O3/UV,O3/TiO2/UV,O3/VO2/TiO2降解磺基水杨酸

实验利用O3/UV,O3/TiO2/UV,O3/VO2/TiO2降解了磺基水杨酸.结果表明,在这三种高级氧化技术中,O3/VO2/TiO2的氧化效果最好,如在相同的条件下,30 min后取样表明三者COD的去除率分别为47%,55%和70%.在不同pH条件下研究表明O3/TiO2/UV对水体pH的影响较为敏感.通过加入自由基猝灭剂研究表明三者产生羟基自由基的活性顺序是O3/VO2/TiO2＞O3/TiO2/UV＞O3/UV.     

H2, CO, N2, O2和CH4在碳膜中的扩散

Diffusion of pure H2, CO, N2,O2 and CH4 gases through nanoporous carbon membrane is investigated by carrying out non-equilibrium molecular dynamics （NEMD） simulations. The flux, transport diffusivity and activation energy for the pure gases diffusing through carbon membranes with various pore widths were investigated. The simulation results reveal that transport diffusivity increases with temperature and pore width, and its values have a magnitude of 10^-7 m^2·s^-1 for pore widths of about 0.80 to 1.21 nm at 273 to 300 K. The activation energies for the gases diffusion through the membrane with various pore widths are about 1-5 kJ·mol^-1, The results of transport diffusivities are comparable with that of Rao and Sircar （J. Membr. Sci., 1996）, indicating the NEMD simulation method is a good tool for predicting the transport diffusivities for gases in porous materials, which is always difficult to be accurately measured by experiments.     

用UV/H2O2,UV/O3,UV/H2O2/O3催化处理城市固体垃圾填埋渗出物

The performance of UV/H2O2, UV/O3, and UV/H2O2/O3 oxidation systems for the treatment of municipal solid-waste landfill leachate was investigated. Main objective of the experiment was to remove total organic carbon (TOC), non-biodegradable organic compounds (NBDOC) and color. In UV/H2O2 oxidation experiment, with the increase of H2O2 dosage, removal efficiencies of TOC and color along with the ratio of biochemical oxygen demand (BOD) to chemical oxygen demand (COD) of the effluent were increased and a better performance was obtained than the system H2O2 alone. In UV/H2O2 oxidation, under the optimum condition H2O2 (0.2 time), removal efficiencies of TOC and color were 78.9% and 95.5%, respectively, and BOD/COD ratio was significantly increased from 0.112 to 0.366. In UV/O3 oxidation, with the increase of O3 dosage, removal efficiencies of TOC and color along with BOD/COD ratio of the effluent were increased and a better performance was obtained than the system O3 alone. Under the optimum condition UV/O3     

Comparative Study of Reactive Dyes Oxidation by H2O2/UV,H2O2/UV/Fe2+ and H2O2/UV/Fe° Processes

The decolorization and mineralization of two reactive dyes C.I. Reactive Blue 4 (RB 4) and C.I. Reactive Blue 268 (RB 268) were studied using various advanced oxidation processes (AOPs) such as H₂O₂/UV, H₂O₂/UV/Fe²⁺, and the H₂O₂/UV/Fe°. All processes were performed within a laboratory-scale photo-reactor setup. The experimental results were assessed in terms of absorbance (A) and total organic carbon (TOC) reduction. The main degradation products were identified by high resolution gas chromatography/high resolution mass spectrometry analyses. The results of our study demonstrated that the additions of moderate concentrations of H₂O₂ and Fe catalyst during the AOPs evidently increased the decolorization efficiencies within the first few minutes of the processing time (5–10 min) for both tested dyes, and prolonged irradiation does not necessarily significantly improve decolorization. On contrary, TOC removal rate increased with the processing time and with the addition of the catalyst from 40–50% up to 70–80% at defined experimental conditions. All the tested AOPs were very successful methods for RB 268 decolorization, having very complex structure and much higher molecular weight compared to the dye RB 4. This is important from both economic and ecological points of view.     

