Isolation of ß-O-4-rich lignin from Birch in high yields enabled by continuous flow supercritical water treatment.

The continuous flow supercritical water (scH2O) treatment of Birch wood (T = 372-382 °C; t = 0.3-0.7 s; p = 260 bar) followed by alkali extraction of lignin allowed for the isolation of lignin and lignin carbohydrate complexes (LCCs) with a high number of ß-O-4 moieties in the range 29-57/100 Ar (evaluated by quantitative 13C NMR analysis) in yields ranging between 13-19 wt% with respect to the initial wood. A "lightning rod effect" of carbohydrates has been claimed to explain the low degradation of ß-O-4 bonds during the process. The structure of the isolated lignin was thoroughly elucidated via comprehensive NMR studies (HSQC, 13C and 31P). A low degree of condensation (DC) < 5% was found for all the lignin samples, which was only slightly dependent on the reaction severity. The number of aliphatic -OH, phenolic -OH, and -COOH groups was in the range 3.37-5.25, 1.41-2.31 and 0.39-0.73 mmol/g, respectively. The number of -COOH groups increased with increased severity, suggesting that oxidation can occur during the scH2O treatment. Furthermore, by simply varying the reaction severity, it was possible to tune important lignin properties, like the molar mass and the glass transition temperature (Tg).

Forming Homogeneous Three-Dimensional Structures from Discrete Silica Microspheres Using Sub/Supercritical Water.

A novel technique for producing highly uniform structures from silica microspheres has been developed and tested. It is based on exploiting the temperature- and pressure-dependent solvent properties of sub/supercritical water toward silicon dioxide. The initial concept aimed to create a "hybrid" capillary chromatographic column on the border between a packed and a monolithic column that would combine the benefits of both. The resultant method that integrates dissolution and coalescence in a continuous process enabled the production of a range of permeable columns with high efficiency and varying sizes. Their internal structures were examined using scanning electron microscopy and characterized using microHPLC chromatography. The structures produced using this method may have diverse applications beyond the scope of analytical chemistry. They prove useful in scenarios where high pressure is necessary because of the high hydraulic resistance of small particles and/or the passing medium with a high flow rate. A simple test of a bridged-microsphere monolithic column and a discrete microsphere-packed column, both after chemical modification to the C18 stationary phase, indicated superior performance of the new type of monolithic columns.

Degradation pathways and product formation mechanisms of asphaltene in supercritical water.

Asphaltene is the compound with the most complex structure and the most difficult degradation in oily sludge, which is the key to limit the efficiency of supercritical water oxidation treatment of oily sludge. In this paper, the supercritical water oxidation process of asphaltene was investigated in terms of free radical reaction, degradation pathway, and product generation mechanism using ReaxFF molecular dynamics simulation method. The results showed that increasing temperature, increasing O2, and increasing H2O have different effects on HO2·generation. Benzene rings undergo fusion and condensation through hydrogenation abstraction and oxygen addition reactions, subsequently breaking down into long-chain alkanes. Increasing O2 can effectively promote the ring-opening of nitrogen-containing heterocycles. -COOH is the most important intermediate fragment for CO and CO2 generation, and there is a reaction competition with -CHO3 and -CO3. When the number of oxygen molecules increases from 300 to 700, the reaction frequency of -CHO3 and -CO3 to generate CO and CO2 increases by 17.14 % and 12.77 %·H2O determines the production of H2 by controlling the number of H·radicals present. As the amount of H2O increases from 500 to 1500, the product ratio of H2 increases from 12.73 % to 21.31 %. ENVIRONMENTAL IMPLICATION: Asphaltene is the most structurally complex organic matter in oily sludge, and its presence makes it difficult for oily sludge to be completely degraded by conventional treatment methods such as pyrolysis and incineration. Polycyclic aromatic hydrocarbons (PAHs) represented by asphaltene increase the carcinogenicity and mutagenicity of oily sludge, and even irreversibly pollute soil and groundwater. Supercritical water oxidation, as an efficient organic waste treatment technology, can realize harmlessness in a green and efficient way. So the study on the mechanism of supercritical water oxidation of asphaltene is of great significance for environmental protection.

Degradation of Waste Tetra Pak Packaging with Hydrothermal Treatment in Sub-/Supercritical Water.

