Screening of Metal Oxides and Hydroxides for Arsenic Removal from Water Using Molecular Dynamics Simulations.

Arsenic in groundwater is a harmful and hazardous substance that must be removed to protect human health and safety. Adsorption, particularly using metal oxides, is a cost-effective way to treat contaminated water. These metal oxides must be selected systematically to identify the best material and optimal operating conditions for the removal of arsenic from water. Experimental research has been the primary emphasis of prior work, which is time-consuming and costly. The previous simulation studies have been limited to specific adsorbents such as iron oxides. It is necessary to study other metal oxides to determine which ones are the most effective at removing arsenic from water. In this work, a molecular simulation computational framework using molecular dynamics and Monte Carlo simulations was developed to investigate the adsorption of arsenic using various potential metal oxides. The molecular structures have been optimized and proceeded with sorption calculations to observe the adsorption capabilities of metal oxides. In this study, 15 selected metal oxides were screened at a pressure of 100 kPa and a temperature of 298 K for As(V) in the form of HAsO4 at pH 7. Based on adsorption capacity calculations for selected metal oxides/hydroxides, aluminum hydroxide (Al(OH)3), ferric hydroxide (FeOOH), lanthanum hydroxide La(OH)3, and stannic oxide (SnO2) were the most effective adsorbents with adsorption capacities of 197, 73.6, 151, and 42.7 mg/g, respectively, suggesting that metal hydroxides are more effective in treating arsenic-contaminated water than metal oxides. The computational results were comparable with previously published literature with a percentage error of 1%. Additionally, SnO2, which is rather unconventional to be used in this application, demonstrates potential for arsenic removal and could be further explored. The effects of pH from 1 to 13, temperature from 281.15 to 331.15 K, and pressure from 100 to 350 kPa were studied. Results revealed that adsorption capacity decreased for the high-temperature applications while experiencing an increase in pressure-promoted adsorption. Furthermore, response surface methodology (RSM) has been employed to develop a regression model to describe the effect of operating variables on the adsorption capacity of screened adsorbents for arsenic removal. The RSM models utilizing CCD (central composite design) were developed for Al(OH)3, La(OH)3, and FeOOH, having R2 values 0.92, 0.67, and 0.95, respectively, suggesting that the models developed were correct.

Modeling of Nitrogen Removal from Natural Gas in Rotating Packed Bed Using Artificial Neural Networks.

Novel or unconventional technologies are critical to providing cost-competitive natural gas supplies to meet rising demands and provide more opportunities to develop low-quality gas fields with high contaminants, including high carbon dioxide (CO2) fields. High nitrogen concentrations that reduce the heating value of gaseous products are typically associated with high CO2 fields. Consequently, removing nitrogen is essential for meeting customers' requirements. The intensification approach with a rotating packed bed (RPB) demonstrated considerable potential to remove nitrogen from natural gas under cryogenic conditions. Moreover, the process significantly reduces the equipment size compared to the conventional distillation column, thus making it more economical. The prediction model developed in this study employed artificial neural networks (ANN) based on data from in-house experiments due to a lack of available data. The ANN model is preferred as it offers easy processing of large amounts of data, even for more complex processes, compared to developing the first principal mathematical model, which requires numerous assumptions and might be associated with lumped components in the kinetic model. Backpropagation algorithms for ANN Lavenberg-Marquardt (LM), scaled conjugate gradient (SCG), and Bayesian regularisation (BR) were also utilised. Resultantly, the LM produced the best model for predicting nitrogen removal from natural gas compared to other ANN models with a layer size of nine, with a 99.56% regression (R2) and 0.0128 mean standard error (MSE).

Rethinking of the future sustainable paradigm roadmap for plastic waste management: A multi-nation scale outlook compendium.

The myriad consumption of plastic regularly, environmental impact and health disquietude of humans are at high risk. Along the line, international cooperation on a global scale is epitomized to mitigate the environmental threats from plastic usage, not limited to implementing international cooperation strategies and policies. Here, this study aims to provide explicit insight into possible cooperation strategies between countries on the post-treatment and management of plastic. First, a thorough cradle-to-grave assessment in terms of economic, environmental, and energy requirements is conducted on the entire life cycle across different types of plastic polymers in 6 main countries, namely the United States of America, China, Germany, Japan, South Korea, and Malaysia. Subsequently, P-graph is introduced to identify the integrative plastic waste treatment scheme that minimizes the economic, environmental, and energy criteria (1000 sets of solutions are found). Furthermore, TOPSIS analysis is also being adapted to search for a propitious solution with optimal balance between the dominant configuration of economic, environmental, and energy nexus. The most sustainable configuration (i.e., integrated downcycle and reuse routes in a closed loop system except in South Korea, which proposed another alternative to treat the plastic waste using landfill given the cheaper cost) is reported with 4.08 × 108 USD/yr, 1.76× 108 kg CO2/yr, and 2.73 × 109 MJ/yr respectively. To attain a high precision result, Monte-Carlo simulation is introduced (10,000 attempts) to search for possible uncertainties, and lastly, a potential global plastic waste management scheme is proposed via the PESTLE approach.

