The 50 most-cited articles in Industrial & Engineering Chemistry Research, 2022

The NIST REFPROP software program is a powerful tool for calculating thermophysical properties of industrially important fluids, and this manuscript describes the models implemented in, and features of, this software. REFPROP implements the most accurate models available for selected pure fluids and their mixtures that are valid over the entire fluid range including gas, liquid, and supercritical states, with the goal of uncertainties approaching the level of the underlying experimental data. The equations of state for thermodynamic properties are primarily of the Helmholtz energy form; a variety of models are implemented for the transport properties. We document the models for the 147 fluids included in the current version. A graphical user interface generates tables and provides extensive plotting capabilities. Properties can also be accessed through third-party apps or user-written code via the core property subroutines compiled into a shared library. REFPROP disseminates international standards in both the natural gas and refrigeration industries, as well as standards for…

Artificial intelligence (AI), machine learning (ML), and data science are leading to a promising transformative paradigm. ML, especially deep learning and physics-informed ML, is a valuable toolkit that complements incomplete domain-specific knowledge in conventional experimental and computational methods. ML can provide flexible techniques to facilitate the conceptual development of new robust predictive models for multiphase flows and reactors by finding hidden pattern/information/mechanism in a data set. Due to such emergence, we thereby comprehensively survey, explore, analyze, and discuss key advancements of recent ML applications to hydrodynamics, heat and mass transfer, and reactions in single-phase and multiphase flow systems from different aspects: (1) development of multiphase closure models of drag force, turbulence stresses and heat/mass transfer to improve the accuracy and efficiency of typical CFD simulations; (2) image reconstruction, regime identification, key parameter predictions, and optimization of multiphase flow and transport fields; (3) reaction kinetics…

Geological H 2 storage plays a central role to enable the successful transition to the renewable H 2 economy and achieve net-zero emission in the atmosphere. Depleted oil and gas reservoirs are already explored with extensive reservoir and operational data. However, residual hydrocarbons can mix with injected H 2 in the reservoirs. Furthermore, low density and high diffusivity of H 2 may establish H 2 leakage from the reservoirs via fault pathways. Interestingly, H 2 can be consumed by microorganisms, which results in pore-network precipitation, plugging, and partial permeability impairment. Therefore, stored H 2 may be lost in the formations if the storage scenario is not planned cautiously. While salt caverns are safe and commercially proven geo-rock for H 2 storage, they have low-storage capacity compared to depleted gas reservoirs. Moreover, salt structures (e.g., domel, bedded) and microorganisms activities in the salt cavern are limiting factors, which can influence the storage process. Accordingly, we discuss challenges and future perspectives of hydrogen storage in different…

With a constant upsurge in energy demand, production from depleted and harsh reservoirs through enhanced oil recovery techniques (EOR) has significantly increased. Among many EOR techniques, chemical EOR (cEOR) is one of the most widely used methods of oil extraction. Surfactants used in cEOR are instrumental in reducing interfacial tension (IFT) and altering the wettability of rock, which leads to additional oil recovery. This review draws attention to detail on surfactants from fundamentals to field scale. Properties of surfactants like phase behaviors, critical micelle concentration (CMC), hydrophilic–lipophilic balance and deviation, zeta potential, and their importance are discussed in depth. The presence of a saline environment, polymer, cosurfactant, and other factors affecting the performance of surfactant during the cEOR process are also elaborated. Key findings on surfactant adsorption on reservoir rock with other influencing aspects have also been reported in this study. Types of surfactants, from basic to the likes of polymeric, viscoelastic, Gemini, natural, and their…

Heavy metal contamination in soil and water has become a serious threat to all forms of life. Finding a sustainable remediation method is the prime concern of researchers worldwide. In this quest, cellulose has emerged as a biocompatible, biodegradable, renewable, tunable, and cost-effective bioadsorbent for heavy metal removal from polluted water. Cellulose is rich in hydroxyl groups which can be chemically modified to enhance the reactivity, binding sites, and mechanical strength. Cellulose in nano size, i.e., nanofibers and nanocrystals, offer myriad opportunities to improve the aspect ratio, surface area, pore size, and hydrophilicity for effective adsorption. In this review, chemical and physical modifications in cellulose (functional group transformations, nanocellulose, nanocomposites, hydrogels, aerogels, beads, and membranes) with respect to adsorption of divalent heavy metal ions, in particular, Pb 2+, Cu 2+, and Cd 2+, have been extensively discussed. This review also examines the effect of pH, concentration, temperature, and contact time on the adsorption process.…

Deep eutectic solvents (DESs) have become a hot topic in many branches of science due to their remarkable properties. They have been studied in a wide variety of applications. In particular, choline chloride (ChCl)-based DESs are one of the most commonly used representatives of these fluids. Nevertheless, in order to apply DESs in some fields, it is essential to guarantee their stability, reusability, and biocompatibility. In this context, the long-term stability of three ChCl-based DESs formed using glucose, malonic acid, and urea as hydrogen bond donors was investigated. Furthermore, the possible formation of toxic byproducts during long-term heating was evaluated for the first time, and toxicological studies using three bacterial strains (Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus) were performed. ChCl:urea DES revealed a high long-term thermal stability and was also found to be less toxic to the bacteria and thus can be considered as green solvent. ChCl:glucose DES started to decompose as a result of possible caramelization at 100 °C, and decomposition…

