UV和H2 O2联合消毒灭活饮用水中大肠杆菌研究

以大肠杆菌为研究对象,对单独紫外线(UV)、H2O2及两者不同组合方式的灭活效果进行了分析.结果表明,单独H2O2对大肠杆菌基本无灭活效果,加入浓度为20 mg·L-1的H2O2接触时间为30 min时,灭活率仅为0.02个对数级;单独UV工艺可在一定程度上灭活大肠杆菌,紫外线剂量为10 mJ·cm-2时,灭活率可达到4.51个对数级.紫外线和H2O2联合消毒在一定程度上提高了消毒效果,且不同的组合方式对灭活效果有很大的影响.先UV后H2O2消毒效果优于先H2O2后UV,当紫外线剂量为5 mJ·cm-2时,加入H2O2分别反应2.5、5、10、20 min后,两者的灭活率分别较单独UV消毒增加0.09、0.35、0.38、0.68和0.01、0.07、0.14、0.53个对数级.而UV与H2O2同时消毒效果优于UV与H2O2顺序消毒,当紫外线剂量为5 mJ·cm-2时,加入H2O2反应20 min后,灭活率较UV-H2O2和H2O2-UV工艺分别增加了0.43和0.58个对数级.随着紫外线强度的增加,大肠杆菌的灭活效果不断提高.     

Characterization and performance of Pt/SBA-15 for low-temperature SCR of NO by C3H6

Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.     

Size effect of Pt nanoparticles in acid-assisted soot oxidation in the presence of NO

Pt/Al₂O₃ catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method, and the sulfated counterparts were prepared by impregnation of sulfuric acid. The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O₂ are positively correlated with the size of platinum. The sulfated Pt/Al₂O₃ exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO₂ production. Such a contradiction is more significant for those catalysts with smaller platinum particles. Herein, the catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), inductive coupled plasma (ICP) emission spectrometry, CO chemisorption, thermogravimetric analysis (TGA), NH₃ temperature-programmed desorption (NH₃-TPD), NO temperature-programmed oxidation (TPO) and NO_x temperature-programmed desorption (TPD). Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO₂ transfer efficiency onto the soot pushed by the acidic catalysts.     

Metal ion catalyzed oxidation of SO2 in the presence of trace H2O2 in aqueous solution under environmental reaction conditions

Aqueous phase oxidation of SO₂ or S(IV) by H₂O₂-metal ions at a H₂O₂ concentration much lower than S(IV), was studied using a continuously flowing stirred reactor. Of the metal ions, Fe²⁺ showed the highest catalytic activity, i.e. the oxidation of S(IV) continued after most of the H₂O₂ was consumed. The dependence of the rate on the concentration of S(IV), H₂O₂, Fe²⁺ or H⁺ and temperature was determined. The following rate expression and low apparent activation energy of 40.7 kJ mole⁻¹ were evaluated,−d[S(IV)]/dt=620[S(IV)]²[Fe²⁺]^0.5(molel⁻¹S⁻¹). The significance of this reaction as the sulfate formation in atmospheric water droplets is discussed and a comparison of the rate with others using H₂O₂, O₃ and dissolved O₂ catalyzed by metal ions is made.     

UV/H2O2降解美罗培南的影响因素及毒性研究

利用波长为254 nm的紫外灯活化过氧化氢(H_2O_2)氧化降解美罗培南(MPN),考察了H_2O_2投加量、初始pH值、水中常见共存阴离子(Cl~-、HCO~-_3、NO~-_3)和天然有机化合物(NOM)等重要影响因素对MPN降解的影响.结果表明,紫外光功率为4 W,初始pH为7.0,n(H_2O_2)/n(MPN)=20∶1时,反应20 min后,MPN的降解率达到97.8%.H_2O_2投加量的增加会加快MPN的降解速率,Cl~-和HCO~-_3对UV/H_2O_2体系中MPN去除效果的影响较小,极少量的NO~-_3会促进MPN的降解,当NO~-_3的浓度≥10 mg·L~(-1)时,MPN的降解受到抑制,且离子浓度越高,抑制程度表现越明显.NOM的存在对MPN的降解有抑制作用.与纯水相比,MPN在实际水体中的去除受到抑制,归因于水体基质的影响.大肠杆菌的急性毒性实验研究表明,MPN的中间转化产物保留了一些抗菌性能,但光解的最终产物无抗菌性能.     

