Catalytic Wet Peroxide Oxidation Research Articles

Enhancing H2O2 utilization efficiency for catalytic wet peroxide oxidation through the doping of La in the Fe-ZSM-5 Catalyst.

Iron-loaded zeolite (Fe-zeolite) has shown great potential as an efficient catalyst for degrading organic pollutants with high concentrations in the catalytic wet peroxide oxidation (CWPO) process under mild conditions. Here, 0.4 wt% Lanthanum (La) was added in the 1.0 wt% Fe-ZSM-5 by two-step impregnation method for an enhanced H2O2 utilization efficiency. For a systematical comparison, the CWPO process at 55 °C, where m-cresol with a high concentration of 1000 mg/L as a substrate, was studied over Fe-ZSM-5 and Fe-La-ZSM-5 catalysts. Compared with Fe-ZSM-5, Fe-La-ZSM-5 showed 15% higher H2O2 utilization efficiency with comparable total organic carbon (TOC) removal at around 40%, meanwhile with a 15% reduced metal leaching. Transmission electron microscopy (TEM) with elemental mapping (EDS), surface acidity analysis by Fourier transform infrared (FT-IR) and NH3-temperature programmed desorption (NH3-TPD), redox property analysis by Raman spectroscopy and H2-temperature-programmed reduction (H2-TPR) of both catalysts revealed, that the La doped Fe-ZSM-5 can provide an altered surface acidity, a more uniform and evenly dispersed surface Fe species with a promoted reducibility, which effectively promoted the accurate decomposition of H2O2 into the reactive •OH radicals, enhanced the H2O2 utilization efficiency, and increased the catalyst stability. Also, more than 90% conversion was maintained during the continuous experiment for more than 10 consecutive test days under 55 °C without pH adjustment, showing a promising possibility of the Fe-La-ZSM-5 for a practical wastewater treatment process.

Nano-CuOx for ciprofloxacin effective removal via wet peroxide oxidation catalysis and its practical application in wastewater

Using Cu(NO3)2·3H2O as active material and citric acid (CA) as complexing agent, heterogeneous catalyst nano-CuOx was prepared by sol-gel method. The catalytic wet peroxide oxidation (CWPO) reaction system was established accordingly. The system was used to treat ciprofloxacin (CIP) in simulated wastewater and real wastewater. The effects of the molar ratio of metal salt to CA, calcination temperature, H2O2 dosage, reaction temperature, and catalyst dosage on the physicochemical structure and the properties of CWPO were investigated. The results showed that when the molar ratio of CA to metal salt (Cu(NO3)2·3H2O) was 1.8, the calcination temperature was 500 °C, the concentration of H2O2 was 10 mmol · L–1, the reaction temperature was 95 °C, and the dosage of catalyst was 1 g · L–1, CWPO system has the best degradation effect on CIP. At thses optical conditions, the removal rate reached 86.8%, chemical oxygen demand (COD) removal rate reached 54.9%, and the recycling rate of the catalyst was very good. The refractory organics in actual pharmaceutical wastewater could be oxidized by this system as well, and the COD removal rate reaches 47%. The degradation mechanism of CIP showed that the main functions of the CWPO system were ·O2– and ·OH radicals. The possible degradation pathways were determined by ion chromatography to be intermediate products generated from piperazine ring cleavage, defluorination, decarboxylation, and quinoline hydroxylation of CIP. The catalyzing mechanism was investigated in detail; some useful information was obtained in this work.

Catalytic wet peroxide oxidation of metronidazole over Fe and Mn supported UiO-66 catalysts: Kinetic study

