电化学法脱除烟气二氧化硫制取硫酸-Br-/Br2电解体系

本文研究了Br-/Br2体系的电化学方法脱除烟道气中二氧化硫的各个影响因素:温度对电解体系的性能影响;温度、酸度以及吸收方式对脱硫效率的影响.     

电化学法脱除烟气二氧化硫制取硫酸—Br^—／Br2电解体系

本文研究了Ｂｒ＾－／Ｂｒ２体系的电化学方法脱除烟道气中二氧化硫的各个影响因素：温度对电解体系的性能影响;温度、酸度以及吸收方式对脱硫效率的影响。     

湿法脱硫除尘产物中CaSO3分解的研究

实际测量表明,由于烟气脱硫除尘一体化技术中缺少氧化设备,其产物中含有大量易分解的CaSO3.CaSO3分解逸出的SO2会对环境产生不利影响,而影响CaSO3分解释放出SO2的因素有很多.对脱硫灰渣所处环境体系的pH、含氧浓度、脱硫灰渣自身的CaSO3含量和温度4个方面进行了研究.结果表明,灰渣体系的pH、灰渣自身的性质是影响灰渣SO2逸出的主要因素;反应气氛和温度也在不同程度上影响灰渣CaSO3分解,但较前两个因素的影响要逊色许多.     

综合利用镁合金废料制氢及氢氧化镁

AZ31B镁合金废片-盐水体系能同时产生氢气和Mg(OH)2,研究了催化剂,Cl-浓度和反应温度对该体系产氢速率的影响,并分析了产物Mg(OH)2的化学成分和形态结构。实验结果表明,与Cu Cl2相比,铜线作为催化剂不仅产氢的速率高,且不会污染形成的Mg(OH)2。Cl-浓度和反应温度影响对体系产氢速率有较大影响,当温度为60℃,盐水浓度为4 mol/L时产氢速率达到最大值为62 m L/(min·g)。采用扫描电镜、X射线能谱仪表征分析中间产物,探讨Cl-点蚀反应的机理,对产物氢氧化镁粉末进行表征和物相分析的结果表明,产物为高纯度Mg(OH)2纳米材料,其晶体结构和分散性随温度的增加变好,80℃下获得规整的六方晶体。     

纳米铁-微生物耦合体系去除硝酸盐的影响因素研究

采用液相还原法制备出纳米铁粒子,并与自养反硝化细菌耦合,以解决单独使用生物反硝化和纳米铁还原法的不足。本实验在纳米铁-微生物耦合体系可以有效还原硝酸盐的基础上,研究了pH、温度和DO等环境因素对该耦合体系脱氮速率和产物的影响,以期通过优化参数达到最好的脱氮效果。结果表明,该体系在中性条件下能够快速将硝酸盐还原,随pH升高,氨氮比例无显著变化,均在40%左右,但还原速率有所下降;随温度的升高,氨氮比例有所上升,而反应速率明显升高,但该体系在5℃时仍能将硝酸盐完全去除;耦合体系中的DO过高或过低都会导致产物中氨氮比例的增加,0.4 mg/L左右为较适宜DO水平,但对硝酸盐还原速率的影响不大,当DO为0.8 mg/L时,硝酸盐仍可以在8 d内完全去除。因此,该耦合脱氮体系对pH、温度和DO的适应能力较强,有利于实际地下水的原位修复。     

聚环氧琥珀酸合成及中试研究

聚环氧琥珀酸（PESA）是一种国际上公认的绿色阻垢剂。实验分析PESA合成过程中的主要工艺参数,如,反应体系pH、温度和时间,对产品阻垢性能的影响,借助中试实验平台,对正交实验结果进行验证和修正。实验结果表明,环氧化过程pH对中间体ESA产率影响显著;聚合反应过程中,体系的温度和反应时间存在关联性。根据自主开发的双反应釜及其反应控制技术,实现了中试规模的PESA化学合成过程温度等反应条件的精确控制,反应副产物减少,中间体ESA纯度高,可达90%以上,系统合成的最终产物PESA 20 mg/L时阻垢性能可达到90%以上,产品具备了较高的阻垢性能水平。     

