Ozone Mass Transfer Research Articles

Applying both kinetic and thermodynamic measures to promote solar-driven photocatalytic ozonation on defect-engineered porous tungsten oxide

Mass transfer of ozone within the inner structure of a catalyst and utilization efficiency of the photo-generated electrons are two decisive factors governing the production of hydroxyl radicals (•OH) in photocatalytic ozonation process from kinetic and thermodynamic perspectives, respectively. For achieving precise dual-control, defect-engineered tungsten oxide with a periodic porous architecture (p-WO3-OV) is synthesized. Compared with pristine WO3, p-WO3-OV achieves a 7.6-fold increase in the reaction rate of solar photocatalytic ozonation, accompanied by a 2.3-fold enhancement in the ozone utilization efficiency. The constructed periodic porous structure shortens the migration path of charge carriers and promotes the fluidity of the reactants. The rich oxygen vacancies in WO3 enhance the generation of charge carriers and promote O3 interactions. This work provides mechanistic insights into both the kinetic boost endowed by porous nanoarchitecture, and the thermodynamic modulation enabled by defect engineering to achieve the synergy in solar-driven photocatalytic ozonation.

Effect of the Fe2O3/SBA-15 Surface on Inducing Ozone Decomposition and Mass Transfer in Water

Effect of the Fe2O3/SBA-15 Surface on Inducing Ozone Decomposition and Mass Transfer in Water

The effect of pre-treatments on atrazine removal from source water by microbubble ozonation.

Ozone-based advanced oxidation processes (AOPs) have emerged a promising avenue for water treatment, offering effective removal of micropollutants. Recent research underscores the potential of ozone microbubbles to enhance ozone mass transfer during water treatment, particularly when combined with pre-treatment steps. This study aimed to evaluate the efficacy of three different combined processes (chlorine/KMnO4/PAC pre-treatment followed by ozonation) in removing atrazine, a common micropollutant from natural source water. Results revealed that all combined processes achieved higher atrazine removal rates compared to individual pre-treatment or ozonation methods. Notably, the highest atrazine removal rates were observed under alkaline pH conditions, with treatment outcomes influenced by oxidant dose and pH levels. Among the combined processes, chlorine pre-treatment followed by ozonation emerged as the most effective approach, achieving a removal rate of 59.7% that exceeded the sum of individual treatments. However, this treatment efficacy was affected by water quality parameters, particularly the presence of organic matter and elevated ammonia nitrogen concentration (> 0.5mg/L). This study highlights the potential for utilizing ozone micro/nanobubbles to enhance ozone mass transfer and offers valuable insights for optimizing the combined application of pre-treatment and ozonation strategies for efficient atrazine removal from natural water sources.

Enhancing ozonation technology: A case study on full-scale airlift reactor upgrades in the existing wastewater treatment plant's ozonation tank using CFD

Traditional pneumatic bubble column reactors (PBCRs) in wastewater treatment often have limitations in ozone distribution and disinfection efficacy. This study introduces an optimized Airlift Reactor (ALR) design, enhanced with Computational Fluid Dynamics (CFD), to improve ozone contact time and uniform distribution. Tailored for the SONATRACH GP1/Z Complex in Bethioua, Algeria, the ALR addresses the treatment needs of the facility's WWTP Phase-1, handling domestic wastewater. The study is unique for its full-scale implementation of the ALR, as previous research focused on lab-scale cases. Advanced CFD simulations optimized the ALR design, focusing on baffle configurations to enhance ozone disinfection. The upgraded One Side Baffled Airlift (OS-BALR) variant achieved a Total Coliform inactivation rate of 94.52 %, compared to 74 % with the traditional design. The OS-BALR also demonstrated a lower ozone mass transfer coefficient (KLa) of 0.0048 s−1, improving treatment efficiency and reducing energy consumption. While the Baffled Bubble Column (BBC) reactor showed a higher KLa of 0.0055 s−1 and a microbial removal efficacy of 96.12 %, it is more energy-intensive. This study advances wastewater treatment by bridging innovation with industrial application, contributing to sustainable wastewater management practices globally.