Progress in thermochemical co-processing of biomass and sludge for sustainable energy, value-added products and circular economy.

To achieve the main goal of net zero carbon emission, the shift from conventional fossil-based energy/products to renewable and low carbon-based energy/products is necessary. Biomass has been perceived as a carbon-neutral source from which energy and value-added products can be derived, while sludge is a slurry waste that inherently contains high amount of minerals and organic matters. Hence, thermochemical co-processing of biomass wastes and sludge could create positive synergistic effects, resulting in enhanced performance of the process (higher conversion or yield) and improved qualities or characteristics of the products as compared to that of mono-processing. This review presents the current progress and development for various thermochemical techniques of biomass-sludge co-conversion to energy and high-value products, and the potential applications of these products from circular economy's point of view. Also, these technologies are discussed from economic and environmental standpoints, and the outlook towards technology maturation and successful commercialization is laid out.

A review on natural based deep eutectic solvents (NADESs): fundamentals and potential applications in removing heavy metals from soil.

Natural based deep eutectic solvent (NADES) is a promising green solvent to replace the conventional soil washing solvent due to the environmental benign properties such as low toxicity, high biodegradability, high polarity or hydrophilicity, and low cost of fabrication process. The application of NADES is intensively studied in the extraction of organic compounds or natural products from vegetations or organic matters. Conversely, the use of the solvent in removing heavy metals from soil is severely lacking. This review focuses on the potential application of NADES as a soil washing agent to remove heavy metal contaminants. Hydrophilicity is an important feature of a NADES to be used as a soil washing solvent. In this context, choline chloride is often used as hydrogen bond acceptor (HBA) whereby choline chloride based NADESs showed excellent performance in the extraction of various solutes in the past studies. The nature of NADES along with its chemistry, preparation and designing methods as well as potential applications were comprehensively reviewed. Subsequently, related studies on choline chloride-based NADES in heavy metal polluted soil remediation were also reviewed. Potential applications in removing other soil contaminants as well as the limitations of NADES were discussed based on the current advancements of soil washing and future research directions were also proposed.

Microwave processing of oil palm wastes for bioenergy production and circular economy: Recent advancements, challenges, and future prospects.

The valorization and conversion of biomass into various value-added products and bioenergy play an important role in the realization of sustainable circular bioeconomy and net zero carbon emission goals. To that end, microwave technology has been perceived as a promising solution to process and manage oil palm waste due to its unique and efficient heating mechanism. This review presents an in-depth analysis focusing on microwave-assisted torrefaction, gasification, pyrolysis and advanced pyrolysis of various oil palm wastes. In particular, the products from these thermochemical conversion processes are energy-dense biochar (that could be used as solid fuel, adsorbents for contaminants removal and bio-fertilizer), phenolic-rich bio-oil, and H2-rich syngas. However, several challenges, including (1) the lack of detailed study on life cycle assessment and techno-economic analysis, (2) limited insights on the specific foreknowledge of microwave interaction with the oil palm wastes for continuous operation, and (3) effects of tunable parameters and catalyst's behavior/influence on the products' selectivity and overall process's efficiency, remain to be addressed in the context of large-scale biomass valorization via microwave technology.

A molecular simulation study on amine-functionalized silica/polysulfone mixed matrix membrane for mixed gas separation.