Na+,Mg2+//Cl-,SO42--H2O四元体系相平衡

针对海水淡化后浓海水综合利用问题,开展相平衡研究,提出硫酸钠水合物法增浓海水的方法。等温法测定了5℃时Na⁺, Mg²⁺//Cl^-, SO₄^2--H₂O四元体系及其子体系的相平衡溶解度数据,绘制并分析相图特征。结果表明：5℃时该体系存在2个等温共饱点和4个结晶区,十水硫酸钠结晶区形成面积较大,可用于硫酸钠水合物法增浓海水研究。相图分析和计算表明：该技术可使浓海水浓缩率高达82.78%,无水硫酸钠回收率99.6%。浓海水经精制处理后可作为制碱生产的原料,节省制碱生产过程中的化盐过程,为综合开发利用淡化后浓海水提供理论和数据基础。     

258.15 K下五元体系Li+,Na+,Mg2+//SO42-,Cl--H2O相平衡研究

中国含锂盐湖大部分位于青藏、新疆等干旱少雨、冬季寒冷且漫长的地区。为指导低温提锂工艺的开发和设计、利用冬季冷能进行目标离子的富集及明确含锂盐湖在低温下的析盐规律,采用等温溶解平衡法对258.15 K、二水氯化钠饱和条件下的交互五元体系Li⁺,Na⁺,Mg²⁺∥SO₄^2-,Cl^--H₂O相平衡关系进行研究并构建等温平衡相图。结果表明,相图中有4个共饱点、6个两盐结晶区(NaCl·2H₂O+Na₂SO₄·10H₂O、NaCl·2H₂O+MgCl₂·8H₂O、NaCl·2H₂O+MgSO₄·7H₂O、NaCl·2H₂O+Li₂SO₄·H₂...     

SO2 Reactions over γ-Al2O3,Pt/γ-Al2O3,Sn/γ-Al2O3 and Pt–Sn/γ-Al2O3

Platinum and Platinum–tin bimetallic catalysts supported on alumina were prepared by co-impregnation of both metallic precursors on the support and used as catalysts for the oxidation of SO₂. Platinum dispersion was determined by means of H₂–O₂ titration. Tin addition (1 and 2 wt%) only slightly decreased the exposed platinum atoms suggesting that tin is mainly over the support. At temperatures lower than 300 °C, SO₂ did not react with oxygen. Nevertheless, when the temperature was increased, the SO₂ oxidation began. The ignition temperatures for SO₂ oxidation (taken at 50% conversion) were 345 °C for 1% Pt/Al₂O₃ and 520 °C for 1% Pt–2% Sn/Al₂O₃. The strong displacement on activity suggests that tin plays an important role as inhibitor of the SO₂ oxidation reaction.     

Preparation and characterization of TiO2, ZnO,and TiO2/ZnO nanofilms via sol–gel process

The preparation of the TiO₂, ZnO, and TiO₂/ZnO nanofilms was conducted on glass via sol–gel process. The prepared film was detailedly characterized by means of OM, SEM, XRD, and EDS. The results showed that the obtained pure TiO₂ was composed of nanoparticles. For pure ZnO it consisted of nanoparticles and large agglomerates. Both the microstructural morphology and the crystallization of the prepared TiO₂/ZnO composite film were strongly related to the Ti/Zn ratio in the film. With a Ti/Zn ratio less than 1/1, the composite film was absence of cracks. Poor crystallization was definitely observed for the composite film with Ti/Zn ratio of 3/1 and 1/1. The EDS analysis revealed homogeneous distribution of Ti and Zn elements in the film.     

Comparative Study on Partial Oxidation of Methane over Ni/ZrO2, Ni/CeO2 and Ni/Ce–ZrO2 Catalysts

The partial oxidation of methane has been studied by sequential pulse experiments with CH₄ O₂ CH₄ and simultaneous pulse reaction of CH₄/O₂ (2/1) over Ni/CeO₂, Ni/ZrO₂ and Ni/Ce–ZrO₂ catalysts. Over Ni/CeO₂, CH₄ dissociates on Ni and the resultant carbon species quickly migrate to the interface of Ni–CeO₂, and then react with lattice oxygen of CeO₂ to form CO. A synergistic effect between Ni and CeO₂ support contributes to CH₄ conversion. Over Ni/ZrO₂, CH₄ and O₂ are activated on the surface of metallic Ni, and then adsorbed carbon reacts with adsorbed oxygen to produce CO, which is composed of the main path for the partial oxidation of methane. The addition of ceria to zirconia enhances CH₄ dissociation and improves the carbon storage capacity. Moreover, it increases the storage capacity and mobility of oxygen in the catalyst, thus promoting carbon elimination.     