Tetra pak packaging is one of the most frequently used types of packaging in the food industry. The recycling of the tetra pak packaging waste presents a difficult task because of its multi-layered, multi-component structure. In this study, the degradation of tetra pak packaging in subcritical (SubCW) and supercritical (SCW) water was investigated. The experiments were carried out in one (SCW) or two stages (SubCW and SCW), whereby the influence of the reaction temperature and time on the yield and composition of the products obtained was investigated. The maximum oil phase yield achieved in a one-stage and a two-stage degradation process was 60.7% and 65.5%, respectively. The oil and gas phases were composed of different types of hydrocarbons. Higher temperature and longer time led to higher amounts of saturated aliphatic hydrocarbons in both the oil and gas phases. The aqueous phase contained sugars (glucose, fructose) and sugar derivatives (levulinic acid, glyceraldehyde, furfurals). Based on these results, the degradation pathway of waste tetra pak packaging in SubCW and SCW was proposed. The results of the study show that the degradation of waste tetra pak packaging with SubCW and SCW is a promising recycling process.

Thermodynamic Model for Hydrogen Production from Rice Straw Supercritical Water Gasification.

Supercritical water gasification (SCWG) technology is highly promising for its ability to cleanly and efficiently convert biomass to hydrogen. This paper developed a model for the gasification of rice straw in supercritical water (SCW) to predict the direction and limit of the reaction based on the Gibbs free energy minimization principle. The equilibrium distribution of rice straw gasification products was analyzed under a wide range of parameters including temperatures of 400-1200 °C, pressures of 20-50 MPa, and rice straw concentrations of 5-40 wt%. Coke may not be produced due to the excellent properties of supercritical water under thermodynamic constraints. Higher temperatures, lower pressures, and biomass concentrations facilitated the movement of the chemical equilibrium towards hydrogen production. The hydrogen yield was 47.17 mol/kg at a temperature of 650 °C, a pressure of 25 MPa, and a rice straw concentration of 5 wt%. Meanwhile, there is an absorptive process in the rice straw SCWG process for high-calorific value hydrogen production. Energy self-sufficiency of the SCWG process can be maintained by adding small amounts of oxygen (ER < 0.2). This work would be of great value in guiding rice straw SCWG experiments.

Supercritical Water: A Simulation Study to Unravel the Heterogeneity of Its Molecular Structures.

(1) Background: In the quest to accurately model the radiolysis of water in its supercritical state, a detailed understanding of water's molecular structure, particularly how water molecules are arranged in this unique state, is essential. (2) Methods: We conducted molecular dynamics simulations using the SPC/E water model to investigate the molecular structures of supercritical water (SCW) over a wide temperature range, extending up to 800 °C. (3) Results: Our results show that at a constant pressure of 25 MPa, the average intermolecular distance around a reference water molecule remains remarkably stable at ~2.9 Å. This uniformity persists across a substantial temperature range, demonstrating the unique heterogeneous nature of SCW under these extreme conditions. Notably, the simulations also reveal intricate patterns within SCW, indicating the simultaneous presence of regions with high and low density. As temperatures increase, we observe a rise in the formation of molecular clusters, which are accompanied by a reduction in their average size. (4) Conclusions: These findings highlight the necessity of incorporating the molecular complexity of SCW into traditional track-structure chemistry models to improve predictions of SCW behavior under ionizing radiation. The study establishes a foundational reference for further exploration of the properties of supercritical water, particularly for its application in advanced nuclear technologies, including the next generation of water-cooled reactors and their small modular reactor variants that utilize SCW as a coolant.

Macro-characteristics and micro-mechanisms of Na2SO4 precipitation dissolved by KNO3 molten salt in a continuous supercritical water system.

This work aims to explore the ability of molten salt to solve salt deposition in supercritical water (SCW) related technologies including supercritical water oxidation and supercritical water gasification, with KNO3 and Na2SO4 as examples. In the pure KNO3 solution, the two-phase layering of high-density KNO3 molten salt (settling at the reactor bottom) and low-density saturated KNO3-SCW salt solution (flowing out at the top outlet of the reactor) was formed in a kettle-reactor with about 6.5 ratio of depth to inner diameter, thereby improving the accuracy of measured solubilities. The precipitation macro-characteristics of mixed KNO3 and Na2SO4 in SCW were investigated under different feed concentration conditions. The results showed that Na2SO4 deposition on the reactor sidewall could be reduced by more than 90 % when the mass ratio of KNO3 to Na2SO4 in the feed was only 0.167. No visible salt deposition was observed on the sidewall when the ratio was 0.374. All solid deposited salts were converted into the liquid molten salt as the ratio reached 3.341, and thus could easily flow out of the reactor, without plugging. 'Molten salt dissolution' mechanism may provide a more plausible explanation for mixed KNO3 and Na2SO4 in SCW. In addition, the precipitation micro-mechanisms of mixed KNO3 and Na2SO4, and the critical conditions of avoiding sidewall deposition and reactor plugging were proposed. This work is valuable for overcoming the salt deposition problem in SCW-related technologies.

