Preparation and application of metal-modified biochar in the purification of micro-polystyrene polluted aqueous environment.

Microplastics (MPs) have already spread across the globe and have been found in drinking water and human tissues. This may pose severe threats to human health and water environment. Therefore, this study accurately evaluated the removal effect of metal-modified biochar on polystyrene microplastics (PS-MPs) (1.0 µm) in the water environment using a high-throughput fluorescence quantification method. The results indicated that Fe-modified biochar (FeBC) and Fe/Zn-modified biochar (Fe/ZnBC) had good removal efficiencies for PS-MPs under the dosage of 3 g/L, which were 96.24% and 84.77%, respectively. Although pore effects were observed (such as "stuck", "trapped"), the electrostatic interaction was considered the main mechanism for the adsorption of PS-MPs on metal-modified biochar, whereas the formation of metal-O-PS-MPs may also contribute to the adsorption process. The removal efficiency of PS-MPs by FeBC was significantly reduced under alkaline conditions (pH = 9 and 11) or in the presence of weak acid ions (PO43-, CO32-, HCO3-). A removal efficiency of 72.39% and 78.33% of PS-MPs was achieved from tap water (TW) and lake water (LW) using FeBC when the initial concentration was 20 mg/L. However, FeBC had no removal effect on PS-MPs in biogas slurry (BS) and brewing wastewater (BW) due to the direct competitive adsorption of high concentrations of chemical oxygen demand (COD). The findings of this study highlighted that metal-modified biochar had a potential application in purifying tap water or lake water which contaminated by MPs.

The Formation of Chitosan-Coated Rhamnolipid Liposomes Containing Curcumin: Stability and In Vitro Digestion.

There is growing interest in developing biomaterial-coated liposome delivery systems to improve the stability and bioavailability of curcumin, which is a hydrophobic nutraceutical claimed to have several health benefits. The curcumin-loaded rhamnolipid liposomes (Cur-RL-Lips) were fabricated from rhamnolipid and phospholipids, and then chitosan (CS) covered the surface of Cur-RL-Lips by electrostatic interaction to form CS-coated Cur-RL-Lips. The influence of CS concentration on the physical stability and digestion of the liposomes was investigated. The CS-coated Cur-RL-Lips with RL:CS = 1:1 have a relatively small size (412.9 nm) and positive charge (19.7 mV). The CS-coated Cur-RL-Lips remained stable from pH 2 to 5 at room temperature and can effectively slow the degradation of curcumin at 80 °C; however, they were highly unstable to salt addition. In addition, compared with Cur-RL-Lips, the bioavailability of curcumin in CS-coated Cur-RL-Lips was relatively high due to its high transformation in gastrointestinal tract. These results may facilitate the design of a more efficacious liposomal delivery system that enhances the stability and bioavailability of curcumin in nutraceutical-loaded functional foods and beverages.

Promoting Aromatic Hydrocarbon Formation via Catalytic Pyrolysis of Polycarbonate Wastes over Fe- and Ce-Loaded Aluminum Oxide Catalysts.

Converting polycarbonate (PC) plastic waste into value-added chemicals and/or fuel additives by catalytic pyrolysis is a promising approach to dispose of solid wastes. In this study, a series of Fe-Ce@Al2O3 metal oxides were prepared by coprecipitation, impregnation, and a direct mixing method. The synthesized catalysts were then employed to investigate the catalytic conversion of PC wastes to produce aromatic hydrocarbons. Experimental results indicated that Fe-Ce@Al2O3 prepared by coprecipitation possessed superior catalytic activity because of its high content of weak acid sites, large pore volume, high surface area, and well dispersion of Fe and Ce active species, leading to an ∼3-fold increase in targeted monocyclic aromatic hydrocarbons compared to that achieved noncatalytically. Moreover, an increase in the catalyst to feedstock (C/F) mass ratio was beneficial to the production of aromatic hydrocarbons at the expense of phenolic products, and elevating the C/F ratio from 1:1 to 3:1 considerably increased the benzene formation as the enhancement factor was increased from 2.3 to 8.8.

