Gas–Liquid Slug Flow Studies in Microreactors: Effect of Nanoparticle Addition on Flow Pattern and Pressure Drop

Colloidal suspensions of nanoparticles (e.g., metals and oxides) have been considered as a promising working fluid in microreactors for achieving significant process intensification. Existing examples include their uses in microflow as catalysts for enhancing the reaction efficiency, or as additives to mix with the base fluid (i.e., to form the so-called nanofluids) for heat/mass transfer intensification. Thus, hydrodynamic characterization of such suspension flow in microreactors is of high importance for a rational design and operation of the system. In this work, experiments have been conducted to investigate the flow pattern and pressure drop characteristics under slug flow between N2 gas and colloidal suspensions in the presence of TiO2 or Al2O3 nanoparticles through polytetrafluoroethylene (PTFE) capillary microreactors. The base fluid consisted of water or its mixture with ethylene glycol. The slug flow pattern with nanoparticle addition was characterized by the presence of a lubricating liquid film around N2 bubbles, in contrast to the absence of liquid film in the case of N2-water slug flow. This shows that the addition of nanoparticles has changed the wall wetting property to be more hydrophilic. Furthermore, the measured pressure drop under N2-nanoparticle suspension slug flow is well described by the model of Kreutzer et al. (AIChE J 51(9):2428–2440, 2005) at the mixture Reynolds numbers ca. above 100 and is better predicted by the model of Warnier et al. (Microfluidics and Nanofluidics 8(1):33–45, 2010) at lower Reynolds numbers given a better consideration of the effect of film thickness and bubble velocity under such conditions in the latter model. Therefore, the employed nanoparticle suspension can be considered as a stable and pseudo single phase with proper fluid properties (e.g., viscosity and density) when it comes to the pressure drop estimation.

Recent Advances in the Development of Highly Conductive Structured Supports for the Intensification of Non-adiabatic Gas-Solid Catalytic Processes: The Methane Steam Reforming Case Study

Structured catalysts are strong candidates for the intensification of non-adiabatic gas-solid catalytic processes thanks to their superior heat and mass transfer properties combined with low pressure drops. In the past two decades, different types of substrates have been proposed, including honeycomb monoliths, open-cell foams and, more recently, periodic open cellular structures produced by additive manufacturing methods. Among others, thermally conductive metallic cellular substrates have been extensively tested in heat-transfer limited exo- or endo-thermic processes in tubular reactors, demonstrating significant potential for process intensification. The catalytic activation of these geometries is critical: on one hand, these structures can be washcoated with a thin layer of catalytic active phase, but the resulting catalyst inventory is limited. More recently, an alternative approach has been proposed, which relies on packing the cavities of the metallic matrix with catalyst pellets. In this paper, an up-to-date overview of the aforementioned topics will be provided. After a brief introduction concerning the concept of structured catalysts based on highly conductive supports, specific attention will be devoted to the most recent advances in their manufacturing and in their catalytic activation. Finally, the application to the methane steam reforming process will be presented as a relevant case study of process intensification. The results from a comparison of three different reactor layouts (i.e. conventional packed bed, washcoated copper foams and packed copper foams) will highlight the benefits for the overall reformer performance resulting from the adoption of highly conductive structured internals.

Spatially Resolved Operando Synchrotron-Based X-Ray Diffraction Measurements of Ni-Rich Cathodes for Li-Ion Batteries

Understanding the performance of commercially relevant cathode materials for lithium-ion (Li-ion) batteries is vital to realize the potential of high-capacity materials for automotive applications. Of particular interest is the spatial variation of crystallographic behavior across (what can be) highly inhomogeneous electrodes. In this work, a high-resolution X-ray diffraction technique was used to obtain operando transmission measurements of Li-ion pouch cells to measure the spatial variances in the cell during electrochemical cycling. Through spatially resolved investigations of the crystallographic structures, the distribution of states of charge has been elucidated. A larger portion of the charging is accounted for by the central parts, with the edges and corners delithiating to a lesser extent for a given average electrode voltage. The cells were cycled to different upper cutoff voltages (4.2 and 4.3 V vs. graphite) and C-rates (0.5, 1, and 3C) to study the effect on the structure of the NMC811 cathode. By combining this rapid data collection method with a detailed Rietveld refinement of degraded NMC811, the spatial dependence of the degradation caused by long-term cycling (900 cycles) has also been shown. The variance shown in the pristine measurements is exaggerated in the aged cells with the edges and corners offering an even lower percentage of the charge. Measurements collected at the very edge of the cell have also highlighted the importance of electrode alignment, with a misalignment of less than 0.5 mm leading to significantly reduced electrochemical activity in that area.

