Catalytic treatment of petrochemical wastewater by electroassisted Fenton technologies

The electro-Fenton process, in which ferrous ions are produced on the anode and used as catalyst, was applied for treating the bioeffluent of petrochemical manufacturing wastewater.     

Optimization of multiple parameters for treatment of coking wastewater using Fenton oxidation

Present study deals with the treatment of coking wastewater (CWW) using Fenton oxidation process for the degradation of pollutants containing chemical oxygen demand (COD), phenol and cyanide. The experiments were performed in batch mode to study the effect of operating parameters like initial pH (pH_i), temperature (T), oxidant H₂O₂ amount, catalyst mass loading (Cw) and treatment time (t_R). The response surface methodology (RSM) gave optimum value of pH, H₂O₂, Cw and t_R as 3, 0.3 M, 1.85 g/L (0.0266 M) and 1.52 h. At this optimum operating condition maximum 84.66% COD, 88.46% phenol and 79.34% cyanide reduction were achieved from initial value of COD (COD_i) = 2810.0 mg/L, phenol_i = 283.0 mg/L and cyanide_i = 18.88 mg/L. Results reflect that Fenton oxidation is an effective process for the reduction of pollutants present in CWW. The CWW treated by Fenton oxidation having average value COD = 590.0 mg/L, phenol = 39.49 mg/L and cyanide = 5.2 mg/L was further treated by adsorption process as second stage treatment, and these values were reached to COD = 199.0 mg/L, phenol = 0.0 mg/L and cyanide = 2.36 mg/L. The response surface methodology (RSM) was used for the designing and optimization of the experiments. Analysis of variance (ANOVA) suggested the high regression coefficient R² = 0.999 and 0.993 for COD and phenol removal respectively. The two stage treated CWW can be recycled and reused in same industry for various purpose.     

Experimental design approach for petrochemical waste water treatment using solar assisted photo Fenton process

In this study, the effect of photo-Fenton process on the treatment of petrochemical waste water treatment was investigated. The influence of process conditions were determined by factorial design. Optimization of the process conditions were performed by central composite design. Under, optimized conditions lab scale and solar assisted pilot scale of petrochemical waste water treatment was performed. Three factors namely initial pH, H₂O₂ concentration (mM) and Fe²⁺ concentration (mM) executed the essential role in petrochemical waste water treatment. Central composite design resulted in the prediction of optimized value as 6.5 initial pH, 15.65 mM of H₂O₂ concentration and 2.09 mM of Fe²⁺ concentration. Under these conditions, the reduction in chemical oxygen demand (COD) percentage reached about 68.67 ± 2.8% after 280 min in pilot scale of solar assisted photo Fenton process of petrochemical waste water treatment. Thus, experimental design combined with advanced Fenton process can become a feasible unconventional method for petrochemical waste water treatment.     

Oxidative Degradation of 2,4‐Dihydroxybenzoic Acid by the Fenton and Photo‐Fenton Processes: Kinetics,Mechanisms, and Evidence for the Substitution of H2O2 by O2

The kinetics and mechanisms of the oxidative degradation of 2,4‐dihydroxybenzoic acid (2,4‐DHBA) by the Fenton and photo‐Fenton processes were investigated in detail by a combination of HPLC, IC, and TOC analyses. The formation of 2,3,4‐trihydroxybenzoic acid (2,3,4‐THBA) at an early oxidation stage shows that hydroxylation of the aromatic ring is the first step of the process. This intermediate was able to reduce Fe^III and to contribute to the recycling of Fe^II. Complete mineralization could only be achieved under irradiation (photo‐Fenton). A detailed study of the dependence of the rate of mineralization on the concentration of H₂O₂ and dissolved O₂ was carried out. It was found that, even at a low initial concentration of H₂O₂, mineralization by the photo‐Fenton process was complete in a relatively short time, provided that the O₂ concentration was high enough, indicating that O₂ may, at least in part, substitute H₂O₂. Channeling reaction pathways toward O₂ rather than H₂O₂ consumption is of particular interest for the technical development of the photo‐Fenton process.     

