Catalytic membrane reactor for Suzuki‐Miyaura C−C cross‐coupling: Explanation for its high efficiency via modeling

A polymeric catalytic membrane was previously prepared that showed remarkable efficiency for Suzuki‐Miyaura C‐C cross‐coupling in a flow‐through configuration. A mathematic model was developed and fitted to the experimental data to understand the significant apparent reaction rate increase exhibited by the catalytic membrane reactor compared to the catalytic system under batch reaction conditions. It appears that the high palladium nanoparticles concentration inside the membrane is mainly responsible for the high apparent reaction rate achieved. In addition, the best performance of the catalytic membrane could be achieved only in the forced flow‐through configuration, that, conditions permitting to the reactants be brought to the catalytic membrane by convection. © 2016 American Institute of Chemical Engineers AIChE J, 63: 698–704, 2017     

Synthese von porösen Voll‐ und Core‐Shell‐Glaskugeln zur Trennung von chiralen Anästhetika

For the separation of chiral anesthetic gases suitable support materials for the selectors are necessary. Due to the controlled texture properties porous glass shows a high potential for such applications. In this study porous glass beads with particle diameters of 40 – 400 µm and 2 – 4 mm could be obtained via a special fluidized‐bed reactor and the method of ionotropic gelation. Furthermore, the first core‐shell beads on the basis of porous glasses could be synthesized via the combination of an ion‐exchange induced phase separation and a selective leaching step. The new materials are characterized by a defined mesoporous shell and a non‐porous glass core.     

Membrane reactor immobilized with palladium‐loaded polymer nanogel for continuous‐flow Suzuki coupling reaction

A catalytic membrane reactor, which was immobilized with palladium‐loaded nanogel particles (NPs), was developed for continuous‐flow Suzuki coupling reaction. Palladium‐loaded membranes were prepared by immobilization of NPs, adsorption of palladium ions, and reduction into palladium(0). The presence of palladium in the membrane was confirmed by the scanning electron microscopy; palladium aggregation was not observed. The catalytic activity of the membrane reactor in continuous‐flow Suzuki coupling reaction was approximately double that of a comparable reactor in which palladium ions were directly adsorbed onto an aminated membrane. This was attributed to the formation of small palladium particles. The reusability in the continuous‐flow system was higher than that in a batch system, and the palladium‐loaded membrane reactor had high long‐term stability. © 2014 American Institute of Chemical Engineers AIChE J, 61: 582–589, 2015     

Non‐thermal plasma degradation of dye using an underwater dielectric barrier discharge created inside a porous hydrophobic ceramic tube

An alternating‐current‐driven, atmospheric‐pressure, non‐thermal plasma reactor was applied to the degradation of dye in water. The plasma reactor, made of a porous hollow ceramic tube, was placed underwater and was able to disperse plasmatic gas containing various reactive species into aqueous dye solution as small bubbles through the micropores of the tube. The hydrophobic coating on the surface of the ceramic tube effectively prevented the water from permeating through it. This wastewater treatment system was able immediately to transfer plasmatic gas to aqueous solution across the porous ceramic tube and provide a large gas–liquid interfacial area, allowing efficient dye treatment. So as to simulate real dyeing wastewater, an aqueous solution comprising two different azo dyes was used. The effect of discharge power, treatment time, and flow rate of oxygen used for the creation of plasma was examined. The results suggest that this system may be useful for the treatment of organic wastewater.     

