Development of a Cryogenic Flow Reactor to Optimize Glycosylation Reactions Based on the Active Donor Intermediate.

The development of a continuous flow reactor for stereospecific glycosylation reactions with deoxy sugars is described. This apparatus that permits optimizing the selectivity of glycosylation reactions based on the stability of the activated intermediate is described. By coupling a flow apparatus with HPLC analysis, we can optimize the yield of TsCl-mediated ß-linked deoxy sugar construction in a matter of hours. In all cases, results from continuous flow processing translate into improved results in batch-scale reactions, as demonstrated by competition experiments. This is the result of carrying out optimization to identify the ideal temperature for the reaction of the activated intermediate, as opposed to the initial activation conditions. Such an approach allows for the rapid development of highly selective glycosylation reactions in cases in which classical neighboring group participation is not possible.

Best Practices for Assessing Performance of Photocatalytic Water Splitting Systems.

Photocatalytic water splitting has become a very popular research subject in recent years. Consequently, it is important to report appropriately standardized experimental data, so that each researcher can properly understand the results generated by others. However, experimental methods and measures of photocatalytic performance are not yet sufficiently systematic. In the present manuscript, experimental procedures and standardization of photocatalytic performance are described in relation to the basic theory of photocatalytic water splitting.

Principles, challenges and prospects for electro-oxidation treatment of oilfield produced water.

The oil industry is facing substantial environmental challenges, especially in managing waste streams such as Oilfield Produced Water (OPW), which represents a significant component of the industrial ecological footprint. Conventional treatment methods often fail to effectively remove dissolved oils and grease compounds, leading to operational difficulties and incomplete remediation. Electrochemical oxidation (EO) has emerged as a promising alternative due to its operational simplicity and ability to degrade pollutants directly and indirectly, which has already been applied in treating several effluents containing organic compounds. The application of EO treatment for OPW is still in an initial stage, due to the intricate nature of this matrix and scattered information about it. This study provides a technological overview of EO technology for OPW treatment, from laboratory scale to the development of large-scale prototypes, identifying design and process parameters that can potentially permit high efficiency, applicability, and commercial deployment. Research in this domain has demonstrated notable rates of removal of recalcitrant pollutants (>90%), utilizing active and non-active electrodes. Electro-generated active species, primarily from chloride, play a pivotal role in the oxidation of organic compounds. However, the highly saline conditions in OPW hinder the complete mineralization of these organics, which can be improved by using non-active anodes and lower salinity levels. The performance of electrodes greatly influences the efficiency and effectiveness of OPW treatment. Various factors must be considered when selecting the electrode material, such as its conductivity, stability, surface area, corrosion resistance, and cost. Additionally, the specific contaminants present in the OPW, and their electrochemical reactivity must be considered to ensure optimal treatment outcomes. Balancing these considerations can be challenging, but it is crucial for achieving successful OPW treatment. Active electrode materials exhibit a high affinity for chloride molecules, generating more active species than non-active materials, which exhibit more significant degradation potential due to the production of hydroxyl radicals. Regarding scale-up, key challenges include low current efficiency, the formation of by-products, electrode deactivation, and limitations in mass transfer. To address these issues, enhanced mass transfer rates and appropriate residence times can be achieved using flow-through mesh anodes and moderate current densities, which have proven to be the optimal configuration for this process.

Exogenous microbubbles contribute to valorization of microalgal compounds by ultrasound-assisted extraction.

Ultrasound-assisted extraction (UAE) shows great potential in exploiting microalgal compounds. However, upgrading the extraction system lacks concerns. This study proposes a novel sono-reactor featuring a microbubble distributor for increasing bubble abundance and correspondingly improving microalgal compound extraction. Results indicate that protein concentrations increase with ultrasound powers and extraction time while an optimized gas flow rate exists. The optimal parameters by Box-Behnken design are power 646.0 W, nitrogen flow rate 25.0 mL/min, and time 40.0 min, with an optimal protein concentration of 249.1 mg/L - a substantial improvement over gas-free extraction. The strategic increase in bubble abundance enhances microalgal compound extraction efficiency and extraction kinetics. The system innovation will contribute to the advancement of bioresource utilization and sustainability.

Microbial electrosynthesis from CO2 reaches productivity of syngas and chain elongation fermentations.