Aromatic free Fenton process for rapid removal of phenol from refinery wastewater in an oscillatory baffled reactor

The need for clean, safe, and unpolluted water has recently become an important issue. Industrial processes such as petrochemical, pharmaceutical, pulp, and paper industries emit organic products in water, such as phenols, which are extremely toxic to aquatic life. The severe operating conditions, such as high pressure and temperature, of the conventional chemical oxidation processes of phenols cost a lot and limited the extensive application of the process. The present work depicts the development of a highly efficient and rapid oxidation process in an oscillating baffled reactor (OBR) to allow continuous and safe phenol removal under moderate operating conditions. Phenol conversion was studied as a function of initial concentration (300–500 ppm), pH (3–5), residence time (1–5 min), at constant amplitude (A = 4 mm), and frequency (f = 4 Hz) of oscillation and room temperature to achieve up to 94.6%. At 70 °C, 300 ppm starting concentration, pH = 3, 4 Hz frequency, and 4 mm amplitude, an exceptional removal of 99.858% phenol was achieved without additional extraction in just 3 min by optimizing the working parameters. This is a significant improvement over comparable processes at this temperature, and it was done in a reactor that scales up reliably, so this performance can likely be replicated on a large scale. Also, the present process was safe as it produced a nil concentration of the hazardous Fenton intermediate compounds.     

A Novel Energy-from-Waste Approach for Electrical Energy Production by Galvano–Fenton Process

A novel approach allowing the production of electrical energy by an advanced oxidation process is proposed to eliminate organic micropollutants (MPs) in wastewaters. This approach is based on associating the Galvano–Fenton process to the generation of electrical power. In the previous studies describing the Galvano–Fenton (GF) process, iron was directly coupled to a metal of more positive potential to ensure degradation of organic pollutants without any possibility of producing electrical energy. In this new approach, the Galvano–Fenton process is constructed as an electrochemical cell with an external circuit allowing recovering electrons exchanged during the process. In this study, Malachite Green (MG) dye was used as a model of organic pollutant. Simultaneous MG degradation and electrical energy production with the GF method were investigated in batch process. The investigation of various design parameters emphasis that utilization of copper as a low-cost cathode material in the galvanic couple, provides the best treatment and electrical production performances. Moreover, these performances are improved by increasing the surface area of the cathode. The present work reveals that the GF process has a potential to provide an electrical power density of about 200 W m⁻². These interesting performances indicate that this novel Energy-from-Waste strategy of the GF process could serve as an ecological solution for wastewater treatment.     

A Review on the Degradation of Pollutants by Fenton-Like Systems Based on Zero-Valent Iron and Persulfate: Effects of Reduction Potentials,pH, and Anions Occurring in Waste Waters

Among the advanced oxidation processes (AOPs), the Fenton reaction has attracted much attention in recent years for the treatment of water and wastewater. This review provides insight into a particular variant of the process, where soluble Fe(II) salts are replaced by zero-valent iron (ZVI), and hydrogen peroxide (H₂O₂) is replaced by persulfate (S₂O₈²⁻). Heterogeneous Fenton with ZVI has the advantage of minimizing a major problem found with homogeneous Fenton. Indeed, the precipitation of Fe(III) at pH > 4 interferes with the recycling of Fe species and inhibits oxidation in homogeneous Fenton; in contrast, suspended ZVI as iron source is less sensitive to the increase of pH. Moreover, persulfate favors the production of sulfate radicals (SO₄^•−) that are more selective towards pollutant degradation, compared to the hydroxyl radicals (^•OH) produced in classic, H₂O₂-based Fenton. Higher selectivity means that degradation of SO₄^•−-reactive contaminants is less affected by interfering agents typically found in wastewater; however, the ability of SO₄^•− to oxidize H₂O/OH⁻ to ^•OH makes it difficult to obtain conditions where SO₄^•− is the only reactive species. Research results have shown that ZVI-Fenton with persulfate works best at acidic pH, but it is often possible to get reasonable degradation at pH values that are not too far from neutrality. Moreover, inorganic ions that are very common in water and wastewater (Cl⁻, HCO₃⁻, CO₃²⁻, NO₃⁻, NO₂⁻) can sometimes inhibit degradation by scavenging SO₄^•− and/or ^•OH, but in other cases they even enhance the process. Therefore, ZVI-Fenton with persulfate might perform unexpectedly well in some saline waters, although the possible formation of harmful by-products upon oxidation of the anions cannot be ruled out.     