Magnetic emulation of microgravity for earth‐bound multiphase catalytic reactor studies—Potentialities and limitations

A method is proposed to generate Earth‐bound artificial microgravity in a controlled facility capable of emulating lunar/Martian gravity or microgravity for experiments on passive/reactive catalytic multiphase flows. Its applicability was illustrated for trickle beds where flowing gas and liquid experience artificial microgravity inside the bore of a superconducting magnet generating large gradient magnetic fields to compensate for gravity. Artificial gravity is realized by commuting into apparent gravity acceleration the magnetization force at work on common “chemical engineering” non‐magnetic fluids. The scaling property to be matched and maintained invariant in multiphase systems to achieve magnetic mimicry is phasic mass magnetic susceptibility. Hydrodynamic (liquid holdup, wetting efficiency, pressure drop) as well as catalytic reaction (conversion and selectivity) measurements were obtained. The main finding is a proof that magnetic fields affect reactor outcomes exclusively via hydrodynamic phenomena making them appealing proxies for emulating non‐terrene reactor applications. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Horizontal Dip‐Spin Casting of aqueous alumina‐polyvinylpyrrolidone suspensions with chopped fiber

A novel ceramic processing method, called Horizontal Dip Spin Casting (HDSC), enabled fabrication of tubular ceramic parts with an aligned chopped fiber phase. HDSC was demonstrated using highly loaded aqueous alumina suspensions with >50 vol.% solids loading and ≤5 vol.% water‐soluble polymer employed as a rheological modifier. Chopped carbon fibers were added to the suspensions to attain maximum loadings of 30 vol.%. During forming, cylindrical foam molds were dipped into the suspension while being rotated radially about the long axis. Simultaneously, a doctor blade was placed at a specified distance from the foam surface to facilitate the flow of the suspension to align the fiber and control the thickness of the material that accrued on the mold. Rheological study of alumina‐PVP suspensions with and without chopped carbon fiber showed that the suspensions exhibited a yield‐pseudoplastic flow behavior. The degree of alignment of the carbon fiber phase in the green bodies was characterized for various suspension formulations, carbon fiber contents and forming speeds. Stereological characterization of green body specimens confirmed the effectiveness of HDSC to attain the desired tubular geometry with considerable fiber alignment for a suspension composition containing ≤20 vol.% chopped fibers.     

3D‐foam‐structured nitrogen‐doped graphene‐Ni catalyst for highly efficient nitrobenzene reduction

We report the preparation of a porous 3D‐foam‐structured nitrogen‐doped graphene‐Ni (NG/NF) catalyst and the evaluation of its performance in the reduction of nitrobenzene (NB) through detailed studies of the kinetics. The NG/NF catalyst showed a significantly higher reaction rate than pure Ni foam (NF). Moreover, the separation of the 3D‐foam‐structured catalyst from the products was more convenient than that of NG powdered catalysts. The obtained kinetics data fit well to the Langmuir‐Hinshelwood model, with an error ratio below 10%. Density functional theory (DFT) calculations indicated that the adsorption of sodium borohydride (NaBH₄) on the NG/NF surface was stronger than that of NB, which strongly agreed with the kinetic parameters determined from the Langmuir‐Hinshelwood model. The excellent catalytic efficiency of the 3D‐foam‐structured catalyst combined with the knowledge of the kinetics data make this catalyst promising for application in larger scale nitrobenzene reduction. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1330–1338, 2018     

Micro‐structured Bi1.5Y0.3Sm0.2O3−δ catalysts for oxidative coupling of methane

Bi_1.5Y_0.3Sm_0.2O_3?δ (BYS), a ceramic material showing great activity and selectivity to oxidative coupling of methane (OCM), has been fabricated into catalyst rings (i.e., capillary tubes) with a plurality of self‐organized radial microchannels. The unique microchannels inside such BYS catalyst rings allow easier access of reactants, as well as increased the surface area, which potentially contributes to higher reaction efficiencies due to improved mass transfer. The micro‐structured BYS catalyst rings were investigated systematically via two types of reactors; (1) randomly packed fixed bed reactor and (2) monolithic‐like structured reactor. These two reactor designs have different flow patterns of reactants, that is, non‐ideal and ideal flows, which can significantly affect the final OCM performance. A remarkable improvement in C₂₊ yield (Y_C2+ > 20%) was obtained in the monolith‐like structured reactor, in contrast to randomly packed powder and micro‐structured rings (Y_C2+ < 15%), which proves the advantages of using a micro‐structured catalyst with an ideal flow in the feed for OCM. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3451–3458, 2015     

