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1.
Heliyon ; 10(17): e36238, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-39296150

RESUMEN

Currently, the steelmaking process uses a pulverized coal injection (PCI) system that serves as the heat source and reductant for ironmaking (blast furnace and FINEX) where system uses expensive high-grade coal and high operating costs. Hydrogen steelmaking is currently being developed to achieve carbon-free operation. To achieve a soft-landing during this phase of rapid change, the use of biomass and inexpensive, thermal coal, and coke dust is necessary. Research on their combustion characteristics is necessary to apply these alternative fuels to PCI. Therefore, this study analyzed the combustion characteristics of ignition delay, devolatilization, and char combustion using a laminar flow reactor visualization equipment that simulates blast furnace (BF) and FINEX PCI tuyere, using flame image data processing. The ignition time were generally longer in BF than in FINEX, and the char combustion length and time also showed the same trend due to the high oxygen rate which indicate under 2 ms on ignition delay, under 16 ms on char combustion. Also, the volatile cloud was qualitatively shown in the image to be highest in thermal coal and biomass with high volatile matter. Based on the correlation and theoretical calculation with proximate analysis and the results, ignition delay time had a combined effect of volatile matter and moisture except coke dust, and char combustion time affected unburned carbon. The combustion chemical characteristics were discussed with chemical percolation devolatilization (CPD) model parameter. Through SEM image and BET analysis, the surface area has been increased more than 10 times after combustion. Consequently, the biomass and high moisture thermal coal could cofired within 10 % and coke dust could be cofired within 9 %, respectively.

2.
Sci Total Environ ; 952: 175840, 2024 Nov 20.
Artículo en Inglés | MEDLINE | ID: mdl-39214360

RESUMEN

Residential wood combustion (RWC) remains a significant global source of particulate matter (PM) emissions with adverse impacts on regional air quality, climate, and human health. The lung-deposited surface area (LDSA) and equivalent black carbon (eBC) concentrations have emerged as important metrics to assess particulate pollution. In this study we estimated combustion phase-dependent emission factors of LDSA for alveolar, tracheobronchial, and head-airway regions of human lungs and explored the relationships between eBC and LDSA in fresh and photochemically aged RWC emissions. Photochemical aging was simulated in an oxidative flow reactor at OH• exposures equivalent to 1.4 or 3.4 days in the atmosphere. Further, the efficiency of a small-scale electrostatic precipitator (ESP) for reducing LDSA and eBC from the wood stove was determined. For fresh emission eBC correlated extremely well with LDSA, but the correlation decreased after aging. Soot-dominated flaming phase showed the highest eBC dependency of LDSA whereas for ignition and char burning phases non-BC particles contributed strongly the LDSA. Deposition to the alveolar region contributed around 60 % of the total lung-deposition. The ESP was found as an effective method to mitigate particulate mass, LDSA, as well as eBC emissions from wood stoves, as they were reduced on average by 72%, 71%, and 69%, respectively. The reduction efficiencies, however, consistently dropped over the span of an experiment, especially for eBC. Further, the ESP was found to increase the sub-30 nm ultrafine particle number emissions, with implications for LDSA. The results of this study can be used for assessing the contribution of RWC to LDSA concentrations in ambient air.

3.
ACS Appl Mater Interfaces ; 16(36): 47563-47570, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39197082

RESUMEN

Electrocatalytic water splitting is a crucial strategy for advancing hydrogen energy and addressing the global energy crisis. Despite its significance, the need for a straightforward and swift method to synthesize electrocatalysts with exceptional performance remains pressing. In this study, we demonstrate a novel approach for the preparation of multimetal-based electrocatalysts in a continuous flow reactor, enabling the quick synthesis of a large number of products through a streamlined process. The resultant NiFe-LDH comprises nanoflakes with a high specific surface area and requires only 255.4 mV overpotential to achieve a current density of 10 mA·cm-2 in 1 M KOH, surpassing samples fabricated by conventional hydrothermal methods. Our method can also be applied to craft a spectrum of other multimetal-based electrocatalysts, including CoFe-LDH, CoAl-LDH, NiMn-LDH, and NiCoFe-LDH. Additionally, the NiFe-LDH electrocatalyst is further applied to anodic methanol electrooxidation coupled with cathodic hydrogen evolution. Moreover, the simplicity and generality of our fabrication method render it applicable for the facile preparation of various multimetal-based electrocatalysts, offering a scalable solution to the quest for high-performance catalysts in advancing sustainable energy technologies.

