Wet Oxidation Research Articles

Mass transfer enhancement for simultaneous desulfurization and denitrification by a venturi reactor

Interphase mass transfer is acknowledged as the rate-limiting step of simultaneous desulfurization and denitrification by wet oxidation. For this issue, this study established a venturi reactor to facilitate interphase mass transfer between flue gas and absorbent (NaClO2 solution), and to improve the efficiency of simultaneous desulfurization and denitrification. The effects of flow rate of jet, NaClO2 concentration, initial pH of solution, SO2 and NO volume concentration on the efficiency of desulfurization and denitrification were investigated. The results showed that SO2 can be completely removed at all experimental conditions. The denitrification efficiency decreased as jet flow rate increased from 8.38 L/ min to 12.87 L/min. The denitrification efficiency and overall mass transfer coefficient increased as the NaClO2 concentration increased from 0.01 wt% to 0.025 wt%. When the pH of the absorbent decreased from 9 to 3, the denitrification efficiency was improved significantly. An increasing SO2 volume concentration promoted NO removal efficiency, while SO2 and NO competed to inhibit denitrification at NaClO2 deficiency. The denitrification efficiency firstly increased and then decreased, with an increasing NO volume concentration from 500 to 1700 ppm. This study provides an important theoretical basis for the industrial application of simultaneous desulfurization and denitrification in venturi reactors.

The degradation of maleic acid with wet peroxide oxidation catalyzed by Al2O3-supported Cu catalyst: effect of inorganic ions

The degradation of maleic acid with wet peroxide oxidation catalyzed by Al2O3-supported Cu catalyst: effect of inorganic ions

Effective decolorization of sulfur black dye and assessment of anti-microbial activity using core/shell nanoparticles based on chitosan

Sulfur dyes, a type of dye produced in large quantities is known for its depth of color. But huge quantities of sulfides, electrolytes, and inorganic salts present in effluents containing sulfur dyes cause serious problems to environment, human, and aquatic life. Hence, in this research, chitosan – sodium tripolyphosphate@TiO2 [chitosan – TPP@TiO2] polymeric core/shell nanoparticles were synthesized by Ionic Gelation Method and their decolorization of sulfur black dye was examined. Structural confirmation was established through XRD and HR-TEM measurements. Surface morphological studies with elemental analysis were investigated using HR-SEM and EDS. Core/shell formation was confirmed through XPS measurements and their optical and thermal properties were explored. Sulfur black dye decolorization studies showed 88.3% decolorization within 6 min under dark conditions at ambient conditions due to the combined effects of adsorption and catalytic wet air oxidation (CWAO). The anti-bacterial and anti-fungal activities of chitosan – TPP@TiO2 core/shell nanoparticles were analyzed.

Performance evaluation of a wet air oxidation reactor with external circulation for high-chemical oxygen demand wastewater treatment

The presence of high-concentration organic contaminants in wastewater poses considerable risks to the health of both humans and ecosystems. Wet air oxidation (WAO) is an attractive treatment option, but current dilution and retreatment processes do not align with economic and environmental principles. Here we report an external circulation wet oxidation treatment process that utilizes oxidizing liquids to reduce feed concentration. By coupling energy consumption model with computational fluid dynamics model, we explore the optimal parameters for an industrial external circulation reactor. A 90 kt/a external circulation wastewater treatment system has been established, achieving a 21.6% increase in chemical oxygen demand (COD) removal efficiency and a 34.8% reduction in energy consumption. These findings provide a promising pathway for the efficient, low-energy treatment of high-concentration organic wastewater while minimizing freshwater resource consumption.

A method for the extraction of microplastics from solid biowastes including biosolids, compost, and soil for analysis by µ-FTIR

