Upcycling of PVC waste to high-value sorbent with KOH-activation for efficient removal of organic dyes.

Polyvinyl chloride (PVC), known for its chemical stability and flame-retardant qualities, has many uses in various fields, such as pipes, electric wires, and cable insulation. Research has established its potential recovery as a fluidic fuel through pyrolysis, but the use of PVC pyrolysis oil, which is tainted by chlorine, is constrained by its low heat value and harmful environmental effects. This study engineered a layered double hydroxide (LDH) to tackle these challenges. The LDH facilitated dechlorination during PVC pyrolysis and bolstered thermal stability via cross-linking. During pyrolysis with LDH, PVC was transformed into carbon-rich precursors to sorbents. Chemical activation of these residues using KOH created sorbents with a specific surface area of 1495.4 m2 g⁻1, rendering them hydrophilic. These resulting sorbents displayed impressive adsorption capabilities, removing up to 486.79 mg g⁻1 of methylene blue and exhibiting the simultaneous removal of cations and anions.

Catalytic pyrolysis of harmful plastic waste to alleviate environmental impacts.

Wax is a detrimental byproduct of plastic waste pyrolysis causing challenges upon its release into the environment owing to persistence and potential toxicity. In this study, the valorization of wax materials through conversion into BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) was achieved via catalytic pyrolysis using zeolite-based catalysts. The potential of two types of waxes, spent wax (SW), derived from the pyrolysis of plastic waste, and commercial paraffin wax (PW), for BTEX generation, was investigated. Using HZSM-5, higher yields of oil (54.9 wt%) and BTEX (18.2 wt%) were produced from the pyrolysis of SW compared to PW (32.3 and 14.1 wt%, respectively). This is due to the improved accessibility of lighter hydrocarbons in SW to Brønsted and Lewis acid sites in HZSM-5 micropores, promoting cracking, isomerization, cyclization, Diels-Alder, and dehydrogenation reactions. Further, the use of HZSM-5 resulted in significantly larger yields of oil and BTEX from SW pyrolysis compared to Hbeta and HY. This phenomenon is ascribed to the well-balanced distribution of Brønsted and Lewis acid sites and the identical geometric structure of HZSM-5 micropores and BTEX molecules. The addition of Ga to HZSM-5 further led to 2.24% and 28.30% enhancements in oil and BTEX yields, respectively, by adjusting the acidity of the catalyst through the introduction of new Lewis acid sites. The regeneration of the Ga/HZSM-5 catalyst by removing deposited coke on the spent catalyst under air partially recovered catalytic activity. This study not only offers an efficient transformation of undesirable wax into valuable fuels but also provides an environmentally promising solution, mitigating pollution, contributing to carbon capture, and promoting a healthier and more sustainable environment. It also suggests future research directions, including catalyst optimization and deactivation management, feedstock variability exploration, and techno-economic analyses for sustainable wax conversion into BTEX via catalytic pyrolysis.

Recent advances of thermochemical conversion processes for biorefinery.

Lignocellulosic biomass is one of the most promising renewable resources and can replace fossil fuels via various biorefinery processes. Through this study, we addressed and analyzed recent advances in the thermochemical conversion of various lignocellulosic biomasses. We summarized the operation conditions and results related to each thermochemical conversion processes such as pyrolysis (torrefaction), hydrothermal treatment, gasification and combustion. This review indicates that using thermochemical conversion processes in biorefineries is techno-economically feasible, easy, and effective compared with biological processes. The challenges experienced in thermochemical conversion processes are also presented in this study for better understanding the future of thermochemical conversion processes for biorefinery. With the aid of artificial intelligence and machine learning, we can reduce time-consumption and experimental work for bio-oil production and syngas production processes.

Synthesis and catalytic properties of calcium oxide obtained from organic ash over a titanium nanocatalyst for biodiesel production from dairy scum.

The fatty acid methyl ester (FAME) production from dairy effluent scum as a sustainable energy source using CaO obtained from organic ash over titanium dioxide nanoparticles (TNPs) as the transesterification nano-catalyst has been studied. The physical and chemical properties of the synthesized catalysts were characterized, and the effect of different experimental factors on the biodiesel yield was studied. It was revealed that the CaO-TiO2 nano-catalyst displayed bifunctional properties, has both basic and acid phases, and leads to various effects on the catalyst activity in the transesterification process. These bifunctional properties are critical for achieving simultaneous transesterification of dairy scum oil feedstock. According to the reaction results, the catalyst without and with a low ratio of TNPs showed a low catalytic activity. In contrast, the 3Ca-3Ti nano-catalyst had the highest catalytic activity and a strong potential for reusability, producing a maximum biodiesel yield of 97.2% for a 3 wt% catalyst, 1:20 oil to methanol molar ratio for the dairy scum, and a reaction temperature of 70 °C for a period of 120 min under a 300 kPa pressure. The physical properties of the produced biodiesel are within the EN14214 standards.

Characteristics of fractionated drop-in liquid fuel of plastic wastes from a commercial pyrolysis plant.

