Characterising gas behaviour during gas–liquid co-current up-flow in packed beds using magnetic resonance imaging

Magnetic resonance (MR) imaging techniques have been used to study gas phase dynamics during co-current up-flow in a column of inner diameter 43 mm, packed with spherical non-porous elements of diameters of 1.8, 3 and 5 mm. MR measurements of gas hold-up, bubble-size distribution, and bubble-rise velocities were made as a function of flow rate and packing size. Gas and liquid flow rates were studied in the range of 20–250 cm3 s−1 and 0–200 cm3 min−1, respectively. The gas hold-up within the beds was found to increase with gas flow rate, while decreasing with increasing packing size and to a lesser extent with increasing liquid flow rate. The gas hold-up can be separated into a dynamic gas hold-up, only weakly dependent on packing size and associated with bubbles rising up the bed, and a ‘static’ hold-up which refers to locations within the bed associated with temporally-invariant gas hold-up, over the measurement times of 512 s, associated either with gas trapped within the void structure of the bed or with gas channels within the bed. This ‘static’ gas hold-up is strongly dependent on packing size, showing an increase with decreasing packing size. The dynamic gas hold-up is comprised of small bubbles – of order of the packing size – which have rise velocities of 10–40 mm s−1 and which move between the packing elements within the bed, along with much larger bubbles, or agglomerates of bubbles, which move with higher rise velocities (100–300 mm s−1). These ‘larger’ bubbles, which may exist as streams of smaller bubbles or ‘amoeboid’ bubbles, behave as a single large bubble in terms of the observed high rise velocity. Elongation of the bubbles in the direction of flow was observed for all packings.We wish to thank ExxonMobil Research and Engineering Co. and EPSRC Platform Grant (EP/F047991/1) for financial support.This is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/j.ces.2016.04.00

A broadband pulsed radio frequency electron paramagnetic resonance spectrometer for biological applications

A time-domain radio frequency (rf) electron paramagnetic resonance (EPR) spectrometer/imager (EPRI) capable of detecting and imaging free radicals in biological objects is described. The magnetic field was 10 mT which corresponds to a resonance frequency of 300 MHz for paramagnetic species. Short pulses of 20-70 ns from the signal generator, with rise times of less than 4 ns, were generated using high speed gates, which after amplification to 283 Vpp, were deposited into a resonator containing the object of interest. Cylindrical resonators containing parallel loops at uniform spacing were used for imaging experiments. The resonators were maintained at the resonant frequency by tuning and matching capacitors. A parallel resistor and overcoupled circuit was used to achieve Q values in the range 20-30. The transmit and receive arms were isolated using a transmit/receive diplexer. The dead time following the trailing edge of the pulse was about 450 ns. The first stage of the receive arm contained a low noise, high gain and fast recovery amplifier, suitable for detection of spin probes with spin-spin relaxation times (T2) in the order of μs. Detection of the induction signal was carried out by mixing the signals in the receiver arm centered around 300 MHz with a local oscillator at a frequency of 350 MHz. The amplified signals were digitized and summed using a 1 GHz digitizer/summer to recover the signals and enhance the signal-to-noise ratio (SNR). The time-domain signals were transformed into frequency-domain spectra, using Fourier transformation (FT). With the resonators used, objects of size up to 5 cm3 could be studied in imaging experiments. Spatial encoding of the spins was accomplished by volume excitation of the sample in the presence of static field gradients in the range of 1.0-1.5 G/cm. The spin densities were produced in the form of plane integrals and images were reconstructed using standard back-projection methods. The image resolution of the phantom objects containing the spin probe surrounded by lossy biologic medium was better than 0.2 mm with the gradients used. To examine larger objects at local sites, surface coils were used to detect and image spin probes successfully. The results from this study indicate the potential of rf FT EPR for in vivo applications. In particular, rf FT EPR may provide a means to obtain physiologic information such as tissue oxygenation and redox status

Preparation and EPR studies of lithium phthalocyanine radical as an oxymetric probe