Few methods exist detailing the extraction of microplastics from organic matrices. A validated method for the successful extraction of microplastics from solid biowastes including biosolids, compost, and soil for spectroscopic analysis by micro-Fourier transform infrared spectroscopy (µ-FTIR) was developed. Solid dry biowastes were first digested with a wet peroxide oxidation (WPO) with iron (II) solution and 30% hydrogen peroxide followed by sequential density separations with ultra-pure water and 1.8 g cm−3 NaI in an optimised sediment-microplastic isolation (SMI) unit. The average recoveries for spiked microplastics were 92, 95 and 98% for bagged compost, biosolids, and soil, respectively. This method ensures a high microplastic recovery by first chemically disintegrating biowaste aggregates without employing destructive methods like milling and allows for successful density separations where the settled fraction is isolated off from the supernatant, allowing thorough rinsing of the equipment and thus a greater transferal of particles into the vacuum filtering device. Minimal processing steps reduce the instance of introducing contamination and particle loss.•Digestion as a first step to disintegrate aggregates to release entrapped microplastics•Density separation with SMI unit with the method adapted for biowastes•Minimal steps to reduce contamination and particle loss

Selective SERS Detection of TATB Explosives Based on Hydroxy-Terminal Nanodiamond-Multilayer Graphene Substrate.

Selective surface-enhanced Raman scattering (SERS) detection of target explosives with good reproducibility is very important for monitoring soldiers' health and ecological environment. Here, the specific charge transfer pathway was constructed between a stable nanodiamond-multilayer graphene (MGD) film substrate and the target explosives. Two-step wet chemical oxidation methods of H2O2 (30%) and HNO3 (65%) solutions were used to regulate the terminal structure of MGD films. The experimental results showed that the hydroxyl (-OH) functional groups are successfully modified on the surface of MGD thin films, and the MGD-OH substrates having good selectivity for 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) explosive in mixed solutions of the TATB, 2,2-dinitroethene-1,1-diamine, 2,4,6-trinitrotoluene, and 1,3,5-trinitroperhydro-1,3,5-triazine explosives compared with MGD substrates were demonstrated. Finally, first-principles density functional theory simulations revealed that the SERS enhancement of the MGD-OH substrate is mainly attributed to the transferred electrons between the -NO2 groups of TATB and the -OH groups of the MGD-OH substrate.

Application of MgO/ZrO2 coating on 309 stainless steel to increase resistance to corrosion at high temperatures and oxidation by an electrochemical method

Abstract 309 stainless steel is one of the steels that have the highest resistance to corrosion and thermal oxidation compared to other steel grades, but it should not be used at temperatures higher than 980°C if there are temperature fluctuations. Additionally, 309 stainless steel is not designed for use in wet environments and has the least corrosion resistance. This study aims to cover 309 stainless steel with MgO/ZrO2 particles using a two-step electroplating deposition method and then sintering to increase its resistance to wet corrosion and oxidation in temperature fluctuations. The intermediate ZrO2 coating makes the outer MgO layer about two times thicker and reduces the corrosion current density. The morphology of the coatings was determined using scanning electron microscopy and X-ray diffraction, and oxidation resistance was determined using cyclic oxidation tests and the wet corrosion test of the corrosion solution. 3.5% NaCl was used. The results showed that the coated samples, due to the use of TiO2 middle layer and MgO protective layer in the electrochemical method, have a 2-fold increase in wet corrosion and an increase in hardness of about 77%, as well as an increase in oxidation resistance of 1.8% compared to the sample without coating. Also, the reason for using the electrochemical deposition method is for better surface smoothness and less porosity of the coating as well as its use on all metals compared to thermal spray methods.

Synthesis of PbOx to graphite felt anodes to improve the electro-assisted catalytic wet air oxidation of oxygen species for efficient dye degradation

Electro-assisted catalytic wet air oxidation (ECWAO) is an environmentally-friendly pollutant removal process with energy-saving and mild reaction properties. However, it requires an electrode with high catalytic capacity and stability, and the catalytic mechanism behind the process still needs to be further clarified. Herein, we report a graphite felt (GF)-supported PbOx catalyst which can chemically adsorb oxygen and activate it into free radicals by an anodic electric field to promote wet air oxidation. XRD, SEM, EDS, XPS, BET and TG measurements indicated that PbO and PbO2 were successfully doped and loaded onto the GF, increasing the specific surface area and number of active sites. The best RhB degradation efficiencies achieved were 91.26 % over 15 min and 96.68 % over 90 min. The PbOx@C/GF maintained good catalytic performance over eight cycles in the pH range of 3–11 with negligible metal leaching. The RhB degradation pathway of RhB was analyzed through GC–MS results. A free radical quenching experiment, a contrast experiment, and an electrochemical test revealed the process of oxygen being adsorbed by Pb(II) and activated to degrade organic matter was revealed. Five kinds of dyes were degraded by the electrode via the ECWAO process, and the degradation rate reached over 93.7 % within 90 min. The degradation specific energy consumption (SEC) of probe pollutant RhB is 48.70 kW·h/kg-COD. The industrial practical dye wastewater COD removal rate was close to 100 %, and the SEC was 24.44 kW·h/kg-COD. Therefore, it can be concluded that a graphite felt (GF)-supported PbOx catalyst can act as an anode for ECWAO to chemically adsorb oxygen and activate it into free radicals using an anodic electric field to promote wet air oxidation.

