J.R. van Ommen

Fluidization of nanopowders: a review

Nanoparticles (NPs) are applied in a wide range of processes, and their use continues to increase. Fluidization is one of the best techniques available to disperse and process NPs. NPs cannot be fluidized individually; they fluidize as very porous agglomerates. The objective of this article is to review the developments in nanopowder fluidization. Often, it is needed to apply an assistance method, such as vibration or microjets, to obtain proper fluidization. These methods can greatly improve the fluidization characteristics, strongly increase the bed expansion, and lead to a better mixing of the bed material. Several approaches have been applied to model the behavior of fluidized nanopowders. The average size of fluidized NP agglomerates can be estimated using a force balance or by a modified Richardson and Zaki equation. Some first attempts have been made to apply computational fluid dynamics. Fluidization can also be used to provide individual NPs with a thin coating of another material and to mix two different species of nanopowder. The application of nanopowder fluidization in practice is still limited, but a wide range of potential applications is foreseen.

Measuring the gas-solids distribution in fluidized beds - a review

In gas-solid fluidized beds, the distribution of the particles typically varies both in time and space. Since the gas-solids distribution and its variation have a strong influence on the performance of a fluidized bed for a given process, it is very important to accurately measure the gas-solids or voidage distribution. This paper reviews techniques for measuring the voidage distribution in gas-solid fluidized beds, with a focus on the developments during the last ten years. We will treat subsequently direct visualisation, tomography, optical probes, capacitance probes, and pressure measurements.Dense gas-solids flows are typically opaque to visible light. This makes optical techniques only of limited use in dense gas-solids flow. However, direct visualization can be useful for very dilute systems, pseudo 2-D beds, and the outer layer of dense, 3-D systems. Tomography is frequently used to obtain the voidage distribution in a horizontal cross-section of the bed. Electric capacitance tomography is fast, but its spatial resolution is limited and image reconstruction is still troublesome. Although some steps forward have been made, research is continuing at this point. For nuclear (X-ray and gamma-ray) tomography, the image reconstruction is much easier and the spatial resolution better, but its temporal resolution is typically much lower. Therefore, research efforts for nuclear tomography are mainly aimed at increasing the measurement frequency. Optical probes determine the voidage as a function of time in a small measurement volume, either by the degree of reflection or by the degree of transmission of a light bundle. Capacitance probes determine the voidage as a function of time in a small measurement volume by measuring the dielectric permittivity of the gas-solids suspension in the measurement volume. Both optical and capacitance probe techniques are reasonably well-developed; the current research effort spent at improving them seems limited, especially for capacitance probes. Time-averaged pressure measurements are commonly used to determine the average bed density and bed height. By sampling the local pressure at a sufficiently high frequency (typically in the order of 200 Hz), much more information can be obtained about the fluidized bed hydrodynamics. However, obtaining quantitative voidage data from pressure fluctuations measurement remains a difficult task; in-bed pressure fluctuation (and acoustic) measurements are mostly used to determine changes in the voidage dynamics and distribution.

Structuring catalyst and reactor – an inviting avenue to process intensification

Multiphase catalytic processes involve the combination of scale-dependent and scale-independent phenomena, often resulting in a compromised, sub-optimal performance. The classical approach of randomly packed catalyst beds using unstructured catalyst particles may be outperformed by the careful design of the catalyst at the nano-scale and by the judicious choice and design of reactor. Application of structured catalysts and reactor internals and the combination of advanced reactor and catalyst systems with in situ separation allow decoupling the various phenomena involved, opening the way to intensified processes on a large scale. The integral approach of Catalysis and Reaction Engineering discussed here will play a pivotal role in the development of novel, future-proof processes.

Atomic and molecular layer deposition: off the beaten track

Atomic layer deposition (ALD) is a gas-phase deposition technique that, by relying on self-terminating surface chemistry, enables the control of the amount of deposited material down to the atomic level. While mostly used in semiconductor technology for the deposition of ceramic oxides and nitrides on wafers, ALD lends itself to the deposition of a wealth of materials on virtually every substrate. In particular, ALD and its organic counterpart molecular layer deposition (MLD), have opened up attractive avenues for the synthesis of novel nanostructured materials. However, as most ALD processes were developed and optimized for semiconductor technology, these might not be optimal for applications in fields such as catalysis, energy storage, and health. For this reason, novel applications for ALD often require new surface chemistries, process conditions, and reactor types. As a result, recent developments in ALD technology have marked a considerable departure from the standard set by well-established ALD processes. The aim of this review is twofold: firstly, to capture the recent departure of ALD from its original development; and secondly, to pinpoint the unexplored paths through which ALD can advance further in terms of synthesis of novel materials. To that end, we provide a review of the recent developments of ALD and MLD of materials that are gaining increasing attention on various substrates, with particular emphasis on high-surface-area substrates. Furthermore, we present a critical review of the effects of the process conditions, namely, temperature, pressure, and time on ALD growth. Finally, we also give a brief overview of the recent advances in ALD reactors and energy-enhanced ALD processes.

