• Clean Technology
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• v.5 no.1
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• pp.49-61
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• 1999

Fenton's oxidation can improve the biodegradability of refractory organic wastewater by generating $OH{\cdot}$ which is one of the most reactive species. Fenton's reagent is used to treat a variety of industrial waste containing a range of toxic organic compounds. But this process cannot be economical because of high chemical cost of $H_2O_2$, ferrous ion solution and high sludge disposal cost. In this study, we proposed a modified Fenton's oxidation process which can reduce the reagent cost and obtain better removal efficiencies with less Fenton's reagents, and have a good potential of sludge recycling. In modified Fenton reaction, ferrous ion solution is adjusted to optimal pH with NaOH. Then it added to the sample and reacted to $H_2O_2$. For the experiment, synthetic wastewater made of phenol, which is one of the typical water pollutants, was used and the ionic strength of this wastewater was controlled by adding $NaHCO_3$. The effects of DO, ionic strength, and $H_2O_2$ dosing methods were investigated. As a result, modified Fenton's treatment efficiencies are better than conventional Fenton's reaction treating leachate and dyeing wastewater. And modified Fenton's treatment efficiencies combined to the sludge recycling for a half of Iron dosage are as good as the conventional Fenton's for a normal Iron dosage.

• Journal of Soil and Groundwater Environment
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• v.10 no.2
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• pp.35-43
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• 2005

Bioslurping combines the three remedial approaches of bioventing, vacuum-enhanced free-product recovery, and soil vapor extraction. Bioslurping is less effective in tight (low-permeability) soils. The greatest limitation to air permeability is excessive soil moisture. Optimum soil moisture is very soil-specific. Too much moisture can reduce air permeability of the soil and decrease its oxygen transfer capability. Too little moisture will inhibit microbial activity. So Modified Fenton reaction as chemical treatment which can overcome the weakness of Bioslurping was experimented for simultaneous treatment. Although the diesel removal efficiency of SVE process increased in proportion to applied vacuum pressure, SVE process was difficulty to remediation quickly semi- or non-volatile compounds absorbed soil strongly. And SVE process had variation of efficiency with distance from the extraction well and depth a air flow form of hemisphere centering around the well. Below 0.1 % hydrogen peroxide shows the potential of using hydrogen peroxide as oxygen source but the co-oxidation of chemical and biological treatment was impossible because of the low efficiency of Modified Fenton reaction at 0.1 % (wt) hydrogen peroxide. NTA was more efficiency than EDTA as chelating agent and diesel removal efficiency of Modified Fenton reaction increased in proportion to hydrogen peroxide concentration. Hexadecane as typical aliphatic compound was removed less than Toluene as aromatic compound because of its structural stability in Modified Fenton reaction. What minimum 10% hydrogen peroxide concentration has good remediation efficiency of diesel contaminated groundwater may show the potential use of Modified Fenton reaction after bioslurping treatment.

• Journal of Soil and Groundwater Environment
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• v.17 no.2
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• pp.15-21
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• 2012

MTBE (Methyl tertiary-butyl ether) has been commonly used as an octane enhancer to replace tetraethyl lead in gasoline, because MTBE increases the efficiency of combustion and decreases the emission of carbon monoxide. However, MTBE has been found in groundwater from the fuel spills and leaks in the UST (Underground Storage Tank). Fenton's oxidation, an advanced oxidation catalyzed with ferrous iron, is successful in removing MTBE in groundwater. However, Fenton's oxidation requires the continuous addition of dissolved $Fe^{2+}$. Zero-valent iron is available as a source of catalytic ferrous iron of MFO (Modified Fenton's Oxidation) and has been studied for use in PRBs (Permeable Reactive Barriers) as a reactive material. Therefore, this study investigated the condition of optimization in MFO-PRBs using waste zero-valent iron (ZVI) with the waste steel scrap to treat MTBE contaminated groundwater. Batch tests were examined to find optimal molar ratio of MTBE : $H_2O_2$ on extent to degradation of MTBE in groundwater at pH 7 with 10% waste ZVI. As the results, the ratio of optimization of MTBE to hydrogen peroxide for MFO was determined to be 1:300[mM]. The column experiment was conducted to know applicability of MFO-PRBs for MTBE remediation in groundwater. As the results of column test, MTBE was removed 87% of the initial concentration during 120days of operational period. Interestingly, MTBE was degraded not only within waste ZVI column but also within sand column. It means the aquifer may affect continuously the MTBE contaminated groundwater after throughout the waste ZVI barrier. The residual products showed acetone, TBF (Tert-butyl formate) and TBA (Tert-butyl acetate) during this test. The results of the present study showed that the recycled materials can be effectively used for not only a source of catalytic ferrous iron but also a reactive material of the MFO-PRBs to remove MTBE in groundwater.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.489-494
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• 2006

