Model Of Catalytic Reactor Research Articles

The Facile Dissociation of Carbon–Oxygen Bonds in CO2and CO on the Surface of LaCoSiHxIntermetallic Compound

AbstractIn catalysis science, the electronic structure of the active site determines the structure–activity relationship of the catalyst to a large extent. Therefore, modulating the electronic structure has become a main route for the rational design of metal‐based catalyst materials. In this work, we prepared a LaCoSiHxmaterial that has more electronegativity and a lower workfunction than traditional supported Co‐based catalysts. Using CO2methanation as a model catalytic reaction, the facile dissociation of CO2and CO (a key reaction intermediate) on the surface of the LaCoSiHxcatalyst is observed by various experimental methods (e.g., in situ Raman and FTIR) at room temperature. Moreover, theoretical calculation results further show that LaCoSiHxhas a much stronger capacity for carbon–oxygen bond activation than the Co surface. The intrinsic mechanism is attributed to the marked electron transfer from catalysts into the antibonding orbital of CO2and CO.

Noisy multistate voter model for flocking in finite dimensions.

We study a model for the collective behavior of self-propelled particles subject to pairwise copying interactions and noise. Particles move at a constant speed v on a two-dimensional space and, in a single step of the dynamics, each particle adopts the direction of motion of a randomly chosen neighboring particle within a distance R=1, with the addition of a perturbation of amplitude η (noise). We investigate how the global level of particles' alignment (order) is affected by their motion and the noise amplitude η. In the static case scenario v=0 where particles are fixed at the sites of a square lattice and interact with their first neighbors, we find that for any noise η>0 the system reaches a steady state of complete disorder in the thermodynamic limit, while for η=0 full order is eventually achieved for a system with any number of particles N. Therefore, the model displays a transition at zero noise when particles are static, and thus there are no ordered steady states for a finite noise (η>0). We show that the finite-size transition noise vanishes with N as η_{c}^{1D}∼N^{-1} and η_{c}^{2D}∼(NlnN)^{-1/2} in one- and two-dimensional lattices, respectively, which is linked to known results on the behavior of a type of noisy voter model for catalytic reactions. When particles are allowed to move in the space at a finite speed v>0, an ordered phase emerges, characterized by a fraction of particles moving in a similar direction. The system exhibits an order-disorder phase transition at a noise amplitude η_{c}>0 that is proportional to v, and that scales approximately as η_{c}∼v(-lnv)^{-1/2} for v≪1. These results show that the motion of particles is able to sustain a state of global order in a system with voter-like interactions.

Lattice Boltzmann model with generalized wall boundary conditions for arbitrary catalytic reactivity.

A lattice Boltzmann model for multispecies flows with catalytic reactions is developed, which is valid from very low to very high surface Damköhler numbers (Da_{s}). The previously proposed model for catalytic reactions [S. Arcidiacono, J. Mantzaras, and I. V. Karlin, Phys. Rev. E 78, 046711 (2008)PLEEE81539-375510.1103/PhysRevE.78.046711], which is applicable for low-to-moderate Da_{s} and encompasses part of the mixed kinetics and transport-controlled regime, is revisited and extended for the simulation of arbitrary kinetics-to-transport rate ratios, including strongly transport-controlled conditions (Da_{s}→∞). The catalytic boundary condition is modified by bringing nonlocal information on the wall reactive nodes, allowing accurate evaluation of chemical rates even when the concentration of the deficient reactant at the wall becomes vanishingly small. The developed model is validated against a finite volume Navier-Stokes CFD (Computational Fluid Dynamics) solver for the total oxidation of methane in an isothermal channel-flow configuration. CFD simulations and lattice Boltzmann simulations with the old and new catalytic reaction models are compared against each other. The new model demonstrates a second order accuracy in space and time and provides accurate results at very high Da_{s} (∼10^{9}) where the old model fails. Moreover, to achieve the same accuracy at moderate-to-high Da_{s} of O(1), the new model requires ∼2^{d}×N coarser grid than the original model, where d is the spatial dimension and N the number of species.