Walnut shell oil-bath torrefaction coupled with fast pyrolysis: Effect of torrefaction heating modes.

Lignocellulosic biomass, renewable with short growth cycle and diverse sources, can be substituted fossil fuel. However, low effective hydrogen-to-carbon ratio (H/Ceff) limits its applications. Torrefaction and co-pyrolysis with high H/Ceff feedstocks are promising technology. This paper investigated the effect of heating modes on oil-bath torrefaction of walnut shells, followed by fast co-pyrolysis. Six heating modes during oil-bath torrefaction were evaluated. Com1 (Microwave 67 %, Lightwave 33 %) yielded the lowest residual yield 84 wt%, while the highest gas production 495.47 mL/g which mainly composed of CO and CO2. Torrefied feedstock under Com1 had the highest H/Ceff. Decarboxylation and decarbonylation reactions dominated among oil-bath torrefaction. Com1 produced the most hydrocarbons and least oxygen-containing compounds. As microwave ratio decreased, the content of olefins, acids and phenols decreased, monocyclic aromatic hydrocarbons and alcohols was showed opposite tend. This study offers new ideas for microwave and lightwave torrefaction and promoting hydrocarbon production from lignocellulosic biomass.

A solid acid derived from fishbone catalyzes the hydrolysis of cellulose into nanocellulose.

The necessity to look into waste biomass resource regeneration has increased due to growing environmental and energy-related problems. This study successfully developed an innovative fishbone-derived carbon-based solid acid catalyst using the carbonation-sulfonation method, which was subsequently applied to catalyze the hydrolysis of cellulose to produce nanocellulose. The data analysis reveals that the sulfonation treatment affects the microstructure of the catalyst, resulting in a decline in its specific surface area (134.48 m2/g decreased to 9.66 m2/g). However, this treatment doesn't hinder the introduction of acidic functional groups. In particular, the solid acid catalyst derived from fishbone exhibited a total acid content of 3.76 mmol/g, with a concentration of -SO3H groups at 0.48 mmol/g. Furthermore, the solid acids originating from fishbones manifested remarkable thermal stability, exhibiting a mass loss of <15 % at temperatures up to 600 °C. Moreover, the catalyst displayed exceptional catalytic performance during the cellulose hydrolysis reaction, achieving an optimum nanocellulose yield of 45.7 % at an optimized reaction condition. An additional noteworthy feature is the solid acid catalyst's impressive recyclability, maintaining a nanocellulose yield of 44.87 % even after undergoing five consecutive usage cycles. This research outcome underscores an innovative approach to for the sustainable utilization of waste biomass resources.

Harvesting Chlorella vulgaris by electro-flotation with stainless steel cathode and non-sacrificial anode.

As a promising method for efficiently harvesting microalgae, electro-flotation's performance is related to various factors including electrode design and process operating parameters. In this paper, bubble generation behavior on stainless-steel cathodes, with wire diameters of 0.8 mm, 0.2 mm and 0.05 mm, was studied. The results show that the bubble size increased with the increasing diameter of the electrode wire. Over 90 % harvesting efficiency was achieved using non-sacrificial anode. Extracellular polymeric substance is the main reason keeping bubbles from bursting.

Microwave catalytic co-pyrolysis of waste cooking oil and low-density polyethylene to produce monocyclic aromatic hydrocarbons: Effect of different catalysts and pyrolysis parameters.