The electron paramagnetic resonance (EPR) spectrum of the paramagnetic center in solid lithium phthalocyanine, LiPc, exhibits a pO<SUB>2 </SUB>(partial pressure of oxygen)dependent line width. The compound is insoluble in water and is not easily biodegradable and, therefore, is a useful spin probe for quantitative in vivo oxymetry. Because EPR spectrometry is potentially a useful technique to quantitatively obtain in vivo tissue pO<SUB>2</SUB>, such probes can be used to obtain physiological information. In this paper, a simple experimental procedure for the preparation of LiPc using potentiostatic electrochemical methods is described. The setup was relatively inexpensive and easy to implement. A constant potential ranging from 0.05 to 0.75 V versus Ag<SUP>+</SUP>//AgCl(s) was used for obtaining LiPc. The EPR spectral studies were carried out using spectrometers operating at X-band and at radiofrequency (RF) at different pO<SUB>2</SUB> values to characterize the spectral response of these crystals. The results indicate that, depending on the electrolysis conditions, the products contain mixtures of crystals exhibiting pO<SUB>2</SUB>-sensitive and pO<SUB>2</SUB>-insensitive line widths. Electrolysis conditions are reported whereby the pO<SUB>2</SUB>-sensitive LiPc crystals were the predominant product. The influence of the working surface of the electrode and the electrolysis time on the yield were also evaluated. The crystals of LiPc were also studied using a time-domain RF EPR spectrometer. In time-domain EPR, the signals that survive beyond the spectrometer dead time are mainly the narrow lines corresponding to the pO<SUB>2-</SUB>sensitive crystals, whereas the signals arising from the pO<SUB>2</SUB>-insensitive component of LiPc were found not to survive beyond the spectrometer dead time. This signal survival makes the time-domain EPR method more sensitive for pO<SUB>2</SUB> measurements using LiPc because the line width becomes very narrow at very low pO<SUB>2</SUB> and, concomitantly, the relaxation time T<SUB>2</SUB> longer, with no modulation or power saturation artifacts that are encountered as in the continuous wave (cw) mode. Further, minimal contributions from object motion in the spectral data obtained using time-domain methods make it an advantage for in vivo applications

Synthesis and Structure of a Layered Fluoroaluminophosphate and Its Transformation to a Three-Dimensional Zeotype Framework

Two-dimensional zeolitic materials have drawn increasing attention because of their structural diversity, high accessible surface areas, and potential as precursors to form novel three-dimensional (3D) structures. Here we report a new layered fluoroaluminophosphate, denoted as EMM-9 (ExxonMobil Material #9), synthesized in the same synthesis system as that for a previously reported 3D framework structure EMM-8 (framework-type code: SFO) using an F- medium and 4-(dimethylamino)pyridine (DMAP) as the organic structure-directing agent. The structure of EMM-9 was solved from rotation electron diffraction data and refined against synchrotron powder X-ray diffraction data. The fluoroaluminophosphate layer of EMM-9 is composed of sti composite building units. The DMAP cations are located between the layers. pi-pi interactions between the DMAP cations and hydrogen bonding between the DMAP cations and layers were identified. The layered EMM-9 structure is closely related to the 3D framework structure of EMM-8 and can be transformed to EMM-8 by calcination

Model for the Synthesis of Self-Assembling Template-Free Porous Organosilicas

High surface area solids are important materials in science and in many industrial applications but often are produced from expensive and inefficient combinations of materials and processes. New principles for the selection of molecular precursors that yield high surface area solids in simple and efficient sol–gel processes would be useful. Focusing on organosilicas, we show that an index based on rigidity theory can be used to quantify the relative strength of the gel and the level of condensation at which it is able to withstand the capillary stresses imposed by drying, thereby preventing loss of surface area. This index correctly orders precursors according to the surface area of the solid materials produced from them and provides, when correlated to a few data points, a predictive relationship between the index and the surface area. Precursor features leading to early formation of a highly connected rigid network include high ratios of nonhydrolyzing (e.g., methylene) to hydrolyzing (e.g., oxy) groups bridging silicate moieties, large SiOH/Si ratios in the hydrolyzed precursors, and low numbers of noncondensing terminal groups (e.g., methyl). These features explain the extremely high surface areas obtained from 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane and high surface areas obtained by similar materials in aqueous, nontemplated syntheses, as shown in a related publication (DOI: 10.1021/acs.chemmater.7b04480)

