过氧化钙的制备及其在废水处理中的应用

开发出一种过氧化钙常温合成新工艺。在氯化铵与过氧化氢质量比为10／130、采用稳定剂ⅠA和稳定剂ⅡB的条件下,使氢氧化钙与过氧化氢反应合成过氧化钙,其收率为35．9％,纯度为72．3％。用制得的过氧化钙去除机械工业废水中的重金属离子,在室温、过氧化钙用量0．1％～0．2％、处理时间30min、处理过程中不调整pH的条件下,含锰35．58μg／mL、铜67μg／mL、锌31．3μg／mL、铬43．56μg／mL(均为质量浓度)的废水经一次处理后,锰、铜、锌浓度和pH均达到国家一级水排放标准,铬的一次去除率达到39％以上。     

Degradation of 4-aminophenol by hydrogen peroxide oxidation using enzyme from Serratia marcescens as catalyst

This paper reports on the degradation of 4-aminophenol using hydrogen peroxide as oxidizer and the enzyme from Serratia marcescens AB 90027 as catalyst. The effecting factors during degradation and the degrading mechanism were studied. Also, the location of the enzyme in the cell, which could catalyze the degradation of 4-aminophenol, was analyzed. The results showed that to degrade 50 mL of 4-aminophenol whose concentration was 500 mg/L, the optimal conditions were: volume of H₂O₂ = 3 mL, temperature = 40–60°C and pH = 9–10. In the degradation process, 4-aminophenol was first converted to benzoquinone and NH₃, then organic acids including maleic acid, fumaleic acid, and oxalic acid were formed, and then finally CO₂ and H₂O were generated as final products. The enzyme that could catalyze the degradation of 4-aminophenol was mainly extracellular enzyme. Translated from Environmental Chemistry, 2006, 25(2): 141–144 [译自: 环境化学]     

掺Fe金红石TiO2的制备及其可见光催化活性的评价研究

为提高金红石型TiO2的可见光吸收性能和光催化活性,以FeC2O4为Fe源,用浸渍法制备了掺铁金红石TiO2光催化剂。采用XRD、UV-Vis等手段对催化剂进行表征;以阿特拉津为目标污染物,在Vis/H2O2条件下对其催化活性进行了评估。结果表明,Fe以Fe2O3的形式负载在金红石型TiO2的表面;掺铁后金红石型TiO2显著拓宽了其可见光的吸收范围;煅烧温度为400℃时制得的光催化剂Fe-R-400℃的粒径结构和光催化活性最好。以Fe质量分数为1%的Fe-R-400℃作为光催化剂,控制反应体系的初始pH=3,催化剂投加质量浓度为1 g/L,H2O2初始浓度为1 mmol/L,经可见光照射反应15 min后,对初始质量浓度为10 mg/L的阿特拉津的去除率可达95.7%。催化剂循环试验表明,Fe在金红石TiO2表面负载比较牢固,催化剂具有较好的稳定性和重复使用性能。     

O3/H2O2法灭活水中剑水蚤类浮游动物

为解决水源水中孳生的水蚤类浮游动物难以被常规的水处理工艺有效地去除,困扰水厂正常生产运行的问题,进行了O₃氧化、H₂O₂氧化和O₃/H₂O₂高级氧化对水体中剑水蚤类浮游动物灭活效果的试验研究.发现3种方法中,O₃/H₂O₂联合时除蚤效果最佳,在蒸馏水中投量为O31.0mg/L、H₂O₂4mg/L时,接触30min达到100%的灭蚤率;单独O₃氧化效果也较好,投加1.0mg/L的灭蚤率为80%;H₂O₂氧化效果不理想,投加4mg/L几乎无灭蚤效果.进而考察确定了O₃/H₂O₂灭活剑水蚤的最佳工艺条件为:先加O₃后加H₂O₂,投加间隔时间30～60s为宜;并探讨了H₂O₂投量、水体pH值以及有机物含量对O₃/H₂O₂系统灭活剑水蚤效果的影响.试验中发现H₂O₂投量在4～10mg/L之间效果无较大变化,有机物含量对灭蚤影响较大,pH值的影响则较小.最后对O₃/H₂O₂预氧化与水处理混凝沉淀工艺的协同除蚤效能进行了考察.结果表明,O₃/H₂O₂预氧化与水处理混凝沉淀工艺的协同作用将会进一步提高除蚤的效果.     