Enhancement of ozone dissolution and oxidation treatment of phenolic wastewater by a static spiral shear rig with a variable screw pitch

A novel static spiral shear rig (SSSR) with variable screw pitch was developed to enhance the ozone–water mass transfer and the oxidative degradation of phenolic wastewater. The effects of critical operational parameters on the dissolution and mass transfer of ozone in water and the oxidative degradation rate of phenol were investigated with the proposed SSSR. Moreover, the mass transfer and oxidative degradation of phenols with the SSSR were compared to conventional static mixer (CSM) methods. The results showed that the mass transfer coefficient obtained with the SSSR is 5.33 times greater than that obtained with CSM. With the SSSR, the degradation percentage of phenolic wastewater with an initial concentration of 100 mg/L reached 97.09% within 12 min, and the reaction kinetic constant for phenol degradation obtained with the SSSR is 3.68 times higher than that obtained with the CSM. The SSSR dramatically enhances ozone dissolution and mass transfer, resulting in a higher phenol oxidative degradation percentage and a constant kinetic reaction.

Can ozone mass transfer in water treatment be enhanced through independent pressurized ozonation?

The dissolved ozone equilibrium concentration is hard to improve by increasing the gas phase partial pressure due to the low initial pressure and difficulty in pressurization. In this study, a novel hydraulic pressurization technology was developed to reliably elevate the ozonation pressure and improve the solubility of ozone. It was located downstream of the ozone generator to avoid generator overpressure. Specifically, at the optimal pressure of 0.30 MPa with an initial ozone flow rate of 1–6 L min−1, the specific surface area of bubbles and turbulent dissipation rate in the ozonation reactor were up to 2.5- and 1.5-fold that of the atmospheric aeration. Meanwhile, the dissolved ozone equilibrium concentration, redox potential, and volumetric mass transfer coefficient were up to 2.4-, 1.6-, and 2.7-fold that of atmospheric aeration, respectively. The increase in bubble-specific surface area and turbulent dissipation rate, synergistically enhanced the mass transfer, contributing 83.2–94.4 % and 5.6–16.8 %, respectively. As the reactor pressure was increased from 0 to 0.30 MPa, the decolorization time of Acid Red 18 was shortened from 20 to 8 min, and the COD removal rate increased from 48.0 % to 85.0 %. This work provides an alternative approach coupled with a novel device that enhances the ozone mass transfer during water treatment.

Method for Determining the Ozone Mass Transfer Coefficient between the Gas and Liquid Phases in a Bubble Column Reactor

Method for Determining the Ozone Mass Transfer Coefficient between the Gas and Liquid Phases in a Bubble Column Reactor

Advanced oxidation of Arsenic(III) to Arsenic(V) using ozone nanobubbles under high salinity

Arsenic, a highly toxic element, is present in various water resources as As(III) and/or As(V). The removal of As(V) using adsorption is considered to be easier than the removal of As(III). In this work, we report the oxidation of As(III) to As(V) using ozone nanobubbles. Ozone has been widely used in the advanced oxidation process (AOP) to remove organics and inorganics in wastewater. The major advantage of ozone nanobubbles is their enhanced half-life, which leads to higher ozone solubility in water. In addition, the rate of mass transfer by using nanobubbles can be enhanced drastically. The effect of ozone flow rates, initial As(III) concentrations, pH levels, and the presence of salt is systematically studied in this work. The present results revealed that ozone nanobubbles positively impacted the oxidation of As(III) to As(V). AOP process based on O3 NBs (nanobubbles) was most efficient with 99 % oxidation rates of 1 ppm of As(III) within 20 minutes at 6.5 ppm ozone concentrations. An acidic pH of 3–7 promoted quick oxidation due to the high mass transfer coefficient of ozone nanobubbles. About ∼70 % degradation of As(III) to As(V) was achieved with 0.10854 min-1 rate constant at acidic (pH = 3) compared to ∼39 % degradation with 0.046 min-1 rate constant at pH =11. The presence of salt (∼50 mM) in the solution not only hindered the ozone mass transfer coefficient but also reduced the stability of nanobubbles. The detection of reactive oxygen species, particularly hydroxyl radical was unravelled by utilizing 2-propanol as a scavenger.

Bubble-less photocatalytic ozonation with ceramic membranes and static mixers enhances the total organic carbon removal and degradation of iodinated X-ray contrast agents

Conventional bubble-based ozonation of wastewater creates several issues, e.g., the low degradation of certain micropollutants like X-ray contrast agents, mass transfer limitations due to inhomogeneous mixing, and the waste of undissolved ozone. In contrast, this work uses tubular ceramic membranes for bubble-free and bubble-less ozonation. Static mixers are placed around the membrane to enhance the radial mixing of ozone, creating homogeneous reaction conditions throughout the membrane contactor. Additionally, the ozone mass transfer significantly increases with static mixers. Furthermore, the membrane is made of a photocatalyst (TiO2) on the shell-side to improve the micropollutant degradation by photocatalytic ozonation. An ozone-stable hydrophobic treatment method is developed to use ceramic membranes as a membrane contactor for the ozonation of water. After hydrophobic treatment, the ozone mass transfer coefficient is in the order of 1.3 ⋅ 10−6 ms−1 using bubble-less operation resulting in an ozone concentration up to 4.0 mg L−1. Overall, bubble-less operation significantly increases the ozone mass transfer compared to bubble-free operation. Photocatalytic ozonation in a membrane contactor with static mixers increases the degradation of diatrizoate by 37% compared to sole ozonation in the same membrane contactor. Furthermore, this process increases the removal of total organic carbon in experiments with a water matrix consisting of four different micropollutants by 115% compared to sole ozonation.

