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This work provides a comparative technical assessment of three technologies for CO2 removal from air: two aqueous-scrubbing processes and one solid sorbent process. We compute productivity and exergy and energy consumption using process simulations and mathematical optimization. Moreover, we evaluate the cost range and discuss the challenges for large-scale deployment. We show that all technologies can provide high-purity CO2 and that the solid-based process has the potential to offer the best performance, owing to an exergy demand of 1.4–3.7 MJ.kgCO2−1 and a productivity of 3.8–10.6 kgCO2.m−3.h−1. Translating productivity and energy into cost of CO2 capture via a simple model, we show that the capital cost is the main cost driver. All technologies have the potential to operate below 200 $.tonCO2−1 under favorable, yet realistic, energy and reactor costs. The solid-sorbent process achieves this under a broader range of conditions and is less dependent on the installation cost when a high mass transfer is achieved.

The formation of Fe-carbide phases is relevant to the synthesis of Fischer-Tropsch synthesis catalysts. We investigated the carburization of Raney Fe as a model catalyst using spectroscopic and temperature-programmed techniques. IR spectroscopy shows that CO dissociation already occurs at −150 °C, while C diffusion into metallic Fe requires much higher temperature (~180 °C). The carburization rate increases with increasing H2/CO ratio, which can be attributed to the lower overall barrier for O removal as H2O as compared to CO2. O removal frees vacancies that are needed for CO dissociation. The resulting higher C coverage increases the driving force for Fe-carbide formation. A higher driving force leads to predominant formation of the more carbon-rich ε(́)-carbide, while χ-Fe5C2 is formed at lower H2/CO ratio. The removal of surface O appears to be the rate-limiting step under all conditions. Initially, most of deposited C is used for Fe-carbide formation with a small contribution to hydrocarbons formation.

International audience; Acidification is an important process in the production of several dairy products and has an impact in taste, viscosity, and shelf life of the products. This paper deals with the development of an empirical mathematical model to describe milk acidification in terms of pH dynamics. The model is built upon experiments of pasteurized skimmed milk acidification for acid-induced casein precipitation and extended to predict the partitioning of calcium and phosphates in the whey and the dynamics of pH during fermentation of yoghurt manufacture. Furthermore, the model can be used directly or in optimization problems to provide recommendations about product design.

With the advent of digitalization and industry 4.0, education in chemical and biochemical engineering has undergone significant revamping over the last two decades. However, undergraduate students sometimes do lack industrial exposure and are unable to visualise the complexity of actual process plants. Thereby, students might graduate without adequate professional hands-on experience. Similarly, in the process industry, operator training-simulators are widely used for the training of new and skilled operators. However, conventional training-simulators often fail to simulate reality and do not provide the user with the opportunity to experience unexpected and hazardous scenarios. In these regards, virtual reality appears to be a promising technology that can cater to the needs of both academia and industry. This paper discusses the opportunities and challenges for the incorporation of virtual reality into chemical and biochemical engineering education with an emphasis on the fundamental areas of technology, pedagogy and socio-economics. The paper emphasises the need for augmenting virtual reality interfaces with mathematical models to develop advanced immersive learning applications. Further, the paper stresses upon the need for novel educational impact assessment methodologies for the evaluation of virtual-reality-based learning. Finally, an ongoing case study application is presented to briefly discuss the social and economic implications, and to identify the bottlenecks involved in the adoption of virtual reality tools across chemical and biochemical engineering education.

A full‐field PIV‐DIA technique has been coupled to concentration measurements in order to characterize the riser performance at different gas superficial velocities and reaction rates for ozone decomposition. Experiments under riser flow conditions were performed with the use of a compact pseudo‐2D lab‐scale riser reactor. The purpose of this work is to generate reliable experimental data to validate computational models for mass transfer in riser flow conditions. The catalytic activity of the particles was characterized. To analyze the reaction rate effect over the performance of a riser reactor, two catalyst batches with different activities were used and their kinetics were measured. The hydrodynamics of the gas‐solid flow was determined using the PIV‐DIA technique. Particle clusters were identified and characterized. By correlating the cluster information and mass concentration measurements, it was shown that a higher frequency of local flow heterogeneities near the walls led to higher conversion rates than in the core of the riser. Reaction rate and gas superficial effects are analyzed.

Hydrogen can be stored and distributed by injecting into existing natural grids, then, at the user site separated and used in different applications. The conventional technology for hydrogen separation is pressure swing adsorption (PSA). The recent NREL study showed the extraction cost for separating hydrogen from a 10% H2 stream with a recovery of 80% is around 3.3–8.3 US$/kg. In this document, new system configurations for low hydrogen concentration separation from the natural gas grid by combining novel membrane-based hybrid technologies will be described in detail. The focus of the manuscript will be on the description of different configurations for the direct hydrogen separation, which comprises a membrane module, a vacuum pump and an electrochemical hydrogen compressor. These technological combinations bring substantial synergy effect of one-another while improving the total hydrogen recovery, purity and total cost of hydrogen. Simulation has been carried out for 17 different configurations; according to the results, a configuration of two-stage membrane modules (in series) with a vacuum pump and an electrochemical hydrogen compressor (EHC) shows highest hydrogen purity (99.9997%) for 25 kg/day of hydrogen production for low-pressure grid. However, this configuration shows a higher electric consumption (configuration B) due to the additional mechanical compressor between the two-stage membrane modules and the EHC. Whereas, when the compressor is excluded, and a double skin Pd membrane (PdDS) module is used in a single-stage while connected to a vacuum pump (configuration A5), the hydrogen purity (99.92%) slightly decreases yet the power consumption considerably improves (1.53 times lower). Besides to these two complementary configurations, the combination of a single membrane module, a vacuum pump and the electrochemical compressor has been also carried out (configuration A) and results show that relatively higher purity can be achieved. Based on four master configurations, this document presents a different novel hybrid system by integrating two to three technologies for hydrogen purification combined in a way that enhances the strengths of each of them. This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 700355. This Joint Undertaking receives support from the European Union's Horizon 2020 research and innovation.