Polysulfone (PSF) based mixed matrix membranes (MMMs) are one of the most broadly studied polymeric materials used for CO2/CH4 separation. The performance of existing PSF membranes encounters a bottleneck for widespread expansion in industrial applications due to the trade-off amongst permeability and selectivity. Membrane performance has been postulated to be enhanced via functionalization of filler at different weight percentages. Nonetheless, the preparation of functionalized MMMs without defects and its empirical study that exhibits improved CO2/CH4 separation performance is challenging at an experimental scale that needs prior knowledge of the compatibility between the filler and polymer. Molecular simulation approaches can be used to explore the effect of functionalization on MMM's gas transport properties at an atomic level without the challenges in the experimental study, however, they have received less scrutiny to date. In addition, most of the research has focused on pure gas studies while mixed gas transport properties that reflect real separation in functionalized silica/PSF MMMs are scarcely available. In this work, a molecular simulation computational framework has been developed to investigate the structural, physical properties and gas transport behavior of amine-functionalized silica/PSF-based MMMs. The effect of varying weight percentages (i.e., 15-30 wt.%) of amine-functionalized silica and gas concentrations (i.e., 30% CH4/CO2, 50% CH4/CO2, and 70% CH4/CO2) on physical and gas transport characteristics in amine-functionalized silica/PSF MMMs at 308.15 K and 1 atm has been investigated. Functionalization of silica nanoparticles was found to increase the diffusion and solubility coefficients, leading to an increase in the percentage enhancement of permeability and selectivity for amine-functionalized silica/PSF MMM by 566% and 56%, respectively, compared to silica/PSF-based MMMs at optimal weight percentage of 20 wt.%. The model's permeability differed by 7.1% under mixed gas conditions. The findings of this study could help to improve real CO2/CH4 separation in the future design and concept of functionalized MMMs using molecular simulation and empirical modeling strategies.

A state-of-the-art review on capture and separation of hazardous hydrogen sulfide (H2S): Recent advances, challenges and outlook.

Hydrogen sulfide (H2S) is a flammable, corrosive and lethal gas even at low concentrations (ppm levels). Hence, the capture and removal of H2S from various emitting sources (such as oil and gas processing facilities, natural emissions, sewage treatment plants, landfills and other industrial plants) is necessary to prevent and mitigate its adverse effects on human (causing respiratory failure and asphyxiation), environment (creating highly flammable and explosive environment), and facilities (resulting in corrosion of industrial equipment and pipelines). In this review, the state-of-the-art technologies for H2S capture and removal are reviewed and discussed. In particular, the recent technologies for H2S removal such as membrane, adsorption, absorption and membrane contactor are extensively reviewed. To date, adsorption using metal oxide-based sorbents is by far the most established technology in commercial scale for the fine removal of H2S, while solvent absorption is also industrially matured for bulk removal of CO2 and H2S simultaneously. In addition, the strengths, limitations, technological gaps and way forward for each technology are also outlined. Furthermore, the comparison of established carbon capture technologies in simultaneous and selective removal of H2S-CO2 is also comprehensively discussed and presented. It was found that the existing carbon capture technologies are not adequate for the selective removal of H2S from CO2 due to their similar characteristics, and thus extensive research is still needed in this area.

A systematic review of the molecular simulation of hybrid membranes for performance enhancements and contaminant removals.

Number of research on molecular simulation and design has emerged recently but there is currently a lack of review to present these studies in an organized manner to highlight the advances and feasibility. This paper aims to review the development, structural, physical properties and separation performance of hybrid membranes using molecular simulation approach. The hybrid membranes under review include ionic liquid membrane, mixed matrix membrane, and functionalized hybrid membrane for understanding of the transport mechanism of molecules through the different structures. The understanding of molecular interactions, and alteration of pore sizes and transport channels at atomistic level post incorporation of different components in hybrid membranes posing impact to the selective transport of desired molecules are also covered. Incorporation of molecular simulation of hybrid membrane in related fields such as carbon dioxide (CO2) removal, wastewater treatment, and desalination are also reviewed. Despite the limitations of current molecular simulation methodologies, i.e., not being able to simulate the membrane operation at the actual macroscale in processing plants, it is still able to demonstrate promising results in capturing molecule behaviours of penetrants and membranes at full atomic details with acceptable separation performance accuracy. From the review, it was found that the best performing ionic liquid membrane, mixed matrix membrane and functionalized hybrid membrane can enhance the performance of pristine membrane by 4 folds, 2.9 folds and 3.3 folds, respectively. The future prospects of molecular simulation in hybrid membranes are also presented. This review could provide understanding to the current advancement of molecular simulation approach in hybrid membranes separation. This could also provide a guideline to apply molecular simulation in the related sectors.

Production of biochar from rice straw and its application for wastewater remediation - An overview.