4.
Chembiochem ; : e202400345, 2024 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-39087277

RESUMEN

Converting fatty acids into specialty chemicals is sustainable but hindered by the low efficiency and thermal instability of current oleic acid hydratases, along with mass transfer limitations in emulsion reactions. This study introduces an optimized continuous flow micro-reactor (CFMR) that efficiently transforms oleic acid at low (15 g·L-1) and high (50 g·L-1) concentrations, improving reaction efficiency and overcoming key conversion barriers. The first CFMR model showed reaction speeds surpassing traditional batch stirred tank reactors (BSTR). Optimizations were performed on three key components: liquid storage, mixer, and reaction section of the CFMR, with each round's best conditions carried into the next. This achieved a space-time yield of 597 g·L-1·d-1 at a 15 g·L-1 oleic acid load. To further enhance the yield, we optimized the emulsifier system to solve incomplete emulsification and developed a two-component feed microreactor (TCFMR) that addressed substrate and product inhibition at high loads, reaching a 91% conversion of 50 g·L-1 oleic acid in 30 minutes, with a space-time yield of 2312 g·L-1·d-1. These advancements represent significant progress in utilizing fatty acids and advancing sustainable chemical synthesis.

5.
J Environ Manage ; 366: 121793, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38991342

RESUMEN

Acidic nitrification, as a novel process for treating wastewater without sufficient alkalinity, has received increasing attention over the years. In this study, a continuous-flow reactor with aerobic granular sludge was successful operated at low pH (<6.5) performing high-rate acidic nitrification. Volumetric ammonium oxidation rate of 0.4-1.2 kg/(m3·d) were achieved with the specific biomass activities of 5.8-13.9 mg N/(gVSS·h). Stable partial nitritation with nitrite accumulation efficiency over 85% could be maintained at pH above 6 with the aid of residual ammonium, whereas the nitrite accumulation disappeared when pH was below 6. Interestingly, the granule morphology significantly improved during the acidic operation. The increased secretion of extracellular polymeric substances (especially polysaccharides) suggested a self-protective behavior of microbes in the aerobic granules against acidic stress. 16S rRNA gene sequencing analyses indicated that Candidatus Nitrospira defluvii was always the dominant nitrite-oxidizing bacteria, while the dominant ammonia-oxidizing bacteria shifted from Nitrosomonas europaea to Nitrosomonas mobilis. This study, for the first time, demonstrated the improved stability of aerobic granules under acidic conditions, and also highlighted aerobic granules as a useful solution to achieve high-rate acidic nitrification.


Asunto(s)
Reactores Biológicos , Nitrificación , Aguas del Alcantarillado , Concentración de Iones de Hidrógeno , Aguas del Alcantarillado/microbiología , Aguas Residuales/química , Eliminación de Residuos Líquidos/métodos , ARN Ribosómico 16S , Nitritos/metabolismo , Oxidación-Reducción
6.
Sci Total Environ ; 947: 174609, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-38997043

RESUMEN

This work presents the changing abundance of surface functional groups (SFGs) on polystyrene (PS) upon weathering within one or a few molecular monolayers from a molecular point of view. PS particles were aged by exposing it to a gas flow of typically (5 %) O3 in O2 (PSO3), UV radiation using a solar simulator under controlled conditions in the laboratory (PSSS) and to the water/air interface immerged in a freshwater lake for 2 months (PSL). The chemical composition of the interface of weathered, compared to pristine (virgin or PSV) material was established using a titration technique that probed the chemical composition of the molecular interface of the polymer. The main conclusions of this exploratory study are: (a) The interface of PS changes significantly compared to ATR-FTIR spectra that do not show additional absorptions in the mid-IR spectrum over a penetration depth of more than hundred monolayers at 10 µm; (b) The average surface functionalization of the gas-solid interface, corresponding to the sum of all examined types of SFG, increases from 20 % of a monolayer for PSV to 40, 50 and 84 % for PSL, PSO3 and PSSS, respectively; (c) in all cases the most important SFG was surface -OH ranging from 11.2 to 64 % for PSV and PSSS, respectively; (d) each PS sample shows a characteristic SFG pattern or fingerprint using several probe gases; (e) O3 interaction led to interface acidification; (f) UV treatment leads to the highest degree of surface -OH functionalization compared to PSO3 and PSL. The accumulation of SFG's renders the interface more reactive towards adsorption of probe gases.