The metronidazole (MNZ) antibiotic is widely used to treat infections caused by anaerobic bacteria and it is difficult to biodegrade in the pharmaceutical wastewaters. In this study, Fe-UiO-66, Mn-UiO-66 and Fe/Mn-UiO-66 catalysts were prepared for the kinetic study of catalytic wet peroxide oxidation (CWPO) degradation of metronidazole in pharmaceutical wastewater. The catalysts were characterized by XRD, FT-IR, N2 adsorption-desorption, SEM, and TGA. The effects of Fe and Mn loading rate, catalyst dosage, MNZ concentrations, calcined temperature of Mn-UiO-66 and Fe/Mn ratio on the CWPO of metronidazole wastewater were systematically studied. Fe-UiO-66 catalysts exhibited better catalytic activity for the CWPO degradation of metronidazole wastewater (XMNZ = 93 %, XH2O2 = 78 %) compared to Mn-UiO-66 catalysts (XMNZ = 20 %, XH2O2 = 30 %). The kinetics study indicates that the CWPO process is fitted for the pseudo-first-order reaction with activation energy of 89.37 kJ/mol and 95.08 kJ/mol obtained on the Fe-UiO-66 and 2Fe/Mn-UiO-66 catalysts, respectively. The supported Fe and Mn UiO-66 catalysts showed good catalytic activity for CWPO of metronidazole which exhibited potential application in the wastewater treatment process.

Preparation and characterisation of alkali-activated blast furnace slag and Na-jarosite catalysts for catalytic wet peroxide oxidation of bisphenol A

ABSTRACT In this study, cost-effective alkali-activated materials made from industrial side streams (blast furnace slag and Na-jarosite) were developed for catalytic applications. The catalytic activity of the prepared materials was examined in catalytic wet peroxide oxidation reactions of a bisphenol A in an aqueous solution. All materials prepared revealed porous structure and characterisation expressed the incorporation of iron to the material via ion exchange in the preparation step. Furthermore, the materials prepared exhibited high specific surface areas (over 200 m2/g) and were mainly mesoporous. Moderate bisphenol A removal percentages (35%–37%) were achieved with the prepared materials during 3 h of oxidation at pH 7–8 and 50°C. Moreover, the activity of catalysts remained after four consecutive cycles (between the cycles the catalysts were regenerated) and the specific surface areas decreased only slightly and no changes in the phase structures were observed. Thus, the prepared blast furnace slag and Na-jarosite-based catalysts exhibited high mechanical stability and showed good potential in the removal of bisphenol A from wastewater through catalytic wet peroxide oxidation.

Carbon Nanomaterials from Polyolefin Waste: Effective Catalysts for Quinoline Degradation through Catalytic Wet Peroxide Oxidation

Quinoline (QN) is highly toxic and carcinogenic and has been detected in soil, groundwater, and biological tissues. Advanced oxidation processes (AOPs) have shown promise to address its degradation in wastewater treatment, with catalytic wet peroxide oxidation (CWPO) being highlighted due to its cost-effectiveness and mild operation. However, developing active and inexpensive catalysts is crucial for CWPO’s effectiveness. Another pressing issue is the accumulation of mixed, dirty plastic solid waste (PSW), particularly polyolefins used in packaging. Although recycling rates have increased, much plastic packaging remains in landfills. However, polyolefins can be converted into carbon-based nanostructured materials (CNMs), such as carbon nanotubes (CNTs), through chemical vapor deposition (CVD) using PSW as a carbon precursor. While many studies focus on CNT preparation, their application is often overlooked. In this context, this work proposes the preparation of CNMs, particularly CNTs, through CVD using a single-stage pyrolysis reactor. Polyolefins (LDPE, HDPE, and PP), both individually and in a mixture simulating PSW, were used as carbon sources. Given a sufficiently high temperature, the desired CNT architecture was successfully synthesized regardless of the starting polymer. These CNMs were then tested as catalysts for CWPO in simulated wastewater containing QN. The results showed a rapid degradation of QN (30–120 min) and high removals of total organic carbon (TOC) and aromatic compounds (75% and >90%, respectively), demonstrating the applicability of PSW-derived CNTs in the CWPO process for QN abatement.

Copper and iron-based monolithic catalysts for phenol Catalytic Wet Peroxide Oxidation (CWPO): Support and iron effects on the catalytic performance

