Fresnel lens to concentrate solar energy for the photocatalytic decoloration and mineralization of orange II in aqueous solution

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.     

Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach

Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.     

Factors influencing the preparation of supported iron oxide in fluidized-bed crystallization

Our previous work applied a novel supported iron oxyhydroxide (FeOOH) catalyst to effectively treat benzoic acid by hydrogen peroxide. The FeOOH catalyst was prepared via the oxidation of Fe2+ by H2O2 in the acidic condition using a fluidized-bed crystallization reactor. The major components coated on the surface were identified as amorphous FeOOH and gamma-FeOOH. In terms of the crystallization conditions of FeOOH, some parameters including the operational pH, superficial velocity, specific iron loading, and influent H2O2 concentration were investigated to quantify their effects on the crystallization efficiency. All these parameters were found to significantly influence the crystallization efficiency. Two types of FeOOH catalysts were synthesized: FeOOH I was prepared at pH 3.5, and FeOOH II was formed by aging FeOOH I at pH 13. The percentages of surface amorphous FeOOH reduced from 70% to 30% after aging. The FeOOH II catalyst presented a higher reactivity toward H2O2 but lower stoichiometric efficiency in oxidizing benzoic acid than FeOOH I, similar to the result of the commercial goethite. Therefore, it is concluded that the crystalline property significantly affects the performance of catalytic oxidation.     

Fe^2＋—H2O2氧化法处理氨基J酸工业废水的研究

用Ｆｅ＾２＋－Ｈ２Ｏ２氧化法处理氨基Ｊ酸工业废水。结果表明,当溶液ｐＨ＝１－３,Ｈ２Ｏ２和Ｆｅ＾２＋用量分别为Ｈ２Ｏ２：Ｆｅ＾２＋１０：１,Ｈ２Ｏ２：ＣＯＤＣｒ＝２ｇ：ｇ时,Ｊ酸废水的ＣＯＤＣｒ去除率达６６．７％,氨基去除率达６８．４％。处理后的废水ＢＯＤ５／ＣＯＤＣｒ＝０．５,已达到生化处理的要求。该法可作为氨基Ｊ酸废水的预处理方法。     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

H2O和SO2对V2O5-WO3/TiO2催化剂催化氧化NO的影响

研究了在120℃的反应温度下,H2O和SO2对V2O5-WO3/TiO2催化剂选择性催化氧化（SCO）NO的影响。结果表明,在H2O和SO2存在的情况下催化剂失活很快,停止通入H2O和SO2后活性不能恢复,但在加热到250℃后催化活性基本恢复。FT-IR分析表明,催化剂表面形成了金属硝酸盐和Ti的硫酸盐,对催化活性有一定影响,但不影响催化剂在250℃下催化活性的恢复。SO2、H2O和NO的竞争吸附与SO2和NO2的铅室反应是影响催化剂活性的主要原因。     

Kinetics and mechanism of color removal of methylene blue with hydrogen peroxide catalyzed by some supported alumina surfaces

The catalyzed kinetics of the oxidative mineralization of the cationic dye methylene blue, phenothiazonium, 3,7-bis(dimethylamino)-chloride, with hydrogen peroxide were studied both in buffered and unbuffered solutions. The supported alumina catalysts used were in the form of copper(II), cobalt(II), manganese(II), and nickel(II)-ions. Also, some copper(II)-complexes were used, e.g. copper(II)-ammine ([Cu(amm)4]2+), copper(II)-ethylenediamine ([Cu(en)2]2+) and copper(II)-monoethanolamine ([Cu(mea)2]2+). The reaction is first order with respect to methylene blue. On the other hand, the order with respect to hydrogen peroxide is concentration range dependent. This range depends strongly on the catalyst used. At lower [H2O2], the order was 1 which then decreases with increasing [H2O2] passing through 0 at the maximum rate and finally becomes negative. This phenomenon is parallel to the formation of a colored intermediate on the surface of the catalyst. This suggests that the intermediate has an inhibiting effect on the rate of color removal. Moreover, the rate of the reaction was found to be strongly dependent on the pH of the solution and its ionic strength. It increases with increasing both pH and the concentration of added potassium chloride. Also, the rate of reaction is inhibited in presence of sodium dodecylsulfate anionic surfactant. The repeated use of the different catalysts showed that their catalytic activities are almost unaffected. A reaction mechanism was proposed with the formation of free radicals as reactive intermediates.     