Since the conventional Haber-Bosch ammonia synthesis loop suffers from harsh process conditions, high energy consumption, and heavy pollution, the artificial catalytic synthetic NH 3 has emerged as a promising alternative method for producing NH 3 . Meanwhile, nitrate (NO 3 – ) accumulation in the environment causes serious problems involving health and environmental issues. The urgent need to eliminate NO 3 – and produce NH 3 perfectly caters to the NO 3 – reduction reaction (NO 3 RR) via an attractive electrocatalytic route. Cu-based catalysts exhibit an inhibiting effect on hydrogen evolution, rapid reduction kinetics, and stable catalytic performance, revealing remarkable advantages for NO 3 RR. In this review, we summarize the recent achievements of Cu-based catalysts in electrocatalytic NO 3 RR, discuss the detection methods for evaluating NO 3 RR performance, and introduce the fundamentals for understanding the thermodynamics and kinetics. This review can provide guidance and help for the rational design and development of non-noble metal catalysts in electrocatalytic NO 3 RR…

High Resolution Image Download MS PowerPoint Slide The economic, environmental, and energetic performance of direct air capture (DAC) processes based on solid sorbents depends significantly on ambient air conditions and the availability of renewable resources. High ambient temperature or low humidity leads to higher energy consumption and lower CO 2 productivity; lack of renewable resources may make the direct air capture process not viable. With this work, we investigated how the performance of sorbent-based direct air capture plants varies when changing ambient conditions and how the system should be optimally designed and operated to match the time-dependent variations. To this end, we formulated a new modeling framework, where thermodynamic modeling of adsorption processes is bridged to mixed integer linear optimization via a portable linear model of DAC. The process is based on a vacuum-temperature swing cycle, whose performance was obtained with a rate-based thermodynamic model at varying ambient conditions for an exemplary sorbent representative of different…

A huge number of spent lithium-ion batteries (LIBs) have caused serious problems such as resource waste and environmental pollution. Lithium iron phosphate (LFP) is one of the major cathode materials in the spent LIBs. It is urgently needed to develop a safe, environmentally friendly, and cost competitive approach to regenerate the LFP cathode collected from the spent LIBs. The nitrate molten salt process has been utilized to regenerate layered cathode materials, which are nevertheless non-compatible with the LFP regeneration process. The LFP crystal lattice will be destroyed during the molten salt process by the oxidative environment, where Fe(II) is oxidized to Fe(III). A new approach is proposed in this work to tackle this issue, where a low-temperature molten salt process is coupled with a reductive environment to suppress oxidation of Fe(II). In detail, lithium nitrate is used as a molten salt medium and lithium source simultaneously. Sucrose is used as a carbon source to provide a reductive environment. Through a short molten-salt relithiation step at 300 °C and further…

In modern society, the multifarious polymeric material polyurethane (PU) is used in household appliances and commercial sectors. Statistics shows the usage of PU as rigid and flexible foams is the highest among different PU-based materials. Industrially viable synthesis, tailor-made porosity and pore morphology, robustness to micro-organisms, weathering, hydrolytic degradation, and resistance to a wide range of chemicals are the excellent attributes of PU foams. Despite achieving significant attention in academia and industries, the prominent tendency to fire-catching or flammability and rapid-fire spread on ignition are the serious concerns of PU foams at their end-use. The figures on home fire accidents and associated fire injuries, loss of civilians, and properties primarily due to fire-catching of furniture are highly devastating. Therefore, a large volume of efforts has been dedicated to decorating flame retardancy in PU foams using a wide range of flame retardants (FRs) (in-situ or post-synthesis). Hence, the focus of this review is to summarize various FRs for rigid and…

Today, consumers are well aware of the functional protection properties of textiles, in addition to their aesthetic appearance. The use of nanoparticles for specialty finishing is an emerging area in textile processing and engineering. With the advancement in technology, it is possible to fabricate nanoparticles of the desired size and shape with various functional properties. Reports are available on the use of nanoparticles for antimicrobial, UV protection, flame retardant, and hydrophilic and hydrophobic finishes on textiles. Pathogens are a potential threat to humans and also gaining resistance to conventional antimicrobial agents. Thus, it is needed to find new and sustainable antimicrobial formulations. Metal nanoparticles have the potential ability to penetrate and destroy the cell membrane structure and eventually cause cell death. The nano-finished textiles could find various medical and hygienic applications. This review discusses recent research attempts to impart antimicrobial finishes to textiles using metal nanoparticles, focusing on the action of microbes on textiles,…

An extensive experimental campaign on Li recovery from relatively dilute LiCl solutions (i.e., Li+ ∼ 4000 ppm) is presented to identify the best operating conditions for a Li2CO3 crystallization unit. Lithium is currently mainly produced via solar evaporation, purification, and precipitation from highly concentrated Li brines located in a few world areas. The process requires large surfaces and long times (18–24 months) to concentrate Li+ up to 20,000 ppm. The present work investigates two separation routes to extract Li+ from synthetic solutions, mimicking those obtained from low-content Li+ sources through selective Li+ separation and further concentration steps: (i) addition of Na2CO3 solution and (ii) addition of NaOH solution + CO2 insufflation. A Li recovery up to 80% and purities up to 99% at 80 °C and with high-ionic strength solutions was achieved employing NaOH solution + CO2 insufflation and an ethanol washing step.

