Search Results (81)

In industrial processes, catalysts—materials that speed up chemical reactions without being consumed—are essential. The goal of this research was to create two new rhenium-based nanocomposite catalysts that can effectively and sustainably reduce nitroaromatic compounds to aromatic amines in continuous-flow systems. Nitroaromatic hydrocarbons (NACs), widely used in manufacturing pharmaceuticals, insecticides, and herbicides, often contaminate soil and water, posing significant environmental and health risks. However, their reduction to aromatic amines enables potential industrial reuse. In this study, we synthesized two nanocomposite catalysts based on a copolymer functionalized with N-methyl-D-glucamine, embedded with rhenium (Re)-based apparent nanoparticles, and used them to reduce the NACs in continuous-flow mode to their aromatic amines using newly designed and stereolithographic (SLA) 3D-printed reactors. Advanced characterization techniques were employed to evaluate their structure, morphology, and catalytical performance. Catalyst 1, prepared from a self-modified Purolite D4869 resin and characterized by higher Re loading, exhibited superior conversion rates in batch mode (k₁ up to 1.406 s⁻¹). In contrast, Catalyst 2, based on a commercial NMDG-functionalized Dowex resin with a mesoporous structure, demonstrated remarkable stability and catalytic capacity under continuous flow (up to 1.383 mmol_NAC mL_cat⁻¹). Overall, Catalyst 1 was found to be better suited for rapid batch reactions, whereas Catalyst 2 was found to be more appropriate for long-term flow applications, offering a sustainable route for the efficient conversion of nitroaromatic compounds into valuable aromatic amines. The reactors enabled the efficient conversion of NACs into aromatic amines while enhancing process sustainability and efficiency. Full article

As a result of the catalytic decomposition of H₂O₂, hydroxyl radicals are produced. Hydroxyl radicals are strong oxidants and effectively inactivate bacteria, ensuring water disinfection without toxic chlorinated organic by-products. The kinetics of bacterial inactivation were studied in a laboratory-scale flow catalytic reactor. A granular cobalt ferrite catalyst was thoroughly characterized using XRD and XRF techniques, SEM with EDS, and Raman spectroscopy. At lower H₂O₂ concentrations, H₂O₂ decomposition follows first-order reaction kinetics. At higher H₂O₂ concentrations, the obtained kinetics lines suggest that the reaction order increases. The kinetics of bacterial inactivation in the developed flow reactor depends largely on the initial number of bacteria. The initial bacterial concentrations in laboratory tests were within the range typical of real river water. A regression model was developed that relates the degree of bacterial inactivation to the initial number of bacteria, the initial H₂O₂ concentration, and the contact time of water with the catalyst. Full article

The co-pyrolysis of straw biomass and polyethylene film at different mass ratios was carried out in a small fixed-bed reactor with CaO as catalyst. The resulting synthesis gas production, liquid and solid products, and pyrolysis kinetics were studied by gas chromatography and thermogravimetric analysis. The results showed that with increasing proportion of plastic in the feedstock, co-pyrolysis had a synergistic effect on the CH₄ yield, reaching as high as 3.124 mol CH₄/kg feedstock, while the H₂ and CO yields continuously decreased. Comparing the experimental and theoretical yields of synthesis gas, the trends for CO and CH₄ were consistent, but those of H₂ and CO₂ differed widely. Examining the influence of element mass ratios in the feedstock on the synthesis gas composition, it was found that the biomass and plastics affected the formation of oxygen- and hydrogen-containing gases, respectively. The activation energy and pre-exponential factor showed increasing and decreasing trends, respectively, when the feedstock proportions and heating rate changed. Fitted linear correlation coefficients for all pyrolysis stages exceeded 0.99. Full article