'Smart' windows which reversibly increase their reflectivity upon heating are attracting considerable attention as devices for maintaining comfortable indoor environmental conditions. In this work, twisted nematic semi‐interpenetrating liquid crystal networks which lose their order upon heating are sandwiched between reflective linear polarizers. This 'smart' window reversibly decreases its transmission from about 50–10% over a wavelength range between 400 and 1100 nm upon heating, resulting in the window becoming darker and reflecting more light. This 'smart' window is potentially interesting for energy saving window applications where variation between privacy and visible light transparency states is required.

Accurate and low-cost wearable or portable monitors for personal solar ultraviolet (UV) exposure are of interest to reduce the risk of adverse UV effects such as eye diseases, sunburn and skin cancer. Here, a novel sensor involving the racemization of a chiral dopant within a nematic liquid crystalline matrix is described, and the suitability of these sensors to act as personal UV dosimeters is explored. It was shown that these sensors respond to UV light with a significant change in the position of the reflection band of the chiral nematic liquid crystal. The sensitivity of these sensors is shown to be 0.23 nm/mJcm−2. This corresponds to a change of 80 nm over a dose equivalent to two hours of solar exposure.

This communication summarizes the use of double-skinned membranes for hydrogen separation in presence of TiO2 based catalyst (PtReCe/TiO2). The use of this type of membrane avoids the direct contact between catalyst particles and surface of the Pd-based hydrogen selective layer due to the presence of a mesoporous YSZ/γ-Al2O3 layer. The PdAg layer is protected by the mesoporous layer from direct contact with catalyst particles, avoiding erosion and possible chemical interactions. In comparison with a conventional PdAg membrane, the hydrogen flux of DS-membrane was observed not to be compromised during test carried out at 400 °C.

Packed bed reactors are among the most common reactor types in chemical industries. The reactions in these reactors are generally exothermic and occur at the surface of or inside the catalytic particle packings. Understanding the fluid flow characteristics, such as the pressure drop over the bed and velocity distribution in the bed, is of great importance in the design of packed bed reactors. As the pressure drop of a packed bed directly affects the reactor’s upstream and downstream equipment, predicting the pressure drop is key in optimizing these reactors. This study uses two methods to predict the pressure drop inside a cylindrical packed bed which is randomly filled with spherical particles. First, a fully resolved Direct Numerical Simulation (DNS) is used to predict the flow behavior and pressure drop inside the packed bed. Here, a ghost cell Immersed Boundary Method (IBM) is applied for describing the fluid-solid coupling. Secondly, the Pore Network Model (PNM) will be fitted to the pressure drop of IBM simulations with different Reynolds numbers and with different bed diameter to particle diameter ratios. The obtained model will be used to investigate the flow hydrodynamics and pressure drop inside the bed.

Animals can modify their body shape and/or color for protection, camouflage and communication. This adaptability has inspired fabrication of actuators with structural color changes to endow soft robots with additional functionalities. Using liquid crystal-based materials for actuators with structural color changes is a promising approach. In this review, we discuss the current state of liquid crystal-based actuators with structural color changes and the potential applications of these structural color actuators in soft robotic devices.

An oscillatory baffled flow reactor (OBR) has been designed with 60 interbaffled cells. The baffled columns of 40 mm internal diameter together result in a reactor length of 5740 mm. The oscillatory amplitude and frequency were in the range of 2–12 mm and 0.3–2 Hz, respectively. The report investigates the impact of U-bends and the number of reactor sections on axial dispersion for scale-up feasibility. A prediction model using operating parameters has been developed to maximize plug flow conditions using the tanks-in-series (TiS) model. The maximum TiS value was 13.38 in a single column compared to 43.68 in the full reactor at a velocity ratio of 2.27 using oscillatory parameters 8 mm and 0.3 Hz. The mixing efficiency along the reactor was found to decrease after each column at amplitudes

Compressing porous carbon electrodes is a common approach to improve flow battery performance, but the resulting impact on electrode structure, fluid dynamics, and cell performance is not well understood. Herein, microtomographic imaging, load cell testing, and flow cell diagnostics are employed to characterize how compression-induced changes impact pressure drop, polarization, and mass-transfer scaling. Five different compressions are tested, spanning ranges typically used in literature, for AvCarb 1071 cloth (0%, 9%, 20%, 25%, 32%) and Freudenberg H23 paper (0%, 8%, 12%, 17%, 22%). It is found that the two electrode structures have distinct responses to compression, resulting in differing optimal conditions identified for each material; specifically, the Freudenberg H23 exhibits lower combined ohmic, charge-transfer, and mass-transport values at 8% compression, resulting in improved electrochemical performance across all compressive values, as compared to the optimal AvCarb 1071 compression (20%). Overall, Freudenberg H23 exhibits a greater sensitivity to compression with peak electrochemical activity correlating with increased permeability, whereas AvCarb 1071 is insensitive to compressive loads but produces lower electrochemical performance. Herein, the trade-offs of mechanical robustness on fluid-dynamic and electrochemical performance between the two electrodes are demonstrated by the aforementioned findings, suggesting each could be used for specific operating environments.

