Analytische Chemie
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We investigate the pore space of rock samples with respect to different petrophysical parameters using various methods, which provide data upon pore size distributions, including micro computed tomography (μ-CT), mercury intrusion porosimetry (MIP), nuclear magnetic resonance (NMR), and spectral induced polarization (SIP). The resulting cumulative distributions of pore volume as a function of pore size are compared. Considering that the methods differ with regard to their limits of resolution, a multiple length scale characterization of the pore space geometry is proposed, that is based on a combination of the results from all of these methods. The findings of this approach are compared and discussed by using Bentheimer sandstone. Additionally, we compare the potential of SIP to provide a pore size distribution with other commonly used methods (MIP, NMR). The limits of resolution of SIP depend on the usable frequency range (between 0.002 and 100 Hz). The methods with similar resolution show a similar behavior of the cumulative pore volume distribution in the overlapping pore size range. The methods μ-CT and NMR provide the pore body size while MIP and SIP characterize the pore throat size. Using this difference, the average pore body to throat ratio is determined to be about three for the Bentheimer sandstone.
Our study shows that a good agreement between the pore radii distributions can only be achieved if the curves are adjusted considering the resolution and pore volume in the relevant range of pore radii. The MIP curve with the widest range in resolution should be used as reference
Process monitoring with online NMR spectroscopy – An enabler for “Industrie 4.0” in process industry
(2018)
Improvement in deep process understanding is a mandatory prerequisite for the application of modern concepts like Industrial Internet of Things (IIoT) or “Industrie 4.0”. This is particularly relevant in new process concepts such as intensified production in modularized plants. The direct hyphenation with online methods of process analytical technology (PAT) allows profound insights into the actual reactions within chemical and pharmaceutical production steps and provides necessary information for associated control strategies.
While the industrial application of online Raman spectroscopy has already been successfully demonstrated, low-field NMR spectroscopy is not yet adequately developed as an online method for use in process industry. The high information content combined with the low calibration effort makes NMR spectroscopy a highly promising method for modern process automation with a high flexibility due to short set-up times and low requirements regarding validation. This is a major advantage especially within multi-purpose production plants, as well as for processes suffering from fluctuating quality of raw materials. NMR spectroscopy has a high potential for direct quantitative information, while cutting the calibration and validation needs to a minimum and thus exhibiting short set-up times.
Within the EU project CONSENS, an NMR analyzer for direct implementation in an industrial process environment was developed based on a commercially available laboratory instrument. The challenge was not only the hyphenation to the production plant itself, but also to fulfill all requirements of chemical industry, e.g., explosion safety regulations (ATEX), robust automation and modern, as well as classical communication interfaces. The presented NMR module involves a compact spectrometer together with an acquisition unit and a programmable logic controller for automated data preparation (phasing, baseline correction), and evaluation. The module transforms the acquired online spectra of various technically relevant reactions to either conventional 4‒20 mA signals as well as WiFi based OPC-UA communication protocols.
The concept was evaluated on two processes of pharmaceutical and chemical industry. As the first example the continuous synthesis of 2-nitrodiphenylamine starting from aniline and o-fluoronitrobenzene, activated by an organometallic lithium reagent, was studied. This application is highly demanding for a reliable automated evaluation of the obtained NMR spectra, which was realized by developing a physically motivated model-based approach.
In the second example, a stage of the synthesis of the industrially important solvent tetrahydrofurane consisting of the catalytic hydrogenation of 2-butine-1,4-diol was monitored. This reaction is proceeding via an intermediate product and suffers from competitive reaction paths. In this application different spectroscopic methods were combined with the data obtained from classical process sensors, e.g., pressure, temperature and flow transducers for the development of innovative control concepts.
Subject of this investigation is the in-situ evolution of pore volume and pore size distribution in Ytong (a porous concrete material) under increasing pressure with two different non-destructive analytical methods: Nuclear Magnetic Resonance (NMR) and X-ray Computed Tomography (CT). For both methods special strain devices to apply external pressure were constructed. The results from the two techniques yield complementary information on the pore size distribution and allows covering different pore size regions.
Capillary active interior insulation materials are an important approach to minimize energy losses of historical buildings. A key factor for their performance is a high liquid conductivity, which enables redistribution of liquid moisture within the material. We set up an experiment to investigate the development of moisture profiles within two different interior insulation materials, calcium-silicate (CaSi) and expanded perlite (EP), under constant boundary conditions. The moisture profiles were determined by two different methods: simple destructive sample slicing with subsequent thermogravimetric drying as well as non-destructive NMR measurements with high spatial resolution. The moisture profiles obtained from both methods show good agreement, when compared at the low spatial resolution of sample slicing, which demonstrates the reliability of this method. Moreover, the measured T2-relaxation-time distributions across the sample depth were measured, which may give further insight into the saturation degree of the different pore sizes. In order to explain differences in the moisture profiles between CaSi and EP, we determined their pore-size distribution with different methods: conversion of the NMR T2 relaxationtime distribution at full saturation, mercury intrusion porosimetry and indirect determination from pressure plate measurements. CaSi shows a unimodal distribution at small pore diameters, while in EP, a bi-modal or wider distribution was found. We assume that the smaller pore diameters of CaSi lead to a higher capillary conductivity, which causes a more distributed moisture profile in comparison with that of EP.
We have compared the performance of the typical Darr and CM moisture testing techniques, which are destructive with several non-destructive testing techniques on two types of floor screeds. In case of cement based screeds these destructive tests failed to deliver reliable results. Moreover, our measurements indicate significantly different drying and moisture transport behavior for the investigated cement based and calcium-sulphate based screeds. Whereas we have strong with depth decreasing moisture gradients in the CT material, we observe in the penetrated volumes of our ndt methods basically no clear moisture gradient in the CA samples. The findings with ndt methods could be supported by moisture gradient studies with nuclear magnetic resonance measurements.
