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.

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.

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.

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.

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.

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.

Experimental study on alkali catalytic gasification of oily sludge in supercritical water with a continuous reactor.

Realizing the harmless resource utilization of oily sludge is urgent for petroleum industry and of great significance for environmental management. The treatment of oily sludge was investigated using supercritical water gasification (SCWG) with a continuous fluidized bed reactor. The effect of operating parameters on gasification efficiency and gas yield without catalyst was tested, and then the influences of catalyst type (K2CO3 and Na2CO3) and concentrations (1-8 wt%) were systematically studied. The results indicated that a medium mass flow ratio and low feedstock concentration were beneficial for gas production. Alkali catalyst improved carbon gasification efficiency (CE) prominently, and Na2CO3 showed better performance due to its better stability. A maximum CE of 95.87% was achieved when 5 wt% Na2CO3 was added at 650 °C, 23 MPa with 5 wt% oily sludge concentration. Besides, according to XRD patterns of solid residues, Na2CO3 was more stable than K2CO3 during SCWG. SEM-EDX results also revealed that more K was migrated into solid residues than Na. The analysis of pore structure demonstrated that alkali catalyst promoted the evolution of pore structure, resulting in higher specific surface areas and total pore volumes. Na2CO3 has a more substantial destructive effect on solid matrix, causing the matrix structure to collapse and inhibiting pore structure development. The FTIR spectra of solid products exhibited a lower content of carbohydrates and aromatic structures than the initial oily sludge. NH4-N results demonstrated that SCWG was a potential green treatment process for oily sludge. This work can not only give an insight into the reaction mechanism of alkali catalytic gasification of oily sludge, but also help to guide the optimal design of reactor and the regulation of operating parameters.

Red mud with enhanced dealkalization performance by supercritical water technology for efficient SO2 capture.

The total de-alkalization treatment of industrial solid waste red mud (RM) has been a worldwide challenge. Removing the insoluble structural alkali fraction from RM is the key to enhancing the sustainable utilization of RM resources. In this paper, supercritical water (SCW) and leaching agents were used for the first time to de-alkalize the Bayer RM and to remove sulfur dioxide (SO2) from flue gas with the de-alkalized RM slurry. The results showed that the optimum alkali removal and Fe leaching rates of RM-CaO-SW slurry were 97.90 ± 0.88% and 82.70 ± 0.95%, respectively. Results confirmed that the SCW technique accelerated the disruption of (Al-O) and (Si-O) bonds and the structural disintegration of aluminosilicate minerals, facilitating the conversion of insoluble structural alkalis to soluble chemical alkalis. The exchangeable Ca2+ displaced Na+ in the remaining insoluble base, producing soluble sodium salts or alkalis. CaO consumed SiO2, which was tightly bound to Fe2O3 in RM, and released Fe2O3, which promoted Fe leaching. RM-SCW showed the best desulfurization performance, which maintained 88.99 ± 0.0020% at 450 min, followed by RM-CaO-SW (450 min, 60.75 ± 6.00%) and RM (180 min, 88.52% ± 0.00068). The neutralization of alkaline components, the redox of metal oxides, and the liquid-phase catalytic oxidation of Fe contributed to the excellent desulfurization performance of the RM-SCW slurry. A promising approach shown in this study is beneficial to RM waste use, SO2 pollution control, and sustainable growth of the aluminum industry.

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

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

Supercritical water gasification of hyperaccumulators for hydrogen production and heavy metal immobilization with alkali metal catalysts.

The high moisture content and heavy metal concentration of hyperaccumulator are the main bottlenecks of resource utilization. Supercritical water gasification technology was used to convert Sedum plumbizincicola (a hyperaccumulator of Zn and Cd) into hydrogen gas and to immobilize HMs into biochar. Homogeneous alkali metal catalysts such as NaOH, Na2CO3 and Ca(OH)2 were added to optimize the experimental conditions. The results showed that NaOH was effective in capturing CO2in-situ, thereby shifting the water-gas shift reaction equilibrium in the forward direction. And the increase of NaOH concentration had a significant promotion effect on hydrogen production. In the non-catalytic gasification of Sedum plumbizincicola, the highest hydrogen (1.5 mol/kg) and H2 selectivity (22.9%) with greater carbon gasification efficiency (19.3%) and lower H2 gasification efficiency (8.7%) of the gas products were obtained at 400 °C with 6 wt% material concentration for 20 min. However, NaOH at 5% mass fraction maximized hydrogen and H2 selectivity up to 7.5 and 98.2%, respectively. Alkali catalyst not only promoted the generation of hydrogen-rich bio-gas but also enhanced the immobilization efficiency of heavy metals. Compared to non-catalytic, when the addition amount of NaOH was 1 wt%, the Zn、Mn、Cd、Pb、Cr accumulated in biochar increased significantly for 76.8, 42.5, 80.8, 75.6 and 80.0%, respectively. This study highlights the remarkable ability of SCWG with alkali catalyst for hydrogen production and heavy metal stabilization.

