scholarly journals Intraparticle Model for Non-Uniform Active Phase Distribution Catalysts in a Batch Reactor

2021 ◽  
Vol 5 (3) ◽  
pp. 38
Author(s):  
Emiliano Salucci ◽  
Vincenzo Russo ◽  
Tapio Salmi ◽  
Martino Di Serio ◽  
Riccardo Tesser

The study and the understanding of the importance of the morphological properties of heterogeneous catalysts can pave the way for important improvements in the performance of catalytic systems. Non-uniform active phase distribution catalysts are normally adopted for consecutive reactions to improve the selectivity to the desired intermediate product. Attributes on which minor attention is paid, such as the distribution and thickness of the active phase, can be decisive in the final rationale of the catalyst synthesis strategy. Starting from a previous work, where a single non-uniform active phase model for catalyst particles was developed, a key step to control the entire system is to include the bulk-phase equations and related transport phenomena. For this purpose, this work proposes a modeling approach of a biphasic reactive system in a batch reactor in the presence of three different kinds of catalytic particles (egg shell, egg white, and egg yolk) whose distinction lies in the localization of the active zone. The reactive network consists of a couple of reactions in series, which take place exclusively on the solid surface, and the intermediate component is the main product of interest. To reveal the influence related to the type of catalyst, an extensive parametric study was conducted, varying several structural coefficients to highlight the changes in the intraparticle and bulk concentration profiles of the different chemical species. The main results can be considered of wide interest for the chemical reaction engineering community, as it was demonstrated that mass and heat transfer limitations affect the catalyst performance. For the chosen system, the egg shell catalyst normally led to better catalytic performances.

Materials ◽  
2019 ◽  
Vol 12 (23) ◽  
pp. 3902 ◽  
Author(s):  
R. Guil-López ◽  
N. Mota ◽  
J. Llorente ◽  
E. Millán ◽  
B. Pawelec ◽  
...  

Technological approaches which enable the effective utilization of CO2 for manufacturing value-added chemicals and fuels can help to solve environmental problems derived from large CO2 emissions associated with the use of fossil fuels. One of the most interesting products that can be synthesized from CO2 is methanol, since it is an industrial commodity used in several chemical products and also an efficient transportation fuel. In this review, we highlight the recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to methanol. The main efforts focused on the improvement of conventional Cu/ZnO based catalysts and the development of new catalytic systems targeting the specific needs for CO2 to methanol reactions (unfavourable thermodynamics, production of high amount of water and high methanol selectivity under high or full CO2 conversion). Major studies on the development of active and selective catalysts based on thermodynamics, mechanisms, nano-synthesis and catalyst design (active phase, promoters, supports, etc.) are highlighted in this review. Finally, a summary concerning future perspectives on the research and development of efficient heterogeneous catalysts for methanol synthesis from CO2 will be presented.


2020 ◽  
Vol 4 (2) ◽  
pp. 24
Author(s):  
Vincenzo Russo ◽  
Luca Mastroianni ◽  
Riccardo Tesser ◽  
Tapio Salmi ◽  
Martino Di Serio

To maximize the performances of heterogeneous catalytic reactors, it is necessary to consider many parameters. Catalytic particle morphology (dimension, shape, active phase distribution) is generally previously established and seldom considered in the optimization of the catalyst to be specific for a given process. In this work, the influence of active phase distribution within spherical catalytic particles (egg-shell, egg-yolk and egg-white), on the yield and selectivity of a product is shown for a consecutive reaction network; here, the intermediate component is the main product of interest. Intraparticle mass and energy balances under non-steady conditions were implemented. Sensitivity studies lead to the identification of the optimal conditions, thus maximizing the yield of the intermediate for each active phase distribution. It was demonstrated that the egg-shell catalyst can maximize the intermediate yield, with a lower active-phase usage.


Author(s):  
Alexis T. Bell

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.


Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1680
Author(s):  
Marta A. Andrade ◽  
Luísa M. D. R. S. Martins

The selective oxidation of styrene under heterogeneous catalyzed conditions delivers environmentally friendly paths for the production of benzaldehyde, an important intermediate for the synthesis of several products. The present review explores heterogeneous catalysts for styrene oxidation using a variety of metal catalysts over the last decade. The use of several classes of supports is discussed, including metal–organic frameworks, zeolites, carbon materials and silicas, among others. The studied catalytic systems propose as most used oxidants tert-butyl hydroperoxide, and hydrogen peroxide and mild reaction conditions. The reaction mechanism proceeds through the generation of an intermediate reactive metal–oxygen species by catalyst-oxidant interactions. Overall, most of the studies highlight the synergetic effects among the metal and support for the activity and selectivity enhancement.


Nanomaterials ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 1081
Author(s):  
Shin-Yi Min ◽  
Won-Ju Cho

In this study, we implemented a high-performance two-terminal memristor device with a metal/insulator/metal (MIM) structure using a solution-derived In-Ga-Zn-Oxide (IGZO)-based nanocomposite as a resistive switching (RS) layer. In order to secure stable memristive switching characteristics, IGZO:N nanocomposites were synthesized through the microwave-assisted nitridation of solution-derived IGZO thin films, and the resulting improvement in synaptic characteristics was systematically evaluated. The microwave-assisted nitridation of solution-derived IGZO films was clearly demonstrated by chemical etching, optical absorption coefficient analysis, and X-ray photoelectron spectroscopy. Two types of memristor devices were prepared using an IGZO or an IGZO:N nanocomposite film as an RS layer. As a result, the IGZO:N memristors showed excellent endurance and resistance distribution in the 103 repeated cycling tests, while the IGZO memristors showed poor characteristics. Furthermore, in terms of electrical synaptic operation, the IGZO:N memristors possessed a highly stable nonvolatile multi-level resistance controllability and yielded better electric pulse-induced conductance modulation in 5 × 102 stimulation pulses. These findings demonstrate that the microwave annealing process is an effective synthesis strategy for the incorporation of chemical species into the nanocomposite framework, and that the microwave-assisted nitridation improves the memristive switching characteristics in the oxide-based RS layer.


Catalysts ◽  
2018 ◽  
Vol 8 (10) ◽  
pp. 418 ◽  
Author(s):  
Muhammad Abdus Salam ◽  
Derek Creaser ◽  
Prakhar Arora ◽  
Stefanie Tamm ◽  
Eva Lind Grennfelt ◽  
...  

Hydrodeoxygenation (HDO) activity of a typical hydrotreating catalyst, sulfided NiMo/γ-Al2O3 for deoxygenation of a fatty acid has been explored in a batch reactor at 54 bar and 320 °C in the presence of contaminants, like phospholipids, which are known to be present in renewable feeds. Oleic acid was used for the investigation. Freshly sulfided catalyst showed a high degree of deoxygenation activity; products were predominantly composed of alkanes (C17 and C18). Experiments with a major phospholipid showed that activity for C17 was greatly reduced while activity to C18 was not altered significantly in the studied conditions. Characterization of the spent catalyst revealed the formation of aluminum phosphate (AlPO4), which affects the active phase dispersion, blocks the active sites, and causes pore blockage. In addition, choline, formed from the decomposition of phospholipid, partially contributes to the observed deactivation. Furthermore, a direct correlation was observed in the accumulation of coke on the catalyst and the amount of phospholipid introduced in the feed. We therefore propose that the reason for the increased deactivation is due to the dual effects of an irreversible change in phase to aluminum phosphate and the formation of choline.


Materials ◽  
2018 ◽  
Vol 12 (1) ◽  
pp. 43 ◽  
Author(s):  
Palaniappan Subramanian ◽  
Dalila Meziane ◽  
Robert Wojcieszak ◽  
Franck Dumeignil ◽  
Rabah Boukherroub ◽  
...  