The Electrocell family of electrolyzers is a set of differently sized commercially available electrochemical flow reactors, suitable for scaling up new electrochemical processes. In this work mass transfer correlations are established for the smallest two flow cells, namely the Microflow cell (MFC) and MP cell (MPC). The empty channel performance of the MFC and MPC is comparable to similar lab-scale reactors in literature, such as the FM01-LC and the larger Electrocell Electro Syn cell. Turbulence promoters enhance mass transfer in the MFC and MPC by only a factor 1.4 and 1.5 respectively. Also, the performance of mesh electrodes was investigated: woven and expanded mesh electrodes result in a factor 2.1 to 2.8 enhancement in mass transfer when the surface area of the mesh is considered. The overall reaction rate is enhanced by a factor 5.9 to 6.7 for woven meshes, and 1.9 to 3.0 for expanded meshes due to the higher surface area of the woven meshes. Fine woven meshes therefore seem the preferred type of electrodes for reactions limited by mass transfer.

The development of high-performance membrane materials for non-aqueous redox flow batteries (NAqRFBs) could unlock a milestone towards widespread commercialization of the technology. Understanding of transport phenomena through membrane materials requires diagnostic tools able to monitor the concentrations of redox active species. While membrane characterization in aqueous media focused the attention of the scientific community, dedicated efforts for non-aqueous electrolytes remain poorly developed. Here, we develop new methodologies to assess critical membrane properties, namely ion exchange capacity and species transport, applied to NAqRFBs. In the first part, we introduce a method based on 19F-NMR to quantify ion exchange capacity of membranes with hydrophobic anions commonly used in non-aqueous systems (e.g., PF6 − and BF4 −). We find a partial utilization of the ion exchange capacity compared to the values reported using traditional aqueous chemistry ions, possibly limiting the performance of NAqRFB systems. In the second part, we study mass transport with a microelectrode placed on the electrolyte tank. We determine TEMPO crossover rates through membranes by using simple calibration curves that relate steady-state currents at the microelectrode with redox active species concentration. Finally, we show the limitations of this approach in concentrated electrolyte systems, which are more representative of industrial flow battery operation.

Nano-silica is an important admixture for ultra-high performance concrete (UHPC). However, complex production process and agglomeration problem of conventional nano-silica significantly limit its application in UHPC. In this study, a novel highly dispersed colloidal olivine nano-silica (C-OnS) is developed. The properties of C-OnS are characterized with laser light scattering, nuclear magnetic resonance and zeta-potential. The C-OnS is applied in UHPC to enhance the cement hydration and reduce the viscosity, while a commercial sol-gel colloidal nano-silica (C-nS) is used as a reference. The effects of C-OnS and C-nS on UHPC are investigated by calorimetry, thermal gravimetry, 29Si and 27Al nuclear magnetic resonance, nitrogen physisorption and mercury intrusion porosimeter. The results show that the performance of UHPC is enhanced by C-OnS at early ages thanks to its higher silanol content, surface area and dispersibility. The advantages of highly dispersive, strong pozzolanic reactivity and tailorable particle size provide new possibilities for application of C-OnS in cement-based materials.

Liquid injection in fluidized beds occurs in well-established industrial processes as fluid coking, spray fluidzed bed granulation and condensed mode gas-phase polymerisation. These processes still suffer performance issues due to their complex nature, where liquid injection adds even more complexity.In this work, the effect of liquid injection on the temperature uniformity in a pseudo-2D fluidized bed was studied using Infra-Red Thermography. The Infra-Red images were also studied to qualify the agglomeration behaviour.Injecting smaller droplets (-90 lm affects the uniformity of the bed more than injecting larger droplets (-225 lm. However, the formation of agglomerates increases with increasing droplet size. The injection velocity influences the average temperature of the bed more for the larger droplets. Additionally, increased solids motion was observed to reduce the agglomeration formation in the bed. Lastly, the particle temperature distribution does not reflect the presence of agglomerates and is thus unsuitable to quantify the agglomeration behaviour.(c) 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http:// creativecommons.org/licenses/by/4.0/).

The mass transfer between a rising bubble and the surrounding liquid is mainly determined by an extremely thin layer of dissolved gas near the bubble interface. Resolving this concentration boundary layer in numerical simulations is computationally expensive and limited to low Péclet numbers. Subgrid-scale models mitigate the resolution requirements by approximating the mass transfer near the interface. In this contribution, we validate an improved subgrid-scale model with a single-phase simulation approach, which solves only the liquid phase at a highly-resolved mesh. The mass transfer during the initial transient rise of moderately deformed bubbles in the range Re = 72–569 and Sc = 102–104 is carefully validated. The single-phase approach is able to mirror the two-phase flow field. The time-dependent local and global mass transfer of both approaches agree well. The difference in the global Sherwood number is below than 2.5%. The improved subgrid-scale model predicts the mass transfer accurately and shows marginal mesh dependency.

Predicting learning curves can give organizations a competitive advantage. This study synthesizes learning curve and design structure matrix (DSM) methodologies to quantify product change and complexity in order to estimate the performance of future generations of products. Based on a small-scale experiment and in-depth case studies, we propose a model that forecasts the disruption and subsequent improvement in manufacturing cycle time due to changes in a product. The study contributes to research on how technological complexity impacts organizational learning curves.