Hydrogenation of Sunflower Oil over M/SiO2 and M/Al2O3 (M = Ni,Pd, Pt,Co, Cu) Catalysts

This work is aimed at evaluating the performance of several catalysts in the partial hydrogenation of sunflower oil. The catalysts are composed of noble (Pd and Pt) and base metals (Ni, Co and Cu), supported on both silica and alumina. The following order can be proposed for the effect of the metal on the hydrogenation activity: Pd > Pt > Ni > Co > Cu. At a target iodine value of 70 (a typical value for oleomargarine), the production of trans isomers is minimum for supported nickel catalysts (25.7–32.4 %, depending on the operating conditions). Regarding the effect of the support, Al₂O₃ allows for more active catalysts based on noble metals (Pd and Pt) and Co, the effect being much more pronounced for Pt. Binary mixtures of catalysts have been studied, in order to strike a balance between catalyst activity and product distribution. The results evidence that Pd/Al₂O₃–Co/SiO₂ mixture has a good balance between activity and selectivity, and leads to a very low production of trans isomers (11.8 %) and a moderate amount of saturated stearic acid (13.5 %). Consequently, the utilization of cobalt‐based catalysts (or the addition of cobalt to other metallic catalysts) could be considered a promising alternative for the hydrogenation of edible oil.     

H2 and H2/CO oxidation mechanism on Pt/C, Ru/C and Pt–Ru/C electrocatalysts

The oxidation kinetics of H₂ and H₂ + 100 ppm CO were investigated on Pt, Ru and Pt–Ru electrocatalysts supported on a high-surface area carbon powder. The atomic ratios of Pt to Ru were 3, 1 and 0.33. XRD, TEM, EDS and XPS were used to characterize the electrocatalysts. When alloyed with ruthenium, a decrease in mean particle size and a modification of the platinum electronic structure were identified. Impedance measurements in H₂SO₄, at open circuit potential, indicated different mechanisms for hydrogen oxidation on Pt/C (Tafel–Volmer path) and Pt–Ru/C (Heyrowsky–Volmer path). These mechanisms also occur in the presence of CO. Best performances, both in H₂ and H₂ + CO, were achieved by the catalyst with the ratio Pt/Ru = 1. This is due to a compromise between the number of free sites and the presence of adsorbed water on the catalyst. For CO tolerance, an intrinsic mechanism not involving CO electroxidation was proposed. This mechanism derives from changes in the electronic structure of platinum when alloyed with ruthenium.     

固体超强酸催化剂S2O82-/聚乙二醇-TiO2-M2O3(M=Al,Cr)制备乙酰丙酸

研制了固体超强酸催化剂S₂O₈^2-/聚乙二醇-TiO₂-M₂O₃(M=Al,Cr), 并以赤砂糖为原料,催化水解法制备乙酰丙酸。通过单变量法考察了催化剂焙烧时间、催化剂用量、赤砂糖浓度、反应温度和反应时间等对乙酰丙酸收率的影响,并通过正交实验确定最佳工艺条件。结果表明,在催化剂焙烧时间120 min、赤砂糖浓度为10 g·L^-1、催化剂用量为赤砂糖质量的15%、反应温度200 ℃和反应时间120 min条件下,乙酰丙酸收率达39.98%。     

A study of the formation of Ln2 + xMe2 ? xO7 ? x/2 (Ln = Gd, Dy; Me = Zr, Hf) nanocrystals

It has been established that the process of producing the Ln_{2 + x} Me_{2 − x} O_{7 − x/2} (Ln = Gd, Dy; Me = Zr, Hf) nanocrystals by calcination of hydroxides, which, in turn, have been produced by coprecipitation of metal salts, includes several stages. At the beginning, the X-ray amorphous structure of the precursors remains unchanged during dehydration; during subsequent heating to 600–700°C, nanocrystals with a disordered fluorite structure begin to be formed. An increase in the temperature above 700°C leads to an increase in the size of crystallites (coherent scattering regions). This process is accompanied by changes occurring in their local structure. In the nanocrystalline powders of Cd₂Hf₂O₇ and Gd₂Zr₂O₇ synthesized at 1200°C (6 h), the pyrochlore-type superstructure with the lattice parameters doubled relative to fluorite has been revealed. It has also been found that, possibly, the Dy₂HfO₅ sample at 1600°C (3 h) has a modulated structure.     

