A Review of the Design and Performance of Catalysts for Hydrothermal Gasification of Biomass to Produce Hydrogen-Rich Gas Fuel.

Supercritical water gasification has emerged as a promising technology to sustainably convert waste residues into clean gaseous fuels rich in combustible gases such as hydrogen and methane. The composition and yield of gases from hydrothermal gasification depend on process conditions such as temperature, pressure, reaction time, feedstock concentration, and reactor geometry. However, catalysts also play a vital role in enhancing the gasification reactions and selectively altering the composition of gas products. Catalysts can also enhance hydrothermal reforming and cracking of biomass to achieve desired gas yields at moderate temperatures, thereby reducing the energy input of the hydrothermal gasification process. However, due to the complex hydrodynamics of supercritical water, the literature is limited regarding the synthesis, application, and performance of catalysts used in hydrothermal gasification. Hence, this review provides a detailed discussion of different heterogeneous catalysts (e.g., metal oxides and transition metals), homogeneous catalysts (e.g., hydroxides and carbonates), and novel carbonaceous catalysts deployed in hydrothermal gasification. The article also summarizes the advantages, disadvantages, and performance of these catalysts in accelerating specific reactions during hydrothermal gasification of biomass, such as water-gas shift, methanation, hydrogenation, reforming, hydrolysis, cracking, bond cleavage, and depolymerization. Different reaction mechanisms involving a variety of catalysts during the hydrothermal gasification of biomass are outlined. The article also highlights recent advancements with recommendations for catalytic supercritical water gasification of biomass and its model compounds, and it evaluates process viability and feasibility for commercialization.

Perspectives on Thermochemical Recycling of End-of-Life Plastic Wastes to Alternative Fuels.

Due to its resistance to natural degradation and decomposition, plastic debris perseveres in the environment for centuries. As a lucrative material for packing industries and consumer products, plastics have become one of the major components of municipal solid waste today. The recycling of plastics is becoming difficult due to a lack of resource recovery facilities and a lack of efficient technologies to separate plastics from mixed solid waste streams. This has made oceans the hotspot for the dispersion and accumulation of plastic residues beyond landfills. This article reviews the sources, geographical occurrence, characteristics and recyclability of different types of plastic waste. This article presents a comprehensive summary of promising thermochemical technologies, such as pyrolysis, liquefaction and gasification, for the conversion of single-use plastic wastes to clean fuels. The operating principles, drivers and barriers for plastic-to-fuel technologies via pyrolysis (non-catalytic, catalytic, microwave and plasma), as well as liquefaction and gasification, are thoroughly discussed. Thermochemical co-processing of plastics with other organic waste biomass to produce high-quality fuel and energy products is also elaborated upon. Through this state-of-the-art review, it is suggested that, by investing in the research and development of thermochemical recycling technologies, one of the most pragmatic issues today, i.e., plastics waste management, can be sustainably addressed with a greater worldwide impact.

Cannabis: Chemistry, extraction and therapeutic applications.

Cannabis, a genus of perennial indigenous plants is well known for its recreational and medicinal activities. Cannabis and its derivatives have potential therapeutic activities to treat epilepsy, anxiety, depression, tumors, cancer, Alzheimer's disease, Parkinson's disease, to name a few. This article reviews some recent literature on the bioactive constituents of Cannabis, commonly known as phytocannabinoids, their interactions with the different cannabinoids and non-cannabinoid receptors as well as the significances of these interactions in treating various diseases and syndromes. The biochemistry of some notable cannabinoids such as tetrahydrocannabinol, cannabidiol, cannabinol, cannabigerol, cannabichromene and their carboxylic acid derivatives is explained in the context of therapeutic activities. The medicinal features of Cannabis-derived terpenes are elucidated for treating several neuro and non-neuro disorders. Different extraction techniques to recover cannabinoids are systematically discussed. Besides the medicinal activities, the traditional and recreational utilities of Cannabis and its derivatives are presented. A brief note on the legalization of Cannabis-derived products is provided. This review provides comprehensive knowledge about the medicinal properties, recreational usage, extraction techniques, legalization and some prospects of cannabinoids and terpenes extracted from Cannabis.

