Removal of 17β-estradiol by powdered activated carbon—Microfiltraion hybrid process: The effect of PAC deposition on membrane surface

The removal of 17β-estradiol (E2) was investigated in a powdered activated carbon-submerged microfiltration (PAC-MF) hybrid system to better understand the effect on the system performance of PAC deposition on the membrane. A series of experiments were carried out under various operating conditions. Although the rejection or adsorption of E2 by MF membrane itself was almost negligible, the concentration of E2 in the permeate was always lower than it was in the reactor. This is because E2 was further removed as it passed through the PAC layer deposited on the membrane. As the E2 removal efficiency by the deposited PAC was lower than that by the PAC in the bulk phase, the overall E2 removal was largely dependent on the fraction of the deposited PAC on the membrane which were influenced by operating parameters such as permeate flux, hydraulic retention time (HRT) and mixing intensity in a PAC-MF system. The effect of these parameters on the overall E2 removal rate were also determined quantitatively using model equations developed in this study.     

Characteristics of major dioxin/furan congeners in melted slag of ash from municipal solid waste incinerators

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in slag of fly ash from three municipal solid waste (MSW) incinerators were analyzed to observe any changes in characteristics and distribution of their congeners by melting process. Actual concentration and Toxic Equivalent (TEQ) concentration profiles of 17 major congeners of PCDDs/PCDFs for gas, fly ash and melted slag were compared. The distributions of PCDDs/PCDFs in different streams macroscopically showed similarities with the generally known profiles for emission gas from a municipal waste incinerator. The total concentrations of PCDDs/PCDFs in off-gas and fly ash have been known to be a function of incineration conditions and of air pollution control device utilization; however, their normalized distributions were independent of such conditions. The concentrations of PCDDs/PCDFs in the melted slag of fly ash were not related to the concentrations of PCDDs/PCDFs congeners in fly ash but were rather a function of the melting furnace type and operation. The total amount of PCDDs/PCDFs in the melted slag of fly ash contained almost 150–27,000 times less dioxin than that in fly ash, however, the TEQ of dioxin in the slag was reduced by 435–43,500 times, which could enable them to be utilized as recycled construction materials. In normalized TEQ concentration profiles of 17 congeners of PCDDs/PCDFs, the ratio of PCDFs to PCDDs changed from 1.32 to 2.19 by melting, which showed relatively higher portion of furans left in melted slag than those in fly ash. By comparing reduction ratios of different congeners, PCDDs (dioxins) were relatively easier to destruct than PCDFs (furans) during melting process. The most difficult congener to destruct could be octa-chlorinated dibenzofuran (OCDF) among major congeners. For slag cooling methods, dioxin concentration in TEQ of slow cooled slag by air was four times higher than that of fast cooled slag by water. Thus cooling by water is more appropriate with the added beneficial effect of producing granules/particles, which can be utilized as roadbed materials.     

垃圾焚烧炉飞灰熔融特性及重金属的分布

对垃圾焚烧炉飞灰进行了差热分析及熔融实验,探讨了不同熔融温度对试样的灼烧减量及重金属分布特性的影响。结果表明,飞灰试样在1132℃时熔融,在1252℃～1290℃发生二次熔融。灼烧减量在1200℃达到最低值27.5％; Cr、Ni、Cu在熔融体中的固溶率随着沸点的升高而依次升高。重金属Pb、Cd、As、Hg挥发率均超过95％,挥发性依次为Pb>Cd>As>Hg;飞灰中Zn的氧化物熔融后转化为Zn2SiO4、ZnSiO3和ZnAl2O4等不易挥发的化合物,且Zn在1200℃时挥发率最低仅有66.7％。     

煤催化气化条件下不同煤种煤灰烧结行为研究

选取9类典型煤种,利用压差法测定烧结温度的实验装置,结合灰渣的XRD分析结果,考察了添加K基碱金属催化剂、不同煤种灰成分对烧结温度的影响。结果表明,碳酸钾催化剂的添加,明显降低高铁钙含量的WJT煤的灰熔点及烧结温度,碱金属K化合物极易同煤中Fe、Ca的矿物质反应生成低温共融物进而加剧煤灰的熔融结渣。不同煤种烧结温度的差异与煤灰中硅、铝、铁、钙含量密切相关。铝、硅含量高的煤灰烧结温度较高,而铁、钙含量高的煤灰烧结温度相对较低。碱金属K催化剂的添加加剧了煤灰的烧结结渣,而钙、铁的存在会加速硅铝酸盐间的反应生成低温共融物进而加速灰熔融。各煤种烧结温度的变化与其灰成分在CaO-SiO₂-Al₂O₃、FeO-SiO₂-Al₂O₃三元相图上的位置相吻合。     

不同的灰熔点调控方式对煤灰熔融特性的影响

对两种原始煤灰进行混合,并分别搭配不同的添加剂,得到3种元素组成相同的煤灰,灰熔点测试结果显示,三者的灰熔点存在较大差异。结合X射线衍射技术和SEM-EDX(扫描电子显微镜与能谱联用)分析了3种煤灰(>800 ℃)在高温时的矿物质转化过程。结果表明,不同的灰熔点调控手段对不同煤的影响是不同的。原因是高温时矿物质组成不仅与煤灰化学元素组成相关,更与元素在矿物质中的赋存状态有关。两者共同决定了煤灰的熔融特性。     

Chemical Speciation of Amphoteric Ions on Semi‐Dry Scrubber Residue and Bag‐House Ash from MSWI

Two series of size‐fractionated combusted residues, a bag‐house ash and a scrubber residue, from a municipal solid waste incinerator (MSWI) were prepared and extracted by means of sequential chemical extraction (SCE) procedures proposed by Tessier. Concentrations of water‐soluble phase, exchangeable phase, carbonated phase, Fe/Mn oxide phase, organic matter phase, and residual phase bound amphoteric metals (Pb and Zn) were obtained, and have been compared with those of single batch extraction of toxic characteristic leaching procedure (TCLP). In each size fraction of baghouse ash or scrubber residue, lead or zinc shows a common phenomena that the TCLP value is always lower than the content of the water‐soluble fraction. For lead, baghouse ash has a significant size‐dependent distribution on the water‐soluble phase to perform a size‐dependent test of lead in the TCLP test. The zinc TCLP data having less size dependence might be due to that neither the baghouse ash nor the scrubber residue has a size‐dependent distribution on the water‐soluble zinc phase.     

