Dynamically structured fluidization: Oscillating the gas flow and other opportunities to intensify gas-solid fluidized bed operation

Various approaches to structure gas-solid fluidized beds are reviewed, followed by detailed discussion on the use of gas pulsation to induce dynamic structuring. Granular media are dissipative systems, which develop complex spatiotemporal patterns when excited by an oscillating energy source. Here, we discuss how such perturbations initiate surface patterns and how these could propagate into a macroscopically organized flow. We call this dynamically structured fluidization. Vibrated shallow granular layers form ordered surface waves. The hydrodynamics of pulsed gas-fluidized layers are related, but more complex: Under appropriate conditions, surface waves transition into a three-dimensionally ordered bubbling flow. This occurs in much deeper granular beds than under vibration, indicating distinct physics. In this dynamically structured state, bubbles organize into a scalable sub-harmonic, triangular lattice that is highly predictable and responsive to changes in oscillation parameters, allowing for an unprecedented level of control. Structured bubbling is observed only under sufficiently dense conditions; thus, a dynamically structured fluidized bed sits between fixed and fluidized beds, offering opportunities for process intensification, due to less macromixing than traditional fluidization, but a higher level of control through micromixing. This informs new intensified designs for processes that are highly exothermic, involve particle formation, thermally sensitive or high-value materials

Pattern formation in pulsed gas-solid fluidized beds - The role of granular solid mechanics

Under certain conditions, gas-solid fluidized beds are known to develop a structured flow of bubbles when exposed to periodically pulsating air flows. In quasi-two-dimensional beds, periodically rising bubbles form a triangular tessellation in the vertical plane. Bubble nucleation sites at the distributor plate alternate during each cycle. This pattern sets an excellent benchmark for fundamental studies of fluidization. Notably, most common Eulerian descriptions of granular flow do not yet capture this interplay between solid mechanics and fluid-solid momentum exchange, which we show to be instrumental to the dynamic rearrangement of bubbles in a pulsed bed. We report the first successful CFD simulations of structured bubble flows in a deep, quasi-2D geometry using a Eulerian-Lagrangian CFD-DEM framework. Numerical results are in quantitative agreement with experiments. The simulated dynamics reveal that the patterns emerge from the transition of the granular collective behavior between solid-like and fluid-like, which is an outcome of dynamical coupling between gas and particles. The simulated results point out the essential role of solid frictional stresses on inducing and maintaining the formation of bubble patterns. This underscores the value of investigating pulsation-induced patterns as a prime manifestation of the mesoscopic physics underpinning fluidization, and highlights the direction for improving current practices

Mesostructure of Mesoporous Silica/Anodic Alumina Hierarchical Membranes Tuned with Ethanol

Hierarchically structured membranes composed of mesoporous silica embedded inside the channels of anodic alumina (MS-AAM) were synthesized using the aspiration method. Ethanol is shown to have a significant effect on the type and organization of the mesoporous silica phase. Detailed textural analysis revealed that the pore size distribution of the mesoporous silica narrows and the degree of ordering increases with decreasing ethanol concentration used in the synthesis mixture. The silica mesopores were synthesized with pores as small as 6 nm in diameter, with the channel direction oriented in lamellar, circular, and columnar directions depending on the ethanol content. This study reveals ethanol concentration as a key factor behind the synthesis of an ordered mesoporous silica-anodic alumina membrane that can increase its functionality for membrane-based applications

Chaperonin-Inspired pH Protection by Mesoporous Silica SBA-15 on Myoglobin and Lysozyme

While enzymes are valuable tools in many fields of biotechnology, they are fragile and must be protected against denaturing conditions such as unfavorable solution pH. Within living organisms, chaperonins help enzymes fold into their native shape and protect them from damage. Inspired by this natural solution, mesoporous silica SBA-15 with different pore diameters is synthesized as a support material for immobilizing and protecting enzymes. In separate experiments, the model enzymes myoglobin and lysozyme are physically adsorbed to SBA-15 and exposed to a range of buffered pH conditions. The immobilized enzymes' biocatalytic activities are quantified and compared to the activities of nonimmobilized enzymes in the same solution conditions. It has been observed that myoglobin immobilized on SBA-15 is protected from acidic denaturation from pH 3.6 to 5.1, exhibiting relative activity of up to 350%. Immobilized lysozyme is protected from unfavorable conditions from pH 6.6 to 7.6, with relative activity of up to 200%. These results indicate that the protective effects conferred to enzymes immobilized by physical adsorption to SBA-15 are driven by the enzymes' electrostatic attraction to the material's surface. The pore diameter of SBA-15 affects the quality of protection given to immobilized enzymes, but the contribution of this effect at different pH values remains unclear

Effect of stirring rate on the morphology of FDU-12 mesoporous silica particles

Ordered mesoporous FDU-12 silica particles with different morphologies were synthesized by varying the stirring rate. The mesoporous structure and textural properties of the FDU-12 samples were characterized by N2 adsorption and desorption, scanning electron microscopy, transmission electron microscopy and small angle X-ray scattering. The influence of the stirring conditions on the morphology was demonstrated, as the FDU-12 particle morphology changes from a regular, hexagonal platelet to a poorly defined shape when the stirring rate is changed from slow to fast. At very fast stirring rate, shear influences the mesophase structure, although the pore diameter and wall thickness remain unchanged

Surface barriers as dominant mechanism to transport limitations in hierarchically structured catalysts – Application to the zeolite-catalyzed alkylation of benzene with ethylene

