediums) werden vorgestellt.
The objective of this experiment was to verify that in regards to the leakproofness bubble test for packagings of dangerous goods, a reduction of the air overpressure from 0.2 to 0.1 bar can be compensated for by reducing the water surface tension to a value of approximately 33.2 mN/m by adding a wetting agent. It was experimentally proven that this method will yield the same leak diameters. This is important to avoid irreversible deformations during the leaktesting of intermediate bulk containers (IBCs) while using a test overpressure of 0.2 bar.
Bubble test experiments were carried out on artificial borehole-shaped leaks manufactured of two different materials high density polyethylene (HDPE) and stainless steel by ultrashort pulse laser technology and with two different immersion test liquids (deionized water and a 0.1% Lutensol FSA fabric softener active 10 solution). The characteristic diameters of the boreholes investigated were from 11.5 to 30.3 µm in length.
Bei der Dichtheitsprüfung von Intermediate Bulk Containern (IBC) für gefährliche Güter ist gemäß den Gefahrgutvorschriften ein Prüfüberdruck von 0,2 bar anzuwenden. Hierbei ist die Verwendung von Prüfschäumen zulässig. In der Praxis kann es jedoch zu irreversiblen Verformungen des Prüflings kommen. Durch eine Reduzierung des Prüfüberdrucks auf nur 0,1 bar kann dies vermieden werden. Im Folgenden werden experimentelle Untersuchungen der Bundesanstalt für Materialforschung und -prüfung (BAM) vorgestellt, um die Gleichwertigkeit dieses Verfahrens mit den Gefahrgutvorschriften nachzuweisen.
Distickstoffmonoxid (N2O, Lachgas) und Helium (He) sind gängige Prüfgase für Dichtheitsprüfungen. Die einfachste Leckgeometrie stellt ein ideal zylindrisches Rohr dar. Es wurden Glaskapillaren verschiedener Abmessungen mit Lachgas und Helium durchströmt. Der Überdruck am Kapillareingang lag zwischen 100 mbar und 400 mbar. Es handelte sich um vier annähernd zylindrische Glaskapillaren mit den mittleren Durchmessern: Kapillare 1: ca. 102 μm; Kapillare 2: ca. 71 μm; Kapillare 3B: ca. 49 μm; Kapillare 4: ca. 53 μm. Zudem wurde eine nichtzylindrische Kapillare geprüft (Kapillare 3A). Die Kapillaren 1, 2 und 3B wurden mit beiden Prüfgasen getestet. Kapillare 3A wurde nur mit Lachgas durchströmt, Kapillare 4 nur mit Helium. Für die Messung der Leckageraten kam das Überdruckverfahren mit Ansammlung (Verfahren B3 nach DIN EN 1779: 1999-10) zum Einsatz. Als Detektor für Lachgas diente der Lachgasdetektor Maihak Unor 6 N, für Helium der Leckdetektor T-Guard der Firma Inficon.
Es wurden verschiedene Theorieansätze verglichen. Beim Theorieansatz Ib erfolgte die Umrechnung der Lachgas-Messwerte auf die Helium-Messwerte und umgekehrt anhand der Druck-, Temperatur- und Gasartabhängigkeit der Leckagerate für laminar-viskose Gasströmung (DIN EN 1779: 1999-10; DGZfP-Richtlinie DP2: 2009-12). Beim Theorieansatz II wurde die Berechnung der Leckagerate für die laminar-viskose Rohrströmung unter der Annahme einer ideal zylindrischen Kapillare durchgeführt. Zusätzlich wurde mit „ANSYS Fluent“ eine CFD-Simulation vorgenommen. Bei Kapillare 3A wurde eine Serienschaltung der Strömungsleitwerte von Rohr und Düse angesetzt. Bei Anwendung des Ansatzes Ib werden bei Umrechnung der Helium-Messwerte auf Lachgas die Lachgas-Messwerte überschätzt. Umgekehrt werden bei der Umrechnung der Lachgas-Messwerte auf Helium die Helium-Messwerte unterschätzt. Bei Analyse der Einlauflängen der Rohrdurchströmung ist festzustellen, dass diese für Lachgas stets größer als für Helium sind. Bei Lachgas liegt daher für einige Messwerte noch keine ausgebildete laminare Rohrströmung vor. Einlaufeffekte können somit nicht vernachlässigt werden. Als Fazit ergibt sich, dass bei Verwendung von Helium als Prüfgas und Umrechnung der Helium-Messwerte auf Lachgas die Lachgas-Leckageraten sicherheitstechnisch konservativ abgeschätzt werden.
