Fixed Catalyst Bed Research Articles

Process intensification in the continuous dehydrogenation of methylcyclohexane to toluene

The toluene/methylcyclohexane cycle is a safe and practical Liquid Organic Hydrogen Carrier (LOHC) for the storage of hydrogen. Nevertheless, the dehydrogenation reaction of methylcyclohexane (MCH) should be improved to assure a total selectivity to toluene (TOL), avoiding the subproducts formation. In this research, a millireactor with channel internal diameter in the range of milimeters has been tested and evaluated in the dehydrogenation of MCH to TOL. The millireactor configuration confers it some features and advantages compared to fixed-bed reactors, e.g., better mass and energy transfer and increased performance (10–20 %). To verify these advantages, a comparison between conventional fixed bed (9 mm i.d.) and millireactor is carried out. Thanks to its configuration, the millireactor could control effectively the heat generated by the reactions to avoid hot-spot formation and the sintering of the catalyst. The results obtained demonstrate that the catalysts activity in the reaction is improved with the application of the millireactor respect the fixed-bed ones and neither catalyst sintering, nor pressure drop was appreciated during the catalytic tests. At the best reaction conditions, Tecnalia´s millireactor converses continuously up to 99 % of MCH to TOL with 100 % selectivity at atmospheric pressure, showing the huge potential of the millireactor concept.

Performance assessment of novel catalytic spouted-bed vapor jet flow heat exchanger in amine-based carbon capture process

This study introduced a spouted bed and jet flow catalytic heat exchanger (SBJ-EX). This novel non-agitated technology can potentially integrate with a conventional desorption column to enhance heat transfer and CO2 desorption performance in amine-based post-combustion carbon capture systems. As its first research in the carbon capture field, this work experimentally evaluated key factors including overall heat transfer coefficient, logarithmic mean temperature difference, temperature distribution along the reactor, and cyclic loading under varied parameters such as inlet temperature of the heating oil, inlet solvent temperature, rich CO2 loadings, and mass of catalysts to simulate real-world operating conditions using benchmark MEA solvent and solid acid catalyst HZSM-5. Compared to conventional plate heat exchangers, the SBJ-EX demonstrated over a 70 % enhancement in heat transfer performance due to its effective overall heat transfer coefficient. It also exhibited impressive CO2 desorption performance even at lower temperatures with sufficient catalysts. Unlike agitated-type heat exchangers, the SBJ-EX could minimize catalyst attrition and offer more excellent stability. In contrast to fixed-bed catalyst desorbed columns, this equipment offered a more compact design for quicker and simpler catalyst replacement to reduce downtime for operators significantly. The SBJ-EX can also function as an optional backup or add-on unit to provide operators with flexibility. This work further discussed advantages and challenges of the SBJ-EX operation. This work enriched the future research outlook for this technology, and contributed a commercially viable approach to catalysts in carbon capture processes.

Selective conversion of ethylene to propylene over rhenium-containing heterogeneous catalysts

The development of new technologies for effective propylene production is a highly important scientific and industrial task nowadays. In this study, the conversion of ethylene to propylene (ETP reaction) was explored over rhenium-containing catalysts supported on a ZrO2 carrier at temperatures 100°C–200°C and atmospheric pressure using a flow catalytic reactor with a fixed catalyst bed without the use of any other hydrocarbons or dilutants. The effect of rhenium presence in the catalysts on the activity and propylene selectivity was examined.

Post‐microwave plasma catalysis: Current developments and future implications

AbstractPost‐microwave plasma catalysis combines plasma preactivation of the gas phase followed by a fixed bed catalyst. This process has the potential to be energy efficient, modular, versatile and to generate high numbers of active species compared with other plasma generation technologies. Specific applications of these post‐microwave plasma systems include the dissociation and activation of stable molecules and the modification of catalyst materials. This concept article will address the current findings in microwave plasma catalysis research and propose future questions that need to be addressed to further develop the technology.

