Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

Removal of humic acid foulant from ultrafiltration membrane surface using photocatalytic oxidation process.

The experimental results indicated that without the TiO2 particles and PCO treatment, the permeate flux of ultrafiltration (UF) membrane declined to 40% of the initial permeate flux after 8 hours filtration. Feeding the humic acid solution with TiO2 particles dosage of 1 g/L with calcium ions into UF membrane, after the same filtration time and PCO reaction at 120 minutes, the permeate flux was increased to about 90% of the initial permeate flux. At longer PCO reaction times, a better water quality of UF permeate was observed. It has been found that with the coexistence of calcium ions in humic acid solution, the smaller molecular fragments of humic acid (HA) generated by PCO reaction may be transferred to the surface of TiO2 by means of adsorption. The humic acid adsorption by TiO2 in the presence of Ca2+ is also pH dependent. The adsorption rates were 21.0, 14.9 and 10.8 ppmTOC/gTiO2 for pH value of 4, 7 and 10 respectively. The combination of effects of PCO mineralization of humic acid into CO2 and adsorption of humic acid by TiO2 through the forming of HA-Ca(2+)-TiO2 aggregate particles were responsible for the removal of humic acid foulant from UF membrane surface.     

Determination of reaction rate constants for phenol oxidation using SnO2/Ti anodes coupled with activated carbon adsorption in the presence of TiO2 as catalyst

Series of experiments for phenol degradation with assistance of TiO2 catalyst at pH of 6.5 and temperature of 25 degrees C were conducted using a lab-scale electrochemical reactor constructed in our laboratory. According to the results, at the presence of the TiO2 catalyst the removal of phenol was increased and first-order kinetics could describe the evolution of phenol concentration. For inspecting the relationship between rate constants and dosage of TiO2, two possible kinetics were proposed in this study. Contrasted to the abundant experimental data, a reasonable kinetics was obtained for the estimation of phenol concentration effluent during continuous flow of raw wastewater, especially when the TiO2 dosage was less than 0.5g L(-1). The model obtained from these experiments could employed for the calculation of rate constants at different TiO2 dosage and the necessary dosage of catalyst when a discharge standard was designed.     

Effective degradation of para-chloronitrobenzene through a sequential treatment using zero-valent iron reduction and Fenton oxidation

In this study, zero-valent iron (ZVI) was used to pretreat para-chloronitrobenzene (p-CNB), and the major product was para-chloroaniline (p-CAN). By adding H(2)O(2) directly, further p-CAN degradation can be attributed to Fenton oxidation because ferrous ions (Fe(2+)) released during the ZVI corrosion could be used as an activator for H(2)O(2) decomposition. In the reduction process, the reduction efficiency of p-CNB as well as Fe(2+) concentration increased with increasing iron dosage and decreasing solution pH. Under the optimal conditions, 25 mg L(-1) of p-CNB could be transformed in 3 h when initial solution pH was 3.0 and ZVI dosage was 2.0 g L(-1). A sufficient amount of Fe(2+) (50.4 mg L(-1)) was obtained after the above reaction to activate H(2)O(2). In the Fenton process, the oxidization of p-CAN was also more effective in acidic conditions and it increased with increasing H(2)O(2) concentration. The control experiments showed that the sequential treatment was more effective than Fenton oxidation alone in treating p-CNB wastewater since the removal rate of total organic carbon (TOC) was improved by about 34%. It suggested that the amino function group is more susceptible to oxidative radical attack than the nitro function group. Therefore, sequential treatment using zero-valent iron reduction followed by Fenton oxidation is a promising method for p-CNB degradation.     

Heterogeneous photocatalytic ozonation of 2,4-D in dilute aqueous solution with TiO2 fiber