Upcycling of waste disposable medical masks to high value-added gasoline fuel and surfactants products by sub/supercritical water degradation and partial oxidation.

The amount of waste disposable medical masks (DMMs) and the potential environmental risk increased significantly due to the huge demand of disposable medical surgical masks. In this study, two effective and environmentally friendly processes, supercritical water degradation (SCWD) and subcritical water partial oxidation (SubCWPO), were proposed for the upcycling of DMMs. The optimal conditions for the SCWD process (conversion ratio>98 %) were 410 â„ƒ, 15 min, and 1:5 g/mL. The oil products obtained from the SCWD process were mainly small molecule hydrocarbons (C7-C12) with a content of 86 % and could be recycled as fuel feedstock for gasoline. Alkyl radicals in the SCWD reaction formed double bonds and ring structures through hydrogen capture reactions, ß-scission, and dehydrogenation reactions, and aromatic hydrocarbons were formed by olefin cyclization and cycloalkane dehydrogenation. The introduction of an oxidant (H2O2) to the reaction system could significantly reduce the reaction temperature and shorten the reaction time. At 350 â„ƒ, 15 min, 1:20 g/mL, V(H2O2): V (H2O) of 1:1, the conversion ratio of the SubCWPO process was 88 %, which was higher than that of the SCWD process at 400 â„ƒ (71.49 %). Oil products produced from the SubCWPO process were rich in alcohols and esters, which could be used as raw materials for nonionic surfactant of polyol and fatty acid ester. The abundant hydroxyl radical in the SubCWPO system trapped hydrogen atoms on PP and reacted with the resulting alkyl radical to form alkanols, which was oxidized to form acids. The esterification of acids and alkanols formed high level of esters. The SCWD and SubCWPO processes proposed in this study are believed to be promising strategies for DMMs degradation and the recovery of high value-added hydrocarbons.

Treatment of pistachio processing industry wastewaters by supercritical water oxidation in a continuous-flow reactor.

The objective of the present study is the treatment of pistachio processing industry wastewaters (PPIW) using the supercritical water oxidation method. The experiments were conducted within a 400-600°C temperature range and a 30-150 s reaction time range, while maintaining a constant pressure of 25 MPa and using an O2/COD ratio of 1:1. To observe the effects of the initial PPIW and O2 concentrations on the treatment efficiency, experiments were also conducted with O2/COD ratios ranging from 0.5 to 3, while maintaining a constant reaction temperature and time of 500°C and 60 s, respectively. The influence of reaction temperature, reaction time and O2/COD ratio on the total organic carbon (TOC) and total nitrogen (TN) contents of the liquid PPIW effluents were investigated. Treatment efficiencies up to 99.75% regarding TOC conversion and 78.72% regarding TN conversion were obtained in very short reaction times. Additionally, the kinetics of oxidation of PPIW was studied, and reaction rate expressions based on TOC and TN were proposed.

Prediction of Individual Gas Yields of Supercritical Water Gasification of Lignocellulosic Biomass by Machine Learning Models.

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.

Mechanistic insights and catalytic enhancement of phenolic wastewater supercritical water gasification: A combined experiment and density functional theory study.