The enzymatic synthesis of statin intermediates offers a sustainable alternative to traditional multistep chemical methods. This study investigates the continuous flow synthesis of statin precursors in a millireactor using 2-deoxy-D-ribose-5-phosphate aldolase (DERA) immobilized on mesoporous silica foam (MCF) and magnetic nanoparticles (MNPs). Two types of flow millireactors, a fixed bed millireactor for MCF and a fluidized bed millireactor for MNP, were designed. Key performance indicators including conversion, selectivity, yield, and productivity were analyzed and compared with the batch reactor results. The MNP-based fluidized bed millisystem demonstrated superior conversion (97.78%) and yield (95.85%) under optimized conditions, outperforming both batch and MCF-based millisystems. This work highlights the importance of optimizing immobilization techniques and reactor configurations to enhance enzyme stability and catalytic efficiency in continuous biocatalytic processes, particularly for pharmaceutical applications. Full article

Discharging oil-contaminated wastewater into the environment without adequate treatment can have a negative impact on water resources, public water and wastewater treatment systems, and even human health. In this sense, it is essential to develop compact, easily automated, low-cost, and highly efficient unitary treatment processes in order to comply with legal requirements regarding effluent emission standards for water bodies. Therefore, the present study consisted of the development of two treatment processes aimed at the separation of oil emulsions stabilised by anionic surfactants: a sorption column using polyurethane/graphene foam composites as sorbent material and a continuous flow AC electroflotation reactor. Initially, composites with 0.5% and 1% w/w graphene (based on polyol mass) were developed using a dispersing agent (1-methyl-2-pyrrolidone). The foams were characterised in terms of morphology and mechanical and sorption properties. In the fixed bed column, the foams retained up to 77.15% of the emulsified oil and 52.36% of the anionic surfactants. In the continuous flow electroflotation reactor, emulsified oil removal efficiencies above 90% were achieved at all electrical currents tested, and up to 88.6% of anionic surfactants were removed at an electrical current of 150 A. Given the advantages and disadvantages of the two oily effluent treatment processes, their combined use in the same system proved promising. Full article

Biodiesel production has gained attention as a sustainable alternative to fossil fuels, but challenges related to catalyst recovery and energy consumption remain. In this study, a novel lithium-impregnated aluminosilicate catalyst (LiSA) was developed using a 3D-printed mold, providing precise control over its structure to optimize performance. The structured catalyst featured a cylindrical shape with multiple circular channels, enhancing fluid dynamics and reactant interaction in a fixed-bed reactor. Catalyst characterization by SEM, TGA, XRD, and ICP-MS confirmed high thermal stability and uniform pore distribution. Jatropha curcas oil was used as feedstock, with diethyl ether (DEE) acting as a cosolvent to improve methanol solubility and enable transesterification at room temperature. The process achieved a high fatty acid methyl ester (FAME) yield, averaging 97.1% over 508 min of continuous operation, demonstrating the catalyst’s stability and sustained activity. By reducing mass transfer limitations and energy demands, this approach highlights the potential of 3D-printed catalysts to advance sustainable biodiesel production, offering a scalable and efficient pathway for green energy technologies. Full article

Hydrogen production from ethanol steam reforming (ESR) was performed using the synthesized LaNi_xCu_1−xO_3−λ perovskite-type catalysts in a continuous two-stage fixed-bed reactor from 450 to 700 °C under atmospheric pressure. The elemental analysis (EA), XRD, SEM, BET, and TGA-DTG technologies were used to characterize the structures and properties of the synthesized catalysts. The thermodynamic equilibrium model, based on the minimization of Gibbs free energy using a non-stoichiometric methodology, was carried out and compared with experimental data. The results demonstrated that the catalytic activity of the perovskite-type catalysts for ESR can be improved after modification with a certain amount of copper (about 0.67 mmol/g) and decreased further with an increase in copper content (about 3.41 mmol/g). The most active catalyst was found to be LaNi_0.9Cu_0.1O_3−λ, with an ethanol conversion value of 96.0% and hydrogen selectivity of 71.3%. The perovskite-type catalysts with an appropriate amount of Cu promoter improved coking resistance and presented excellent stability with no loss of activity over 101 h at 700 °C. Based on the power-law kinetic model with the first reaction order, the activation energy and the frequency factor for ethanol steam reforming by perovskite-type catalysts were calculated. Our studies indicated the enhanced effects of Ni and Cu on the small Ni-Cu bimetallic particles in the water gas shift (WGS) reaction, which could also contribute to the activity and stability of the LaNi_xCu_1−xO_3−λ perovskite-type catalysts in hydrogen production. Full article