Other than commonly assumed the relaxation times observed in the electrical low-frequency range (1 mHz – 40 kHz) of natural porous media like sandstones and tuff stones cannot be directly related to the dominant (modal) pore throat sizes, measured (e.g.) with mercury intrusion porosimetry (MIP). Working with a great variety of sandstones from very different origins and featuring great variations in textural and chemical compositions as well as in geometrical pore space properties, it was observed that particularly samples with narrow pore throats were characterized by long (low-frequency) relaxations. These, however, can (following the current theories) be rather explained by long “characteristic length scales” in these media or low diffusion coefficients along the electrical double layer. However, there is no straightforward way (or single approved method) of getting reliable numbers for properties such as the lengths of pore throats, the diameter and length of the wide pores and their respective distributions. Consequently we follow a multi-methodical approach and combine the benefits of MIP, micro-computed tomography (μ-CT) and nuclear magnetic resonance (NMR) to achieve much deeper insight due to the different resolutions and sensitivities to either pore constrictions (throats) or wide pores. This helps us to understand, whether the observed electrical relaxation phenomena actually depend on geometric length scales or rather on other properties such as chemical composition, clay content, clay type or cation exchange capacity. In this paper, we showcase selected results of a systematic study of a total of 16 sandstones and three tuffs. Findings and the particular advantage of the used method combination are discussed and shown in detail for a representative sample selection.
Relaxation phenomena observed in the electrical low-frequency range (approximately 1 mHz-10 kHz) of natural porous media like sandstones is often assumed to be directly related to the dominant (modal) pore throat sizes measured, for instance, with mercury intrusion porosimetry. Attempts to establish a universally valid relationship between pore size and peak Spectral Induced Polarization (SIP) relaxation time have failed, considering sandstones from very different origins and featuring great variations in textural and chemical compositions as well as in geometrical pore space properties. In addition working with characteristic relaxation times determined in Cole-Cole or Debye decomposition fits to build the relationship have not been successful. In particular, samples with narrow pore throats are often characterized by long SIP relaxation times corresponding to long “characteristic length scales” in these media, assuming that the diffusion coefficients along the electrical double layer were constant. Based on these observations, three different types of SIP relaxation can be distinguished. We present a new way of assessing complex pore spaces of very different sandstones in a multi-methodical approach to combine the benefits of mercury intrusion porosimetry, micro-computed tomography, and nuclear magnetic resonance. In this way, we achieve much deeper insight into the pore space due to the different resolutions and sensitivities of the applied methods to both pore constrictions (throats) and wide pores (pore bodies). We experimentally quantify pore aspect ratios and volume distributions within the two pore regions. We clearly observe systematic differences between three SIP relaxation types identified previously and can attribute the SIP peak relaxation times to measured characteristic length scales within our materials. We highlight selected results for a total of nine sandstones. It seems that SIP relaxation behavior depends on the size difference of the narrow pore throats to the wide pore bodies, which increases from SIP Type 1 to Type 3.
Nuclear magnetic resonance (NMR) with focus on 1H protons is increasingly applied for non-destructive testing applications. Besides mobile NMR, laboratory devices such as the NMR core-analyzing tomograph are used. As their magnetic field is more homogeneous, they enable measurements with higher signal-to-noise ratios (SNR), but with limited sample sizes. The tomograph presented here (8.9 MHz) was constructed for a maximum sample diameter of 70 mm and length of up to 1 m. The resolution, the echo time (min. 50 µs), the SNR and the measurement type can be adjusted by means of exchangable coils. The tomograph enables measurements along the complete sensitive length, slice-selective and even 2- or 3-dimensional measurements. A movable sample lifting system thereby allows a precise positioning of the sample.
Because of its mobility and ability to investigate exposed surfaces, single-sided (SiS) nuclear magnetic resonance (NMR) technology enables new application fields in geosciences. To test and assess its corresponding potential, we compare longitudinal (T1) and transverse (T2) data measured by SiS NMR with those of conventional geoscientific laboratory NMR. We use reference sandstone samples covering a broad range of pore sizes. Our study demonstrates that the lower signal-to-noise ratio of SiS NMR data generally tends to slightly overestimated widths of relaxation time distributions and consequently pore size distributions. While SiS and conventional NMR produce very similar T1 relaxation data, unbiased SiS NMR results for T2 measurements can only be expected for fine material, i.e. clayey or silty sediments and soils with main relaxation times below 0.05s. This limit is given by the diffusion relaxation rate due to the gradient in the primary magnetic field associated with the SiS NMR. Above that limit, i.e. for coarse material, the relaxation data is strongly attenuated. If considering the diffusion relaxation time of 0.2 s in the numerical data inversion process, the information content >0.2s is blurred over a range larger than that of conventional NMR. However, our results show that principle range and magnitudes of the relaxation time distributions are reconstructed to some extent. Regarding these findings, SiS NMR can be helpful to solve geoscientific issues, e.g. to assess the hydro-mechanical properties of the walls of underground facilities or to provide local soil moisture data sets for calibrating indirect remote techniques on the regional scale. The greatest opportunity provided by the SiS NMR technology is the acquisition of profile relaxation data for rocks with significant bedding structures at the µm scale. With this unique feature, SiS NMR can support the understanding and modeling of hydraulic and diffusional anisotropy behavior of sedimentary rocks.