Water disinfection using hydrogen peroxide with fixed bed hematite catalyst - kinetic and activity studies.

A lab-scale reactor with a fixed-bed hematite catalyst for the effective decomposition of H2O2 and bacteria inactivation was designed. The bactericidal effect is the largest at a low initial bacterial count of 2·103CFU/L, which is typical for natural surface waters. When using a 5mM H2O2 solution and a residence time of 104min, the reduction in the number of E. coli bacteria is about 3.5-log. At a higher initial bacterial count of 1-2·104CFU/L, a 5mM H2O2 solution reduces the bacteria number by about 4-log. The H2O2 decomposition follows the log-linear kinetics of a first-order reaction while the bacterial inactivation does not. The kinetics of bacterial inactivation was described using the Weibull model in the modified form: log10(N0/N) =b · tn. The values of the non-linearity parameter n were found to be lower than 1, indicating that bacterial inactivation slows down over time. With increasing initial H2O2 concentration, the rate parameter b increases while the non-linearity parameter n decreases. With increasing temperature, both parameters increase. The stability of the catalyst has been proved by XRD, FTIR, SEM, and ICP-OES. The concentration of iron leaching into water during disinfection is much lower than the limit declared by WHO for iron in drinking water. The results show that technical-grade hematite is a promising Fenton-like catalyst for water disinfection. The fixed-bed reactor can be the basis of the mobile installations for water purification in emergencies.

3D-Printing of Hierarchical Porous Copper-Based Metal-Organic-Framework Structures for Efficient Fixed-Bed Catalysts.

Metallic structures with hierarchical open pores that span several orders of magnitude are ideal candidates for various catalyst applications. However, porous metal materials prepared using alloy/dealloy methods still struggle to achieve continuous pore distribution across a broad size range. Herein, we report a printable copper (Cu)/iron (Fe) composite ink that produces a hierarchical porous Cu material with pores spanning over 4 orders of magnitude. The manufacturing process involves four steps: 3D-printing, annealing, dealloying, and reannealing. Because of the unique annealing process, the resulting hierarchical pore surface becomes coated with a layer of Cu-Fe alloy. This feature imparts remarkable catalytic ability and versatile functionality within fixed bed reactors for 4-nitrophenol (4-NP) reduction and Friedländer cyclization. Specifically, for 4-NP reduction, the porous Cu catalyst demonstrates an excellent reaction rate constant (kapp = 86.5 × 10-3 s-1) and a wide adaptability of the substrate (up to 1.26 mM), whilst for Friedländer cyclization, a conversion over 95% within a retention time of only 20 min can be achieved by metal-organic-framework-decorated porous Cu catalyst. The utilization of dual metallic particles as printable inks offers valuable insights for fabricating hierarchical porous metallic structures for applications, such as advanced fixed-bed catalysts.

Pd nanoparticles decorated N-doped holey graphene assembled on aluminum silicate fibers agglomerate for catalytic continuous-flow reduction of nitroarenes

Rational design and preparation of efficient fixed-bed catalysts for continuous-flow system are highly desired but remain daunting challenges. Herein, we report the synthesis of an assembly catalyst consisted of aluminium silicate fibers (ASFs) agglomerate and Pd nanoparticles (PdNP) decorated N-doped holey graphene (NHG) through a facile hydrothermal co-assembling strategy. Due to the interconnect network and porous structure, the as-obtained PdNP/NHG-ASFs assembly is suitable to be utilized as a fixed-bed catalyst for organic reactions in continuous-flow mode. The processing rate is much higher than that of the previously reported fixed-bed systems based on metal-based catalysts. In addition, the catalytic continuous-flow system displays a remarkable durability and good substrate generality to other substituted nitrobenzenes. This work provides rational design concept for efficient fixed-bed catalyst with dual active components and paves a way for the industrial application in organic synthesis.