Hydrothermal treatment of metal impregnated biomass for the generation of H2 and nanometal carbon hybrids.

The nanocatalyst impregnation onto the biomass matrix has gained importance in enhancing the H2 yield and overcoming the catalyst deactivation problems. In-situ catalytic gasification of Ru/Fe-impregnated sugarcane bagasse and citrus limetta (mosambi peels) were examined and compared with their raw biomass at subcritical and supercritical water conditions. Bagasse having a higher amount of lignocellulosic content produces a maximum yield of H2 over moambi peels. Besides, Ru and Fe nano-metal carbon hybrids with crystalline sizes between 10 and 25 nm were formed during in-situ hydrothermal gasification. The performance of hydrothermal gasification based on hydrogen yield was studied, and it relatively follows the order as temperature, nanoparticle composed, metal loading onto biomass matrix, type of catalyst, and biomass used. At the maximum operating temperature of 600 °C, B: W ratio 1:10 for the resident time of 60 min, highest H2 yield of 12.75 ± 0.17 and 11.20 ± 0.13 mmol/g attained for Ru and Fe impregnated bagasse with the CGE of 72.28 ± 2.17% and 67.08 ± 1.97% respectively. At similar operating conditions, H2 yields of 8.75 ± 0.18 and 8.13 ± 0.16 mmol/g were achieved with the CGE of 62.4 ± 1.91% and 53.7 ± 1.66% for Ru and Fe impregnated mosambi peels, respectively. Based on the H2 and CH4 production, Ru shows the highest performance than Fe catalyst.

Antioxidant and Skin Whitening Activities of Sub- and Super-Critical Water Treated Rutin.

We focused on the functional components, antioxidant activity, skin-whitening, and anti-wrinkle properties of subcritical and supercritical water (SCW)-treated rutin. Rutin treatments were performed at the following temperature and pressure conditions: 200 °C/15 bar, 300 °C/100 bar, and 400 °C/250 bar. ABTS and DPPH radical scavenging activities and reducing power presented their highest values (1193.72 mg AAE/g, 728.73 mg AAE/g, and 0.65, respectively) at 300 °C/100 bar. The tyrosinase inhibitory activity of SCW-treated rutin was 21.72-60.05% at 1 mg/mL. The ethyl acetate fraction showed 14.91% melanin inhibitory activity at a concentration of 10 µg/mL compared to the α-MSH treatment group. The protein expression inhibition rates of MITF, tyrosinase, TRP-1, and TRP-2 in the ethyl acetate fractions were 14.05%, 72%, 93.05%, and 53.44%, respectively, at a concentration of 10 µg/mL, compared to the control. These results indicate that SCW treatment could be used to develop cosmetic materials and functional food with physiological activity, and that SCW-treated rutin can be used as a skin-whitening cosmetic material.

Subcritical and supercritical water oxidation for dye decomposition.

The total annual output of synthetic dyes exceeds 7 × 105 tons. About 1,000 tons of non-biodegradable synthetic dyes are released every year into the natural streams and water sources from textile wastes. The release of these colored wastewater exerts negative impact on aquatic ecology and human beings because of the poisonous and carcinogenic repercussions of dyes involved in coloration production. Therefore, with a growing interest in the environment, efficient technologies need to be developed to eliminate dyes from local and industrial wastewater. Supercritical water oxidation as a promising wastewater treatment technology has many advantages, such as a rapid reaction and pollution-free products. However, due to corrosion, salt precipitation and operational problems, supercritical water oxidation process did not gain expected industrial development. These technical difficulties can be overcome by application of non-corrosive subcritical water as a reaction medium. This work summarizes the negative impacts of dyes and role of subcritical and supercritical water and their efficiencies in dye oxidation processes.