This study investigates a continuous deoxygenation of bio-oil vapor in a catalytic fixed-bed reactor coupled to a continuous drop tube reactor (DTR) for biomass pyrolysis. Beech wood pyrolysis was initially examined without catalysts at various temperatures (500–600 °C). The products were characterised using GC-MS, Karl Fischer titration, GC-FID/TCD, and thermogravimetric analysis. The highest bio-oil yield (58.8 wt.%) was achieved at 500 °C with a 500 mL/min N₂ flow rate. Subsequently, ex situ catalytic pyrolysis was performed using an HZSM-5 catalyst in a fixed-bed reactor at a DTR outlet, operating at 425 °C, 450 °C, and 500 °C. The HZSM-5 catalyst exhibited declining deoxygenation efficiency over time, which was evidenced by decreasing conversion rates of chemical families. Principal component analysis was employed to interpret the complex dataset, facilitating a visualisation of the relationships between the experimental conditions and product compositions. This study highlights the challenges of continuous operation as experimental durations were limited to 120 min due to clogging issues. This research contributes to understanding continuous biomass pyrolysis coupled with catalytic deoxygenation, providing insights into the reactor configuration, process parameters, and catalyst performance crucial for developing efficient and sustainable biofuel production processes. Full article

The selective hydrogenolysis of glycerol to 1,3-Propanediol (1,3-PDO) presents a sustainable approach, leveraging a bio-renewable feedstock and significantly enhancing the economic viability of biodiesel production. However, the limited selectivity toward 1,3-PDO in glycerol hydrogenolysis has hindered its widespread adoption on an industrial scale. In this work, we synthesized a series of Pt/WO₃–Al₂O₃ catalysts using a simple wetness sequential impregnation method. Comprehensive characterization and kinetic studies revealed that the surface tungsten content of the catalyst exerted a critical and multifaceted influence on the catalytic performances. Under optimal conditions, glycerol could be selectively converted to 1,3-PDO with a yield of 43% in a fixed-bed continuous flow reactor. Furthermore, a plausible reaction mechanism for glycerol hydrogenolysis was proposed based on the correlations between catalyst structure and catalytic performance. Full article

Mesoporous HZSM-5 zeolites with nanocrystal stacking morphology were directly synthesized via hydrothermal methods without mesoporous templates. The synthesized mesoporous HZSM-5 was subjected to hydrothermal–citric acid washing treatment. The structural and acidic properties of the samples before and after modification were characterized using various techniques. The catalytic performance for butene conversion to propylene was investigated under atmospheric pressure, 500 °C, and a butene weight hourly space velocity (WHSV) of 10 h⁻¹ in a continuous-flow micro-fixed bed reactor. The results show that propylene selectivity increased significantly from 24.7% before modification to 44%, and propylene yield increased from 22% to 38%. After 2 h of hydrothermal–citric acid washing modification, the catalyst maintained a butene conversion rate of 76% and a selectivity of 47% at 525 °C and a WHSV of 10 h⁻¹ after 130 h of continuous reaction, with a propylene yield of 37%. The results indicate that moderate hydrothermal–citric acid washing modification leads to the removal of aluminum from the zeolite framework, reducing the amount and strength of acid but increasing the mesopore quantity. This helps control the reaction pathways and diffusion of intermediate products, suppresses some side reactions, and improves the selectivity and yield of the desired product, propylene, while significantly enhancing catalytic stability. Full article