The objective of this work was to determine the maximum gauge pressure in the vapour phase above the liquid in different design types of dangerous goods packagings under normal conditions of carriage. The design types investigated were steel and plastic packagings with a volume of approximately 6 l.
Two different methods were applied. In method 1, the pressure inside the packaging filled with a certain filling substance (dichloromethane) was directly measured under simulated conditions of carriage (degree of filling: 90%; filling temperature: 15°C; temperature during storage: 31°C). The maximum measured gauge pressures were between 89 mbar for a light plastic jerrican and 336 mbar for a steel drum.
In method 2, the gauge pressure was calculated. The consideration of a rigid packaging combined with the assumption of a vapour pressure of zero during filling and sealing can serve as a worst case scenario. The calculated gauge pressure is approximately 1061 mbar. This procedure leads to the highest safety factor and does not require any experimental investigations.
For a more realistic approximation of the gauge pressure of a non-rigid packaging, a packaging-specific function of relative expansion can be used, which is determined by a hydraulic pressure test. The calculated values ranged from 105 to 347 mbar. Method 2 provides conservative results. No hazardous filling substance is needed, and it allows a prediction of gauge pressure for other temperatures, substances and filling degrees. Therefore, this method could serve as alternative to UN Model Regulations 6.1.5.5.4 (a).
Der innere Überdruck, der sich unter Beförderungsbedingungen im freien Dampfraum einer Gefahrgutverpackung bildet, die mit einer gefährlichen Flüssigkeit gefüllt ist, hängt von verschiedenen Faktoren ab: Den spezifischen Stoffeigenschaften des jeweiligen Füllguts, dem Füllgrad, der Nachgiebigkeit der Verpackungsbauart, der Befülltemperatur und der Temperatur bei Beförderungsbedingungen.
Zu den normalen Beförderungsbedingungen von befüllten Gefahrgutverpackungen zählt der interkontinentale Transport in Frachtcontainern. Es werden die Ergebnisse einer Klimamessfahrt vorgestellt, die mit einem instrumentierten Frachtcontainer auf der Fahrt von Hamburg nach Singapur und zurück gewonnen wurden. Hierdurch lassen sich durchschnittliche und maximale Beförderungstemperaturen beim interkontinentalen Containertransport ermitteln. Es werden Modellgleichungen vorgestellt, mit denen sich für verschiedene Annahmen der sich einstellende Überdruck in einer Gefahrgutverpackung berechnen lässt.
Für die Durchführung einer Dichtheitsprüfung und für die Bewertung des Ergebnisses ist es wichtig, den sich unter Betriebsbedingungen im Prüfobjekt einstellenden Überdruck zu kennen. Entspricht der Prüfüberdruck nicht dem Betriebsüberdruck, so ist es oft erforderlich, die unter Prüfbedingungen gemessenen Leckageraten auf den realen Betriebsüberdruck umzurechnen. Im Bereich der Gefahrgutverpackungen ist jedoch der spätere maximale Betriebsüberdruck nicht genau bekannt. Er hängt für jede einzelne Verpackungsbauart von dem eingefüllten Füllmedium mit seinen spezifischen Stoffeigenschaften, dem Füllgrad sowie den Beförderungsbedingungen, insbesondere der mittleren Transporttemperatur, ab. Es werden Berechnungsansätze vorgestellt, mit denen sich der Überdruck in Gefahrgutverpackungen unter Beförderungsbedingungen rechnerisch ermitteln lässt. Die theoretisch berechneten Überdrücke werden mit Überdruck-Messwerten verglichen, die mit verschiedenen Füllmedien in unterschiedlichen Verpackungsbauarten ermittelt wurden.