Hydrothermal flames for subaquatic, terrestrial and extraterrestrial applications.

Hydrothermal flames are formed in supercritical water in the presence of a fuel and an oxidant (usually air or oxygen). Integrating hydrothermal flames as the heat source for supercritical water oxidation helps to minimize the reaction time (to milliseconds), improve the reaction kinetics and reduce the chances of corrosion and reactor plugging. This review outlines state-of-the-art research on hydrothermal flames including the impacts of process parameters on flame ignition. The ignition and sustainability of hydrothermal flames are dependent on several factors such as the type of fuel and its concentration, type of oxidant (air and oxygen) as well as the temperatures and flow rate of the feed and oxidant. The article describes some novel applications of hydrothermal flames for clean energy production, geothermal energy recovery, deep well spallation, wastewater treatment, degradation of recalcitrant nitrogen-containing compounds and heavy oil upgrading. Finally, the challenges and future perspectives of hydrothermal flame applications are discussed. This review also highlights some technical considerations relating to hydrothermal flames such as the choice of organic solvent and its characteristics, preheating, ignition mechanism, flame stability and propagation, advanced reactor configurations, mixing with subcritical and supercritical components, recirculation zones, cooling mechanisms, corrosion and salt precipitation.

Innovations in applications and prospects of bioplastics and biopolymers: a review.

Non-biodegradable plastics are continually amassing landfills and oceans worldwide while creating severe environmental issues and hazards to animal and human health. Plastic pollution has resulted in the death of millions of seabirds and aquatic animals. The worldwide production of plastics in 2020 has increased by 36% since 2010. This has generated significant interest in bioplastics to supplement global plastic demands. Bioplastics have several advantages over conventional plastics in terms of biodegradability, low carbon footprint, energy efficiency, versatility, unique mechanical and thermal characteristics, and societal acceptance. Bioplastics have huge potential to replace petroleum-based plastics in a wide range of industries from automobiles to biomedical applications. Here we review bioplastic polymers such as polyhydroxyalkanoate, polylactic acid, poly-3-hydroxybutyrate, polyamide 11, and polyhydroxyurethanes; and cellulose-based, starch-based, protein-based and lipid-based biopolymers. We discuss economic benefits, market scenarios, chemistry and applications of bioplastic polymers.

Valorization of Wild-Type Cannabis indica by Supercritical CO2 Extraction and Insights into the Utilization of Raffinate Biomass

Supercritical CO2 extraction (SCCO2) extraction of cannabis oil from Indian cannabis (Cannabis indica) leaves was optimized through a central composite design using CO2 pressure (150-250 bar), temperature (30-50 °C) and time (1-2 h). From the regression model, the optimal CO2 pressure, extraction temperature and time were 250 bar, 43 °C and 1.7 h, respectively resulting in the experimental yield of 4.9 wt% of cannabis oil via SCCO2 extraction. The extract contained cannabidiol, tetrahydrocannabivarin, Δ9-tetrahydrocannabinol and Δ8-tetrahydrocannabinol as well as two terpenoids such as cis-caryophyllene and α-humulene. Besides SCCO2 extraction of cannabis oil, the raffinate biomass was utilized to extract polyphenols using water as the extraction medium. Cannabis oil and water extractive were investigated for their half-maximal inhibitory concentration (IC50) values, which were found to be 1.3 and 0.6 mg/mL, respectively. This is comparable to the commercially available antioxidant such as butylated hydroxytoluene with an IC50 value of 0.5 mg/mL. This work on SCCO2 extraction of cannabinoids and other valuable bioactive compounds provides an environmentally sustainable technique to valorize cannabis leaves.

Comparative study on fuel characteristics and pyrolysis kinetics of corn residue-based hydrochar produced via microwave hydrothermal carbonization.