Multi‐phase electro‐chemical catalytic oxidation of wastewater

The removal of organic pollutants from synthetic wash wastewater by a combined multi‐phase electro‐catalytic oxidation method was evaluated using porous graphite as anode and cathode, and CuO–Co₂O₃–PO₄^3? modified kaolin as catalyst. The synergic effect on COD removal was studied when integrating the electro‐chemical reactor with the effective modified kaolin in a single undivided cell; the results showed that higher COD removal efficiency was obtained than those obtained using the individual processes. Under optimal conditions of pH 3, 30 mA cm^?2 current density, very effective reduction of organic pollutants was achieved with this combined electro‐chemical method. High removal efficiency (90%) of the chemical oxygen demand (COD) was obtained in 60 min in the treatment of simulated wash wastewater (anionic surfactant, sodium dodecyl benzene sulfonate [DBS]). This method was also applied to treat wastewater form paper‐making and resulted in a COD reduction of 84%. Based on the investigation, a possible mechanism of this combined electro‐chemical process was proposed. The pollutants in wastewater could be decreased by the high reactive OH? that were produced via the decomposition of electro‐generated H₂O₂ activated by the synergic effect of electro‐field and catalyst. The results indicate that the multi‐phase catalytic electro‐chemical oxidation process is a promising technique for wastewater treatment. Copyright © 2006 Society of Chemical Industry     

Chemical kinetic modeling of i‐butane and n‐butane catalytic cracking reactions over HZSM‐5 zeolite

A chemical kinetic model for i‐butane and n‐butane catalytic cracking over synthesized HZSM‐5 zeolite, with SiO₂/Al₂O₃ = 484, and in a plug flow reactor under various operating conditions, has been developed. To estimate the kinetic parameters of catalytic cracking reactions of i‐butane and n‐butane, a lump kinetic model consisting of six reaction steps and five lumped components is proposed. This kinetic model is based on mechanistic aspects of catalytic cracking of paraffins into olefins. Furthermore, our model takes into account the effects of both protolytic and bimolecular mechanisms. The Levenberg–Marquardt algorithm was used to estimate kinetic parameters. Results from statistical F‐tests indicate that the kinetic models and the proposed model predictions are in satisfactory agreement with the experimental data obtained for both paraffin reactants. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2456–2465, 2012     

Preparation Method for Ruthenium Catalysts Supported by Carbon‐Coated Aluminum Foams

A preparation method is proposed for coating aluminum and aluminum alloy foams with a porous carbon layer for application as a catalyst support. The polymerization of furfuryl alcohol with diluted oxalic acid was used as precursor for the carbon layer. The polymer layer was distributed by applying centrifugal forces via spinning foam substrates during the polymerization process to prevent clogging and for homogeneous growth of the polymer layer. A homogeneous deposition precipitation method was applied for incorporation of ruthenium on carbon‐coated foam substrates. The carbon coating was characterized by X‐ray tomography to measure the thickness distribution. The specific surface and pore volume distribution were determined by gas adsorption (BET) and mercury porosimetry. The prepared Ru/C foam catalysts were adopted as a stirrer in a rotating foam reactor for hydrogenation of glucose, a simple biomass model substance.     

Producing Large Complex‐Shaped Ceramic Particle Stabilized Foams

Highly porous ceramic foams can be produced by combining particle stabilized foams and gelcasting concepts. Sulfonate‐type surfactants are selected to weakly hydrophobize the alumina surface and stabilize air bubbles in suspensions containing gelcasting additives, polyvinyl alcohol (PVA), and 2,5‐dimethoxy‐2,5‐dihydrofurane (DHF). The aim of this work was to prepare large complex‐shaped ceramic foam objects with homogeneous microstructure and high porosity. A key to avoiding drying cracks is to strengthen the wet green body via gelcasting. The influence of the amount of gelcasting additives on the mechanical strength of the ceramic foam green bodies is investigated as well as the effect of using cross‐linking agent versus the addition of just a binder. The presence of a cross‐linked polymeric network within the green body increases its mechanical strength and minimizes crack formation during drying.     