Nuclear Magnetic Resonance (NMR) is used to study the early-age hydration as well as autogenous shrinkage and drying shrinkage of cement paste with the addition of coir fibers. The dosage and water content of coir fibers are evaluated. The results show that added coir fibers have a negligible influence on cement hydration kinetics. However, the internal curing effect of saturated coir fibers and water competition induced by dry fibers are visualized. As the saturated fiber content increases, autogenous shrinkage and drying shrinkage decrease due to the internal curing and reinforcing effects of fibers. Dry fibers generate more autogenous shrinkage but less drying shrinkage than saturated fibers of the same dosage due to the introduced water competition. NMR is proven able to track water transportation and shrinkage in cement composites.

In this work, large-scale simulations of the blast furnace hearth are presented, conducted using a model combining Computational Fluid Dynamics, the Volume of Fluid method, and the Discrete Element Method. Using a 5 m diameter, full-3D geometry, the influence of burden weight, bi-disperse packing, and blocked tuyeres on the liquid and solids flow within the hearth are investigated. Horizontal and vertical porosity profiles are presented, and the influence of the dynamic liquid level on the state of the deadman is evaluated. The liquid iron flow during tapping is visualised, and the influence of a coke-free space on the flow pattern is analysed. The magnitude of the circumferential flow through the corner of the hearth is analysed, and found to decrease with increasing burden weight pressure and coke diameter in the bed centre. A significant influence of the dynamic deadman on the liquid flow pattern is found, especially in case of a floating deadman. In addition to the liquid flow, the solid coke flow towards the raceways is analysed. Two pathways for coke particles towards the raceway are uncovered, one path through the actively flowing layer above the deadman, and a second path moving through the deadman and entering the raceways from below. The balance between these two mechanisms was found to change during the tapping cycle. Lastly, implementations for heat and dissolved carbon mass transfer are presented, and demonstrated using a full-scale 10 m hearth simulation. Additional closures for heat and mass transfer rates are required, but the current model is found in good shape for future work.

With the use of bipolar membranes (BPMs) in an expanding range of applications, there is an urgent need to understand and improve the catalytic performance of BPMs for water dissociation, as well as to increase their physical and chemical stability. In this regard, electrospinning BPMs with 2D and 3D junction structures have been suggested as a promising route to produce high-performance BPMs. In this work, we investigate the effect of entangling anion and cation exchange nanofibers at the junction of bipolar membranes on the water dissociation rate. In particular, we compare the performance of different tailor-made BPMs with a laminated 2D junction and a 3D electrospun entangled junction, while using the same type of anion and cation exchange polymers in a single/dual continuous electrospinning manufacturing method. The bipolar membrane with a 3D entangled junction shows an enhanced water dissociation rate as compared to the bipolar membrane with laminated 2D junction, as measured by the decreased bipolar membrane potential. Moreover, we investigate the use of a third polymer, that is, poly(4-vinylpyrrolidine) (P4VP), as a catalyst for water dissociation. This polymer confirmed that a 3D entangled junction BPM (with incorporated P4VP) gives a higher water dissociation rate than does a 2D laminated junction BPM with P4VP as the water dissociation catalyst. This work demonstrates that the entanglement of the anion exchange polymer with P4VP as the water dissociation catalyst in a 3D junction is promising to develop bipolar membranes with enhanced performance as compared to the conventionally laminated membranes.

Lithium fluoride films were prepared by atomic layer deposition (ALD) using a new route in which LiN(SiMe3)2 is used as a precursor and SF6 plasma as a coreactant. Conformal LiF films were deposited at 150 °C at a growth rate of ∼0.4 A per cycle. All deposited films were polycrystalline and slightly lithium-rich with a composition of LiF0.8, independently of the plasma conditions (e.g. exposure time, pressure and power). The levels of H, C, N, O, Si, and S were all

The separation and purification of light hydrocarbons are significant challenges in the petrochemical and chemical industries. Because of the growing demand for light hydrocarbons and the environmental and economic issues of traditional separation technologies, much effort has been devoted to developing highly efficient separation techniques. Accordingly, polymeric membranes have gained increasing attention because of their low costs and energy requirements compared with other technologies; however, their industrial exploitation is often hampered because of the trade-off between selectivity and permeability. In this regard, high-performance mixed matrix membranes (MMMs) are prepared by embedding various organic and/or inorganic fillers into polymeric materials. MMMs exhibit the advantageous and disadvantageous properties of both polymer and filler materials. In this review, the influence of filler on polymer chain packing and membrane sieving properties are discussed. Furthermore, the influential parameters affecting MMMs affinity toward hydrocarbons separation are addressed. Selection criteria for a suitable combination of polymer and filler are discussed. Moreover, the challenges arising from polymer/filler interactions are analyzed to allow for the successful implementation of this promising class of membranes.