Supercritical Water Oxidation as an Innovative Technology for PFAS Destruction.

Water above 374 °C and 22.1 MPa, becomes supercritical, a special state where organic solubility increases and oxidation processes are accelerated. Supercritical water oxidation (SCWO) has been previously shown to destroy hazardous substances such as halogenated compounds. Three separate providers of SCWO technology were contracted to test the efficacy of SCWO systems to reduce per- and poly-fluoroalkyl substances (PFAS) concentrations from solutions of dilute aqueous film-forming foam (AFFF). The findings of all three demonstration studies, showed greater than 99% reduction of the total PFAS identified in a targeted-compound analysis, including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). PFOS was reduced from 26.2 mg/L to 240 µg/L, 30.4 mg/L to 0.310 µg/L, and 190 mg/L to 8.57 µg/L, from the Aquarden, Battelle, and 374Water demonstrations, respectively. Similarly, PFOA was reduced from 930 to 0.14 µg/L, 883 to 0.102 µg/L, and 3,100 µg/L to non-detect in the three evaluations. Additionally, chemical oxygen demand of the dilute AFFF was shown to reduce from 4,750 to 5.17 mg/L after treatment, indicating significant organic compound destruction. In one demonstration, a mass balance of the influent and effluent found that the targeted compounds accounted for only 27% of the generated fluoride, suggesting that more PFAS were destroyed than measured and emphasizing the limitations of targeted analysis alone. As a destructive technology, SCWO may be an alternative to incineration and could be a permanent solution for PFAS-laden wastewaters rather than disposal by injection into a deep-well or landfilling. Additional investigation of reaction by-products remains to be conducted for a complete assessment of SCWO's potential as a safe and effective PFAS treatment technology.

A successful general fluid-to-fluid similarity theory for heat transfer at supercritical pressure.

The present paper introduces a successful and general fluid-to-fluid similarity theory for heat transfer to fluids at supercritical pressure, having a high degree of universality. This work shortly follows the recent publication of a "local" successful similarity theory developed for fluids at supercritical pressures in a range of conditions in which the values of their molecular Prandtl number were quantitatively similar, extending its conclusions to the case of different molecular Prandtl numbers. The reason why this further step requested a short time to be elaborated is due to recognising that previous work by the Authors had actually already solved the related problems, though in a slightly different way, now interpreted in a more significant frame owing to a better problem understanding. The present similarity theory is based on first ideas developed more than one and a half decade ago by one of the authors, while addressing flow stability of supercritical fluids in heated channels, which encountered immediate problems to be applied in a straightforward way to heat transfer. These ideas were revised and considerably improved during the PhD thesis of the other author, also overcoming a sort of prejudicial assumption that finally resulted to limit their applicability. More recently, published DNS data triggered further reflections on the role of the Prandtl number, leading to the mentioned "local" form of the successful similarity theory. This led to the present step, by just recognising that the mentioned PhD thesis had already proposed a sufficient rationale to extend this local interpretation to a broader range of conditions. The rather convincing results presented herein, obtained making use of RANS CFD analyses with four different fluids, demonstrate the interesting capabilities of this final form of the theory. The establishment of an effective set of dimensionless numbers for heat transfer problems is hoped to pave the way for the development of the still lacking successful engineering heat transfer correlations for supercritical pressure fluids. It further calls for dedicated experiments needed to confirm the suitability of the present theory beyond any reasonable doubt.

Nano-etched fused-silica capillary used for on-line preconcentration and electrophoretic separation of bacteriophages from large blood sample volumes with off-line MALDI-TOF mass spectrometry identification.

The properties of staphylococcal phages from the Siphoviridae, Podoviridae, and Myoviridae families were monitored using capillary electrophoretic methods on fused-silica capillaries with different morphology of surface roughness. Isoelectric points of the examined phages were determined by capillary isoelectric focusing in the original, smooth fused-silica capillary, and they ranged from 3.30 to 3.85. For capillary electrophoresis of phages, fused-silica capillaries with the "pock" and "cone" roughened surface types were prepared by etching a part of the capillary with supercritical water. The best resolution of the individual phages (to range from 3.2 to 4.6) was achieved with the "cone" surface-type fused-silica capillary. Direct application of phage K1/420 at the infection site, represented by human plasma or full blood spiked with Staphylococcus aureus, was on-line monitored by micellar electrokinetic chromatography. The phage particles were dynamically adhered onto the roughened surface of the capillary from 10 µL of the prepared sample at the optimized flow rate of 6.5 µL min-1. The limit of detection was determined to be 104 phage particles. The linearity of the calibration lines was characterized by the regression coefficient, R2 = 0.998. The relative standard deviation (RSD) of the peak area, calculated from ten independent measurements, was (±) 2%. After analysis, viability of the detected phages was verified by the modified "double-layer drop assay" method, and collected phage fractions were simultaneously off-line analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Graphical abstract.