Evaluation of a mixed chelator as heavy metal stabilizer for municipal solid‐waste incineration fly ash: Behaviors and mechanisms

This paper compares the stabilization performances of three dithiocarbamate and three phosphate chemical stabilizing agents, selects the best agents from each group, combines them as a mixed heavy metal stabilizer for municipal solid‐waste incineration (MSWI) fly ash, and investigates the effectiveness of the mixed chelator in stabilizing heavy metals in MSWI fly ash from southwest China. The mechanism of stabilization is also analyzed. Results indicate that piperazine dithiocarbamate can stabilize Cd, Cu, and Ni effectively, while sodium dihydrogen phosphate can stabilize Pb better. With the addition of the mixed chelator (2% sodium dihydrogen phosphate and 1% piperazine dithiocarbamate), all the targeted heavy metal concentrations in the leachate were below the standards for pollution control on municipal solid waste landfill sites in China. The stabilizing agents combined with the heavy metals in fly ash could not generate insoluble crystals; however, the heavy metals could combine with the agents' effective groups, generating flocs in the pores or on the surfaces of the fly ash and offering significant densification. The mixed chelator could transfer heavy metals from unstable fractions to stable fractions, so the leaching of heavy metals from the fly ash was greatly decreased.     

Elution behaviour and environmental impact of heavy metals and rare-earth elements from volcanic ashes of Mt. Oyama,Miyake Island

To obtain information on the environmental impact of materials eluted from volcanic ashes of Mt. Oyama, Miyake Island, which erupted in July 2000, the dissolution behaviours of heavy metals and rare-earth elements from the volcanic ashes were examined. The most important characteristic of the Mt. Oyama eruption is that sulphur dioxide (SO₂) gas has been continuously released, and all persons living on Miyake Island have been required to evacuate. To estimate in terms of the volcanic eruption using SO₂ gas, the ash nature in Mt. Usu, Hokkaido, was also examined and compared with that in Mt. Oyama. When rain water mixed the ashes, the water from the ashes of Mt. Oyama became acidic because of the sulphuric acid. Therefore, SO₂ gas in Mt. Oyama can accelerate the dissolution of protons and heavy metals in the ashes, whereas the rain water in Mt. Usu was not acidic and the dissolution of the heavy metals was not so evident compared with that in the case of Mt. Oyama. With this sulphuric acid, heavy metals such as As, Cd, Pb and Hg in the ashes in Mt. Oyama easily dissolved owing to the low pH. The ashes in Mt. Oyama had been released for eight years and the amount of fallen ashes was estimated to be 33 billion tons. The weights of the harmful heavy metals in the volcanic ashes, such as As, Cd, Pb and Hg, were estimated to be 3.8?×?10², 1.3?×?10³, 1.1?×?10³ and 29?kg, respectively, and these heavy metals were dissolved and diluted in seawater. Therefore, the concentration and species (chemical form) of these metals should be carefully monitored in the future. Moreover, SO₂ gas, which has a direct effect on human health and has been monitored continuously, causes other effects, such as facilitation of metal ion elution and rock aeration.     

流动注射-电化学发光法测定煤灰中痕量钼(Ⅵ)

基于钼(Ⅵ)在-0.60V(vs.Ag/AgCl)电位下在线还原为钼(Ⅲ),且在碱性条件下钼(Ⅲ)与鲁米诺发生化学发光反应,据此提出了流动注射-电化学发光法测定煤灰中痕量钼(Ⅵ)的方法。钼(Ⅵ)的质量浓度与化学发光强度的增加值在5.0×10-7～5.0×10-4g.L-1范围内呈线性关系,检出限(3s/k)为5×10-8g.L-1。对1.0×10-6g.L-1钼(Ⅵ)标准溶液进行11次测定,测定值的相对标准偏差为2.6%。方法可用于煤灰中痕量钼(Ⅵ)的测定,测定值与国标方法测定值相符。     

磁性壳聚糖复合微球的制备及其Cu~(2+)吸附性能

以球磨后的粉煤灰磁珠(MS)颗粒为磁核,通过溶胶凝胶法和反相微乳液法依次包覆SiO_2和壳聚糖(CS),制备了MS@SiO_2@CS磁性微球。利用扫描电镜及能量色散谱仪、热重分析仪、红外光谱仪、X射线衍射仪、振动样品磁强计对所得样品的结构和磁性进行了系统表征。结果表明,磁珠颗粒表面实现了逐层包覆,较均匀的分散于壳聚糖基体中,MS@SiO_2@CS微球的比饱和磁化强度可达7.04 emu·g~(-1)。Cu~(2+)离子吸附实验表明,所得磁性壳聚糖微球对Cu~(2+)具有良好的吸附能力,最大吸附量可达11.08 mg·g~(-1);而且可通过磁选法高效固液分离。吸附动力学研究表明,MS@SiO_2@CS微球对Cu~(2+)离子的吸附符合准二级动力学模型,以化学吸附为主。