Structured and Micro-Structured Catalysts and Reactors

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Environmental Catalysis".

Deadline for manuscript submissions: closed (15 September 2017) | Viewed by 33746

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Sciences Department, Institute for Advanced Materials and Mathematics, Public University of Navarre, Campus de Arrosadia, Edificio de los Acebos, 31006 Pamplona, Spain
Interests: chemical engineering; chemical reaction engineering; catalysis; hydrogen energy; biogas; syngas; biofuels; methane conversion; CO2 capture and valorization, microfluidics, computational fluid dynamics
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Department of Applied Chemistry, University of the Basque Country, San Sebastián, Spain
Interests: Structured Catalysts and Reactors; Monolith Catalysts; Microchannel Reactors; Fischer-Tropsch Synthesis; Biofuels; Dimethyl Ether

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Special Issue Information

Dear Colleagues,

Structured catalysts and reactors (SC&R) are being successfully employed in a number of processes, mostly related with Environmental Catalysis applications. These well-stablished technologies include the control of pollutants emissions from transportation vehicles, of NOx emissions from stationary sources or the removal of volatile organic compounds and the catalytic combustion for power generation plants. The selective catalytic reduction of NOx in power and nitric acid production plants, refineries and waste incinerators is an excellent example of the use of SC&R.

SC&R are characterized by relatively large void fractions and many more ordered paths of the fluids compared to conventional packed beds of particulate catalysts. These facts together with the laminar regime that typically governs the flow of the fluids lead up to two orders of magnitude lower pressure drops in structured reactors than in fixed-bed reactors. This opens the possibility of using SC&R in processes involving very high flow rates of the reactants (environmental applications) or requiring very short contact times, such as in the selective oxidation of hydrocarbons.

In the case of the micro-structured systems, such as microreactors and catalytic-wall microchannel reactors, the very small characteristic dimensions (typically below 1 mm) prevailing in these devices allow a significant enhancement of the mass and heat transport rates. This results in an incomparable intensification of the process with an excellent temperature control, and improved product quality and process safety.

Structured catalysts normally consist in a ceramic or metallic substrate that can adopt several configurations, such as parallel channels monoliths, open cell foams, stacked wire meshes, and microchannel reactors. The substrate provides structural entity and determines the flow pattern of the fluids inside the reactor. The catalyst, typically composed of a porous support, the active component, and eventually modifiers to tune some properties or provide new ones, is incorporated in the form of a thin layer that coats the substrate walls or even forming micro-packed-beds inside the substrate cavities.

Structured catalysts based on ceramic substrates are being traditionally employed in a number of applications. On the other hand, the use of metallic substrates is being increasingly considered for reactions with a strong thermal effect for which a very good heat transfer capacity is required in order to avoid problems associated to hot spots and temperature gradients. Nevertheless, preparing structured catalysts on metallic substrates remains still challenging due to the difficulties associated to the deposition of the catalyst on the substrate surface. The formation of homogeneous and adherent thin layers of catalyst on these substrates is very difficult and the procedures employed are in many cases halfway between science and art. These difficulties are related with the very different characteristics of the substrate and the catalyst, the modifications suffered by the catalyst during the deposition process, and the increasing complexities of the shapes of the new substrate designs and of the new technology employed, such as in the case of additive manufacturing.

In this context, the aim of this Special Issue is to collect a series of novel contributions in the field of SC&R and microreactors that allow updating the state-of-the-art. The special issue is devoted although not limited to parallel channels monoliths, open cell foams, stacked wire meshes and microchannel reactors. Topics to be covered are SC&R preparation and characterization, microreactors fabrication and applications for process intensification, as well as modeling and simulation of SC&R and microreactors.

