Influence of Substrate Concentration on Kinetic Parameters of Ethanol Dehydration in MFI and CHA Zeolites and Relation of These Kinetic Parameters to Acid–Base Properties

The catalytic activity of zeolites is often related to their acid–base properties. In this work, the relationship between the value of apparent activation energy of ethanol dehydration, measured in a fixed bed reactor and by means of a temperature-programmed surface reaction (TPSR) depending on the amount of ethanol in the zeolite lattice and the value of activation energy of H/D exchange as a measure of acid–base properties of MFI and CHA zeolites, was studied. Tests in a fixed bed reactor were unable to provide reliable reaction kinetics data due to internal diffusion limitations and rapid catalyst deactivation. Only the TPSR method was able to provide activation energy values comparable to the activation energy values obtained from the H/D exchange rate measurements. In addition, for CHA zeolite, it has been shown that the values of ethanol dehydration activation energies depend on the amount of ethanol in the CHA framework, and this effect can be attributed to the substrate clustering effects supporting the deprotonation of zeolite Brønsted centers.

Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity

Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as homogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in diene ring-closing metathesis reactions, leading to increased macrocylization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O = 1.30) of up to 44% compared to the homogeneous catalyst (MMC:O = 0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement.

Model-Based Quality, Exergy, and Economic Analysis of Fluidized Bed Membrane Reactors

In petroleum refineries, naphtha reforming units produce reformate streams and as a by-product, hydrogen (H2). Naphtha reforming units traditionally deployed are designed as packed bed reactors (PBR). However, they are restrained by a high-pressure drop, diffusion limitations in the catalyst, and radial and axial gradients of temperature and concentration. A new design using the fluidized bed reactor (FBR) surpasses the issues of the PBR, whereby the incorporation of the membrane can improve the yield of products by selectively removing hydrogen from the reaction side. In this work, a sequential modular simulation (SMS) approach is adopted to simulate the hydrodynamics of a fluidized bed membrane reactor (FBMR) for catalytic reforming of naphtha in Aspen Plus. The reformer reactor is divided into five sections of plug flow reactors and a continuous stirrer tank reactor with the membrane module to simulate the overall FBMR process. Similarly, a fluidized bed reactor (FBR), without membrane permeation phenomenon, is also modelled in the Aspen Plus environment for a comparative study with FBMR. In FBMR, the continuous elimination of permeated hydrogen enhanced the production of aromatics compound in the reformate stream. Moreover, the exergy and economic analyses were carried out for both FBR and FBMR.

Electrochemical Deposition of ZnS Films from Electrolyte Based on Na2SO3

The paper considers the features of electrochemical growth of zinc sulfide from an aqueous electrolyte based on sodium sulfite and zinc sulfate. The conditions for the electrochemical production of ZnS films are determined. It is shown that the value of the potential at which a ZnS layer is formed is limited by the achievement of the critical current due to the diffusion limitations of the electrochemical process of reducing the sulfite ion. It is shown that the resulting films contain an excess of sulfur, which is removed, and the stoichiometric composition is obtained by heat treatment. Aed mechanism of reactions resulting in the formation of zinc sulfide is proposed.

Nanofluidic voidless electrode for electrochemical capacitance enhancement in gel electrolyte

Porous electrodes with extraordinary capacitances in liquid electrolytes are oftentimes incompetent when gel electrolyte is applied because of the escalating ion diffusion limitations brought by the difficulties of infilling the pores of electrode with gels. As a result, porous electrodes usually exhibit lower capacitance in gel electrolytes than that in liquid electrolytes. Benefiting from the swift ion transport in intrinsic hydrated nanochannels, the electrochemical capacitance of the nanofluidic voidless electrode (5.56% porosity) is nearly equal in gel and liquid electrolytes with a difference of ~1.8%. In gel electrolyte, the areal capacitance reaches 8.94 F cm−2 with a gravimetric capacitance of 178.8 F g−1 and a volumetric capacitance of 321.8 F cm−3. The findings are valuable to solid-state electrochemical energy storage technologies that require high-efficiency charge transport.