Water is an invaluable resource of our planet, and our lives and those of the future generations rely on it. Phenolic compounds are part of many industries effluents and they are highly toxic and not biodegradable. Therefore, they could be eliminated from water through the Catalytic Wet Peroxide Oxidation (CWPO) reaction. In this work, alumina-supported and cordierite-supported copper and iron-based monolithic catalysts were synthesized and tested in the CWPO of phenol. These structured catalysts were characterized by stereoscopic microscopy, N2 adsorption, XRD, LRS, SEM/EDX and XPS, and their mechanical resistance was analyzed. The effect of both, the support and the presence of iron as a co-active phase on the metal species leaching, and therefore on the catalytic performance, were evaluated. Alumina-supported copper species were more accessible and reducible than cordierite-supported ones and, as a consequence, these rapidly converted the totality of phenol and achieved high mineralization and COD reduction. On the other hand, iron addition as a co-active phase decreased copper leaching in all cases due to Cu-Fe interactions. The bimetallic alumina-supported catalyst exhibited the best catalytic performance with low copper and iron leachings. Consequently, it was tested in a more complex reaction media (tap water). This catalyst resulted promising, converting all the phenol with high mineralization and COD reduction, although suffering some copper and iron leaching.

Hybrid multi-core shell magnetic nanoparticles for wet peroxide oxidation of paracetamol: Application in synthetic and real matrices

Clean water availability is becoming a matter of global concern in the last decades. The responsible entities for wastewater treatment do not have the proper facilities to deal with a wide range of pollutants. Special attention should be given to emerging contaminants, whose presence in water bodies may cause adverse effects on the aquatic ecosystem and human health. Most studies in the literature do not consider the development of their solution in real matrices, which can hinder the applicability of the explored alternative in the real scenario. Therefore, in this work, we demonstrate the applicability of hybrid magnetic nanoparticles for removing paracetamol (PCM) from simulated and real matrices by catalytic wet peroxide oxidation (CWPO). To achieve carbon coating, the nanoparticles were prepared via the traditional route (resorcinol/formaldehyde, CoFe@CRF). A new methodology was also considered for synthesizing thin-layered carbon-coated magnetic nanoparticles (phloroglucinol/glyoxalic acid, CoFe@CPG). TEM images revealed a multi-core shell structure formation, with an average carbon layer size of 7.8 ± 0.5 and 3.2 ± 0.3 nm for resorcinol/formaldehyde and phloroglucinol/glyoxalic acid methodology, respectively. Screening the materials’ activity for PCM oxidation by CWPO revealed that the nanoparticle prepared by phloroglucinol/glyoxalic acid methodology has higher performance for the degradation of PCM, achieving 63.5% mineralization after 24 h of reaction, with similar results for more complex matrices. Iron leaching measured at the end of all reactions has proven that the carbon layer protects the core against leaching.

Catalytic wet peroxide oxidation with in-situ generated H2O2: An efficient strategy for improving the stability of metal-organic framework catalysts

Although catalytic wet peroxide oxidation (CWPO) may offer an efficient method for wastewater treatment, the use of metal-organic framework (MOF) catalysts for the CWPO reaction in the presence of H2O2 is challenging because the MOF structure is highly vulnerable to water and/or oxidizing agents. Herein, a range of M-1,3,5-benzenetricarboxylate (BTCs) (M = Fe, Co, Mn, and Cu) were prepared, and their catalytic activities in the CWPO of methyl orange (MO) were evaluated. To examine the stability of the M-BTCs under different reaction conditions, the CWPO reaction was performed with ready-made H2O2 (CWPO-I) or in-situ generated H2O2 using H2 and O2 (CWPO-II). In the latter, Pd was supported onto an M-BTC (Pd/M-BTC). The CWPO-I reaction rate was significantly affected by the metal nodes of the M-BTC, with the Fe-BTC catalyst showing the fastest MO degradation rate. However, regardless of the type of metal node, the M-BTC catalysts underwent significant decomposition during the CWPO-I reaction, leading to a considerable decrease in their textural properties. This result suggests that the M-BTC structure collapsed due to attack by the hydroxyl radicals generated during the reaction. Therefore, the activity of the regenerated Fe-BTC catalyst significantly decreased to 40% of that of the fresh catalyst. In contrast, the catalyst stability in CWPO-II outperformed that in CWPO-I. The Pd/Fe-BTC catalyst exhibited a moderate decrease in activity owing to the gradually reduced surface area of the catalyst during the recycling runs, and the crystallinity of Fe-BTC was preserved. Moreover, the content, particle size, and electronic properties of Pd supported on Fe-BTC showed little change after the reaction. These results demonstrate that the use of in-situ generated H2O2 is superior for impeding the catalyst deactivation caused by structural deformation of the MOF.

