Oxidative decolorization of methylene blue using pelagite

Pelagite generally has large surface area and high adsorbing and oxidizing reactivity due to highly amorphous nature, and high reducing potential of Mn (hydro)oxide phases present in it. In the present study, pelagite, collected from the East Pacific Ocean, was tested as a potential oxidant for decolorization of methylene blue (MB) in a batch system under air-bubbling and motor-stirring conditions. The effects of suspension pH (3.0-10.0), MB concentration (10-100 mgL(-1)) and loading (0.2-3.0 gL(-1)), and particle size (100-200 mesh) of pelagite on kinetics of MB decolorization were assessed. Results show that in typical concentration range of dye wastewaters (10-50 mgL(-1)), pelagite can be used as a highly efficient material for oxidative degradation of MB. MB decolorization was through a surface mechanism, that is, formation of surface precursor complex between MB and surface bound Mn(III, IV) center, followed by electron transfer within the surface complex. Iron (hydro)oxide phases present in the pelagite did not play an important role in MB decolorization. Suspension pH exerted double-edged effects on MB decolorization by influencing the formation of surface precursor complex, and reducing potential of the system. Kinetic rate of MB decolorization is directly proportional to saturation degree of available reaction sites by MB adsorption. At the initial and later stages, the kinetics for MB decolorization with respect to MB concentration, pelagite loading, and particle size could be described separately using two pseudofirst rate equations, except at very high pelagite loading (3.0 mgL(-1)). Accumulation of Mn(2+) and probably some organic intermediates exerted marked inhibitory effect on MB decolorization. Vigorous dynamic condition was favorable for MB decolorization. The presence of oxygen could enhance MB decolorization to a limited extent.     

Wet electrolytic oxidation of cationic red X-GRL

Wet electrolytic oxidation (WEO) under mild condition, a relatively less reported process which coupled the advantages of both wet air oxidation (WAO) and electrochemical oxidation (EO) was investigated for the removal of one azo dye, cationic red X-GRL, in a 2L autoclave reactor. It was found that this novel process showed synergistic effect for TOC removal compared with that by the individual WAO and EO, and presented much higher dye removal efficiency. At similar conditions of temperature of 100-180 degrees C, P(N(2))= 0.50 MPa and P(O(2))= 0.14 MPa, a little introduction of current density of 2 mA cm(-2) led to the apparent reaction constants for WEO two times larger than those of WAO. Possible mechanism for the synergistic effect was discussed based on the analysis of free-radical generation and intermediates detected by GC/MS.     

Photocatalytic degradation for methylene blue using zinc oxide prepared by codeposition and sol-gel methods

Zinc oxide nanoparticle was obtained by zinc hydrate deposited on the silica nanoparticle surface and zinc hydrate was dispersed in starch gel. The structure of zinc oxide particle was characterized by nitrogen adsorption-desorption and XRD, the morphology was observed by TEM. The result showed that the zinc oxide nanoparticle deposited on the silica nanoparticle surface was well-dispersed and less than 50nm, displayed higher photocatalytic activity for methylene blue degradation. However, the zinc oxide nanoparticle in a size of 60nm was derived from starch gel and showed poorer photocatalytic activity. It provided a simple and effective route to prepare zinc oxide nanoparticle with higher photocatalytic activity through depositing zinc oxide on the silica particle surface, moreover, the catalyst is easier to recover due to its higher density.     

Wet peroxide oxidation and catalytic wet oxidation of stripped sour water produced during oil shale refining

Catalytic wet oxidation (CWO) and wet peroxide oxidation (WPO) of stripped sour water (SSW) from an oil shale refinery was investigated. Greater than 70% total organic carbon (TOC) removal from SSW was achieved using Cu(NO(3))(2) catalysed WO under the following conditions using a glass lined reaction vessel: 200 degrees C, pO(2)=0.5MPa, 3h, [Cu(NO(3))(2)]=67mmol/L. Significant TOC removal ( approximately 31%) also occurred in the system without added oxygen. It is proposed that this is predominantly due to copper catalysed oxidative decarboxylation of organics in SSW based on observed changes in copper oxidation state. Greater than 80% TOC removal was achieved using WPO under the following conditions: 150 degrees C, t=1.5h, [H(2)O(2)]=64g/L. Significantly more TOC could be removed from SSW by adding H(2)O(2) in small doses as opposed to adding the same total amount in one single dose. It was concluded that WPO was a far more effective process for removing odorous compounds from SSW.     