It is promising to convert waste oil and plastics to renewable fuels and chemicals by microwave catalytic co-pyrolysis, enabling pollution reduction and resource recovery. The purpose of this study was to evaluate the effect of catalysts on the product selectivity of microwave-assisted co-pyrolysis of waste cooking oil and low-density polyethylene and optimize the pyrolysis process, including pyrolysis temperature, catalytic temperature, waste cooking oil to low-density polyethylene ratio, and catalyst to feedstocks ratio. The results indicated that catalysts had a great influence on the product distribution, and the yield of BTX (benzene, toluene, and xylenes), which increased in the following order: SAPO-34 < Hß < HY < HZSM-5. HZSM-5 was more active for the formation of light aromatic hydrocarbons as compared to others, where the concentrations of toluene, benzene and xylenes reached 252.59 mg/mL, 114.7 mg/mL and 132.91 mg/mL, respectively. The optimum pyrolysis temperature, catalytic temperature, waste cooking oil to low-density polyethylene ratio and catalyst to feedstocks ratio could be 550 °C, 450 °C, 1:1 and 1:2, respectively, to maximize the formation of BTX and inhibit the formation of polycyclic aromatic hydrocarbons.

Evolution of membrane fouling and cleaning strategy development in municipal wastewater reclamation by nanofiltration.

Membrane fouling is a serious concern in municipal wastewater treatment using nanofiltration (NF). The variation of NF membrane fouling at different operational durations were monitored and evaluated to understand the evolution of fouling mechanism in the present study. Six representative cleaning methods were picked for tests to deconstruct the structure and composition of the fouling layers on membrane surface. Characteristics of membrane surface morphology and foulants were analysed using advanced methods to investigate the evolution of membrane fouling. Both the composition and concentration of foulants on membrane surface showed significant variations with time during the whole operational duration, indicating the necessity of clear and precise understanding for the evolution of membrane fouling to expound its mechanism in depth. The fouling layers were mainly composed of hydrophobic organics while most inorganic salts were deposited on the surface or embedded into the upper layer of the cake in a short duration. However, after a long duration, the cake layer became thinner with much higher proportion of hydrophilic organics. Meanwhile, more inorganic foulants penetrated deep into the cake layer or even directly absorbed on the membrane surface, which resulted in more complicated fouling scenarios. Moreover, more efficient and effective targeted cleaning strategies could be further established based on the fouling mechanism identified.

A review on selective production of value-added chemicals via catalytic pyrolysis of lignocellulosic biomass.

Increasing fossil fuel consumption and global warming has been driving the worldwide revolution towards renewable energy. Biomass is abundant and low-cost resource whereas it requires environmentally friendly and cost-effective conversion technique. Pyrolysis of biomass into valuable bio-oil has attracted much attention in the past decades due to its feasibility and huge commercial outlook. However, the complex chemical compositions and high water content in bio-oil greatly hinder the large-scale application and commercialization. Therefore, catalytic pyrolysis of biomass for selective production of specific chemicals will stand out as a unique pathway. This review aims to improve the understanding for the process by illustrating the chemistry of non-catalytic and catalytic pyrolysis of biomass at the temperatures ranging from 400 to 650 °C. The focus is to introduce recent progress about producing value-added hydrocarbons, phenols, anhydrosugars, and nitrogen-containing compounds from catalytic pyrolysis of biomass over zeolites, metal oxides, etc. via different reaction pathways including cracking, Diels-Alder/aromatization, ketonization/aldol condensation, and ammoniation. The potential challenges and future directions for this technique are discussed in deep.

Microwave-assisted synthesis of bifunctional magnetic solid acid for hydrolyzing cellulose to prepare nanocellulose.

The conventional studies on the preparation of nanocellulose used a high concentration of sulfuric acid that is difficult to remove and recover. A biochar-based solid acid with magnetic properties was developed to hydrolyze cellulose to prepare nanocellulose in this work. Two different methods were selected to investigate the properties of the synthesized magnetic carbon-based solid acids. The synthesized catalysts were characterized by SEM, TEM, XRD, NH3-TPD and FT-IR. The experimental results showed that two solid acids by the microwave-assisted synthesis had good magnetic properties by a magnet adsorption. Analysis by SEM and TEM showed that the two solid acids had rich pore structures. According to mineral element analysis, both solid acids contained high sulfur content. The solid acid was an amorphous carbon structural material with a surface rich in active groups. The catalytic activity of the biochar-based solid acids in cellulose hydrolysis to prepare nano-scale cellulosic material was evaluated. It was found that magnetic biochar-based solid acid (MBC-SA1) could achieve a high yield, which produced up to 57.68% for hydrolyzing cellulose into nanometers.