Functionalization of lactose as a biological carrier for bovine serum albumin by electrospraying

Electrohydrodynamic atomization (EHDA) is an attractive technique to make new types of composite particles for pharmaceutical use. The aim of this work is to prove that EHDA can be successfully used to attach nano/micro-particles of protein to lactose, the commonly used excipient for pulmonary delivery, keeping all the biological properties of the protein after dissolution of the complex. Bovine serum albumin (BSA) was used as a model protein. The atomization of BSA was tested with two different solvents, dimethyl sulfoxide (DMSO) and ethanol. The process using DMSO resulted in the formation of a thin layer of protein while the tests using ethanol resulted in the formation of spherical particles with mean diameters around 700 nm. Ethanol as solvent was also used to produce a composite formed by BSA adsorbed at the surface of lactose by electrostatic forces. No denaturation or significant conformational changes of the protein were observed, although an increase in the exposition of the lactose to the jet of the solution decreases the reproducibility of the method. Due to the absence of denaturation in the model protein, this new approach can be tested for the production of new formulations for dry powders for drug delivery systems.

Bubble size reduction in a fluidized bed by electric fields

The reduction of the size of bubbles can improve both selectivity and conversion in gas-solid fluidized beds. Results are reported of the reduction of bubble size by the application of electric fields to uncharged, polarizable particles in fluidized beds. It is shown how average bubble diameters can be drastically reduced, with little change of the bed expansion. A literature review shows that to maintain smooth fluidization, electric fields in the direction of the gas flow, with a relatively low alternating frequency, are optimal. To measure average bubble diameters, a spectral decomposition technique of pressure fluctuation time series is used. Using this method, based on non-intrusive measurements, a characteristic length scale for bubble diameters can be found. It is shown experimentally, using video analysis, that this length scale is of constant proportionality for a given bed material and bed dimensions. The proportionality of the length scale to bubble diameter is independent of measuring height or gas velocity. With this, we have a tool for measuring bubble diameters in both 2-D and 3-D fluidized beds. Electric fields were applied to fluidized beds using thin wire electrodes placed inside the column. Both 2-D and 3-D columns were tested over a range of frequencies and field strengths. For Geldart A glass beads, an optimal range was determined at 5-20 Hz and 400-1600 V/cm fields. The reduction of bubble diameter was measured to be up to 25% for this system. Larger Geldart B glass particles show a larger reduction of bubble diameters - up to 85%. For these particles, the optimal frequency was at a higher range, 20-70 Hz. At higher frequencies (up to 100 Hz), bubble size reduction is less, but still substantial. Experiments in the 3-D column using Geldart A particles show a similar reduction in bubble diameters.The reduction of the size of bubbles can improve both selectivity and conversion in gas-solid fluidized beds. Results are reported of the reduction of bubble size by the application of electric fields to uncharged, polarizable particles in fluidized beds. It is shown how average bubble diameters can be drastically reduced, with little change of the bed expansion. A literature review shows that to maintain smooth fluidization, electric fields in the direction of the gas flow, with a relatively low alternating frequency, are optimal. To measure average bubble diameters, a spectral decomposition technique of pressure fluctuation time series is used. Using this method, based on non-intrusive measurements, a characteristic length scale for bubble diameters can be found. It is shown experimentally, using video analysis, that this length scale is of constant proportionality for a given bed material and bed dimensions. The proportionality of the length scale to bubble diameter is independent of measuring height or gas velocity. With this, we have a tool for measuring bubble diameters in both 2-D and 3-D fluidized beds. Electric fields were applied to fluidized beds using thin wire electrodes placed inside the column. Both 2-D and 3-D columns were tested over a range of frequencies and field strengths. For Geldart A glass beads, an optimal range was determined at 5-20 Hz and 400-1600 V/cm fields. The reduction of bubble diameter was measured to be up to 25% for this system. Larger Geldart B glass particles show a larger reduction of bubble diameters - up to 85%. For these particles, the optimal frequency was at a higher range, 20-70 Hz. At higher frequencies (up to 100 Hz), bubble size reduction is less, but still substantial. Experiments in the 3-D column using Geldart A particles show a similar reduction in bubble diameters.