Studies on the formation of H2O2 in the ozonolysis of alkenes

The formation of H₂O₂ in the reactions of ozone with alkenes, isoprene and some terpenes has been studied with tunable diode laser absorption spectroscopy. The measured yields of H₂O₂ were found to be considerably enhanced in the presence of water vapour. H₂O₂ is thought to be formed in the ozonolysis of the alkene with O₃ by direct reaction of an intermediate with water vapour. The yield of H₂O₂ relative to the reacted alkene in the ozonolysis of trans-2-butene in the presence of water vapour was also studied with long path FTIR spectroscopy. Irrespective of the analytical methods and reaction conditions applied, the H₂O₂ yields in the reaction of O₃ with the different alkenes in the presence of water vapour were found to be in the range of a few per cent or less. Under the assumption that the reactive species forming H₂O₂ in the ozonolysis is the Criegee biradical, the overall rate constants for the reactions of some biradicals with water vapour were measured relative to the rate constant of the biradical with SO₂. For the H₂COO biradical a rate constant of (5.8 ± 2.5) × 10⁻¹⁷ cm³ s⁻¹ was determined and for the (CH₃)₂COO biradical (2.9 ± 1.5) × 10⁻¹⁷ cm³ s⁻¹; in the latter case with the assumption that (CH₃)₂COO reacts with SO₂ as fast as CH₂COO.     

Fe/Zn-TMS体系吸收去除催化裂化干气中H2S的性能

本研究采用FeCl3·6H2O、ZnCl2和环丁砜(TMS)复配形成的Fe/Zn-TMS体系脱除催化裂化(FCC)干气中的H2S,并用30%H2O2氧化再生Fe/Zn-TMS体系.同时,研究了各活性成分比例、吸收液体积浓度、吸收液pH值等对脱硫效率的影响,以及H2O2用量、吸收富液pH值对Fe2+氧化率的影响.结果表明,n(FeCl3·6H2O)∶n(ZnCl2)∶n(TMS)为0.45∶0.55∶1,吸收液pH为0.75,体积浓度(W)为50%的条件下能长时间高效脱硫,最高脱硫率达99.9%;在n(Fe2+)∶n(H2O2)为2∶1,吸收富液pH为0.65的条件下,Fe2+氧化率达96.7%.体系可循环使用3次,且能耗低、操作简单.     

Pt/CeO2催化氧化甲苯反应机制研究

采用浸渍法制备了Pt/CeO_2和Pt/Al2O_3催化剂,并通过XRD、BET、ICP-OES、H2-TPR、XPS等手段表征其物理化学性质.结果发现,Pt/CeO_2和Pt/Al2O_3催化剂上Pt负载量约为0.6%,Al2O_3载体上Pt颗粒尺寸更小,Pt/CeO_2的可还原性更强.甲苯催化氧化活性评价结果表明,Pt/CeO_2催化剂表现出更好的催化活性,T50=170℃,T90=190℃.通过UV-Raman、甲苯TPD、GC/MS、In-situ FTIR等手段进一步研究发现,Pt/CeO_2活化甲苯及反应供氧的机制与Pt/Al2O_3存在区别,其活性更好是因为:(1)负载在CeO_2表面存在高电子密度的Pt原子,具有更强的活化甲苯能力,可以直接使苯基和甲基间的C—C链发生断裂;(2)Pt的负载促进了CeO_2氧空位形成,进一步提高了CeO_2的储氧性能,加速氧循环.除了Pt解离气相氧之外,CeO_2还可以提供活性氧物种参与催化氧化甲苯的反应,进一步提高甲苯催化氧化效率.     