Carbon-based products are essential to society, yet producing them from fossil fuels is unsustainable. Microorganisms have the ability to take up electrons from solid electrodes and convert carbon dioxide (CO2) to valuable carbon-based chemicals. However, higher productivities and energy efficiencies are needed to reach a viability that can make the technology transformative. Here, we show how a biofilm-based microbial porous cathode in a directed flow-through electrochemical system can continuously reduce CO2 to even-chain C2-C6 carboxylic acids over 248 days. We demonstrate a threefold higher biofilm concentration, volumetric current density, and productivity compared with the state of the art. Most notably, the volumetric productivity (VP) resembles those achieved in laboratory-scale and industrial syngas (CO-H2-CO2) fermentation and chain elongation fermentation. This work highlights key design parameters for efficient electricity-driven microbial CO2 reduction. There is need and room to improve the rates of electrode colonization and microbe-specific kinetics to scale up the technology.

Advanced Nanocarbons Toward two-Electron Oxygen Electrode Reactions for H2O2 Production and Integrated Energy Conversion.

Hydrogen peroxide (H2O2) plays a pivotal role in advancing sustainable technologies due to its eco-friendly oxidizing capability. The electrochemical two-electron (2e-) oxygen reduction reaction and water oxidation reaction present an environmentally green method for H2O2 production. Over the past three years, significant progress is made in the field of carbon-based metal-free electrochemical catalysts (C-MFECs) for low-cost and efficient production of H2O2 (H2O2EP). This article offers a focused and comprehensive review of designing C-MFECs for H2O2EP, exploring the construction of dual-doping configurations, heteroatom-defect coupling sites, and strategic dopant positioning to enhance H2O2EP efficiency; innovative structural tuning that improves interfacial reactant concentration and promote the timely release of H2O2; modulation of electrolyte and electrode interfaces to support the 2e- pathways; and the application of C-MFECs in reactors and integrated energy systems. Finally, the current challenges and future directions in this burgeoning field are discussed.

Thermophysical Properties of FUNaK (NaF-KF-UF4) Eutectics.

General interest in the deployment of molten salt reactors (MSRs) is growing, while the available data on uranium-containing fuel salt candidates remains scarce. Thermophysical data are one of the key parameters for reactor design and understanding reactor operability. Hence, filling in the gap of the missing data is crucial to allow for the advancement of MSRs. This study provides novel data for two eutectic compositions within the NaF-KF-UF4 ternary system which serve as potential fuel candidates for MSRs. Experimental measurements include their melting point, density, fusion enthalpy, and vapor pressure. Additionally, their boiling point was extrapolated from the vapor pressure data, which were, at the same time, used to determine the enthalpy of vaporization. The obtained thermodynamic values were compared with available data from the literature but also with results from thermochemical equilibrium calculations using the JRCMSD database, finding a good correlation, which thus contributed to database validation. Preliminary thoughts on fluoride salt reactor operability based on the obtained results are discussed in this study.

Wall-Immobilized Biocatalyst vs. Packed Bed in Miniaturized Continuous Reactors: Performances and Scale-Up.

Sustainable biocatalysis syntheses have gained considerable popularity over the years. However, further optimizations - notably to reduce costs - are required if the methods are to be successfully deployed in a range of areas. As part of this drive, various enzyme immobilization strategies have been studied, alongside process intensification from batch to continuous production. The flow bioreactor portfolio mainly ranges between packed bed reactors and wall-immobilized enzyme miniaturized reactors. Because of their simplicity, packed bed reactors are the most frequently encountered at lab-scale. However, at industrial scale, the growing pressure drop induced by the increase in equipment size hampers their implementation for some applications. Wall-immobilized miniaturized reactors require less pumping power, but a new problem arises due to their reduced enzyme-loading capacity. This review starts with a presentation of the current technology portfolio and a reminder of the metrics to be applied with flow bioreactors. Then, a benchmarking of the most recent relevant works is presented. The scale-up perspectives of the various options are presented in detail, highlighting key features of industrial requirements. One of the main objectives of this review is to clarify the strategies on which future study should center to maximize the performance of wall-immobilized enzyme reactors.

Pickering emulsion biocatalysis: Bridging interfacial design with enzymatic reactions.