Influence of the aqueous matrix on the degradation of cyanotoxins by CWPO: A study on the Iberian Peninsula freshwaters

The increasing occurrence of toxic cyanobacterial blooms worldwide represents a critical health and environmental risk. Catalytic wet peroxide oxidation (CWPO) has emerged as an efficient and environmentally friendly technology for the removal of cyanotoxins in water. Nevertheless, its effectiveness has just been demonstrated in deionized water or simple synthetic aqueous matrices. In this work, the effect of the different components of the aqueous matrix on the CWPO of cyanotoxins was deeply evaluated considering the widespread properties of the Iberian Peninsula freshwaters. The presence of Cl-, HCO3- and SO42- ions reduced the oxidation rate of cylindrospermopsin (CYN) up to 70–80% at the highest concentrations tested (2000, 250 and 500 mg L−1 for Cl-, HCO3- and SO42-, respectively) due to their hydroxyl radical scavenging capacity. The presence of natural organic matter (NOM) resulted in a similar outcome (oxidation rate reduction up to 90% at the highest concentration tested, 20 mg L−1), but in this case due to the consumption of hydroxyl radicals in competition with CYN oxidation. The presence of NO3- and H2PO4- did not show any significant effect on CYN oxidation. Similarly, the presence of cyanobacteria (Chrysosporum ovalisporum, 50 µg chlorophyll-a L−1) did not appreciably affect the CYN oxidation rate. These results were consistent with those obtained by evaluating the impact of real aqueous matrices from drinking water treatment plants (DWTPs) located in Castilla y León and Extremadura regions (Spain) on CWPO performance. This knowledge is key to the implementation of the technology for the treatment of surface waters affected by toxic cyanobacterial blooms.

Polyolefin-derived carbon nanotubes as magnetic catalysts for wet peroxide oxidation of paracetamol in aqueous solutions

This work deals with developing feasible valorization technologies to prepare carbon nanotubes (CNTs) from plastic solid waste and demonstrate their application in catalytic wet peroxide oxidation (CWPO). CNTs were synthesized by catalytic chemical vapor deposition (CCVD) at 850 ºC, considering low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP) as carbon precursors representative of urban plastic solid waste. Iron oxide nanoparticles supported in alumina, previously synthesized by sol-gel, were used as catalysts in the CCVD process. TEM micrographs allow us to determine 41 nm as the average outer diameter of the CNTs and to visualize magnetic iron nanoparticles (ca. 10 nm) embedded inside the CNTs (ca. 6.4 % of content measured as ashes). These magnetic nanoparticles were kept in the CNT structure even after the purification of the CNTs with sulphuric acid, allowing to obtain magnetic CNTs. All purified and non-purified CNTs prepared from the polyolefins were assessed as catalysts in CWPO of paracetamol (PCM), used as a model pharmaceutical contaminant in water at CPCM,0 = 100 μg mL−1 (CH2O2,0 = 472 μg mL−1, CCNT = 2.5 g L−1, pH0 = 3.5 and T = 80 °C). The concentrations of PCM, H2O2, aromatic and total phenolic compounds were monitored for 24 h. All CNTs showed catalytic activity, allowing the complete degradation of PCM at 6 h of reaction time. The stability and reusability of materials are tested and proved in CWPO.

Use of Fe and Al Containing Electrocoagulation Sludge as an Adsorbent and a Catalyst in Water Treatment

In this study, three different electrocoagulation (EC) sludges were studied as an adsorbent (removal of humic acids) and as a catalyst [catalytic wet peroxide oxidation (CWPO) of bisphenol A (BPA)]. The sludges originated from electrocoagulation process in which aluminum (Al) and iron (Fe) electrodes were used for the treatment of mining industry wastewater. All the materials were used as dried sludge and calcined material. The stability of these materials was studied in neutral and alkaline conditions with analysis of the leached iron content in solution. Based on the EC sludge characterization with X-ray fluorescence (XRF), X-ray diffractometer (XRD), and diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy different forms of Fe occurring in EC sludges were found. The Brunauer–Emmett–Teller (BET) method showed reduced surface area after calcination process. Stability of the sludges was studied in neutral conditions, and the amount of iron leaching was low (<1.4 ppm). Adsorption experiments showed that the removal of humic acids (measured as total organic carbon) was over 50% in all tested materials in the pH range of 3–9, and over 92% with the S3 calcined material in all studied pH range. The calcined samples were catalytically more active than raw material in CWPO of BPA. The highest removal of BPA was 85% over calcined sludge. Therefore, calcined EC sludges are suitable materials for catalyst and adsorbent use. The main novelty of this paper was the finding of sludge modification in the EC process of water treatment through different electrode material and current density. This modification can be made in EC water treatment process, and it may provide low-cost materials to different utilization of EC sludge.