Single-Atom Ni Heterogeneous Catalysts Supported UiO-66 Structure: Synthesis and Catalytic Activities

Herein, the single-atom Ni site heterogeneous catalysts supported by the UiO-66 structure (University of Oslo-66 metal organic framework) were successfully synthesized by a postsynthetic metalation method, where Ni ions are covalently attached to the missing-linker defect sites at zirconium oxide clusters (Zr6O4(OH)4) in as-prepared UiO-66 structure, [Zr6O4(OH)4(BDC)(DMF)10(OH)10] (BDC (benzene-1,4-dicarboxylate), DMF (dimethylformamide)). The structure properties of the catalysts were characterized using powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), N2 adsorption-desorption isotherms (BET), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). It was found that single-atom Ni heterogeneous catalysts supported by the UiO-66 structure, UiO-66/Ni1.0 [Zr6O4(OH)4(C8H4O4)(DMF)10(OH)8Ni2(OH)2(Cl)2], showed a sphere-like morphology with a high specific surface area as well as good thermal stability. Specifically, the as-prepared UiO-66/Ni1.0 exhibited the excellent catalytic activity and stability for 4-nitrophenol reduction in terms of low activation energy ( E a = 23.15 kJ mo l − 1 ), high turnover frequency (76.19 molecules g-1 min-1), and high apparent rate constant ( k app = 0.956 mi n − 1 ). In addition, methylene blue (MB) was also chosen as the organic dye model for catalytic reduction reaction. The k app and TOF for the reduction of MB using UiO-66/Ni1.0 were 0.787 min−1 and 33.89 × 10 20 molecules g−1 min−1, respectively.

Numerical simulations of dead zone formation in the catalytic flow-through membrane reactor

The use of catalytic membranes in chemical reactor engineering has significantly improved the reactor performance. Therefore, mathematical modelling and numerical simulations of catalytic membrane reactors are important for optimal parameter design increasing the selectivity and yield of certain products in chemical reactions. In this paper, the mathematical model of the flow-through catalytic membrane reactor is based on coupled nonlinear convection-diffusion-reaction equations with temperature-dependent reaction rate constants. The series reactions in the reactor are characterized by the power-law kinetics of fractional order which until now has been rarely investigated in the literature. Under specific reaction and process conditions the reactant can be depleted and a dead-zone can be formed in the membrane reactor. The numerical simulation of this phenomenon requires special solvers. The key idea of this work is to construct an appropriate time-marching scheme for solving the steady-state model equations. The effects of parameters such as reaction order, Peclet number, and Thiele modulus on solution profiles and formation of dead-zones are studied numerically. The simulation results show how these parameters influence the appearance and size of the dead zone for the non-isothermal multi-reaction systems.

Ignition–extinction analysis of catalytic reactor models

Abstract A detailed analysis of the ignition–extinction and hysteresis behavior of the two widely used catalytic reactor models (packed-bed and monolith) for the case of a single exothermic reaction is presented. First, limiting models are used to determine the minimum adiabatic temperature rise and/or catalyst activity needed to observe hysteresis behavior. Next, explicit expressions are provided for estimating the feed temperature or space time at ignition (light-off) and extinction (blow-out) as a function of the adiabatic temperature rise (or inlet concentration of limiting reactant), effective thermal conductivity, time and length scales (reactor, tube/channel diameter, effective diffusion length and pore size), catalyst activity (or dilution) and heat loss. It is shown that various limiting reactor models such as the thin-bed, long-bed, lumped thermal, adiabatic and strongly cooled cases that are defined in terms of various inter- and intraphase heat and mass dispersion time scales can be used to derive scaling relations that are useful in predicting the ignition/extinction loci for both laboratory scale (with heat exchange) and large scale (near adiabatic) reactors.

Parameter estimation in kinetic models of complex heterogeneous catalytic reactions using Bayesian statistics

Kinetic analysis of the gas-phase and liquid phase hydrogenation of toluene to methylcyclohexane on Ni catalysts was performed. For complex reaction mechanisms comprising several kinetically significant steps, nonlinear regression, while giving an adequate description of experimental data, leads to kinetic parameters which are poorly defined. The approach based on Bayesian statistics allows identification of the values of such parameters which are the most statistically probable.

