Supercritical Water Oxidation Research Articles

Experimental and kinetic study of methanol/ethanol assisted oxidative degradation of ammonia in supercritical water

Ammonia is a refractory intermediate during supercritical water oxidation (SCWO) of nitrogen-containing wastes, and alcohols are usually introduced as auxiliary fuels to accelerate its degradation. The kinetics of methanol/ethanol assisted oxidative degradation of ammonia in supercritical water have been investigated in a flow reactor, covering alcohol-to-ammonia ratios of 0.2–2.0. During SCWO of ammonia-methanol mixtures, ammonia was mostly converted to N2, with N2O as the main by-product. Increasing methanol concentration facilitated effectively the degradation of ammonia. For the cases with ethanol assistance, high concentrations of HCN were detected at the investigated temperature. Increase in ethanol concentration enhanced ammonia conversion, but had a non-monotonic influence on N2 production. A detailed chemical kinetic model was developed by integrating the nitrogen chemistry with methanol/ethanol mechanisms. The model performance was further validated by comparing to the present and literature data. The model reproduced the ammonia conversions at different conditions fairly well, but overpredicted the N2 yield and underpredicted the NO2 and HCN yields slightly. Based on the model, reaction mechanism was inferred and important elementary steps were identified through kinetic analyses. Finally, the influence of process parameters on ammonia degradation rate was numerically explored. This study is expected to facilitate the application of SCWO technology for N-containing wastes treatment.

Field Demonstration of PFAS Destruction in Various Alcohol-Resistant AFFFs Using Supercritical Water Oxidation (SCWO)

Field Demonstration of PFAS Destruction in Various Alcohol-Resistant AFFFs Using Supercritical Water Oxidation (SCWO)

Thermodynamic analysis of a solar-driven supercritical water gasification-oxidation system for ammonia production and heat supply from chicken manure

Faced with the dual challenges of energy shortage and environmental pollution, researchers are turning to extracting clean energy from waste resources. The coupled system of solar energy and supercritical water gasification offers a novel solution to these issues. In this study, a solar-driven supercritical water gasification-oxidation system for ammonia production and heat supply from chicken manure was simulated. Additionally, the effects of temperature of supercritical water gasification, chicken manure slurry concentration, water-dry matter ratio, and pressure of supercritical water gasification and oxidation on the system's products, efficiency, and device exergy losses were examined. Under typical working conditions (the temperature of supercritical water gasification: 750 °C, chicken manure slurry concentration: 50 wt%, water-dry matter ratio: 5, the pressure of supercritical water gasification and oxidation: 25 MPa), and the system had a treatment capacity of 5 t/h of dry chicken manure. The system yielded 2604.04 kg/h of NH3 and 23763.9 kg/h of heating steam. It demonstrated an energy efficiency of 68.38% and an exergy efficiency of 46.85%. The total exergy losses of the system amounted to 34704.73kw, with the solar collector accounting for the largest share at 49.6%. The temperature of supercritical water gasification and water-dry matter ratio significantly impacted the system efficiency. Conversely, chicken manure slurry concentration and the pressure of supercritical water gasification and oxidation exerted minimal influence. The solar collector and gasification reactor emerged as the primary contributors to exergy losses in the entire system. Notably, the lower temperatures of supercritical water gasification, chicken manure slurry concentrations, pressures of supercritical water gasification and oxidation, and water-dry matter ratios can reduce exergy losses in both the solar collector and the gasification reactor.

Thermodynamic and economic comparisons of supercritical water oxidation and gasification of oily sludge under hydrothermal flames

Dual-shell reactors using hydrothermal flames as internal heat source were proposed for supercritical water gasification (SCWG) and oxidation (SCWO) of oily sludge to achieve fast preheating and avoid corrosion, salt plugging, and overheating. The SCWG and SCWO systems with hydrogen-rich syngas and electricity outputs, respectively, were established and simulated using Aspen Plus 11. Simulation models were validated by comparing with experimental products and temperature profiles. The maximum exergy destruction coefficients of 28.01% and 24.31% appear in the combustion reactor for both the SCWG and SCWO systems, respectively, indicating the indirect preheating method with hydrothermal flame is critical to the energy efficiency. The increase of reaction temperature promotes hydrogen but inhibits methane formation in the SCWG, and more steam but less syngas is output at higher reaction temperatures. Although more steam and electricity outputs are present at higher reaction temperatures for the SCWO, more fuel input is required. Lower exergy efficiencies are obtained at higher reaction temperatures in both the SCWG and SCWO systems for more energy is output as low grade steam. Less fuel input is required for both the SCWG and SCWO systems at higher feed concentrations, and higher exergy efficiencies can be obtained. The net treatment cost for the SCWG and SCWO systems are 119.19 and 215.47 USD/t, respectively, indicating the SCWG is more economically competitive compared with the SCWO.

