Algae Pyrolysis in Molten NaOH-Na2CO3 for Hydrogen Production.

Biomass pyrolysis within the alkaline molten salt is attractive due to its ability to achieve high hydrogen yield under relatively mild conditions. However, poor contact between biomass, especially the biomass pellet, and hydroxide during the slow heating process, as well as low reaction temperatures, become key factors limiting the hydrogen production. To address these challenges, fast pyrolysis of the algae pellet in molten NaOH-Na2CO3 was conducted at 550, 650, and 750 °C. Algae were chosen as feedstock for their high photosynthetic efficiency and growth rate, and the concept of coupling molten salt with concentrated solar energy was proposed to address the issue of high energy consumption at high temperatures. At 750 °C, the pollutant gases containing Cl and S were completely removed, and the HCN removal rate reached 44.92%. During the continuous pyrolysis process, after a slight increase, the hydrogen yield remained stable at 71.48 mmol/g-algae and constituted 86.10% of the gas products, and a minimum theoretical hydrogen production efficiency of algae can reach 84.86%. Most importantly, the evolution of physicochemical properties of molten NaOH-Na2CO3 was revealed for the first time. Combined with the conversion characteristics of feedstock and gas products, this study provides practical guidance for large-scale application of molten salt including feedstock, operation parameters, and post-treatment process.

Sustainable management of plastic wastes in COVID-19 pandemic: The biochar solution.

To prevent the COVID-19 transmission, personal protective equipment (PPE) and packaging materials have been extensively used but often managed inappropriately, generating huge amount of plastic waste. In this review, we comprehensively discussed the plastic products utilized and the types and amounts of plastic waste generated since the outbreak of COVID-19, and reviewed the potential treatments for these plastic wastes. Upcycling of plastic waste into biochar was addressed from the perspectives of both environmental protection and practical applications, which can be verified as promising materials for environmental protections and energy storages. Moreover, novel upcycling of plastic waste into biochar is beneficial to mitigate the ubiquitous plastic pollution, avoiding harmful impacts on human and ecosystem through direct and indirect micro-/nano-plastic transmission routes, and achieving the sustainable plastic waste management for value-added products, simultaneously. This suggests that the plastic waste could be treated as a valuable resource in an advanced and green manner.

Characteristics and Evolution of Nitrogen in the Heavy Components of Algae Pyrolysis Bio-Oil.

Algae pyrolytic bio-oil contains a large quantity of N-containing components (NCCs), which can be processed as valuable chemicals, while the harmful gases can also be released during bio-oil upgrading. However, the characteristics of NCCs in the bio-oil, especially the composition of heavy NCCs (molecular weight ≥200 Da), have not been fully studied due to the limitation of advanced analytical methods. In this study, three kinds of algae rich in lipids, proteins, and carbohydrates were rapidly pyrolyzed (10-25 °C/s) at different temperatures (300-700 °C). The bio-oil was analyzed using a Fourier transform ion cyclotron resonance mass spectrometer equipped with electrospray ionization, and the characteristics and evolution of nitrogen in heavy components were first obtained. The results indicated that the molecular weight of most heavy NCCs was distributed in the 200-400 Da range. N1-3 compounds account for over 60% in lipid and protein-rich samples, while N0 and N4 components are prominent in carbohydrate-rich samples. As temperature increases, most NCCs become more aromatic and contain less O due to the strong Maillard and deoxygenation reactions. Moreover, the heavier NCCs were promoted to form lighter compounds with more nitrogen atoms through decomposition (mainly denitrogenation and deoxygenation). Finally, some strategies to deal with the NCCs for high-quality bio-oil production were proposed.

Where do we stand to oversee the coronaviruses in aqueous and aerosol environment? Characteristics of transmission and possible curb strategies.

