Mass transfer during dissolution of solids using hydrodynamic cavitation devices

Experimental investigations are performed to explore the mass transfer during dissolution of solids under hydrodynamic cavitation conditions and to evaluate the effect of cavitation on the dissolution rate after pretreatment of the liquid phase. The results obtained are compared with theoretical data.     

Stochastic sedimentation and hydrodynamic diffusion

Molecular collisions with very small particles induce Brownian motion. Consequently, such particles exhibit classical diffusion during their sedimentation. However, identical particles too large to be affected by Brownian motion also change their relative positions. This phenomenon is called hydrodynamic diffusion. Long before this term was coined, the variability of individual particle trajectories had been recognized and a stochastic model had been formulated. In general, stochastic and diffusion approaches are formally equivalent. The convective and diffusive terms in a diffusion equation correspond formally to the drift and diffusion terms of a Fokker–Planck equation (FPE). This FPE can be cast in the form of a stochastic differential equation (SDE) that is much easier to solve numerically. The solution of the associated SDE, via a large number of stochastic paths, yields the solution of the original equation. The three-parameter Markov model, formulated a decade before hydrodynamic diffusion became fashionable, describes one-dimensional sedimentation as a simple SDE for the velocity process {V(t)}. It predicts correctly that the steady-state distribution of particle velocities is Gaussian and that the autocorrelation of velocities decays exponentially. The corresponding position process {X(t)} is not Markov, but the bivariate process {X(t), V(t)} is both Gaussian and Markov. The SDE pair yields continuous velocities and sample paths. The other approach does not use the diffusion process corresponding to the FPE for the three-parameter model; rather, it uses an analogy to Fickian diffusion of molecules. By focusing on velocity rather than position, the stochastic model has several advantages. It subsumes Kynch’s theory as a first approximation, but corresponds to the reality that particle velocities are, in fact, continuous. It also profits from powerful theorems about stochastic processes in general and Markov processes in particular. It allows transient phenomena to be modeled by using parameters determined from the steady-state. It is very simple and efficient to simulate, but the three parameters must be determined experimentally or computationally. Relevant data are still sparse, but recent experimental and computational work is beginning to determine values of the three parameters and even the additional two parameters needed to simulate three-dimensional motion. If the dependence of the parameters on solids concentration is known, this model can simulate the sedimentation of the entire slurry, including the packed bed and the slurry–supernate interface. Simulations using half a million particles are already feasible with a desktop computer.     

Drying in active hydrodynamic regimes

It is shown that the activation of hydrodynamic regimes is one way of solving the problem of increasing the efficiency of drying processes, which includes solving the problems of the process intensity and cost effectiveness, as well as the quality of the final product. A method for estimating the degree of the activity of a hydrodynamic regime is recommended. A strategy for choosing the optimal apparatus-technological design of the drying process is developed that includes the complex analysis of the materials to be dried and the classification of wet disperse materials according to sorption-structural characteristics taking into account adhesion-autohesion properties. Standard apparatuses for each class of materials are recommended. The problem of drying materials with increased adhesion-autohesion properties is chosen. Drying in vortex apparatuses with simultaneous size reduction is considered as an example.     

Capillary hydrodynamic phenomena in gas-free combustion

The capillary effects of gradient filtration and melt microflows in combustion waves of heterogeneous systems are analyzed on the basis of experimental data obtained by video recording, local dynamic pyrometry, and investigation of hardening structures. Relations between the parameters of convective phenomena and combustion dynamics and the mechanism of activation of the heterogeneous combustion interaction by melts are established for Ti-B-Cu, FeO-Al-Al₂O₃, Ni-Al, and Ti-Ni powder mixtures and model bimetallic compositions. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 31–39, November–December, 2007.     

Monoliths in Heterogeneous Catalysis

The use of structured catalysts in the chemical industry has been considered for years. Conventional fixed-bed reactors have some obvious disadvantages such as maldistributions of various kinds (including a nonuniform access of reactants to the catalytic surface), high pressure drop in the bed, etc. Structured catalysts are promising as far as elimination of these setbacks is concerned. Two basic kinds of structured catalysts can be distinguished:

1. Structural packings covered with catalytically active material, similar in design to those used in distillation and absorption columns and/or static mixers. Good examples of catalysts of this kind are those offered by Sulzer, clearly developed by Sulzer column packings and static mixers. As in packed beds, there is an intensive radial convective mass transport over the entire cross-section of these packings. Structural packing catalysts and the reactors containing them are, however, not within the scope of this review.
2. Monolithic catalysts are continuous unitary structures which contain many small, mostly parallel passages. A ceramic or metallic support is coated with a layer of material in which active ingredients are dispersed. An interaction between these passages can occur if walls are permeable. The catalytically active material is present on or inside the walls of these passages. Radial mass transport can occur only by diffusion through the pores of the permeable walls.