Performance, mechanism, and kinetics of NO removal using ligand-enhanced UV-Fenton driven by O2 from flue gas

Wet free radical advanced oxidation technology such as Fenton reaction is thought to be a very efficient method to remove NO from flue gas, but it requires the consumption of additional oxidants to achieve high removal efficiency. For this purpose, a ligand-enhanced UV-Fenton system without additional oxidants was proposed for NO removal. Three common chelating ligands, EDTA, NTA, and Citrate, were selected to promote UV-Fenton reaction for NO removal. The NO removal performance, mechanism, and kinetics of three different ligand-enhanced photochemical Fenton systems including EDTA/UV/Fe(II), NTA/UV/Fe(II), and Citrate/UV/Fe(II), were studied. Results showed that ligand addition can greatly promote a NO removal in the UV-Fenton system, in the following order of efficiency: EDTA > NTA > Citrate. The mechanism research indicated that these ligands not only enhanced NO oxidation removal by promoting the generation of •OH, but also provided NO complexation removal, which synergized oxidative denitrification and complexation denitrification in the same reaction system, greatly promoting wet NO removal. NO from simulated flue gas was mainly converted into NO3−, NO2−, NH4+, N2, and N2O through synergistic complexation-oxidation. The optimum ratio of ligand to Fe(II) was 1:1 for EDTA and NTA and 3:1 for citrate. NO removal efficiency was increased and then decreased with the increase in pH value or O2 concentration. The low temperature was found to be favorable for NO removal. Furthermore, the kinetics demonstrated that the L/UV/Fe(II) system reaction was a pseudo-first-order process involving nitric oxide. Finally, compared with other Fenton and Fenton-like denitrification systems, EDTA(NTA)-enhanced UV-Fenton system had shown great priority in terms of removal performance, absorbent cost, and waste disposal.

The Treatment of Antibiotic Excess Sludge via Catalytic Wet Oxidation with Cu-Ce/γ-Al2O3 and the Production of a Carbon Source

In the present study, the effectiveness of catalytic wet oxidation triggered by using Cu-Ce/γ-Al2O3 to degrade antibiotic excess sludge was investigated, during which some small molecule carboxylic acids were produced, which are valuable in biological wastewater treatment as an organic carbon source. The influence of reaction parameters on the degradation efficiency was explored through single-factor and orthogonal experiments, including catalyst amount, reaction temperature and time, and oxygen supply amount. The results illustrated that the treatment system can achieve 81.2% COD and 93.8% VSS removal rates under optimized reaction conditions. Carboxylic acids produced after the sludge degradation mainly included acetic acid, propanoic acid, etc. The results of wastewater biological treatment experiments exhibited that the degraded solution after catalytic wet oxidation has potential to be used as a carbon source to meet the demand of biological treatment, which helps the removal of COD and TN. This work confirms the effectiveness of catalyst for enhancing antibiotic excess sludge treatment, which provided a new idea for the rational disposal of antibiotic excess sludge.