Photocatalytic ozonation (O(3)/UV/TiO2) is an emerging oxidation method for recalcitrant organic contaminants in water. However, immobilised TiO2 catalysts suffer from reduced photonic efficiency. Therefore, TiO2 catalysts with excellent mechanical and thermal properties and enhanced photonic efficiencies are sought. This paper aimed to elucidate the mineralisation of low concentration 2,4-D (45.0 microM) by O(3)/UV/TiO2 using the world's first high-strength TiO2 fibre in laboratory batch experiments. 2,4-D degradation and TOC removal followed pseudo first-order reaction kinetic. The removal rates for 2,4-D and TOC in O(3)/UV/TiO2 were 1.5 and 2.4-fold larger than the summation of the values for ozonation (O3)) and photocatalysis (UV/TiO2), respectively. O(3)/UV/TiO2 was characterised by few aromatic intermediates with low abundance, fast degradations of aliphatic intermediates and dechlorination as a major step. The significantly enhanced 2,4-D mineralisation in O(3)/UV/TiO2 was attributed to increased ozone dissolution and decomposition, and reduced electron-hole recombination resulting in large number of hydroxyl radical (*OH) formation from more than one parallel path. The discrepancies in the organic carbon mass budget were attributed to few apparently major unidentified intermediates, while chlorine mass balance was reasonably acceptable. The mineralisation efficiency of O(3)/UV/TiO2 with the TiO2 fibre can further be enhanced by optimisation of experimental design parameters. The new TiO2 fibre is very promising to overcome the problem of reduced efficiency of TiO2 catalyst in an immobilised state.     

Removal of organic impurities in waste glycerol from biodiesel production process through the acidification and coagulation processes

Treatment of waste glycerol, a by-product of the biodiesel production process, can reduce water pollution and bring significant economic benefits for biodiesel facilities. In the present study, hydrochloric acid (HCl) was used as acidification to convert soaps into salts and free fatty acids which were recovered after treatment. The pH value, dosages of polyaluminum chloride (PACl) and dosage of polyacrylamide (PAM) were considered to be the factors that can influence coagulation efficiency. The pH value of waste glycerol was adjusted to a pH range of 3-9. The PACl and PAM added were in the range of 1-6 g/L and 0.005-0.07 g/L. The results showed best coagulation efficiency occurs at pH 4 when dosage of PACl and PAM were 2 and 0.01 g/L. The removal of chemical oxygen demand (COD), biochemical oxygen demand (BOD(5)), total suspended solids (TSS) and soaps were 80, 68, 97 and 100%, respectively. The compositions of organic matters in the treated waste glycerol were glycerol (288 g/L), methanol (3.8 g/L), and other impurities (0.3 g/L).     

新型微介孔复合材料La/13X/MCM-41光催化降解壬基酚的研究

以碱处理后的13X分子筛、硅酸钠为原料,加入模板剂,同时引入La2O3,在水热条件下晶化生成具有良好的吸附性能和光催化性能的新型微孔-介孔复合材料La/13X/MCM-41,并将其应用于壬基酚(NP)的光催化降解.通过XRD、TEM、FT-IR、N2吸附-脱附等技术对复合材料的微观结构进行了表征分析.考察了催化剂用量、NP初始浓度、初始pH、光照时间等对NP光催化降解效率的影响.结果表明:在催化剂用量为0.1 g/L、初始浓度为1 mg/L、初始pH为6、光照时间为210 min的最佳条件下,NP的光催化降解效率可达93％以上,反应符合一级动力学方程,复合材料La/13X/MCM-41具有较高的催化活性.     

Gas-phase photocatalytic oxidation of motor fuel oxygenated additives.

Methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) were oxidized in the gas phase by photocatalytic oxidation (PCO). Transient PCO was carried out at room temperature on TiO2 (Degussa P25), 0.2% Pt-TiO2, and 2% Pt-TiO2 catalysts. Surface-adsorbed reaction by-products were characterized by temperature-programmed desorption (TPD) and oxidation (TPO). Continuous flow PCO was also carried out at 373 K on TiO2. Acetone, H2O, and CO2 were the gas-phase products for PCO of TBA and MTBE, and formic acid was adsorbed on the TiO2 surface. Temperature-programmed desorption of TBA and MTBE formed 2-methyl-1-propene, water (TBA), and methanol (MTBE). During continuous-flow PCO, acetone desorbed in molar amounts equal to the amount of decomposed TBA and MTBE. The Pt/TiO2 catalysts had higher rates of complete oxidation during PCO and TPO. Injection of water during transient PCO increased the rates of oxidation of adsorbed TBA, formic acid, and acetone. Photocatalytic oxidation of TBA proceeded faster in humid air than dry air, but MTBE oxidation was less sensitive to humidity. The TiO2 catalyst was stable for MTBE, TBA, and acetone PCO at 373 K. The PCO at low conversions followed the Langmuir-Hinshelwood model.     

Advanced oxidation of bleached eucalypt kraft pulp mill effluent.