Noble metal nanostructures are exceptional light absorbing systems, in which electron–hole pairs can be formed and used as “hot” charge carriers for catalytic applications. The main goal of the emerging field of plasmon-induced catalysis is to design a novel way of finely tuning the activity and selectivity of heterogeneous catalysts. The designed strategies for the preparation of plasmonic nanomaterials for catalytic systems are highly crucial to achieve improvement in the performance of targeted catalytic reactions and processes. While there is a growing number of composite materials for photochemical processes-mediated by hot charge carriers, the reports on plasmon-enhanced electrochemical catalysis and their investigated reactions are still scarce. This review provides a brief overview of the current understanding of the charge flow within plasmon-enhanced electrochemically active nanostructures and their synthetic methods. It is intended to shed light on the recent progress achieved in the synthesis of multi-component nanostructures, in particular for the plasmon-mediated electrocatalysis of major fuel-forming and fuel cell reactions.


2014 ◽  
Vol 70 (a1) ◽  
pp. C1178-C1178
Author(s):  
David Billing

During the course of the last couple of years, my collaborators and I have studied a number of catalytic systems using a lab based PXRD facility at our disposal. Of particular interest to us has been the supported catalysts used in Fischer Tropsch catalysis as well as those used in the synthesis of multiwalled carbon nano tubes. These studies have all proven invaluable to the understanding of the often complex phase evolution that is an intricate and inherent part of the heterogeneous processes of interest to us. Selected results will be presented to illustrate the usefulness and value of these studies. For example below is the intensity profile of the diffraction patterns collected during the heat-treatment of the pre-catalyst: A – anatase, R – rutile, S – silicon, H – hematite and P – pseudobrookite


2013 ◽  
Vol 68 (10) ◽  
pp. 2309-2315 ◽  
Author(s):  
C. P. Theologides ◽  
P. G. Savva ◽  
G. G. Olympiou ◽  
N. A. Pantelidou ◽  
B. K. Constantinou ◽  
...  

The present paper involves a detailed study of the selective catalytic reduction of nitrates in aqueous mediums by the use of H2 in the presence of O2 over monometallic and bimetallic supported catalysts. In this study, an attempt has been made to improve the denitrification efficiency (XNO3−, SN2) of several catalysts by regulating some experimental parameters that are involved in the process. Therefore, the effects of the type of reactor (semi-batch reactor vs continuous flow reactor), the nature of the active phase (Pd, Cu, and Pd-Cu) and the particle size of γ-Al2O3 spheres (particle diameter = 1.8 mm and 3 mm) on catalytic activity and reaction selectivity, as well as the adsorption capacity of γ-Al2O3 spheres for nitrates, were examined. As the review indicates, most of the research has so far been conducted on batch or semi-batch reactors. This study successfully demonstrates the benefits of using a continuous flow reactor in terms of catalytic activity (XNO3−, %) and reaction selectivity (SN2, %). Another important aspect of this study is the crucial role of bimetallic Pd-Cu clusters for the prevention of NH4+ formation. Moreover, the use of 1.8 mm diameter γ-Al2O3 spheres as a support was proved to significantly enhance the catalytic performance of bimetallic Pd-Cu catalysts towards nitrate reduction compared to 3 mm diameter γ-Al2O3 spheres. This difference may be attributed to mass (NO3−, OH−) transfer effects (external mass transfer phenomena).


Author(s):  
Negisa Ebadipour ◽  
Sébastien Paul ◽  
Benjamin Katryniok ◽  
Franck Dumeignil

Polyglycerols (PGs) are biocompatible and highly functional polyols with a wide range of applications, such as emulsifiers, stabilizers, antimicrobial agents, in many industries including cosmetics, food, plastic and biomedical. The demand increase for biobased PGs encourages researchers to develop new catalytic systems for glycerol polymerization. This review focuses on alkaline homogeneous and heterogeneous catalysts. The performances of the alkaline catalysts are compared in terms of conversion and selectivity, and their respective advantages and disadvantages are commented. While homogeneous catalysts exhibit a high catalytic activity, they cannot be recycled and reused, whereas solid catalysts can be partially recycled. The key issue for heterogenous catalytic systems, which is unsolved so far, is linked to their instability due to partial dissolution in the reaction medium. Further, this paper also reviews the proposed mechanisms of glycerol polymerization over alkaline-based catalysts and discuss the various operating conditions with an impact on the performances. More particularly, temperature and amount of catalyst proved to have a significant influence on glycerol conversion and on its polymerization extent.


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