The valorization of biochar as a green and low-cost adsorbent provides a sustainable alternative to commercial wastewater treatment technologies that are usually chemical intensive and expensive. This review presents an in-depth analysis focusing on the rice straw-derived biochar (RSB) for removal of various types of contaminants in wastewater remediation. Pyrolysis is to date the most established technology to produce biochar. Subsequently, biochar is upgraded via physical, chemical or hybrid activation/modification techniques to enhance its adsorption capacity and robustness. Thus far, acid-modified RSB is able to remove metal ions and organic compounds, while magnetic biochar and electrochemical deposition have emerged as potential biochar modification techniques. Besides, temperature and pH are the two main parameters that affect the efficiency of contaminants removal by RSB. Lastly, the limitations of RSB in wastewater remediation are elucidated based on the current advancements of the field, and future research directions are proposed.

Immobilized enzyme/microorganism complexes for degradation of microplastics: A review of recent advances, feasibility and future prospects.

Environmental prevalence of microplastics has prompted the development of novel methods for their removal, one of which involves immobilization of microplastics-degrading enzymes. Various materials including nanomaterials have been studied for this purpose but there is currently a lack of review to present these studies in an organized manner to highlight the advances and feasibility. This article reviewed more than 100 peer-reviewed scholarly papers to elucidate the latest advances in the novel application of immobilized enzyme/microorganism complexes for microplastics degradation, its feasibility and future prospects. This review shows that metal nanoparticle-enzyme complexes improve biodegradation of microplastics in most studies through creating photogenerated radicals to facilitate polymer oxidation, accelerating growth of bacterial consortia for biodegradation, anchoring enzymes and improving their stability, and absorbing water for hydrolysis. In a study, the antimicrobial property of nanoparticles retarded the growth of microorganisms, hence biodegradation. Carbon particle-enzyme complexes enable enzymes to be immobilized on carbon-based support or matrix through covalent bonding, adsorption, entrapment, encapsulation, and a combination of the mechanisms, facilitated by formation of cross-links between enzymes. These complexes were shown to improve microplastics-degrading efficiency and recyclability of enzymes. Other emerging nanoparticles and/or enzymatic technologies are fusion of enzymes with hydrophobins, polymer binding module, peptide and novel nanoparticles. Nonetheless, the enzymes in the complexes present a limiting factor due to limited understanding of the degradation mechanisms. Besides, there is a lack of studies on the degradation of polypropylene and polyvinyl chloride. Genetic bioengineering and metagenomics could provide breakthrough in this area. This review highlights the optimism of using immobilized enzymes/microorganisms to increase the efficiency of microplastics degradation but optimization of enzymatic or microbial activities and synthesis of immobilized enzymes/microorganisms are crucial to overcome the barriers to their wide application.

Life-cycle assessment of hydrogen production via catalytic gasification of wheat straw in the presence of straw derived biochar catalyst.

The environmental footprints of H2productionviacatalytic gasification of wheat straw using straw-derived biochar catalysts were examined. The functional unit of 1 kg of H2was adopted in the system boundaries, which includes 5 processes namely biomass collection and pre-treatment units (P1), biochar catalyst preparation using fast pyrolysis unit (P2), two-stage pyrolysis-gasification unit (P3), products separation unit (P4), and H2distribution to downstream plants (P5). Based on the life-cycle assessment, the hot spots in this process were identified, the sequence was as follows: P4 > P2 > P1 > P3 > P5. The end-point impacts score for the process was found to be 93.4017 mPt. From benchmarking analysis, the proposed straw-derived biochar catalyst was capable of offering almost similar catalytic performance with other metal-based catalysts with a lower environmental impact.

A Molecular Simulation Study of Silica/Polysulfone Mixed Matrix Membrane for Mixed Gas Separation.

Polysulfone-based mixed matrix membranes (MMMs) incorporated with silica nanoparticles are a new generation material under ongoing research and development for gas separation. However, the attributes of a better-performing MMM cannot be precisely studied under experimental conditions. Thus, it requires an atomistic scale study to elucidate the separation performance of silica/polysulfone MMMs. As most of the research work and empirical models for gas transport properties have been limited to pure gas, a computational framework for molecular simulation is required to study the mixed gas transport properties in silica/polysulfone MMMs to reflect real membrane separation. In this work, Monte Carlo (MC) and molecular dynamics (MD) simulations were employed to study the solubility and diffusivity of CO2/CH4 with varying gas concentrations (i.e., 30% CO2/CH4, 50% CO2/CH4, and 70% CO2/CH4) and silica content (i.e., 15-30 wt.%). The accuracy of the simulated structures was validated with published literature, followed by the study of the gas transport properties at 308.15 K and 1 atm. Simulation results concluded an increase in the free volume with an increasing weight percentage of silica. It was also found that pure gas consistently exhibited higher gas transport properties when compared to mixed gas conditions. The results also showed a competitive gas transport performance for mixed gases, which is more apparent when CO2 increases. In this context, an increment in the permeation was observed for mixed gas with increasing gas concentrations (i.e., 70% CO2/CH4 > 50% CO2/CH4 > 30% CO2/CH4). The diffusivity, solubility, and permeability of the mixed gases were consistently increasing until 25 wt.%, followed by a decrease for 30 wt.% of silica. An empirical model based on a parallel resistance approach was developed by incorporating mathematical formulations for solubility and permeability. The model results were compared with simulation results to quantify the effect of mixed gas transport, which showed an 18% and 15% percentage error for the permeability and solubility, respectively, in comparison to the simulation data. This study provides a basis for future understanding of MMMs using molecular simulations and modeling techniques for mixed gas conditions that demonstrate real membrane separation.