     

Fractals in Heterogeneous Catalysis

In a recent review on the influence of particle size on catalytic properties of supported metals [l], evidently a most important aspect of heterogeneous catalysis by any account, the authors end on a fairly discouraging note since they suggest doing even more work — with ever more sophisticated techniques and methods as well as normalized procedures — on top of an already formidable amount of literature. At such a state of the art it may be appropriate to reflect and to ask whether full pursuit of reductionism as scientific method needs fresh thinking in order to progress more effectively. Perhaps the difficulties are rooted in emphasis on mere data collection, the lack of a good empirical guiding principle, inappropriate models; in brief, the frequent simplification of a vastly complicated object — the real catalyst — into the sum of phenomena of better-understood idealized subsets. It might even be argued that a thorough knowledge of a well-characterized prototype or a particular model catalyst would be actually of little help in seeing the real world where catalysts are of irregular shape, suffer sintering, become poisoned; in other words, lose their ideal state after some time of operation. Also, we realize that a change in “quantity” often engenders a change in “quality”: For instance, a material with a BET area of hundreds of square meters per gram can hardly be considered to have a surface like a huge tennis court or ball field: it is rather “convoluted” in some very irregular fashion, having a shape that is difficult to realistically construct as a linear combination of planar portions.     

Monoliths in Heterogeneous Catalysis

Nitration of aromatics is a key process in the catalytic manufacturing of semiproducts for the synthesis of drugs, pesticides, and dyes. However, the large-scale synthesis, involving the concentrated mineral acids used as catalysts, makes nitration one of the most environmentally harmful processes, producing huge amounts of organic wastes, exhausted acids, and the products of their neutralization. A search for environmentally safer catalysts and nitrating agents appears to be an actuality. Numerous data concerning the aromatics nitration in homogeneous media have been summarized in a set of books and reviews [l-41. Recent papers are of considerable interest, since they reflect the attempts to perform nitration on heterogeneous catalysts, for example, zeolites [5–8]. The data on aromatic nitration on the surface of solid acids [9, 111 and in the gas phase [12–14] allowed us to clarify the role of intermediate Tand a-complexes, estimate the substrate and position selectivity, and elucidate the main approaches of nitration mechanism in various media. In this review the data concerning nitration on solid catalysts are summarized. We hope this information will make it possible to estimate the perspectives of heterogeneous catalyst application on a large scale.     

多相催化反应工程

<正> 多相催化反应工程是研究使用固体催化剂的气-固相反应、气-液-固三相反应和液相中含有催化作用的液相物质的气-液反应的反应动力学、反应器工程设计和操作性能的科学,它是化学反应工程学科的主要分支。     

Nanomaterials for Heterogeneous Combustion

Nanophase materials and nanocomposites, characterized by an ultra fine grain size (less than 100 nm) have attracted wide spread interest in recent years by virtue of their unusual mechanical, electrical, optical, magnetic, and energetic properties. Studies have shown that the thermal behavior of nano‐scaled materials is quite different from micron‐sized powders. Nanosized metallic and explosive powders have been used as solid propellant and explosive mixtures to increase efficiency. At the same time recent studies reveal that the presence of nanosized metals in propellants does not necessary translate into an increased burning rate and burning temperature. The reasons of this effect are far from being clear. This paper presents a new approach to the production of nanocomposites of some energetic materials – ammonium nitrite, cyclotrimethylene trinitramine (RDX), and aluminum – by the vacuum co‐deposition technique. The thermal behavior of the synthesized nanopowder and nanocomposites is investigated. A substantial difference in burning rate of RDX nanopowder has been found in comparison to micron‐sized material. Experimental results allow investigating the effects of nanosized materials on the combustion characteristics.     