NaCl在Zn(Ⅱ)-NaOH-H_2O体系中溶解度的测定及去除

等温溶解平衡法测定了283.2～323.2 K温度范围内NaCl在Zn(Ⅱ)-NaOH-H2O体系(cZn(Ⅱ)=0.6 mol/L、cNaOH=5.00mol/L)及NaOH-H2O体系(cNaOH=5.00 mol/L)中的溶解度。与NaOH-H2O、纯水体系相比,相同温度下NaCl在Zn(Ⅱ)-NaOH-H2O体系中溶解度最小。运用正交实验法对Zn(Ⅱ)-NaOH-H2O体系中NaCl的溶解度进行因素分析。结果表明,较高的cNaOH和cZn(Ⅱ)是造成NaCl溶解度急剧降低的主要原因,提高温度虽然对NaCl的溶解有促进作用但影响较小。最后,通过加热浓缩方式提高溶液NaOH和Zn的浓度,促使NaCl因溶解度骤降而结晶析出,首次实现了碱锌溶液中高浓度Cl-的大量去除。实验结果具有重要的工程应用价值。     

污泥焚烧中Cd形态转化的热力学平衡模拟

采用热力学平衡分析方法,结合典型污泥成分和焚烧条件预测了污泥焚烧过程中重金属Cd的转化和迁移规律。模拟计算中考虑了主量矿物质与Cl、S对Cd的形态转化的影响。研究结果表明,污泥焚烧过程中,在低温的条件下Cd主要以固体碳酸盐形式存在,随着温度升高,碳酸盐分解为固态CdO,随后有气态Cd(OH)2、Cd和CdO生成,并且在较高温度主要以气态Cd存在。焚烧体系中,矿物质SiO2对Cd的形态转化影响大于其他矿物质,SiO2能与Cd结合生成稳定的CdSiO3,从而可有效抑制含Cd气态污染物的排放。焚烧体系中Cl较易与Cd结合形成CdCl2而导致Cd的挥发,Cl含量的增加促进了Cd在焚烧体系中的挥发。在低温阶段,Cd易与S结合形成固态硫酸盐,抑制了金属的挥发;在高温阶段,金属的形态转化基本不受S的影响,但是可以影响气态金属Cd的生成温度。根据污泥在不同焚烧温度、Cl含量、S含量条件下Cd的不同产物形态,可以对Cd的污染进行有效控制。     

K-Ca-Mg-Cl-H_2O体系中硫酸钙结晶介稳区的研究

对K-Ca-Mg-Cl-H2O体系中硫酸钙结晶介稳区进行了研究。以一定浓度氯化钙溶液与硫酸镁溶液反应结晶的方式,采用激光散射法测定了不同浓度复合盐溶液和温度下硫酸钙过饱和度与结晶之间的关系,并测定了与之平衡的溶解度,从而确定该体系中硫酸钙结晶介稳区宽度,探讨了影响结晶介稳区的因素,以及硫酸钙结晶和结晶相与复合盐溶液浓度、温度、结晶介稳区之间的关系。     

磁性交联壳聚糖对铬(Ⅵ)吸附性能的研究

用壳聚糖包埋磁流体 ,并用戊二醛交联制成磁性交联壳聚糖 ,考察了其对铬 ( )离子的吸附性能 ;探讨了酸度、体系温度、时间、初始离子浓度对磁性壳聚糖吸附性能的影响。实验表明 ,在 p H 2 .0 0、温度 2 5℃、吸附 2 4 h的条件下 ,吸附率可达 99%以上 ,并具有良好的重复使用性     