Synthesis of Air-Stable Cu Nanoparticles Using Laser Reduction in Liquid

We report the synthesis of air-stable Cu nanoparticles (NPs) using the bottom-up laser reduction in liquid method. Precursor solutions of copper acetlyacetonate in a mixture of methanol and isopropyl alcohol were irradiated with femtosecond laser pulses to produce Cu NPs. The Cu NPs were left at ambient conditions and analyzed at different ages up to seven days. TEM analysis indicates a broad size distribution of spherical NPs surrounded by a carbon matrix, with the majority of the NPs less than 10 nm and small numbers of large particles up to ∼100 nm in diameter. XRD collected over seven days confirmed the presence of fcc-Cu NPs, with some amorphous Cu2O, indicating the stability of the zero-valent Cu phase. Raman, FTIR, and XPS data for oxygen and carbon regions put together indicated the presence of a graphite oxide-like carbon matrix with oxygen functional groups that developed within the first 24 h after synthesis. The Cu NPs were highly active towards the model catalytic reaction of para-nitrophenol reduction in the presence of NaBH4.

Magnetic Actuation of Hollow Swarming Spheres for Dynamic Catalysis.

Untethered robots with smart human-machine interactions can execute complex activities such as target cargo delivery or assembly of functional scaffolds. However, it remains challenging for fabricating microscale hollow hydrogel robots that can go with autonomous transformation of their geometric formations to adapt to unstructured environments. We herein report hydrogel-based microscopic hollow swarming spheres (HSSs) with anisotropic/isotropic alignments of Fe3O4 particles in the porous wall that can navigate under complex topography conditions by altering their geometric formation, including passing around or jumping over obstacles, assembling into various formation patterns, and swimming in a high-viscosity system. We introduce HSSs into a catalytic reaction model, in which HSSs as a catalyst can shift between water and oil phases to initiate or terminate the decomposition reaction of H2O2. This dynamic catalysis is expected to construct free-radical "living" polymerization for controlling the reaction rate and polymer dispersity index in the future.

Quest for an Efficient 2-in-1 MOF-Based Catalytic System for Cycloaddition of CO2 to Epoxides under Mild Conditions.

We have devised a straightforward tandem postsynthetic modification strategy for Zr-based metal–organic framework (MOF) materials, which resulted in a series of well-defined 2-in-1 heterogeneous catalysts, cat1–cat8, exhibiting high catalytic activity in the synthesis of cyclic carbonates under solvent-free and co-catalyst-free conditions. The materials feature precisely located co-catalyst moieties decorating the metal nodes throughout the bulk of the MOF and yield cyclic carbonates with up to 99% efficiency at room temperature. We use diffuse reflectance infrared Fourier transform (DRIFT) and solid-state nuclear magnetic resonance (NMR) measurements to elucidate the role of each component in this model catalytic reaction. Establishing a method to precisely control the co-catalyst loading allowed us to observe the cooperativity between Lewis acid sites and the co-catalyst in the 2-in-1 heterogeneous system.

Mild oxidative functionalization of cycloalkanes catalyzed by novel dicopper(II) cores

The search for new transition metal based catalytic systems that are active in the oxidative functionalization of such inert substrates as saturated hydrocarbons continues to be an important research direction in molecular catalysis. In the present study, two new copper(II) coordination compounds, namely a discrete dimer [Cu2(μ-H2tea)2(nfa)2]·2H2O (1) and a 1D coordination polymer [Cu2(μ-H2tea)2(μ-Htma)]n·4nH2O (2) were synthesized and applied as homogeneous catalysts for the mild oxidative functionalization of cycloalkanes (cyclopentane, cyclohexane, cycloheptane, and cyclooctane). Both products 1 and 2 were self-assembled in aqueous medium from copper(II) nitrate, triethanolamine (H3tea), sodium hydroxide, and 2-naphthoic (Hnfa) or trimesic (H3tma) acids, isolated as stable crystalline solids, and fully characterized by standard methods including single-crystal X-ray diffraction. Their structures feature a similar type of dicopper(II) triethanolaminate cores that are decorated by terminal or bridging aromatic carboxylate ligands. Two model catalytic reactions were investigated, namely the oxidation of cycloalkanes by H2O2 to produce cycloalkyl hydroperoxides as intermediate products and then a mixture of cyclic alcohols and ketones as final products, and the carboxylation of cycloalkanes with CO/S2O82−/H2O to form cycloalkanecarboxylic acids as main products. These model reactions undergo under very mild conditions (50−60 °C) and show good efficiency. Substrate scope, selectivity features, and the effects of reaction parameters were investigated and discussed in detail. This study widens the family of multicopper(II) cores capable of catalyzing the oxidative functionalization of saturated hydrocarbons under mild conditions.