7.
Polymers (Basel) ; 16(13)2024 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-39000617

RESUMEN

Due to the specificity, high efficiency, and gentleness of enzyme catalysis, the industrial utilization of enzymes has attracted more and more attention. Immobilized enzymes can be recovered/recycled easily compared to their free forms. The primary benefit of immobilization is protection of the enzymes from harsh environmental conditions (e.g., elevated temperatures, extreme pH values, etc.). In this paper, catalase was successfully immobilized in a poly(aryl ether sulfone) carrier (PAES-C) with tunable pore structure as well as carboxylic acid side chains. Moreover, immobilization factors like temperature, time, and free-enzyme dosage were optimized to maximize the value of the carrier and enzyme. Compared with free enzyme, the immobilized-enzyme exhibited higher enzymatic activity (188.75 U g-1, at 30 °C and pH 7) and better thermal stability (at 60 °C). The adsorption capacity of enzyme protein per unit mass carrier was 4.685 mg. Hydrogen peroxide decomposition carried out in a continuous-flow reactor was selected as a model reaction to investigate the performance of immobilized catalase. Immobilized-enzymes showed a higher conversion rate (90% at 8 mL/min, 1 h and 0.2 g) compared to intermittent operation. In addition, PAES-C has been synthesized using dichlorodiphenyl sulfone and the renewable resource bisphenolic acid, which meets the requirements of green chemistry. These results suggest that PAES-C as a carrier for immobilized catalase could improve the catalytic activity and stability of catalase, simplify the separation of enzymes, and exhibit good stability and reusability.

8.
Environ Sci Technol ; 58(24): 10652-10663, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38829825

RESUMEN

Secondary organic aerosol (SOA) formation from gasoline vehicles spanning a wide range of emission types was investigated using an oxidation flow reactor (OFR) by conducting chassis dynamometer tests. Aided by advanced mass spectrometric techniques, SOA precursors, including volatile organic compounds (VOCs) and intermediate/semivolatile organic compounds (I/SVOCs), were comprehensively characterized. The reconstructed SOA produced from the speciated VOCs and I/SVOCs can explain 69% of the SOA measured downstream of an OFR upon 0.5-3 days' OH exposure. While VOCs can only explain 10% of total SOA production, the contribution from I/SVOCs is 59%, with oxygenated I/SVOCs (O-I/SVOCs) taking up 20% of that contribution. O-I/SVOCs (e.g., benzylic or aliphatic aldehydes and ketones), as an obscured source, account for 16% of total nonmethane organic gas (NMOG) emission. More importantly, with the improvement in emission standards, the NMOG is effectively mitigated by 35% from China 4 to China 6, which is predominantly attributed to the decrease of VOCs. Real-time measurements of different NMOG components as well as SOA production further reveal that the current emission control measures, such as advances in engine and three-way catalytic converter (TWC) techniques, are effective in reducing the "light" SOA precursors (i.e., single-ring aromatics) but not for the I/SVOC emissions. Our results also highlight greater effects of O-I/SVOCs to SOA formation than previously observed and the urgent need for further investigation into their origins, i.e., incomplete combustion, lubricating oil, etc., which requires improvements in real-time molecular-level characterization of I/SVOC molecules and in turn will benefit the future design of control measures.