Droplet Micro‐Reactor for Internal Gelation to Fabricate ZrO2 Ceramic Microspheres

A droplet micro‐reactor was developed to realize the internal sol–gel reaction of ZrO₂ inside the droplet. The reactants are only allowed to combine when the droplet forms, meanwhile, they are able to mix well and react to form gel particles with a proper designed structure of the micro‐reactor. In this condition, the mixing efficiency was determined by the structure of the micro‐reactor and the flow rate ratio of the two components. After sintering, ZrO₂ ceramic microspheres are acquired with high sphericity and narrow size distribution. This droplet micro‐reactor overcomes the gelation of the premixed sol and reactant in the channel, and it has been demonstrated to be more stable with a longer running time.     

Performance of silicon‐carbide foams as supports for Pd‐based methane combustion catalysts

BACKGROUND: Cellular foam materials are a new type of catalyst support that provides improved mass and heat transport characteristics and similar pressure drops to other well‐established structured supports such as monoliths. RESULTS: A Pd‐based catalyst has been prepared using a moderate surface area (25 m² g^?1) β‐SiC foam support without further washcoating. The stability of this catalyst has been tested for methane combustion at lean conditions, showing a small decrease of activity during the first 10 h followed by stable performance. Characterization of fresh and aged catalyst shows no significant changes. The influence of the most important reaction conditions, such as reactor loading (0.25–1 g), temperature (300–550 °C) and inlet methane concentration (833 and 1724 ppm), was studied in a fixed‐bed reactor. The results were fitted to three kinetic models: Mars‐van Krevelen; Langmuir‐Hinselwood; power‐law kinetics. CONCLUSIONS: The Pd/β‐SiC foam catalyst, prepared without the previous addition of a washcoating has been demonstrated to be stable for the combustion of methane‐air lean mixtures. A Mars‐van Krevelen kinetic model provides the best fit to the results obtained. Copyright © 2011 Society of Chemical Industry     

Nanoparticle formation through solid‐fed flame synthesis: Experiment and modeling

The preparation of silica nanoparticles through solid‐fed flame synthesis was investigated experimentally and theoretically. Monodispersed submicrometer‐ and micrometer‐sized silica powders were selected as solid precursors for feeding into a flame reactor. The effects of flame temperature, residence time, and precursor particle size were investigated systematically. Silica nanoparticles were formed by the nucleation, coagulation, and surface growth of the generated silica vapors due to the solid precursor evaporation. Numerical modeling was conducted to describe the mechanism of nanoparticle formation. Evaporation of the initial silica particles was considered in the modeling, accounting for its size evolution. Simultaneous mass transfer modeling due to the silica evaporation was solved in combination with a general dynamics equation solution. The modeling and experimental results were in agreement. Both results showed that the methane flow rate, carrier gas flow rate, and initial particle size influenced the effectiveness of nanoparticle formation in solid‐fed flame synthesis. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

催化型多孔陶瓷球制备及催化玉米秸秆热解

针对生物质热解液化过程中生物油品质差的问题,本文以陶瓷球作热载体为研究基础,制备了5种负载金属氧化物（ZnO、NiO、CeO₂、Cr₂O₃、Fe₂O₃）的多孔陶瓷球,在固定床反应器上研究多孔陶瓷球催化剂对玉米秸秆热解过程的催化效果。结果表明：多孔陶瓷球基体在热解过程中有一定催化活性,经浸渍改性处理后,都能促进生物油产率的提高,其中Ni基多孔陶瓷球热解的产率高达41.62%。多孔陶瓷球负载的5种金属氧化物可促使生物油中酚类、呋喃类物质的含量明显增加,酸类物质的含量明显降低,且种类减少,其中CeO₂降酸效果显著,降低幅度为37.15%。此外,催化型多孔陶瓷球的引入促进了不可冷凝气中C _n H _m （n≥2）的生成,烯烃类中乙烯的增长幅度最大,为50.53%,同时生物炭的理化特性在一定程度上得到改善和提高。     