An experimental and modeling study of propane oxidation kinetics in low temperature supercritical water

Propane oxidation in supercritical water was investigated at iso-thermal iso-baric conditions using a batch reactor facility. Mixtures were comprised of 0.014 % propane by volume with an equivalence ratio of 0.8 and a total density of 222 mg/mL or 610 mg/mL. Reaction times ranged from 8 to 30 min for a temperature of 375ºC at 220 or 400 bar, or 400ºC at 220 bar. Major reaction products were CO and CO2 and minor products were propene, acetone, ethene, ethanol, methane, methanol and hydrogen. New detailed chemical kinetic models were developed by combining and refining existing models using genetic optimization. Model predictions exhibited excellent agreement with experimental observations, and indicated that rates of H-abstraction and OH addition reactions involving alkanes and alkenes are affected by the supercritical water environment. Model accuracy was highly sensitive to the rates of CH3O2H = CH3O + OH and CH3 + H2O2 = CH4 + HO2.

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 implicationAsphaltene 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.

Effect of methane addition on supercritical water oxidation of poultry manure in the flow mode

The paper presents the research results of the supercritical water oxidation (SCWO) of poultry manure continuously fed into a tubular reactor both in the absence and presence of methane as an auxiliary fuel. The tests were conducted at a temperature gradient along the vertical axis of the reactor (top to bottom: 390–600 °C), a pressure of 25 MPa, and varying reagent flow rates. It is shown that due to heat generation during methane oxidation the energy consumption from external sources is reduced by 1.3–1.5 times depending on the ratio of reagent flow rates. The gas products contain CO2, N2, and trace amounts of N2O. The ash residues are predominantly composed of calcite and hydroxyapatite. The addition of methane results in a reduction in the content of phenols and polycyclic aromatic hydrocarbons present in the aqueous effluent, while content of N-bearing aromatics increases. The formation of nitrophenols was observed at elevated oxygen concentrations in the reaction mixture. It was revealed that excess oxygen plays a pivotal role in the efficacy of organic nitrogen removal. The formation of mineral acids and a high level of ammonia in the reaction mixture during the SCWO of poultry manure result in corrosion of stainless steel and copper seals, which in turn leads to an increased concentration of chromium and copper in the aqueous effluent. The results obtained indicate the potential for utilizing natural gas in an environmentally friendly and resource-saving manner for poultry manure processing by SCWO in autothermal mode.

Corrosion characteristics of Fe, Ni and Ti based alloys near the critical point of water and during supercritical water gasification and oxidation of municipal sludge

Supercritical water gasification (SCWG) and oxidation (SCWO) were promising technologies for treating municipal sludge; however, corrosion hindered their development. To obtain the candidate material for preheaters, corrosion characteristics of 316, 316 L, Incoloy 800, 825, and TA-10 were investigated at 350 °C and 400 °C. For SCWG and SCWO reactors, corrosion behaviors of 316, Incoloy 800, 825, Inconel 600, 625, and Hastelloy C276 were explored at 450 °C and 520 °C, with and without oxidants. Near the critical point of water, corrosion rates of all materials were below 0.4 mm·a−1, with 316 L being the candidate material. According to the pH variation, materials underwent activation (350 °C) and passivation (400 °C) pathways. During SCWG and SCWO, Incoloy 825 and Inconel 625 were prioritized at 450 ℃ and 520 ℃, exhibiting corrosion rates below 0.40 mm·a−1 and 0.50 mm·a−1, respectively. Chemical corrosion dominated and double-layer oxide films (Fe3O4-FeCr2O4 and NiO-Cr2O3) formed.

Safety Management and Accident-Control Strategy for a Commercial-Scale Plant for Supercritical Water Oxidation of Sludge

Supercritical water oxidation is a promising technology for decomposition of industrial wastewater and sludge. However, the system is operated under high temperature and pressure (usually higher than 500 °C and 25 MPa). Corrosion of component materials and salt deposition may lead to leakage or even the burst of the pressure vessel in the SCWO system, resulting in a high level of worry about the safe operation of the system. In this paper, the safety management and accident- control strategies are introduced according to a commercial-scale SCWO plant in China. The safety management strategy refers to the special design and operation strategies of some facilities. Different types of potential accidents are analyzed and the coping strategies for accidents of different levels of severity are described in detail. The strategies are valuable for the safe operation of commercial SCWO plants and other plants operated in high temperature and high pressure.

