微乳液法合成掺硫纳米TiO_2及其光催化性能研究

以钛酸四丁酯为钛源,硫脲为掺硫前驱物,采用聚乙二醇辛基苯基醚（Triton X-100）/正己醇/环己烷/氨水的微乳液体系合成了掺硫的纳米TiO2粉体;对其结构进行了表征,以甲基橙为目标降解物考察了其光催化性能。烧结温度通过影响TiO2的晶型转变和颗粒尺寸来影响其光催化性能,随着烧结温度的升高,TiO2的光催化性能先是提高,然后迅速降低;在600℃烧结2 h时催化剂的降解性能达到最佳。掺杂硫可提高TiO2的光催化活性,随着掺杂量的增加,催化剂对甲基橙的降解率先快速增加然后缓慢降低,当掺杂量为S/Ti（摩尔比）=0.01∶1时TiO2的光催化降解效果最好。催化剂在用量较小时迅速提高TiO2的光催化降解性能,而后随着用量的增大反而降低,当催化剂用量为1.5 g/L时,对甲基橙的降解效果最好。     

乌江流域梯级水库入出库河流中总汞和甲基汞的时空分布

2006年1~12月,每月采集乌江流域梯级水库入出库河流水样,用两次金汞齐-冷原子荧光光谱法和蒸馏-乙基化结合GC CVAFS法测定了水中总汞和甲基汞的浓度。结果表明：（1）入出库河流中总汞年均加权浓度分别为317和 2.34 ng/L,甲基汞为014和 0.18 ng/L。（2）不同水库入出库河流中总汞和甲基汞的时空分布特征不同,位于上游第一级的普定和洪家渡水库入库河流中总汞有明显的季节变化趋势,且显著低于出库河流;而甲基汞的季节变化在出库河流中较为明显,而且库龄大的普定、东风、乌江渡水库出库河流中甲基汞浓度显著高于入库河流。（3）相关分析发现水库入库河流中总汞、甲基汞浓度主要受悬浮颗粒物的影响,而与水量间的相关性因水库所处位置的不同而有差异,上游的普定和洪家渡水库中呈显著正相关,其它水库中呈负相关。     

陶瓷负载Ag、Ce共掺杂TiO_2光催化剂降解甲基橙的研究

以陶瓷为载体,采用溶胶-凝胶法制备了银离子和铈离子共掺杂TiO2的负载型光催化剂——T-AC/陶瓷,研究了pH值、双氧水用量、催化剂用量、紫外灯强度、废水的初始浓度等因素对T-AC/陶瓷光催化剂降解甲基橙染料废水的影响。结果表明,当pH为2、双氧水用量为0.5 mL/100 mL、催化剂用量为3 g/L、紫外灯功率为20 W、废水初始浓度为10mg/L时,甲基橙的降解率可达85.9%,并且甲基橙的光催化降解属于一级动力学方程,T-AC/陶瓷催化剂有较高的活性和稳定性,在废水处理中具有较好的应用前景。     

沸石负载Cu_2O光催化剂降解甲基橙

采用化学沉积法,以Cu SO4·5H2O和Na2SO3为原料,以人造沸石为载体,在HAC-Na AC缓冲溶液中制备了沸石-Cu2O复合型光催化剂。在仿日光光源照射下,分别从降解时间、甲基橙初始浓度及初始p H、降解温度等不同方面考察了对复合光催化剂降解甲基橙的影响。结果表明,当甲基橙初始浓度为25 mg/L、初始p H在7.00~10.00之间,降解温度为40℃,复合型光催化剂对甲基橙的降解效果最好;样品重复性使用实验表明,沸石-Cu2O复合光催化剂在可见光区具有良好的光催化活性和稳定性;离子干扰实验证明,Cl-浓度控制在1.2 g/L之内时对甲基橙降解效果影响较小。     

磁性活性炭催化臭氧氧化降解水中甲基橙

通过浸渍法制备了钕铁硼磁性活性炭(Nd Fe B/AC),采用SEM和VSM技术对其进行了表征,并将其作为非均相催化剂用于臭氧氧化降解水中甲基橙(MO)。表征结果显示:Nd Fe B/AC具有硬磁特性;当m(Nd Fe B)∶m(AC)=1∶2时,其比饱和磁化强度和比剩余磁化强度分别为15.9 A·m2/kg和6.0 A·m2/kg,矫顽力可达104.5k A/m。实验结果表明:在Nd Fe B/AC投加量为3.0 g/L、初始溶液p H为5.0、初始MO质量浓度为20 mg/L、臭氧质量浓度为15.0 mg/L、室温的条件下反应40 min,MO降解率达93.9%,显著优于投加AC的64.4%;AC和Nd Fe B/AC催化臭氧氧化降解MO的反应过程均遵循一级动力学规律,且Nd Fe B/AC的反应速率常数为AC的近3倍。     

Effects of injection timing,injector opening pressure and nozzle geometry on the performance of cottonseed oil methyl ester-fuelled diesel engine

Increasing petroleum prices, increasing threat to the environment from exhaust emissions and global warming have generated intense international interest in developing renewable and alternative non-petroleum fuels for engines. Evolving technology and a recurring energy crisis necessitates a continuous investigation into the search for sustainable and clean-burning renewable fuels. In this paper, cottonseed oil methyl ester (COME) was used in a four-stroke, single-cylinder variable compression ratio diesel engine. Tests were carried out to study the effects of fuel injection timing, fuel injector opening pressure (IOP) and injector nozzle geometry on the performance and combustion of COME biodiesel fuel used in a compression ignition engine with a single fuel mode. Fuel injection timing varied from 19° to 27° before top dead centre (bTDC) in incremental steps of 4° bTDC; fuel IOP varied from 210 to 240 bar in incremental steps of 10 bar. Fuel nozzle injectors with three, four and five holes, each of 0.3 mm size, were selected for the study. The results suggested that with retarded injection timing of 19° bTDC, increased IOP of 230 bar and a four-hole nozzle injector of 0.3 mm size resulted in overall better engine performance with an increased brake thermal efficiency and reduced HC, CO and smoke emission levels.     