Continuous Synthesis of Nanominerals in Supercritical Water.

The synthesis of minerals should play a crucial role in the development of new and advanced materials. Since 2016, a renewal of interest to enlarge the mineral synthesis towards industrial requirements has been observed, especially thanks to three main recent papers. The innovative process exposed combines a continuous process with the use of supercritical water. In addition to curtail synthesis times, this process offers a control on the particle characteristics (size, crystallinity, structure, etc.) and a capacity to be easily transferable at an industrial scale. This innovative concept is demonstrated with the synthesis of three minerals which are the talc (a phyllomineral), the xonotlite and the tobermorite (two inominerals). This article proposes an overview of the possibilities to synthesize nanominerals in continuous processing for the development of advanced materials with promising industrial applications.

Hydrothermal Ethanol Flames in Co-Flow Jets.

Results on the autoignition and stabilization of ethanol hydrothermal fames in a Supercritical Water Oxidation (SCWO) reactor operating at constant pressure are reported. The flames are observed as luminous reaction zones occurring in supercritical water; i.e., water at conditions above its critical point (approximately 22 MPa and 374 °C). A co-flow injector is used to inject fuel (inner flow), comprising an aqueous solution ranging from 20 %-v to 50 %-v ethanol, and air (annular flow) into a reactor filled with supercritical water at approximately 24.3 MPa and 425 °C. Results show hydrothermal fames are autoignited and form diffusion flames which exhibit laminar and/or turbulent features depending upon flow conditions. Two orthogonal camera views are used; one providing a backlit shadowgraphic image of the co-flow jet and the other providing color images of the flame. In addition, spectroscopic measurements of flame emissions in the UV and visible spectrum are discussed.

Influences of operating parameters on liquefaction performances of Tetra Pak in sub-/supercritical water.

Liquefaction performances of waste Tetra Pak in sub-/supercritical water were evaluated in micro-batch reactors. The influences of temperature (300-420 °C), pressure (16-24 MPa), residence time (5-60 min) and feed concentration (5-40 wt%) on bio-oil yield, high heating value (HHV), and functional groups in bio-oil were investigated. The results showed that bio-oil yield firstly increased with increasing temperature and then decreased when the temperature exceeded 360 °C. Reaction time longer than 30 min gave a negative effect on bio-oil yield. The influence of pressure on bio-oil yield increased markedly from 16 MPa to 22 MPa, and then stabilized. The feed concentration higher than 20 wt% showed little influence on bio-oil yield. Maximum bio-oil yield of 35.55% was found at 360 °C, 22 MPa, 30 min and feed concentration of 20 wt%. HHV and energy recovery efficiency increased significantly with temperature, and maximum HHV of 48.747 MJ/kg and energy recovery efficiency of 46.49% were found at 420 °C, 20 MPa, 30 min and feed concentration of 20 wt%. The main compounds in bio-oil and morphology of the solid residue were also analyzed, and the possible liquefaction pathways of Tetra Pak were proposed.

Novel design concept for a commercial-scale plant for supercritical water oxidation of industrial and sewage sludge.

Supercritical water oxidation (SCWO) is a promising chemical technology for organic waste water and sludge treatment. Our team has successfully constructed the first pilot-scale SCWO plant in China, and the design concept for our first commercial-scale plant is reported in this paper. The challenges that hinder the commercial development of SCWO are introduced, including corrosion, plugging, high investment and operating costs. Some important lab-scale and pilot-scale experimental results are shown, and some key design parameters for the commercial plant are proposed. The technological process, specialized equipment design and new system flowsheet are described objectively. Moreover, an estimate of the equipment investment and operating costs of this commercial plant is carried out, and a comparison is made with other commercial sludge SCWO plants. This information is valuable for guiding how to best design commercial SCWO plants for the treatment of sludge and other feedstocks including solid particles.