微波辐射Bi2O3/沸石-H2O2体系降解废水中的硝基苯

研究了微波辐射下,以负载于沸石上的三氧化二铋为催化剂,以双氧水为氧化剂的催化氧化体系处理硝基苯工艺。通过单因素实验法,从反应催化剂负载量、pH、双氧水用量、微波功率、反应时间、催化剂用量等方面初步考察了硝基苯在该体系中的催化氧化效果。在氧化铋负载量3%（质量比）,pH=2,2 mL 30%双氧水,火力为中火,催化剂投加量为0.7 g,反应2 m in,对降解过程所得的中间产物和终产物进行了分析。结果表明,该体系对硝基苯的去除率能够达到99.2%,COD去除率为73.91%。     

活性炭协同Fe2+催化H2O2氧化处理染料废水及其表面附着污染物对催化活性的影响

采用动态连续处理装置研究颗粒活性炭（GAC）催化H2O2氧化活性红X-3B染料（RRX-3B）的效能以及GAC表面吸附污染物对催化性能的影响,考察GAC与Fe2+协同催化作用。研究结果表明：RRX-3B的处理效果随着流速的增加而逐渐降低;新GAC/H2O2体系降解效果优于单独GAC吸附与单独H2O2氧化,GAC重复使用存在部分失活现象使其脱色率和COD去除率下降,且表面预先吸附污染物的GAC在重复使用过程中下降更为明显;固定H2O2投加量为5 mmol·L-1,按n（Fe2+）：n（H2O2）为1:20投加Fe2+,GAC与Fe2+联合体系能持续有效使RRX-3B氧化脱色,重复使用4次后脱色率仍可达99.65%,GAC和Fe2+之间存在协同催化H2O2降解RRX-3B的作用。GAC表面附着的Fe2+能够加强催化作用,且有效延长其使用寿命。     

Catalytic oxidation of pentachlorophenol in contaminated soil suspensions by Fe+3-resin/H2O2

Pentachlorophenol (PCP) is a wood preserving agent that is commonly found in contaminated soils at wood treatment sites. The catalytic properties of Fe+3-resin for the oxidation of PCP in aqueous solution and soil suspension with H2O2 were tested. Batch tests in aqueous solution were performed at various dosages of catalyst and H2O2, and reaction temperatures. The results showed that the oxidation of PCP in aqueous solution depends on the dose of H2O2 and the temperature. Essentially complete oxidation of 100 mgl(-1) PCP was obtained with 0.5% Fe+3-resin catalyst, 0.1 M H2O2 and at a reaction temperature of 80 degrees C. The oxidation of PCP achieved in three different soil suspensions was more than 94% within 30-50 min. Moreover, it was demonstrated that the same Fe+3-resin could be reused for at least six cycles of PCP oxidation in soil solutions without loss in efficiency unless the pH of the reaction falls below 5. It was proposed that the loss in used Fe+3-resin catalyst activity could be related to the leaching of Fe+3 at low pH.     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

低频超声协同Fe-Ni-Mn／Al2O3催化降解酸性绿B的研究

采用低频超声与Fe-Ni-Mn／Al2O3催化剂协同降解偶氮染料酸性绿B模拟废水,考察染料初始浓度和pH值、催化剂、饱和气体及H2O2等因素对酸性绿B降解效果的影响,结果表明：催化剂Fe-Ni-Mn／Al2O3与低频超声存在协同效应,催化剂的最佳投加量为6g／L;酸性条件有利于染料的超声降解,当pH=3．8时,可取得最佳的降解效果;酸性绿B降解率随初始浓度的增大而降低,其优化初始浓度为100mg／L,此外,在反应体系中鼓入饱和气体也可促进酸性B的降解,且影响顺序为混合气体（air＋Ar）〉氧气〉氩气;在反应过程中投加H2O2有利于染料降解率的提高。在优化实验条件下降解150min,酸性绿B色度去除率达到91．4％。     

Fe/沸石对偶氮染料活性黑5的催化降解

为了对水中偶氮染料活性黑5的去除进行研究,通过沉淀法在沸石上负载Fe2O3制备出一种具有较高催化活性的催化剂,采用X-射线衍射仪（XRD）和扫描电镜（SEM）对其结构和形貌进行了表征,并利用Fe/沸石进行非均相Fenton反应处理模拟染料废水的研究,考察不同操作条件对活性黑5降解效果的影响。实验结果表明,活性黑5的脱色率随催化剂投加量的升高而升高,但是随着染料初始浓度的升高而降低。H2O2浓度和pH的升高均使得活性黑5的脱色率先升高而后降低。在最佳pH为3,最佳H2O2浓度为200 mg·L-1的条件下,活性黑5的脱色率达到最大,为95.7%。通过对催化剂Fe/沸石稳定性研究,发现经5次连续循环使用后,活性黑5脱色率仍然可保持在94%以上,说明该催化剂具有良好的循环使用性能。     

Catalytic performance of Ag/Al2O3-C2H5OH-Cu/Al2O3 system for the removal of NOx from diesel engine exhaust

The selective catalytic reduction (SCR) of NOx by C(2)H(5)OH was studied in excess oxygen over Ag/Al(2)O(3) catalysts with different Ag loadings at lab conditions. The 4% Ag/Al(2)O(3) has the highest activity for the C(2)H(5)OH-SCR of NOx with a drawback of simultaneously producing CO and unburned THC in effluent gases. An oxidation catalyst 10% Cu/Al(2)O(3) was directly placed after the Ag/Al(2)O(3) to remove CO and unburned THC. Washcoated honeycomb catalysts were prepared based on the 4% Ag/Al(2)O(3) and 10% Cu/Al(2)O(3) powders and tested for the C(2)H(5)OH-SCR of NOx on a diesel engine at the practical operating conditions. Compared with the Ag/Al(2)O(3) powder, the Ag/Al(2)O(3) washcoated honeycomb catalyst (SCR catalyst) has a similar activity for NOx reduction by C(2)H(5)OH and the drawback of increasing the CO and unburned THC emissions. Using the SCR+Oxi composite catalyst with the optimization of C(2)H(5)OH addition, the diesel engine completely meets EURO III emission standards.     