Gas-Phase Deposition of Ultrathin Aluminium Oxide Films on Nanoparticles at Ambient Conditions

We have deposited aluminium oxide films by atomic layer deposition on titanium oxide nanoparticles in a fluidized bed reactor at 27 ± 3 °C and atmospheric pressure. Working at room temperature allows the coating of heat-sensitive materials, while working at atmospheric pressure would simplify the scale-up of this process. We performed 4, 7 and 15 cycles by dosing a predefined amount of precursors, i.e., trimethyl aluminium and water. We obtained a growth per cycle of 0.14–0.15 nm determined by transmission electron microscopy (TEM), similar to atomic layer deposition (ALD) experiments at a few millibars and ~180 °C. We also increased the amount of precursors dosed by a factor of 2, 4 and 6 compared to the base case, maintaining the same purging time. The growth per cycle (GPC) increased, although not linearly, with the dosing time. In addition, we performed an experiment at 170 °C and 1 bar using the dosing times increased by factor 6, and obtained a growth per cycle of 0.16 nm. These results were verified with elemental analysis, which showed a good agreement with the results from TEM pictures. Thermal gravimetric analysis (TGA) showed a negligible amount of unreacted molecules inside the alumina films. Overall, the dosage of the precursors is crucial to control precisely the growth of the alumina films at atmospheric pressure and room temperature. Dosing excess precursor induces a chemical vapour deposition type of growth due to the physisorption of molecules on the particles, but this can be avoided by working at high temperatures.

Transition of Emission Colours as a Consequence of Heat-Treatment of Carbon Coated Ce3+-Doped YAG Phosphors

To modify the luminescence properties of Ce3+-doped Y3Al5O12 (YAG) phosphors, they have been coated with a carbon layer by chemical vapor deposition and subsequently heat-treated at high temperature under N2 atmosphere. Luminescence of the carbon coated YAG:Ce3+ phosphors has been investigated as a function of heat-treatment at 1500 and 1650 °C. The 540 nm emission intensity of C@YAG:Ce3+ is the highest when heated at 1650 °C, while a blue emission at 400–420 nm is observed when heated at 1500 °C but not at 1650 °C. It is verified by X-ray diffraction (XRD) that the intriguing luminescence changes are induced by the formation of new phases in C@YAG:Ce3+-1500 °C, which disappear in C@YAG:Ce3+-1650 °C. In order to understand the mechanisms responsible for the enhancement of YAG:Ce3+ emission and the presence of the blue emission observed for C@YAG:Ce3+-1500 °C, the samples have been investigated by a combination of several electron microscopy techniques, such as HRTEM, SEM-CL, and SEM-EDS. This local and cross-sectional analysis clearly reveals a gradual transformation of phase and morphology in heated C@YAG:Ce3+ phosphors, which is related to a reaction between C and YAG:Ce3+ in N2 atmosphere. Through reaction between the carbon layer and YAG host materials, the emission colour of the phosphors can be modified from yellow, white, and then back to yellow under UV excitation as a function of heat-treatment in N2 atmosphere.

Measurement, monitoring and control of fluidized bed combustion and gasification

Abstract: The measurement of hydrodynamic phenomena in a fluidized bed for monitoring and control is important, yet difficult. Difficulties arise due to the bed’s opaque nature, chemically aggressive environment, and/or mechanical wear of solids. This chapter briefly reviews several measurement techniques, such as tomography, radiography, optical and capacitance probing. We will focus on pressure (fluctuation) measurements, since this is the only technique that is routinely applied in industrial practice. Pressure fluctuations can give information on dynamic changes in the voidage distribution of a fluidized bed when analyzed with statistical time series methods. The chapter ends with a discussion of the industrial application of monitoring and measurement techniques.

Suppressing the Photocatalytic Activity of TiO2 Nanoparticles by Extremely Thin Al2O3 Films Grown by Gas-Phase Deposition at Ambient Conditions

This work investigated the suppression of photocatalytic activity of titanium dioxide (TiO2) pigment powders by extremely thin aluminum oxide (Al2O3) films deposited via an atomic-layer-deposition-type process using trimethylaluminum (TMA) and H2O as precursors. The deposition was performed on multiple grams of TiO2 powder at room temperature and atmospheric pressure in a fluidized bed reactor, resulting in the growth of uniform and conformal Al2O3 films with thickness control at sub-nanometer level. The as-deposited Al2O3 films exhibited excellent photocatalytic suppression ability. Accordingly, an Al2O3 layer with a thickness of 1 nm could efficiently suppress the photocatalytic activities of rutile, anatase, and P25 TiO2 nanoparticles without affecting their bulk optical properties. In addition, the influence of high-temperature annealing on the properties of the Al2O3 layers was investigated, revealing the possibility of achieving porous Al2O3 layers. Our approach demonstrated a fast, efficient, and simple route to coating Al2O3 films on TiO2 pigment powders at the multigram scale, and showed great potential for large-scale production development.