Software complex for modeling and optimization of chemical processes kinetics

A program is designed to optimize chemical reactions, allowing to carry out modeling and optimization of catalytic reactions has been developed. Implemented export and import of the reaction model and calculation of the direct kinetic problem. As an object of study, the catalytic reaction of the synthesis of benzyl butyl ether is considered. A mathematical reaction model is given and the concentrations of all reaction components are calculated.

Synthesis and Characterization of Ni-Pt Alloy Thin Films Prepared by Supercritical Fluid Chemical Deposition Technique

Ni-Pt alloy thin films have been successfully synthesized and characterized; the films were prepared by the supercritical fluid chemical deposition (SFCD) technique from Ni(hfac)2·3H2O and Pt(hfac)2 precursors by hydrogen reduction. The results indicated that the deposition rate of the Ni-Pt alloy thin films decreased with increasing Ni content and gradually increased as the precursor concentration was increased. The film peaks determined by X-ray diffraction shifted to lower diffraction angles with decreasing Ni content. The deposited films were single-phase polycrystalline Ni-Pt solid solution and it exhibited smooth, continuous, and uniform distribution on the substrate for all elemental compositions as determined by scanning electron microscopy and scanning transmission electron microscopy analyses. In the X-ray photoelectron spectroscopy (XPS) analysis, the intensity of the Pt 4f peaks of the films decreased as the Ni content increased, and vice versa for the Ni 2p peak intensities. Furthermore, based on the depth profiles determined by XPS, there was no evidence of atomic diffusion between Pt and Ni, which indicated alloy formation in the film. Therefore, Ni-Pt alloy films deposited by the SFCD technique can be used as a suitable model for catalytic reactions due to their high activity and good stability for various reactions.

One-pot three-step mechanically assisted synthesis and catalytic performance of tripodal metallic complexes

All-green matters. Synthesis of the ligand and metal–ligand complexes and a model catalytic oxidation reaction can be sequentially processed under solventless conditions using a planetary ball mill, via fast, high yielding and selective processes.

Analysis of Periodic Solution of DNA Catalytic Reaction Model With Random Disturbance

The realization of molecular logic circuit is inseparable from the design and analysis of catalytic reaction chain, and the DNA catalytic gate plays an important role in it. Discuss the nature of the solution to DNA catalytic reaction system, using Khasminskii's periodicity and Lyapunov analysis methods to obtain the existence of non-trivial positive periodic solutions of the system, and the solution is globally attractive. The existence of the solution indicates that according to the mathematical model established by the DNA catalytic reaction system, the system may reach the expected concentration value of an ideal state and obtain better reaction data, which provides a theoretical basis for the realization of the DNA catalytic gate function. Numerical simulation results show that under the influence of random disturbance and periodic parameters, the solution to the random DNA catalytic reaction system exists and is globally attractive, which also reflects that the DNA catalytic reaction system can reach an ideal reaction state. The solution to the DNA catalytic system with random disturbance will converge on a certain value and oscillate periodically between the solution to the deterministic system.

Mechanistic modeling and numerical simulation of axial flow catalytic reactor for naphtha reforming unit.

Naphtha catalytic reforming (NCR) process has been of tremendous attention all over the world owing to the significant requirement for high-quality gasoline. Industrialized naphtha reforming unit at oil refineries applies a series of fixed bed reactors (FBRs) to improve the quality of the low-octane hydrocarbons and convert them to more valuable products. The prominent purpose of this research is to understand the catalytic reactor of naphtha reforming unit. For this aim, an appropriate mechanistic modeling and its related CFD-based computational simulation is presented to predict the behavior of the system when the reactors are of the axial flow type. Also, the triangular meshing technique (TMT) is performed in this paper due to its brilliant ability to analyze the results of model’s predictions along with improving the computational accuracy. Additionally, mesh independence analysis is done to find the optimum number of meshes needed for reaching the results convergence. Moreover, suitable kinetic and thermodynamic equations are derived based on Smith model to describe the NCR process. The results proved that the proceeding of NCR process inside the reactor significantly increased the concentration amount of aromatic materials, lighter ends and hydrogen, while deteriorated the concentration amount of naphthene and paraffin. Moreover, the pressure drop along the reactor length was achieved very low, which can be considered as one of the momentous advantages of NCR process.