Heat and mass transfer of a novel CO2 desorption process integrated with highly turbulent catalytic heat exchanger

This was the first work that pioneered the development a novel catalytic CO2 desorption process using an agitated jacket vessel with a coil heat exchanger (JVC) into a bench-scale pilot plant for post-combustion carbon capture technology. The key parameters of heat and mass transport e.g., overall heat transfer coefficient, overall volumetric liquid-side mass transfer coefficient and the enhancement factor for catalyst effect, were experimentally investigated by varying the operating conditions, including temperature, stirring speed, and heating methods. The proposed investigations revealed that the utilization of the JVC was a promising technology for improving heat transfer and mass transfer performance in the desorption process due to the high turbulence flow and more favorable thermal distributions achieved by the JVC. In comparison to the conventional process with a fixed catalyst bed, the JVC demonstrated a remarkable approximately 30 % catalytic enhancement and a substantial 50 % reduction in catalyst demand. Additionally, other potential benefits and challenges of further practical operations were discussed in this paper. This research carried significant potential to contribute to the advancement of knowledge and offer valuable insights into the practicability of the catalytic desorption process for further commercial application in carbon capture. The integration of catalyst and JVC could potentially motivate the utilization of catalyst towards commercial-scale applications.

A Novel Method for γ-Aminobutyric Acid Biosynthesis Using Glutamate Decarboxylase Entrapped in Polyvinyl Alcohol-Sodium Alginate Capsules.

γ-aminobutyric acid (GABA) has essential physiological functions in the human body. A novel method using glutamate decarboxylase (GAD) entrapped in polyvinyl alcohol (PVA)-sodium alginate (SA) capsules provides a green biological strategy for GABA synthesis. In this investigation, the stability range of immobilized GAD was effectively broadened, and immobilized GAD could be repeatedly used as a batch and fixed-bed column catalyst. The immobilized enzymes were stable and retained 89% of their activity in a pH range of 4.0-5.6, while there was an approximately 50% decrease in free GAD activity in the pH range of 4.8 ± 0.4. The immobilized GAD affinity to the substrate improved, and this was evidenced by the apparent decrease in Km to 13.3 mmol/L from the 30.9 mmol/L for free GAD. The immobilized GAD retained >90.6% activity after eight cycles and a near-100% enzyme activity retention after 120 h of a continuous fixed-bed column catalyst operation. This study has thus presented an effective PVA-SA-GAD immobilization method that could be used to continuously scale-up GABA biosynthesis.

N-Doped graphene fiber anchored Pd nanoparticles as a fixed-bed catalyst for continuous-flow reduction of N-containing unsaturated compounds

Catalytic fixed-bed is an efficient and facile system for scalable organic synthesis due to its continuous and fast flow operation process. As a key unit in the fixed-bed system, catalytically active packing materials are required to possess some properties, such as high activity, excellent stability, and porous packing structure. Herein, we prepare a fibrous fixed-bed catalyst by anchoring Pd nanoparticles on N-doped graphene fiber (NHG) (Pd/NGF). Due to the porous and loose packing structure, the resultant Pd/NGF catalyst can be easily filled into the continuous-flow reactor to construct a fixed-bed system with low flow resistance. The corresponding catalytic fixed-bed system exhibits a favourable flow rate (8 ​mL/min) and excellent durability toward reduction reactions of N-containing unsaturated compounds to produce aromatic amines. This work provides a new design concept of fibrous fixed-bed catalysts with dual-active components (i.e., graphene-derived active materials and metal nanoparticles) and catalytic organic synthesis in a continuous-flow process.