Experimental investigation and thermomechanical performance evaluation of supercritical water oxidation of n‐dodecane/tributyl phosphate

AbstractBACKGROUNDNuclear energy has brought immense benefits while also generating a large amount of wastewater that urgently needs to be processed. Supercritical water oxidation (SCWO) technology serves as an efficient method for wastewater treatment. In this study, a SCWO experiment was carried out with organic solvent of 30% tributyl phosphate (TBP) and 70% n‐dodecane. This study investigated the operating parameters and the effects of enhanced oxidation techniques on chemical oxygen demand (COD) removal efficiency. An organic solvent SCWO process was developed, and its energy and exergy efficiencies were assessed using Aspen Plus.RESULTSThe COD removal was about 96.18% at the experimental parameters of 500 °C, 10 min, 25 MPa, oxidation coefficient of 1.5 and material concentration of 4 wt%. COD removal increased by 3.09% with the addition of CeO2. Finally, the overall energy and exergy efficiencies of the SCWO system were found to be 58.8% and 9.1% respectively by Aspen Plus.CONCLUSIONIt was found that the reaction temperature had the greatest effect on the COD removal rate compared with other reaction parameters. The decomposition of organic solvents can be divided into two stages, fast and slow, and the addition of alkali and catalyst can effectively promote the decomposition of waste organic solvents. The experiments showed that SCWO is feasible for the treatment of n‐dodecane/TBP. © 2024 Society of Chemical Industry (SCI).

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.

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

ABSTRACT 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.

Effect analysis on recycling of cathode material from spent ternary lithium-ion batteries via supercritical water oxidation and acid-leaching

This study proposed a recycling method for spent batteries by combining supercritical water oxidation and acid-leaching. In supercritical water oxidation process, the cathode material was separated from the electrode plate, and 98% of lithium in the cathode was leached to achieve the separation of lithium from Ni, Co and Mn. Ni, Co and Mn were then leached during the acid leaching process. The effect of solid-liquid ratio, oxidant mass concentration, reaction time and temperature in supercritical process on metal leaching was analyzed. The leaching rate of Ni, Co and Mn was improved by increasing the mass concentration of oxidant and the reaction temperature. The effect of reaction time on metal leaching is related to the mass concentration of oxidant in the solution. Through the control of paraments, the leaching efficiencies of Ni, Co and Mn were significantly improved from 90.4%, 84.7%, 86.4–99.7%, 96.8% and 98.5%.

Bench-scale supercritical and near-supercritical water oxidation assays to treat Propylene Oxide-Styrene Monomer (POSM) wastewater

Supercritical Water Oxidation is a promising technology to deal with the phenolic-benzoic nature of the wastewater from Propylene Oxide-Styrene Monomer processes. To assess its feasibility to meet discharge regulations for a continuous process, lab-scale assays were conducted with real wastewater. After a screening to maximize Chemical Oxygen Demand (COD) removal efficiency, a supercritical, four-hour duration test was run at 550 °C, 235 bar g, with 50% excess oxygen and residence time of 120 seconds. Though a successful COD degradation of 99.97 ± 0.01% was achieved, salt scaling and corrosion occurred. The key findings are that to redissolve salts and avoid corrosion, focus must be on the supercritical to subcritical transition location. Near-supercritical oxidation was also tested as a cost-effective alternative to avoid scaling. Residence times up to 192 min were required at 300 °C, 165 bar g and 40% excess oxygen to achieve similar degradation obtained to supercritical conditions.

Tracking contaminants in the aqueous effluent during supercritical water gasification and oxidation of swine manure in the flow mode

Biomass waste processing is an area of great interest due to its potential for reducing environmental impact and recovering resources. The present work investigates for the first time the composition of products resulting from supercritical water (SCW) gasification and oxidation of swine manure (SM) continuously fed into a tubular reactor at a temperature gradient along its vertical axis of 390–600 °C and a pressure of 25 MPa. Special attention is paid to how the operating parameters, including SM flow rate (6.5–10.7 g/min), oxidation ratio (OR ≤ 1.78), and the presence of NaOH additive (1 wt%) influenced the composition and concentration of contaminants (phenols, N-bearing aromatics, polyaromatic hydrocarbons (PAHs), and ammonia) in the effluent collected at the reactor outlet. The results of gas chromatography-mass spectrometry indicate that water-soluble products comprise predominantly of phenols, pyridines, pyrroles, indoles, pyrazines, anilines, and quinolines. Increasing the reagent’s residence time during SCW gasification was observed to lower the amount of phenols in the effluent. In addition, the introduction of NaOH increases the yields of syngas and NH3 while lowering the concentration of N-bearing aromatics and PAHs. SCW oxidation of SM not only reduces contaminant levels in the effluent by several orders of magnitude, but also partially compensates for thermal inputs needed for the process implementation. Among N-bearing compounds, ammonia, pyridines, indoles, and quinolines display the highest resistance to oxidation. The paper explores the resource-saving and ecological benefits of SCW gasification and oxidation of SM.