In this work, the pyrolysis process and the characteristics of biochar produced using a bench-scale fixed-bed reactor and a prototype-scale auger reactor were studied. Residual forest biomass (RFB) from acacia, broom, gorse, and giant reed was used as feedstock. Besides information on pyrolysis characteristics of these specific biomass species from the Iberian Peninsula, new knowledge on the understanding of how results from small-scale reactors can be used to predict the behavior of higher-scale and continuous-operation reactors is offered. Batch pyrolysis was carried out using 40 g of biomass sample in a fixed-bed reactor with a heating rate of 20 °C∙min⁻¹, pyrolysis temperature of 450 and 550 °C, and a residence time of 30 min, while for the continuous process it was used a prototype of an auger reactor with continuous operation with a biomass flow rate up to 1 kg/h, with temperatures of 450 and 550 °C, and a solids residence time of 5 min. The biochar yield was in the range of 0.26 to 0.36 kg/kg biomass dry basis, being similar for both types of reactors and slightly lower when using the auger reactor. The proximate analysis of the biochar shows volatile matter in the range 0.10 to 0.27 kg/kg biochar dry basis, fixed carbon in the range 0.65 to 0.84 kg/kg biochar dry basis, and ash in the range 0.04 to 0.08 kg/kg biochar dry basis. The carbon, oxygen, and hydrogen content of the biochar was in the range of 0.71 to 0.81, 0.09 to 0.22, and 0.02 to 0.03 kg/kg biochar dry basis, respectively. The results show that the up-scaling of the reactor and regime of operation does not have an important influence on the yield and characteristics of the biochar produced. The biochar obtained in the two types of reactors has characteristics appropriate for environmental applications, such as an additive to improve soil properties. It is possible to see that the characteristics of the biochar are influenced by the type of biomass and the conditions and parameters of the process; therefore, it is of major importance to control and know of these conditions, especially when considering upscaling scenarios. Full article

The objective of this study was to evaluate the applicability of zeolite Y as a catalyst for producing bisphenol F (BPF) from phenol and formaldehyde. Catalyst extrudates were prepared by extrusion after adding pseudoboehmite sol (PS) and Ludox (Lu) as alumina and silica binders, respectively. The compressive strength of the catalyst extrudates increased with the addition of Ludox. However, the formaldehyde conversion decreased as more Ludox was used as a binder, resulting in a decrease in the yield of BPF. This decrease is attributed to the reduction in the total amount of acid sites caused by the addition of Ludox. In this study, the Y_PS5_Lu5 catalyst was selected as the most suitable for BPF synthesis. In the BPF synthesis over the Y_PS5_Lu5 catalyst in a catalyst basket reactor, the optimum reaction temperature was determined to be 110 °C. The effect of stirring speed on the yield of BPF was found to be negligible in the range of 200 rpm to 350 rpm. The spent catalyst was able to recover a specific surface area and reaction activity similar to those of a fresh catalyst through regeneration in an air atmosphere at 500 °C. When the Y_PS5_Lu5 extruded catalyst was used in a continuous reaction in a fixed-bed reactor, there was no noticeable deactivation of the catalyst at low space velocities of the reactants. However, when the space velocity was increased to 18.0 h⁻¹, catalyst deactivation was clearly observed. This suggests that periodic regeneration of the catalyst is inevitable in a continuous reaction using the Y_PS5_Lu5 extruded catalyst. Full article

This study compared the behavior of the biomass in two fixed-film anaerobic reactors operated under equivalent organic loading rates but at different temperatures, i.e., 30 °C (RMM) and 55 °C (RMT). The reactors were fed with sugarcane vinasse and molasses (both fermented) in a simulation of sequential periods of season and off-season. The dynamics of biomass growth and retention, as well as the microbial composition, were assessed throughout 171 days of continuous operation, coupled with an additional 10-day test assessing the microbial activity in the bed region. Despite the different inoculum sources used (mesophilic granular vs. thermophilic flocculent sludge types), the biomass growth yield was identical (0.036–0.038 g VSS g⁻¹COD) in both systems. The retention rates (higher in RMT) were regulated according to the initial amount of biomass provided in the inoculation, resulting in similar amounts of total retained biomass (46.8 vs. 43.3 g VSS in RMT and RMM) and biomass distribution patterns (30–35% in the feeding zone) at the end of the operation. Meanwhile, hydrogenotrophic methanogenesis mediated by Methanothermobacter coupled to syntrophic acetate oxidation prevailed in RMT, while the Methanosaeta-mediated acetoclastic pathway occurred in RMM. The results show that different anaerobic consortia can behave similarly in quantitative terms when subjected to equivalent organic loads, regardless of the prevailing methane-producing pathway. The community grows and reaches a balance (or a given cell activity level) defined by the amount of substrate available for conversion. In other words, while the metabolic pathway may differ, the endpoint (the amount of biomass) remains the same if operational stability is maintained. Full article