Supercritical water gasification technology provides a favorable technology to achieve pollution elimination and resource utilization of phenolic wastewater. In this study, the reaction mechanism of phenolic wastewater supercritical water gasification was investigated using a combination of experimental and computational methods. Five reaction channels were identified to elucidate the underlying pathway of phenol decomposition. Importantly, the rate-determining step was found to be the dearomatization reaction. By integrating computational and experimental analyses, it was found that phenol decomposition via the path with the lowest energy barrier generates cyclopentadiene, featuring a dearomatization barrier of 70.97 kcal/mol. Additionally, supercritical water plays a catalytic role in the dearomatization process by facilitating proton transfer. Based on the obtained reaction pathway, alkali salts (Na2CO3 and K2CO3) are employed as a catalyst to diminish the energy barrier of the rate-determining step to 40.00 kcal/mol and 37.14 kcal/mol. Alkali salts catalysis significantly improved carbon conversion and pollutant removal from phenolic wastewater, increasing CGE from 58.44% to 93.55% and COD removal efficiency from 94.11% to 99.79%. Overall, this study provides a comprehensive understanding of the decomposition mechanism of phenolic wastewater in supercritical water.

Supercritical water oxidation for the treatment and utilization of organic wastes: Factor effects, reaction enhancement, and novel process.

Supercritical water oxidation (SCWO) has been regarded as a new and efficient technology for the harmless treatment and energy utilization of organic wastes, resulting in the quickly homogeneous oxidation between organics and oxidizers and the former being wholly degraded into small environment-friendly green molecules such as H2O and N2 and inorganic salts. This paper systematically analyzed the influencing behavior and mechanisms of the reaction factors, such as temperature, pressure, residence time, oxidant type, oxidation coefficient, and the concentration and pH values of the raw material, on the treatment effect of organic wastes. For most organic wastes, the SCWO conditions at 550 °C with a residence time of 1min and an oxidation coefficient of 100% can meet the removal rate of more than 99%. To further enhance the degradation rate of organics, the principles, implementation cases, and related equipment components of general enhancement technologies of supercritical water oxidation were discussed, such as fractional oxygen injection, auxiliary fuel co-oxidation, and hydrothermal flame-assisted degradation. This paper proposes a novel supercritical flame-assisted oxidation process in which the reactor performs preheating, corrosion protection, and desalination functions. The use of additive-enhanced oxidation, segmented oxidation, and supercritical hydrothermal flame-assisted oxidation has achieved good results in the complicated treatment process of brutal degradation of organic matter.

Catalytic Supercritical Water Gasification of Canola Straw with Promoted and Supported Nickel-Based Catalysts.

Lignocellulosic biomass such as canola straw is produced as low-value residue from the canola processing industry. Its high cellulose and hemicellulose content makes it a suitable candidate for the production of hydrogen via supercritical water gasification. However, supercritical water gasification of lignocellulosic biomass such as canola straw suffers from low hydrogen yield, hydrogen selectivity, and conversion efficiencies. Cost-effective and sustainable catalysts with high catalytic activity for supercritical water gasification are increasingly becoming a focal point of interest. In this research study, novel wet-impregnated nickel-based catalysts supported on carbon-negative hydrochar obtained from hydrothermal liquefaction (HTL-HC) and hydrothermal carbonization (HTC-HC) of canola straw, along with other nickel-supported catalysts such as Ni/Al2O3, Ni/ZrO2, Ni/CNT, and Ni/AC, were synthesized for gasification of canola straw on previously optimized reaction conditions of 500 °C, 60 min, 10 wt%, and 23-25 MPa. The order of hydrogen yield for the six supports was (10.5 mmol/g) Ni/ZrO2 > (9.9 mmol/g) Ni/Al2O3 > (9.1 mmol/g) Ni/HTL-HC > (8.8 mmol/g) Ni/HTC-HC > (7.7 mmol/g) Ni/AC > (6.8 mmol/g) Ni/CNT, compared to 8.1 mmol/g for the non-catalytic run. The most suitable Ni/ZrO2 catalyst was further modified using promotors such as K, Zn, and Ce, and the performance of the promoted Ni/ZrO2 catalysts was evaluated. Ni-Ce/ZrO2 showed the highest hydrogen yield of 12.9 mmol/g, followed by 12.0 mmol/g for Ni-Zn/ZrO2 and 11.6 mmol/g for Ni-K/ZrO2. The most suitable Ni-Ce/ZrO2 catalysts also demonstrated high stability over their repeated use. The superior performance of the Ni-Ce/ZrO2 was due to its high nickel dispersion, resilience to sintering, high thermal stability, and oxygen storage capabilities to minimize coke deposition.

Integration of hydrothermal liquefaction of Cyanophyta and supercritical water oxidation of its aqueous phase products: Biocrude production and nutrient removal.