In this study a poorly biodegradable (BOD/COD = 0.3) industrial alkaline ECF bleaching filtrate was treated using different advanced oxidation processes to evaluate their use in combined chemical-biological treatment aimed at increasing recalcitrant COD removal and improving final effluent quality. Oxidative treatments included ozonation combined with hydrogen peroxide (2, 5, 10, 20 mmol L(-1) O3/0.7, 2, 5, 10 mmol L(-1) H2O2) and photocatalysis with hydrogen peroxide (UV/2, 4 and 8 mmolL(-1) H2O2) and with TiO2 (UV/TiO2/0.7 and 4 mmol L(-1) H2O2). The O3/H2O2 process increased effluent biodegradability by up to 68% as a result of increasing BOD and decreasing COD. Increasing the O3 dose had a greater effect on biodegradability improvement and lignin and colour removal efficiencies than increasing the H2O2 dose. A combined oxidant dose of 5 mmol L(-1) O3 and 2 mmol L(-1) H2O2 resulted in 75% lignin removal, 40% colour removal and 6% carbohydrate loss without mineralizing the organic carbon. The photocatalytic processes led to a decrease in effluent biodegradability through combined decrease in BOD and increase in COD and did not result in efficient lignin or colour removal. Photocatalytic oxidation was apparently inhibited by the high chloride and COD levels in the alkaline filtrate, and may be more efficient in recalcitrant COD removal if performed after biological.     

二氧化氯催化氧化降解铬黑T试验研究

在常温常压下,对Fe2O3/γ—A12O3+H2O2和ClO2+TiO2两种催化氧化体系处理铬黑T废水的效果进行了分析。试验结果表明,处理甲基橙废水效果较好的Fe2O3/γ—Al2O3+H2O2组合对铬黑T的降解效果非常有限,而ClO2+TiO2组合的处理效果较好:以500 mg/L的铬黑T溶液为模拟废水,当pH为4,C102投加量为200 mg/L,TiO2投加量为500 mg/L,反应时间为90 min时,脱色率达89.96%,CODCr的去除率可达45.36%。     

催化湿式氧化技术处理焦化废水

以非贵金属氧化物CuO、Co3O4、La2O3为主要活性成分,以TiO2-ZrO2为载体,制备了CuO-Co3O4-La2O3/TiO2-ZrO2复合负载型催化剂,用该催化剂采用催化湿式氧化技术处理焦化企业在生产过程中产生的焦化废水。系统考察了工艺条件如催化剂加入量、反应温度、反应时间和氧气分压等对催化湿式氧化反应的影响,得到最佳的工艺条件为:催化剂加入量10 g/L,反应温度220℃,氧气分压3.5MPa。在此条件下反应2 h,COD去除率达到98.7%,NH3-N去除率达到97.9%。反应15次COD和NH3-N去除率分别维持在90%和88%左右,表明使用该催化剂在处理焦化废水时显示出良好的催化活性和稳定性。     

Decolorization of anthraquinone dye Reactive Blue 19 by the combination of persulfate and zero-valent iron

Decolorization of anthraquinone dye Reactive Blue 19 (RB19) with sulfate radicals generated in situ from persulfate and zero-valent iron (ZVI) was investigated. The effects of initial solution pH, initial concentration of RB19, ZVI and persulfate, reaction temperature and common dissolved anions were studied. 100% color removal efficiency and 54% TOC removal efficiency were achieved in 45 min with an initial RB19 concentration of 0.1 mM under typical conditions (pH 7.0, 0.8 g L(-1) ZVI, 10 mM persulfate and 30 C). The decolorization efficiency of RB19 increased with higher iron dosage, higher initial persulfate concentration, and higher reaction temperature. It is also an acid driven process. The decolorization process followed pseudo-first order kinetics and the activation energy was 98.1 kJ mol-1. RB19 decolorization was inhibited by common dissolved anions such as CL-, NO3-, H2PO4- and HCO3- since they reacted with sulfate radicals that retarded the oxidation process. The experiment demonstrated that the combination of persulfate and ZVI was a promising technology for the decolorization of dye wastewater.     

Photocatalytic degradation of di(2-ethylhexyl)phthalate adsorbed by chitin A.