In the pathway towards decarbonization, hydrogen can provide valid support in different sectors, such as transportation, iron and steel industries, and domestic heating, concurrently reducing air pollution. Thanks to its versatility, hydrogen can be produced in different ways, among which steam reforming of natural gas is still the most commonly used method. Today, less than 0.7% of global hydrogen production can be considered low-carbon-emission. Among the various solutions under investigation for low-carbon hydrogen production, membrane reactor technology has the potential, especially at a small scale, to efficiently convert biogas into green hydrogen, leading to a substantial process intensification. Fluidized bed membrane reactors for autothermal reforming of biogas have reached industrial maturity. Reliable modelling support is thus necessary to develop their full potential. In this work, a mathematical model of the reactor is used to provide guidelines for their design and operations in off-design conditions. The analysis shows the influence of temperature, pressures, catalyst and steam amounts, and inlet temperature. Moreover, the influence of different membrane lengths, numbers, and pitches is investigated. From the results, guidelines are provided to properly design the geometry to obtain a set recovery factor value and hydrogen production. For a given reactor geometry and fluidization velocity, operating the reactor at 12 bar and the permeate-side pressure of 0.1 bar while increasing reactor temperature from 450 to 500 °C leads to an increase of 33% in hydrogen production and about 40% in HRF. At a reactor temperature of 500 °C, going from 8 to 20 bar inside the reactor doubled hydrogen production with a loss in recovery factor of about 16%. With the reactor at 12 bar, a vacuum pressure of 0.5 bar reduces hydrogen production by 43% and HRF by 45%. With the given catalyst, it is sufficient to have only 20% of solids filled into the reactor being catalytic particles. With the fixed operating conditions, it is worth mentioning that by adding membranes and maintaining the same spacing, it is possible to increase hydrogen production proportionally to the membrane area, maintaining the same HRF.

Contrary to traditional electrolysers which operate continuously at their nominal load, future alkaline electrolysers need to be able to operate over a wide load range due to the variability of renewable electricity supply. We have investigated how the residual ripples from thyristor-based power supplies are influenced by the operating load of the system, and how these ripples affect the efficiency of alkaline electrolysers. For this, a simulation tool was developed which combines a six-pulse bridge thyristor rectifier model with closed-loop current control and semi-empirical electrolysis models. The electrolysis models can simulate the potential response to both direct and high amplitude alternating currents for lab-scale and industrial electrolysers. The electrolysis model of the lab-scale electrolyser was validated with experiments with a square wave current input. The models show that without filters the ripples result in a total system efficiency loss of 1.2–2.5% at full load and of 5.6–10.6% at a part load of 20% depending on the type of electrolyser. The implementation of an optimized L-filter suppresses residual ripples and reduces the efficiency losses to 0.5%–0.8% at full load and to 0.8–1.2% at the minimum load.

Layer-by-layer assembly of polyelectrolyte layers is a versatile method to produce nanofiltration membranes. The membrane formation and subsequently performance is easily tailored with pH as it varies the polyelectrolyte charge density. Here, membranes are fabricated at different pH (4,8, and 9) with branched polyethyleneimine (PEI)/poly(sodium-4-styrenesulfonate) (PSS) layers (symmetric membranes) or a combination of poly(diallyldimethylammonium chloride) (PDADMAC)/PSS base layers terminated with PEI/PSS layers (asymmetric membranes). Overall, increasing the pH lowers the PEI charge density, which increases PEI adsorption, as measured by optical reflectometry and positive zeta potential. For symmetric systems, decreasing the charge density decreases the salt retention, because fewer intrinsic linkages are formed. Contrarily, asymmetric membranes, independent of charge density, show retentions >90% for MgSO4 and Na2SO4. Additionally, the benefit of asymmetric membrane formation is proven by comparing the best membrane performances. Asymmetric membranes prepared at pH = 4 form an open base layer and defect-free dense selective layer, resulting in much higher permeabilities compared to symmetric membranes (∼13 and ∼9 L/(m2hbar)), and significantly improving MgSO4 and Na2SO4 retentions (>95% compared to >90%). By combining two well-known polycations and tailoring the pH, versatile membranes are produced, without the need for synthesis or modification steps while obtaining improved water fluxes and salt retentions.

The diffusive fluxes in porous media are inherently influenced by a reaction occurring at the internal surface. This investigation analyses this impact via a Fourier-mode analysis in a spherical coarsely porous model geometries consisting of random agglomerates of spheres. Trends are determined from the results and the overall impact for the given geometries estimated.

Bottom-up methods for the fabrication of nanoporous polymer membranes have numerous advantages. However, it remains challenging to fabricate nanoporous membranes that are mechanically robust and have aligned pores, that is, with a low tortuosity. Here, a mechanically robust thin-film composite membrane was fabricated consisting of a two-dimensional (2D) porous smectic liquid crystalline polymer network inside an anisotropic, microporous polymer scaffold. The polymer scaffold allows for relatively straightforward planar alignment of the smectic liquid crystalline mixture, which consisted of a diacrylate cross-linker and a dimer forming benzoic acid-based monoacrylate. Polymerized samples displayed a smectic A (SmA) phase, which formed the eventual 2D porous channels after base treatment. The aligned 2D nanoporous membranes showed a high rejection of anionic solutes bigger than 322 g/mol. Cleaning and reusability of the system were demonstrated by intentionally fouling the porous channels with a cationic dye and subsequently cleaning the membrane with an acidic solution. After cleaning, the membrane properties were unaffected; this, combined with numerous pressurizing cycles, demonstrated reusability of the system.

Syngas is traditionally used in industry for production of fuels in the kerosene, gasoline and diesel range via Fischer-Tropsch, for the manufacture of bulk chemicals like ammonia, methanol and dimethyl ether and for synthesis of a whole array of fine chemicals. The carbon monoxide/hydrogen ratio of the syngas is an important design variable to maximize production of these compounds. Therefore, the search of effective processes that enable said ratio adjustment as well as individual compound purification is an essential and ongoing effort for industry. In this work, we propose a development of a zeolite-based separation process to obtain carbon dioxide-neutral fuels and chemicals. The process designed is based on gas uptake and release, combining separation efficiency with low separation costs. Calculation of separation behavior has been done for mixtures generated by plasmolysis of CO2. Carbon dioxide dissociation into CO and O2 and as a result a mixture of carbon monoxide, oxygen and a residual carbon dioxide is obtained. Therefore, the purification of CO becomes necessary. Here we provide a purification process design based in multicomponent adsorption and separation in commercial available zeolites. The process identifies NaX and NaY as the most suitable zeolites for separation in a wide range of operating conditions.