AuFe3@Pd/γ-Fe2O3 Nanosheets as an In Situ Regenerable and Highly Efficient Hydrogenation Catalyst

Heterogenous Pd catalysts play a pivotal role in the chemical industry; however, it is plagued by S2- or other strong adsorbates inducing surface poisoning long term. Herein, we report the development of AuFe3@Pd/γ-Fe2O3 nanosheets (NSs) as an in situ regenerable and highly active hydrogenation catalyst. Upon poisoning, the Pd monolayer sites could be fully and oxidatively regenerated under ambient conditions, which is initiated by •OH radicals from surface defect/FeTetra vacancy-rich γ-Fe2O3 NSs via the Fenton-like pathway. Both experimental and theoretical analyses demonstrate that for the electronic and geometric effect, the 2-3 nm AuFe3 intermetallic nanocluster core promotes the adsorption of reactant onto Pd sites; in addition, it lowers Pd's affinity for •OH radicals to enhance their stability during oxidative regeneration. When packed into a quartz sand fixed-bed catalyst column, the AuFe3@Pd/γ-Fe2O3 NSs are highly active in hydrogenating the carbon-halogen bond, which comprises a crucial step for the removal of micropollutants in drinking water and recovery of resources from heavily polluted wastewater, and withstand ten rounds of regeneration. By maximizing the use of ultrathin metal oxide NSs and intermetallic nanocluster and monolayer Pd, the current study demonstrates a comprehensive strategy for developing sustainable Pd catalysts for liquid catalysis.

Bifunctional cobalt catalyst for the synthesis of waxy diesel fuel by the Fischer–Tropsch method – from development to introduction. Part 2. Optimization of the catalyst component composition

The effect exerted by the content of metallic (Co-Al2O3/SiO2 catalyst) and acidic (ZSM-5 zeolite in the H-form) components on the properties of bifunctional catalyst for the integrated synthesis of waxy diesel fuel by the Fischer–Tropsch method was studied. Catalysts represented by a composite mixture with a boehmite binder were characterized by XRD, BET and TPR methods. The testing was performed in a flow reactor with a fixed catalyst bed at a pressure of 2.0 MPa, temperature 240 °С and gas hourly space velocity 1000 h–1. Activity and selectivity of the catalysts as well as the fractional and hydrocarbon composition of the products were investigated in dependence on the ratio of components. It was found that productivity of the synthesis for С5+ hydrocarbons and selectivity for the С11–С18 diesel fraction products with a high content of isomeric products correlated with the ratio of metallic and acidic components in the catalysts. The composition of the catalyst recommended for the diesel fuel production has the 1.17 ratio of metallic and acidic components.

Performance of the ρ- Al2O3 based Ag promoted Pd/ Al2O3 catalyst during Acetylene hydrogenation with an ideal feed

Catalytic hydrogenation of acetylene was studied with an ideal feed with a catalyst prepared from different alumina support and with varying quantities of promoter addition. Silver promoted palladium alumina catalysts were prepared on the transition alumina, ρ-alumina and the catalyst performance was compared with the traditional palladium alumina catalyst based on α-alumina. The catalyst supports were prepared using the granulation technique and sequential impregnation method was used for the catalyst preparation. The silver metal loading was varied in the catalysts and the impact of varied promoter quantity was also studied. The supports were characterized for the acidity, alumina phase, and catalyst characterization was done using TEM, TPR, and BET method to understand the difference between catalysts prepared on different types of alumina support. A fixed bed catalyst reaction was used for the performance evaluation and an ideal gas with acetylene and nitrogen was used as the feed. The catalyst evaluation gives the comparative performance of the catalysts at different temperature conditions. Acetylene conversion and ethylene selectivity in the product were evaluated. The spent catalyst analysis was done using TGA and CHN analysis was performed to understand the carbon deposition and by-product formation during the reaction with different types of catalysts.