By 17 October 2020, the severe acute respiratory syndrome coronavirus (SARS-CoV-2) has caused confirmed infection of more than 39,000,000 people in 217 countries and territories globally and still continues to grow. As environmental professionals, understanding how SARS-CoV-2 can be transmitted via water and air environment is a concern. We have to be ready for focusing our attention to the prompt diagnosis and potential infection control procedures of the virus in integrated water and air system. This paper reviews the state-of-the-art information from available sources of published papers, newsletters and large number of scientific websites aimed to provide a comprehensive profile on the transmission characteristics of the coronaviruses in water, sludge, and air environment, especially the water and wastewater treatment systems. The review also focused on proposing the possible curb strategies to monitor and eventually cut off the coronaviruses under the authors' knowledge and understanding.

Experimental studies of hydrothermal liquefaction of kitchen waste with H+, OH- and Fe3+ additives for bio-oil upgrading.

Kitchen waste (KW) has gradually become a prominent problem in municipal solid waste treatment. Hydrothermal liquefaction (HTL) is a promising method used to make fuel oil from food and KW. However, the upgrading of bio-oil is particularly important for the sake of industrial reuse. In this study, the KW from university restaurants was subjected to HTL experiments in order to study theoretical feasibility. With the change of conversion temperature and residence time, the optimal conversion working conditions in this study were determined according to the quality and yield of the bio-oil. Moreover, the bio-oil upgrading effects of different additives (hydrogen chloride, sodium hydroxide, and iron(III) chloride) on the HTL of KW were studied. Alkaline additives have an inhibitory effect on the bio-oil yield and positive effect on coke yield. Acidic additives and iron (Fe)-containing additives can promote bio-oil yield. As an important aspect of upgrading, the effect on the nitrogen content of bio-oil with additives was revealed. The alkaline and Fe-containing additives have little effect on reducing the viscosity of the bio-oil while with the appropriate ratio (2.5 mol•kg-1) of acidic additives to the raw material, the static and dynamic fluidity of the oil phase products are reduced to about 0.1 Pa•s.

Renewable and high-purity hydrogen from lignocellulosic biomass in a biorefinery approach.

Unprecedented efforts are being deployed to develop hydrogen production from bioresources in a circular economy approach, yet their implementation remains scarce. Today's Challenges are associated with the shortage in the value chain, lack of large-scale production infrastructure, high costs, and low efficiency of current solutions. Herein, we report a hydrogen production route from cellulose pulp, integrating biomass fractionation and gasification in a biorefinery approach. Softwood sawdust undergoes formic acid organosolv treatment to extract cellulose, followed by steam gasification. High-purity hydrogen-rich syngas at a concentration of 56.3 vol% and a yield of 40 gH2/kgcellulose was produced. Char gasification offers the advantage of producing free-tar syngas reducing cleaning costs and mitigating downstream issues. A comprehensive assessment of mass and energy balance along the hydrogen value chain revealed an efficiency of 26.5% for hydrogen production, with an energy requirement of 111.1 kWh/kgH2. Optimizing solvent recovery and valorization of other constituents as added-value products in a biorefinery approach would further improve the process and entice its industrial takeoff.

Fabrication of eco-friendly nanocellulose-chitosan-calcium Phosphate ternary nanocomposite for wastewater remediation.

Nanocomposites have emerged as promising materials for pollutant removal due to their unique properties. However, conventional synthesis methods often involve toxic solvents or expensive materials. In this study, we present a novel ternary nanocomposite synthesized via a simple, cost-effective vacuum filtration method. The composite consists of calcium phosphate (CaP), biowaste-derived nanocellulose (diameter <50 nm) (NC), and chitosan (CH). The nanocomposite exhibited exceptional pollutant removal capabilities due to the hybrid approach of combining adsorption and size exclusion that widens and accelerates pollutant removal. When tested with synthetic wastewater containing 10 ppm of Ni ions and 10 ppm of Congo red (CR) dye, it achieved impressive removal rates of 98.7% for Ni ions and 100% for CR dye. Moreover, the nanocomposite effectively removed heavy metals such as Cd, Ag, Al, Fe, Hg, Mo, Li, and Se at 100%, and Ba, Be, P, and Zn at 80%, 92%, 87%, and 97%, respectively, from real-world municipal wastewater. Importantly, this green nanocomposite membrane was synthesized without the use of harmful chemicals or complex modifications and operated at a high flux rate of 146 L/m2.h.MPa. Its outstanding performance highlights its potential for sustainable pollutant removal applications.