Asunto(s)
Aerosoles , Gasolina , Emisiones de Vehículos , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/química , Compuestos Orgánicos/química
9.
Polymers (Basel) ; 16(12)2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38932095

RESUMEN

In this study, a flash pyrolysis process is developed using an entrained flow reactor for recycling of waste tires. The flash pyrolysis system is tested for process stability and reproducibility of the products under similar operating conditions when operated continuously. The study is performed with two different feedstock materials, i.e., passenger car (PCT) and truck tire (TT) granulates, to understand the influence of feedstock on the yield and properties of the pyrolysis products. The different pyrolytic products i.e., pyrolytic carbon black (pCB), oil, and pyro-gas, are analyzed, and their key properties are discussed. The potential applications for the obtained pyrolytic products are discussed. Finally, a mass and energy balance analysis has been performed for the developed pyrolysis process. The study provides insight into the governing mechanisms of the flash pyrolysis process for waste tires, which is useful to optimize the process depending on the desired applications for the pyrolysis products, and also to scale up the pyrolysis process.

10.
J Hazard Mater ; 474: 134596, 2024 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-38820744

RESUMEN

Because of the significant environmental and health hazards imposed by di(2-ethylhexyl) phthalate (DEHP), a common plasticizer, developing safe and green techniques to degrade DEHP plasticizer is of huge scientific significance. It has been observed that environmental contamination of DEHP may also induce serious food safety problems because crops raised in plasticizers contaminated soils would transfer the plasticizer into foods, such as Baijiu. Additionally, when plastic packaging or vessels are used during Baijiu fermentation and processing, plasticizer compounds frequently migrate and contaminate the product. In this study, hairpin-like structured peptides with catalytically active sites containing serine, histidine and aspartic acid were found to degrade DEHP. Furthermore, after incorporating caffeic acid molecules at the N-terminus, the peptides could be attached onto foam titanium (Ti) surfaces via enediol-metal interactions to create an enzyme-mimicking flow reactor for the degradation of DEHP in Baijiu. The structure and catalytic activity of peptides, their interaction with DEHP substrate and the hydrolysis mechanism of DEHP were discussed in this work. The stability and reusability of the peptide-modified foam Ti flow reactor were also investigated. This approach provides an effective technique for the degradation of plasticizer compounds.


Asunto(s)
Dietilhexil Ftalato , Péptidos , Plastificantes , Titanio , Dietilhexil Ftalato/química , Dietilhexil Ftalato/metabolismo , Plastificantes/química , Titanio/química , Péptidos/química , Péptidos/metabolismo , Hidrólisis
11.
Water Res ; 257: 121531, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38701553

RESUMEN

The development of continuous flow reactors (CFRs) employing aerobic granular sludge (AGS) for the retrofit of existing wastewater treatment plants (WWTPs) using a continuous-flow activated sludge (CFAS) system has garnered increasing interest. This follows the worldwide adoption of AGS technology in sequencing batch reactors (SBRs). The better settleability of AGS compared to AS allows for process intensification of existing wastewater treatment plants without the difficult conversion of often relatively shallow CFRs to deeper AGS-SBRs. To retrofit existing CFAS systems with AGS, achieving both increased hydraulic capacity and enhanced biological nutrient removal necessitates the formation of granular sludge based on the same selective pressures applied in AGS-SBRs. Previous efforts have focussed mainly on the selective wasting of flocculent sludge and retaining granular sludge to drive aerobic granulation. In this study a pilot-scale CFR was developed to best mimic the implementation of the granulation mechanisms of full-scale AGS-SBRs. The pilot-scale reactor was fed with pre-settled municipal wastewater. We established metrics to assess the degree to which the proposed mechanisms were implemented in the pilot-scale CFR and compared them to data from full-scale AGS-SBRs, specifically with respect to the anaerobic distribution of granule forming substrates (GFS). The selective pressures for granular sludge formation were implemented through inclusion of anaerobic upflow selectors with a water depth of 2.5 meters, which yielded a sludge with properties similar to AGS from full-scale SBRs. In comparison to the CFAS system at Harnaschpolder WWTP treating the same pre-settled wastewater, a more than twofold increase in volumetric removal capacity for both phosphorus and nitrogen was achieved. The use of a completely mixed anaerobic selector, as opposed to an anaerobic upflow selector, caused a shift in EBPR activity from the largest towards the smallest size class, while nitrification was majorly unaffected. Anaerobic selective feeding via bottom-feeding is, therefore, favorable for the long-term stability of AGS, especially for less acidified wastewater. The research underlines the potential of AGS for enhancing the hydraulic and biological treatment capacity of existing CFAS systems.