Nature has inspired scientists to develop green and sustainable nanomaterials with biomimetic functions. Particularly, biomimetic metallic nanostructures (biometal NPs) with unique optical, catalytic, and electrical properties have received tremendous attention in many fields, ranging from healthcare and agriculture to energy and environmental sciences. Biometal NPs synthesized by various natural resources such as plant extracts, biomolecules, bacteria, and even viruses possess unique biomimetic functions including but not limited to precise biorecognition, self-assembly, antibacterial/antiviral, and enzymatic properties. In this report, we first review the bioinspired synthesis of industrially important metal nanoparticles, followed by the discussion on how the different biological sources affect the biomimetic functions of the as-synthesized biometal NPs. Next, we review the recent advancement and applications of these biometal NPs in the fields of biomedical engineering and catalysis, which include the development of metallic nanobiosensors, biomedical imaging probes,…

Conductive hydrogel strain sensors have triggered extensive research interest in artificial intelligence, human motion detection, electronic skin, and other technical fields. However, it is still challenging work to prepare conductive hydrogels integrated with good biocompatibility, recyclability, self-healing, and strong adhesion properties both in air and underwater. Herein, a novel, ultraexcellent self-healing, adhesive, and multifunctional gelatin composite hydrogel was fabricated through a simple and rapid one-pot method in which gelatin (Gel) and polyvinyl alcohol (PVA) were used as the polymeric skeletons, Tara tannin as the cross-linking agent, and multiwalled carbon nanotubes (CNTs) as the conducting medium. Inspired by the vegetable tanning mechanism in tanning chemistry, the multiple hydrogen bonding and hydrophobic interactions of Tara tannin with Gel were used to build the cross-linking network of the hydrogel. The obtained GTPC (Gel-Tara tannin-PVA-CNTs) hydrogel exhibited considerable stretchability (760%), strong adhesion strength (16 kPa to pigskin), and high…

High Resolution Image Download MS PowerPoint Slide This review describes progress in the design and synthesis of biomass-derived carbon materials with different morphologies. It also covers respective composites and their applications in the field of electrochemical sensing of (bio) chemical species. Generally, carbon-based materials have paved the way for advanced electrochemical sensing devices because of their unique physical and chemical properties. Carbon materials are typically created from chemical precursor materials; however, researchers are increasingly focusing on fabricating carbon materials from waste biomass resources due to economic and environmental constraints. Compared with other carbon materials, biomass-derived carbon materials (BCMs) are more environment-friendly with lower toxicity. In this review, we concentrated on providing researchers with a complete overview to develop an alternative strategy to improve the sensitivity of electrochemical sensors in actual samples by using numerous biomass-derived carbon-based materials modified electrodes. This review…

High Resolution Image Download MS PowerPoint Slide A Cu-BTC metal–organic framework hybrid with graphene oxide (GO) having ultralow GO content (1 wt %) was developed in situ and was explored as a medium for hydrogen storage at ambient temperature. The structural integration of both counterparts in the Cu-BTC/GO hybrid was attained through interaction of the Cu centers with the oxygen-bearing groups of GO by equatorial and axial coordination upon in-situ growth. As a result, Cu-BTC/GO showed enhanced surface area, pore volume, and microporosity, while its hydrogen storage capacity was increased by ∼60%, compared to pure Cu-BTC at 298 K and 1 bar, accompanied by low heat of adsorption (<16.3 kJ mol –1 ), and 100% recovery of the initial capacity, as tested upon six successive PSA cycles. For hydrogen purification applications, selective hydrogen storage was also investigated and it was found that Cu-BTC/GO exhibited a 49% and 38.5% higher H 2 /O 2 and H 2 /N 2 selectivity, respectively (10.13 for H 2 /O 2 and 8.64 for H 2 /N 2 ), at 298 K and 1 bar compared to that of the pure Cu-BTC.…

Hydrogel-based flexible sensors have attracted extensive attention of researchers due to their great application potential in soft robots, electronic skin, motion monitoring, and disease diagnosis. However, it is still a challenge for hydrogel-based flexible sensors to be integrated with good mechanical performance, sensitivity, self-adhesion, fatigue resistance, antibacterial activity, and recyclability. Here, a novel supramolecular polyoxymethylene cross-linking agent (PCD-Fc-CHO) was designed and synthesized by the host–guest interaction between poly(β-cyclodextrin) and ferrocene. Then, a double network (DN) hydrogel was prepared by a PVA crystallization domain via the freeze-thaw cycle method (first network) and Schiff base between PCD-Fc-CHO and chitosan (second network). The obtained DN hydrogel was immersed in the NaCl solution to form a conductive DN hydrogel. The resulting hydrogel has excellent mechanical properties [tensile (314%, 0.5 MPa), compress (50%, 0.663 MPa)], good fatigue resistance (stretching and compressing cycles at least five times), reliable conductivity…

Hydrogels are a soft material that undergoes cross-linking between polymers to form a hydrophilic three-dimensional network. In fact, similarity to body tissue, soft consistency, biocompatibility, and elasticity, impart a protagonic role of hydrogel to be applied as a biomaterial. In response to external cues, stimuli-responsive hydrogels are particularly impactful, enabling remarkable levels of control over material properties. They can endure changes in swelling behavior, permeability, network structure, and mechanical strength. Nevertheless, such changes induce single-cycle or reversible transitions, so hydrogels can regain their initial state once the trigger is removed. Recently, polysaccharide-based hydrogels with stimuli-responsive properties resulted in developing biomimetic structures for a widespread biotechnological application owing to their excellent biodegradability, biocompatibility, nonimmunogenicity, functional properties, ease of gelation, and derivatization. This review will initially highlight recent advances in cross-linking methods and chemistry for preparing…