Photoelectrocatalytic oxidation of remazol turquoise blue and toxicological assessment of its oxidation products

The ability of photoelectrocatalytic oxidation to degrade the commercially important copper-phtalocyanine dye, remazol turquoise blue 15 (RTB) was investigated. The best experimental condition was optimized, evaluating the performance of Ti/TiO2 thin-film electrodes prepared by sol-gel method in the decolourization of 32 mg L(-1) RTB dye in 0.5 mol L(-1) Na2SO4 pH 8 and applied potential of +1.5 V versus SCE under UV irradiation. Spectrophotometric measurements, high performance liquid chromatography, dissolved organic carbon (TOC) evaluation and stripping analysis of yielding solution obtained after 3 h of photoelectrolysis leads to 100% of absorbance removal from wavelength of 250-800 nm, 79.6% of TOC reduction and the releasing of up to 54.6% dye-bound copper (0.85 mg L(-1)) into the solution. Both, original and oxidized dye solution did not presented mutagenic activity with the strains TA98 and TA100 of Salmonella in the presence and absence of S9 mix at the tested doses. Nevertheless, the yielding photoelectrocatalytic oxidized solution showed an increase in the acute toxicity for Vibrio fischeri bacteria, explained by copper liberation during treatment.     

Photodecomposition of 4-chlorophenol by reactive oxygen species in UV/air system

In this article, the photo-degradation of 4-chlorophenol (4-CP) under UV irradiation was studied with focus on the photodecomposition of 4-CP by reactive oxygen species (ROS). 4-CP underwent much faster and more complete degradation in UV/air system than in UV/N₂ system. In UV/air system, the addition of t-butanol, a well-known ^•OH scavenger, significantly impeded the degradation of 4-CP. In the presence of t-butanol, the tendencies for the degradation of 4-CP and the formation of intermediates in UV/air system were very similar to those in UV/N₂ system. In UV/air system, 4-CP was degraded by two pathways, direct photolysis by absorbing the photons and the oxidation via ^•OH. The contribution of direct photolysis and the oxidation via ^•OH to 4-CP decomposition were 17.2% and 82.8%, respectively based on the apparent kinetic constants. Hydrogen peroxide, which could produce ^•OH through photolysis, was formed in UV/air system. It was shown that dissolved oxygen, organic matter in excited state and hydrogen ion are all necessary for the formation of hydrogen peroxide. The formation mechanism of H₂O₂ was proposed based on experimental evidence.     

Phenol oxidation by a sequential CWPO–CWAO treatment with a Fe/AC catalyst

Catalytic wet peroxide oxidation (CWPO) of phenol with a homemade Fe/activated carbon (Fe/AC) catalyst has been studied in a stainless steel fixed-bed reactor at different operating conditions (T = 23–100 °C, P_T = 1–8 atm, W = 0–2.5 g, and τ = 20–320 g_CAT h/g_Phenol). The results show that, thanks to the incorporation of Fe on the activated carbon, phenol conversion improved dramatically, reaching a 90% at 65 °C, 2 atm, and 40 g_CAT h/g_Phenol. However, TOC conversion values remain fairly low, (around 5% at 40 g_CAT h/g_Phenol), and no improvement was obtained with the inclusion of Fe. The presence of Fe seems to promote the nondesirable coupling reactions that take place in CWPO of phenol due to the condensation of the ring intermediates (the primary phenol oxidation products). These condensation products are quite refractory to CWPO at the conditions employed. Taking advantage of the high phenol conversions in CWPO and the high phenol mineralization in CWAO, along with the good stability of the Fe/AC catalyst, a CWPO–CWAO sequential treatment has been successfully performed by using a fixed-bed and trickle-bed reactor in series. A CWPO treatment at ambient conditions followed by a CWAO treatment at mild conditions (100 °C and 8 atm) is presented as high efficiency process for the decontamination of phenolic wastewaters.     

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.     

Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering

Zn-doped TiO₂ films were prepared by means of pulsed DC reactive magnetron sputtering method using Ti and Zn mixed target. The deposition condition was optimized to produce uniform and transparent TiO₂ films. Titanium was in the Ti⁴⁺ oxidation state in all Zn-doped TiO₂ films. The zinc oxide deposited on the substrate was in the fully oxidized state of ZnO. Increase of zinc concentration inhibited the crystal growth in the TiO₂ films. The surface morphology gradually changed from crystalline to amorphous along with the increase of doped zinc concentration. The optical transmittances of these films decreased only slightly with increasing zinc concentration due to very similar band edges of ZnO and anatase TiO₂. The doped ZnO had weak influence on light absorption of the TiO₂ films. When zinc concentration was very low (<1 at%), the photocatalytic activities of the doped films had nearly no difference from that of pure TiO₂ film. Photocatalytic activities decreased obviously in the films containing high amount of zinc oxide.     

Characteristics of titania supported copper oxide catalysts for wet air oxidation of phenol

Various techniques have been used to characterize the CuO(x)/TiO(2) catalysts with different copper loading. Surface area, pore volume and pore size distribution of the prepared catalysts were estimated from nitrogen adsorption isotherm. Temperature programmed reduction (TPR), X-ray diffraction (XRD), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) experiments were performed to investigate the chemical state of the copper species. The chemical state of copper in the CuO(x)/TiO(2) catalysts varied with copper loading (1-25wt.%): highly dispersed Cu(2+) cluster for 1 and 5wt.%, and bulk CuO for 7-25wt.%. The activity and mineralization selectivity of the CuO(x)/TiO(2) catalysts increased with copper loading up to 20wt.%, and remained almost constant for higher copper loading. The optimum copper loading was 20wt.% for the wet air oxidation of phenol over the CuO(x)/TiO(2) catalysts in this work. The stability of the CuO(x)/TiO(2) catalysts with different copper loading was also studied with respect to carbonaceous deposits and copper leaching.     

Catalytic wet peroxide oxidation of azo dye (Congo red) using modified Y zeolite as catalyst

The present study explores the degradation of azo dye (Congo red) by catalytic wet peroxide oxidation using Fe exchanged commercial Y zeolite as a catalyst. The effects of various operating parameters like temperature, initial pH, hydrogen peroxide concentration and catalyst loading on the removal of dye, color and COD from an aqueous solution were studied at atmospheric pressure. The percent removals of dye, color and COD at optimum pH₀ 7, 90 °C using 0.6 ml H₂O₂/350 ml solution and 1 g/l catalyst was 97% (in 4 h), 100% (in 45 min) and 58% (in 4 h), respectively. The % dye removal has been found to be less in comparison to % color removal at all conditions, e.g. dye removal in 45 min and at above conditions was 82%, whereas the color removal was 100%. The results indicate that the Fe exchanged Y zeolite is a promising catalyst for dye removal. Fe exchanged catalyst is characterized using XRD, SEM/EDAX, surface area analyzer and FTIR. Though the dye, color and COD removals were maximum at pH₀ 2 but as the leaching of Fe from the catalyst was more in acidic pH range, pH₀ 7 was taken as operating pH due to almost comparable removals as of pH₀ 2 and no leaching of Fe ions.     

Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation

Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.     

Comparison of various advanced oxidation processes for the degradation of 4-chloro-2 nitrophenol

In the present study an attempt is made efficiently to degrade USEPA listed 4-chloro-2-nitrophenol (4C-2-NP), widely available in bulk drug and pesticide wastes using various advanced oxidation processes (AOPs). A comparative assessment using various AOPs (UV, H(2)O(2,) UV/H(2)O(2), Fenton, UV/Fenton and UV/TiO(2)) was attempted after initial optimization studies, viz., varying pH, peroxide concentration, iron concentration, and TiO(2) loading. The degradation of the study compound was estimated using chemical oxygen demand (COD) reduction and compound reduction using spectrophotometric methods and further validated with high performance liquid chromatography (HPLC). The degradation trends followed the order: UV/Fenton > UV/TiO(2) > UV/H(2)O(2) > Fenton > H(2)O(2) > UV(.) It can be inferred from the studies that UV/Fenton was the most effective in partial mineralization of 4C-2-NP. However, lower costs were obtained with H(2)O(2). Kinetic constants were evaluated using first order equations to determine the rate constant K.     