Cyanophyta has the potential to produce biocrude via hydrothermal liquefaction (HTL). However, aqueous phase products (APs), as by-products of HTL, pose a risk of eutrophication for the high levels of carbon, nitrogen, and phosphorus. Supercritical water oxidation (SCWO) can efficiently convert organics into small molecules, offering a technique for the harmless treatment of APs. Effects of holding time, pressure, and moisture content on the biocrude yields from isothermal HTL (300 °C) and fast HTL (salt bath temperature of 500 °C) were comprehensively investigated. Biocrude properties were characterized by elemental analysis, FT-IR and GC-MS. Subsequently, the APs obtained under the conditions producing the highest biocrude yield were subjected to SCWO at 550 °C with different oxidation coefficients (n) from 0 to 2. Removal rates of chemical oxygen demand (COD), ammonia nitrogen (NH3-N), and total phosphorus (TP) were further explored. The results show that the highest biocrude yields from isothermal HTL and fast HTL were 24.2 wt% (300 °C, 1800 s, 25 MPa, and 80 wt% moisture content) and 21.9 wt% (500 °C, 40 s, 25 MPa, and 80 wt% moisture content), respectively. The biocrude primarily consisted of N-containing heterocyclic compounds, amides, and acids. SCWO effectively degraded the COD and TP in APs, while the NH3-N required further degradation. At n = 2, the highest removal rates of COD, NH3-N and TP were 98.5 %, 22.6 % and 89.1 %, respectively.

Numerical study on particle behavior in a Y-junction mixer for supercritical water hydrolysis.

In the continuous-type supercritical water hydrolysis process, rapid mixing of supercritical and subcritical streams is important to maximize yield and minimize degradation from over-reaction. This work investigated the particle behavior in a Y-junction mixer using large eddy simulation coupled with a discrete phase model, aiming to optimize the supercritical hydrolysis process for biomass conversion. A series of numerical simulations analyzed the influence of the mixer's orientation, flow directions, and flow rates on effective mixing and backflow prevention. The results demonstrated that the most effective mixing occurred in a vertically oriented Y-junction mixer with an upward-directed supercritical water inlet, aligning the momentum direction of natural and forced convection effectively. Consequently, over 80% of particles reached the temperatures close to the mixing temperature of supercritical and subcritical water within the Y-junction mixing zone, indicating enhanced mixing effectiveness and potential for efficient hydrolysis. This configuration also minimized backflow.

Hydrogen-rich gas production via supercritical water gasification (SCWG) of oily sludge over waste tire-derived activated carbon impregnated with Ni: Characterization and optimization of activated carbon production.

In this study, the production of activated carbon (AC) through the chemical activation of waste tire (WT) using H3PO4 and KOH for H2 production by SCWG of oily sludge (OS) donated by Persian Gulf Star Oil Company was investigated. H3PO4 was the best activating agent based on some pretests results, and then the synthesis of AC was optimized using Response Surface Methodology. Based on BET surface area of synthesized ACs, thirty combinations of the four variables namely; activation temperature (350-550 °C); activation time (1-4 h); H3PO4 to WT ratio (1-3 w.w-1); and H3PO4 concentration (20-40 wt%) were optimized. CHNS, TGA, FE-SEM, and EDS-mapping analyses were used to characterize the AC and catalyst synthesized in optimum condition (activation temperature: 450 °C; activation time: 2.5 h; H3PO4 to WT ratio: 2 w.w-1; and H3PO4 concentration: 40 wt%), which presented a surface area of 170 m2 g-1. Finally, Ni was impregnated on the optimized AC with different loadings (5-15 wt%) to evaluate its performance in H2 production by SCWG of OS. Although H2 yield in catalytic experiments was higher than that observed in non-catalytic experiment, results showed that the maximum H2 selectivity was 66% in SCWG of OS using AC impregnated with 10 wt% Ni.

Experimental analysis on products distribution, characterization and mechanism of waste polypropylene (PP) and polyethylene terephthalate (PET) degradation in sub-/supercritical water.