Di(2-ethylhexyl)phthalate (DEHP) is a ubiquitous environmental contaminant due to its extensive use as a plasticiser and its persistence. Currently, there is no cost-effective treatment method for its removal from industrial wastewater. In a previous study, DEHP was effectively adsorbed from aqueous solution by biosorption onto chitinous materials. Biosorption can pre-concentrate DEHP from the aqueous phase for further treatment. As biosorption cannot degrade DEHP, in this study the degradation (and detoxification) of DEHP adsorbed onto chitinous material by photocatalytic oxidation (PCO) is attempted. PCO relies on hydroxyl radical (.OH), which is a strong oxidising agent, for the oxidative degradation of pollutants. It is a non-selective process which can degrade DEHP adsorbed onto chitinous material. The first part of this study is the optimisation of the degradation of adsorbed DEHP by PCO. Adsorption was carried out in the physicochemical conditions optimised in the previous study, with 500 mg/L chitin A and 40 mg/L DEHP at initial pH 2, 22+/-2 degrees C and 150 rpm agitation for 5 min. After optimisation of PCO, a 61% removal efficiency of 10 mg/L of DEHP was achieved within 45 min under 0.65 mW/cm2 of UV-A with 100 mg/L TiO2, and 10 mM of H2O2 at initial pH 12. The optimisation study showed that UV-A and TiO(2) are essential for the degradation of DEHP by PCO. The degradation intermediates/products were identified by GC-MS analysis. GC-MS results showed that the di(2-ethylhexyl) side chain was first degraded, producing phthalates with shorter side chains. Further reaction produced phathalic anhydride and aliphatic compounds such as alkanol and ester. The toxicities of parental and degradation intermediates in the solution phase and on chitinous materials were followed by the Microtox test. Results indicated that toxicity can be removed after 4 h treatment by PCO. Thus the decontamination of DEHP by integrating biosorption and PCO is feasible.     

Inorganic greywater matrix impact on photocatalytic oxidation: does flocculation of TiO2 nanoparticles impair process efficiency?

This study was conducted in order to clarify whether photocatalyst flocculation--as observed in biologically pretreated greywater--contributes to photocatalytic oxidation (PCO) efficiency impairment. Aqueous solutions of tetraethyleneglycol dimethylether spiked with different inorganic salts in concentrations as found in biologically treated greywater were investigated with respect to TiO2 flocculation and PCO mineralisation kinetics. Flocculation of the photocatalyst primarily depended on pH (which was affected by the salts) and how close pH was to the point of zero charge (PZC). Photocatalyst agglomeration was maximum at pH 5.5. With salt concentrations >7 mmol L(-1), flocculation was strong even at pH far above PZC due to electric double layer compression. PCO rate constants were not unequivocally related to flocculation. Increasing pH was observed as the clearest factor deteriorating PCO efficiency. This was interpreted to result from impaired adsorbability of negatively charged oxidation intermediates as well as from enhanced CO2 absorption with increasing pH and subsequent formation of HCO3(-) anions which are OH radical scavengers.     

Removal of C.I. Reactive Red 2 from aqueous solutions by chitin: an insight into kinetics, equilibrium, and thermodynamics

In this study, C.I. Reactive Red 2 (RR2) was removed from aqueous solutions by chitin. Exactly how the RR2 concentration, chitin dosage, pH, and temperature affected adsorption of RR2 by chitin was then determined. After reaction for 120 min, the amount of 10 and 20 mg/L RR2 absorbed onto chitin was 5.7 and 7.5 mg/g, respectively. The adsorption percentage increased from 56 to 94% when the chitin dosage was increased from 1.5 to 2.5 g/L. Experimental results indicated that the pseudo-second-order model best represents adsorption kinetics. Adsorption of RR2 increased as the temperature increased; however, it decreased with an increased pH. Experimental results further demonstrated that the Freundlich model is superior to the Langmuir model in fitting experimental isotherms. The ΔH° and ΔS° were 16.34 kJ/mol and 152.10 J/mol K, respectively. ΔH° suggested that adsorption of RR2 onto chitin was via physisorption.     

Preparation and characterization of CTAB-HACC bentonite and its ability to adsorb phenol from aqueous solution

A novel type of adsorbent was prepared by modifying bentonite with N-2-hydroxypropyl trimethyl ammonium chloride chitosan (HACC) with cetyl trimethylammonium bromide (CTAB). The adsorbent was named CTAB-HACC bentonite. Its characteristics were investigated using thermogravimetric, Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction. The adsorption of phenol onto CTAB-HACC bentonite was evaluated by changing various parameters, such as contact time, adsorbent dosage, initial pH of the solution, and temperature. The maximum adsorption was observed at pH 12. Adsorption of phenol on CTAB-HACC bentonite favored at lower temperature and established the equilibrium in 30 min. The adsorption efficiency reached 82.1%, and the adsorption capacity was 7.12 mg/g from the phenol solution with a concentration of 500 mg/L at pH 12.0 and 20 degrees C.     

