粉煤灰改性吸附材料的研究

本文阐述了粉煤灰的主要化学成份、结构、物理性质，指出粉煤灰改性的物质基础，并结合笔者的研究情况，分析了改性粉煤灰处理废水和废气的机理，介绍了其在处理废水和废气的研究与应用情况，提出了应用改性粉煤灰处理废水和废气中存在的问题及今后研究的重点。     

Experimental study on MSW gasification and melting technology

In order to develop municipal solid waste (MSW) gasification and melting technology, two preliminary experiments and a principle integrated experiment were fulfilled respectively. The gasification characteristics of MSW are studied at 500-750℃ when equivalence ratio (ER) was 0.2-0.5 using a fluidized-bed gasifier. When temperature was 550-700℃ and ER was 0.2-0.4, low heat value (LHV) of syngas reaches 4000-12000 kJ/Nm3. The melting characteristics of fly ash were investigated at 1100-1460℃ using a fixed-bed furnace. It was proved that over 99.9% of dioxins could be decomposed and most heavy-metals could be solidified when temperature was 1100-1300℃. The principle integrated experiment was carried out in a fluidized-bed gasification and swirl-melting system. MSW was gasified efficiently at 550-650℃, swirl-melting furnace maintains at 1200-1300℃ stably and over 95% of fly ash could be caught by the swirl-melting furnace. The results provided much practical experience and basic data to develop MSW gasification and melting technology.     

燃煤电厂灰场环评技术评估中存在的问题与建议

在比较我国一般工业固体废物贮存处置场、生活垃圾填埋、危险废物贮存和危险废物填埋污染控制标准的基础上,结合欧共体和德国对固体废物的分类和填埋要求、德国灰场的防渗实例和我国燃煤电厂实际运行灰场对地下水的环境影响,分析了《一般工业固体废物贮存、处置场污染控制标准》(GB 18599-2001)存在的问题,并建议在干灰场环评技术评估中,燃煤电厂的灰渣和脱硫石膏除非按GB 5086规定方法进行浸出试验获得的浸出液中第一类污染物超过GB 8978最高允许排放浓度外,均应按第I类一般工业固体废物处理;同时对燃煤电厂的干灰场场址选择等方面的环保要求提出了建议.     

响应面优化制备粉煤灰基PASC混凝剂性能与表征

研究了以粉煤灰为原料制备聚硅氯化铝（PASC）混凝剂的影响因素、产品性能和微观结构.选取A（碱化度）、B（n（Si）：n（Al））、C（聚合温度）和D（反应时间）对混凝高岭土模拟废水后透光率进行四因素三水平响应面实验.最终优化方案为：A为1.18,B为5.64,C为47.40℃,D为2.48h,透光率预测值达86.58%,验证试验均值相对误差仅为0.18%,模型相关系数为0.9984,表明RSM优化模型可靠.混凝剂性能随投加量增加而不断增加,最终趋于稳定;随废水pH值增大呈现先增大后减小的趋势.XRD分析PASC主要物相为氯化钠,非晶态衍射峰形成预示着浸出液和聚硅酸加碱聚合形成了新的无定形物;FT-IR测试表明聚硅酸与Al³⁺及其水解产物间络合形成了金属-OH等非离子键;SEM显示产品为高聚集度和枝化度的空间网状结构.     

谷壳灰对稻田土壤镉、砷生物有效性及糙米镉、砷累积的影响

为研究富硅材料谷壳灰（HA）对稻田土壤Cd、As生物有效性及糙米中Cd、As累积的影响,以稻壳为原料制备中性HA（总硅量6.26×10⁵ mg·kg^-1）,开展水稻盆栽试验.HA按质量比设置4个添加水平（0、0.5%、1%、2%）,种植3种水稻（黄华占、湘晚籼13、隆优4945）.研究结果表明：①在土壤Cd总量为2.30 mg·kg^-1、As总量为90.45 mg·kg^-1的复合污染土壤中,HA施用后,与对照相比,土壤Cd的TCLP提取态、CaCl₂提取态及酸可提取态含量呈现不同程度的降低,分别降低了7.8%~18.7%、7.4%~18.7%、0.9%~16.7%;土壤As的交换态和TCLP提取态含量也有降低,分别降低了6.1%~47.1%、4.3%~26.7%.②HA施用可促进土壤中酸可提取态Cd向难溶态Cd的转变,水稻湘晚籼13、隆优4945根际土壤残渣态Cd含量分别增大9.8%~23.5%、5.9%~28.1%;土壤中As主要以残渣态存在,HA的施用对土壤专性吸附As含量有增大效应.③HA施用能够降低糙米中Cd和无机As含量,施用0.5%~2% HA能使水稻隆优4945和湘晚籼13糙米Cd含量降低到0.2 mg·kg^-1以下,施用2% HA能使黄华占糙米无机As含量降低到0.2 mg·kg^-1以下.施用HA能够有效降低土壤Cd、As生物有效性和糙米Cd、As含量,同时增大土壤有效Si含量,有利于提高土壤质量.     