Catalytic wet oxidation degradation of malachite green with Cu-coated sediment as catalyst: parameter optimization using response surface methodology

Catalytic wet oxidation degradation of malachite green with Cu-coated sediment as catalyst: parameter optimization using response surface methodology

Wet oxidation of TiZrHfNbTaV high-entropy alloys: Role of grain-boundary and interdendritic diffusion

Refractory high-entropy alloys (RHEAs) are sensitive to thermal oxidation, significantly restricting their service performance and potential applications. However, the wet oxidation behavior of RHEAs has remained poorly understood despite the potential risk of catastrophic oxidation caused by water vapor. In this study, the oxidation mechanism of an equiatomic TiZrHfNbTaV high-entropy alloy (HEA) has been investigated in a wet atmosphere at elevated temperatures. Synchronous oxidation of all elements occurs at temperatures below 800 °C. At temperatures above 800 °C, preferential oxidation of Nb, Ti, and Zr, and internal oxidation of V occur on HEAs, which are thermodynamically less preferred as compared with oxidations of more reactive Hf and Ta. Experimental and theoretical analyses show that the oxide grain boundaries and substrate interdendritic regions of HEAs act as diffusion pathways for V and oxidizing species during preferential and internal oxidation processes. This work provides a fundamental understanding of the oxidation of multicomponent alloys in wet environments, which is helpful in the development of effective oxidation resistance strategies and innovative surface engineering techniques.

New perspectives of Pt–CeO2 system: stabilization on MWCNTs for boosting activity and water‐resistance in CO oxidation at ambient temperatures

The present study elucidates new perspectives regarding the Pt–CeO2 system for CO oxidation. The successful deposition of highly dispersed Pt–CeO2 species onto the surface of multiwalled carbon nanotubes (MWCNTs) led to the formation of abnormally active and water‐resistant catalysts. The catalysts were investigated by structural (XRD, TEM), spectral (XPS), and kinetic (TPR–CO+O2, TPR–CO, TPR–H2) methods. The application of TPR–CO+O2 revealed the remarkably high activity of all Pt–CeO2/MWCNTs catalysts at temperatures below 0 °C. The study of the catalysts at ambient temperature demonstrated high CO conversion in the presence of water vapor at a concentration of 100 ppm CO. The experimental findings suggest that active sites, comprising platinum structures stabilized directly on the surface of MWCNTs, play a pivotal role in the oxidation of CO under humid conditions. A dual–site approach was employed to develop a kinetic model that effectively describes the experimental data. This model provides valuable insights into the mechanism of wet CO oxidation.

Lodo do Curtimento de couro em Argamassa: Valorização Sustentável

Purpose: This study aims to investigate the valorisation of sludge from Leather Tannery Wastewater Treatment Plants (LTWWTP) by incorporating it into cement mortars. Theoretical framework: The substantial quantity of waste generated by industries coupled with the scarcity of natural resources calls for the analysis, development, and implementation of treatment methods to recover and reuse materials, thereby minimising the environmental impact of waste disposal. The leather tanning industry, a significant polluter due to its use of hazardous and heavy materials, requires sustainable solutions for waste management. One promising approach is the incorporation of waste into cementitious matrices. Method: Three scenarios were examined: low-moisture sludge, ash obtained via incineration, and wet oxidation. Test specimens were prepared with varying proportions of cement replacement (0, 3, 5, 7, and 10%), and their flexural and compressive strengths were evaluated. Additionally, chemical analyses were conducted to assess solubility. Results and Conclusion: The results indicate that sludge can be used in small proportions without compromising the mechanical strength of the mortar. Substituting 10% cement with ash using the INC-2 incineration method improved mortar quality, exhibiting a higher compressive strength of 41 MPa and minimal water absorption (3.28%). Research implications: Drawing from these promising findings, it can be confidently asserted that utilising WWTP sludge in mortar is a practical, eco-conscious solution for civil construction. Furthermore, it is a pivotal step towards addressing the challenge of hazardous sludge disposal. Originality/value: The findings from this research will contribute to sustainable waste management practices and pave the way for responsible and eco-friendly utilisation of industrial waste in cementitious materials, thus minimising environmental burdens.

Stormwater runoff microplastics: Polymer types, particle size, and factors controlling loading rates