Renewable jet-fuel range hydrocarbons production from co-pyrolysis of lignin and soapstock with the activated carbon catalyst.

The current study aims to investigate the effects of agricultural waste-derived activated carbon catalyst on the jet-fuel range hydrocarbons distribution from raw biomass pyrolysis under the hydrogen donor condition provided by a solid waste. Ex-situ catalytic fast co-pyrolysis of lignin with and without soapstock was carried out using the corn stover-derived activated carbon catalyst in a facile fixed bed reactor. Results showed that the soapstock, as the hydrogen donor, exhibited a positive synergistic effect with lignin on enhancing the production of valuable aromatics in the obtained bio-oil. Additionally, biomass-derived activated carbon catalyst has the robust catalytic ability to convert pyrolysis vapors into high-density jet fuel-ranged aromatic hydrocarbons rather than phenols with the assistance of soapstock solid waste. Results indicated that the proportions of jet-fuel range aromatics increased monotonically with elevating pyrolytic temperatures from 400 to 550 °C, and the optimal lignin/soapstock ratio was 1:2 with regarding the yield of attained bio-oils. The maximum proportion of jet-fuel ranged aromatics (87.8%) and H2 concentration (76.4 vol%) could be achieved with the pyrolytic temperature, lignin/soapstock ratio, and catalyst/feedstock ratio of 550 °C, 2:1, and 1:1, respectively. The current study may provide a novel route of converting solid wastes into value-added jet fuels and hydrogen-enriched fuel gases, which will advance the utilization of renewable biomass.

Comparative study on characteristics of the bio-oil from microwave-assisted pyrolysis of lignocellulose and triacylglycerol.

Microwave-assisted pyrolysis of Camellia oleifera shell (COS) and stillingia oil (SO) was performed in the temperature range of 400-600 °C. The effects of feedstock and pyrolysis temperatures on product yield and bio-oil composition were discussed in detail. The bio-oil yield from COS pyrolysis varied from 37.30 wt% to 40.27 wt%, which was 11.32 wt% to 21.62 wt% lower than that from SO pyrolysis. Gas chromatography-mass spectrometry analysis indicated that SO bio-oil was rich in hydrocarbons, whereas COS pyrolysis produced mainly oxygen-containing compounds predominantly comprising phenols and acids. Fourier transform infrared and 1H-nuclear magnetic resonance spectra showed significant differences in the chemical structure of bio-oils from COS and SO pyrolysis. Elemental-composition and physical-property analyses further revealed that SO bio-oils were similar to gasoline and heavy fuel oil.

Microwave-assisted co-pyrolysis of lignin and waste oil catalyzed by hierarchical ZSM-5/MCM-41 catalyst to produce aromatic hydrocarbons.

Microwave-assisted catalytic fast co-pyrolysis (MACFP) of lignin and waste oil with SiC as microwave absorbent and hierarchical ZSM-5/MCM-41 as catalyst were implemented in a microwave-induced reactor. ZSM-5/MCM-41 is a kind of composite catalyst with MCM-41 as shell and ZSM as core. The effects of catalyst temperature, the ratio of feedstock-to-catalyst and the ratio of two reactants (lignin and waste oil) on product distribution and yield were studied. The study shows that catalytic co-pyrolysis is a complex reaction process, and many reaction conditions could affect the final reaction results. The optimum reaction conditions are as follows: catalytic temperature 400 °C, the feedstock-to-catalyst ratio of 10:1 and the ratio of lignin to waste oil of 2:1. Under this reaction condition, the conversion of feedstocks reached 76.00%, the proportion of aromatics was 50.31% and the selectivity of monocyclic aromatic hydrocarbons (MAHs) was 42.83%.