Corn residues are an important source of bioenergy. Due to their highly diverse lignocellulosic structures, the hydrochar produced from microwave-assisted carbonization of different corn residues may have distinct fuel properties and pyrolysis kinetics. This study comprehensively investigated the effect of processing temperature on the basic fuel properties of hydrochar and examined the pyrolysis behavior of hydrochar as a precursor through kinetic analysis. The results indicate that the fuel quality of corn straw hydrochar prepared by microwave-assisted hydrothermal carbonization at 230 °C was significantly improved over that of its feedstock, with a higher heating value of approximately 20.7 MJ/kg. Hydrochar prepared by microwave-assisted hydrothermal carbonization of corn cob at 230 °C presents noticeable environmental advantages because it contains the lowest ash and nitrogen contents (0.5% and 0.5%, respectively) and lower sulfur content (0.05%). Moreover, regarding the kinetic modeling, the Doyle and Coats-Redfern models, which are both first-order and single-step kinetic models, were identified as satisfactory in interpreting the key pyrolysis kinetic parameters. Additionally, the microwave-assisted hydrothermal process increased the apparent activation energy of hydrochar due to the increase in crystallinity and the increase in the number of CC and CO bonds.

Hydrothermal pretreatment technologies for lignocellulosic biomass: A review of steam explosion and subcritical water hydrolysis.

The pretreatment of lignocellulosic biomass enhances the conversion efficiency to produce biofuels and value-added chemicals, which have the potential to replace fossil fuels. Compared to physicochemical and other pretreatment techniques, the hydrothermal methods are considered eco-friendly and cost-effective. This paper reviews the strengths, weaknesses, opportunities and threats of steam explosion and subcritical water hydrolysis as the two promising hydrothermal technologies for the pretreatment of lignocellulosic biomass. Although the principle of the steam explosion in depolymerizing the lignin and exposing the cellulose fibers for bioconversion to liquid fuels is well known, its underlying mechanism for solid biofuel production is less identified. Therefore, this review provides an insight into different operating conditions of steam explosion and subcritical water hydrolysis for a wide variety of feedstocks. The mechanisms of subcritical water hydrolysis including dehydration, decarboxylation and carbonization of waste biomass are comprehensively described. Finally, the role of microwave heating in the hydrothermal pretreatment of biomass is elucidated.

Slow pyrolysis of agro-food wastes and physicochemical characterization of biofuel products.

Effective management and utilization of food waste and agricultural crop residues are highly crucial to mitigate the challenges of greenhouse gas generation upon natural decomposition and waste accumulation. Conversion of biogenic wastes to biofuels and bioproducts can address the energy crisis and promote environmental remediation. This study was focused on exploring the characteristics of food waste and agricultural crop residues (e.g., canola hull and oar hull) to determine their candidacy for slow pyrolysis to produce biochar and bio-oil. Process parameters of slow pyrolysis such as temperature, reaction time and heating rate were optimized to obtain maximum biochar yields. Maximum biochar yield of 28.4 wt% was recorded at optimized temperature, heating rate and reaction time of 600 °C, 5 °C/min and 60 min, respectively. Furthermore, the physicochemical, spectroscopic and microscopic characterization of biochar, bio-oil and gases were performed. The carbon content and thermal stability of biochar were found to increase at higher temperatures. Moreover, bio-oil generated at higher temperatures showed the presence of phenolics and aromatic compounds.

Taguchi-based process optimization for activation of agro-food waste biochar and performance test for dye adsorption.

The optimization of process parameters for biochar activation is crucial for enhancing its surface area and adsorptive potentials. This work attempts to investigate the influence of activating agent (e.g., steam and KOH), temperature (700-900 °C) and activation time (60-120 min) using Taguchi L18 (21 × 32) experimental design for the activation of biochar derived from food waste and agricultural crop residues such as canola hull and oat hull. Among all the factors, activating agent and temperature influenced surface area considerably. KOH-assisted chemical activation of biochar at 800 °C for 90 min was found to be optimal with higher specific surface areas of 1760, 1718 and 1334 m2/g for food waste, canola hull and oat hull derived biochar, respectively. Finally, the comparative evaluation of the performances of biochar and activated carbon samples was achieved through the adsorption of common dyes such as methylene blue, methyl violet and rhodamine B. Activated carbon samples derived from food waste biochar and canola hull biochar exhibited a complete removal of methylene blue and methyl violet from model aqueous solution within 1-2 h of contact time at room temperature, whereas in case of rhodamine B only 91-94% removal was achieved.

