木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂对二元重金属离子溶液中Pb^2＋的吸附

采用自制木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂R1、R2、R3对二元金属离子Cu2＋/Pb2＋和Zn2＋/Pb2＋溶液中的吸附性能进行了较系统考察。Pb2＋离子溶液中存在竞争离子Cu2＋、Zn2＋时,随竞争离子浓度增加,3种吸附树脂R1、R2、R3对Pb2＋的吸附量明显下降,而竞争离子吸附量显著增加。二元溶液中各金属离子浓度相同时,3种树脂对竞争离子Cu2＋、Zn2＋的吸附量大于对Pb2＋的吸附量;各溶液中分别加入NaCl及NaNO3、尿素后,对Pb2＋离子的吸附量下降迅速。随吸附树脂用量增加,竞争离子Cu2＋、Zn2＋的吸附量逐渐减小,Pb2＋的吸附量在吸附树脂用量0.10 g/L（Zn2＋/Pb2＋溶液）或0.15 g/L（Cu2＋/Pb2＋溶液）时出现最大值。溶液pH值对树脂吸附性能有显著影响。3.0     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.     

Surface flux measurements of CO2 and N2O from a dried rice paddy in Japan during a fallow winter season

The CO2 and N2O soil emissions at a rice paddy in Mase, Japan, were measured by enclosures during a fallow winter season. The Mase site, one of the AsiaFlux Network sites in Japan, has been monitored for moisture, heat, and CO2 fluxes since August 1999. The paddy soil was found to be a source of both CO2 and N2O flux from this experiment. The CO2 and N2O fluxes ranged from -27.6 to 160.4 microg CO2/m2/sec (average of 49.1 +/- 42.7 microg CO2/m2/sec) and from -4.4 to 129.5 ng N2O/m2/sec (average of 40.3 +/- 35.6 ng N2O/m2/ sec), respectively. A bimodal trend, which has a sub-peak in the morning around 10:00 a.m. and a primary peak between 2:00 and 3:00 p.m., was observed. Gas fluxes increased with soil temperature, but this temperature dependency seemed to occur only on the calm days. Average CO2 and N2O fluxes were 27.7 microg CO2/m2/sec and 13.4 ng N2O/m2/sec, with relatively small fluctuation during windy days, while averages of 69.3 microg CO2/m2/sec and 65.8 ng N2O/m2/sec were measured during calm days. This relationship was thought to be a result of strong surface winds, which enhance gas exchange between the soil surface and the atmosphere, thus reducing the gas emissions from soil surfaces.     

钛基氧化物涂层电极在污水处理方面的实验研究

用涂刷热分解氧化法研究制作了3种钛基金属氧化物涂层电极：SnO₂-Sb₂O₃-CeO₂/SnO₂-Sb₂O₃/Ti、SnO₂-Sb₂O₃-CoO₂/SnO₂-Sb₂O₃/Ti和SnO₂-Sb₂O₃-CoO₂/IrO₂/Ti，用于处理生活污水，筛选出了处理效果最好的电极：SnO₂-Sb₂O₃-CeO₂/SnO₂-Sb₂O₃/Ti电极。通过SnO₂-Sb₂O₃-CeO₂/SnO₂-Sb₂O₃/Ti电极处理生活污水的静态实验，研究了电解时间、电流密度等因素对电解效果的影响，得出该电极较佳的运行参数是：极板间距1 cm、电流密度10 mA/cm²、电解时间2 h，此时，COD、NH₃-N、总磷、总氮、SS和大肠菌群的去除率分别为94.0％、99.8％、51.8％、70.8%、100％和100％；并用该参数进行了动态实验，连续运行60 d，得到了稳定的出水水质数据。     

Predictions of binary sorption isotherms for the sorption of heavy metals by pine bark using single isotherm data

The adsorption of three heavy metal ions by pine bark was studied. The study was divided into two parts; single component adsorption of the metals Cu2+, Cd2+ and Ni2+ and bisolute adsorption of the three binary systems Cu2+-Cd2+, Cu2+-Ni2+ and Cd2+-Ni2+. Extended Langmuir model, extended Freundlich model. Sips model and ideal adsorption solution theory (IAST) models were used to predict the equilibrium uptake for Cu2+, Cd2+ and Ni2+ in the binary diluted solutions using the single adsorption constants. The experimental data of single isotherm adsorption process were found to follow Langmuir isotherm model with less accuracy than Freundlich and Sips models. Whereas, the predictions of bisolute adsorption isotherms of the mentioned three systems, Cu2+-Cd2+, Cu2+-Ni2+ and Cd2+-Ni2+, showed good agreement with experimental data when using Extended-Langmuir, Extended-Freundlich and IAST. However, the only good fit of the Sips model was with the Cu2+-Cd2+ system.     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