Positive vs. false detection: A comparison of analytical methods and performance for analysis of cyclic volatile methylsiloxanes (cVMS) in environmental samples from remote regions

Contamination and analytical variation can significantly hinder trace analysis of cyclic methyl volatile siloxanes (cVMS); potentially resulting in the report of false positives at concentrations approaching detection limits. To assess detection and variation associated with trace cVMS analysis in environmental matrices, a co-operative laboratory comparison for the analysis of octametylcyclotetrasiloxane (D4), decamethylcylcopentasiloxane (D5), and dodecametylcyclohexasiloxane (D6) in sediment and biota from the Svalbard Archipelago was conducted. Two definitions of detection limits were evaluated in this study; method detection limits (MDL, matrix defined) and limits of detection (LOD, solvent defined). D5 was the only cVMS detected above both LOD (0.08–0.81 ng g⁻¹ ww) and MDL (0.47–2.36 ng g⁻¹ ww) within sediment by all laboratories where concentrations ranged from 0.55 to 3.91 ng g⁻¹ ww. The percentage of positive detects for D5 decreased by 80% when MDL was defined as the detection limit. D5 was also detected at the highest frequency among all laboratories in fish liver with concentrations ranging from 0.72 to 345 ng g⁻¹ ww. Similar to sediment, percentage of positive detects for D5 decreased by 60% across all laboratories for fish livers when using MDL (0.68–3.49 ng g⁻¹ ww). Similar observations were seen with both D4 and D6, indicating that sample matrix significantly contributes to analytical response variation. Despite differences in analytical methods used between laboratories, good agreement was obtained when using MDL to define detection limits. This study shows the importance of incorporating variation introduced by sample matrices into detection limit calculations to insure data accuracy of cVMS at low concentrations.     

Investigation of metal ions binding of humic substances using fluorescence emission and synchronous‐scan spectroscopy

Abstract

The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous‐scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern‐Volmer constants, K_SV for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3–10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous‐scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers.     

Optimization of esterification of fatty acid rubber seed oil for methyl ester synthesis in a plug flow reactor

To date, non-food vegetable oil has been considered as the primary source for biodiesel production. Rubber seed oil has high acid value (34 mgKOH/g) and can be used for biodiesel synthesis. The purpose of this study was to investigate esterification of fatty acid, which derived from rubber seed oil, in a plug flow reactor system at high temperature and low methanol consumption. Response surface methodology was applied for design experiment and optimization of esterification reaction. Temperature, methanol consumption, and sulfuric acid were chosen as variables to examine their influence in a conversion to methyl ester. At 140°C, at 5:1 methanol to fatty acid ratio (by mole), H₂SO₄ 1.5 (%v/w), and space time 20 min, the conversion to methyl ester attained 98.2%. Fourier transform infrared spectroscopy (FTIR) and gas chromatography-Mass spectrometry (GC-MS) were used for analysis and to confirm the formation of methyl ester. Methyl ester was characterized for biodiesel fuel properties in accordance to ASTM standard.     

Removal of mixed pesticides from drinking water system by photodegradation using suspended and immobilized TiO2

Lindane (1α, 2α, 3β, 4α, 5α, 6β-hexachloro cyclohexane), methyl parathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate) and dichlorvos (2,2-dichlorovinyl-O-O-dimethyl phosphate) are removed from water individually and as a mixture by photo degradation using suspended and immobilized forms of TiO₂ (Degussa P-25). Studies were conducted to optimize the coating thickness of immobilized photo catalyst. The rate of degradation of pesticides was compared in both suspended and immobilized TiO₂ systems. Degradation studies of mixed pesticides were carried out with low concentrations (1.0 and 2.5 mg/L) of pesticides. Only three intermediate byproducts such as methyl paraoxon, O,O,O-trimethyl phosphonic thionate and p-nitrophenol were observed during the methyl parathion degradation in suspended, immobilized TiO₂ systems and mixed pesticides degradation studies. At the end of the reaction methyl parathion and its by-products were completely degraded. During lindane degradation hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene, 1-hydroxy 2,3,4,5,6-chlorocyclohexane, 1-hydroxy 2,3,4,5,6-chlorobenzene, pentachloro cyclopentadiene, 1,2,3,4,5-hydroxy cyclopentene and 1,2,3-hydroxy cyclobutane were identified in suspended and immobilized TiO₂ systems, whereas only hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene and pentachloro cyclopentadiene were observed during mixed pesticides degradation. No intermediate by-product was observed during the photo degradation of dichlorvos. Langmuir-Hinshelwood pseudo first order kinetic equation showed that there was not much change in the rates of degradation in both suspended and immobilized TiO₂ systems irrespective of the pesticide. During mixed pesticides degradation, the degradation pattern was not similar to that of single pesticide.