This work develops a framework for building machine learning models and machine-learning-based predictive control schemes for batch crystallization processes. We consider a seeded fesoterodine fumarate cooling crystallization and dissolution process in a batch reactor and present the methodology and implementation of simulation, modeling, and controller design. Specifically, to address the experimental data scarcity problem, we first develop a one-dimensional population balance model based on published kinetic parameters that were obtained empirically to describe the formation of crystals via nucleation, growth, and agglomeration. Then, recurrent neural network (RNN) and autoencoder–RNN (AERNN) models are developed using data from extensive open-loop simulations of the semi-empirical population balance model under various operating conditions to capture the process dynamic behavior. Two model predictive control (MPC) schemes using the respective RNN and AERNN models are developed to optimize the crystallization process with respect to product yield, crystal size, number of fines in…

emissions of the sector. In this sense, the hydrogen content of coke oven gas (COG) has positioned it as a promising source toward a hydrogen-based economy which could lead to economic and environmental benefits in the iron and steel industry. COG is presently used for heating purposes in coke batteries or furnaces, while in high production rate periods, surplus COG is burnt in flares and discharged into the atmosphere. Thus, the recovery of the valuable compounds of surplus COG, with a special focus on hydrogen, will increase the efficiency in the iron and steel industry compared to the conventional thermal use of COG. Different routes have been explored for the recovery of hydrogen from COG so far: i) separation/purification processes with pressure swing adsorption or membrane technology, ii) conversion routes that provide additional hydrogen from the chemical transformation of the methane contained in COG, and iii) direct use of COG as fuel for internal combustion engines or gas turbines with the aim of power generation. In this study, the strengths and bottlenecks of the main…

With the renewed interest for hydrogen as an energy carrier, means to produce, but most importantly store, transport, and distribute, “green” hydrogen over long distances has become important. In this context, liquid organic molecules that can be hydrogenated and dehydrogenated under mild conditions of temperature and pressure continue to attract significant attention. These liquid organic molecules referred as “liquid organic hydrides” in the early 1980s include molecules such as cyclohexane, methylcyclohexane, decalin, N-heterocycles, methanol, ethanol, and formic acid. However, current liquid organic hydrides still suffer from limitations along with the emergence of more effective catalysts to meet the requirement of competing (de)hydrogenation reactions, as well as new chemistry to enable their (de)hydrogenation reactions under milder conditions and extended cycle lives. Herein, we critically review common state-of-the-art catalyst designs, which remain one of the main barriers to the effective emergence of liquid organic hydrogen carriers enabling the widespread transport and…

The reactor is one of the most important equipment to be designed for optimal process operations. An appropriate reactor modeling leads to an efficient and optimal process conceptual design, simulation, and eventually construction. The key for success in this step is mainly related to kinetics. The present work is centered toward process simulation and aims at comparing three different kinetic models for methanol synthesis. The comparison shows how the refitted Graaf model, presented in a previous study, effectively predicts the performance of modern methanol synthesis loops. To pursue this objective, we simulated in Aspen HYSYS three methanol synthesis technologies (the most popular technologies in modern plants) and compared the results with industrial data. The proposed case study demonstrates that the refitted Graaf model is more accurate in output prediction than the well-established original Graaf and Vanden Bussche-Froment models, which are currently considered the industrial benchmark, thus showing how the refitted Graaf model is a potential candidate for future industrial…

The indubitable rise of metal–organic framework (MOF) technology has opened the potential for commercialization as alternative materials with a versatile number of applications that range from catalysis to greenhouse gas capture. However, there are several factors that constrain the direct scale-up of MOFs from laboratory to industrial plant given the insufficient knowledge about the overall safety in synthesis processes. This article focuses on the study of MOF thermal stability, from concept to prediction, and the factors that influence such stability. The core of this work is a thermal stability prediction model for MOFs. This model can be applied to existing and new MOF structures, and it will allow for an estimation of the thermal stability temperature range of MOFs. This work contributes to the overall advancement of MOF technology and the efforts for its commercial use at industrial scale, combining both experimental data and computational techniques.

Climate change has driven attention toward promoting sustainable policies and processes to contain global warming below +1.5 & DEG;C. Negative emission technologies (NET)-bioenergy with carbon capture and storage in particular (BECCS)-are expected to contribute to the achievement of that target. Recent research and development concerning NET focused on chemical looping combustion (CLC) and chemical looping gasification (CLG), as they should limit cost-and energy-penalties associated with carbon capture and storage thanks to solid materials known as oxygen carriers (OCs). This review aims to provide an introductory tool about CLC and CLG and their possible role as NET if fed with biomasses to obtain BECCS. A critical overlook is proposed concerning chemical looping reactions, fuels, types of OCs, and reactor systems developed at different scales, focusing on recent and current European research projects and remarks on the subsequent developments.

Heavy metal ion pollution in water and soil is a formidable environmental problem. Due to their desired heavy metal capture capacity and excellent chemical and physical stability, resin chelating ligands have been widely used in heavy metal adsorption. In this Review, we outline the latest progress in chelating resin adsorbents toward heavy metals. This paper reviews the methods of selectively separating the target ions in various solutions and screens the excellent performances of chelating resins; the types and synthesis methods of chelating resins are also summarized. Different adsorption mechanisms existing between chelating resins and heavy metal ions are summarized, and the influencing factors of the adsorption processes are analyzed. On this basis, we propose the opportunities, challenges, and prospects faced by researchers studying chelating resin materials in the adsorption of heavy metals, and the reasonable design of advanced chelated resin-based adsorption systems should achieve an eco-friendly and sustainable environment.