Stormwater runoff is a pathway of entry for microplastics (MPs, plastics <5 mm) into aquatic ecosystems. The objectives of this study were to determine MP size, morphology, chemical composition, and loading across urban storm events. Particles were extracted from stormwater samples collected at outfall locations using wet peroxide oxidation and cellulose digestion followed by analysis via attenuated total reflectance (ATR) FTIR. Concentrations observed were 0.99 ± 1.10 MP/L for 500–1000 μm and 0.41 ± 0.30 MP/L for the 1000–5000 μm size ranges. Seventeen different polymer types were observed. MP particle sizes measured using a FTIR-microscope camera indicated non-target size particles based on sieve-size classification, highlighting a potential source of error in studies reporting concentration by size class. A maximum MP load of 38.3 MP/m2 of upstream catchment was calculated. MP loadings had moderate correlations with both rainfall accumulation and intensity (Kendall τ = 0.54 and 0.42, respectively, both p ≤ 0.005). First flush (i.e. rapid wash-off of pollutants from watershed surfaces during rainfall early stages) was not always observed, and antecedent dry days were not correlated with MP abundance, likely due to the short dry periods between sampling events. Overall, the results presented provide data for risk assessment and mitigation strategies.

An improved method for isotopic and quantitative analysis of dissolved organic carbon in natural water samples.

A wet chemical oxidation (WCO) method has been widely used to obtain the dissolved organic carbon (DOC) content and carbon isotope (δ13CDOC) ratios. However, it is sometimes difficult to get high precision results because not enough CO2 was oxidized from the natural water samples with low DOC concentrations. This improvement primarily aims to increase the water sample volume, improve the removal rate of dissolved inorganic carbon (DIC), and minimize the blank DOC from the standard solution. Following the improved procedure, the δ13C ratios of standardized DOC solutions were consistent with their actual values, and their differences were less than 0.2‰. The improved method demonstrated good accuracy and stability when applied to natural water samples with DOC concentrations ≥0.5 mg L-1, with the precisions of DOC concentrations and δ13C ratios were better than 0.07 mg L-1 and 0.1‰, respectively. More importantly, this method saved much pre-treatment time and realized batch processing of water samples to obtain their DOC contents and isotope ratios.

Continuous wet air oxidation of aqueous phase from hydrothermal liquefaction of sewage sludge

The conversion of organic waste into advanced fuels through hydrothermal liquefaction (HTL) is a promising route. However, for the commercialisation of HTL technology, treatment and valorisation of the generated aqueous by-product are required for its economic viability. This study investigates subcritical non-catalytic continuous wet air oxidation (WAO) for the treatment of the aqueous phase from hydrothermal liquefaction (HTL-AP) of sewage sludge. A custom-made tubular reactor was used at temperatures and residence times similar to the HTL process (300–350 °C; 6–50 min), with excess air equivalent to 1.5–2 times the oxygen demand. The WAO process removed up to 95.3 % of the chemical oxygen demand and 91.8 % of the total organic carbon, generating volatile fatty acids, mainly acetic acid, as intermediary compounds from the oxidation reactions, and CO2 and H2O from the pollutant’s complete degradation. The process effectively eliminated almost all of the organonitrogen compounds, generating NH4+, which reached values of up to 97 % of the total nitrogen. Comprehensive molecular characterization performed by FT−Orbitrap MS analysis revealed that the main basic organonitrogen compounds in HTL-AP are distributed in the O1N1, N2, O1N2, N1 classes. For neutral to acidic organonitrogen species, O3N1 is the most representative chemical class. The energy consumption for heating the WAO reactor was up to 40 % lower using HTL-AP compared to blanks experiments. Despite good process water clean-up, autothermal operation was not achieved, and improvements in the reactor design are suggested.

UV-A assisted catalytic wet peroxide oxidation: Activity of iron minerals in the degradation of DEET

The widespread use of insect repellent N,N’-diethyltoluamide (DEET), along with its low biodegradability, has made this an ubiquitous contaminant in waterbodies. This work explores the elimination of DEET (10 mg/L) in aqueous matrices employing natural iron minerals ilmenite (FeTiO3), hematite (Fe2O3), goethite (Fe(OOH)) and magnetite (Fe3O4) as low-cost catalysts in UV-assisted Catalytic Wet Peroxide Oxidation, using UV-A LEDs (λ: 395 nm) as radiation source in a 500 mL useful-volume reactor. Under the studied conditions, magnetite presented a higher activity, significantly superior to that of the other minerals. A parametric study evaluating the effect of the catalyst load, initial pH, H2O2 dose, UV irradiance and water matrix was performed. Magnetite is able to carry out DEET degradation working at circumneutral pH (pH: 5) with outstanding results in terms of DEET removal even in complex matrices such as river water and WWTP effluent. Furthermore, the catalyst presented an excellent stability. Still, under the optimal operating conditions of this study ([Fe3O4]: 500 mg/L, [H2O2]0: 61.1 mg/L, pH0: 5, T: 25ºC, t: 120 min), only 27.8% mineralization was reached in ultrapure water. Nonetheless, the remaining organic compounds are mainly short-chain organic acids (malonic, oxalic, acetic and formic acids), which account for 98.7% of the residual organic carbon. These compounds, which are readily biodegradable, present a lower phytotoxicity than that of DEET, demonstrating the potential of UV-CWPO for the elimination of this emerging contaminant.