Quantum chemistry study on the formation of OH radical for NO oxidation by heterogeneous Fenton reaction

The denitrification of low-temperature flue gas is a difficult problem facing the industry. OH radicals can effectually oxidize NO in flue gas, which can achieve denitrification of low-temperature flue gas. Heterogeneous Fenton reaction is an important method for the formation of OH radicals. A four-step reaction mechanism of the formation of OH radicals by heterogeneous Fenton reaction is proposed and investigated in this paper. Theoretical results show that activation energy of the formation of OH radicals catalyzed by ZSM5-Si/Fe is much lower than that without catalyst. After doping Al/Ce/Ti, the activation energy is further reduced significantly. The activity is related to the active center atom of the catalyst. By comparing, ZSM5-Ce/Al–Fe has better catalytic performance because of its more fluffy structure. This study would provide an important theoretical reference for the design of the catalysts in heterogeneous Fenton reaction and their industrial applications.     

A Novel and Convenient Assay for the Determination of OH Produced by Fenton Reaction

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Parametric study for the treatment of tannery dye wastewater by electro-oxidation

Degradation of tannery effluents is a difficult operation because of their intricate chemical structures. Most of the conventional approaches are becoming ineffective because of the wide variation in the composition of tannery effluent. Dyes from the wastewater is also dangerous, as the wastewater has negative impact on the health of human being, plants and aquatic animals. For the first time once through continuous approach was employed for the removal of Acid yellow 110 tannery dye in electro-oxidation process on Mix Metal Oxide of ruthenium and iridium on titanium sheet electrode. The effects of pH, time (t) and current (i) on % color removal and energy consumed were investigated in a batch setup and found the optimum condition with the help of RSM design. The values of the responses Y₁ and Y₂ were found to be 93.08% and 1.07 kWh/m³ respectively at the optimum condition. Toxicity Bioassay analysis, GC-MS analysis and the kinetic study were performed at optimum condition. At the flow rates of 10–40 ml/min once through continuous experiments was conducted to found the feasibility of the process at pilot scale or industrial scale application.     

A novel comparative study of different layered silicate clay types on exfoliation process and final nanostructure of trifunctional epoxy nanocomposites

The effect of three different organically modified layered silicate clays (Nanomer I.30E, Cloisite 30B and Nanofil SE 3000) on the exfoliation process and on the thermal properties and nanostructure of cured trifunctional epoxy resin based nanocomposites was studied. Optical microscopy showed that the best and poorest qualities of clay distribution in the epoxy matrix were obtained with Nanofil SE 3000 and Nanomer I.30E, respectively. However, the isothermal differential scanning calorimetry scans show that, of the three systems, it is only the Nanomer clay that promotes intra-gallery reaction due to homopolymerisation, appearing as an initial rapid peak prior to the cross-linking reaction. This rapid intra-gallery reaction is not present in the curing curve for the Cloisite and Nanofil systems. This fact implies that the fully cured nanostructure of the Cloisite and Nanofil system is poorly exfoliated, which is confirmed by small angle X-ray scattering which shows a scattering peak for these systems at around 2.53°, corresponding to about 3.5 nm d-spacing.     

A comparative study of different cellulase preparations in the enzymatic treatment of cotton fabrics

Twenty-nine cellulase preparations from different sources were compared interms of their abrasive activities (the ability to remove Indigo from denim) and their ability tosaccharify cellulose. Nodirectrelationship could be found between these two abilities. The preparations were divided into three groups: (1) with a high yield of reducing sugars after 24 h hydrolysis of Avicel cellulose but low abrasive activity; (2) universal cellulases that could both effectively hydrolyze cellulose and remove Indigo from denim; and (3) cellulase samples with high abrasive activity but low saccharification ability. Cellobiohydrolase (CBH) and xylanase were purified from different fungi by chromatofocusing on a Mono P column and subjected to limited proteolysis with papain yielding cellulose-binding and core (catalytic) domains. The adsorption ability and backstaining index of both CBH and xylanase core proteins were notably lower than the respective parameters for the in itial nondigested enzymes indicating that protein adsorption on the surface of cotton fibers is a crucial factor causing Indigo backstaining during the enzymatic denim washing procedure.     