Among the approaches to facilitating negative CO₂ emissions is biochar production. Biochar is generated in the pyrolysis of certain biomasses. In the pyrolysis process, carbon in the biomass is turned into a solid, porous, carbon-rich, and stable material that can be captured from the soil after a period of from a few decades to several centuries. In addition to this long-term carbon sequestration role, biochar is also beneficial for soil performance as it helps to restore soil fertility and improves the retention and diffusion of water and nutrients. This work presents a Life Cycle Assessment of different pyrolysis approaches for biochar production. Biomass pyrolysis is performed in a fixed-bed reactor, which operates at a mild temperature (550 °C). Biochar is obtained as solid product of the pyrolysis, but there are also liquid (bio-oil) and gaseous products (syngas). The pyrolysis gas is partly used to fulfil the energy demand of the pyrolysis process, which is highly endothermic. In the conventional approach, CO₂ is produced during the combustion of syngas and emitted to the atmosphere. Another approach to facilitate CO₂ capture and thus obtain more negative CO₂ emissions in the pyrolysis process is burning syngas and bio-oil in a Chemical Looping Combustion unit. Life Cycle Assessment was performed of these approaches toward biomass pyrolysis to evaluate their environmental impact. The Chemical Looping Combustion approach significantly reduced the values of 7 of the 16 environmental impact indicators studied, along with the Global Warming Potential among them, it slightly increased the value of one indicator related to the use of fossil resources, and it maintained the values of the remaining 8 indicators. Environmental impact reduction occurs due to the avoidance of CO₂ and NO_x emissions with Chemical Looping Combustion. The CO₂ balances of the different pyrolysis approaches with Chemical Looping Combustion configurations were compared with a base case, which constituted the direct combustion of wheat straw to obtain thermal energy. Direct biomass combustion for the production of 17.1 MJ of thermal energy had CO₂ positive emissions of 0.165 kg. If the gaseous fraction was burned by Chemical Looping Combustion, CO₂ was captured and the emissions became increasingly negative, until a value of −3.30 kg/17.1 MJ was generated. If bio-oil was also burned by this technology, the negative trend of CO₂ emissions continued, until they reached a value of −3.66 kg. Full article

Inhibiting homoacetogens is one of the main challenges in fermentative hydrogen production because these hydrogen consumers have similar growth features to hydrogen producers. Homoacetogens have been related to the excessive accumulation of biomass in fermentative reactors. Therefore, a suitable food/microorganism ratio has the potential to minimize the homoacetogenic activity. In this work, the specific organic loading rate (SOLR) was controlled in two fermentative fixed-bed up-flow reactors through scheduled biomass discharges. Reactors were differentiated by the bed arrangement, namely, packed and structured conformation. The SOLR decay along the time in both reactors was previously simulated according to the literature data. The volume and volatile suspended solids (VSS) concentration of discharges was estimated from the first discharge, and then additional discharges were planned. Biomass discharges removed 21% of the total biomass produced in the reactors, maintaining SOLR values of 3.0 ± 0.4 and 3.9 ± 0.5 g sucrose g⁻¹ VSS d⁻¹ in the packed-bed and structured-bed reactors, respectively. Such a control of the SOLR enabled continuous and stable hydrogen production at 2.2 ± 0.2 L H₂ L⁻¹ d⁻¹ in the packed-bed reactor and 1.0 ± 0.3 L H₂ L⁻¹ d⁻¹ in the structured-bed one. Controlling biomass was demonstrated to be a suitable strategy for keeping the continuous hydrogen production, although the fermentative activity was impaired in the structured-bed reactor. The homoacetogenic was partially inhibited, accounting for no more than 30% of the total acetic acid produced in the reactor. Overall, the high amount of attached biomass in the packed-bed reactor provided more robustness to the system, offsetting the periodic suspended biomass losses via the planned discharges. Better characterizing both the VSS composition (aiming to differentiate cells from polymeric substances) and the bed hydrodynamics could be useful to optimize the online SOLR control. Full article