The stability of metal-organic frameworks is a key factor in many applications in some fields that require working under harsh conditions. It is known that a large number of MOFs are vulnerable to humid air. It means that when they are exposed to water, a structural collapse of the crystal happens. In this work, Molecular Dynamics simulations using a reactive force field have been performed to study the stability of MOF-74 against the adsorption of catechol, resorcinol and hydroquinone in the presence of water. We reproduced the water instability of Zn-MOF-74 and we studied the resistance of the structure. Our simulations showed that the three isomers generate a volume change in the framework but the structural collapse does not happen. In contrast, for water-isomer mixtures, there is structural collapse. Not only do catechol, resorcinol and hydroquinone not behave as stabilizing agents but they do enhance the hydration effect on the structure.

Non-thermal plasma is a promising technology for high purity nanomaterial synthesis in a fast, flexible and controllable process. Gliding arc discharge, as one of the most efficient non-thermal plasmas, has been widely used in gas treatment but rarely studied for the nanomaterial synthesis. In this study, a comparison study for carbon nanosheets synthesis including toluene dissociation and graphite exfoliation was investigated in a 2D gliding arc reactor at atmospheric pressure. The effects of gas flow rate, precursor concentration and power input on the structures of carbon nanosheets produced through the two synthesis routes were explored and compared. Amorphous carbon nanosheets were produced in both approaches with a few crystalline structures formation in the case of toluene dissociation. The thickness of carbon nanosheets synthesized from graphite exfoliation was less than 3 nm, which was thinner and more uniform than that from toluene dissociation. The flow rate of carrier gas has direct influence on the morphology of carbon nanomaterials in the case of toluene dissociation. Carbon spheres were also produced along with nanosheets when the flow rate decreased from 2 to 0.5 L/min. However, in the case of graphite exfoliation, only carbon nanosheets were observed regardless of the change in flow rate of the carrier gas. The generated chemical species and plasma gas temperatures were measured and estimated for the mechanism study, respectively.

Owing to the recent breakthrough in thermochemical storage technology, a novel closed-loop thermal energy storage (TES) system, the heat battery (HB), has been introduced. With higher energy density and no storage loss, this system is believed to have a greater potential of helping the energy transition in the built environment compared to other conventional TES systems. To identify the most promising use case of the HB, this research proposes a simulation approach to predict and assess how the HB will influence the performance of Dutch residential buildings. Based on a literature review and discussions with developers of the HB, a list of potential use cases is defined and the most important stakeholders are identified (homeowner, distribution system operator, and district heating system operator). Next, the simulation approach was conducted. The results show that the HB has the potential of both reducing the operational energy cost for the homeowner and reducing the peak heating load from the building to the district heating system., CLIMA 2022 conference, 2022: CLIMA 2022 The 14th REHVA HVAC World Congress

One of the important parameters in water management of proton exchange membranes is the electro-osmotic drag (EOD) coefficient of water. The value of the EOD coefficient is difficult to justify, and available literature data on this for Nafion membranes show scattering from in experiments and simulations. Here, we use a classical all-atom model to compute the EOD coefficient and thermodynamic properties of water from molecular dynamics simulations for temperatures between 330 and 420 K, and for different water contents between λ = 5 and λ = 20. λ is the ratio between the moles of water molecules to the moles of sulfonic acid sites. This classical model does not capture the Grotthuss mechanism; however, it is shown that it can predict the EOD coefficient within the range of experimental values for λ = 5 where the vehicular mechanism dominates proton transfer. For λ > 5, the Grotthuss mechanism becomes dominant. To obtain the EOD coefficient, average velocities of water and ions are computed by imposing different electric fields to the system. Our results show that the velocities of water and hydronium scale linearly with the electric field, resulting in a constant ratio of ca. 0.4 within the error bars. We find that the EOD coefficient of water linearly increases from 2 at λ = 5 to 8 at λ = 20 and the results are not sensitive to temperature. The EOD coefficient at λ = 5 is within the range of experimental values, confirming that the model can capture the vehicular transport of protons well. At λ = 20, due to the absence of proton hopping in the model, the EOD coefficient is overestimated by a factor of 3 compared to experimental values. To analyze the interactions between water and Nafion, the partial molar enthalpies and partial molar volumes of water are computed from molecular dynamics simulations. At different water uptakes, multiple linear regression is used on raw simulation data within a narrow composition range of water inside the Nafion membrane. The partial molar volumes and partial molar excess enthalpies of water asymptotically approach the molar volumes and molar excess enthalpies of pure water for water uptakes above 5. This confirms the model can capture the bulklike behavior of water in the Nafion at high water uptakes.