Non-homogeneous enzyme-catalyzed systems are more widely used than homogeneous systems. Distinguished from the conventional biphasic approach, Pickering emulsion stabilized by ultrafine solid particles opens up an innovative platform for biocatalysis. Their vast specific surface area significantly enhances enzyme-substrate interactions, dramatically increasing catalytic efficiency. This review comprehensively explores various aspects of Pickering emulsion biocatalysis, provides insights into the multiple types and mechanisms of its catalysis, and offers strategies for material design, enzyme immobilization, emulsion formation control, and reactor design. Characterization methods are summarized for the determination of drop size, emulsion type, interface morphology, and emulsion potential. Furthermore, recent reports on the design of stimuli-responsive reaction systems are reviewed, enabling the simple control of demulsification. Moreover, the review explores applications of Pickering emulsion in single-step, cascade, and continuous flow reactions and outlines the challenges and future directions for the field. Overall, we provide a review focusing on Pickering emulsions catalysis, which can draw the attention of researchers in the field of catalytic system design, further empowering next-generation bioprocessing.

Scaling up of dual-chamber microbial electrochemical systems - An appraisal using systems design approach.

Impetus to minimise the energy and carbon footprints of evolving wastewater resource recovery facilities has promoted the development of microbial electrochemical systems (MES) as an emerging energy-neutral and sustainable platform technology. Using separators in dual-chamber MES to isolate anodic and cathodic environments creates endless opportunities for its myriad applications. Nevertheless, the high internal resistance and the complex interdependencies among various system factors have challenged its scale-up. This critical review employed a systems approach to examine the complex interdependencies and practical issues surrounding the implementation and scalability of dual-chamber MES, where the anodic and cathodic reactions are mutually appraised to improve the overall system efficiency. The robustness and stability of anodic biofilms in large-volume MES is dependent on its inoculum source, antecedent history and enrichment strategies. The composition and anode-respiring activity of these biofilms are modulated by the anolyte composition, while their performance demands a delicate balance between the electrode size, macrostructure and the availability of substrates, buffers and nutrients when using real wastewater as anolyte. Additionally, the catholyte governed the reduction environment and associated energy consumption of MES with scalable electrocatalysts needed to enhance the sluggish reaction kinetics for energy-efficient resource recovery. A comprehensive assessment of the dual-chamber reactor configuration revealed that the tubular, spiral-wound, or plug-in modular MES configurations are suitable for pilot-scale, where it could be designed more effectively using efficient electrode macrostructure, suitable membranes and bespoke strategies for continuous operation to maximise their performance. It is anticipated that the critical and analytical understanding gained through this review will support the continuous development and scaling-up of dual-chamber MES for prospective energy-neutral treatment of wastewater and simultaneous circular management of highly relevant environmental resources.

Rational PCR Reactor Design in Microfluidics.

Limit of detection (LOD), speed, and cost for some of the most important diagnostic tools, i.e., lateral flow assays (LFA), enzyme-linked immunosorbent assays (ELISA), and polymerase chain reaction (PCR), all benefited from both the financial and regulatory support brought about by the pandemic. From those three, PCR has gained the most in overall performance. However, implementing PCR in point of care (POC) settings remains challenging because of its stringent requirements for a low LOD, multiplexing, accuracy, selectivity, robustness, and cost. Moreover, from a clinical point of view, it has become very desirable to attain an overall sample-to-answer time (t) of 10 min or less. Based on those POC requirements, we introduce three parameters to guide the design towards the next generation of PCR reactors: the overall sample-to-answer time (t); lambda (λ), a measure that sets the minimum number of copies required per reactor volume; and gamma (γ), the system's thermal efficiency. These three parameters control the necessary sample volume, the number of reactors that are feasible (for multiplexing), the type of fluidics, the PCR reactor shape, the thermal conductivity, the diffusivity of the materials used, and the type of heating and cooling systems employed. Then, as an illustration, we carry out a numerical simulation of temperature changes in a PCR device, discuss the leading commercial and RT-qPCR contenders under development, and suggest approaches to achieve the PCR reactor for RT-qPCR of the future.

Advanced treatment of industrial wastewater by ozonation with iron-based monolithic catalyst packing: From mechanism to application.