Effects of synthesis methods on the performance of Pt + Rh/Ce0.6Zr0.4O2 three-way catalysts

The 0.7 wt% Pt + 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction(UAMR) co-precipitation, UAMR separation precipitation, co-impregnation, and sequential impregnation. The catalysts were physico-chemically characterized by N2 adsorption, XRD, TEM, and H2-TPR techniques, and evaluated for three-way catalytic activities with simulated automobile exhaust. UAMR co-precipitation- and UAMR separation precipitationprepared catalysts exhibited a high surface area and metal dispersion, wide λ window and excellent conversion for NOx reduction under lean conditions. Both fresh and aged catalysts from UAMRprecipitation showed the high surface areas of ca. 60–67 m2/g and 18–22 m2/g, respectively, high metal dispersion of 41%–55%, and small active particle diameters of 2.1–2.7 nm. When these catalysts were aged, the catalysts prepared by the UAMR method exhibited a wider working window(Δλ = 0.284–0.287) than impregnated ones(Δλ = 0.065–0.115) as well as excellent three-way catalytic performance, and showed lower T50(169.C) and T90(195.C) for NO reduction than the aged catalysts from impregnation processes, which were at 265 and 309.C, respectively. This implied that the UAMR-separation precipitation has important potential for industrial applications to improve catalytic performance and thermal stability. The fresh and aged 0.7 wt% Pt + 0.3 wt% Rh/Ce0:6Zr0:4O2 catalysts prepared by the UAMR-separation precipitation method exhibited better catalytic performance than the corresponding catalysts prepared by conventional impregnation routes.     

Photodegradation of amoxicillin by catalyzed Fe3+/H2O2 process

Three oxidation processes of UV-Fe³⁺(EDTA)/H₂O₂ (UV: ultraviolet light; EDTA: ethylenediaminetetraacetic acid), UV-Fe³⁺/H₂O₂ and Fe³⁺/H₂O₂ were simultaneously investigated for the degradation of amoxicillin at pH 7.0. The results indicated that, 100% amoxicillin degradation and 81.9% chemical oxygen demand (COD_Cr) removal could be achieved in the UV-Fe³⁺ (EDTA)/H₂O₂ process. The treatment efficiency of amoxicillin and COD_Cr removal were found to decrease to 59.0% and 43.0% in the UV-Fe³⁺/H₂O₂ process; 39.6% and 31.3% in the Fe³⁺/H₂O₂ process. Moreover, the results of biodegradability (biological oxygen demand (BOD₅)/COD_Cr ratio) revealed that the UV-Fe³⁺ (EDTA)/H₂O₂ process was a promising strategy to degrade amoxicillin as the biodegradability of the effluent was improved to 0.45, compared with the cases of UV-Fe³⁺/H₂O₂ (0.25) and Fe³⁺/H₂O₂ (0.10) processes. Therefore, it could be deduced that EDTA and UV light performed synergetic catalytic effect on the Fe³⁺/H₂O₂ process, enhancing the treatment efficiency. The degradation mechanisms were also investigated via UV-Vis spectra, and high performance liquid chromatography-mass spectra. The degradation pathway of amoxicillin was further proposed.     