Bromine in waste incineration partitioning and influence on metal volatilisation

INTENTION, GOAL, SCOPE, BACKGROUND: The halogen bromine is far less abundant than chlorine, but it can be found at high concentrations in special materials like flame retarded plastics. The fate and effects of Br in waste incineration are not well understood. It may have similar implications like Cl for the volatilisation of heavy metals and the formation of low volatile organic compounds. Due to its lower oxidation potential, there is a risk of formation of elementary Br2 in the offgas. OBJECTIVE: Co-combustion tests of different types of Br containing plastic waste materials (up to 22%) and MSW in the TAMARA pilot plant for waste incineration were conducted to investigate the Br partitioning and the influence of Br on metal volatilisation. METHODS: The Br inventory of the fuel mix was elevated to approx. 1 wt-%. All input and output mass flows of the furnace have been sampled and the partitioning of Cl, Br, S, and a number of heavy metals, has been calculated on the basis of closed mass balances. RESULTS AND DISCUSSION: Organically-bound Br was typically released to more than 90% into the raw gas. Elementary Br2 was detected at high Br levels. Its presence was always analysed when all SO2 in the raw gas was oxidised to SO3. Br enhances the volatilisation of metals like K, Zn, Cd, Sn, Sb, and Pb out of the fuel bed principally in the same way as Cl. The tests gave strong indication that the promoting influence of the halogens on metal volatilisation is more pronounced than that of the fuel bed temperature. The volatilised metals are condensated on the fly ashes and are discharged along with the filter ashes. CONCLUSIONS: As long as a surplus of SO2 is present in the raw gas no Br2 is formed. Although the halogen induced transfer out of the fuel bed causes high concentrations of volatile metals in the filter ashes, a recovery is not economically feasible for the time being. The volatilisation gives no rise to metal emission problems as long as efficient dedusting is achieved. RECOMMENDATION AND OUTLOOK: If there is a risk of Br2 formation, in wet scrubbing a reducing agent has to be added to the neutral scrubber for efficient abatement. Filter ashes should be disposed of in a way that enables access for recovery in the future. The exact volatilisation characteristics of the various metals have to be studied in future using specifically tailored experiments.     

Study of the transference rules for bromine in waste printed circuit boards during microwave-induced pyrolysis

The production of waste printed circuit boards (WPCBs) has drawn increasing global concern, especially because the high bromine (Br) content (5-15%) places obstacles in the way of simple disposal techniques. Microwave-induced pyrolysis of WPCBs provides a promising way to dispose of these hazardous and resource-filled wastes. The transference rules for Br during microwave-induced pyrolysis have been investigated experimentally. It was found that the microwave energy could be used more efficiently to accelerate the heating rate and improve the final pyrolysis temperature by adding some activated carbon (AC) as microwave absorbents. The high temperature and rapid pyrolysis process promoted the yields of gaseous products and the decomposition of brominated compounds into hydrogen bromide and then benefited the capture of Br and the debromination of byproducts. The application of a calcium carbonate (CaCO3) layer overhead led to over 95% debromination of the liquid products and over 50% capture of the total Br. It can be concluded that the presented method is suitable for the control of Br transference in the recycling of WPCBs. This method can also be extended to the disposal of the electronic scraps.     

Elemental analysis of airborne particulates in Chile

Aerosol samples collected in three characteristic Chilean cities-including urban and remote zones-have been analyzed by the PIXE spectroscopic technique. Elemental composition, total suspended particulate matter (TSP), particle size distribution, and the peculiar geographic and meteorological parameters have been included in this study. Santiago--the polluted capital of Chile--registered high TSP indexes and important amounts of hazardous elements in air such as S, V, Cr, Zn, Br and Pb. The atmosphere of Antofagasta city showed marine and mineral activity influence. Results from Chillán city are similar to those from rural environments. Protons and deuterons-provided by the isochronous cyclotron of the University of Chile-were used to excite X-ray radiation from the sample. Signals were processed by an energy dispersive detection system, including a cryogenic Si(Li) detector, electronic for pulse amplification and an analog to digital converter. The absolute elemental concentration of the particulate matter in air was obtained through a fundamental parameter equation. Samples consist of particulate material collected directly on Nuclepore filters or deposited over Kapton foils. Typical elements analyzed were Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, As, Br and Pb.     