In vivo imaging of a stable paramagnetic probe by pulsed-radiofrequency electron paramagnetic resonance spectroscopy

Imaging of free radicals by electron paramagnetic resonance (EPR) spectroscopy using time domain acquisition as in nuclear magnetic resonance (NMR) has not been attempted because of the short spin-spin relaxation times, typically under 1 μs, of most biologically relevant paramagnetic species. Recent advances in radiofrequency (RF) electronics have enabled the generation of pulses of the order of 10-50 ns. Such short pulses provide adequate spectral coverage for EPR studies at 300 MHz resonant frequency. Acquisition of free induction decays (FID) of paramagnetic species possessing inhomogenously broadened narrow lines after pulsed excitation is feasible with an appropriate digitizer/averager. This report describes the use of time-domain RF EPR spectrometry and imaging for in vivo applications. FID responses were collected from a water-soluble, narrow line width spin probe within phantom samples in solution and also when infused intravenously in an anesthetized mouse. Using static magnetic field gradients and back-projection methods of image reconstruction, two-dimensional images of the spin-probe distribution were obtained in phantom samples as well as in a mouse. The resolution in the images was better than 0.7 mm and devoid of motional artifacts in the in vivo study. Results from this study suggest a potential use for pulsed RF EPR imaging (EPRI) for three-dimensional spatial and spectral-spatial imaging applications. In particular, pulsed EPRI may find use in in vivo studies to minimize motional artifacts from cardiac and lung motion that cause significant problems in frequency-domain spectral acquisition, such as in continuous wave (cw) EPR techniques

EMM-23: A Stable High-Silica Multidimensional Zeolite with Extra-Large Trilobe-Shaped Channels

Stable, multidimensional, and extra-large pore zeolites are desirable by industry for catalysis and separation of bulky molecules. Here we report EMM-23, the first stable, three-dimensional extra-large pore aluminosilicate zeolite. The structure of EMM-23 was determined from submicron-sized crystals by combining electron crystallography, solid-state nuclear magnetic resonance (NMR), and powder X-ray diffraction. The framework contains highly unusual trilobe-shaped pores that are bound by 21–24 tetrahedral atoms. These extra-large pores are intersected perpendicularly by a two-dimensional 10-ring channel system. Unlike most ideal zeolite frameworks that have tetrahedral sites with four next-nearest tetrahedral neighbors (Q⁴ species), this unusual zeolite possesses a high density of Q² and Q³ silicon species. It is the first zeolite prepared directly with Q² species that are intrinsic to the framework. EMM-23 is stable after calcination at 540 °C. The formation of this highly interrupted structure is facilitated by the high density of extra framework positive charge introduced by the dicationic structure directing agent

High-Throughput Synthesis and Structure of Zeolite ZSM-43 with Two-Directional 8‑Ring Channels

The aluminosilicate zeolite ZSM-43 (where ZSM = Zeolite Socony Mobil) was first synthesized more than 3 decades ago, but its chemical structure remained unsolved because of its poor crystallinity and small crystal size. Here we present optimization of the ZSM-43 synthesis using a high-throughput approach and subsequent structure determination by the combination of electron crystallographic methods and powder X-ray diffraction. The synthesis required the use of a combination of both inorganic (Cs⁺ and K⁺) and organic (choline) structure-directing agents. High-throughput synthesis enabled a screening of the synthesis conditions, which made it possible to optimize the synthesis, despite its complexity, in order to obtain a material with significantly improved crystallinity. When both rotation electron diffraction and high-resolution transmission electron microscopy imaging techniques are applied, the structure of ZSM-43 could be determined. The structure of ZSM-43 is a new zeolite framework type and possesses a unique two-dimensional channel system limited by 8-ring channels. ZSM-43 is stable upon calcination, and sorption measurements show that the material is suitable for adsorption of carbon dioxide as well as methane