Prof. Luis M. Gandía
Prof. Mario Montes
Prof. José Antonio Odriozola

Guest Editors

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Keywords

  • structured catalysts and reactors
  • monoliths
  • foams
  • meshes
  • microreactors
  • microchannels
  • coating
  • catalytic layer
  • thermal properties

Published Papers (6 papers)

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Research

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20 pages, 10932 KiB  
Article
FeCrAlloy Monoliths Coated with Ni/Al2O3 Applied to the Low-Temperature Production of Ethylene
by Paula Brussino, Juan Pablo Bortolozzi, Oihane Sanz, Mario Montes, María Alicia Ulla and Ezequiel David Banús
Catalysts 2018, 8(7), 291; https://doi.org/10.3390/catal8070291 - 19 Jul 2018
Cited by 4 | Viewed by 4035
Abstract
This paper investigates the oxidative dehydrogenation of ethane to produce ethylene at low temperatures (500 °C) in metallic structured substrates. To check this point, the FeCrAlloy® monoliths with different channel sizes (289–2360 cpsi) were prepared. The monoliths were coated with a Ni/Al [...] Read more.
This paper investigates the oxidative dehydrogenation of ethane to produce ethylene at low temperatures (500 °C) in metallic structured substrates. To check this point, the FeCrAlloy® monoliths with different channel sizes (289–2360 cpsi) were prepared. The monoliths were coated with a Ni/Al2O3 catalyst (by washcoating of alumina and the latter nickel impregnation) and characterized by Scanning Electron Microscopy and Energy-Dispersive X-ray analysis (SEM-EDX), Temperature-Programmed Reduction (TPR), X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). The catalytic results showed that all monoliths coated with ~300 mg of catalyst presented similar ethane conversion (15%) at 450 °C. However, the lowest selectivity to ethylene was found for the monolith with the lower channel size and the higher geometric surface area, where a heterogeneous catalyst layer with Ni enriched islands was generated. Therefore, it can be said that the selectivity to ethylene is linked to the distribution of Ni species on the support (alumina). Nevertheless, in all cases the selectivity was high (above 70%). On the other hand, the stability in reaction tests of one of the coated monoliths was done. This structured catalyst proved to be more stable under reaction conditions than the powder catalyst, with an initial slight drop in the first 8 h but after that, constant activity for the 152 h left. Full article
(This article belongs to the Special Issue Structured and Micro-Structured Catalysts and Reactors)
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16 pages, 16440 KiB  
Article
Stacked Wire Mesh Monoliths for the Simultaneous Abatement of VOCs and Diesel Soot
by María Laura Godoy, Ezequiel David Banús, Oihane Sanz, Mario Montes, Eduardo Miró and Viviana Guadalupe Milt
Catalysts 2018, 8(1), 16; https://doi.org/10.3390/catal8010016 - 10 Jan 2018
Cited by 21 | Viewed by 7278
Abstract
Structured catalysts based on Pt,CeO2 deposited on stainless steel wire meshes were developed to build catalytic cartridges for the treatment of diesel exhaust gases. The cartridges were tested for the simultaneous combustion of volatile organic compounds (VOCs) and soot. To this end, [...] Read more.
Structured catalysts based on Pt,CeO2 deposited on stainless steel wire meshes were developed to build catalytic cartridges for the treatment of diesel exhaust gases. The cartridges were tested for the simultaneous combustion of volatile organic compounds (VOCs) and soot. To this end, n-hexane, acetyl acetate, and toluene were selected as probe molecules. Each of them were loaded together with real soot into the cartridges showing that while VOCs abatement takes place between 200 °C and 350 °C, soot combustion occurs in the 300–500 °C temperature range with an average maximum combustion rate at 420 °C. The catalytic cartridges were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Brunauer-Emmett-Teller (BET) techniques. The mechanical stability of the coatings was confirmed by the ultrasound method. Air permeability of the cartridges prepared with different mesh sizes was also measured and the results were correlated using the Payri equation. Full article
(This article belongs to the Special Issue Structured and Micro-Structured Catalysts and Reactors)
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3198 KiB  
Article
Novel Ni-Ce-Zr/Al2O3 Cellular Structure for the Oxidative Dehydrogenation of Ethane
by Juan Pablo Bortolozzi, Raquel Portela, Pedro Ávila, Viviana Milt and Eduardo Miró