Polyimide (PI) films with simultaneously low dielectric loss (D f ) values at high frequencies and excellent general properties are urgently needed with the rapid development of high frequency communication technology. Herein, we proposed that dielectric loss can be decreased by reducing intermolecular friction work. Inspired by liquid crystals with low intermolecular frictions, novel liquid-crystal-like PI films were designed by simultaneously introducing mesogen units and promoting groups (−CF 3 ) and then being thermally imidized via a unique solvent-assisted continuous ramping process without any stretching or shearing process. The liquid-crystal-like PI films exhibited ultralow D f values such as 0.00365 at 1 MHz, 0.00184 at 10 GHz, and 0.0027 at 0.75THz, which were 28.7%, 45.4%, and 97.0% lower, respectively, than those of PI films without liquid-crystal-like structures. The results of molecule simulations further demonstrated that liquid-crystal-like structures can reduce intermolecular friction work by slowing dipole rotation, leading to ultralow D f values of PI films. The…

High Resolution Image Download MS PowerPoint Slide The reverse water gas shift reaction (RWGS) has attracted much attention as a potential means to widespread utilization of CO 2 through the production of synthesis gas. However, for commercial implementation of RWGS at the scales needed to replace fossil feedstocks with CO 2, new catalysts must be developed using earth abundant materials, and these catalysts must suppress the competing methanation reaction completely while maintaining stable performance at elevated temperatures and high conversions producing large quantities of water. Herein we identify molybdenum phosphide (MoP) as a nonprecious metal catalyst that satisfies these requirements. Supported MoP catalysts completely suppress methanation while undergoing minimal deactivation, opening up possibilities for their use in CO 2 utilization.

High Resolution Image Download MS PowerPoint Slide This work examines the role of oxygen supply in the improvement of the hydrogen peroxide (H 2 O 2 ) electrochemical production efficiency and the generation of high H 2 O 2 concentrations in electrochemical processes operated in a discontinuous mode. To conduct this study, a highly efficient Printex L6 carbon-based gas diffusion electrode (GDE) as a cathode was employed for the electrogeneration of H 2 O 2 in a flow-by reactor and evaluated the effects of lowering the operation temperature (to increase solubility) and increasing the air supply in the system on H 2 O 2 electrogeneration. The results obtained in this study show that unlike what is expected in flow-through reactors, the efficiency in the H 2 O 2 production is not affected by the solubility of oxygen when GDE is employed in the electrochemical process (using the flow-by reactor); i.e., the efficiency of H 2 O 2 production is not significantly dependent on O 2 solubility, temperature, and pressure. The application of the proposed PL6C-based GDE led to the generation of…

Thermodynamic models are often vital when characterizing complex systems, particularly natural gas, electrolyte, polymer, pharmaceutical, and biological systems. However, their implementations have historically been abstruse and cumbersome, and as such, the only options available were black box commercial tools. In this article, we present Clapeyron.jl: a pioneering attempt at an open-source fluid thermodynamics toolkit to build and make use of thermodynamic models. This toolkit is built using Julia, a modern language for scientific computing known for its ease of use, extensibility, and first-class support for differentiable programming. We currently support more models than any package available, including standard cubic (SRK, PR, PSRK, etc.), activity coefficient (NRTL, UNIFAC, etc.), COSMO-based, and the venerable SAFT equations. The property estimation methods supported are extensive, including bulk, VLE, LLE, VLLE, and critical properties. With Clapeyron.jl, researchers and enthusiasts alike will be able to focus on the application and worry less about the implementation.

High Resolution Image Download MS PowerPoint Slide Thermodynamics is the science of the interactions between energy and matter. It was formalized in the late 19th century and remains an essential piece in solving many technological challenges that society faces today. Yet, it is often considered complex and challenging, perhaps because it is often taught within a rigid mathematical framework, without highlighting the extensive range of applications and the tools that it offers for understanding and elaborating a sustainable future. The authors of this paper have performed an industrial survey (Kontogeorgis et al., Ind. Eng. Chem. Res., 2021, 60, 13, 4987-5013), which pointed out that thermodynamics is indeed a cornerstone of many processes in a large range of industries, but that as of today, many questions and needs remain unanswered. Some missing answers are caused by a lack of knowledge of the existing tools (educational issue), some by the unavailability of models, parameters or by the lack of transferability of the concepts from one system to another. In other cases, simply, no…

Lithium has been a high-demand element with the rapid development of lithium-ion batteries. The recovery of lithium from salt lake brine via solvent extraction is considered a promising technique. In this study, the solvent extraction process in the tributyl phosphate (TBP)–FeCl 3 /brine system was investigated. The order of metal ions competitively combining with TBP–FeCl 3 was Li + > Na + > K + > Mg 2+, and the compositions of main cationic extraction complexes were Li(TBP) 2 (H 2 O) 2 +, Na(TBP) 2 (H 2 O) 4 +, K(TBP) 2 (H 2 O) 4 +, and Mg(TBP) 2 (H 2 O) 4 2+, respectively. The energy decomposition analysis showed that the electrostatics was the major interaction between the metal ions and the solvent (TBP and water). Compared with water, TBP bound more competitively with the metal ions. The calculated species distribution results showed that the ferric ion reacted with the chloride ion to form FeCl 2 +, FeCl 3, and FeCl 4 – in high Cl – concentration brine. Co-extractant FeCl 3 was found to exist in the organic phase in the form of FeCl 4 – upon comparing the experimental and…