The mechanisms of calcium-catalyzed graphenization of cellulose and lignin biochars uncovered.

A recent study has shown that highly crystalline graphene-based materials can be obtained from poorly organized carbon precursors using calcium as a non-conventional catalyst. XRD and TEM analyses of calcium-impregnated cellulose and lignin biochars showed the formation of well-ordered graphenic structures (Lc > 7 nm, d002 < 0.345 nm) above 1200 °C, far below the standard graphenization temperatures (T > 2000 °C). Herein, we propose new insights on the mechanism controlling the formation of highly graphenic biochars using Ca as a catalyst. We postulate that the calcium-catalyzed graphenization occurs through the formation of a metastable calcium carbide by reaction between CaO particles and amorphous carbon between 1000 and 1200 °C. CaC2 decomposes into calcium vapor and a graphenic shell covering the CaC2 particles as confirmed by TEM analysis. The thickness and planarity of the graphenic shell increase with the CaC2 initial particle size (between 20 and 200 nm), and its growth is controlled by the diffusion of the calcium vapor through the graphene layer. A much effective graphenization was obtained for the lignin biochars compared to cellulose, with Lc > 10 nm and d002 < 0.340 nm, attributed to the insertion of sulfur in the graphenic shells, which favors their ruptures and the decomposition of CaC2 into graphene. We believe that these findings would enable the reduction of costs and environmental impact of graphene-based materials synthesis using cheap and abundant renewable feedstocks and catalysts as well.

Phosphorus recovery from municipal sludge-derived hydrochar: Insights into leaching mechanisms and hydroxyapatite synthesis.

Hydrothermal liquefaction has the potential to exploit resources from municipal sewage sludge. It converts most organics into a liquid biofuel (biocrude), concentrates P in the solid residue (hydrochar), and consequently enables its efficient recovery. This study thoroughly evaluated the effects of extraction conditions on P and metal release from hydrochar by nitric acid. Among assessed factors, acid normality (0.02-1 N), liquid-to-solid ratio (5-100 mL/g), and contact time (0-24 h) had positive effects while decreasing eluate pH (0.5-4) improved leaching efficiencies of P and metals. Notably, eluate pH played a dominant role in P leaching and pH < 1.5 was crucial for complete extraction. P and metal leaching from hydrochar have strong interactions and their leaching mechanism was identified as product layer diffusion using the shrinking core model. This suggests that the leaching efficiency is susceptible to agitation and particle size but not temperature. Using 10 mL/g of 0.6 N HNO3 for 2 h was considered the best extraction condition for efficient P leaching (nearly 100%) and minimization of cost and contaminants (heavy metals). Following extraction, adding Ca(OH)2 at a Ca:P molar ratio of 1.7-2 precipitated most P (99-100%) at pH 5-6, while a higher pH (13) synthesized hydroxyapatite. The recovered precipitates had high plant availability (61-100%) of P and satisfactory concentrations of heavy metals as fertilizers in Canada and the US. Overall, this study established reproducible procedures for P recovery from hydrochar and advanced one step closer to wastewater biorefinery.

Synthesis and Growth of Green Graphene from Biochar Revealed by Magnetic Properties of Iron Catalyst.

Understanding the mechanism of iron-catalyzed graphitization of biomass is an important step for the large-scale synthesis of green graphene. Although iron is known to be the most active transition metal for the catalytic graphitization of cellulose-derived biochar, the direct effect of the iron molecular structure on the formation of highly graphitic carbon remains elusive. Here, biochar was produced from pyrolysis of iron-impregnated cellulose at three different temperatures (1000, 1400, and 1800 °C). X-ray diffraction, X-ray photoelectron spectroscopy, and magnetic measurements were used to probe changes in biochar nanostructure catalyzed by the inclusion of iron. An increase of pyrolysis temperature led to an increase in the iron particle size and the degree of iron reduction, as well as the formation of larger graphitic carbon crystallite sizes, and these two attributes of iron were seen to positively affect the biochar graphitization usually challenging under 2000 °C.

Calcium as an innovative and effective catalyst for the synthesis of graphene-like materials from cellulose.