Asunto(s)
Reactores Biológicos , Aguas del Alcantarillado , Eliminación de Residuos Líquidos , Anaerobiosis , Aerobiosis , Eliminación de Residuos Líquidos/métodos , Aguas Residuales , Proyectos Piloto
12.
J Hazard Mater ; 469: 134042, 2024 May 05.
Artículo en Inglés | MEDLINE | ID: mdl-38521031

RESUMEN

The indirect chloride-mediated ammonia oxidation encounters challenges in maintaining the effectiveness of metal oxide anodes when treating wastewaters with complex compositions. This study aims to develop a highly stable anode with RuO2-SnO2 coatings for treating an etching effluent from semiconductor manufacturing, which majorly contains NH3 and organic compounds. The RuSnOx/Ti electrode was synthesized using wet impregnation and calcination processes. The metal oxide configuration on Ti plate substrate was tuned by varying the step-dipping process in RuCl3 and SnCl4 baths. A 10-day continuous-flow electrolysis was conducted for studying the ammonia removal and chlorine yield under variable conditions, including detention, pH, current density, and initial ammonia and chloride concentrations. In the RuSnOx coatings, the configuration comprising RuO2 nanorods as the surface layer and an intermediate layer of SnO2 crystallites (by plating Ru3+ for three times to cover one Sn4+ layer, denoted as the Ru3Sn/Ti electrode) exhibited the best durability for acid washing, along with relatively high Faradaic efficiency and low energy consumption. To further improve the treatability of real wastewater (NH3-N = 634 mg L-1, chemical oxygen demand (COD) = 6700 mg L-1, Cl- = 2000 mg L-1, pH 11), the duel-cell electrolyzers were constructed in series under a current density of 30 mA cm-2 and 45 min detention. Ultimately, removals of NH3 and COD reached 95.8% and 76.3%, respectively, with successful limitation of chloramine formation.

13.
Carbohydr Polym ; 330: 121837, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38368114

RESUMEN

Cellulose monolith materials have interconnected open porous structures with very high porosity, making them attractive structures for use as support materials in heterogeneous catalysis applications. In this study, we developed a highly efficient and reusable continuous-flow reactor for Cr(VI) remediation by combining the advantageous features of cellulose monoliths with suitable reinforcement techniques. We fabricated a porous monolithic cellulose/graphene oxide (GO) composite with a continuous three-dimensional skeletal framework using the thermally induced phase separation technique. Pd nanocrystals were synthesized in situ on the surface of the composite monolith, and then converted to porous Pd-Pt bimetallic nanocrystals through a galvanic replacement reaction. This approach eliminated the need for additional reductants and stabilizers, making the process simpler and more environmentally friendly. Under carefully optimized conditions, the cellulose/GO/Pd-Pt nanocomposite monolith exhibited outstanding performance in continuous-flow reactions for Cr(VI) reduction, achieving a maximum conversion rate of 98 %. Moreover, the nanocomposite monolith-based heterogeneous catalyst exhibited remarkable long-term stability, maintaining its catalytic activity even after extended periods of storage in the dried state. These findings highlight the potential of cellulose-based composite monoliths as versatile and robust support materials for heterogeneous catalysis.

14.
Environ Res ; 251(Pt 1): 118542, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38403149

RESUMEN

Secondary aerosols constitute a significant fraction of atmospheric aerosols, yet our understanding of their formation mechanism and fate is very limited. In this work, the secondary organic aerosol (SOA) formation and aging of ambient air of Delhi are studied using a potential aerosol mass (PAM) reactor, an oxidation flow reactor (OFR), coupled with aerosol chemical speciation monitor (ACSM), proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS), and scanning mobility particle sizer with counter (SMPS + C). The setup mimics atmospheric aging of up to several days with the generation of OH radicals. Variations in primary volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) as a function of photochemical age were investigated. Primary VOCs such as benzene, toluene, xylene, trimethyl benzene, etc. decrease and OVOCs like formic acid, formaldehyde, acetone, ethanol, etc. increase substantially upon oxidation in OFR. The highest organic aerosol (OA) enhancement was observed for the 4.2 equivalent photochemical days of aging i.e., 1.84 times the ambient concentration, and net OA loss was observed at very high OH exposure, typically after 8.4 days of photochemical aging due to heterogeneous oxidation followed by fragmentation/evaporation. In ambient air, OA enhancement is highest during nighttime due to the high concentrations of precursor VOCs in the atmosphere. SMPS + C results demonstrated substantial new particle formation upon aging and decrement in preexisting aerosol mass. This is the first experimental study conducting an in-situ evaluation of potential SOA mass generated from the ambient aerosols in India.