Goethite, hematite, magnetite and synthesized iron oxide are used as catalysts for Fenton-type oxidation of phenol. The synthesized iron oxides were characterized by X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR). The catalytic activity of these materials is classified according to the observed rate of phenol oxidation. The effectiveness of the catalysts followed the sequence: ferrous ion > synthesized iron oxide >> magnetite hematite > goethite. According to these results, the most effective iron oxide catalyst had the structure similar to natural hematite. The surface oxidation state of the catalyst was between magnetite and hematite (+2.5 ~ +3.0). Phenol degraded completely in 40 min at neutral pH (pH = 7). Soluble ferric and ferrous ions were not detected in the filtrate from Fenton reaction solution by AAS. The formation of hydroxyl radicals was confirmed by EPR.

• Journal of Soil and Groundwater Environment
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• v.11 no.6
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• pp.76-82
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• 2006

Fenton's reaction are difficult to apply in the field due to the low pH requirements for the reaction and the loss of reactivity caused by the precipitation of iron (II) at neutral pH. Moreover, Fenton-like reactions using iron mineral instead of injection of iron ion as a catalyst are operated to get high removal result at low pH. Because hydroxyl radical can generate at the surface of iron mineral, there are competition with a lot of hydroxide at around neutral pH. On the other side, to operate Fenton's reaction series at neutral pH, modified Fenton reaction is suggested. The complexes, composed by iron ions (ferrous ion or ferric ion)-chelating agent, could be acted as a catalyst and presented in the solution at neutral pH. However, modified Fenton reaction requires a lot of hydrogen peroxide. Accordingly, the purpose of this experiment was to effectively combine Fenton-like reaction and modified Fenton reaction for extending application of Fenton's reaction. i.e., injecting chelating agents in Fenton-like reaction at around neutral pH is increasing the concentration of dissolved iron ion and highly promoting the oxidation effect. 2,4,6-trinitrotoluene (TNT) was used as a probe compound for comparing reaction efficiencies in this study. If the concentration of dissolved iron ion in combined Fenton process were existed more than 0.1 mM, the total TNT removal were increased. Magnetite-NTA system showed the best TNT removal (76%) and Magnetite-EDTA system indicated about 56% of TNT removal. The results of these experiments proved more promoted 40-60% of TNT removal than Fenton-like reaction's.

• Journal of Korean Society of Water and Wastewater
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• v.34 no.6
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• pp.445-462
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• 2020

Industrial wastewater often contains a number of recalcitrant organic contaminants. These contaminants are hardly degradable by biological wastewater treatment processes, which requires a more powerful treatment method based on chemical oxidation. Advanced oxidation technology (AOT) has been extensively studied for the treatment of nonbiodegradable organics in water and wastewater. Among different AOTs developed up to date, ozonation and the Fenton process are the representative technologies that widely used in the field. Based on the traditional ozonation and the Fenton process, several modified processes have been also developed to accelerate the production of reactive radicals. This article reviews the chemistry of ozonation and the Fenton process as well as the cases of application of these two AOTs to industrial wastewater treatment. In addition, research needs to improve the cost efficiency of ozonation and the Fenton process were discussed.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2002.04a
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• pp.26-29
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• 2002

We describe a modified method for effectively pretreating soil highly contaminated with ANT or BaA (both initial Conc. are 500 mg/kg soil), i.e., we apply Fenton oxidation in which ethanol is added to increase ANT and BaA removal. At least 0.5 $m\ell$ or 0.75 $m\ell$ of ethanol were added to 1 g of artificially ANT or BaA-contaminated soils (i.e., alluvial and sandy soil), respectively. This was followed by Feton oxidation in which various amounts of $H_2O$$_2$ and Fe$^{2+}$ were added. The results showed more than 98 % of ANT or BaA removal efficiency However less than 10 % of ANT and BaA removal efficiency was obtained in addition of distilled water or sodium dodecy1 sulfate. Additionally, we employ GC-MS to identify the main oxidation product generated by the optimized Fenton reaction [i.e., ANT or BaA degraded in to 69-73% 9,10-anthracenedione (ANTDI) or 43-51% 7,12-benz(a)anthracenedione (BaADI), respectively]. The biodegradability of ANTDI or BaADI are subsequently confirmed to be much more rapid than that of ANT or BaA, respectively, results suggesting that Fenton oxidation with ethanol-microbial treatment can be effectively applied to remove ANT or BaA from soil.l.