An Fe-based catalyst was prepared by oxidising waste Fe shavings directly in a solution. In engineering applications, Fe shavings were compressed and modified to form Fe-based monolithic catalyst packing. Both of which exhibited excellent catalytic activity in catalytic ozonation industrial wastewater after biochemical treatment. Fe-based monolithic catalyst packing has irregular channels, large porosity, small pore diameter, and the effective specific surface area (SSA) up to 3500 m2/m3, these characteristics are conducive to mass transfer, and promote the effective utilisation of •OH in the catalyst "action zone". A tower reactor (<3000 m3/d) and reinforced concrete construction reactor (>5000 m3/d) were designed according to the wastewater flow. Regression analysis showed that hydraulic residence time (HRT) and O3/CODin are important parameters in engineering design and operation. In addition, strategies for the application of Fe-based monolithic catalyst packing to wastewater with high salinity and high inorganic carbon concentration have been proposed. Fe-based monolithic catalyst packing catalytic ozonation is a relatively cost-effective and eco-friendly process with extremely broad application prospects in the advanced treatment of industrial wastewater.

A comparison of reactor configuration using a fruit waste fed two-stage anaerobic up-flow leachate reactor microbial fuel cell and a single-stage microbial fuel cell.

Food waste generation and its consequent environmental impacts are increasing due to rapid urbanization, the global population, and associated food demand. Microbial fuel cells (MFCs) are a sustainable technology through which this food waste can be treated and used to produce bioelectricity. This study used two MFC configurations, a two-stage anaerobic up-flow leachate reactor MFC and a single-stage MFC, comparing the potential to treat solid fruit waste and fruit waste leachate. The two-stage MFC showed a higher potential to remove substrate at a shorter time compared to single-stage MFC. In 30 days, the two-stage anaerobic up-flow leachate reactor had a power density of 221 mW/m2. It was able to remove more total solids (by 95 %), volatile solids (by 70 %), total chemical oxygen demand (by 83 %), soluble chemical oxygen demand (by 87 %), and carbohydrates (by 33 %) compared to the single-stage MFC. However, the single-stage MFC showed higher coulombic efficiency (by 86.7 %) compared to the two-stage MFC. The efficiency of single-stage MFC improved by adding buffer and maintaining a neutral pH level of the substrate. The results of this study emphasize the importance of reactor design and demonstrate that MFC can be a viable technology to generate bioenergy from food waste.

Destruction of PFAS in AFFF-impacted fire training pit water, with a continuous hydrothermal alkaline treatment reactor.

As regulations are being established to limit the levels of per- and polyfluoroalkyl substances (PFAS) in drinking water and wastewater, effective treatment technologies are needed to remove or destroy PFAS in contaminated liquid matrices. Many military installations and airports have fire training ponds (FTPs) where PFAS-containing firefighting foams are discharged during training drills. FTP water disposal is expensive and challenging due to the high PFAS levels. Hydrothermal alkaline treatment (HALT) has previously been shown to destroy a wide range of PFAS compounds with a high degree of destruction and defluorination. In this study, we investigate the performance of a continuous flow HALT reactor for destroying PFAS in contaminated FTP water samples. Processing with 5 M-NaOH and 1.6 min of continuous processing results in >99% total PFAS destruction, and 10 min processing time yields >99% destruction of every measured PFAS species. Operating with 0.1 M-NaOH or 1 M-NaOH shows little effect on the destruction of measured perfluorosulfonic acids, while all measured perfluorocarboxylic acids and fluorotelomer sulfonates are reduced to levels below the method detection limits. Continuous HALT processing with sufficient NaOH loading appears to destroy parent PFAS compounds significantly faster than batch HALT processing, a positive indicator for scaling up HALT technology for practical applications in environmental site remediation activities.

Photocatalytic Oxidation for Volatile Organic Compounds Elimination: From Fundamental Research to Practical Applications.

Photocatalysis is regarded as one of the most promising technologies for indoor volatile organic compounds (VOCs) elimination due to its low cost, safe operation, energy efficiency, and high mineralization efficiency under ambient conditions. However, the practical applications of this technology are limited, despite considerable research efforts in recent decades. Until now, most of the works were carried out in the laboratory and focused on exploring new catalytic materials. Only a few works involved the immobilization of catalysts and the design of reactors for practical applications. Therefore, this review systematically summarizes the research and development on photocatalytic oxidation (PCO) of VOCs, with emphasis on recent catalyst's immobilization and reactor designs in detail. First, different types of photocatalytic materials and the mechanisms for PCO of VOCs are briefly discussed. Then, both the catalyst's immobilization techniques and reactor designs are reviewed in detail. Finally, the existing challenges and future perspectives for PCO of VOCs are proposed. This work aims to provide updated information and research inspirations for the commercialization of this technology in the future.