Natural magnetite as an effective and long-lasting catalyst for CWPO of azole pesticides in a continuous up-flow fixed-bed reactor

The global occurrence of micropollutants in water bodies has raised concerns about potential negative effects on aquatic ecosystems and human health. EU regulations to mitigate such widespread pollution have already been implemented and are expected to become increasingly stringent in the next few years. Catalytic wet peroxide oxidation (CWPO) has proved to be a promising alternative for micropollutant removal from water, but most studies were performed in batch mode, often involving complex, expensive, and hardly recoverable catalysts, that are prone to deactivation. This work aims to demonstrate the feasibility of a fixed-bed reactor (FBR) packed with natural magnetite powder for the removal of a representative mixture of azole pesticides, recently listed in the EU Watch Lists. The performance of the system was evaluated by analyzing the impact of H2O2 dose (3.6–13.4 mg L−1), magnetite load (2–8 g), inlet flow rate (0.25–1 mL min−1), and initial micropollutant concentration (100–1000 µg L−1) over 300 h of continuous operation. Azole pesticide conversion values above 80% were achieved under selected operating conditions (WFe3O4 = 8 g, [H2O2]0 = 6.7 mg L−1, flow rate = 0.5 mL min−1, pH0 = 5, T = 25 °C). Notably, the catalytic system showed a high stability upon 500 h in operation, with limited iron leaching (< 0.1 mg L−1). As a proof of concept, the feasibility of the system was confirmed using a real wastewater treatment plant (WWTP) effluent spiked with the mixture of azole pesticides. These results represent a clear advance for the application of CWPO as a tertiary treatment in WWTPs and open the door for the scale-up of FBR packed with natural magnetite.

Microplastic contamination in rivers: a survey from the Nan River, Thailand

BackgroundSince the 1970s, microplastic contamination has been discovered in various environments. These emerging pollutants threaten water quality and freshwater ecosystems. We aimed to assess microplastic contamination in the Nan River by quantifying their presence, characterising their morphology, and identifying their polymer composition. MethodsThe survey was conducted along the Nan River in northern Thailand, which is divided into three distinct zones based on land use (ie, community areas, agricultural areas, and natural areas). A wide array of samples, including surface water, sediment, and specimens from five aquatic species—Barbonymus altus, Laides hexanema, Kryptopterus cryptopterus, Pomacea canaliculata, and Pseudodon cambodjensis cambodjensis—were collected. The presence of microplastics was analysed via the wet peroxide oxidation process for sample digestion, morphological characteristics were assessed through microscopic examination, and Fourier transform infrared spectrophotometry was used to identify the polymer composition of the microplastics. FindingsNatural areas had the highest mean concentration of microplastics in surface water (23·67 pcs/L, SD 14·22), whereas community areas had the highest mean concentration in soil sediment (24·67 pcs/g, 15·04). No statistically significant differences in the amounts of microplastics were observed among the various land-use zones. Microplastics were predominantly found in the gastrointestinal tracts of fish specimens, with varying quantities observed among different aquatic species; B altus had the highest concentration (11·80 pcs/g, 8·98). The primary microplastic shapes identified were filaments (53·99%), fragments (35·58%), and cylindrical forms (10·43%). We identified ten different polymer types, with polypropylene, nylons, and polymethyl methacrylate being the most prevalent among them. InterpretationAnalysing microplastic pollution in this area brings attention to the issues affecting the rivers of Thailand and emphasises ecological risks, particularly microplastic presence in aquatic species. Because of the Nan River's ecological importance, we call for increased research and collaboration to address the increasing threat of microplastic pollution. FundingNaresuan University.