The meso-macropore network of a hierarchically structured zeolite catalyst is numerically optimized to maximize the volume-integrated reaction yield in the ethylation of benzene to produce ethylbenzene over zeolite H-ZSM-5. A hierarchical approach is used at multiple length scales to determine the optimal pore network properties. The maximum volume-integrated reaction yield of the hierarchically structured zeolite catalyst containing meso- and macropores is nearly twice the yield of a zeolite pellet containing only macropores, at the same macroporosity. To bridge the gap between modeling and experiments, a series of physical mixtures of ZSM-5 crystals and mesoporous silica, containing different weight fractions of zeolite is synthesized and used in fixed bed reactor experiments to determine the optimal pellet structure to maximize the conversion of ethylene. Comparison with reactor simulations of the zeolite composites shows that the performance of the zeolite composites might be limited by surface barriers at the external surface of the zeolite crystals, rather than by diffusion limitations within the meso-macropore network of the pellets

Nature-Inspired, Computer-Assisted Optimization of Hierarchically Structured Zeolites

Zeolite catalysis is often affected by transport limitations, which significantly influence overall performance. Introducing wide pores as molecular transport highways can reduce transport limitations, control the product distribution, and mitigate effects of catalyst deactivation. Nevertheless, the importance to rationally design the meso‐ and macropore space remains underappreciated. This article reviews multiscale modelling approaches to optimize overall catalytic performance. It provides a general methodology and rules of thumb to guide catalyst synthesis with optimal pore network characteristics. Inspiration is taken from nature, such as the structure of leaves and tissues, with similar requirements and associated features. In optimal hierarchically structured zeolites, the added macro‐/mesopore volume fraction, connectivity, crystal size, and minimum wide pore size are crucial. The broad pore size distribution is secondary. No uncontrolled diffusion limitations should exist within the zeolite crystals. Surface barriers, however, can significantly affect, even dominate overall transport. Understanding their origin and ways to control them is an emergent research area. Synthesis methods to realize hierarchically structured zeolites are briefly reviewed. Significant gaps exist between laboratory synthesis methods and industrial requirements. Zeolite catalysis could benefit from computer‐assisted design of their hierarchical pore network, embracing principles used by natural transport networks for scalable efficiency, selectivity, and robustness

One-pot Synthesis of Hierarchical, Micro-macroporous Zeolites with Encapsulated Metal Particles as Sinter-resistant, Bifunctional Catalysts

We report a new one-pot synthesis procedure for hierarchical zeolites with intracrystalline macropores and metal particles encapsulated within the zeolitic walls. The synthesis allows to prepare macroporous zeolites of MFI topology with different heteroatoms (silicalite-1, ZSM-5 and TS-1) and different encapsulated noble metal particles, such as gold, platinum and palladium. The hierarchically structured zeolites contain large macropores with diameters around 400 nm, which are well distributed and interconnected and should significantly enhance mass transport properties. The encapsulation of metal nanoparticles within the zeolitic walls leads to remarkable sinter resistance of the particles. Encapsulated gold nanoparticles (2.6 nm) do not significantly change in size during an 18-hour treatment at 600 °C under air, while non-encapsulated gold particles sinter heavily during the same treatment. Catalytic experiments for the direct epoxidation of propene with hydrogen and oxygen show that both catalytic functions of a macroporous TS-1 sample that encapsulates gold particles are accessible and active. This catalyst displays high activity, although PO selectivity could still be improved. These materials show great potential for use in catalytic applications, due to their bifunctional nature, high sintering resistance, shape selective properties and hierarchical structure

Fractal injectors to intensify liquid-phase processes by controlling the turbulent flow field

Fractal injectors can be used to intensify liquid-phase processes. The flow field, vortex structure and turbulent mixing performance induced by fractal injectors with three different fractal dimensions (D = 2, 2.58 and 3) are investigated. CFD simulations, using a renormalization group (RNG) k-ε turbulence model, are validated with particle image velocimetry (PIV) measurements. The structure and formation mechanism of the vortices are studied. Both spiral and double toroidal vortices are produced, the latter by jet impingement. These vortices interact with each other within a fractal generating unit. For the same total volumetric flow rate, a fractal injector with D = 2.58 can achieve better mixing uniformity than fractal injectors with D = 2 or D = 3, while maintaining a similarly high mixing rate to when D = 2. This is due to enhanced entrainment by mutually interacting double toroidal vortex pairs and turbulent mixing

Pattern formation in fluidized beds as a tool for model validation: A two-fluid model based study

Computational fluid dynamics (CFD) models have been broadly used during the last twenty years to engineer and understand fluidized beds. Nevertheless, there is some controversy about the rigor of their current validation methodologies (Powder Technol. 139 (2004), 99). A robust tool to determine whether or not a model reproduces-let alone, can predict-the dynamics of a fluidized bed is still missing. This is especially relevant for the validation of the fluid-particle closures that are emerging with the help of direct numerical simulation.More than a decade ago, it was demonstrated experimentally that regular patterns emerge in pulsed fluidized beds under certain experimental conditions. These patterns are not a singular feature of the dynamics, such as average bubble size or bed expansion, but form as a result of a precise coupling between multi-scale physical phenomena. Remarkably, CFD has not been able, so far, to reproduce the experimental bubble patterns convincingly.In this work, we want to bring to the attention of the fluidization community the power of pattern formation in fluidized beds as a tool for model validation. As a proof of concept, we apply this validation test to two-fluid models. Our two-fluid simulations reproduce bubble properties reasonably well, but fail to reproduce the experimentally witnessed patterns, suggesting that the physics of the fluidized state are not correctly captured by this approach, under any of its common implementations