A study of rubber flow in a mold during the tire shaping process using experiment and computer simulation

Automobile tires consist of more than ten layers, including tread, belt, carcass, sidewall, etc. The outermost layer, known as the tread, plays an important role during driving as it comes in direct contact with the road. This tread has grooves with complicated shapes, which are formed by a mold during the shaping process. When the tread rubber does not fill the mold properly, tire quality deteriorates crucially. As such, it is important to observe the flow of the tread rubber during the shaping process. To determine the flow of tread rubber in the mold, we conducted an experiment and computer simulation with white rubber strips inserted into specific areas of the tread. The white rubber strips showed detailed flow behavior of the tread rubber visually in the mold during the shaping process. No significant flows were observed for rubber in the central area of each block of the mold, but more changes were found near the edges of each block. The strips of rubber below the grooves exhibited more significant changes as they were pressed down by the protruding area of the mold. Moreover, there was no flow of rubber between blocks in the mold. This implies the profile design of the extruded tread should match the mold profile and the volume of each block. The experiment and simulation had similar results, and the observations of rubber flow in the mold using simulation proved to be highly useful.     

Determination of aqueous ozone for potable water treatment applications by chemiluminescence flow-injection analysis. A feasibility study

The feasibility of determining aqueous ozone by chemiluminescence flow-injection analysis (CL-FIA) was studied for applications in potable water treatment. The ozonated water sample is injected into a pure water carrier and mixed with a dye reagent in front of a photodetector. Many reagents undergo fast CL reactions with aqueous ozone. Most of these reactions display considerable selectivity for ozone over other oxidants of importance in water treatment. Even when there is steady-state response to another oxidant, significant discrimination against the interferents is possible by taking advantage of the much faster kinetics of the CL reaction with ozone. A simple design of a Siemens-type ozone generator and preparation of standard ozone solutions are also described.     

有机分子生成热计算的对比研究

采用20种理论方法计算了180个中小型有机分子的生成热.结果表明:HF是最差的方法,一般不宜采用;OLYP,B3PW91和M05-2X分别是GGA,Hybrid GGA和Hybridmeta-GGA方法中计算偏差最小的一种方法;对于所有的计算方法,中型分子的计算偏差要大于小型分子的计算偏差;小型分子和中型分子计算偏差最小的方法分别是B3PW91和M05-2X;M05-2X所计算的偏差比其他方法集中;随着分子尺度的增加,M05-2X,M06-2X,M06-HF和经典G4方法所计算结果的偏差呈波浪型缓慢增加.     

Functionalized mesoporous materials for adsorption and release of different drug molecules: A comparative study

The adsorption capacity and release properties of mesoporous materials for drug molecules can be improved by functionalizing their surfaces with judiciously chosen organic groups. Functionalized ordered mesoporous materials containing various types of organic groups via a co-condensation synthetic method from 15% organosilane and by post-grafting organosilanes onto a pre-made mesoporous silica were synthesized. Comparative studies of their adsorption and release properties for various model drug molecules were then conducted. Functional groups including 3-aminopropyl, 3-mercaptopropyl, vinyl, and secondary amine groups were used to functionalize the mesoporous materials while rhodamine 6G and ibuprofen were utilized to investigate the materials’ relative adsorption and release properties. The self-assembly of the mesoporous materials was carried out in the presence of cetyltrimethylammonium bromide (CTAB) surfactant, which produced MCM-41 type materials with pore diameters of ∼2.7-3.3 nm and moderate to high surface areas up to ∼1000 m²/g. The different functional groups introduced into the materials dictated their adsorption capacity and release properties. While mercaptopropyl and vinyl functionalized samples showed high adsorption capacity for rhodamine 6G, amine functionalized samples exhibited higher adsorption capacity for ibuprofen. While the diffusional release of ibuprofen was fitted on the Fickian diffusion model, the release of rhodamine 6G followed Super Case-II transport model.     