Modification of carbon-coated TiO2 by iron to increase adsorptivity and photoactivity for phenol

Carbon-coated TiO(2) modified by iron, were prepared from TiO(2) of anatase structure and PET modified by FeC(2)O(4). Catalysts were prepared by mixing powders of TiO(2) and modified PET and heating at different temperatures, from 400 to 800 degrees C under flow of Ar gas. High adsorption of phenol was observed on the catalyst heated at 400 degrees C, confirmed by FT-IR analysis. On this catalyst, fast rate of phenol decomposition was achieved by addition of small amount of H(2)O(2) to the reaction mixture. Phenol decomposition proceeded mainly through the direct oxidation of phenol species adsorbed on the catalyst surface due to the photo-Fenton reaction. Iron-modified carbon-coated TiO(2) catalysts heated at 500-800 degrees C showed almost no phenol adsorption or oxidation.     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.     

低频超声协同Fe-Ni-Mn/Al_2O_3催化降解酸性绿B的研究

采用低频超声与Fe-Ni-Mn/Al2O3催化剂协同降解偶氮染料酸性绿B模拟废水,考察染料初始浓度和pH值、催化剂、饱和气体及H2O2等因素对酸性绿B降解效果的影响,结果表明:催化剂Fe-Ni-Mn/Al2O3与低频超声存在协同效应,催化剂的最佳投加量为6 g/L;酸性条件有利于染料的超声降解,当pH=3.8时,可取得最佳的降解效果;酸性绿B降解率随初始浓度的增大而降低,其优化初始浓度为100 mg/L,此外,在反应体系中鼓入饱和气体也可促进酸性B的降解,且影响顺序为混合气体(air+Ar)>氧气>氩气;在反应过程中投加H2O2有利于染料降解率的提高.在优化实验条件下降解150 min,酸性绿B色度去除率达到91.4%.     

Characterization and reactivity of natural manganese ore catalysts in the selective catalytic oxidation of ammonia to nitrogen

Natural manganese ore (NMO) catalysts were characterized and tested in the selective catalytic oxidation of ammonia to nitrogen oxides under dilute conditions. Also, the oxidation of ammonia (NH(3)) was carried out using pure MnO(2), Mn(2)O(3) for comparing with the activity. It is found that the activity of NMO was similar to that of MnO(2) at low temperature below 150 degrees C but above this temperature, the activity of these catalysts showed the difference. In the course of NH(3) oxidation, N(2), NO, N(2)O and H(2)O were produced. But the quantity of NO(2) produced in this experiment was negligible. At temperature below 250 degrees C, selectivity into N(2) from NH(3) oxidation was in the order, NMO > MnO(2) > Mn(2)O(3). This is the reverse of activity of these manganese oxides. Also the characterization of NH(3) oxidation was proposed and supported by the effect of space velocity, inlet O(2) and NH(3) concentration. The increase of space velocity remarkably influenced not only the conversion but also selectivity into N(2). The higher the reaction temperature was, the higher the effect of inlet O(2) and NH(3) concentration on the reaction rate was. By introducing NO during NH(3) oxidation reaction, the possibility of NMO as selective catalytic reduction catalyst at low temperature was studied and showed positive results.     

Dibenzothiophene oxidation by horseradish peroxidase in organic media: effect of the DBT:H2O2 molar ratio and H2O2 addition mode

Its is well known that in the biodesulfurization (BDS) process the low water solubility of sulfur compounds hinders its transference from the oil phase to the cells being the rate-limiting step in the metabolism of dibenzothiophenes (DBT). Thus sulfur compounds derivatives with high water solubility could be more easily transported increasing the BDS efficiency. The present work performed a stepwise evaluation of the enzymatic oxidation of DBT by horseradish peroxidase (HRP). Reactions were carried out in monophasic organic media containing 25% (v/v) acetonitrile. The following parameters were evaluated: DBT:H2O2 molar ratio (1:1-1:20); H2O2 addition mode (single or stepwise); pH (6.0-8.0) and temperature (37-50 degrees C). Best results were observed in a reaction medium at pH 8.0 presenting HRP 0.06IUml(-1), DBT 0.267mM, DBT:H2O2 molar ratio of 1:20 (stepwise hydrogen peroxide addition) and incubated at 45 degrees C for 60min. Under these conditions 60% of DBT was converted into dibenzothiophene sulfoxide (12%) and dibenzothiophene sulfone (46%). The DBT oxidation rate observed in this work, of 5mmolmin(-1)g(-1) of HRP, was 250-fold higher than the BDS rate, 20mumolmin(-1)g(-1) of catalyst. As such a combined enzyme-microbial desulfurization process could be envisaged. Products were determined by HPLC RP C-18.     

Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.