The reaction kinetics of CO2 methanation over a highly active 8.5% Ni/CeO2 catalyst was determined in a fixed-bed reactor, in the absence of heat- and mass-transfer limitations. Once the catalyst activity was stabilized, more than 120 kinetic experiments (with varying values of reaction temperature, total pressure, space velocity (GHSV), and partial pressure of products and reactants) were performed. From initial reaction rates, an apparent activation energy of 103.9 kJ mol–1 was determined, as well as the effect of reactants (positive) and water partial pressures (negative) on CO2 methanation rate. Three mechanistic models reported in the literature, in which CO2 is adsorbed dissociatively (carbon and formyl routes) or directly (formate route), were explored for modeling the entire reaction kinetics. For that, the corresponding rate equations were developed through the Langmuir–Hinshelwood–Hougen–Watson (LHHW) approach. In agreement with DRIFTS experiments, formate route, in which the hydrogenation of bicarbonate to formate is considered to be the rate-determining step, reflects…

In this era of Industry 4.0, there are continuing efforts to develop fault detection and diagnosis methods that are fully autonomous; these methods are self-learning, with little or no human intervention. This paper proposes a methodology for the autonomous diagnosis of the root cause of a detected fault in a complex processing system. The methodology comprises steps to detect and classify any newly encountered fault, classify the known faults, and find the root cause of the detected fault condition. The one-class support vector machine (SVM) model is used in the framework to detect the unlabeled fault, and the neural network is used for fault classification and root cause analysis. The developed methodology is capable of self-updating the fault database by detecting and diagnosing any new fault condition. A permutation algorithm is applied in the neural network framework to extract the variable’s contribution to the classified fault condition. Also, Spearman’s rank correlation approach is used to investigate and justify the data correlation and causation. The proposed framework is…

Heavy metals in food and water sources are potentially harmful to humans. Determination of these pollutants is critical for improving safety. Effective recognition systems are a contemporary challenge; several novel technologies for the quick, easy, selective, and sensitive determination of these compounds are in demand. Metal-organic framework (MOF)-based sensors and biosensors have crucial applications in identifying these potentially harmful substances. Here, we review electrochemical and optical biosensors for in situ sensing that are sensitive and cost effective, with a simple protocol and wide linear range. Despite the abundance of articles in this field, we assessed and checked out various basic features of MOFs as porous compounds that include clusters or ions, and some of the ligands connected to these clusters have a variety of useful properties. Afterward, we also assessed various electrochemical and optical sensing assays, which have recently gathered interest because of their potential applications for recognizing certain compounds in the environment. Their operation…

High Resolution Image Download MS PowerPoint Slide We performed H-cell and flow cell experiments to study the electrochemical reduction of CO 2 to oxalic acid (OA) on a lead (Pb) cathode in various nonaqueous solvents. The effects of anolyte, catholyte, supporting electrolyte, temperature, water content, and cathode potential on the Faraday efficiency (FE), current density (CD), and product concentration were investigated. We show that a high FE for OA can be achieved (up to 90%) at a cathode potential of −2.5 V vs Ag/AgCl but at relatively low CDs (10–20 mA/cm 2 ). The FE of OA decreases significantly with increasing water content of the catholyte, which causes byproduct formation (e.g., formate, glycolic acid, and glyoxylic acid). A process design and techno-economic evaluation of the electrochemical conversion of CO 2 to OA is presented. The results show that the electrochemical route for OA production can compete with the fossil-fuel based route for the base case scenario (CD of 100 mA/cm 2, OA FE of 80%, cell voltage of 4 V, electrolyzer CAPEX of $20000/m 2, electricity price…

The accumulation of plastic wastes has become a global environmental issue, because of their ever-growing production, slow degradation, and potential environmental hazards. Consequently, reducing their presence in the environment by upcycling has sparked tremendous research interest. Herein, we report the valorization of poly(ethylene terephthalate) (PET) plastic wastes to produce nanofibrous adsorptive membranes for their applications in oil removal. In this study, plastic wastes derived from PET bottles were dissolved in trifluoroacetic acid (TFA) or a TFA/dichloromethane (DCM) binary solvent system and then electrospun into nanofibrous recycled PET (rPET) membranes. The nanofiber morphology was tuned by adjusting the polymer concentration. The nanofibers produced via electrospinning from TFA solutions were more uniform than those produced using TFA/DCM. The influence of acid-mediated recycling on the PET structure was explored via thermogravimetric and X-ray photoelectron spectroscopy analyses. A dynamic mechanical analysis showed that the membranes exhibited high flexibility…

High Resolution Image Download MS PowerPoint Slide Bipolar membrane electrodialysis (BPMED) could allow for the complete electrification of direct air capture (DAC) technologies. In this work, we have modeled and optimized two DAC processes based on different electrodialysis cell designs. The technical assessment has been complemented by a detailed economic analysis, showing the advantages but also the current shortcomings of this technology and pathways for advancement. A minimum energy demand of 24 MJ kg CO 2 –1 has been estimated for the base-case scenario, a result comparable to what has been reported for other liquid-scrubbing DAC technologies. Several solutions to further abate power consumption have been reviewed, with the most promising case providing a 29% reduction. Membrane cost and performance are currently the main limiting factors. In a scenario where cheaper membranes with better performance are assumed to be available, total costs below $250 ton CO 2 –1 may be feasible, making BPMED a viable fully electrified alternative to other technologies requiring natural gas.