The International Dangerous Goods Regulations prescribe the immersion under water method (“bubble test”) as standard method for the leakproofness test of dangerous goods packagings. But this test procedure acts as a test method for leak localisation, not for quantitative leakage rates measurement. Additionally, the sensitivity in detecting leaks of small diameters is restricted, depending on the test liquid and the test pressure. The bubble test is not suitable for a comparison with quantitative limit leakage rates based on realistic transport conditions. This is especially important when estimating the risk of the formation of an explosive atmosphere during the intercontinental carriage of dangerous goods packagings in freight containers.
To compare measured leakage rates with limit leakage rates, a quantitative leak testing procedure is required. Therefore a new approach for dangerous goods packagings is implemented: The pressure technique by accumulation using Helium as a tracer gas.
This work presents the test equipment necessary for the quantitative measurement of Helium leakage rates through closures of different kinds of dangerous goods packagings. The essential steps to achieve good repeatable results are: A controlled Helium filling process to reach a defined test pressure in the test sample, a sufficient homogenisation of the Helium-air-mixture inside the test sample and the ensuring of a constant pressure level of the test sample during the test. The Helium loss rate of the accumulation chamber has to be measured separately to receive a correction factor for the measured leakage rates. Different constructional measures are introduced to prevent a disturbing influence of the Helium leakage rate of the filling valves on the measurement results. Methods to estimate the disturbing effect of Helium permeation through permeable parts of the test sample are also presented. As a supporting method for the experimental investigations the Helium sniffer test can be applied. This practical application-oriented advice can enable other users to establish a pressure technique by accumulation for their own technical field.
Sift-proofness is a requirement for different types of dangerous goods packagings for solid substances according to the international Dangerous Goods Regulations. In these regulations, a sift-proof packaging is defined as a packaging that is completely impermeable to dry contents. This means indirectly that absolutely no mass transport of solid substances is allowed. Moreover, this requirement applies both to the original filling substance and to fine solid material generated during transport. Further specifications, test conditions or tolerable limit values are not given. This is in contrast to physical principles and the usual practice in other fields of technology in which sift-proofness is relevant. This paper shows the necessary steps for how the requirements for sift-proofness of dangerous goods packagings can be defined more precisely. Physical basics of the term ‘sift-proofness’ are explained. A qualitative as well as a quantitative approach is possible. In any case, it is essential to carry out appropriate vibration tests to assess the siftproofness. There is a need for systematical investigations of the sift-proofness of dangerous goods packagings.
The objective was to find out whether an explosive atmosphere can be created in a freight container by gaseous leakage flow of vapour-air-mixture through leaks in the closures of dangerous goods packagings filled with hazardous liquids. Because of high temperatures during intercontinental carriage, there is a gauge pressure in the free vapour phase inside the packagings which can cause a gaseous leakage flow. Two different methods were applied:
Helium limit leakage rates for 23 quantitatively important hazardous liquids concerning their lower explosion limit (LEL) were calculated for a worst case transport scenario (Method 1).
Helium leakage rates of five closure types of dangerous goods packagings with volumes of approximately 6 l were measured using the pressure technique by accumulation (Method 2).
All types of closures of steel packagings were uncritical. The maximum measured leakage was 33% of the limit leakage rate. The leakage rates of screw closures of plastic jerricans can exceed the LEL if there are production-related patterns such as non-concentricity of the closures and flashes on the neck. Especially for plastic packagings it is important to minimize gaseous leakage flow, because an explosive atmosphere can also be reached by permeation of the individual filling substance or by a combination of both effects. For the assessment of potentially explosive mixtures in freight containers, both mass transfer mechanisms have to be taken into account.