1B05

Cuttlefish can modify their body shape and both their pigmentary and structural colors for protection. This adaptability has inspired the development of appearance-changing polymers such as structural color actuators, although in most cases, the original shape has been confined to being flat, and pigmented structural color actuators have not yet been reported. Here, we have successfully created a pigmented structural color actuator using a cholesteric liquid crystal elastomer with a lower actuation temperature where both actuation and coloration (structural and pigmental) are tunable with temperature and NIR light. The shape, structural color, and absorption of the NIR-absorbing dye pigment of the actuator all change with temperature. Light can be used to trigger local in-plane bending actuation in flat films and local shape changes in a variety of 3D-shaped objects. A cuttlefish mimic that can sense light and respond by locally changing its appearance was also made to demonstrate the potential of pigmented structural color actuators for signaling and camouflage in soft robotics.

Battery technology is crucial in the transition towards electric mobility. Lithium-ion batteries are conquering the market but are facing fire safety risks that might threaten further applications. In this study, we address the problem and potential solutions for traction batteries in the European Union area. We do so by taking a unique socio-technical system perspective. Therefore, a novel, mixed-method approach is applied, combining literature review; stakeholder interviews; Failure Mode, Mechanisms, and Event Analysis (FMMEA); and rapid prototyping. Our findings confirm that fire safety is an upcoming concern. Still, most stakeholders lack a full understanding of the problem. Improving safety is a shared responsibility among supply chain and societal stakeholders. For automotive applications, voluntary standard-setting on safety risks is an appropriate tool to improve fire safety, whereas for niche applications, a top-down approach setting regulations seems more suited. For both groups, the adaptation of battery pack designs to prevent thermal runaway propagation is shown to be promising from a technological, practical, and organizational perspective. The chosen mixed-method approach allowed for a holistic analysis of the problems and potential solutions. As such, it can serve as an empowerment strategy for stakeholders in the field, stimulating further discussion, agenda building, and action.

Magnetic particle tracking (MPT) was employed to study a rotating drum filled with cork particles, using both air and water as interstitial medium. This noninvasive monitoring technique allows for the tracking of both particle translation and rotation in dry granular and liquid–solid systems. Measurements on the dry and floating bed rotating drum were compared and detailed analysis of the bed shape and velocity profiles was performed. It was found that the change of particle–wall and particle–particle interaction caused by the presence of water significantly affects the bed behavior. The decreased friction leads to slipping of the particles with respect to the wall, rendering the circulation rate largely insensitive to increased drum speed. It was also found that the liquid–particle interaction is determining for the behavior of the flowing layer. The well-defined experiments and in-depth characterization performed in this study provide an excellent validation case for multiphase flow models.

This work investigates kinetics and transport of CO2 microwave plasmas through simulation results from a 1D radial fluid model and experiments. Simulation results are validated against spatially resolved measurements of neutral species mole fractions, gas temperature, electron number density and temperature obtained by means of Thomson and Raman scattering diagnostics, yielding good agreement. As such, the model is used to complement experiments and assess the main chemical reactions, mass and energy transport in diffuse and contracted plasma regimes. From model results, it is found that, as pressure is raised, the inhomogeneous gas heating induces significant gradients in neutral and charged species mole fractions profiles. Moreover, the transition from diffuse to contracted plasma is accompanied by a change in the dominant charged species, which favours electron–ion recombination over dissociative attachment. Associative ionization rates increase in the plasma core from diffuse to contracted regime. These processes contribute to the increase in the peak electron number density with pressure, that determines radial plasma contraction.

We develop a model which couples the flow in a discrete fracture to a deformable porous medium. To account for the discrete representation of the fracture, a dimensionally-reduced fluid flow model is proposed. The fluid flow model incorporates both a reduced permeability of the fracture walls due to the skin effect, and a slip of fluid flowing along the permeable fracture walls. Biot's model for poroelastic media is coupled to a fracture flow model based on a thin-film approximation of the compressible Navier-Stokes equations. The fracture flow model incorporates a fluid entry resistance parameter to relate the leak-off through the fracture walls to a pressure jump across the fracture walls, and the Beavers-Joseph-Saffman slip rate coefficient to represent the fluid slip along the fracture walls. The numerical model is based on a thermodynamic framework in which all energy storage and dissipative mechanisms in the problem are identified, including the mechanisms related to the interface effects. The thermodynamic framework is employed to solve the nonlinear coupled problem up to a specified energy range through a Picard iteration technique and to study the model and its results. Studies are presented for a range of fluid entry resistance parameters and Beavers-Joseph-Saffman slip rate coefficients, showing the capability of the model to simulate skin and slip effects in a dimensionally-reduced fracture setting.

Porous electrodes are core components that determine the performance of redox flow batteries. Thus, optimizing their microstructure is a powerful approach to reduce system costs. Here we present a pore network modeling framework that is microstructure and chemistry agnostic, iteratively solves transport equations in both half-cells, and utilizes a network-in-series approach to simulate the local transport phenomena within porous electrodes at a low computational cost. In this study, we critically assess the versatility and robustness of pore network models to enable the modeling of different electrode geometries and redox chemistries. To do so, the proposed model was validated with two commonly used carbon fiber-based electrodes (a paper and a cloth), by extracting topologically equivalent networks from X-ray tomograms, and evaluated for two model redox chemistries (an aqueous iron-based and a non-aqueous TEMPO-based electrolyte). We find that the modeling framework successfully captures the experimental performance of the non-aqueous electrolyte but is less accurate for the aqueous electrolyte which was attributed to incomplete wetting of the electrode surface in the conducted experiments. Furthermore, the validation reveals that care must be taken when extracting networks from the tomogram of the woven cloth electrode, which features a multiscale microstructure with threaded fiber bundles. Employing this pore network model, we elucidate structure-performance relationships by leveraging the performance profiles and the simulated local distributions of physical properties and finally, we deploy simulations to identify efficient operation envelopes.