The emissions of CO 2 have been recognized as the main cause of climate change. As an important strategy being used to reduce the CO 2 concentration in the atmosphere, carbon capture, utilization and storage (CCUS) has attracted significant attention in recent years. Geological formations, including depleted oil and gas reservoirs and saline aquifers, are popular CO 2 storage options. During the process of CO 2 storage in subsurface formations, the interactions between CO 2 and formation fluids must be considered as they could greatly affect the CO 2 trapping mechanisms and CO 2 storage capacity. In this paper, we give a brief review of the phase behavior mechanisms associated with CO 2 storage in subsurface formations. Two different CO 2 -storage strategies are considered in this paper: CO 2 storage in saline aquifers and CO 2 storage in oil reservoirs. Multiphase equilibria, including two-phase, three-phase, and four-phase equilibria, can be observed during CO 2 injection into underground formations. Both the experimental and modeling studies on the related phase behavior…

Two-dimensional (2D) materials have a wide range of applications in the field of corrosion protection and wear resistance. The use of MXene (Ti 3 C 2 T x ) in epoxy coatings is limited due to its natural restacking tendency. Herein, MXene-ZrP@PDA was obtained through the polydopamine (PDA) functionalization of a heterojunction composed of MXene and exfoliated α-zirconium phosphate (α-ZrP). MXene-ZrP@PDA (MZP) was incorporated into a waterborne epoxy (WEP) coating to prepare an MZP/WEP composite coating. The results show that the corrosion rate of MZP/WEP (1.70 × 10 –4 mpy) is one order of magnitude lower than that of blank WEP (1.28 × 10 –3 mpy). Moreover, the average coefficient of friction (COF) of the MZP/WEP composite coating decreased by 82.06% compared with that of the blank WEP coating. The results reveal that the addition of MXene-ZrP@PDA can significantly improve the anticorrosion/antiwear properties of WEP. Our results provide new ideas for the application of MXene/ZrP in the field of metal protection.

Hydrogen has gained renewed and growing interest around the world in the recent decades as a high-quality and renewable energy carrier, owing primarily to advances in fuel cells as well as growing environmental concerns. Steam reforming of fossil-based resources is currently the main route to H2 production. The downside of this process, however, is generation of massive amounts of greenhouse gases including CO2 as the byproduct which in turn must be captured to fully exploit the potential of H2. Membrane separation technology has seen significant growth, breakthroughs, and advancements over the last few decades and could be the key component in achieving inexpensive and highly pure H2. However, only a few numbers of membrane materials can withstand the harsh conditions of H2 production through steam reforming. Polybenzimidazole (PBI)-based membranes show excellent chemical, thermal, and mechanical stabilities as well as high intrinsic H2/CO2 selectivity. The objective of this review is to overview the recent development of structurally modified, cross-linked, mixed matrix, and…

Design and development of sustainable metal-free heterogeneous catalysts for organic transformation reactions is a challenging task. In this work, an amine-functionalized graphitic carbon nitride (NH 2 –GCN) was prepared and used as a heterogeneous solid base catalyst for Knoevenagel condensation reaction. The amine functionalization led to increased basicity due to the presence of additional −NH 2 groups. The catalytic potential of NH 2 –GCN was tested for Knoevenagel condensation, which showed good catalytic activity. The detailed optimizations of various reaction conditions, such as time, temperature, solvent, and catalyst amount, were performed. The catalyst showed the highest yield of 92% with excellent selectivity, wherein only a single product was formed. Furthermore, the wide applicability was investigated by studying the substrate scope, and a high turnover number was obtained with almost all the substrates. In addition, green metrics parameters were also determined, and the stability and recyclability of the catalyst were also studied. Overall, the work provides a green,…

The metal–oxide interaction in heterogeneous catalysis is of significance to fundamental studies and practical applications. This study examines the catalytic role of the Cu–ZrO 2 interaction and mechanistic pathways in the CO 2 hydrogenation to methanol. A series of Cu–ZrO 2 catalysts with different extents of interaction are achieved via tuning the component (Cu and ZrO 2 ) particle sizes over Cu/ZrO 2 and inverse ZrO 2 /Cu catalysts. The methanol synthesis from CO 2 hydrogenation does not exclusively depend on the metallic Cu sites or the surface oxides but rather on the extent of the interaction between the metal and oxide. A highly dispersed Cu–ZrO 2 interface with appropriate compositions can provide efficient active sites and promote the selective conversion to methanol. The mechanistic analysis demonstrates that surface formate and methoxy species are the major intermediates under the condition where methanol is the dominant product. The methanol formation principally follows the formate–methoxy intermediate pathway.

This paper presents an investigation of a storage option of green hydrogen (H 2 ) in the form of ammonia (NH 3 ) based on system simulations considering detailed technical properties. Experimental data from a 1 MW PEM electrolyzer is used to develop an electrolyzer model and downstream a kinetic reactor for NH 3 synthesis. Exemplarily, the electricity is supposed to be supplied by a hydropower plant in Norway. An economical evaluation of the plant is performed for optimized process parameters. The costs of H 2 and NH 3 are calculated based on electrolyzer investment costs published for deployment between 2020 and 2030 and several electricity cost scenarios. From the results, a broad economic optimum of the operating range of the electrolyzer in the entire plant is obtained. This work provides a basis for the future evaluation of complex plants with electrolyzers for the production of green ammonia as well as strategies for the reduction of costs of green NH 3 in the future.