Insights on the removal of the azole pesticides included in the EU Watch List by Catalytic Wet Peroxide Oxidation

Insights on the removal of the azole pesticides included in the EU Watch List by Catalytic Wet Peroxide Oxidation

Cu-based perovskite as a novel CWPO catalyst for petroleum refining wastewater treatment: Performance, toxicity and mechanism

For the first time, Cu-based perovskite oxides were used as catalysts to treat highly toxic and refractory petroleum refining wastewater based on catalytic wet peroxide oxidation (CWPO) technology. Perovskite La2CuO4 was synthesized by sol-gel method. A series of characterizations showed that the synthesized catalyst particles are tetragonal phase perovskite structure. The experimental results showed that under the conditions of catalyst dosage of 0.75 g, temperature of 100 ℃ and reaction time of 30 min, the COD removal rate was 89.58 %, the TOC removal rate was 87.38 %. The morphology and structure of the catalyst before and after the reaction proved that the catalyst has strong stability and catalytic activity. The components of raw water, Wet Air Oxidation (WAO) effluent and CWPO effluent were compared and analyzed by Gas Chromatography-Mass Spectrometry (GC-MS), and the possible mechanism and path of WAO and CWPO degradation of petroleum refining wastewater were further explored. The changes of Cu components in La2CuO4 before and after CWPO reaction and the transformation of lattice oxygen and adsorbed oxygen were analyzed by X-ray Photoelectron Spectroscopy (XPS). The involvement of Cu (Ⅱ) /Cu (Ⅰ) in the activation of H2O2 was speculated. Finally, the biotoxicity of raw water, WAO effluent and CWPO effluent was predicted. The results provide reference value for the application of catalyst La2CuO4 in various petrochemical wastewater.

Selective denitrification of simulated oily wastewater by oxidation using Janus-structured carbon nanotubes

The intense industrial development has resulted in several consequences for human and environmental health, including the increased discharge of oily products in water bodies. Oily products are widely used in industry, often bearing an associated high cost. Finding alternatives to treat oily wastewater aiming at recovering oily and water phases is an approach allowing recovery of products of economic interest. In this work, Janus-like carbon nanotubes (CNTs) were synthesized by varying the feed time of acetonitrile and ethylene, respectively, as nitrogen/carbon and carbon precursors in a chemical vapor deposition (CVD) approach. The CVD approach allowed the synthesis of completely undoped, completely doped and partially doped CNTs with a Janus structure. The CNTs were then tested as catalysts for the selective oxidation of 4-nitrophenol (4-NP) contained in a simulated oily wastewater (2,2,4-trimethylpentane/water (O/W) = 1:9, volume basis) by catalytic wet peroxide oxidation (CWPO). The CWPO experiments were conducted for 24 h, 80 °C, 2.5 g L−1 of catalyst, and the stoichiometric concentration of H2O2 (3.6 g L−1) for the degradation of 4-NP (1 g L−1). The same conditions were kept for experiments conducted under a biphasic system. The catalysts bearing a Janus-like structure were demonstrated to be more effective in CWPO experiments in aqueous-only and biphasic systems for the abatement of 4-NP.