Application of biomass derived products in mid-size automotive industries: A review.

The automotive industry is directly affected by the shortage of fossil fuels and the excessive pollution resulting from crude oil-based fuels has many adverse effects on the environment. The search for a greener and sustainable source of materials and fuels to power automobiles has ultimately led to the usage of biomass and biobased sources as the main precursor due to its graft availability and renewability. Biobased fuels developed have been shown to easily blend in with the existing automobile engines and to provide sustainable performance. Similarly, the usage of various biobased polymers, plastics, and composite materials as the structural materials for the construction of automobiles instead of crude oil sources have shown to be invaluable. The powering of automobiles with electricity is the future of the transportation industry to address the greenhouse gas emissions caused by fossil fuels. Hence, biobased lithium-ion batteries and supercapacitors have started to enter the mid-sized automotive industry. However, extensive commercialization of biobased products application in the automotive sector is underdeveloped. Hence it is customary to assess the various drawbacks of using biobased materials and identify the correct pathway for new research and development in this field. Therefore, this review covers various applications of biobased products in the automotive industries and mentions the active researches going on in this field to replace petroleum and crude oil-based sources with biobased sources.

Optimization studies for hydrothermal gasification of partially burnt wood from forest fires for hydrogen-rich syngas production using Taguchi experimental design.

Forest fires significantly affect the wildlife, vegetation, composition and structure of the forests. This study explores the potential of partially burnt wood recovered in the aftermath of a recent Canadian forest fire incident as a feedstock for generating hydrogen-rich syngas through hydrothermal gasification. Partially burnt wood was gasified in hydrothermal conditions to study the influence of process temperature (300-500 °C), residence time (15-45 min), feed concentration (10-20 wt%) and biomass particle size (0.13 mm and 0.8 mm) using the statistical Taguchi method. Maximum hydrogen yield and total gas yield of 5.26 mmol/g and 11.88 mmol/g, respectively were obtained under optimized process conditions at 500 °C in 45 min with 10 wt% feed concentration using biomass particle size of 0.13 mm. The results from the mean of hydrogen yield show that the contribution of each experimental factors was in the order of temperature > feed concentration > residence time > biomass particle size. Other gaseous products obtained at optimum conditions include CO2 (3.43 mmol/g), CH4 (3.13 mmol/g) and C2-C4 hydrocarbons (0.06 mmol/g).

Techno-economic evaluation and sensitivity analysis of a conceptual design for supercritical water gasification of soybean straw to produce hydrogen.

This paper proposes a conceptual design for the catalytic supercritical water gasification of soybean straw. The design consists of four process units for pretreatment, gasification, separation, purification and combustion. The economic feasibility of hydrogen production was evaluated based on a comprehensive cash flow analysis. The economic analysis suggested a minimum selling price of U.S. $1.94/kg for hydrogen. The cost of hydrogen produced is relatively lower compared to that of other biomass conversion processes. Besides, the net rate of return (NRR) estimated was 37.1%. A positive NRR value indicates that the project is profitable from an economic perspective. Sensitivity analysis indicates that the minimum selling price of hydrogen is affected by the feedstock price, utility cost, tax rate and labor cost. Moreover, feedstock price and labor cost show the greatest effect. Other factors such as land cost, working capital and utility cost showed the least effect on the minimum selling price.

A technical review of bioenergy and resource recovery from municipal solid waste.

Population growth, rapid urbanization, industrialization and economic development have led to the magnified municipal solid waste generation at an alarming rate on a global scale. Municipal solid waste seems to be an economically viable and attractive resource to produce green fuels through different waste-to-energy conversion routes. This paper reviews the different waste-to-energy technologies as well as thermochemical and biological conversion technologies for the valorization of municipal solid waste and diversion for recycling. The key waste-to-energy technologies discussed in this review include conventional thermal incineration and the modern hydrothermal incineration. The thermochemical treatments (e.g. pyrolysis, liquefaction and gasification) and biological treatments (e.g. anaerobic digestion and composting) are also elaborated for the transformation of solid wastes to biofuel products. The current status of municipal solid waste management for effective disposal and diversion along with the opportunities and challenges has been comprehensively reviewed. The merits and technical challenges of the waste-to-energy technologies are systematically discussed to promote the diversion of solid wastes from landfill disposal to biorefineries.