水泥、粉煤灰及DTCR固化/稳定化重金属污染底泥

采用水泥、粉煤灰及有机硫稳定剂DTCR固化/稳定化处理重金属污染的底泥,考察固化体的抗压强度及重金属浸出毒性,确定了底泥固化/稳定化的最佳工艺条件。结果表明:仅用水泥固化/稳定化重金属污染底泥,固化体抗压强度随水泥用量的增加而上升,重金属浸出浓度则下降,当水泥∶干底泥质量比为0.6∶1.0时,固化体7 d抗压强度能达到0.99 MPa的标准值;进一步研究发现,水泥∶粉煤灰∶干底泥质量比为0.54∶0.06∶1.0时,重金属浸出浓度有所上升,但7 d及28 d抗压强度仍能分别达到1.2 MPa和2.8 MPa;加入DTCR后,当水泥∶粉煤灰∶DTCR∶干底泥质量比为0.54∶0.06∶0.012∶1.0时,固化体7 d及28 d抗压强度分别为1.1 MPa和2.1 MPa,醋酸缓冲溶液法浸出的Cd、Pb、Zn和Cu浓度分别为0.102、0.189、0.180和0.032 mg/L。     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Effects of selected metal oxides on the dechlorination and destruction of PCDD and PCDF

OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T₄CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)₂ exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.     

粉煤灰深度处理低浓度的磷

为了探讨低浓度磷吸附的方法,比较了粉煤灰、煤质活性炭和粉煤灰碎砖块颗粒这3种价廉易得的吸附材料的除磷效果。经对比确定以粉煤灰为吸附剂,研究了反应时间、粉煤灰投加量以及溶液p H对深度除磷效果的影响。同时为了解粉煤灰高效除磷原理,利用SEM和XRD对其表面形状、所含元素及其内部结构进行了表征。结果表明,粉煤灰比煤质活性碳和粉煤灰砖砖块颗粒的除磷效果更好,去除率高达98.9%;SEM和XRD表征结果显示,由于粉煤灰表面积较大、表面能高、含有Si—O—Si和Si—O—Al—O偶极键及铝、铁和钙的氧化物,使得粉煤灰对低浓度的磷有着高效的去除率;吸附磷后的粉煤灰表面形成了一层絮状物,经EDS分析显示其组成以钙磷沉淀为主;1 g粉煤灰对1 mg/L的磷酸盐溶液在p H=10、反应时间60 min时表现出最佳吸附性能。     

Chemical Behaviour of Calcium in Stabilized Oil Ash Reef Blocks After Five Years in the Ocean

Reef blocks made from stabilized oil ash were taken from the sea after five years in the ocean to examine the chemical behaviour of calcium. Experiments included (1) determination of the calcium leaching rate and a comparison with the rate for unexposed blocks to test the validity of a diffusion model for predicting long term (5 years) leaching rates, (2) determination of the effect of biological cover (shell) on the leaching rate, (3) determination of the leaching rate of the core of exposed reef blocks, (4) determination of the calcium content in 'ring areas' - regions of discoloration observed in sectioned exposed reef blocks, and (5) determination of the leachable fraction of the total calcium in exposed reef blocks. Results showed the presence of a pronounced calcium discontinuity zone located 3-7 cm from the outside surface of the reef blocks. Cumulated calcium release rates ranged from 2.81-3.14 μmol cm^-2 day^-1 for original unexposed reef blocks and the core of exposed (in the ocean for five years) blocks, respectively, to 0.47-0.50 μmol cm^-2 day^-1 for outside (facing sea water) surfaces of exposed reef blocks. Tank leaching studies also showed that the presence or absence of hard biological cover (shells) had little or no effect on the calcium release rate. the diffusion model normally used in modelling the chemical behaviour of calcium cannot be used to predict the long term (five years) leaching of calcium. the core of the exposed blocks released calcium at a rate similar to new, unexposed reef block material. Overall, it appears that the calcium discontinuity zone is probably responsible for restricting the release of calcium and hence the failure of the diffusion model.