Pyrolysis of lignocellulosic biomass (hard carbon) produces poorly graphitic biochar. In this study, nano-structured biochars were produced from microcrystalline cellulose using calcium as a non-conventional catalyst. Calcium is abundant, environmental-friendly and widely accessible. Graphitization of calcium-impregnated cellulose was carried out at 1800 °C, a temperature below 2000 °C where the graphitization usually occurs. XRD, Raman spectroscopy, high-resolution TEM together with the in-house numerical tool developed enable the quantification of the graphene fringes in the biochars. The non-impregnated cellulose biochar was composed of short and poorly stacked graphene fringes. The impregnation with 2 wt.% of calcium led to the conversion of the initial structure into a well-organized and less defective graphene-like one. The graphene-like structures obtained were composed of tens of stacked graphene fringes with a crystallite size up to 20 nm and an average interlayer spacing equal to 0.345 nm, close to the reference value of standard hexagonal graphite (0.3354 nm). The increase of the calcium concentration did not significantly improve the crystallite sizes of the graphene-like materials but rather drastically improved their rate. Our results propose a mechanism and provide new insights on the synthesis of graphene-like materials from bio-feedstocks using calcium where the literature is focused on transition metals such as iron and nickel among others. The decrease of the graphitization temperature below 2000 °C should lower the production cost as well as the environmental impact of the thermal graphene-like materials synthesis using biomass. This finding should stimulate further research in the field and broaden the application perspectives.

Hydrogen-Rich and Clean Fuel Gas Production from Co-pyrolysis of Biomass and Plastic Blends with CaO Additive.

The treatment and disposal of waste biomass and plastics are of great importance to achieve both waste management and resource recycling. In this work, pyrolysis of biomass and plastic blends were investigated to identify the influence of temperature and in situ CaO addition on the production of hydrogen-rich, HCl-free, and low tar content fuel gases. The results show that the increase in temperature and the use of CaO significantly improved both the quantity and quality of the fuel gas and mitigated the formation of tar compounds and HCl. Moreover, H2 yield was significantly improved from 0.30 to 3.68 mmol/g with the increase in temperature from 550 to 850 °C. Also, the use of in situ CaO significantly increased the H2 yield by 28-88%. The H2/CO ratio was also enhanced from 0.35 to 1.50 with the temperature increase and CaO addition. Tar removal efficiency reached approximately 70.09% with the use of CaO at 850 °C. The produced HCl gas could be effectively absorbed by CaO through dechlorination reactions to form CaClOH at a highest mitigation efficiency of 92.37%. The results could be used to develop clean and efficient treatment technologies of waste biomass and plastics.

Hydrochar derived from municipal sludge through hydrothermal processing: A critical review on its formation, characterization, and valorization.

Additional options for the sustainable treatment of municipal sludge are required due to the significant amounts of sludge, high levels of nutrients (e.g., C, N, and P), and trace constituents it contains. Hydrothermal processing of municipal sludge has recently been recognized as a promising technology to efficiently reduce waste volume, recover bioenergy, destroy organic contaminants, and eliminate pathogens. However, a considerable amount of solid residue, called hydrochar, could remain after hydrothermal treatment. This hydrochar can contain abundant amounts of energy (with a higher heating value up to 24 MJ/kg, dry basis), nutrients, and trace elements, as well as surface functional groups. The valorization of sludge-derived hydrochar can facilitate the development and application of hydrothermal technologies. This review summarizes the formation pathways from municipal sludge to hydrochar, specifically, the impact of hydrothermal conditions on reaction mechanisms and product distribution. Moreover, this study comprehensively encapsulates the described characteristics of hydrochar produced under a wide range of conditions: Yield, energy density, physicochemical properties, elemental distribution, contaminants of concern, surface functionality, and morphology. More importantly, this review compares and evaluates the current state of applications of hydrochar: Energy production, agricultural application, adsorption, heterogeneous catalysis, and nutrient recovery. Ultimately, along with the identified challenges and prospects of valorization approaches for sludge-derived hydrochar, conceptual designs of sustainable municipal sludge management are proposed.