Fe2+催化H2O2、S2O82-、S2O82--H2O2降解橙黄G

以偶氮染料橙黄G(OG)为目标污染物,研究Fe2+分别催化H2O2、S2O82-、H2O2-S2O82-降解0.1 mmol/LOG Fe2+/H2O2体系,[Fe2+]=1 mmol/L,pH=3,[H2O2]0=10 mmol/L,降解30 min OG脱色率为96%,随着pH值增大和[H2O2]0>10 mmol/L,OG脱色率减小,呈线性变化。Fe2+/S2O82-体系,随着S2O82-初始浓度增加OG脱色率增大,随着pH值增大OG脱色率减小,呈非线性变化。Fe2+/H2O2-S2O82-体系,pH=3,[H2O2]0=2 mmol/L,[S2O82-]0>10 mmol/L时OG脱色率持续增大。Fe2+/H2O2-S2O82-体系矿化率最高。利用乙醇和硝基苯作为分子探针,采用分子探针竞争实验鉴定该体系中产生的SO4.和OH.。     

P2O5对(K,Na)2O-CaO-Al2O3-B2O3-SiO2系分相乳浊釉性能及结构的影响

在(K,Na)₂O-CaO-Al₂O₃-B₂O₃-SiO₂分相乳浊釉中引入P₂O₅,用热膨胀仪、色度仪、维氏硬度计、扫描电子显微镜、透射电子显微镜、红外光谱等测试方法探究其对釉面性能及釉玻璃结构的影响。结果表明:釉面白度和维氏硬度随P₂O₅引入量的增加而显著提高,白度由46.58%提高至71.79%,维氏硬度由737.94 HV提高至1 153.03 HV;在P₂O₅组分引入量较低时(0.58%,摩尔分数,下同),[PO₄]易夺取基质玻璃相中[BO₄]的桥氧促使[BO₄]向[BO₃]转变,促进釉熔体分相,此时P₂O₅多存在于富硼分相液滴中。当P₂O₅组分...     

四元体系Na+,K+,Sr2+//Br-–H2O 308 K相平衡研究

针对四川盆地地下卤水富含钾锶的特点,采用等温溶解平衡法研究308K下四元体系Na⁺,K⁺,Sr²⁺//Br^-–H₂O的相平衡关系,测定平衡液相的溶解度,通过实验数据绘制该四元体系308 K下的平衡相图和水图,同时对该四元体系Na⁺,K⁺,Sr²⁺//Br^-–H₂O在不同温度下的溶解度数据进行比较分析和讨论。结果表明在308K下该四元体系是一个简单的共饱和类型,且既无复盐也无固溶体形成,该相图包含一个共饱点,3条单变量曲线和3个固相结晶区,分别对应为KBr、NaBr·2H₂O和SrBr₂·6H₂O,其中KBr结晶区最大,而NaBr·2H₂O和SrBr₂·6H₂O的结晶区较小。通过对比多温相图发现,NaBr和SrBr₂的溶...     

SiO2-Al2O3-Na2O-MO(M=Ca,Ba)玻璃在SOFC中的性能研究

从玻璃的粘结强度与气密性角度出发,对在固体氧化物燃料电池(SOFC)领域中应用较为广泛的SiO₂-Al₂O₃-Na₂O-CaO(S1)和SiO₂-Al₂O₃-Na₂O-BaO(S2)两款密封玻璃进行了研究对比。研究发现,S1与SOFC的粘结强度为2.00 MPa, 30 kPa下的气体泄漏率为0.041 sccm/cm,而S2与SOFC的粘结强度为3.93 MPa, 30 kPa下的气体泄漏率为0.027 sccm/cm,结果表明,S2的密封效果优于S1。750℃下H₂/Air=0.6/3.0 slm时,分别以S1和S2密封的SOFC开路电压(OCV)对比验证了以上结果,前者(S1)的OCV值只有0.949 V,远低于后者(S2)的1.08 V。最后结合热膨胀系数(TEC)以及微观形貌对两款密封材料进行了深入探讨分析,为Ca系和Ba系高温密封玻璃的优化提供了借鉴。