Challenges Arising from Continuous-Flow Olefin Metathesis.

The versatility of olefin metathesis is evident from its successful applications ranging from natural product synthesis to the valorization of renewable feedstocks. On the other side, flow chemistry has recently gained particular interest among the synthetic community, offering valuable alternatives to classic batch chemistry and paving the way to the development of new transformations. The application of continuous-flow methods to olefin metathesis represents one of the most promising evolutions in the field at the interface of industrially relevant synthesis and reactor engineering, significantly improving some of the typical problems such as undesired self-reactions and ethylene-mediated catalyst deactivation. This Minireview aims to provide a brief survey covering the major aspects of those techniques which we hope may be of interest for the chemical community as well as those interested in catalysis, continuous processing, enabling technologies and reactor design.

Towards the Configuration of a Photoelectrocatalytic Reactor: Part 2-Selecting Photoreactor Flow Configuration and Operating Variables by a Numerical Approach.

This work aims to select a photoreactor flow configuration and operational conditions that maximize the Photocatalytic Space-time Yield in a photoelectrocatalytic reactor to degrade Reactive Red 239 textile dye. A numerical study by Computational Fluid Dynamics (CFD) was carried out to model the phenomena of momentum and species transport and surface reaction kinetics. The photoreactor flow configuration was selected between axial (AF) and tangential (TF) inlet and outlet flow, and it was found that the TF configuration generated a higher Space-time Yield (STY) than the AF geometry in both laminar and turbulent regimes due to the formation of a helical movement of the fluid, which generates velocity in the circumferential and axial directions. In contrast, the AF geometry generates a purely axial flow. In addition, to maximize the Photocatalytic Space-time Yield (PSTY), it is necessary to use solar radiation as an external radiation source when the flow is turbulent. In conclusion, the PSTY can be maximized up to a value of 45 g/day-kW at an inlet velocity of 0.2 m/s (inlet Reynolds of 2830), solar radiation for external illumination, and internal illumination by UV-LEDs of 14 W/m2, using a photoreactor based on tangent inlet and outlet flow.

Towards the Configuration of a Photoelectrocatalytic Reactor: Part 1-Determination of Photoelectrode Geometry and Optical Thickness by a Numerical Approach.

Photoelectrocatalysis has been highlighted as a tertiary wastewater treatment in the textile industry due to its high dye mineralisation capacity. However, design improvements are necessary to overcome photo-reactors limitations. The present work proposes a preliminary configuration of a photoelectrocatalytic reactor to degrade Reactive Red 239 (RR239) textile dye, using computational fluid dynamics (CFD) to analyse the mass transfer rate, radiation intensity loss (RIL), and its effect on kinetics degradation, over a photoelectrode based on a TiO2 nanotube. A study to increase the space-time yield (STY) was carried out through mass transfer rate and kinetic analysis, varying the optical thickness (δ) between the radiation entrance and the photocatalytic surface, photoelectrode geometry, inlet flow rate, and the surface radiation intensity. The RIL was determined using a 1D Beer-Lambert-based model, and an extinction coefficient experimentally determined by UV-Vis spectroscopy. The results show that in RR239 solutions below concentrations of 6 mg/L, a woven mesh photoelectrode and an optimal optical thickness δ of 1 cm is enough to keep the RIL below 15% and maximise the mass transfer and the STY in around 110 g/m3-day.

Two-stage anaerobic digestion: State of technology and perspective roles in future energy systems.

Two-stage anaerobic digestion (TSAD) systems have been studied on a laboratory scale for about 50 years. However, they have not yet reached industrial scale despite their potential for future energy systems. This review provides an analysis of the TSAD technology, including the influence of process parameters on biomass conversion rates. The most common substrate (35.2% of the 38 selected studies) used in the analysed data was in the category of rapidly hydrolysable industrial waste with an average dry matter content of 7.24%. The highest methane content of 85% was reached when digesting food waste in a combination of two mesophilic continuously stirred tank reactors with an acidic (pH 5.5) first stage and alkaline (pH 7) second stage. Therefore, the review shows the limitations of the TSAD technology, future research directions, and the effect of integration of TSAD systems into the current strategy to reduce greenhouse gas emissions.