Artificial neural network modeling of cefixime photodegradation by synthesized CoBi2O4 nanoparticles.

CoBi2O4 (CBO) nanoparticles were synthesized by sol-gel method using polyvinylpyrrolidone (PVP) as a complexing reagent. For a single phase with the spinel structure, the formed gel was dried and calcined at four temperatures stages. Various methods were used to identify and characterize the obtained spinel, such as X-ray diffraction (XRD), scanning electron micrograph (SEM-EDX), transmission electron microscope (TEM), Fourier transform infrared (FT-IR), X-ray fluorescence (XRF), Raman, and UV-Vis spectroscopies. The photocatalytic activity of CBO was examined for the degradation of a pharmaceutical product cefixime (CFX). Furthermore, for the prediction of the CFX degradation rate, an artificial neural network model was used. The network was trained using the experimental data obtained at different pH with different CBO doses and initial CFX concentrations. To optimize the network, various algorithms and transfer functions for the hidden layer were tested. By calculating the mean square error (MSE), 13 neurons were found to be the optimal number of neurons and produced the highest coefficient of correlation R2 of 99.6%. The relative significance of the input variables was calculated, and the most impacting input was proved to be the initial CFX concentration. The effects of some scavenging agents were also studied. The results confirmed the dominant role of hydroxyl radical OH• in the degradation process. With the novel CoBi2O4/ZnO hetero-system, the photocatalytic performance has been enhanced, giving an 80% degradation yield of CFX (10 mg/L) at neutral pH in only 3 h.

Graphene Oxide-Induced Interfacial Transcrystallization of Single-Fiber Milkweed/Polycaprolactone/Polyvinylchloride Composites.

Understanding the interfacial crystallization is crucial for semi-crystalline polymer/natural fiber composites because it links to the final properties. This work reports, for the first time, the interfacial crystallization of a miscible blend between polycaprolactone (PCL) and polyvinylchloride (PVC) with milkweed fibers. We have first described the morphology of the fibers and the chemical composition of waxes covered on its surface. Our findings show that the transcrystallization (TC) layer of PCL/PVC could appear at the interface by simply coating with a layer of graphene oxide (GO) on the milkweed fiber. In our study, atomic force microscopy-infrared spectroscopy analysis shows that the crystallinity of the blends is higher at the vicinity of the interface compared to that in the bulk. The kinetic of the interfacial crystallization in terms of spherulite morphology and crystal growth rates at the nanoscale is examined. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy were used to analyze the prepared GO and evaluate its relationship with the interfacial crystallization behavior of the blends.

Recent Applications of Advanced Atomic Force Microscopy in Polymer Science: A Review.

Atomic force microscopy (AFM) has been extensively used for the nanoscale characterization of polymeric materials. The coupling of AFM with infrared spectroscope (AFM-IR) provides another advantage to the chemical analyses and thus helps to shed light upon the study of polymers. This paper reviews some recent progress in the application of AFM and AFM-IR in polymer science. We describe the principle of AFM-IR and the recent improvements to enhance its resolution. We also discuss the latest progress in the use of AFM-IR as a super-resolution correlated scanned-probe infrared spectroscopy for the chemical characterization of polymer materials dealing with polymer composites, polymer blends, multilayers, and biopolymers. To highlight the advantages of AFM-IR, we report several results in studying the crystallization of both miscible and immiscible blends as well as polymer aging. Finally, we demonstrate how this novel technique can be used to determine phase separation, spherulitic structure, and crystallization mechanisms at nanoscales, which has never been achieved before. The review also discusses future trends in the use of AFM-IR in polymer materials, especially in polymer thin film investigation.