Catalysts 2017, 7(11), 331; https://doi.org/10.3390/catal7110331 - 08 Nov 2017
Cited by 7 | Viewed by 5117
Abstract
A novel γ-alumina-supported Ni-Ce-Zr catalyst with cellular structure was developed for oxidative dehydrogenation of ethane (ODHE). First, powdered samples were synthesized to study the effect of both the total metal content and the Ce/Zr ratio on the physicochemical properties and performance of these [...] Read more.
A novel γ-alumina-supported Ni-Ce-Zr catalyst with cellular structure was developed for oxidative dehydrogenation of ethane (ODHE). First, powdered samples were synthesized to study the effect of both the total metal content and the Ce/Zr ratio on the physicochemical properties and performance of these catalysts. All synthesized powdered samples were highly active and selective for ODHE with a maximum ethylene productivity of 6.94 µmolethylene gact cat−1 s−1. According to the results, cerium addition increased the most reducible nickel species population, which would benefit ethane conversion, whereas zirconium incorporation would enhance ethylene selectivity through the generation of higher amounts of the least reducible nickel species. Therefore, the modification of active site properties by addition of both promoters synergistically increases the productivity of the Ni-based catalysts. The most efficient formulation, in terms of ethylene productivity per active phase amount, contained 15 wt% of the mixed oxide with Ni0.85Ce0.075Zr0.075 composition. This formulation was selected to synthesize a Ni-Ce-Zr/Al2O3 structured body by deposition of the active phase onto a homemade γ-alumina monolith. The structured support was manufactured by extrusion of boehmite-containing dough. The main properties of the Ni0.85Ce0.075Zr0.075 powder were successfully preserved after the shaping procedure. In addition, the catalytic performance of the monolithic sample was comparable in terms of ethylene productivity to that of the powdered counterpart. Full article
(This article belongs to the Special Issue Structured and Micro-Structured Catalysts and Reactors)
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1088 KiB  
Article
DeNOx Abatement Modelling over Sonically Prepared Copper USY and ZSM5 Structured Catalysts
by Przemysław J. Jodłowski, Łukasz Kuterasiński, Roman J. Jędrzejczyk, Damian Chlebda, Anna Gancarczyk, Sylwia Basąg and Lucjan Chmielarz
Catalysts 2017, 7(7), 205; https://doi.org/10.3390/catal7070205 - 06 Jul 2017
Cited by 17 | Viewed by 4550
Abstract
Metallic supports play an important role as structured reactor internals. Due to their specific properties including enhanced heat and mass transport, high mechanical resistivity and elimination of local hot-spots, they are commonly used in gas exhaust abatement from stationary and automotive industries. In [...] Read more.
Metallic supports play an important role as structured reactor internals. Due to their specific properties including enhanced heat and mass transport, high mechanical resistivity and elimination of local hot-spots, they are commonly used in gas exhaust abatement from stationary and automotive industries. In this study, the performance of three structured supports with deposited Cu/USY (Ultrastabilised Y—zeolite) for deNOx abatement were modelled. Based on kinetic and flow resistance experimental results, the one-dimensional (1D) model of structured reactor was developed. The performance of the structured reactors was compared by the length of the reactor necessary to achieve an arbitrary 90% NOx conversion. The performed simulations showed that the sonochemically prepared copper USY and ZSM-5 zeolites deposited on metallic supports may be successfully used as catalysts for deNOx process. Full article
(This article belongs to the Special Issue Structured and Micro-Structured Catalysts and Reactors)
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4749 KiB  
Article
In Search of Governing Gas Flow Mechanism through Metal Solid Foams
by Anna Gancarczyk, Marcin Piątek, Marzena Iwaniszyn, Przemysław J. Jodłowski, Joanna Łojewska, Jolanta Kowalska and Andrzej Kołodziej
Catalysts 2017, 7(4), 124; https://doi.org/10.3390/catal7040124 - 21 Apr 2017
Cited by 7 | Viewed by 4350
Abstract
Solid foams have been intensely studied as promising structured catalytic internals. However, mechanisms governing flow and transport phenomena within the foam structures have not been properly addressed in the literature. The aim of this study was to consider such flow mechanisms based on [...] Read more.