Fractals in Heterogeneous Catalysis

In a recent review on the influence of particle size on catalytic properties of supported metals [l], evidently a most important aspect of heterogeneous catalysis by any account, the authors end on a fairly discouraging note since they suggest doing even more work — with ever more sophisticated techniques and methods as well as normalized procedures — on top of an already formidable amount of literature. At such a state of the art it may be appropriate to reflect and to ask whether full pursuit of reductionism as scientific method needs fresh thinking in order to progress more effectively. Perhaps the difficulties are rooted in emphasis on mere data collection, the lack of a good empirical guiding principle, inappropriate models; in brief, the frequent simplification of a vastly complicated object — the real catalyst — into the sum of phenomena of better-understood idealized subsets. It might even be argued that a thorough knowledge of a well-characterized prototype or a particular model catalyst would be actually of little help in seeing the real world where catalysts are of irregular shape, suffer sintering, become poisoned; in other words, lose their ideal state after some time of operation. Also, we realize that a change in “quantity” often engenders a change in “quality”: For instance, a material with a BET area of hundreds of square meters per gram can hardly be considered to have a surface like a huge tennis court or ball field: it is rather “convoluted” in some very irregular fashion, having a shape that is difficult to realistically construct as a linear combination of planar portions.     

Nano-Particles in Heterogeneous Catalysis

The introduction of in situ techniques has had a vast impact on research and development in the area of heterogeneous catalysis as emphasized in many reviews and monographs. Recently, the number of in situ techniques that can give information at the atomic scale has increased significantly and new possibilities exist for making the measurements under industrially relevant conditions. In order to fully exploit the results from the in situ and operando studies, it has also become increasingly gainful to combine the experimental studies with theoretical methodologies based on, for example, Density Functional Theory (DFT). This has allowed one to extract more detailed atomic-scale information from the measurements and it has also allowed the establishment of detailed structure-activity relationships. Furthermore, the interplay between in situ techniques and theory has helped bridging the pressure gap such that in situ information obtained at conditions far from industrial ones may be used in a more relevant manner. Here, we will illustrate how microscopy-, spectroscopy- and X-ray-based techniques in combination with experimental and theoretical surface science methods can aid industrial catalyst developments. We will do this by presenting examples of our current understanding and latest developments in the areas of heterogeneous nano-particle catalysts for methanol synthesis, steam reforming and hydrotreating.     

水力空化对化学反应的强化效应

在由孔板产生的水力空化条件下对KI水溶液分解反应进行了实验研究.通过测定反应产物碘的释放量,检测了水力空化的化学效应.分析了实验装置的几何特性、水力学特性及溶液浓度等对空化强化效应的影响.研究结果表明：水力空化能够引发或强化某些化学反应,其作用强度取决于空化发生的状态、空化引发自由基的数量和反应物浓度等.寻求最佳的水力空化条件,可以获得较好的化学反应强化效果.     

Prediction of hydrodynamic behaviour in bubble columns

A simple theoretical model is used to describe hydrodynamic behaviour in bubble columns. The model is based on an energy balance which takes into account the energy dissipation in the liquid motion and the energy dissipation at the gas–liquid interface. Gas hold-up, liquid velocity at the column axis and radial profile of liquid velocity are predicted in a wide range of operating conditions (J_G up to 1·452 m s⁻¹) and column sizes (D = 0·1–1 m and H = 1·22–9·5 m) with good accuracy. Predictions of liquid velocity are also compared with one of the most widely accepted models.     

Dimensional hydrodynamic similitude in three-phase fluidized beds

This study tests the scaling approach for three-phase fluidized bed hydrodynamics proposed by Safoniuk, Grace, Hackman, & McKnight (Chem. Eng. Sci. 54 (1999) 4961) based on geometric and dynamic similitude with a limited number (5) of dimensionless groups. Experiments were carried out in two systems in which all five dimensionless groups were matched: an aqueous glycerol solution with glass beads (system 1) and silicone oil with porous alumina particles (system 2), with air as the gas in both cases. Although bed expansions were similar for the two systems, trends differed. Gas holdups were always slightly higher for system 1. The dimensionless transition velocities from dispersed to coalesced flow were similar. The minimum liquid fluidization velocity Reynolds number was slightly higher for system 1 without gas, but somewhat lower with gas present. Differences between the systems are statistically significant, but generally less than 12%, so the dimensional similitude approach gives a reasonable basis for estimating global hydrodynamic parameters under the present operating conditions. The differences between the two systems are attributed to the complex coalescence behavior of liquid mixtures, suggesting that additional dimensionless groups are needed to fully characterize the local dynamic bed behavior.