Environmental assessment of different photo-Fenton approaches for commercial reactive dye removal

An environmental study using life cycle assessment (LCA) has been applied to three bench-scale wastewater treatments for Cibacron Red FN-R hetero-bireactive dye removal: artificial light photo-Fenton process, solar driven photo-Fenton process and artificial light photo-Fenton process coupled to a biological treatment. The study is focused on electricity and chemicals consumption, transports and atmosphere and water emissions generated by the different processes involved. Results show that the artificial light photo-Fenton process is the worst treatment in terms of environmental impact. On the other hand, both solar driven and coupled to biological photo-Fenton processes reduce significantly the environmental damage, although none can be identified as the best in all impact categories. The major environmental impact is attributed to the H2O2 consumption and to the electrical energy consumption to run the UVA lamp. An economic analysis of the different photo-Fenton processes has also been performed and the results are discussed together with those obtained from the environmental assessment.     

凹凸棒土负载CeO2催化氧化处理亚甲基蓝染料废水

采用均相沉淀法,以Ce(NO3)3·6H2O为原料,HMT为沉淀剂,制备了ATP/CeO2纳米复合材料.并以H2O2为氧化剂,利用该复合材料对亚甲基蓝(MB)染料模拟废水进行了催化氧化处理,分别考察了催化剂的投加量及CeO2的负载量对MB降解的影响规律.研究结果表明,负载CeO2凹凸棒土纳米复合催化剂的催化活性明显高于相同条件下制备的纯的CeO2,CeO2负载量及ATP/CeO2的投加量分别为40%和0.2g时,最大降解率可达96%,对亚甲基蓝表现出较强的催化活性.     

改性亚麻屑纤维素对活性翠蓝染料的吸附性能研究

采用环氧氯丙烷和三乙胺对分离出来的亚麻屑纤维素进行改性,制备了一种新型吸附剂。采用扫描电子显微镜和傅里叶变换红外光谱仪分别观察了所制备的吸附剂的表面形貌并分析了主要官能团,研究了其对活性翠蓝染料的吸附性能,探讨了吸附时间、吸附剂用量、染料初始浓度及pH等对吸附的影响。结果表明,随时间延长吸附容量逐渐增加,180 min后吸附即可达到平衡,升高温度有利于吸附反应的进行,40℃时最大吸附容量为198.45 mg/g;染料初始浓度较高时,吸附容量较大,吸附受pH的影响较为明显。     

Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Adsorption of reactive dye from an aqueous solution by chitosan: isotherm, kinetic and thermodynamic analysis

The adsorption of Remazol black 13 (Reactive) dye onto chitosan in aqueous solutions was investigated. Experiments were carried out as function of contact time, initial dye concentration (100-300mg/L), particle size (0.177, 0.384, 1.651mm), pH (6.7-9.0), and temperature (30-60 degrees C). The equilibrium adsorption data of reactive dye on chitosan were analyzed by Langmuir and Freundlich models. The maximum adsorption capacity (qm) has been found to be 91.47-130.0mg/g. The amino group nature of the chitosan provided reasonable dye removal capability. The kinetics of reactive dye adsorption nicely followed the pseudo-first and second-order rate expression which demonstrates that intraparticle diffusion plays a significant role in the adsorption mechanism. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. The positive value of the enthalpy change (0.212kJ/mol) indicated that the adsorption is endothermic process. The results indicate that chitosan is suitable as adsorbent material for adsorption of reactive dye form aqueous solutions.     

Photocatalytic oxidation of nitric oxide with immobilized titanium dioxide films synthesized by hydrothermal method

Gas-phase photocatalytic oxidation (PCO) of nitric oxide (NO) with immobilized TiO2 films was studied in this paper. The immobilized TiO2 films were synthesized by hydrothermal method. The characterization for the physicochemical properties of catalysts prepared under different hydrothermal conditions were carried out by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller measurements (BET) and scanning electron micrograph (SEM). It was found that the PCO efficiency of the catalyst was mainly depended on the hydrothermal conditions. The optimal values of hydrothermal temperature and hydrothermal time were 200 degrees C and 24 h, respectively. Furthermore, it was also known that the photocatalytic efficiency would decrease remarkably when the calcination temperature was over than 450 degrees C. Under the optimal conditions (hydrothermal condition: 200 degrees C for 24 h; calcination temperature: 450 degrees C), the photocatalytic efficiency of catalyst could reach 60% higher than that of Degussa P25.