Gas-phase reaction of CCl2F2 (CFC-12) with methane

Gas-phase reaction of CFC-12 (CCl2F2) with methane was carried out in a plug flow reactor over the temperature range of 873-1123 K. The major organic halocarbons formed during the reaction were C2F4, C2H2F2, CHClF2, CH3Cl, C3H2F6 and CCl3F. The formation of all products except C2H2F2 decreased with temperature, while the selectivity to C2H2F2 (difluoroethylene) increased with temperature and reached approximately 80% at 1123 K. Under these reaction conditions, methane acts as hydrogen and carbon source, resulting in the formation of an unsaturated C2 hydrofluorocarbon from two C1 precursors.     

不同态二氧化钛处理模拟印染废水的研究

以普通载玻片为基底材料,负载态和悬浮态的纳米二氧化钛/普通二氧化钛被用于处理甲基红模拟印染废水,实验结果表明:纳米二氧化钛的脱色效果明显优于普通的二氧化钛,适当增加负载量和处理时间,负载态的处理效果与悬浮态相当。首次提出了由光源决定的纳米光催化活性激发理论,解释了不同光源辐照时脱色率变化曲线差异的问题,并发现纳米TiO2光催化氧化模拟印染废水的脱色反应,主要由吸附过程控制的表面反应机理;150 mL模拟印染废水中,加入3块纳米TiO2负载量1 mg/cm2的普通载玻片,3~5 mL ClO2或H2O2,紫外光照60 min后,脱色率达到99.2%。     

Photo-oxidation of cork manufacturing wastewater

Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).     

Superior pillared clay catalysts for selective catalytic reduction of nitrogen oxides for power plant emission control

Fe(3+)-, Cr(3+)-, Cu(2+)-, Mn(2+)-, Co(2+)-, and Ni(2+)-exchanged Al2O3-pillared interlayer clay (PILC) or TiO2-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe(3+)-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO2-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H2O and SO2 increase both the activity and the product selectivity to N2. The maximum activity on the Ce-Fe-TiO2-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V2O5-WO3/TiO2 catalyst, the Fe-TiO2-PILC catalysts show higher N2/N2O product selectivities and substantially lower activities (by approximately 85%) for SO2 oxidation to SO3 under the same reaction conditions. A 100-hr run in the presence of H2O and SO2 for the CeO2/Fe-TiO2-PILC catalyst showed no decrease in activity.     

UV/TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜,研究了UV-V is/TiO2以及UV/TiO2/H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明,TiO2在暗处对酞酸酯没有降解作用;UV/TiO2体系能有效光降解DBP和DEHP,TiO2具有明显的光催化作用,增强因子分别为fDBP=2.06,fDEHP=1.53;在一定浓度范围内DBP在UV/TiO2体系中的降解速率与其初始浓度成负一级动力学关系;UV/TiO2/H2O2体系对DBP的光降解能力远大于UV/TiO2和UV/H2O2体系,H2O2能显著提高TiO2的光催化活性。     

Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Replacement of H2O2 by O2 in Fenton and photo-Fenton reactions

The consumption of oxygen during the degradation of aniline by Fenton and photo-Fenton reactions is studied. The effect that parameters like aniline, Fe(II) and H2O2 initial concentration, pH, temperature and O2 flow rate have on the ratio O2 consumed/H2O2 consumed is examined. The determination of those combinations of experimental conditions for which an effective partial replacement of H2O2 by O2 as electron acceptor takes place is investigated. The results show that this replacement takes place in a variable extent, but the presence of H2O2 is necessary along the reaction, and the maximum consumption of O2 only takes place when the ratio amount of aniline mineralized vs. initial aniline concentration is minimal.     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

Fe-exchanged zeolite as the effective heterogeneous Fenton-type catalyst for the organic pollutant minimization: UV irradiation assistance