Bubbleless membrane contactor for enhanced ozone mass transfer and ozonation for water purification

Membrane contactor, a physical barrier separating two phases to introduce gas into aqueous solutions through the bubbleless process, has gained considerable development for its improved gas transfer and contaminant removal efficiencies for water purification. However, a comprehensive assessment of a contactor with liquid flowing on the shell side and gaseous ozone flowing on the lumen side is scarce for ozonation. Therefore, we have developed a membrane contactor equipped with commercial hydrophobic polytetrafluoroethylene (PTFE) hollow fibers and investigated theoretically and experimentally the interaction between ozone and solution. Mass transfer behavior was evaluated by comparing experimental value and computational model of corresponding coefficients. Phenol was then selected as a model contaminant to evaluate the treatment performance of membrane contactors in ozonation. Crucial operating conditions involving the gas/liquid flow rate, concentrations of ozone and phenol, pH and geometry of fibers were assessed for their impacts on both ozone mass transfer and pollutant degradation. The results showed that the membrane presented high chemical resistance to ozone and could achieve stable mass transfer through bubbleless aeration. Under the optimum operating conditions, the overall liquid mass transfer coefficient was 1.12 × 10−5 m/s. The percentage removal and mineralization of phenol with 30 min hydraulic retention time could reach ∼100 % and 21.1 %, respectively, which have demonstrated the high treatment efficiency of the membrane contactor as an alternative technique in water purification.

On the geometry and material stability of tubular PVDF-TiO2 static mixer membrane contactors for photocatalytic ozonation of micropollutants

The prevention of ozone hotspots in ozonation reactors for wastewater treatment is essential for effective degradation of micropollutants without forming harmful by-products. Membrane contactors can provide a bubble-free ozonation process that is able to decrease by-product formation, e.g., bromate formation in bromide-charged wastewater. Furthermore, the geometry of the reactor influences the distribution of dissolved ozone in a membrane contactor. Turbulence promoters can significantly decrease ozone hotspots and increase ozone mass transfer into wastewater. This work presents a fabrication methodology to produce PVDF-TiO2 helical static mixer membranes using the rotation-in-a-spinneret technology. Static mixer membranes combine the functionality of a membrane contactor and a static mixer in a single component. Furthermore, the PVDF matrix is doped with TiO2 particles as photocatalyst. Thus, we present a membrane-based photocatalytic ozonation process to increase the concentration of hydroxyl radicals for degradation of micropollutants under UV radiation. Static mixer membranes increase the ozone mass transfer coefficient by 70% compared to conventional hollow fiber membranes. Furthermore, the specific photocatalytic degradation rate of methylene blue increases by 50% using static mixer membranes. However, this work also reveals a lack of long-term stability of PVDF-TiO2 membranes in the corrosive environment of photocatalytic ozonation. The molecular weight of PVDF decreases by 11% after use in photocatalytic ozonation resulting in a loss of mechanical stability of the membranes. Similar material concepts are required based on ceramic materials which avoid wetting of the porosity.

Ultrasound catalytic ozonation to remove 5-hydroxy-1,3-phthalic acid from strongly alkaline and high-salt solutions: Aiding nuclear waste disposal and human health

As a typical precipitation inhibitor and the main component of plasticizers, 5-hydroxy-1,3-phthalic acid (5-HPA) seriously threatens the nuclear waste disposal and human health. OH, 1O2, and O2− induced by the ultrasound catalytic ozonation (US/O3) process achieves a removal rate of 60.67 % of 5-HPA in strongly alkaline and high-salt solutions within 60 min, which is significantly higher than the O3 alone process. This technology is highly resistant to inorganic anions that coexist in industrial production, but the mineralization process is inhibited. Ozone utilization and mass transfer are significantly improved by ultrasound, including reducing the ozone bubble size by 38 %, increasing the ozone utilization rate from 52 % to 75 %, increasing the volumetric mass transfer coefficient by 61 %, and increasing the specific interfacial area by 60 %, reducing the molar ratio of ozone to TOC from 0.45 to 0.23. Through a combination of Density functional theory (DFT) and GC–MS, four pathways for removing 5-HPA are clearly proposed, which are significantly different from the evolution behavior in acidic systems. The US/O3 system has significant application potential in reducing the threat of 5-HPA to nuclear waste disposal and human health.