Integrating alum sludge with waste-activated sludge in co-conditioning and dewatering: a case study of a city in south France.

The unique geographical location of waterworks and wastewater treatment plant (WWTP) in Graulhet (France) profited the environmental resource integration and "Circular Economy." Alum sludge from a local waterworks was introduced to co-conditioning and dewatering with waste-activated sludge from a nearby WWTP to examine the role of the alum sludge in improving the dewaterability of the mixed sludge. Experiments demonstrated that the optimal mixing ratio was 1:1 (waste-activated sludge/alum sludge, v/v). Alum sludge has been shown to beneficially enhance mixed sludge dewaterability, by decreasing both the specific resistance to filtration (SRF) and the capillary suction time (CST). Moreover, the optimal polymer (Sueprfloc-492HMW) dose for the mixed sludge (mix ratio 1:1) was 200 mg/L, highlighting a huge savings (14 times) in polymer addition without alum sludge involvement. In addition, cost-effective analysis of its potential full-scale application has demonstrated that the initial investment could be returned in 11 years. The co-conditioning and dewatering strategy can be viewed as a "win-win" strategy for the Graulhet, France, water and wastewater industry. Graphical abstract.

Alum sludge as an efficient sorbent for hydrogen sulfide removal: Experimental, mechanisms and modeling studies.

This paper firstly reported a systematic study of using alum sludge (waterworks residue) for H2S adsorption. Various trials were performed at ambient temperature in a fixed bed column to study the effects of H2S flow rate, sorbent bed depth on the alum sludge adsorption efficiency of H2S. The Breakthrough Curves were simulated by the Thomas model, Bed Depth Service Time model and Yoon-Nelson models. The mechanisms of H2S adsorption onto alum sludge was examined by different physiochemical characterizations of exhausted and raw alum sludge. Moreover, the mass transfer coefficients were determined from mathematical descriptions of breakthrough curves. The alum sludge adsorption capacity was determined to be 374.2 mg of H2S/g, slightly decreasing with the increasing flow rate and increasing with the increasing bed depth. All the three models successfully predict breakthrough curves which could be used for scaling-up purposes. The microporous structure, alkaline pH and the inherent metal species of the alum sludge promoted the formation of metal sulphate species. This study demonstrated that alum sludge could be used as cost-effective, largely available, and efficient sorbent for H2S removal.

New insights on mercury abatement and modeling in a full-scale municipal solid waste incineration flue gas treatment unit.

Modeling approaches are generally used to describe mercury transformations in a single step of flue gas treatment processes. However, less attention has been given to the interactions between the different process stages. Accordingly, the mercury removal performance of a full-scale solid waste incineration plant, equipped with a dry flue gas treatment line was investigated using two complementary modeling strategies: a thermochemical equilibrium approach to study the mercury transformation mechanisms and speciation in the flue gas, and a kinetic approach to describe the mercury adsorption process. The modeling observations were then compared to real-operation full-scale data. Considering the typical flue gas composition of waste incineration facilities (high concentrations of HCl compared to Hg), it was found that a process temperature decrease results in better mercury removal efficiencies, associated with a higher oxidation extent of Hg in HgCl2, and the enhancement of the sorbent capacity. Improvements can also be attained by increasing the sorbent injection rate to the process, or the solid/gas separation cycles. An empirical correlation to predict the mercury removal efficiency from the main operating parameters of dry flue gas treatment units was proposed, representing a useful tool for waste incineration facilities. The presented modeling approach proved to be suitable to evaluate the behavior of full-scale gas treatment units, and properly select the most adequate adjustments in operating parameters, in order to respect the increasingly constraining mercury emissions regulations.

Gas Barrier, Rheological and Mechanical Properties of Immiscible Natural Rubber/Acrylonitrile Butadiene Rubber/Organoclay (NR/NBR/Organoclay) Blend Nanocomposites.

