Ming-Chun Lu

Catalytic decomposition of hydrogen peroxide and 2-chlorophenol with iron oxides.

The aim of this study was to examine the catalyzed decomposition of hydrogen peroxide and 2-chlorophenol (2-CP) in the presence of iron oxides. Granular ferrihydrite, goethite, and hematite were selected as catalysts in this study. 2-CP was used as the model compound because it is a typical toxic compound and has not been investigated in the catalytic decomposition by iron oxides. The catalytic activity for hydrogen peroxide decomposition followed the sequence: granular ferrihydrite > goethite > hematite. However, hematite exhibited the highest activity in catalyzing 2-CP oxidation. The oxidation efficiency of 2-CP corresponded with the inverse sequence of specific area and pHpzc of the iron oxides. The catalytic activity of granular ferrihydrite was affected significantly by the mixing speed and particle size for its large value of Thiele modulus (phi) and Damkohler number (Da). The strong diffusion resistance for granular ferrihydrite was attributed either to its microporous structure or to the formation of oxygen in the pores of the iron oxide leading to the unexpected catalytic activity of granular ferrihydrite to hydrogen peroxide and 2-CP.

Chemical oxidation of 2,6-dimethylaniline in the fenton process.

2,6-Dimethylaniline degradation by Fenton process has been studied in depth for the purpose of learning more about the reactions involved in the oxidation of 2,6-dimethylaniline under various reaction conditions. The effect of reaction conditions including the initial pH value, and the dosages of ferrous ions and hydrogen peroxide on 2,6-dimethylaniline and COD removal were investigated. 2,6-Dimethylaniline removal efficiency of 70% was achieved under optimal reaction conditions of pH value of 2, dosage of 2 mM of ferrous ion, and 20 mM of hydrogen peroxide after 3 h. A series of intermediates were identified, corresponding to ring compounds and short-chain organic acids. The intermediates were 2,6-dimethylphenol, 2,6-dimethylnitrobenzene, 2,6-dimethylbenzoquinone, 3-hexanone, maleic acid, acetic acid, formic acid, and oxalic acid. An oxidation pathway of the target organic was also proposed in this study.

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.

Role of goethite dissolution in the oxidation of 2-chlorophenol with hydrogen peroxide.

It is well known that the dissolution of goethite plays an important role in catalyzing the oxidation of organic chemicals. Therefore, this study investigates how surface dissolution of goethite affects 2-chlorophenol oxidation in the goethite/H2O2 process. Experimental results indicate that ligand and reductant can enhance the dissolution rate of goethite, which is surface-controlled. Our results further indicate 2-chlorophenol degradation depends on goethite concentration. In addition, the oxidation rate of 2-CP is correlated with reductive dissolution rate at various dosages of goethite. Moreover, the oxidation mechanism of 2-CP is also a surface-controlled reaction. A mechanism proposed herein indicates that, in addition to the contaminant, its intermediate species affect the oxidation rate as well.

Oxidation of explosives by Fenton and photo-Fenton processes

In this study, the Fenton process was used to explore the possibility of treating explosives, namely 2,4,6-trinitrophenol (PA), ammonium picronitrate (AP), 2,4-dinitrotoluene (DNT), methyl-2,4,6-trinitrophenylnitramine (Tetryl) and 2,4,6-Trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The photo-Fenton process was also conducted to compare its oxidation efficiency with the Fenton process. The inhibition of hydroxyl radical and theory of crystal field stabilization energy were introduced in this study. Results show that oxidation efficiencies in Fenton system are in the following sequence: DNT > PA > AP > TNT > Tetryl > RDX > HMX. The degradation of the explosives obeys a pseudo-first-order behavior, and possible decomposing mechanisms are also discussed. For all explosives, the oxidation rates significantly increased with increasing the concentration of Fe(II), as well as illumination with UV light.

Acetaminophen degradation by electro-Fenton and photoelectro-Fenton using a double cathode electrochemical cell.

Acetaminophen is a widely used drug worldwide and is one of the most frequently detected in bodies of water making it a high priority trace pollutant. This study investigated the applicability of the electro-Fenton and photoelectro-Fenton processes using a double cathode electrochemical cell in the treatment of acetaminophen containing wastewater. The Box-Behnken design was used to determine the effects of initial Fe(2+) and H(2)O(2) concentrations and applied current density. Results showed that all parameters positively affected the degradation efficiency of acetaminophen with the initial Fe(2+) concentration being the most significant parameter for both processes. The acetaminophen removal efficiency for electro-Fenton was 98% and chemical oxygen demand (COD) removal of 43% while a 97% acetaminophen removal and 42% COD removal were observed for the photoelectro-Fenton method operated at optimum conditions. The electro-Fenton process was only able to obtain 19% total organic carbon (TOC) removal while the photoelectro-Fenton process obtained 20%. Due to negligible difference between the treatment efficiencies of the two processes, the electro-Fenton method was proven to be more economically advantageous. The models obtained from the study were applicable to a wide range of acetaminophen concentrations and can be used in scale-ups. Thirteen different types of intermediates were identified and a degradation pathway was proposed.