Distickstoffmonoxid (N2O, Lachgas) und Helium (He) sind gängige Prüfgase für Dichtheitsprüfungen. Die einfachste Leckgeometrie stellt ein ideal zylindrisches Rohr dar. Es wurden Glaskapillaren verschiedener Abmessungen mit Lachgas und Helium durchströmt. Der Überdruck am Kapillareingang lag zwischen 100 mbar und 400 mbar. Es handelte sich um vier annähernd zylindrische Glaskapillaren mit den mittleren Durchmessern: Kapillare 1: ca. 102 μm; Kapillare 2: ca. 71 μm; Kapillare 3B: ca. 49 μm; Kapillare 4: ca. 53 μm. Zudem wurde eine nichtzylindrische Kapillare geprüft (Kapillare 3A). Die Kapillaren 1, 2 und 3B wurden mit beiden Prüfgasen getestet. Kapillare 3A wurde nur mit Lachgas durchströmt, Kapillare 4 nur mit Helium.
Für die Messung der Leckageraten kam das Überdruckverfahren mit Ansammlung (Verfahren B3 nach DIN EN 1779: 1999-10) zum Einsatz. Als Detektor für Lachgas diente der Lachgasdetektor Maihak Unor 6 N, für Helium der Leckdetektor T-Guard der Firma Inficon.
Es wurden verschiedene Theorieansätze verglichen. Beim Theorieansatz Ib erfolgte die Umrechnung der Lachgas-Messwerte auf die Helium-Messwerte und umgekehrt anhand der Druck-, Temperatur- und Gasartabhängigkeit der Leckagerate für laminar-viskose Gasströmung (DIN EN 1779: 1999-10; DGZfP-Richtlinie DP2: 2009-12). Beim Theorieansatz II wurde die Berechnung der Leckagerate für die laminar-viskose Rohrströmung unter der Annahme einer ideal zylindrischen Kapillare durchgeführt. Zusätzlich wurde mit „ANSYS Fluent“ eine CFD-Simulation vorgenommen. Bei Kapillare 3A wurde eine Serienschaltung der Strömungsleitwerte von Rohr und Düse angesetzt. Bei Anwendung des Ansatzes Ib werden bei Umrechnung der Helium-Messwerte auf Lachgas die Lachgas-Messwerte überschätzt. Umgekehrt werden bei der Umrechnung der Lachgas-Messwerte auf Helium die Helium-Messwerte unterschätzt. Bei Analyse der Einlauflängen der Rohrdurchströmung ist festzustellen, dass diese für Lachgas stets größer als für Helium sind. Bei Lachgas liegt daher für einige Messwerte noch keine ausgebildete laminare Rohrströmung vor. Einlaufeffekte können somit nicht vernachlässigt werden. Als Fazit ergibt sich, dass bei Verwendung von Helium als Prüfgas und Umrechnung der Helium-Messwerte auf Lachgas die Lachgas-Leckageraten sicherheitstechnisch konservativ abgeschätzt werden.
In practice, checks on dangerous goods transports often detect leaks of powdered dangerous goods from valved bags. In this work, the influence factors of a sudden release of powdery substances from the valves of valved bags were investigated.
Drop tests were performed on paper bags of UN design type 5M2 with internal sleeve valve using 2 different powdery substances (Esplas H130 and zinc oxide “Rotsiegel”).
The internal sleeve valves of all test samples were not sift‐proof with respect to both filling substances. For almost all test samples, the Esplas H130 powder already leaked out of pasted joints during manual filling. This is a contradiction to the requirement in UN 6.1.4.18.1, according to which closures and joints of paper bags 5M2 should be sift‐proof.