Asunto(s)
Aerosoles , Contaminantes Atmosféricos , Oxidación-Reducción , Compuestos Orgánicos Volátiles , Aerosoles/análisis , Aerosoles/química , India , Compuestos Orgánicos Volátiles/análisis , Contaminantes Atmosféricos/análisis , Contaminantes Atmosféricos/química , Monitoreo del Ambiente
15.
BMC Chem ; 18(1): 28, 2024 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-38331896

RESUMEN

The electrochemical conversion of biobased intermediates offers an attractive and sustainable process for the production of green chemicals. One promising synthesis route is the production of the total vanillin-based polymer polyvanillin, which can be produced by electrochemical pinacolization of divanillin (5-5´bisvanillyl). Divanillin can be easily enzymatically generated from vanillin, a renewable intermediate accessible from lignin on an industrial scale. This study investigates systematically the electrochemical production of polyvanillin in a divided plane parallel flow reactor in recirculation mode. Several analytic methods, such as online UV-VIS spectroscopy, size exclusion chromatography (SEC), 2D-NMR (HSQC, 13C/1H), TGA and DSC were used to monitor the reaction progress and to characterize the reaction products under different galvanostatic reaction conditions revealing new insights into the reaction mechanism and structural features of the polymer. Further, by using an electrochemical engineering-based approach determining the limiting current densities, we readily achieved high current densities over 50 mA cm-2 for the polyvanillin synthesis and reached averaged molecular weights up to Mw = 4100 g mol-1 and Mn = 2700 g mol-1. The cathodic polymerization to polyvanillin offers an innovative approach for the electrochemical production of biobased polymers presented on flow cell level.

16.
Bioengineering (Basel) ; 11(2)2024 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-38391651

RESUMEN

With the increasing use of renewable energy resources for the power grid, the need for long-term storage technologies, such as power-to-gas systems, is growing. Biomethanation provides the opportunity to store energy in the form of the natural gas-equivalent biomethane. This study investigates a novel plug flow reactor that employs a helical static mixer for the biological methanation of hydrogen and carbon dioxide. In tests, the reactor achieved an average methane production rate of 2.5 LCH4LR∗d (methane production [LCH4] per liter of reactor volume [LR] per day [d]) with a maximum methane content of 94%. It demonstrated good flexibilization properties, as repeated 12 h downtimes did not negatively impact the process. The genera Methanothermobacter and Methanobacterium were predominant during the initial phase, along with volatile organic acid-producing, hydrogenotrophic, and proteolytic bacteria. The average ratio of volatile organic acid to total inorganic carbon increased to 0.52 ± 0.04, while the pH remained stable at an average of pH 8.1 ± 0.25 from day 32 to 98, spanning stable and flexible operation modes. This study contributes to the development of efficient flexible biological methanation systems for sustainable energy storage and management.

17.
Chempluschem ; 89(5): e202300643, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38230921

RESUMEN

The selective hydrogenation of 5-(hydroxymethyl)furfural (HMF) into 2,5-bis-(hydroxymethyl)tetrahydrofuran (BHMTHF) in flow reactor using water as a green solvent, has been achieved on a non-noble metal catalyst based on monodispersed CoNi alloy nanoparticles covered by a thin carbon layer. The alloyed catalyst containing CoNi (molar ratio 1 : 1) was prepared in a one-step synthesis following a hydrothermal method. Total conversion of HMF with 91 % selectivity to BHMTHF was achieved. The reaction network has been stablished, in which the carbonyl group of HMF is first reduced to alcohol giving the 2,5-bis-(hydroxymethyl)furan (BHMF) with an apparent activation energy of 25 KJ/mol, and then the double bonds of the furan ring are hydrogenated (apparent Ea=31 KJ/mol). Formation of byproducts, mainly proceed from furan ring opening and ring rearrangement processes of BHMF, promoted by water. BHMTHF resulted a compound highly stable under reaction conditions. The fixed bed flow reactor was maintained operational for 65 h without observing any loss of catalytic activity and selectivity.