Modeling and Simulation of Reaction Environment in Photoredox Catalysis: A Critical Review

From the pharmaceutical industry’s point of view, photoredox catalysis has emerged as a powerful tool in the field of the synthesis of added-value compounds. With this method, it is possible to excite the catalyst by the action of light, allowing electron transfer processes to occur and, consequently, oxidation and reduction reactions. Thus, in association with photoredox catalysis, microreactor technology and continuous flow chemistry also play an important role in the development of organic synthesis processes, as this technology offers high yields, high selectivity and reduced side reactions. However, there is a lack of a more detailed understanding of the photoredox catalysis process, and computational tools based on computational fluid dynamics (CFD) can be used to deal with this and boost to reach higher levels of accuracy to continue innovating in this area. In this review, a comprehensive overview of the fundamentals of photoredox catalysis is provided, including the application of this technology for the synthesis of added-value chemicals in microreactors. Moreover, the advantages of the continuous flow system in comparison with batch systems are pointed out. It was also demonstrated how modeling and simulation using computational fluid dynamics (CFD) can be critical for the design and optimization of microreactors applied to photoredox catalysis, so as to better understand the reagent interactions and the influence of light in the reaction medium. Finally, a discussion about the future prospects of photoredox reactions considering the complexity of the process is presented.

Enabling Production of Algal Biofuels by Techno-Economic Optimization of Co-Product Suites

Recent techno-economic analysis (TEA) has underscored that for algal biofuels to be cost competitive with petroleum fuels, co-products are necessary to offset the cost of fuel production. The co-product suite must scale with fuel production while also maximizing value from the non-fuel precursor components. The co-product suite also depends on algal biomass composition, which is highly dynamic and depends on environmental conditions during cultivation. Intentional shifts in composition during cultivation are often associated with reduced biomass productivity, which can increase feedstock production costs for the algae-based biorefinery. The optimal algae-based biorefinery configuration is thus a function of many factors. We have found that comprehensive TEA, which requires the construction of process models with detailed mass and energy balances, along with a complete accounting of capital and operating expenditures for a commercial-scale production facility, provides invaluable insight into the viability of a proposed biorefinery configuration. This insight is reflected in improved viability for one biorefining approach that we have developed over the last 10 years, namely, the Combined Algal Processing (CAP) approach. This approach fractionates algal biomass into carbohydrate-, lipid-, and protein-rich fractions, and tailors upgrading chemistry to the composition of each fraction. In particular, transitioning from valorization of only the lipids to a co-product suite from multiple components of high-carbohydrate algal biomass can reduce the minimum fuel selling price (MFSP) from more than $8/gallon of gasoline equivalent (GGE) to $2.50/GGE. This paper summarizes that progress and discusses several surprising implications in this optimization approach.

Synthesis and Characterization of NiMo Catalysts Supported on Fine Carbon Particles for Hydrotreating: Effects of Metal Loadings in Catalyst Formulation

The by-products collected during the synthesis of carbon nanohorns via the arc discharge synthesis method is comprised of other carbon particles (OCP). At a hydrotreating operating temperature of 370°C, preliminary investigations using a bimetallic catalyst with support originating from the fine fractions of other carbon particles (OCPf) and containing 13 wt% Mo and 2.5 wt% Ni resulted in an HDS and HDN conversion of 78 and 25%, respectively. Variation of metal compositions in catalyst formulation and its impact on hydrotreating activity was therefore considered in this study to enhance the hydrotreating activity of OCPf–supported catalyst, and to determine if the best NiMo/OCPf catalyst achieved from this study could be a viable catalyst for hydrotreating applications. The co-incipient wetness impregnation was used in preparing series of hydrotreating catalysts with Ni and Mo loadings within the range of (2.5–5.0 wt%) and (13–26 wt%) respectively. Overall, the catalyst samples with maximum Ni loading of 5.0 wt% and Mo loadings of either 13 or 19 wt% showed higher dispersion and the ability to form a Type II Ni-Mo-S phase with enhanced activity. The effects of metal compositions on both HDS and HDN activities were correlated with their physicochemical properties.