Lignocellulosic residue as bio-carrier for algal biofilm growth: Effects of carrier physicochemical proprieties and toxicity on algal biomass production and composition.

Five types of lignocellulosic materials were applied as the bio-carriers for low-cost algal biofilm cultivation of three algal strains. The effects of bio-carrier physicochemical properties and toxicity on algal cells growth and attachment were investigated. Rougher and hydrophilic bio-carrier could yield more algal biomass than smoother and hydrophobic bio-carrier. Pine sawdust (diameter: 0.420-0.595 mm) performed the best when cultured Diplosphaera sp. (9.61 g·m-2·day-1) biofilm. Meanwhile, bio-carriers could be leached by the culture medium during cultivation, and their energy conversion proprieties could be improved due to the reduced ash contents and the decreased crystallinities. In addition, Chlorella vulgaris growth tests indicated that pine sawdust (15.45%) leachate promoted cell growth, whereas rick husk (15.48%) and sugarcane bagasse (13.19%) leachate inhibited cell growth. And bio-carriers leachates also modified the chemical compositions (lipid, protein and carbohydrate) of algal cells and increased the corresponding saturated fatty acids methyl ester content (from 48.71 to 55.58-57.08%).

Bamboo (Phyllostachys pubescens) as a Natural Support for Neutral Protease Immobilization.

Lignin polymers in bamboo (Phyllostachys pubescens) were decomposed into polyphenols at high temperatures and oxidized for the introduction of quinone groups from peroxidase extracted from bamboo shoots and catalysis of UV. According to the results of FT-IR spectra analysis, neutral proteases (NPs) can be immobilized on the oxidized lignin by covalent bonding formed by amine group and quinone group. The optimum condition for the immobilization of NPs on the bamboo bar was obtained at pH 7.0, 40 °C, and duration of 4 h; the amount of immobilized enzyme was up to 5 mg g-1 bamboo bar. The optimal pH for both free NP (FNP) and INP was approximately 7.0, and the maximum activity of INP was determined at 60 °C, whereas FNP presented maximum activity at 50 °C. The Km values of INP and FNP were determined as 0.773 and 0.843 mg ml-1, respectively; INP showed a lower Km value and Vmax, than FNP, which demonstrated that INP presented higher affinity to substrate. Compared to FNP, INP showed broader thermal and storage stability under the same trial condition. With respect to cost, INP presented considerable recycling efficiency for up to six consecutive cycles.

Microwave-assisted acid pretreatment of alkali lignin: Effect on characteristics and pyrolysis behavior.

This study performed microwave-assisted acid pretreatment on pure lignin. The effects of microwave temperature, microwave time, and hydrochloric acid concentration on characteristics and pyrolysis behavior of lignin were examined. Results of ultimate analysis revealed better properties of all pretreated samples than those of raw lignin. Fourier transform infrared spectroscopy analysis showed breakage of ßO4 bond and aliphatic side chain, decrease in OH groups, and formation of CO groups in pretreatment. Microwave temperature exerted more significant influence on lignin structure. Thermal stability of treated lignin was improved and insensitive to short microwave time and acid concentration under mild conditions. Resulting from improved alkyl-phenols and decreased alkoxy-phenols, microwave-assisted acid pretreatment of lignin yielded bio-oil with excellent quality. Total yield of phenols in pyrolysis vapors (200 °C) improved to 14.15%, whereas that of guaiacols decreased to 22.36%. This study shows that microwave-assisted acid pretreatment is a promising technology for lignin conversion.

Fast microwave-assisted ex-catalytic co-pyrolysis of bamboo and polypropylene for bio-oil production.