In the drop tests, longer valve lengths had a greater sealing effect for both filling substances (for filling degrees of at least 95% and for test samples which had already been mechanically loaded). As an extreme example, at the drop height of 1.20 m and a filling degree of 100%, the released amount of zinc oxide powder from a 10‐cm‐long valve was about 16 times higher than from a valve length of 12.5 cm.
The valve length is therefore a safety‐relevant parameter and should be specified by the manufacturer.
To ensure that only filling goods with similar physical properties in comparison with the test substance are used for valved bags, the user must be informed of the particle size of the test substance.
The dangerous goods regulations UN/ADR 6.1.5.5.4 (a) prescribe a maximum filling degree for determining the test pressure for the hydraulic pressure test by real measurements. The assumption is that the maximum filling degree of the liquid phase is the worst case concerning the gauge pressure. Therefore, the main objective of this study is to investigate the effect of the filling degree on the gauge pressure. Gauge pressure measurements and calculations for different substances were carried out at different filling degrees for a steel drum and a steel jerrican (heating up from 15°C to 55°C). The assumption that the maximum filling degree is the most critical is only valid for relatively rigid packagings: If the relative expansion of the packaging is smaller than the volume increase of the liquid phase due to heating up, the gauge pressure increases with increasing filling degree. But the opposite is true for relatively flexible packagings: If the relative expansion of the packaging exceeds the relative volume expansion of the liquid, the gauge pressure increases for decreasing filling degrees. The current regulations for the hydraulic test pressure determination at a maximum filing degree do not lead to the intended safety level. For a lower level than the maximum filling degree, the prescribed safety factor of 1.5 is not respected. Under transport conditions, it is possible that the inner gauge pressure exceeds the test pressure. This can result in a failure of the packaging. There is a need to reconsider the regulations.
This work focuses on the question if the bubble test prescribed in the Dangerous Goods Regulations has sufficient sensitivity to detect leakage rates, which could result in the formation of explosive atmospheres during transport. The sensitivity of the bubble test is not directly comparable with other leak testing methods because of its different flow conditions. Therefore, a normalized minimum detectable leakage rate under Helium test conditions is calculated for the bubble test. This sensitivity of the bubble test under reference conditions is compared with limit leakage rates for a worst‐case transport scenario. The sensitivity of the bubble test is not sufficient to prove the limit leakage rates for 6‐L packagings. The formation of explosive vapour‐air‐mixtures cannot be excluded. Therefore, more sensitive leak testing methods should be considered for smaller packaging design types.
There have been an increasing number of publications on flow chemistry applications of compact NMR. Despite this, there is so far no comprehensive workflow for the technical design of flow cells. Here, we present an approach that is suitable for the design of an NMR flow cell with an integrated static mixing unit. This design moves the mixing of reactants to the active NMR detection region within the NMR instrument, presenting a feature that analyses chemical reactions faster (5–120 s region) than other common setups. During the design phase, the targeted mixing homogeneity of the components was evaluated for different types of mixing units based on CFD simulation. Subsequently, the flow cell was additively manufactured from ceramic material and metal tubing. Within the targeted working mass flow range, excellent mixing properties as well as narrow line widths were confirmed in validation experiments, comparable to common glass tubes.
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.
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.
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.
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.
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.
The application of compact NMR instruments to hot flowing samples or exothermically reacting mixtures is limited by the temperature sensitivity of permanent magnets. Typically, such temperature effects directly influence the achievable magnetic field homogeneity and hence measurement quality. The internal-temperature control loop of the magnet and instruments is not designed for such temperature compensation. Passive insulation is restricted by the small dimensions within the magnet borehole. Here, we present a design approach for active heat shielding with the aim of variable temperature control of NMR samples for benchtop NMR instruments using a compressed airstream which is variable in flow and temperature. Based on the system identification and surface temperature measurements through thermography, a model predictive control was set up to minimise any disturbance effect on the permanent magnet from the probe or sample temperature. This methodology will facilitate the application of variable-temperature shielding and, therefore, extend the application of compact NMR instruments to flowing sample temperatures that differ from the magnet temperature.