Calcination temperature effects on the physicochemical properties of copper-based wire-meshes: The implications in the CWPO of phenol

This work investigates phenol elimination from water through the Catalytic Wet Peroxide Oxidation (CWPO) reaction using CuO/TiO2-ZrO2 supported on wire-meshes, all with 5 wt.% Cu and calcined at different temperatures. These were characterized by SEM/EDX, elemental mappings, XRD, LRS and XPS, and their mechanical stability was studied. The increment in the calcination temperature generated less reducible Cu2+ species, which impacted in phenol conversion rate, slowing it down. Particularly, when the lower temperatures were applied (500 – 800 °C), copper was found well-distributed on the support and high mineralization values (above 85%) were obtained. Nevertheless, these high TOC conversions were the result of elevated copper leaching (∼ 40 ppm), markedly contributing as a homogeneous catalyst. Contrarily, the application of more extreme temperatures, such as 850 and 900 °C, led to the migration of copper to the inner part of the coating, and consequently to lower copper leaching (7.6 and 0.9 ppm, respectively), due to a protective effect of the support. Accordingly, the corresponding mineralization degrees were lower, 60 and 40%, respectively. An adequate temperature was found (850 °C), with higher mineralization and better mechanical resistance than the catalyst calcined at 900 °C.

Cu(II) impregnated clay-derived HS zeolite: Synthesis, characterization and catalytic activity on catalytic wet peroxide oxidation (CWPO) of phenol

The majority of phenol-containing liquid industrial wastes are discharged into natural waters. As a result, several investigations, such as catalytic wet peroxide oxidation (CWPO), have been conducted to remediate these effluents. Copper-supported heterogeneous catalysts were prepared by an impregnation technique and tested in CWPO of phenol. Both the raw pyrophyllite clay and its zeolite form were used as supports. The samples were characterized by BET specific surface area analysis, X-ray diffraction, X-ray fluorescence, and X-ray photoelectron spectra. The effect of temperature (25–70 °C), the concentration of hydrogen peroxide (2–10 mmol·L−1), and the amount of catalyst (0.5–3 g·L−1) were selected for optimization of the catalytic system H2O2-2.5% Cu/ZP using the response surface methodology based on central composite design. The catalyst (2.5% Cu/ZP), with support of synthesized hydroxysodalite zeolite form, showed the best catalytic activity in comparison to that based on raw pyrophyllite support (2.5% Cu/RP). The maximized degradation was 100% after 4 h at optimum conditions (T = 50 °C, [H2O2] = 6.39 mmol·L−1, catalyst amount = 1.82 g·L−1) with 87.73% of mineralization.

Catalytic Wet Peroxide Oxidation of Anionic Pollutants over Fluorinated Fe3O4 Microspheres at Circumneutral pH Values

Fluorinated Fe3O4 microspheres with 7.1 ± 1.4 wt% of fluoride (F-Fe3O4-1) were prepared via glycothermal synthesis. Fluorination significantly enhanced the activity of F-Fe3O4-1 in catalytic wet peroxide oxidation of anionic dyes (including orange G (OG) and congo red) at pH ~7. However, the promotional effect of fluorination became less obvious for amphoteric rhodamine B and was not observed for cationic methylene blue. After reacting with H2O2 (40 mM) for 2 h at pH 6.5 and 40 °C, the decolorization rates of OG (0.1 mM) and the pseudo-first-order rate constant were 96.8% and 0.0284 min−1 over F-Fe3O4-1 versus 17.6% and 0.0011 min−1 over unmodified Fe3O4. The effects of reaction parameters (initial H2O2 concentration and pH value and reaction temperature) on OG decolorization with H2O2 over F-Fe3O4-1 were investigated. The reusability of F-Fe3O4-1 was demonstrated by OG decolorization in eight consecutive runs. Fluorination increased the isoelectric point of F-Fe3O4-1 to 8.7 and facilitated the adsorption and degradation of anionic dyes on the surface of F-Fe3O4-1 at pH ~7. Scavenging tests and EPR spectra supported that hydroxyl radicals were the main reactive species for the OG decolorization over F-Fe3O4-1.