The ex-catalytic co-pyrolysis of bamboo and polypropylene (PP) with HZSM-5 was investigated with microwave assistance. The influences of catalytic temperature, feedstock/catalyst ratio, and bamboo/PP ratio on the product yields and chemical components of bio-oil from the co-pyrolysis were studied. When the catalytic temperature, feedstock/catalyst ratio, and bamboo/PP ratio were 250 °C, 1:2, and 2:1, respectively, the bio-oil yield reached its maximum value at 61.62 wt%. The oxygenate proportion compounds decreased with increasing catalyst content. The PP addition improved the proportions of aromatics and naphthenic hydrocarbons. The bio-oil was upgraded significantly from the jet fuel perspective. A synergistic effect also existed between bamboo and PP.

Microwave-assisted co-pyrolysis of pretreated lignin and soapstock for upgrading liquid oil: Effect of pretreatment parameters on pyrolysis behavior.

The co-pyrolysis of pretreated lignin and soapstock was carried out to upgrade vapors under microwave irradiation. Results showed that the yield of 29.92-42.21 wt% of upgraded liquid oil was achieved under varied pretreatment conditions. Char yield decreased from 32.44 wt% for untreated control to 24.35 wt% for the 150 °C pretreated samples. The increased temperature, irradiation time and acid concentration were conducive to decrease the relative contents of phenols and oxygenates in liquid oils. The main components of the liquid oil were gasoline fraction (mono-aromatics and C5-C12 aliphatics), which ranged from 57.38 to 71.98% under various pretreatment conditions. Meanwhile, the diesel fraction (C12+ aliphatics) ranged from 13.16 to 22.62% from co-pyrolysis of pretreated lignin and soapstock, comparing with 10.18% of C12+ aliphatics from co-pyrolysis of non-pretreated lignin and soapstock. A possible mechanism was proposed for co-pyrolysis of pretreated lignin and soapstock for upgraded liquid oils.

Improving hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and HZSM-5.

The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein a dual-catalyst bed of CaO and HZSM-5 was developed to convert acids in the pyrolytic products of xylan to valuable hydrocarbons. Meanwhile, LLDPE was co-pyrolyzed with xylan to supplement hydrogen during the catalysis of HZSM-5. The results showed that CaO could effectively transform acids into ketones. A minimum yield of acids (2.74%) and a maximum yield of ketones (42.93%) were obtained at a catalyst to feedstock ratio of 2:1. The dual-catalyst bed dramatically increased the yield of aromatics. Moreover, hydrogen-rich fragments derived from LLDPE promoted the Diels-Alder reactions of furans and participated in the hydrocarbon pool reactions of non-furanic compounds. As a result, a higher yield of hydrocarbons was achieved. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose.

In-situ and ex-situ catalytic upgrading of vapors from microwave-assisted pyrolysis of lignin.

In-situ and ex-situ catalytic upgrading with HZSM-5 of vapors from microwave-assisted pyrolysis of lignin were studied. The in-situ process produced higher bio-oil and less char than ex-situ process. The gas yield was similar for both processes. The ex-situ process had higher selectivity to aromatics and produced more syngas and less CO2 than the in-situ process. Additional experiments on ex-situ process found that the bio-oil yield and coke deposition decreased while the gas yield increased at higher catalyst-to-lignin ratios and catalytic upgrading temperatures. The increased catalyst-to-lignin ratio from 0 to 0.3 reduced the selectivity of methoxy phenols from 73.7% to 22.6% while increased that of aromatics from 1.1% to 41.4%. The highest selectivity of alkyl phenols (31.9%) was obtained at 0.2 of catalyst-to-lignin ratio. Higher catalytic temperatures favored greater conversion of methoxy phenols to alkyl phenols and aromatics. Appropriate catalyst-to-lignin ratio (0.3) together with higher catalytic temperatures favored syngas formation.