Optimization, equilibrium, adsorption behavior and role of surface functional groups on graphene oxide-based nanocomposite towards diclofenac drug.

Aquatic contamination of diclofenac (DCF), an emergent non-steroidal anti-inflammatory drug (NSAIDs), can result in adverse effects to many ecosystems through biomagnification. Hence, introducing effective remediation techniques to sequester the pharmaceutical wastes is highly fundamental to prevent their accumulation in the environment. Generally, adsorption has been presented as a green and efficient approach. Herein, we report the characterization and application of the novel magnetic nanocomposite (GO@CoFe2O4) derived from cobalt-based ferrite (CoFe2O4) and graphene oxide (GO) for DCF adsorption. For the optimization procedure, the response surface methodology (RSM) was adopted to investigate the impacts of DCF concentration (1.6-18.4 mg/L), DCF dosage (0.08-0.92 g/L), and solution pH (2.6-9.4) to find the optimum conditions for DCF removal, at 10.5 mg/L, 0.74 g/L, and pH 4, respectively. For the adsorption experiments, the kinetic, isotherm, thermodynamic, and intraparticle diffusion models were systematically studied. Moreover, we have elucidated the role of functional groups on the surface of GO@CoFe2O4 in enhancing the adsorption of DCF drug. With good removal efficiency (up to 86.1%), high maximum adsorption capacity (32.4 mg/g), GO@CoFe2O4 can be a potential candidate to eliminate DCF drug from water.

Enhanced fuel characteristics and physical chemistry of microwave hydrochar for sustainable fuel pellet production via co-densification.

Microwave assisted hydrothermal treatment (MHTC) was compared with torrefaction in terms of carbonization efficiency and physicochemical characteristics of char products. The utilization of produced char was optimized for composite solid biofuel production. The results show that MHTC significantly improved the binding capability of the microwave hydrochar (MHC) particles during co-densification with unprocessed biomass and coal. One possible contributor to the improved binding is the pseudo lignin formed during the MHTC, which led to a better interlocking of the feedstock particles and promoted the solid bridge formation. Composite pellet prepared with 80 wt% of torrefaction char (TC-120), 10 wt% of microwave hydrochar (MHC-30), and 10 wt% of Coal-04 showed a higher heating value of 24.54 MJ/kg and energy density of 26.43 GJ/m3, which is significantly higher than that of the raw cotton stalk pellet (16.77 MJ/kg and 18.76 GJ/m3, respectively), showing great promise as a solid biofuel. The moisture resistance and oxidation reactivity are also significantly improved. The results demonstrate that MHCs provides dual functionalities in acting as binder and fuel promoter in the production of composite biofuel. This study can provide new insight into the unique functions of MHC during fuel application, which demonstrates the great potential of applying MHTC in energy recovery from lignocellulosic biomass.

Application of Fe-based metal-organic framework and its pyrolysis products for sulfonamide treatment.

The occurrence and fate of antibiotic compounds in water can adversely affect human and animal health; hence, the removal of such substrates from soil and water is indispensable. Herein, we described the synthesis method of mesoporous carbon (MPC) via the pyrolysis route from a coordination polymer Fe-based MIL-53 (or MIL-53, shortly). The MPC structure was analyzed by several physical techniques such as SEM, TEM, BET, FT-IR, VSM, and XRD. The response surface methodology (RSM) was applied to find out the effects of initial concentration, MPC dosage, and pH on the removal efficiency of trimethoprim (TMP) and sulfamethoxazole (SMX) antibiotics in water. Under the optimized conditions, the removal efficiencies of TMP and SMX were found to be 87% and 99%, respectively. Moreover, the adsorption kinetic and isotherm studies showed that chemisorption and the monolayer adsorption controlled the adsorption process. The leaching test and recyclability studies indicated that the MPC structure was stable and can be reused for at least four times without any considerable change in the removal efficiency. Plausible adsorption mechanisms were also addressed in this study. Because of high maximum adsorption capacity (85.5 mg/g and 131.6 mg/g for TMP and SMX, respectively) and efficient reusability, MPC is recommended to be a potential adsorbent for TMP and SMX from water media.