In this paper, gas permeability studies were performed on materials based on natural rubber/acrylonitrile butadiene rubber blends and nanoclay incorporated blend systems. The properties of natural rubber (NR)/nitrile rubber (NBR)/nanoclay nanocomposites, with a particular focus on gas permeability, are presented. The measurements of the barrier properties were assessed using two different gases-O2 and CO2-by taking in account the blend composition, the filler loading and the nature of the gas molecules. The obtained data showed that the permeability of gas transport was strongly affected by: (i) the blend composition-it was observed that the increase in acrylonitrile butadiene rubber component considerably decreased the permeability; (ii) the nature of the gas-the permeation of CO2 was higher than O2; (iii) the nanoclay loading-it was found that the permeability decreased with the incorporation of nanoclay. The localization of nanoclay in the blend system also played a major role in determining the gas permeability. The permeability of the systems was correlated with blend morphology and dispersion of the nanoclay platelets in the polymer blend.

Compressive deformation and failure of trabecular structures in a turtle shell.

Turtle shells comprising of cortical and trabecular bones exhibit intriguing mechanical properties. In this work, compression tests were performed using specimens made from the carapace of Kinixys erosa turtle. A combination of imaging techniques and mechanical testing were employed to examine the responses of hierarchical microstructures of turtle shell under compression. Finite element models produced from microCT-scanned microstructures and analytical foam structure models were then used to elucidate local responses of trabecular bones deformed under compression. The results reveal the contributions from micro-strut bending and stress concentrations to the fractural mechanisms of trabecular bone structures. The porous structures of turtle shells could be an excellent prototype for the bioinspired design of deformation-resistant structures. STATEMENT OF SIGNIFICANCE: In this study, a combination of analytical, computational models and experiments is used to study the underlying mechanisms that contribute to the compressive deformation of a Kinixys erosa turtle shell between the nano-, micro- and macro-scales. The proposed work shows that the turtle shell structures can be analyzed as sandwich structures that have the capacity to concentrate deformation and stresses within the trabecular bones, which enables significant energy absorption during compressive deformation. Then, the trends in the deformation characteristics and the strengths of the trabecular bone segments are well predicted by the four-strut model, which captures the effects of variations in strut length, thickness and orientation that are related to microstructural uncertainties of the turtle shells. The above results also suggest that the model may be used to guide the bioinspired design of sandwich porous structures that mimic the properties of the cortical and trabecular bone segments of turtle shells under a range of loading conditions.

Robust Superhydrophobic Cellulose Nanofiber Aerogel for Multifunctional Environmental Applications.

The fabrication of superadsorbent for dye adsorption is a hot research area at present. However, the development of low-cost and highly efficient superadsorbents against toxic textile dyes is still a big challenge. Here, we fabricated hydrophobic cellulose nanofiber aerogels from cellulose nanofibers through an eco-friendly silanization reaction in liquid phase, which is an extremely efficient, rapid, cheap, and environmentally friendly procedure. Moreover, the demonstrated eco-friendly silanization technique is easy to commercialize at the industrial level. Most of the works that have reported on the hydrophobic cellulose nanofiber aerogels explored their use for the elimination of oil from water. The key novelty of the present work is that the demonstrated hydrophobic cellulose nanofibers aerogels could serve as superadsorbents against toxic textile dyes such as crystal violet dye from water and insulating materials for building applications. Here, we make use of the possible hydrophobic interactions between silane-modified cellulose nanofiber aerogel and crystal violet dye for the removal of the crystal violet dye from water. With a 10 mg/L of crystal violet (CV) aqueous solution, the silane-modified cellulose nanofiber aerogel showed a high adsorption capacity value of 150 mg/g of the aerogel. The reason for this adsorption value was due to the short-range hydrophobic interaction between the silane-modified cellulose nanofiber aerogel and the hydrophobic domains in crystal violet dye molecules. Additionally, the fabricated silane-modified cellulose nanofiber hydrophobic aerogels exhibited a lower thermal conductivity value of 0.037 W·m-1 K-1, which was comparable to and lower than the commercial insulators such as mineral wools (0.040 W·m-1 K-1) and polystyrene foams (0.035 W·m-1 K-1). We firmly believe that the demonstrated silane-modified cellulose nanofiber aerogel could yield an eco-friendly adsorbent that is agreeable to adsorbing toxic crystal violet dyes from water as well as active building thermal insulators.