Complex Modelling and Design of Catalytic Reactors Using Multiscale Approach—Part 2: Catalytic Reactions Modelling with Cellular Automata Approach

The presented work is devoted to reactions of obtaining 4,4’-Diaminodiphenylmethane (MDA) in the presence of a catalyst model. The work describes the importance of studying the MDA obtaining process and the possibility of the cellular automata (CA) approach in the modelling of chemical reactions. The work suggests a CA-model that makes it possible to predict the kinetic curves of the studied MDA-obtaining reaction. The developed model was used to carry out computational experiments under the following different conditions—aniline:formaldehyde:catalyst ratios, stirrer speed, and reaction temperature. The results of computational experiments were compared with the corresponding experimental data. The suggested model was shown to be suitable for predicting MDA-obtaining reaction kinetics. The proposed CA model can be used with the CFD model, suggested in Part 1, allowing the implementation of complex multiscale modeling of a flow catalytic reactor from the molecule level to the level of the entire apparatus.

Thiazoline‐Iridium (III) Complexes and Immobilized Nanomaterials as Selective Catalysts in N‐Alkylation of Amines with Alcohols

In this research, a new series of thiazoline‐iridium (III) complexes (4–7) derived from cysteine were prepared and fully characterized by conventional methods. The molecular structure of complex 5 was also determined by single‐crystal X‐ray diffraction. These complexes were evaluated as catalysts for hydrogen‐borrowing reactions of amines with alcohols. In particular, complex 5 showed the best activity as catalyst. Various amines have been alkylated with alcohols affording moderate to good yield (33–99%). Moreover, the immobilized nanomaterials (M1,2) were fabricated by sonication process from the best catalyst 5 with the multi‐walled carbon nanotubes (MWCNTs) and graphene oxide (GO), respectively, and characterized by X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) spectroscopy, field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray (EDX) spectroscopy, and inductively coupled plasma‐mass spectrometry (ICP‐MS). The M1,2 nanomaterials were also tested as catalysts in model catalytic reaction for N‐alkylation. The M1 nanomaterial showed significantly higher activity than the M2 nanomaterial. The M1 catalyst was recovered by filtration and reused for four catalytic cycles with high conversion (99%, 97%, 96%, and 86%).

CFD Simulation of a Hydrogen-Permeable Membrane Reactor for CO2 Reforming of CH4: The Interplay of the Reaction and Hydrogen Permeation

A symmetric 2D CFD model of catalytic membrane reactor for dry reforming of methane (DRM) was built up. Nondimensionalization method was employed and the governing equations were simplified. Crucia...

Role of chemical reactions in the stagnation point heat flux of rarefied hypersonic cylinder flows

This work investigates the variations of the stagnation point heat flux (SPHF) in hypersonic cylinder flows using the direct simulation Monte Carlo method, with the consideration of a constant freestream Knudsen number but different cylinder diameters. Four different freestream Mach numbers and the accompanying chemical reactions are considered. The result reveals a high-density effect in chemical reactions inside the thermal boundary layer, which induces an increasingly rising SPHF with a decreased cylinder diameter for all the cases. The cases at Ma∞ = 30 exhibit a characteristic of peculiarity that the value of SPHF increases the fastest, which is strongly correlated with the different high-density effects at different Ma∞. Further analysis demonstrates that the NO dissociation and recombination reactions always play a vitally important role in the high-density effect. A secondary NO dissociation reaction was observed inside the thermal boundary layer when Ma∞ > 30. This observation is the result of the shift of chemical equilibrium induced by violent recombination reaction and sufficiently high flow temperature. Subsequently, the newly emerging secondary dissociation reaction weakens the influence of recombination reaction; thus, the growth of SPHF at a high Mach number is not so strong as that with Ma∞ ≤ 30. Furthermore, in order to provide more reliable results, additional simulations are discussed by employing the widely accepted total collision energy and catalytic surface reaction models.