Integrated model of ozone mass transfer and oxidation kinetic: Construction, solving and analysis

Ozone-based advanced oxidation process (O3-AOPs) is rapidly evolving, but the surge of emerging pollutants brings new challenges for ozone oxidation research. Herein, we proposed a state-of-the-art model for simultaneously analyzing both ozone mass transfer and oxidation kinetics during ozone oxidation of emerging organic contaminants. The numerical solution and graphical representations of the integrated model were utilized to analyze the dynamics of ozone and pollutant concentration. An in-depth analysis of the integrated model revealed that the reaction rate constants in this present study were higher than previously reported apparent reaction rate constants, and catalysts were not always necessary. Finally, we developed an installable mobile application (APP) that allowed the simulation of the dynamic process for ozone oxidizing organic pollutants in the laboratory, which offered theoretical support for the selection of experimental conditions. The results of model simulation not only provide scientific explanations for counter-intuitive experimental phenomena, but also optimized experimental conditions to enhance ozone utilization.

Investigation of Mass Transfer of Ozone in Jet Loop Reactor

Investigation of Mass Transfer of Ozone in Jet Loop Reactor

Surface Aerophilicity Engineering of Heterogeneous Catalysts for Enhanced Catalytic Ozonation

AbstractHeterogeneous catalysts for catalytic ozonation are elaborately designed with commendable intrinsic activity, while their industrial applications are limited by inadequate mass transfer of ozone (O3). In this work, it is demonstrated that engineering the surface aerophilicity of heterogeneous catalyst enables fast mass transfer of O3 reactant, giving rise to much enhanced catalytic ozonation performance. Taking active 4A zeolite catalyst as an example, the aerophilicity of spherical 4A zeolite can be greatly enhanced by coating polytetrafluoroethylene (PTFE) with low surface energy, and the optimized sample exhibits a 99.5% removal of atrazine (ATZ) within 20 min (corresponding to a k of 0.269 min−1), much better than 4A zeolite without surface aerophilicity engineering (k≈0.156 min−1). The PTFE coating does not change the ozone activation mechanism and degradation pathways for ATZ, further demonstrating that the enhanced ozonation activity is attributed to the enhanced mass transfer process. In addition, the general applicability of this surface aerophilicity and the potential ozonation application for industrial wastewater treatment are both demonstrated.

Groundwater remediation by in-situ membrane ozonation: Removal of aliphatic 1,4-dioxane and monocyclic aromatic hydrocarbons

Groundwater contamination by widespread and persistent organic compounds requires extensive treatment efforts, for example by in-situ chemical oxidation (ISCO). In this study, we investigated ozone mass transfer and removal mechanisms of ozone-resistant monocyclic aromatic and non-aromatic compounds in a novel in-situ treatment method using ozone-permeable membranes as reactive barrier. Initial batch experiments confirmed fast depletion of ozone in presence of sub-stoichiometric benzoic acid (BA), in contrast to the non-aromatic 1,4-dioxane (DIOX), where ozone depleted much slower. Simulated in-situ membrane ozonation treatment of contaminated groundwater led to lower removal of 5 mg L−1 BA (52.7%) compared to DIOX (60.6%). Inhibited removal of BA compared to additional batch experiments could be explained by quick depletion of ozone by reactive intermediates on the membrane surface. Surprisingly, reactive porous media did not lead to substantial changes of in-situ DIOX oxidation, although a stronger impact of the media on DIOX oxidation was hypothesized. Furthermore, experimental ozone mass transfer coefficients were determined (3.94∙10−7 – 3.12∙10−6 m s−1) and compared to modeled values for different membrane types (polydimethylsiloxane and polytetrafluoroethylene). Finally, a mathematical model based on mass transfer data was developed to support upscaling efforts. We concluded that contaminant properties are crucial for the feasibility assessment of in-situ ozone membrane treatment technology.