Vapor-phase oxidation of propylene glycol-methanol mixture to methyl lactate on CeO2/Al2O3 catalyst

The vapor-phase oxidation of mixtures of propylene glycol with methanol and ethanol to methyl and ethyl lactate, respectively, on supported CeO2/Al2O3 catalyst at 210-2500С was investigated. Air oxygen and a flow reactor with a fixed catalyst bed were used. A 20% solution of propylene glycol in alcohol was supplied to the reactor inlet. Oxidation of propylene glycol in the presence of methanol occurs according to the overall reaction CH3CHOHCH2OH +O2 + СН3OH = CH3CHOHCOOСН3 +2H2O. First, hydroxyacetone is formed, which is further oxidized to pyruvic aldehyde, which adds alcohol to form a hemiacetal. Next, this hemiacetal is rearranged according to Cannizzaro into methyl lactate. At 2200C and catalyst load < 2 mmol PG/gcat/h, the selectivity for methyl lactate reached 70 wt.% at 100% propylene glycol conversion. In the presence of ethanol, the formation of a significant amount of acetaldehyde and its aldol condensation products, as well as the formation of diethoxyethane, was observed. Therefore, the selectivity for ethyl lactate at 100% propylene glycol conversion did not exceed 45%.

Study of methane carbonate conversion process in fixed catalyst layer in different membrane reactors

The work studied the characteristics of membrane catalysts in the reaction of methane carbonate conversion as a model reaction. This process produces synthesis gas (a 1:1 mixture of Н2 and СО), which can be used to make many products, including synthetic fuels (in the FischerTropsch process). One of the serious problems of methane carbonate conversion is the presence of side reactions that prevent the production of synthesis gas with the required ratio of products (H2:CO=1:1).Membrane catalysts were investigated in carbonate conversion of methane and membrane catalytic reactors: extractor, contactor, and distributor. Carbonate conversion of methane was compared with their material performance characteristics in the ground state in a conventional catalytic reactor with a fixed catalyst bed on membrane catalysts in the contactor and distributor. As the main parameters of the process of catalytic methane carbonate conversion, the change of the main parameters of the process -the concentration of the components in the products, the degree of change of the initial reagents and the ratio of the resulting synthesis gas components, depending on the contact time - were considered. The work aims to study methane's carbonate conversion process in a fixed catalyst layer in different membrane reactors.

One-step drawing of continuous basalt fibers coated with palladium nanoparticles and used as catalysts in benzyl alcohol oxidation

The continuous basalt fibers (CBFs) coated with palladium (Pd) nanocatalysts were prepared via one-step drawing strategy by using dispersion of Pd/montmorillonite (Pd@MMT) as the sizing. The prepared composite fibers (Pd@MMT/CBFs) were woven into fabrics and were used as fixed-bed catalyst for oxidation of benzyl alcohol (BzOH). The woven Pd@MMT/CBFs monolith was featured with “three-dimensional architecture” which afforded excellent catalytic performance (conversion 96%, selectivity 90%) and superior resistance to sustaining liquid flow shock. It was found that the tensile strength of CBFs was well preserved even the catalyst was exposed to a violent flow of BzOH+H2O2 at velocity of 0.1–0.6 m/s, and the mass loss was < 2.0% demonstrating rockiness stability of such CBFs-based catalysts.

Особенности каталитической трансформации метанола в углеводороды в условиях микроструктурированных потоков