Solar degradation of Direct Blue 71 using surface modified iron doped ZnO hybrid nanomaterials

This paper reports photodegradation of Direct Blue 71 under irradiation by sunlight. We synthesized Fe:ZnO nanomaterials under mild hydrothermal conditions (P = autogenous, T = 100 °C, t = 18 h). The precursors were Fe(2)O(3) as dopant, n-butylamine as surface modifier, NaOH as mineralizer and reagent grade ZnO. The systematic experiments on the photodegradation of Direct Blue 71 were carried out by changing different effective parameters. The variables in this study were type of nanomaterials synthesized (4 types), nanomaterial dosage (0.4-1.0 g/L), contact time (30-120 min), pH (3-11), and dye concentration (20-100 ppm). The photodegradation efficiency was determined using a UV-Vis spectrophotometer. Determination of total organic carbon (TOC) amount was used to find out mineralization efficiency. Our experimental results revealed that the nanomaterials synthesized had higher efficiency compared with the reagent grade ZnO. The best efficiency was achieved at the following conditions: 1.0 g/L nanomaterials loading, 120 min contact time, pH 5, and photodegradation efficiency from more than 75 up to 99% depending upon the dye concentration.     

Degradation of wine industry wastewaters by photocatalytic advanced oxidation.

Wine industry wastewaters contain a high concentration of organic biodegradable compounds as well as a great amount of suspended solids. These waters are difficult to treat by conventional biological processes because they are seasonal and a great flow variation exists. Photocatalytic advanced oxidation is a promising technology for waters containing high amounts of organic matter. In this study we firstly investigated the application of H2O2 as oxidant combined with light (artificial or natural) in order to reduce the organic matter in samples from wine industry effluents. Secondly, we studied its combination with heterogeneous catalysts: titanium dioxide and clays containing iron minerals. The addition of photocatalysts to the system reduces the required H2O2 concentration. Although the H2O2/TiO2 system produces higher efficiencies, the H2O2/clays system requires a H2O2 dosage between three and six times lower.     

Fenton试剂处理选矿废水的试验研究

研究用Fenton试剂处理含苯胺黑药(二苯胺基二硫代磷酸)模拟废水和实际选矿废水,分别考查了反应初始pH值、Fe2+浓度及H2O2用量对COD去除率的影响。结果表明:氧化时间为10 min,反应初始pH值为4,ρ(Fe2+)=1.83 g/L,ρ(H2O2)=5.55 g/L,模拟废水苯胺黑药的质量浓度为300 mg/L时,COD去除率达到83.6%;对于实际废水,当ρ(Fe2+)=50mg/L,pH值=3.5,ρ(H2O2)=1800mg/L时,出水ρ(COD)从1000mg/L降到32 mg/L,COD去除率为96.8%,达到废水排放标准,药剂成本估计为每处理1 m3废水需要费用18元。     

Fe-O/CeO_2催化剂的制备、表征及其对垃圾渗滤液微波催化氧化活性的研究

以浸渍法制备用于常温常压微波催化氧化工艺的负载型Fe-O/CeO_2催化剂并通过XRD和SEM手段进行表征;利用优化制备后的催化剂进行微波催化氧化垃圾渗滤液的研究.结果表明:Fe-O/CeO_2催化剂中活性组分Fe以α-Fe_2O_3和CeFe_2的形式存在.在渗滤液初始COD_(Cr)5 736 mg/L、氨氮1 840 mg/L、色度500倍和pH 8.69的条件下,在Fe-O/CeO_2投加量10 g/L、H_2O_2(30%)投加量22.5 mL/L、微波功率800 W、微波辐射时间10 min和水样初始浓度C_(水样)/C_(原水)为100%的最佳运行条件下,微波催化氧化工艺对COD_(Cr)、氨氮和色度的去除率分别为73%、78%和85%;在反应的第4～8 min和第2～8 min,COD_(Cr)和氨氮去除率分别与反应时间呈近似直线的关系.