Pyrolysis is a waste conversion technology to solve an increasing plastic waste issue worldwide. Waste plastic pyrolysis fuel from a commercial-scale pyrolysis plant (10 ton/day) was comprehensively investigated using distillation methods by separating the crude pyrolysis fuel to isolate the diesel-like pyrolysis fuel fraction (C9-C25 for fraction 2 + fraction 3, middle distillate). Other fractions were C5-C10 for the light distillate (fraction 1), and >C25 for the heavy distillate (fraction 4). The relationship between the fuel boiling point and liquid vapor temperature were found for designing a scaled-up oil separation process. The diesel grade pyrolysis fuel fraction comprised approximately 70-80% of the crude pyrolysis fuel, wherein it had values of 43-45 MJ/kg, 1-6 cSt, and 12-42 mgKOH/goil. Meanwhile, the elemental ratios of the crude pyrolysis oil improved to 0.1 for O/C and 1.9 for H/C after separation, close to petroleum fuels (0.0 O/C and 1.95 H/C). The highest relative chemical composition was the olefins (46% in fraction 1 and 41% in fraction 2), whereas the paraffin was approximately 15-20% in the light fraction. Finally, the potential CO2 reduction for the plastic waste-to-energy process was evaluated, revealing that a total of 0.26 tCO2/tonwaste of emissions could be avoided during the waste plastic pyrolysis process.

Effect of gasification biochar application on soil quality: Trace metal behavior, microbial community, and soil dissolved organic matter.

Compared to pyrolysis biochar (PBC), gasification biochar (GBC) differs in both composition and surface functionalities due to the use of an oxidizing purging gas. This work compares the effect of using PBC and GBC as soil amendments on the soil properties, trace metal bioavailability, soil microbial activity, and soil dissolved organic matter (DOM). Biochar-driven reduction of bioavailable metals does not necessarily result in a positive impact on the soil microbial growth. The DOM in the soil was strongly related to the soil microbial activity, as revealed by the strong correlation between the soil dehydrogenase activity (DHA) and soil dissolved organic carbon (r = 0.957, p < 0.01). Three identified fluorescent components (C1, C2, C3) in the soil DOM were closely associated with the soil microbial activity, for instance, with a clear positive correlation between the soil DHA and C1 (r = 0.718, p < 0.05) and a significant negative correlation between the total bacterial fatty acid methyl ester content and C3 (r = -0.768, p < 0.05). The bioavailability of Cd and Zn is not only related to the pH and surface functionalities of the biochar, but also to its aromatic carbon and inorganic mineral composition. This study further demonstrates that a fluorescence excitation-emission matrix coupled with parallel factor analysis is a useful tool to monitor changes in the soil quality after application of biochar, which is greatly relevant to the soil biota.

Decentralized biorefinery for lignocellulosic biomass: Integrating anaerobic digestion with thermochemical conversion.

Anaerobic digestion (AD) of lignocellulosic biomass i.e. Napier grass (Pennisetum purpureum), was investigated via a series of batch and bench-scale experiments. Two semi-continuous bench-scale horizontal bioreactors were operated in parallel for nearly 300 days, and the reactors were able to handle the organic loading rate (OLR) up to 6 kg volatile solids (VS)/m3-d, which was among the highest OLR reported in the literature for lignocellulosic biomass. Hemicellulose was the main structural carbohydrate of lignocellulosic biomass per unit respective mass (dry weight) basis contributing to methane production. The cellulose- and lignin-rich digestate was further examined for its bioenergy potential via torrefaction and hydrothermal carbonization, and was found to have higher mass and energy yield compared with those of raw Napier grass. The produced solid char has energy content similar to bituminous coal with low ash content. Thus, this study provided a successful integration of anaerobic digestion with thermochemical conversion representing a biorefinery concept for lignocellulosic feedstocks.

Characterization of bioenergy biochar and its utilization for metal/metalloid immobilization in contaminated soil.

This study is a comparison of the effect of biochar produced by bioenergy systems, via the pyrolysis and gasification processes, on the immobilization of metals/metalloids in soil. Because the processes for these two techniques vary, the feedstocks undergo different heating regimens and, as a result, their respective char products exhibit different physico-chemical properties. Therefore, this study focuses on (1) the characterization of derivative biochar from the bioenergy system to understand their features and (2) an exploration of various biochar impacts on the mobility of As and Pb in contaminated soil. The results showed bioenergy biochars (BBCs) performed well in mitigating Pb extractability (1 M ammonium acetate) with a Pb immobilization >80%, but unfavorably mobilized the bioavailable As, likely because of electrostatic repulsion and ion exchange competition. The BBC surface functional group would chemically bond with the As and remain stable against the pH change. An increment in aromatic carbon would effectively enhance cation-π interaction for Pb immobilization. Nevertheless, an amendment with richer condensed structure and higher inorganic minerals (Ca2+, K+, Mg2+, and Na+) can lead to better performance in retaining Pb.

Influence of biochemical composition during hydrothermal liquefaction of algae on product yields and fuel properties.

Hydrothermal liquefaction (HTL) of nine algae species were performed at two reaction temperatures (280 and 320°C) to compare the effect of their biomass composition on product yields and properties. Results obtained after HTL indicate large variations in terms of bio-oil yields and its properties. The maximum bio-oil yield (66wt%) was obtained at 320°C with a high lipid containing algae Nannochloropsis. The higher heating value of bio-oils ranged from 31 to 36MJ/kg and around 50% of the bio-oils was in the vacuum gas oil range while high lipid containing algae Nannochloropsis contained a significant portion (33-42%) in the diesel range. A predictive relationship between bio-oil yields and biochemical compositions was developed and showed a broad agreement between predictive and experimental yields. The aqueous phases obtained had high amount of TOC (12-43g/L), COD (35-160g/L), TN (1-18g/L), ammonium (0.34-12g/L) and phosphate (0.7-12g/L).