Enhanced Catalytic Activity of Boron Nitride Nanotubes by Encapsulation of Nickel Wire Toward O2 Activation and CO Oxidation: A Theoretical Study

Perfect boron nitride (BN) nanotubes are chemically inert, and hardly considered as catalysts. Nevertheless, metal wire encapsulated BN nanotubes show extraordinarily high chemical activity. We report nickel (Ni) nanowire encapsulated BN(8.0) and BN(9.0) nanotubes toward O2 activation and CO oxidization on the basis of first-principles calculations. Our results suggest that Ni wire encapsulated BN(8.0) and BN(9.0) nanotubes can easily adsorb and activate O2 molecules to form peroxo or superoxo species exothermically. Meanwhile, superoxo species are ready to react with CO molecules forming OCOO intermediate state and finally yielding CO2 molecules. Meanwhile, the rate-limiting step barrier is only 0.637 eV, implying excellent performance for CO oxidation on Ni nanowire encapsulated BN nanotubes. Furthermore, encapsulation of nickel wire improves the catalytic activity of BN nanotubes by facilitating electron transfer from Ni wire to BN nanotubes, which facilitates the adsorption of highly electronegative O2 molecules and subsequent CO oxidation. This study provides a practical and efficient strategy for activating O2 on a metal encapsulated BN nanotube toward CO oxidation.

Synthesis of Hydrophilic Derivative Surfactants From Algae-Derived Unsaponifiable Lipids

In the context of decarbonizing the economy, the utilization of biologically sourced feedstocks to produce replacements for petroleum-derived materials is becoming more urgent. Improving renewable biomass production and utilization is imperative for commercializing future biorefineries. Algae-derived biomass is a particularly promising feedstock thanks to its attractive oil content and composition; specifically, the high-value products in the unsaponifiable lipids have not been included in a conversion process. Here we demonstrate surfactant synthesis from a complex oil fraction as the hydrophobic donor moieties, yielding products that are similar to commercially available surfactants such as the linear alkyl benzene sulfonates. Unsaponifiable lipids extracted from algae were derivatized to non-ionic surfactants using a green chemical synthesis route based on a double esterification with succinic acid and polyethylene glycol. The in-depth molecular and structural surfactant characterization is included and indicates that the resulting properties fall between those of pure cholesterol and phytol used as surrogates for the reaction synthesis demonstration. This is the first demonstration of an effective and potentially high-value synthesis of functional surfactants with properties that can be tailored based on the relative composition of the resulting hydrocarbon alcohol components in the mixture. This novel green chemistry synthesis approach provides a route to high-value product synthesis from algae.

Numerical Simulation of Mixing Process in a Splitting-and-Recombination Microreactor

The mixing process between miscible fluids in a splitting-and-recombination microreactor is analyzed numerically by solving the Navier–Stokes equation and species transfer equation. The commercial microreactor combines rectangular channels with comb-shaped inserts to achieve the splitting-and-recombination effect. The results show that the microreactor with three-layer standard inserts have the highest mixing rate as well as good mixing efficiency within a wide range of Reynolds numbers from 0.1 to 160. The size parameters of the inserts, both the ratio of the width of comb tooth (marked as l) and the spacing distance (marked as s) between two comb teeth, and the ratio of the vertical distance (marked as V) of comb teeth and the horizontal distance (marked as H) are essential for influencing the liquid–liquid mixing process at low Reynolds numbers (e.g., Re ≤ 2). With the increase of s/l from 1 to 4, the mixing efficiency drops from 0.99 to 0.45 at Re = 0.2. Similarly, the increase in V/H is not beneficial to promote the mixing between fluids. When the ratio of V/H changes from 10:10 to 10:4, the splitting and recombination cycles reduce so that the uniform mixing between different fluids can be hardly achieved. The width of comb tooth (marked as l) is 1 mm and the spacing distance (marked as s) between two comb teeth is 2 mm. The vertical distance (marked as V) of comb teeth and the horizontal distance (marked as H) are both 10 mm.

Production of Succinic Acid From Basfia succiniciproducens

Basfia succiniciproducens is a facultative anaerobic capnophilic bacterium, isolated from rumen, that naturally produces high amounts of succinic acid by fixing CO2 and using fumarate as final electron acceptor. This metabolic feature makes it one of the ideal candidates for developing biotechnological industrial routes that could eventually replace the polluting and environment unfriendly petrochemical ones that are still main sources for the production of this value-added compound. In fact, due to the large number of applications of succinic acid that range from the more traditional ones as food additive or pharmaceutical intermediate to the most recent as building block for biopolymers and bioplastic, increasing demand and market size growth are expected in the next years. In line with a “green revolution” needed to preserve our environment, the great challenge is the establishment of commercially viable production processes that exploit renewable materials and in particular preferably non-food lignocellulosic biomasses and waste products. In this review, we describe the currently available literature concerning B. succiniciproducens since the strain was first isolated, focusing on the different renewable materials and fermentation strategies used to improve succinic acid production titers to date. Moreover, an insight into the metabolic engineering approaches and the key physiological characteristics of B. succiniciproducens deduced from the different studies are presented.