• Environmental Engineering Research
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• v.25 no.1
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• pp.36-42
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• 2020

Fenton process is one of the most effective advanced oxidation processes for the removal of pollutants from wastewater. In this study, while ferrous iron was used in conventional Fenton process (CFP); nano-sized iron(II, III) oxide was experienced in modified Fenton process (MFP) as a new catalyst alternative. In order to enhance their oxidation efficiencies, both CFP and MFP were combined with ultrasonication at 53 kHz fixed frequency. Thus, the influences of both catalyst iron species and ultrasonication on color and chemical oxygen demand (COD) removals from synthetic textile wastewater including Maxilon Red GRL 200% dyestuff were investigated experimentally. While the COD and color removal rates were found as 72.5% and 69.7% via CFP; they were 87% and 75.8% by ultrasonicated CFP, respectively. The color and COD removals were 40.6% and 64.8% via MFP, and 49.9 and 73.1% by ultrasonicated MFP, respectively. Therefore, it was found that the simultaneously usage of ultrasonication with CFP and MFP was improved the COD and color removal efficiencies and oxidation rates even at lower H₂O₂ dosages, compared to individual CFP and MFP. Moreover, the color and COD removal kinetics were also modelled mathematically and compared in the study.

• Applied Chemistry for Engineering
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• v.33 no.4
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• pp.419-424
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• 2022

The oxidative degradation performance of the Erionyl Navy R dye was studied in this article. The investigation mainly focused on a comparative study between chemical oxidations by sodium hypochlorite (NaClO) and hydrogen peroxide (H₂O₂), and catalytic oxidations including the Fenton (Fe²⁺-H₂O₂) and Fenton-Like (Fe²⁺/ Fe³⁺/Co²⁺/ Mn²⁺-H₂O₂) or modified Fenton-like (Fe²⁺/ Fe³⁺ -NaClO) reactions. A discoloration and degradation of the Erionyl Navy R occurred after 30 minutes, which varies according to the oxidation system involved; 31%, 54%, <20%, 95%, and >96% losses were observed for Co²⁺-H₂O₂, Mn²⁺-H₂O₂, Fe²⁺-NaClO, Fe³⁺-NaClO), and Fe²⁺-H₂O₂ and Fe³⁺-H₂O₂, respectively.

• Journal of Soil and Groundwater Environment
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• v.12 no.2
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• pp.27-36
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• 2007

A recent study showed that MTBE can be degraded by Fenton's Reagent (FR). The treatment of MTBE with FR, however, has a definite limitation of extremely low pH requirement (optimum pH $3{\sim}4$) that makes the process impracticable under neutral pH condition on which the ferrous ion precipitate forming salt with hydroxyl anion, which result in the diminishment of the Fenton reaction and incompatible with biological treatment. Consequently, this process using only FR is not suitable for in-situ remediation of MTBE. In order to overcome this limitation, modified Fenton process using NTA, oxalate, and acetate as chelating reagents was introduced into this study. Modified Fenton reaction, available at near neutral pH, has been researched for the purpose of obtaining high performance of oxidation efficiency with stabilized ferrous or ferric ion by chelating agent. In the MTBE degradation experiment with modified Fenton reaction, it was observed that this reaction was influenced by some factors such as concentrations of ferric ion, hydrogen peroxide, and each chelating agent and pH. Six potential chelators including oxalate, succinate, acetate, citrate, NTA, and EDTA were tested to identify an appropriate chelator. Among them, oxalate, acetate, and NTA were selected based on their remediation efficiency and biodegradability of each chelator. Using NTA, the best result was obtained, showing more than 99.9% of MTBE degradation after 30 min at pH 7; the initial concentration of hydrogen peroxide, NTA, and ferric ion were 1470 mM, 6 mM, and 2 mM, respectively. Under the same experimental condition, the removal of MTBE using oxalate and acetate were 91.3% and 75.8%, respectively. Optimum concentration of iron ion were 3 mM using oxalate which showed the greatest removal efficiency. In case of acetate, $[MTBE]_0$ decreased gradually when concentration of iron ion increased above 5 mM. In this research, it was showed that modified Fenton reaction is proper for in-situ remediation of MTBE with great efficiency and the application of chelatimg agents, such as NTA, was able to make the ferric ion stable even at near neutral pH. In consequence, the outcomes of this study clearly showed that the modified Fenton process successfully coped with the limitation of the low pH requirement. Furthermore, the introduction of low molecular weight organic acids makes the process more available since these compounds have distinguishable biodegradability and it may be able to use natural iron mineral as catalyst for in situ remediation, so as to produce hydroxyl radical without the additional injection of ferric ion.