Supercritical Fluids as Solvents for the Future

High pressure technologies involving sub and supercritical fluids offer the possibility to obtain new products with special characteristics or to design new processes, which are environmentally friendly and sustainable. Supercritical fluids are flexible tools for processing materials. Supercritical fluids have been applied to mass-transfer processes, phase-transition processes, reactive systems, materials-related processes, and nanostructured materials. In addition to extraction, application areas include impregnation and cleaning, multistage countercurrent separation, particle formation, coating, and reactive systems such as hydrogenation, biomass gasification, and supercritical water oxidation. Polymers are modified with supercritical fluids, and colloids and emulsions as well as nanostructured materials exhibit interesting phenomena when in contact with supercritical fluids that can be industrially exploited.

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.

Experimental and kinetic modeling study of acetic acid oxidation and hydrolysis in supercritical water

The oxidation and hydrolysis of 0.11–0.14 M acetic acid in supercritical water (SCW) have been investigated at temperatures of 773–873 K and a pressure of 25.0 MPa in a flow reactor. CO and CO2 were the main products at oxygen-rich conditions. For hydrolysis experiments, CH4 and CO2 were produced in nearly equal amounts while the yield of CO was negligibly small. A detailed chemical kinetic model was developed by revising the kinetic parameters of key elementary reactions. The model performance was evaluated by comparison to the present data as well as data from literature. The model predicted the kinetic behavior of acetic acid oxidation fairly well, despite of slight underprediction of CO and overprediction of CH4. It also reproduced satisfactorily the species concentrations during acetic acid hydrolysis at high temperatures. Based on the model, kinetic analyses were further conducted to identify important elementary steps and to infer reaction mechanisms.

Energy yield from wastewater by supercritical water oxidation process: Experimental validation and simulation from the viewpoint of energy system

The degradation of high concentration organic wastewater and the recovery of energy using supercritical water oxidation (SCWO) technology have the potential to become viable in the future. High concentration organic wastewater contains a significant amount of energy. This paper focuses on utilizing high concentrated wastewater as a renewable energy source, from an energy system perspective, an experimental rig was designed to determine the optimal working conditions. The experiments were conducted with an oxidation coefficient of 1.1, a flow rate of high concentration organic wastewater of 9 ml/min, a heating temperature of 400 °C, and a reaction pressure of 25 MPa. Under these conditions, the COD and TOC removal rates of the high concentration organic wastewater were found to be 99.383 % and 99.876 % respectively. Additionally, the phenomenon of “Abnormalities in pressure sensitivity” observed during high concentration organic wastewater the experiment was further explained through additional experiments. Finally, by comparing the experimental energy recovery with the simulation results, an energy recovery efficiency of 78.95 % was achieved. The feasibility of the simulated energy recovery in practice was verified, confirming the potential to convert the previous energy-consuming wastewater treatment process into a productive one. This study provides a theoretical and experimental foundation for further related research.

Tube explosion during continuous supercritical water oxidation of sludge: An incident investigation

Supercritical water oxidation (SCWO) is well known as a promising end-of-pipe technology for treatment of hazardous wastes. Safety is undoubtedly the first concern as the SCWO should be operated under a harsh chemical and physical environment, including high temperature, high pressure, and high corrosive medium and plugging risk. This paper is the first report about a tube explosion incident that encountered during continuous SCWO treatment of industrial sludge. 3D imaging, Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) and 3D finite element analysis are used to analyze the incident tube comprehensively. The results indicate that the incident tube was working at a hash corrosive environment of subcritical water and chloride, which leads to all of general, pitting and intergranular corrosions. Of which, the pitting is the most severe one that finally results to perforation. Then, leakage took place. Soon afterwards, the hard inorganic particle from sludge plugged the leaking pore for a second, but immediately split it as a big hole due to the local high pressure around the leaking pore. Finally, explosion occurred. Three lessons are drawn for the future safe design and operation of SCWO, i.e., selecting suitable pressure bearing material, checking regularly, and executing safety regulations.