Fe<Superscript>0</Superscript>-based system as innovative technology for degrading trichloromethane: Redox removal characteristics

BACKGROUND: The spent waste of aliphatic chlorinated solvents has caused severe deterioration of groundwater quality. Trichloromethane (TCM), which shows health and toxicological effects on human beings, was selected as a model compound to be dechlorinated through a redox system. METHODS: The Fe0-based system including Fe0/H2O, Fe0/UV, Fe0/H2O2, and Fe0/UV/H2O2 was explored to evaluate its performance in dechlorinating TCM. H2O2 was dosed at later reaction time points to initiate Fenton or photo-Fenton reactions. The first two systems demonstrate the reductive dechlorination of TCM by Fe0-released electrons, while the latter two show dechlorination of TCM by both electron reduction and hydroxyl radical oxidation. The system parameters of TCM remaining, Cl- buildup, Fe2+ accumulation, H2O2 residue, and ORP were measured to describe different redox characteristics of TCM dechlorination. The Cl- buildup was used as a way to describe the degree of TCM dechlorination in an open reaction system. RESULTS: Reductive dechlorination efficiencies of TCM were 5% and 6% for the systems of Fe0/H2O and Fe0/UV, respectively. In contrast, the Fe/H2O2 and Fe0/UV/H2O2 systems were capable of dechlorinating TCM reductively and oxidatively by 14% and 15%, respectively. The presence of UV light was found to retard the dissolution of Fe2+, but it enhanced the rate of chloride buildup, based on the comparison of Fe0/H2O and Fe0/UV systems. In addition, WV irradiation plays only a minor role in the Fe0/UV/H2O2 system, in view of TCM dechlorination. Application of small amount of H2O2 results in the increase of Fe2+ accumulation rate in the Fe0/H2O2 system. CONCLUSIONS: TCM was dechlorinated mostly through post Fenton oxidation; reductive reaction represents a less efficient way to dechlorinate TCM. The efficiencies of overall TCM dechlorination for the two systems of Fe0/H2O2 and Fe0/UV/ H2O2 are comparable to each other, and this implies that the presence of UV irradiation imposes no significant enhancement. RECOMMENDATIONS AND OUTLOOKS: It is highly recommended to initiate effective redox dechlorination of TCM with the system of Fe0/H2O2, where the H2O2 in excess is applied at a later reaction time point.     

硫化亚铁引发储油罐火灾危险性的研究

笔者通过模拟储油罐中硫化亚铁的生成方式 ,分析和研究了硫化氢气体与氢氧化铁、三氧化二铁和四氧化三铁反应 ,生成的硫化亚铁的氧化倾向性 ,并采用自然氧化绝热装置 ,测定了硫化亚铁的温度变化曲线。实验研究结果表明 ,不同方式生成的硫化亚铁 ,其氧化性不同 ,自燃性也不同 ,均有较显著差异。硫化亚铁的温度变化曲线表明 ,氧化反应随着时间增加 ,其他应进行得越来越快 ,将会造成热量的聚集 ,使油品温度快速上升 ,导致油品自燃和储罐发生着火爆炸。实验研究证明 ,硫化亚铁氧化反应放出热量是构成油罐着火危险性的最大因素。     

Hydrogen-rich synthesis gas production from waste wood via gasification and reforming technology for fuel cell application

The purpose of this study was to establish a fuel process for an advanced power generation system in which hydrogen-rich synthesis gas, as the fuel for the molten carbonate fuel cell (MCFC), can be extracted from biomass via gasification and reforming technologies. Experiments on waste wood gasification were performed using a bench-scale gasification system. The main factors influencing hydrogen generation in the noncatalytic process and in the catalytic process were investigated, and temperature was identified as the most important factor. At 950°C, without employing a catalyst, hydrogen-rich synthesis gas containing about 54 vol% hydrogen was extracted from feedstock with appropriately designed operation parameters for the steam/carbon ratio and the equivalence ratio. However, by employing a commercial steam reforming catalyst in the reforming process, similar results were obtained at 750°C.     