Solid foams have been intensely studied as promising structured catalytic internals. However, mechanisms governing flow and transport phenomena within the foam structures have not been properly addressed in the literature. The aim of this study was to consider such flow mechanisms based on our experimental results on flow resistance. Two mechanisms were considered: developing laminar flow in a short capillary channel (flow-through model), and flow around an immersed solid body, either a cylinder or sphere (flow-around model). Flow resistance experiments were performed on three aluminum foams of 10, 20, and 40 PPI (pores per inch), using a 57 mm ID test column filled with the foams studied. The foam morphology was examined using microtomography and optical microscopy to derive the geometric parameters applied in the model equations. The flow-through model provided an accuracy of 25% for the experiments. The model channel diameter was the foam cell diameter, and the channel length was the strut thickness. The accuracy of the flow-around model was only slightly worse (35%). It was difficult to establish the geometry of the immersed solid body (sphere or cylinder) because experiment characteristics tended to change from sphere to cylinder with increasing PPI value. Full article
(This article belongs to the Special Issue Structured and Micro-Structured Catalysts and Reactors)
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10361 KiB  
Review
Nano-Array Integrated Structured Catalysts: A New Paradigm upon Conventional Wash-Coated Monolithic Catalysts?
by Junfei Weng, Xingxu Lu and Pu-Xian Gao
Catalysts 2017, 7(9), 253; https://doi.org/10.3390/catal7090253 - 28 Aug 2017
Cited by 18 | Viewed by 6421
Abstract
The monolithic catalyst, namely the structured catalyst, is one of the important categories of catalysts used in various fields, especially in catalytic exhaust after-treatment. Despite its successful application in conventional wash-coated catalysts in both mobile and stationary catalytic converters, washcoat-based technologies are facing [...] Read more.
The monolithic catalyst, namely the structured catalyst, is one of the important categories of catalysts used in various fields, especially in catalytic exhaust after-treatment. Despite its successful application in conventional wash-coated catalysts in both mobile and stationary catalytic converters, washcoat-based technologies are facing multi-fold challenges, including: (1) high Pt-group metals (PGM) material loading being required, driving the market prices; (2) less-than ideal distribution of washcoats in typically square-shaped channels associated with pressure drop sacrifice; and (3) far from clear correlations between macroscopic washcoat structures and their catalytic performance. To tackle these challenges, the well-defined nanostructure array (nano-array)-integrated structured catalysts which we invented and developed recently have been proven to be a promising class of cost-effective and efficient devices that may complement or substitute wash-coated catalysts. This new type of structured catalysts is composed of honeycomb-structured monoliths, whose channel surfaces are grown in situ with a nano-array forest made of traditional binary transition metal oxide support such as Al2O3, CeO2, Co3O4, MnO2, TiO2, and ZnO, or newer support materials including perovskite-type ABO3 structures, for example LaMnO3, LaCoO3, LaNiO, and LaFeO3. The integration strategy parts from the traditional washcoat technique. Instead, an in situ nanomaterial assembly method is utilized, such as a hydro (solva-) thermal synthesis approach, in order to create sound structure robustness, and increase ease and complex-shaped substrate adaptability. Specifically, the critical fabrication procedures for nano-array structured catalysts include deposition of seeding layer, in situ growth of nano-array, and loading of catalytic materials. The generic methodology utilization in both the magnetic stirring batch process and continuous flow reactor synthesis offers the nano-array catalysts with great potential to be scaled up readily and cost-effectively. The tunability of the structure and catalytic performance could be achieved through morphology and geometry adjustment and guest atoms and defect manipulation, as well as composite nano-array catalyst manufacture. Excellent stabilities under various conditions were also present compared to conventional wash-coated catalysts. Full article
(This article belongs to the Special Issue Structured and Micro-Structured Catalysts and Reactors)
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