The issue of investigations in this study was an application of heterogeneous Fenton-type catalyst, Fe-exchanged zeolite FeZSM5, for the minimization of phenol and overall organic content in the model wastewater. Applied treatment systems included variation of heterogeneous and homogeneous Fenton-type catalyst with and without the assistance of UV irradiation, FeZSM5/H2O2, Fe2+/H2O2/NH4ZSM5, Fe3+/H2O2/NH4ZSM5, UV/FeZSM5/H2O2, UV/Fe2+/H2O2/NH4ZSM5 and UV/Fe3+/H2O2/NH4ZSM5. Processes efficiency was evaluated on the basis of phenol removal, mineralization extent, H2O2 consumption and concentration of iron ions in the bulk after the treatment. By all applied systems, complete phenol removal was achieved in less than 30 min of treatment time. Systems including heterogeneous Fenton-type catalyst showed somewhat lower mineralization efficiency in comparison to the corresponding systems applying homogeneous Fenton-type catalysts and the addition of synthetic zeolite NH4ZSM5. Significantly lower concentration of iron ions in the bulk after the treatment could give these systems, particularly UV/FeZSM5/H2O2, a great advantage over the homogeneous Fenton-type systems.     

Decomposition of SF6 in an RF plasma environment

Sulfur hexafluoride (SFd)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF6. The decomposition fraction of SF6 [etaSF6 (C(in)-C(out))/C(in) x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O2/SF6 ratio in an SiO2 reactor. The species detected in both SF6/Ar and SF6/O2/ Ar RF plasmas were SiF4, SO2, Fe2, SO2F2, SOF2, SOF4, S2F10, S2OF10, S2O2F10, and SF4. The results revealed that at 40 W, etaSF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF4, SO2, and F2 with or without the addition of oxygen. Sulfur oxyfluorides such as SO2F2, SOF2, SOF4, S2OF10, and S2O2F10 were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF6-containing exhaust gases.     

Composite tin and zinc oxide nanocrystalline particles for enhanced charge separation in sensitized degradation of dyes

Composite ZnO/SnO2 catalyst has been studied for the sensitized degradation of dyes e.g. Eosin Y (2', 4', 5', 7'-tetrabromofluorescein disodium salt) in relation to efficient charge separation properties of the catalyst. Improved photocatalytic activity was observed in the case of ZnO/SnO2 composite catalyst compared to the catalytic activity of ZnO, SnO2 or TiO2 powder. The suppression of charge recombination in the composite ZnO/SnO2 catalyst led to higher catalytic activity for the degradation of Eosin Y. Degradation of Eosin follows concomitant formation of CO2 and formation of CO2 followed a pseudo-first-order rate. Photoelectrochemical cells constructed using SnO2, ZnO, ZnO/SnO2 sensitized with Eosin Y showed V(oc) of 175, 306, 512 mV/cm2 and I(sc) of 50, 70, 200 microA/cm2 respectively. A higher irreversible degradation of Eosin Y and higher V(oc) observed on composite ZnO/SnO2 than ZnO and SnO2 separately can be considered as a proof of enhanced charge separation of ZnO/SnO2 catalyst. Eosin Y showed a higher emission decreases on ZnO/SnO2 composite than on individual ZnO, SnO2 or TiO2 indicating dominance of the charge injection process. Photoinjected electrons are tunneled from ZnO to SnO2 particles accumulating injected electrons in the conduction bands allowing wider separation of excited carriers.     

TiO_2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料,采用微波辐射法制备TiO2/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO2/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO2均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO2负载量为18.2%、TiO2/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H2O2、AgNO3、K2S2O8、KIO4和KMnO4均能提高TiO2/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO2/AC光催化效率的强化作用大小顺序为：H2O2〉AgNO3〉K2S2O8〉KMnO4〉KIO4。     

改性TiO2对X-3B的光催化性能及其降解动力学研究

以活性艳红X-3B为模型化合物,比较了改性前后TiO2光催化活性的变化.试验结果表明,通过改性大大提高了TiO2的光催化活性,Fe3+和Ag+的掺杂量均有一个最佳值,在试验的掺杂范围内Fe3+和Ag+的最佳掺杂量分别是0.1%和0.05%.对其宏观降解反应动力学的研究表明,X-3B在TiO2、Fe3++TiO2和Ag++TiO2 3种催化剂上的光催化降解动力学均能很好地符合Langmiur-Hinshelwood动力学模型.其表观反应速率常数的大小顺序依次是Ag++TiO2＞Fe3++TiO2＞TiO2;吸附平衡常数则是Fe3++TiO2和Ag++TiO2两者基本相等,两者均比纯TiO2大2～3倍.