Atmospheric lead and bromine in Germany: post-abatement levels,variabilities and trends

INTENTION, GOAL, SCOPE, BACKGROUND: Abatement measures since the 1970s have depleted lead and bromine levels in the atmosphere over large parts of Europe. Our knowledge of the atmospheric cycling of these elements while a several decade-long period of intensive mobilization reaches its end is incomplete. OBJECTIVE: We have characterized the trends in the atmospheric levels of Pb and Br and present-day temporal and spatial variabilities. METHODS: This was achieved by short-term (weeks) and long-term (years) measurements of particulate Pb and Br at various sites in Germany. Samples of atmospheric particulate matter were collected on filter membranes and analyzed by x-ray fluorescence. RESULTS AND DISCUSSION: Average Pb levels at rural and urban inland sites did not exceed concentrations in background aerosols, sampled at a Baltic Sea coastal site, by more than a factor of 3. Due to sea salt, bromide inland particulate Br levels are below those at a coastal site. There, non-sea salt Br, however, is significant as well. Urban Pb and Br levels are not necessarily higher than rural levels. The concentration levels have decreased in such a way that the previously common source, local vehicular traffic emissions, is no longer predominant. Regional rather than local sources have been increasingly determining the concentrations since the 1990s. This is more pronounced for Br than for Pb. We found indications for coal burning and long-range transport as significant Pb sources. For particulate Pb species, a range of ages (elapsed time since Pb emission) has been found. This range shows two maxima corresponding to characteristic times of 72 and 24 h. CONCLUSIONS: The (mean) atmospheric residence time of particulate Pb is longer than the residence time of Br, in particular in the wintertime. The chemical species contributing to atmospheric Pb should be addressed in future studies. RECOMMENDATION AND OUTLOOK: Clearly, despite effective abatement measures, atmospheric Pb will continue to be dominated by anthropogenic mobilization. The influence from long-range transport can be expected to decrease with the effectiveness of abatement programmes in neighbouring countries of the region.     

Absorption of NO and NO2 in caprolactam tetrabutyl ammonium halide ionic liquids

To explore environmentally benign solvents for the absorption of NO and NO2, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO2 was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO2 in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO2 decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO2 was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO2.     

Spatial and temporal variations in the trace elemental data over the northeastern United States

Time series of trace elemental concentrations (14 species) of atmospheric fine particles measured in the northeastern United States between 1988 and 1998 are analyzed for spatial and temporal variations. The influence of synoptic-scale systems to the transport and accumulation of pollutants can be investigated successfully if the short-term fluctuations (i.e. weather-induced variations) embedded in the time series of pollutant concentrations are separated from the original time series. The spatial short-term correlation coefficients for Al, Br, Fe, Se, and Zn permit good predictions of pollutant concentrations up to distances of about 350 km from a given monitor. The species correlation matrices for individual sites reveal that As, Br, Se, and Zn are highly correlated in New York State, while Fe, Mn, and V show also strong correlations, suggesting the commonality of source regions for these industrial and urban pollutants impacting New York.     

活性炭纤维吸附含溴甲烷气体的性能

采用动态吸附法在25℃下,测定了3种活性炭纤维(ACF-1、ACF-2和ACF-3)对含溴甲烷气体的吸附性能和回收效果,并对活性炭纤维的孔结构进行表征.探讨了孔结构、溴甲烷浓度、气体流量、循环使用次数等因素对活性炭纤维吸附溴甲烷性能的影响.结果表明,活性炭纤维比表面积大小及0.4～0.8 nm左右的微孔数量决定了其对溴甲烷吸附性能的优劣;气体中溴甲烷的浓度的提高使活性炭纤维对溴甲烷的穿透和饱和吸附量增加,而气体流量的增加则使活性炭纤维对溴甲烷的穿透和饱和吸附量降低,但两者均使穿透和饱和吸附时间缩短;活性炭纤维多次循环使用后,对溴甲烷的吸附容量明显地降低,循环12次后达到稳定吸附,其稳定吸附值为133.5 mg/g.     