On the Use of Dual Cell Density Monoliths

Monolith-type substrates are extensively used in automotive catalytic converters and have gained popularity in several other industrial processes. Despite their advantages over traditional unstructured catalysts, such as large surface area and low pressure drop, novel monolith configurations have not been investigated in depth. In this paper, we use a detailed computational model at the reactor scale, which considers entrance length, turbulence dissipation and internal diffusion limitations, to investigate the impact of using a dual cell substrate on conversion efficiency, pressure drop, and flow distribution. The substrate is divided into two concentric regions, one at its core and one at its periphery, and a different cell density is given to each part. According to the results, a difference of 40% in apparent permeability is sufficient to lead to a large flow maldistribution, which impacts conversion efficiency and pressure drop. The two mentioned variables show a positive or negative correlation depending on what part of the substrate—core or ring—has the highest permeability. This and other results contribute relevant evidence for further monolith optimization.

Study of the properties for stabilized polyacrylonitrile thermally treated in air

Developing of nanotechnology-based electronics entails developing of new carbon nanocrystalline materials with predetermined physicochemical properties, e.g., obtained by synthesis of polyacrylonitrile (PAN) in conditions of heat treatment. We have studied the properties of PAN heat-treated in air in the temperature range 150 – 250°C and the effect of stabilization on the kinetic parameters of synthesis and thermochemical properties of carbon material upon heat treatment in N2 atmosphere. It is shown that an increase in the temperature of a preliminary treatment up to 200°C leads to a decrease in the activation energy and pre-exponential factor compared to the corresponding values characteristic for the initial polymer (from 90.9 and 3.1 × 106 to 53.3 kJ/mol and 1.1 × 103 min–1, respectively), which indicates to the occurrence of diffusion limitations. When the temperature of a preliminary treatment in air increases from 180 to 250°C, the difference between temperature peaks for DSC and TGA curves decreases due to appearance of a «core-shell» structure. XRD data indicate that the initial PAN structure does not change up to 150°C. Further increase in the temperature leads to significant changes in the initial structure of the polymer which are manifested in a decrease in the peak area in the X-ray diffraction pattern of the polymer. The results obtained can be used in the development of a method for the synthesis of carbon materials with controlled properties predetermined at the stage of stabilization.

Structure-Properties Correlation of Cross-Linked Penicillin G Acylase Crystals

In biocatalytic processes, the use of free enzymes is often limited due to the lack of long-term stability and reusability. To counteract this, enzymes can be crystallized and then immobilized, generating cross-linked enzyme crystals (CLECs). As mechanical stability and activity of CLECs are crucial, different penicillin G acylases (PGAs) from Gram-positive organisms have proven to be promising candidates for industrial production of new semisynthetic antibiotics, which can be crystallized and cross-linked to characterize the resulting CLECs regarding their mechanical and catalytic properties. The greatest hardness and Young’s modulus determined by indentation with an atomic force microscope were observed for CLECs of Bacillus species FJAT-PGA CLECs (26 MPa/1450 MPa), followed by BmPGA (Priestia megaterium PGA, 23 MPa/1170 MPa) and BtPGA CLECs (Bacillus thermotolerans PGA, 11 MPa/614 MPa). In addition, FJAT- and BtPGA CLECs showed up to 20-fold higher volumetric activities compared to BmPGA CLECs. Correlation to structural characteristics indicated that a high solvent content and low number of cross-linking residues might lead to reduced stability. Furthermore, activity seems to be restricted by small water channels due to severe diffusion limitations. To the best of our knowledge, we show for the first time in this study that the entire process chain for the characterization of diverse industrially relevant enzymes can be performed at the microliter scale to discover the most important relationships and limitations.