H2O2和NO互作调控SO2诱导的胡杨细胞死亡

二氧化硫(SO_2)是一种常见的大气污染物,目前关于SO_2对木本植物的毒害作用及相关机制并不清楚.本文以木本植物胡杨的愈伤细胞为材料,研究SO_2衍生物对胡杨细胞的致死效应,以及过氧化氢(H_2O_2)与一氧化氮(NO)在SO_2诱导胡杨细胞死亡中的信号调节作用.研究发现:SO_2衍生物处理(1~5 mmol·L-1)可诱发胡杨细胞死亡,且SO_2衍生物浓度越大、处理时间越长,细胞死亡率越高.2 mmol·L-1SO_2衍生物处理胡杨细胞后,胞内H_2O_2和NO水平显著升高,且H_2O_2水平的升高先于NO.一定浓度的外源H_2O_2或NO供体SNP能够提高SO_2胁迫下胡杨细胞的死亡率;而使用H_2O_2清除剂CAT和ASA、NO清除剂c PTIO、NO合成抑制剂钨酸钠后,SO_2诱导的细胞死亡率明显降低.进一步实验发现,外源H_2O_2可以提高SO_2胁迫下胡杨细胞的硝酸还原酶(NR)活性,促进胞内NO产生;而利用CAT和ASA清除H_2O_2后,细胞NR活性和NO产生均受到明显抑制.此外,SO_2胁迫下,外源SNP能够抑制抗氧化酶(CAT和APX)活性,增加胡杨细胞内的H_2O_2水平,而一定浓度的c PTIO和钨酸钠均可提高CAT和APX活性,降低胞内H_2O_2水平.结果表明:SO_2胁迫下,胡杨细胞快速产生的H_2O_2能够激活硝酸还原酶活性,促进NO生成,同时NO能够通过抑制抗氧化酶活性而提高H_2O_2水平.H_2O_2与NO互作调控SO_2诱导的胡杨细胞死亡.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

O3/H2O2降解Atrazine效能研究

利用O₃/H²O²降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5 mg/L的O₃单独氧化去除率为27.2%;相同O₃投量下,H²O²/O₃摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H²O²/O₃体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H²O²/O₃并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.     

纳米TiO2水悬浮液对大肠杆菌生长的影响

为了考察纳米TiO2(<100nm)水悬浮液对典型环境微生物--革兰氏阴性菌大肠杆菌生长的影响,制备并表征了水中分散的平均粒径和含量分别为74.3nm、1.5 mg·L-1(样品1)和82.2nm、3.1 mg·L-1(样品2)的2种纳米TiO2水悬浮液,并在有、无紫外光照条件下进行细菌培养实验.实验结果显示,在无紫外光照条件下,2个样品对大肠杆菌的生长均有抑制作用,在大肠杆菌生长稳定期,样品1和样品2分别使OD600值平均下降0.03和0.11;单独紫外光照可对大肠杆菌生长产生抑制作用,使OD600值平均下降0.04,而同样紫外光照剂量下样品2可使OD600值平均下降0.18,显示出纳米TiO2对大肠杆菌生长的协同抑制作用.     

Decontamination of alachlor herbicide wastewater by a continuous dosing mode ultrasound/Fe2+/H2O2 process

We used a ultrasound/Fe2+/H2O2 process in continuous dosing mode to degrade the alachlor.Experimental results indicated that lower pH levels enhanced the degradation and mineralization of alachlor. The maximum alachlor degradation(initial alachlor concentration of 50 mg/L) was as high as 100% at pH 3 with ultrasound of 100 Watts, 20 mg/L of Fe2+, 2 mg/min of H2O2 and 20℃ within60 min reaction combined with 46.8% total organic carbon removal. Higher reaction temperatures inhibited the degradation of alachlor. Adequate dosages of Fe2+and H2O2 in ultrasound/Fe2+/H2O2process not only enhance the degradation efficiency of alachlor but also save the operational cost than the sole ultrasound or Fenton process. A continuous dosing mode ultrasound/Fe2+/H2O2 process was proven as an effective method to degrade the alachlor.     

Insights into properties of activated carbons prepared from different raw precursors by pyrophosphoric acid activation

Low-cost activated carbons (ACs) were prepared from four kinds of solid wastes: petroleum coke, Enteromorpha prolifera, lignin from papermaking black liquid and hair, by pyrophosphoric acid (H₄P₂O₇) activation. Thermo-gravimetric analysis of the pyrolysis of H₄P₂O₇-precursor mixtures implied that H₄P₂O₇ had different influences on the pyrolysis behavior of the four raw materials. N₂ adsorption/desorption isotherms, scanning electron microscopy, Fourier transform infrared spectroscopy and adsorption capacities for dyes were used to characterize the prepared activated carbons. AC derived from E. prolifera exhibited the highest surface area (1094 m²/g) and maximum monolayer adsorption capacity for malachite green (1250 mg/g). Kinetic studies showed that the experimental data were in agreement with the pseudo-second-order model. The adsorption isotherms were well described by the Langmuir isotherm model, indicating the adsorption of dye onto the ACs proceeded by monolayers.     