Kinetics of 2,6-dimethylaniline degradation by electro-Fenton process.

A new approach for promoting ferric reduction efficiency using a different electrochemical cell and the photoelectro-Fenton process has been developed to degrade organic toxic contaminants. The use of UVA light and electric current as electron donors can efficiently initiate the Fenton reaction. 2,6-Dimethylaniline (2,6-DMA) was the target compound in this study. Effects of initial pH (pH(i)), Fe(2+) loading, H(2)O(2) concentration and current density were determined to test and to validate a kinetic model for the oxidation of organic compound by the electro-Fenton process. Kinetic results show evidence of pseudo-first-order degradation. When reaction pH was higher than 2, amorphous Fe(OH)(3(s)) was generated. Increasing ferrous ion concentration from 1.0 to 1.5 mM increased the hydroxyl radicals and then promote the degradation efficiency of 2,6-DMA. The optimal H(2)O(2) concentration for 2,6-DMA degradation in this study was 25 mM. The degradation of 2,6-DMA was increased with the increase of current density from 3.5 to 10.6 A/m(2). Oxalic acid was the major detected intermediate of 2,6-DMA degradation. The final TOC removal efficiencies were 10%, 15%, 60% and 84% using the electrolysis, Fenton, electro-Fenton and photoelectro-Fenton processes, respectively.

Effect of hydrogen peroxide on aniline oxidation by electro-Fenton and fluidized-bed Fenton processes

In this study, the electro-Fenton and fluidized-bed Fenton processes under the given conditions were used to oxidize aniline. Factors such as feeding mode and concentration of the hydrogen peroxide were explored. Results showed that the feeding mode of H(2)O(2) did not significantly affect the aniline oxidation in the electro-Fenton process. However, the aniline oxidation slightly decreased with the two-step addition of H(2)O(2) in the fluidized-bed Fenton process. Presumably the decline of remaining Fe(2+) led to destitute hydrogen radicals from the Fe(2+)-catalyzed H(2)O(2). In addition, the removal efficiency of aniline was maintained at a maximum as H(2)O(2) concentration was higher than 0.04 M in the electro-Fenton process. Meanwhile, the almost exhausted H(2)O(2) would increase the amount of Fe(2+) in the solution for the electro-Fenton process. This is because the Fe(2+) is regenerated through the reduction of Fe(3+) on the cathode. The electro-Fenton process has a stronger oxidative ability with regard to the production of the oxalic acid than fluidized-bed Fenton process which was attributed to a higher consumption of H(2)O(2). Therefore, in the aspect of H(2)O(2) depletion, the mineralization efficiency of the fluidized-bed Fenton process was higher than that of the electro-Fenton process.

The reactor design and comparison of Fenton, electro-Fenton and photoelectro-Fenton processes for mineralization of benzene sulfonic acid (BSA)

A new approach for promoting ferric reduction efficiency using a different electrochemical cell and the photoelectro-Fenton process has been developed. The use of UVA light and electric current as electron donors can efficiently initiate the Fenton reaction. Benzene sulfonic acid (BSA) was the target compound in this study. The parameters investigated to evaluate the reactor design include the electrode working area, electrode distance, energy consumption. Furthermore, the study also contains the intermediates and the mineralization efficiency of electrolysis, Fenton, electro-Fenton and photoelectro-Fenton process. Oxalic acid, the major intermediate of aromatic compound degradation, can complex with ferric ions. Meanwhile, a double cathode reactor could increase the current efficiency by 7%, which would translate to greater ferrous production and a higher degradation rate. Although the current efficiency of an electrode distance 5.5 cm device is 19% higher than 3.0 cm, results show that after 2 h of electrolysis the electronic expense using an electrode gap of 5.5 cm is much higher than 3.0 cm. The final TOC removal efficiency was 46, 64 and 72% using the Fenton, electro-Fenton and photoelectron-Fenton processes, respectively.

Chemical oxidation of 2,6-dimethylaniline by electrochemically generated Fenton's reagent.

Oxidation of 2,6-dimethylaniline by electro-Fenton process in acidic solution at pH 2 was investigated. The effects of pH, Fe(2+), H(2)O(2) and current density were assessed to determine the optimum operating parameters. The oxidation efficiency of 2,6-dimethylaniline was determined by the reduction of 2,6-dimethylaniline, COD and TOC in the solutions. Results reveal that 1 mM of 2,6-dimethylaniline can be completely degraded in 4 h with 1 mM of Fe(2+) and 20 mM of H(2)O(2) and current density of 15.89 A m(-2) at pH 2. The highest COD and TOC removal were observed when 120 mM of hydrogen peroxide was applied. Consequently, the electro-Fenton process is a reliable alternative in the degradation of 2,6-dimethylaniline. 2,6-dimethylphenol, 2,6-dimethylnitrobenzene, 2,6-dimethylbenzoquinone, 3-hexanone, lactic acid, oxalic acid, acetic acid, maleic acid and formic acid were detected during the degradation of 1 mM of 2,6-dimethylaniline solution by electro-Fenton method. A reaction pathway that includes these products is proposed for 2,6-dimethylaniline degradation.