18.
ChemSusChem ; 17(2): e202301149, 2024 Jan 22.
Artículo en Inglés | MEDLINE | ID: mdl-37737522

RESUMEN

The utilization of water as a sustainable reaction medium has important advantages over traditional organic solvents. Hydroxypropyl methylcellulose has emerged as a biomass-based polymeric additive that enables organic reactions in water through hydrophobic effects. However, such conditions imply slurries as reaction mixtures, where the efficacy of mass transfer and mixing decreases with increasing vessel size. In order to circumvent this limitation and establish an effectively scalable platform for performing hydroxypropyl methylcellulose-mediated aqueous transformations, we utilized oscillatory plug flow reactors that feature a smart dimensioning design principle across different scales. Using nucleophilic aromatic substitutions as valuable model reactions, rapid parameter optimization was performed first in a small-scale instrument having an internal channel volume of 5 mL. The optimal conditions were then directly transferred to a 15 mL reactor, achieving a three-fold scale-up without re-optimizing any reaction parameters. By precisely fine-tuning the oscillation parameters, the system achieved optimal homogeneous suspension of solids, preventing settling of particles and clogging of process channels. Ultimately, this resulted in a robust and scalable platform for performing multiphasic reactions under aqueous conditions.

19.
J Gen Appl Microbiol ; 69(4): 206-214, 2024 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-37197975

RESUMEN

α-1,3-Glucanase Agl-KA from Bacillus circulans KA-304 consists of a discoidin domain (DS1), a carbohydrate binding module family 6 (CBM6), a threonine-proline-rich-linker (TP linker), a discoidin domain (DS2), an uncharacterized domain, and a catalytic domain. The binding of DS1, CBM6, and DS2 to α-1,3-glucan can be improved in the presence of two of these three domains. In this study, DS1, CBM6, and TP linker were genetically fused to histamine dehydrogenase (HmDH) from Nocardioides simplex NBRC 12069. The fusion enzyme, AGBDs-HmDH, was expressed in Escherichia coli Rosetta 2 (DE3) and purified from the cell-free extract. AGBDs-HmDH bound to 1% micro-particle of α-1,3-glucan (diameter: less than 1 µm) and 7.5% coarse-particle of α-1,3-glucan (less than 200 µm) at about 97 % and 70% of the initial amounts of the enzyme, respectively. A reactor for flow injection analysis filled with AGBDs-HmDH immobilized on the coarse-particle of α-1,3-glucan was successfully applied to determine histamine. A linear calibration curve was observed in the range for about 0.1 to 3.0 mM histamine. These findings suggest that the combination of α-1,3-glucan and α-1,3-glucan binding domains is a candidate for novel enzyme immobilization.


Asunto(s)
Glucanos , Histamina , Oxidorreductasas actuantes sobre Donantes de Grupo CH-NH , Glucanos/metabolismo , Dominio Catalítico
20.
Nanomaterials (Basel) ; 13(23)2023 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-38063689

RESUMEN

The need to replace conventional fuels with renewable sources is a great challenge for the science community. H2 is a promising alternative due to its high energy density and availability. H2 generation from formic acid (FA) decomposition occurred in a batch and a packed-bed flow reactor, in mild conditions, using a 2% Pd6Zn4/HHT (high heated treated) catalyst synthesised via the sol-immobilisation method. Experimental and theoretical studies took place, and the results showed that in the batch system, the conversion was enhanced with increasing reaction temperature, while in the continuous flow system, the conversion was found to decrease due to the deactivation of the catalyst resulting from the generation of the poisoning CO. Computational fluid dynamics (CFD) studies were developed to predict the conversion profiles, which demonstrated great validation with the experimental results. The model can accurately predict the decomposition of FA as well as the deactivation that occurs in the continuous flow system. Of significance was the performance of the packed-bed flow reactor, which showed improved FA conversion in comparison to the batch reactor, potentially leading to the utilisation of continuous flow systems for future fuel cell applications for on-site H2 production.

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