Supercritical water (SCW) treatment of plastics is a clean technology in the 'waste-to-energy' path. In this work, PP and PET plastics were processed by sub-/supercritical water. The results showed that temperature was the most important factor of the PP and PET degradation. The influence of factors on the degradation of plastics follows the following order: temperature > residence time > plastic/water ratio. These factors influenced the yield of gas products by promoting or inhibiting various reactions (such as reverse water gas shift reaction, methylation reaction, and Fischer-Tropsch synthesis reaction). Besides, the composition of liquid oil was also analyzed. The main composition of the liquid oil produced by PET was benzoic acid and acetaldehyde, which were generated from the decarboxylation of terephthalic acid (TPA) and dehydration reaction of ethylene glycol (EG). The liquid oil from PP was mainly long-chain olefins, long-chain alkanes, cycloalkanes, etc., which were formed by the interaction of various methyl, alkyl, hydroxyl, and other free radicals. This study could build fundamental theories of plastic mixture treatment.

Directional transformation and migration pathways of nitrogen during pig manure supercritical water gasification.

Nitrogen is a valuable nutrient element in pig manure. This work focuses on investigating the distribution, directional transformation, and migration pathways to facilitate the recovery of nitrogen from supercritical water gasification products. Results indicated that no nitrogen-containing gas was detected and 12.65 % of nitrogen remained in solid products. 82.49 % of nitrogen migrated into liquid products, which are predominated by ammonia. Catalysts were employed to promote the conversion of solid nitrogen to liquid nitrogen and organic nitrogen to ammonia. Finally, 85 % of nitrogen is enriched into liquid products and ammonia predominated the liquid nitrogen. The percentage of ammonia increased to 97.51 % at 620 °C in the presence of potassium carbonate. The migration pathways indicated that nitrogen was transformed into ammonia by various intermediates such as indole. The rest of the nitrogen remained in solid products with stable quaternary-nitrogen. These findings provide valuable insights into nitrogen management and recovery.

An experimental and thermodynamic equilibrium investigation of heavy metals transformation in supercritical water gasification of oily sludge.

Supercritical water gasification (SCWG) is an advanced and highly efficient method for treating oily sludge. However, it is crucial to consider the transformation characteristics of heavy metals (HMs) during the SCWG process to prevent potential secondary pollution. This work studied the transformation and distribution characteristics of Cu, Cr and Zn after SCWG of oily sludge in a batch reactor at temperatures ranging from 550 to 700 °C. Additionally, thermodynamic equilibrium analysis was conducted to assess the distribution of HMs based on the minimization of Gibbs free energy. Experimental results indicated that higher temperatures led to the conversion of HMs into more stable forms, effectively immobilizing them within solid products. Furthermore, the addition of Na2CO3 enhanced this process and contributed to a reduction in HMs pollution in the effluent. Thermodynamic equilibrium results were consistent with our experimental data, indicating that the molar fraction of stable HMs forms followed the order: Cr > Cu > Zn. Besides, it is worth noting that Na2CO3 had a limited impact on the distribution of Cu and Cr. However, it played a significant role in inhibiting the formation of silicate Zn at lower temperatures, promoting the decomposition of ZnO*Al2O3 into unstable Zn. This may explain the higher presence of unstable Zn when Na2CO3 was introduced. In summary, this study offers valuable insights into the transformation characteristics of heavy metals and strategies for pollution control during SCWG of oily sludge.

The interactions between mixed waste from discarded surgical masks and face shields during the degradation in supercritical water.

The widespread use of surgical masks made of polyolefin and face shields made of polyester during pandemics contributes significantly to plastic pollution. An eco-friendly approach to process plastic waste is using supercritical water, but the reaction of mixed polyolefin and polyester in this solvent is not well understood, which hinders practical applications. This study aimed to investigate the reaction of waste surgical masks (SM) and face shields (FS) mixed in supercritical water. Results showed that the optimal treatment conditions were 400 °C and 60 min, achieving a liquid oil yield of 823.03 mg·g-1 with 25 wt% FS. The interaction between polypropylene (PP), polyethylene terephthalate (PET), and iron (Fe) in SM and FS mainly determined the production of liquid oil products such as olefins and benzoic acid. The methyl-branched structure of PP enhanced PET hydrolysis, resulting in higher production of terephthalic acid (TPA). The degradation of PP was facilitated by the acidic environment created by TPA and benzoic acid in the reaction. Moreover, the hydrolysis of PET produced carboxylic acid, which coordinated with Fe3+ to form Fe-H that catalyzed the polymerization of small olefins, contributing to higher selectivity for C9 olefins. Therefore, this study provides valuable insights into the degradation mechanism of mixed PPE waste in supercritical water and guidance for industrial treatment.