O3/H2O2氧化苯乙烯气体性能及机制

O3/H2O2体系能产生大量自由基,臭氧与自由基的耦合氧化作用能提高苯乙烯的氧化去除效率.采用O3/H2O2氧化高浓度苯乙烯有机废气,研究了臭氧投加量、停留时间、H2O2体积分数、循环液喷淋密度和O3/C8H8摩尔比对苯乙烯去除率的影响.结果表明,O3/H2O2气液两相氧化能高效净化苯乙烯有机废气,苯乙烯去除率可达85.7%.适宜运行条件:停留时间为20.6 s,H2O2体积分数为10%,喷淋密度为1.72 m3·(m2·h)-1,O3/C8H8摩尔比为0.46.采用GC-MS分析O3/H2O2气液两相高级氧化苯乙烯出口气样,研究结果表明苯甲醛(C6H5CHO)和苯甲酸(C6H5COOH)为O3/H2O2氧化苯乙烯的中间产物,并推测出苯乙烯的降解机制.     

UV/TiO2/H2O2体系对制药废水二级出水的处理特性研究

以某制药企业的二级出水为研究对象,对比了UV/TiO₂、UV/H₂O₂、UV/TiO₂/H₂O₂ 3种高级氧化工艺的处理效果,利用自主设计的一体化光催化装置进行了连续动态试验,并通过凝胶渗透色谱（GPC）、傅里叶变换红外光谱（FT-IR）、三维荧光光谱（EEM）、斑马鱼急性毒性试验等方法研究了处理前后有机物特性和生物毒性的变化.结果表明,与UV/TiO₂和UV/H₂O₂体系相比,UV/TiO₂/H₂O₂光芬顿体系对有机物的去除效果更好,当TiO₂投加量为1 g·L^-1,H₂O₂投加量为100 mg·L^-1时,处理效果达到最佳.一体化光催化装置能够利用UV/TiO₂/H₂O₂光芬顿技术快速高效地降解二级出水中的有机污染物,反应30 min时COD去除率达到50%以上.经UV/TiO₂/H₂O₂深度处理后,废水中的大分子有机物分解转换为小分子,有机物中的不饱和结构明显减少,腐殖质等溶解性有机物基本降解完全.毒性试验结果表明,该二级出水的生物毒性经深度处理后显著降低,对斑马鱼胚胎不存在致畸致死效应.     

UV/H_2O_2氧化处理水中去污剂

表面活性剂是一类特殊的有机污染物,在去污、洗衣、印染等废水中广泛存在.本文以某电厂实用的5种去污剂为研究对象,考察了UV/H2O2对5种去污剂的矿化能力,研究了H2O2和去污剂初始浓度、初始p H值、去污剂种类、辐照时间等因素对氧化效果的影响.结果表明,5种去污剂在254 nm处均无较强吸收,单独UV辐照对其降解效果不明显.当去污剂初始DOC浓度为50 mg·L-1,H2O2最佳投加量为1 m L·L-1,反应时间为90 min时,对5种去污剂的矿化率(即DOC去除率)在53%~87%,矿化率随去污剂种类的不同而不同.对去污剂的矿化率随着UV辐照时间的延长而增大,去除率曲线符合一级反应动力学方程.废水初始p H值对氧化效果的影响不显著,H2O2/DOC比值对氧化效果有显著影响.研究表明,UV/H2O2技术能高效矿化水中的去污剂,H2O2/DOC比值和UV辐照时间是影响氧化效率的关键因素.