Methyl bromide as a building disinfectant: interaction with indoor materials and resulting byproduct formation

Several buildings were contaminated with Bacillus anthracis in the fall of 2001. These events required consideration of how to disinfect large indoor spaces for continued worker occupation. The interactions of gaseous disinfectants with indoor materials may inhibit the disinfection process, cause persistence of the disinfectant, and lead to possible byproduct formation and persistence. Methyl bromide (CH3Br) is a candidate for disinfection/deactivation of biological agents in buildings. In this study, 24 indoor materials were exposed to CH3Br for 16 hr at concentrations ranging from 100 to 2500 ppm in 48-L electropolished stainless steel chambers. CH3Br concentrations were measured during and after disinfection. Its interactions with materials were observed to be small, with nearly complete and rapid desorption. Between 3% and 8% of CH3Br adsorbed to four materials (office partition, ceiling tile, particle-board, and gypsum wallboard with satin paint), and the degree of adsorption decreased with increasing relative humidity. The percentage of adsorption to all other materials was <2%. This result suggests that when designing disinfection events with CH3Br, loss to indoor materials can be neglected in terms of disinfectant dose calculations. Possible reaction products were identified and/or quantified before and after exposure to CH3Br. Several monomethylated and dimethylated aliphatic compounds were observed in chamber air at low concentrations after the exposures of six materials to CH3Br. Concentration increases also occurred for chemicals that were observed to naturally off-gas from materials before exposure to CH3Br, suggesting that CH3Br may play a role in enhancing the natural off-gassing of chemicals, for example, by competitive displacement of compounds that already existed in the materials. The results described in this paper should facilitate the design of building disinfection systems involving CH3Br.     

Concentrations of chlorine, bromine and iodine in Japanese rivers

Concentrations of halogens (Cl, Br and I) in 30 Japanese rivers were measured by ion chromatography and inductively coupled plasma mass spectrometry to understand their behavior in the terrestrial environment. Concentrations of Cl, Br and I in each river, obtained at 10 sampling points from the upper stream to the river mouth, tended to increase near the river mouth. The ranges of geometric means of Cl, Br and I in each river were 1.0–19.4 mg l⁻¹, 2.5–67.9 μg l⁻¹, and 0.18–8.34 μg l⁻¹, respectively. To compare halogen behavior, the concentration ratios, Br/Cl and I/Cl, were calculated. The Br/Cl range was (2.3–7.8) × 10⁻³ (geometric mean: 3.74 × 10⁻³), and it was nearly constant except for the Yoneshiro river. It was estimated that 60–80% of total Br in the middle to lower parts of this river was the excess Br. The Br chemical form in all the rivers is generally considered to be Br⁻. The I/Cl ratios had different trends in rivers flowing into the Japan Sea and Pacific Ocean, possibly due to the different geological features in the river catchments.     

Direct spectral analysis and determination of high content of carcinogenic bromine in bread using UV pulsed laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) was applied for the detection of carcinogenic elements like bromine in four representative brands of loaf bread samples and the measured bromine concentrations were 352, 157, 451, and 311 ppm, using Br I (827.2 nm) atomic transition line as the finger print atomic transition. Our LIBS system is equipped with a pulsed laser of wavelength 266 nm with energy 25 mJ pulse^?1, 8 ns pulse duration, 20 Hz repetition rate, and a gated ICCD camera. The LIBS system was calibrated with the standards of known concentrations in the sample (bread) matrix and such plot is linear in 20–500 ppm range. The capability of our system in terms of limit of detection and relative accuracy with respect to the standard inductively coupled plasma mass spectrometry (ICPMS) technique was evaluated and these values were 5.09 ppm and 0.01–0.05, respectively, which ensures the applicability of our system for Br trace level detection, and LIBS results are in excellent agreement with that of ICPMS results.