Recent advances in green solvents for lignocellulosic biomass pretreatment: Potential of choline chloride (ChCl) based solvents.

Biomass wastes exhibit a great potential to be used as a source of non-depleting renewable energy and synthesis of value-added products. The key to the valorization of excess lignocellulosic biomass wastes in the world lies on the pretreatment process to recalcitrant barrier of the lignocellulosic material for the access to useful substrates. A wide range of pretreatment techniques are available and advances in this field is continuously happening, in search for cheap, effective, and environmentally friendly methods. This review starts with an introduction to conventional approaches and green solvents for pretreatment of lignocellulosic biomass. Subsequently, the mechanism of actions along with the advantages and disadvantages of pretreatment techniques were reviewed. The roles of choline chloride (ChCl) in green solvents and their potential applications were also comprehensively reviewed. The collection of ideas in this review serve as an insight for future works or interest on biomass-to-energy conversion using green solvents.

Biomethane generation from biogas upgrading by means of thin-film composite membrane comprising Linde T and fluorinated polyimide: optimization of fabrication parameters.

Generation of biogas from organic substances is an attractive evolution of energy generation from fossil-based energy supply to renewable resources. In order to exhibit viability in terms of technical execution while being economically feasible, successful purification strategies for biomethane formation must be applicable to industrial gas streams at realistic pressures and temperatures. Membrane-based upgrading technologies have great potential to promote biogas processes because they involve less energy and low maintenance. However, the development of membranes with good polymer-filler contact and minimum defects remains a great challenge. Hitherto, researchers have been making many attempts at developing an established route to fabricate thin-film composite membranes. In the present work, an innovative coupling between Linde T and fluorinated polyimide was employed for biogas upgrading. A facile technique for membrane fabrication was proposed via optimization of the fabrication parameters. The results indicated that composite membrane fabricated with 2 hours of total dispersion duration demonstrated a homogeneous distribution of Linde T particles in the fluorinated polyimide matrix and improved the separation characteristics by up to 172% in upgrading biomethane quality. Thus, the fabricated membrane is feasible to be employed for large-scale and lucrative production with enhanced performance in biogas purification via the feasible fabrication method employed in this work.

Effect of a Different Number of Amine-Functional Groups on the Gas Sorption and Permeation Behavior of a Hybrid Membrane Comprising of Impregnated Linde T and 4,4'- (Hexafluoroisopropylidene) Diphthalic Anhydride-Derived Polyimide.

The bottleneck of conventional polymeric membranes applied in industry has a tradeoff between permeability and selectivity that deters its widespread expansion. This can be circumvented through a hybrid membrane that utilizes the advantages of inorganic and polymer materials to improve the gas separation performance. The approach can be further enhanced through the incorporation of amine-impregnated fillers that has the potential to minimize defects while simultaneously enhancing gas affinity. An innovative combination between impregnated Linde T with different numbers of amine-functional groups (i.e., monoamine, diamine, and triamine) and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-derived polyimide has been elucidated to explore its potential in CO2/CH4 separation. Detailed physical properties (i.e., free volume and glass transition temperature) and gas transport behavior (i.e., solubility, permeability, and diffusivity) of the fabricated membranes have been examined to unveil the effect of different numbers of amine-functional groups in Linde T fillers. It was found that a hybrid membrane impregnated with Linde T using a diamine functional group demonstrated the highest improvement compared to a pristine polyimide with 3.75- and 1.75-fold enhancements in CO2/CH4 selectivities and CO2 permeability, respectively, which successfully lies on the 2008 Robeson's upper bound. The novel coupling of diamine-impregnated Linde T and 6FDA-derived polyimide is a promising candidate for application in large-scale CO2 removal processes.