The CO 2 sorption behavior of commercially available zeolites such as 3A, 4A, 5A, and 13X is considered at low temperatures for CO 2 removal from ambient air or direct air capture (DAC). Low silica zeolites are typically not effective CO 2 sorbents in the presence of water, as they preferentially competitively adsorb water from humid gas streams, resulting in high sorbent regeneration costs. We hypothesize that low silica zeolites may function as efficient physisorbents for DAC if deployed at cold temperatures where the absolute humidity of air is low. Two modes of deployment of low silica zeolites for DAC at cold temperatures are explored here. Based on the CO 2 isotherms of the zeolites at −20 °C with different H 2 O surface loadings, zeolite 5A was selected for evaluation in a competitive H 2 O and CO 2 coadsorption process as the first mode of deployment. Despite the low absolute humidity at −20 °C compared to that at 25 °C, H 2 O adsorption and accumulation result in a 39% decrease in the CO 2 adsorption capacity of 5A, rendering the process energetically expensive. In the…

The removal of tetracycline antibiotics from wastewater is currently an important environmental issue due to the serious water environment pollution caused by tetracycline. However, the complex composition of industrial wastewater, including a wide variety of metal ions, may affect the removal efficiency of tetracycline. In this paper, ALK-MXene with a hydroxyl-rich surface was prepared using an alkaline intercalation method to remove tetracycline from wastewater. The effects of the presence of metal ions, including Co(II), Cu(II), Cr(III), Cd(II), and Ni(II), on the adsorption of tetracycline by ALK-MXene were explored. Batch adsorption experiments showed that the presence of metal ions could improve the tetracycline adsorption capacity and that the removal capacity could be increased by 750% when coexisting with Ni(II). Three adsorption isotherm models, including the Langmuir model, Freundlich model, and monolayer model, were used to investigate the adsorption mechanism, and the results indicated that the adsorption follows the Freundlich model. Finally, systematic…

The monomer concentration is a key factor affecting the diffusion rate and reaction rate of the monomers and determines the physicochemical property of polyamide nanofiltration membranes. However, the mechanism of the monomer concentration effect on the polyamide nanofiltration membrane remains unclear. The properties of nascent membranes fabricated with different monomer concentrations with a fixed ratio presented completely new results in the absence of heat treatment. The results reveal that the polyamide layer thickness increases linearly with the monomer concentration when the concentration is high. The nanofiltration membranes prepared at a low concentration have a larger pore size and a lower cross-linking degree, which contributed to high water permeability. The optimal membrane presented a high pure water permeability of 36.1 L h –1 m –2 bar –1, with the Na 2 SO 4 rejection maintained at 98.4%. This work provides a novel insight into the relationship between the properties of the nanofiltration membrane and monomer concentration.

High Resolution Image Download MS PowerPoint Slide Carbonyl sulfide (molecular formula COS) is the most abundant organic sulfur compound present in the atmosphere, and its removal to satisfy the worldwide limitations on emissions of injurious substances is one of the challenging issues in the desulfurization technologies scenario. The hydrolysis of carbonyl sulfide can be addressed as a new frontier in the removal of sulfur compounds. The interest toward this process arose significantly in the past 20 years, mainly because of the new regulations on harmful gases emissions and because of the exploitation of fossil fuels with higher sulfur content. According to the current literature, COS hydrolysis can be performed as low-temperature and high-temperature processes, giving rise to the establishment of different mechanisms and phenomena. Through a detailed analysis of the recent advances in the field, low-temperature hydrolysis was identified as the most promising alternative for the industrial scenario. To overcome the kinetic limitations, the modification of alumina-based catalysts…

Deep eutectic solvents (DES) are a category of a new class of solvents that can overcome some of the main drawbacks of typical solvents and ionic liquids (ILs). DES have been widely investigated and applied by the research community in several applications since their invention. Over the past years, the use of DES has been directed to the production of new materials and items for new products and processes. This is the case for the implementation of DES in various fields of chemical engineering directed to separations. DES have been very recently initiated to be combined into membranes for membrane processes. In this regard, this Review timely elucidates the current progress in utilizing this new generation of solvents in membrane preparation. In this work, different techniques, methods, and strategies for incorporating DES into polymer membranes for different concepts of membranes according to the final application have been reviewed. Particular emphasis has been devoted to the most relevant development works and results. After the current literature was analyzed, the main…

High Resolution Image Download MS PowerPoint Slide The continuous depletion of minerals caused by land mining and the increase in their demand have pushed the development of novel sustainable technological processes for mineral recovery from unconventional sources. In this context, magnesium (Mg) has gained considerable attention for its peculiar properties and high relevance of its compounds, such as magnesium hydroxide, Mg(OH) 2 . In the present work, the influence of several operating conditions on the Mg(OH) 2 precipitation process was thoroughly investigated by adopting a novel multiple feed-plug flow reactor. The influence of (i) initial Mg 2+ concentrations in the feed stream; (ii) brine and alkaline flow rates; and (iii) the product recycling strategy (seeded crystallization) was considered. The results marked the possibility of improving sedimentation and filterability properties of Mg(OH) 2 suspensions by adopting the recycling strategy to overcome industrial issues associated with the production of Mg(OH) 2 suspensions using NaOH solutions.

Development of a new packaging material with superior high-temperature stability is becoming increasingly crucial in high-power and high-density electronics industry. In this study, we employed bis(3-ethyl-5-methyl-4-maleimidephenyl)methane (BMI), para -xylene phenolic resin (PF), and triphenylmethane novolac epoxy resin (EP) as matrix resins to develop high-temperature-stable BPE ternary resin molding compounds for power device packaging. BMI was first melt-blended with PF to obtain the premix with a reduced softening point for meeting the requirement of melt-kneading process. 2-Ethyl-4-methylimidazole with a dosage of 2 wt % of the ternary resins, could effectively promote the curing reaction, making the molding process of BPE molding compounds be compatible with that of the existing epoxy molding compounds (EMC). The introduction of BMI component could enhance the chain rigidity and heat resistance of cured resins. When the BMI content was more than 70 wt % of the ternary resins, the cured BPE molding compounds exhibited the glass transition temperature and initial decomposing…