Catalytic wet peroxide oxidation of phenol through mesoporous silica-pillared clays supported iron and/or titanium incorporated catalysts

Catalytic performances of Silica Pillared Clay (SPC) supports synthesized in different silica amounts both from standard SWy-2 clay mineral and Hançılı region bentonite rock (HWB), and iron (Fe) and/or titanium (Ti) incorporated SPCs in different combinations were evaluated in various advanced Catalytic Wet Peroxide Oxidation (CWPO) of phenol. Host clay mineral type led to different oxidation performances and metal loading created significant increases in the catalytic performance. CWPO performance of Fe-loaded SPCs was better than Ti-loaded ones, so oxidation parameters for Fe–SPCs were studied in detail. Catalyst amount and rise in temperature increased phenol conversion values significantly, and catalysts were more effective in lower pH reaction medium. Aromatic intermediates such as catechol, hydroquinone and benzoquinone formed at the beginning of oxidation were oxidized to carboxylic acids with an advancing oxidation time. The presence of carboxylic acids such as oxalic and formic acid resulted in relatively low total organic carbon (TOC) conversion values. The highest catalytic activity was obtained with high silica content Fe–SPCs synthesized with both host clays. Complete conversion was nearly achieved within 60 min with an experimental condition of T = 30 °C, pH = 3.7 and catalyst/solution ratio = 2 g/L for SWy-2 based catalyst by applying either CWPO or PCWPO (Photo Catalytic Wet Peroxide Oxidation) techniques. SCWPO (Sono Catalytic Wet Peroxide Oxidation) technique also yielded this value at the same oxidation conditions for HWB based catalyst. TOC conversion values at 240 min oxidation time were determined as 33% and 48% for SWy-2 based catalyst with CWPO and PCWPO techniques, respectively, and 37% for HWB based catalyst with SCWPO technique. SWy-2 based catalyst still retained its performance after 3 cycles.

Highly active Mn-Cu bimetallic oxide catalyst assembled as 3D-printed monolithic agitating paddles for advanced oxidation process

Catalytically agitating paddles are essential to perform liquid-solid heterogeneous catalytic reactions on an industrial scale due to the improved mass transfer and easy catalyst recovery. Herein, bimetallic oxides were formed after the calcination of nanomaterials derived from metal-organic frameworks (MOFs). Particularly, Mn(M)-BTC nanomaterials were synthesized by self-assembly of Mn2+ ions (mixed with various dopants such as Cu2+, Ce3+, or Fe2+) and H3BTC ligands in a mixed solvent of ethanol and water. It was found that in the powdery form, the Mn-Cu oxide derivate exhibited the highest degradation rate in the catalytic wet peroxide oxidation process (CWPO process), which was significantly higher than that of single metal oxide as well as Mn-Fe and Mn-Ce oxide derivates. The reason was caused by the synergistic effect between Mn-Cu promoted the formation of Mn3+ and Cu+ species to boost the CWPO reaction. Furthermore, the obtained Mn-Cu powdery catalysts were 3D-printed to obtain monolithic agitating paddles with different geometries, which were then mounted on a central shaft in the stirred reactor. An advanced oxidation process was used to investigate the effect of 3D patterns on the degradation efficiency of various organic dyes. It was discovered that the 3D-printed grid with higher cell density (484 cpsi) had better liquid mixing efficiency and thus better catalytic performance, which could be repeatedly used more than seven times. Additionally, the numerical simulation analysis (computational fluid dynamics) revealed a good mixing efficiency and improved mass transfer in the entire reactor equipped with the designed monolithic agitating impellers.

Removal of Malachite Green Dye from Aqueous Solution by Catalytic Wet Oxidation Technique Using Ni/Kaolin as Catalyst.

In this study, natural Algerian kaolin was used as a support and impregnated with nickel at different loading amounts (2 wt.%, 5 wt.%, and 7 wt.%) in order to prepare a supported catalyst. The wet impregnation technique was used in this preparation; nickel oxide (NiO) was the active phase precursor of the catalyst, and the catalysts were designated as follows: 2%, 5%, and 7% Ni/kaolin. These catalysts were put to the test in catalytic wet peroxide oxidation (CWPO) for degrading the organic contaminant malachite green dye (MG). Analytical techniques such as FTIR spectroscopy, X-ray diffraction, BET, and X-fluorescence were used to examine the structure, morphology, and chemical composition of the support and the produced catalysts. Several parameters, including temperature, catalytic dose, metal loading, hydrogen peroxide volume, and kinetic model were systematically investigated. The combination of improved parameters resulted in a significant increase in the catalytic activity, achieving a high removal rate of MG dye of 98.87%.