A study of catalysts for desulphurization process by thermal analysis

A number of catalysts were prepared for the desulphurization process of tail gases. Their carrier was alumina oxide while the active phase was manganese. The catalysts were being tested in an lab apparatus. The effect of calcination temperature and process temperature of model gas (1 vol% of SO₂+99 vol% of N₂) were studied. The increase in the desulphurization temperature up to about 500°C causes the efficiency of the desulphurizing yield to be increased, a further increase of the temperature process decreases the SO₂ conversion. The DTA curves of catalysts after the desulphurizing process display the additional peak at a temperature of about 900°C being, perhaps, responsible for deactivation of the catalysts.     

Selection of solvent for the mechanical activation process: A molecular dynamics simulation and experiment study

Herein, molecular dynamics simulations and experiments were carried to select solvent for the mechanical activation process. The interaction between solvent and each component of the Al‐PTFE mechanical activated energy composites has been studied by means of molecular dynamics. Then, the status of Al and PTFE in solvent was analyzed, and the microstructure of the composite was also studied combined with experiment. At last, the mechanical activated energy composites were prepared with n‐hexane as the solvent. The results show that the adsorption of PTFE, toluene, and hexane on the (0 0 1), (0 1 0), and (100) surface of Al₂O₃ is stable. Al₂O₃ (0 0 1) surface and Al₂O₃ (0 1 0) surface interact with 3 substances mainly via the electrostatic force. Al₂O₃ (1 0 0) surface interacts with 3 substances mainly via the van der Waals force. The binding energies of toluene‐Al₂O₃ and hexane‐Al₂O₃ are larger than PTFE‐Al₂O₃. PTFE cannot adsorb on the surface of aluminum in the existence of n‐hexane and toluene. n‐Hexane can make PTFE disperse uniformly, and a considerable part of these PTFE will be coated on the surface of Al after n‐hexane is removed. The uniformity of Al/PTFE mechanical activated energetic composites prepared in n‐hexane is good, and it increases with the milling time.     

Flow injection analysis of ethyl xanthate by gas diffusion and UV detection as CS2 for process monitoring of sulfide ore flotation

A sensitive and robust analytical method for spectrophotometric determination of ethyl xanthate, CH₃CH₂OCS₂⁻ at trace concentrations in pulp solutions from froth flotation process is proposed. The analytical method is based on the decomposition of ethyl xanthate, EtX⁻, with 2.0 mol L⁻¹ HCl generating ethanol and carbon disulfide, CS₂. A gas diffusion cell assures that only the volatile compounds diffuse through a PTFE membrane towards an acceptor stream of deionized water, thus avoiding the interferences of non-volatile compounds and suspended particles. The CS₂ is selectively detected by UV absorbance at 206 nm (? = 65,000 L mol⁻¹ cm⁻¹). The measured absorbance is directly proportional to EtX⁻ concentration present in the sample solutions. The Beer's law is obeyed in a 1 × 10⁻⁶ to 2 × 10⁻⁴ mol L⁻¹ concentration range of ethyl xanthate in the pulp with an excellent correlation coefficient (r = 0.999) and a detection limit of 3.1 × 10⁻⁷ mol L⁻¹, corresponding to 38 μg L⁻¹. At flow rates of 200 μL min⁻¹ of the donor stream and 100 μL min⁻¹ of the acceptor channel a sampling rate of 15 injections per hour could be achieved with RSD < 2.3% (n = 10, 300 μL injections of 1 × 10⁻⁵ mol L⁻¹ EtX⁻). Two practical applications demonstrate the versatility of the FIA method: (i) evaluation the free EtX⁻ concentration during a laboratory study of the EtX⁻ adsorption capacity on pulverized sulfide ore (pyrite) and (ii) monitoring of EtX⁻ at different stages (from starting load to washing effluents) of a flotation pilot plant processing a Cu-Zn sulfide ore.