The methanol into hydrocarbons transformation is a complex catalytic reaction accompanied by the formation of a wide range of hydrocarbons and proceeding on the surface of acid sites of various zeolites. Zeolite H-ZSM-5 considered to be most often used catalyst for this process. H-ZSM-5 is a highly dispersed material with a crystal diameter of 1–20 microns, which complicates its direct use in reactors with a fixed catalyst bed due to the high hydraulic pressure drop of the catalytic bed. Traditionally in industry, this issue is solved by using complex reactor systems with a fluidized bed, which is justified for large-scale production. In small and medium-size plants, the use of fluidized bed systems is not economically feasible. One of the possible solutions to this problem is the use of a monolithic catalyst with a supported layer of H-ZSM-5 zeolite. This article presents a study of the catalytic activity of a zeolite-containing microstructured monolith in methanol into hydrocarbons transformation. The monolith was synthesized by pressing a zeolite-containing mass followed by drying, calcining, and secondary growth of the zeolite on the monolith surface. A sample of a monolith with an average channel diameter of 0.5, 1.0, 1.5, 2.0 mm were synthesized this way. Samples of the microstructured catalyst were tested at varying temperatures from 250 to 450 °C and at varying the specific methanol feed rate from 0.65 to 2.3 kg (MeOH)/(kg (Cat) h). For this purpose, the monolithic catalyst was placed in a reactor for testing microstructured catalysts, which consisted of a pump, a temperature controller, a catalytic reactor, a condenser, a separating funnel, and a chromatograph. Varying the conditions showed that for the preferential production of gaseous C1–C4 hydrocarbons, it is advisable to carry out the reaction under the following conditions: the average diameter of the catalyst channels is 2 mm, the reaction temperature is 350 °C, the methanol feed rate is 1.65 kg (MeOH)/(kg (Cat) h). For the predominant formation of liquid hydrocarbons of the C5–C8 fraction, it is advisable to carry out the transformation of methanol into hydrocarbons under the following conditions: the average diameter of the catalyst channels is 1 mm, the reaction temperature is 350 °C, the methanol feed rate is 0.65 kg (MeOH) / (kg (Cat) h). For the predominant formation of liquid hydrocarbons of the C9–C12 fraction, it is advisable to carry out the transformation of methanol into hydrocarbons under the following conditions: the average diameter of the catalyst channels is 0.5 mm, the reaction temperature is 350 °C, and the methanol feed rate is 0.65 kg (MeOH) / (kg (Cat) h).

Оценка эффективности процесса одностадийной дегидроароматизации природного и попутного нефтяного газа

The following sequential problems were solved in article for methane dehydroaromatization feasibility validation: a methane dehydroaromatization kinetic model and a mathematical model of an industrial axial reactor with a fixed catalyst bed were developed, a process flow diagram was proposed, corresponded material and heat balances were calculated. Based on the results, methane dehydroaromatization performance was compared with related commercial hydrogen production technologies.

Обзор применяемых катализаторов и реакторов для дегидроароматизации природного и попутного нефтяного газа

The review discusses catalysts and implementation ways used for natural and oilwell gas dehydroaromatization process, as well as product gas mixture separation methods. Membrane reactors, fluidized catalyst bed, moving catalyst bed and fixed catalyst bed reactors used for dehydroaromatization of natural and oilwell gas are mentioned in the review.

Effect of Acid Treatment on the Properties of Zeolite Catalyst for Straight-Run Gasoline Upgrading

The objective of this research was to analyze the effect of different concentrations of nitric and hydrochloric acids on the structural, acidic, and catalytic properties of a post-synthetic treated ZSM-5 type zeolite at various temperatures. The properties of zeolite catalysts were determined using different methods, such as the Brunauer-Emmett-Teller (BET) method for specific surface area, temperature-programmed desorption (TPD) of ammonia method for acidic properties, and a flow-through unit with fixed bed catalyst (with upgrading straight-run gasoline fraction of oil) for catalytic activities of initial zeolite and acid-treated samples. The structural and acidic properties of both untreated and treated zeolites were investigated, and the effect of acid treatment on the catalytic properties of the samples in the course of upgrading the straight-run gasoline fraction of oil was determined. The post-synthetic treatment with aqueous nitric acid increased the specific surface area and volume of micropores of ZSM-5 zeolite, while the treatment with aqueous hydrochloric acid led to the formation of mesopores. Acid treatments of zeolite decreased the number of acid sites, mainly due to diminished concentration of low-temperature sites. The yield of liquid products in the conversion of straight-run gasoline fraction of oil, i.e., generation of high-octane gasolines with improved environmental features, was increased using acid-treated zeolites, which was due to the decrease in arene content.