Электроозонная технология очистки навозных стоков: реализация математической модели

The disposal of animal waste products is especially urgent at large livestock facilities. In order to develop an effective technology of processing animal manure effluents, the authors have developed an effective method of their treatment and designed an experimental installation - a manure effluent treatment station including an electro-ozonizer. Cleaning is carried out in two stages: at the first stage, manure effluent is subjected to separation and flotation to remove large dispersed impurities, at the second stage, liquid fraction is treated with ozone. The technical result is achieved by fine atomization of manure effluents with a droplet diameter from 1.0 to 10.0 microns in the ozone-air mixture at an ozone concentration of 450 to 500 mg/m3 . Calculations based on the developed mathematical model have shown that fine atomization of manure effluents in a chamber with the ozone-air mixture increases the ozone concentration gradient and ozone mass transfer through the interface in 360 times as compared with barbotization of ozone into liquid. This makes it possible to increase significantly the rate of ozone consumption in chemical reactions, increase the efficiency factor, and reduce energy consumption for manure effluent treatment. The experiment was conducted at the pig-breeding farm of LLC “Novye Agrarnye Tekhnologii”, Beysuzhek Vtoroy, the Vyselki district, the Krasnodar region. The results of chemical, organoleptic and microbiological analyses confirm the high efficiency of the developed method and equipment for wastewater treatment of pig farms. The developed electro-ozonization technology and equipment improve the ecological situation on livestock farms by preventing the discharge of harmful emissions of ecologically toxic volatile compounds into the atmosphere.

Synergistic effect by supported activated carbon between functional groups and metal oxygen vacancies: enhancing ibuprofen degradation by improving ozone mass transfer

The fabrication and application of CuMn2O4@WAC and CuMn2O4@CSAC in heterogeneous catalytic ozonation for degrading IBP were investigated. The adsorption and decomposition mechanisms of ozone on the surfaces of AC and CuMn2O4 were explored.

Effective removal of As from a high arsenic-bearing ZnSO4 solution by ultrasonic enhanced ozonation in a one-pot method

Currently, removing arsenic (As) from ZnSO4 solution using lime presents several drawbacks, including high wet precipitate content, long reaction time, and the introduction of new impurities. In this study, we propose a novel ultrasonic (US) ozone one-pot method for effectively removing As from a high-arsenic ZnSO4 solution. In this method, as in ZnSO4 solution was removed by ultrasound enhanced ozone oxidation combined with zinc roasting dust (ZRD). No secondary pollution will occur with the addition of ZRD and ozone, as neither introduces new impurities. The experimental results show that under the conditions of initial As and Fe concentrations of 1640 mg/L and 2963 mg/L, US power of 480 W, frequency of 20 kHz, reaction temperature of 60 °C, reaction time of 1 h, ZRD dose of 12 g/L and gas flow rate of 900 mL/min, the removal rate of As can reach 99.4%. The introduction of US can further enhance the oxidation effect of ozone on As(III) and Fe2+ by increasing the solubility of ozone and promoting the production of OH radicals. Additionally, US cavitation and mechanical action increase the probability of contact between various reactants in the solution, facilitating the occurrence of reactions. US also reduces the aggregation of arsenic-containing precipitates and the encapsulation of ZRD by arsenic containing precipitates, thereby decreasing the amount of arsenic-containing precipitates. In comparison to the traditional lime method, this approach results in a significant reduction in the amount of arsenic-containing precipitate by 54.5% and a 60% decrease in the total reaction time. The As removal mechanism of our method encompasses ZRD neutralization, US-enhanced ozone mass transfer and decomposition, oxidation of As(III) and Fe2+, and adsorption and coprecipitation. Consequently, the proposed method provides a cost-effective, fast, safe and environmentally friendly alternative for treating arsenic-contaminated ZnSO4 solutions.

Electrochemical generation of ozone for application in environmental remediation

This work focuses on the production, in continuous mode, of ozone using a new electrochemical cell, specially designed and manufactured with 3-D printing to produce in a very efficient way high concentrations of this powerful oxidant. The gaseous ozone produced is tested in the degradation of a synthetic waste containing methomyl. The new cell has been characterized in terms of flow distribution, mass transfer, and production of ozone, being able to reach efficiencies as high as 9.5 g/kWh, which may be even competitive with those produced with the corona discharge technology. The prototype manufactured with an electrode area of 1.5 cm2 can produce a stream containing 30 mg/h of O3. This stream can be used to degrade methomyl. However, the direct bubbling was not found to be very efficient and activation of ozone with the simultaneous irradiation of UV light or the dosing of hydrogen peroxide was needed to improve performance, showing important synergism. The efficient removal of methomyl from wastewater opens the window for the development of alternative technologies to direct anodic oxidation based on the production and dosing of gaseous oxidants such as ozone. The operation of these new technologies does not depend on the salts contained in wastewater and prevents the deterioration in the quality of the waste because it does not leave any residue after application in the treated waste.