Heat‐resistant hydrophobic–oleophobic coatings

Thermally and chemically durable hydrophobic oleophobic coatings, containing different ceramic particles such as SiO₂, SiC, Al₂O₃, which can be alternative instead of Teflon, have been developed and applied on the aluminum substrates by spin‐coating method. Polyimides, which are high‐thermal resistant heteroaromatic polymers, were synthesized, and fluor oligomers were added to these polymers to obtain hydrophobic–oleophobic properties. After coating, Al surface was subjected to Taber‐abrasion, adhesion, corrosion, and thermal tests. The effects of the particle size of ceramic powders, organic matrix, and heat on the coating material were investigated. Coating material was characterized by FTIR spectrophotometer. Surface properties and thermal resistance of the coating materials were investigated by SEM and TGA analyses. After thermal curing, contact angles of these coatings with H₂O and n‐hexadecane were measured. It was observed that coatings like ceramic particles are more resistant against scratch and abrasion than the other coatings. Also, they are harder than coatings, which do not include ceramic particles. It was seen that coatings, containing Fluorolink D10H, have high‐contact angles with water and n‐hexadecane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2386–2392, 2006     

A novel method based on ultrastable foam and improved gelcasting for fabricating porous mullite ceramics with thermal insulation–mechanical property trade-off

Foam instability and long drying cycle limits the widespread use of foaming method. In this paper, a kind of porous mullite ceramic with thermal insulation–mechanical property trade-off were fabricated via novel ultrastable foam and improved gelcasting procedure. The solidification process and stability of foam slurry, as well as the thermal, mechanical property and pore structure of the porous mullite ceramics were investigated. The results showed that porous mullite ceramics with different bulk densities could be prepared via varying volume of foam which was stable enough to be maintained in slurry for a long time. The accelerated gelation rate as well as the gelation degree resulted in the improved gelcasting method led to a shortened period of drying and demould. The obtained pores, which were small, smooth, and unimodal distributed in size in porous mullite ceramics, contributed to achieving the trade-off between thermal insulation and mechanical property.     

Nano‐hydroxyapatite (HAp) and hydroxyapatite/platinum (HAp/Pt) core shell nanorods: Development,structural study,and their catalytic activity

The development of a new kind of material that is a nanostructured catalytic material with an environmentally benign nature that can be used for alternative energy has acquired significance in recent years. In this context, the use of heterogeneous catalysts for the transesterification of vegetable oils has gained prominence due to their eco‐friendly and reusable nature. Hence in the present study, pure hydroxyapatite (HAp) and hydroxyapatite/platinum (HAp/Pt) nanostructured particles have been prepared successfully through a facile chemical method without templates and surfactants and their catalytic activity investigated for transesterification of natural vegetable oil to bioenergy (biodiesel). The textural and structural features of pure HAp and HAp/Pt were investigated using various characterization techniques such as x‐ray diffraction, Fourier transform infrared (FTIR) and Raman spectroscopy, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). The elements present in the prepared nanostructures were confirmed through energy dispersive spectroscopy (EDS) and x‐ray photoelectron spectroscopy (XPS) techniques. The XPS analysis also confirms the metallic nature of the platinum in HAp/Pt. The specific surface area and porous nature of the prepared nanostructured catalysts were studied using the N₂ physisorption Brunauer‐Emmett‐Teller‐Barrett‐Joyner‐Halenda (BET‐BJH) method. The catalytic activity of the pure HAp nanoparticles and HAp/Pt core shell nanorods with the Simarouba glauca plant seed oil was investigated. The obtained results indicate that the pristine HAp nanoparticles and HAp/Pt core shell nanorods (NRs) show 91.4% and 87.1% fatty acid methyl ester (FAME) conversion, respectively, potentially offering environmental benign biocatalysts for biofuel production from natural feed stock.