Influence of H<Subscript>2</Subscript> on the decomposition of halides by nonthermal plasma incorporated with in situ alkaline absorption

To control the emission of halides into the environment, an experiment on the nonthermal plasma decomposition of the halides CF₄, CHF₃, C₂HCl₃, and CHClF₂ was conducted in a wire-in-tube corona reactor. It was found that the decomposition of C₂HCl₃ and CHClF₂ was easy compared with the decomposition of CF₄ and CHF₃. With the addition of H₂ in N₂ gas, the decomposition ratio of CF₄, C₂HCl₃, and CHClF₂ increased. In contrast, the decomposition ratio of CHF₃ in a hydrogen-rich atmosphere was lower than that in an N₂ atmosphere. It was demonstrated that the yields of HF and/or HCl formed during halide decomposition clearly increased in the presence of H₂ in N₂ gas. Furthermore, in order to prevent the production of unwanted products from halide decomposition, a combination of plasma decomposition and in situ alkaline absorption was devised by coating a layer of Ca(OH)₂ onto the surface of the grounding electrode. It was demonstrated that the Ca(OH)₂ sorbent played an effective role as a scavenger, participating in halide decomposition by capturing reaction products such as HCl and HF, therefore resulting in increased halide decomposition.     

An influence of oxygen content in an oxidizing atmosphere on inhibitive action of fluorinated agents on a hydrogen flame

An experimental investigation of the influence of inhibitors of various chemical natures on flammability limits in mixtures H₂+oxidizer (O₂+N₂)–suppressant (C₂HF₅; CHF₃; C₄F₁₀; inhibitor AKM, which is a mixture of olefins) was carried out. Compositions of N₂ and O₂ with elevated (25 vol%) and reduced (15 vol%) oxygen concentrations and air were used as oxidizing atmospheres. Experiments were done at room temperature and atmospheric pressure. Flammability limits were determined in a closed vessel of volume of 4.2 dm³ (internal diameter 20 cm). Mixtures were prepared immediately in the preliminary evacuated reaction vessel by partial pressures. The mixtures were ignited by an electrical spark of energy near 1 J in the center of the reaction vessel. A flame propagation was detected by a pressure transducer. Twelve flammability curves were measured, which allowed to compare effectiveness of the inhibitors at various oxygen contents in the atmosphere. A qualitative analysis of the obtained results was done, which showed an important role of an inhibitor regeneration.     

Explosibility of hydrogen–graphite dust hybrid mixtures

To evaluate the hazard of combined hydrogen/dust explosions under severe accident conditions in International Thermonuclear Experimental Reactor (ITER), standard method of 20-L-sphere was used to measure the explosion indices of 4-μm fine graphite dust in lean hydrogen/air mixtures. The mixtures were ignited by a weak electric spark. The tested fuel concentrations were 8–18 vol% H₂ and 25–250 g/m³ dust. If the hydrogen content is higher than 10 vol%, the dust constituent can be induced to explode by the hydrogen explosion initiated by a weak electric spark. Depending on the fuel component concentrations, the explosions proceed in either one or two stages. In two-stage explosions occurring at low hydrogen and dust concentrations, the mixture ignition initiates first a fast hydrogen explosion followed by a slower phase of the dust explosion. With increasing dust concentration, the dust explodes faster and can overlap the hydrogen-explosion stage. At higher hydrogen concentrations, the hybrid mixtures explode in one stage, with hydrogen and dust reacting at the same time scale. Maximum overpressures of hybrid explosions are higher than those observed with hydrogen alone; maximum rates of pressure rise are lower in two-phase explosions and, generally, higher in one-stage explosions, than those characteristic of the corresponding H₂/air mixtures.