Understanding the process-property relations of helical polymers using molecular simulations has been an attractive research field over the years. Specifically, isotactic polypropylene still remains a challenge for current computational experimentation, as it exhibits phenomena such as crystallization that emerge on large spatial and temporal scales. Coarse-graining is an efficient technique for approaching such phenomena, although previous coarse-grained models lack in preserving important atomistic and structural details. In this paper we develop a new coarse-grained model, based on the popular MARTINI force field, that is able to reproduce the helical behavior of isotactic polypropylene. To test the model, the predicted statistical and structural properties (characteristic ratio, density, entanglement molecular weight, solubility parameter in the melt) are compared with previous simulation results and available experimental data. For the development of the new coarse-grained force field, a single unperturbed chain Monte Carlo algorithm has been implemented: an efficient algorithm which samples conformations representative of a melt by simulating just a single chain.

Electrochemical CO2reduction is a promising process to store intermittent renewable energy in the form of chemical bonds and to meet the demand for hydrocarbon chemicals without relying on fossil fuels. Researchers in the field have used gas diffusion electrodes (GDEs) to supply CO2to the catalyst layer from the gas phase. This approach allows us to bypass mass transfer limitations imposed by the limited solubility and diffusion of CO2in the liquid phase at a laboratory scale. However, at a larger scale, pressure differences across the porous gas diffusion layer can occur. This can lead to flooding and electrolyte breakthrough, which can decrease performance. The aim of this study is to understand the effects of the GDE structure on flooding behavior and CO2reduction performance. We approach the problem by preparing GDEs from commercial substrates with a range of structural parameters (carbon fiber structure, thickness, and cracks). We then determined the liquid breakthrough pressure and measured the Faradaic efficiency for CO at an industrially relevant current density. We found that there is a trade-off between flooding resistance and mass transfer capabilities that limits the maximum GDE height of a flow-by electrolyzer. This trade-off depends strongly on the thickness and the structure of the carbon fiber substrate. We propose a design strategy for a hierarchically structured GDE, which might offer a pathway to an industrial scale by avoiding the trade-off between flooding resistance and CO2reduction performance.

The suppression of CO2-induced plasticization in polyimide membranes at supercritical conditions up to 120 bar is investigated. Three approaches (polymer blending, thermal treatments and chemical crosslinking) known from relatively low-pressure applications are applied and their effectiveness to suppress membrane plasticization at high CO2 pressures and under supercritical conditions is systematically identified. CO2 sorption measurements reveal that especially Henry sorption promotes plasticization and that the corresponding Henry sorption parameter (kD) correlates with the d-spacing and Tg of the membranes. A lower d-spacing and higher Tg results in a reduced kD parameter and thus a higher resistance to plasticization. A high interchain rigidity is required to suppress plasticization at the highly plasticizing liquid-like CO2 densities. Chemical and thermo-oxidative crosslinking results in the largest decrease in interchain mobility and therefore shows the highest resistance to plasticization, but also a significantly lower permeability. Thermally treating the membranes in N2 retains a high permeability, while still displaying significant plasticization resistance. Polymer blending does increase the plasticization resistance, but strongly reduces the permeability. All three methods manage to suppress plasticization at supercritical conditions, but crosslinking offers superior plasticization resistance. However, proper tailoring strategies are required to combine a high plasticization resistance with a high permeability.

The rapid advances in performance and miniaturization of electronic devices require a cooling technology that can remove the produced heat at a high rate with small temperature variations, as is obtained in flow boiling. To obtain insight in flow boiling, we performed numerical simulations in a 200 μm square microchannel using the local front reconstruction method. Besides validation with literature results, a parametric study shows an increasing heat removal rate and bubble growth rate with increasing wall temperature, liquid mass density, and liquid heat capacity and decreasing inlet velocity indicating the importance of phase change compared to convective transport. Finally, the heat transfer in the liquid film is studied using a Nusselt number defined with the film thickness, which is comparable to Nusselt number for falling films on hot surfaces. It is observed that convective effects are more pronounced at the bubble rear compared to the bubble front.

This paper presents systematic analysis of value creation chains and their economic and environmental hotspots within a multi-product biorefinery with the primary goal to promote sustainable biorefining. Lignocellulosic biorefinery producing ethanol, crude lignin oil (CLO) and electricity was analysed. The methodology involves transformation of technological model into an input-output one with the use of matrix notation for the analysis of economic and environmental attributes along value chains. The results show that the accumulation of biomass through energy supply grows by a factor of 1.2 for ethanol and electricity, and by 1.4 for CLO value chains, of which solid recovery, lignin solvolysis and biomass pretreatment are responsible for the most significant growth indicating the necessity for energy optimization of those steps. The analysis reveals a superfluous role of infrastructure in pretreatment and lignin drying processes. Of infrastructural costs related to the equipment required for the pretreatment step, wastewater treatment (WWT) facility is responsible for 58%, and of the costs of lignin drying, the combined heat and power plant is responsible for 56%. WWT determines 75% of infrastructural GHG emissions attributable to pretreatment, and 57% of those related to lignin drying. This points at an advantage of a biorefinery concept involving the removal of lignin fraction before the valorization of carbohydrates. Another hotspot, the lignin solvolysis technology, shows environmental and economic advantages of its further optimization in terms of production costs and GHG emissions. The proposed method is helpful for analyzing economic and environmental hotspots in new biorefinery concepts and integration pathways.