粉煤灰免烧陶粒制备及其重金属废水净化性能

摘要重金属废水对环境的污染已经引起科研人员的广泛关注。以粉煤灰和水泥为原料、添加活性成分FeS,制备一种免烧陶粒用于含重金属Cu2＋、Zn2＋、Pb2＋的废水处理。探讨了物料配比及蒸养时间对陶粒筒压强度及其比表面积的影响;研究了固液比、接触时间、pH、温度及初始溶液浓度等因素对Cu2＋、Zn2＋、Pb2＋离子净化效果的影响规律,并对实验结果进行了等温线拟合。XRD分析显示,免烧陶粒中存在Ca（OH）2、C—D—H、FeS等矿物相,对重金属离子具有非常好的固定化作用。该免烧陶粒对重金属离子具有很好的去除效果,具备较好的应用前景。     

Total arsenic and selenium analysis in Marcellus shale, high-salinity water, and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

垃圾焚烧飞灰熔融过程中重金属的固化机理以及熔渣浸出特性的研究

研究了中国垃圾焚烧飞灰中主要重金属在熔融过程的固定化机理,定义了固定率这个参数来表征此过程。采用了中国和美国的危险废物浸出毒性鉴别方法来判别飞灰及其熔融渣的浸出毒性。研究结果表明,固定率能够较好地表征重金属在熔融过程不同温度阶段的固定情况;按照中国和美国废物浸出毒性鉴别标准,飞灰熔融处理后的熔渣不属于危险废物,具备资源化利用的条件。     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

粉煤灰和电石渣对聚丙烯塑举裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响，讨论了加入量对裂解速度和裂解产物的影响。结果表明：粉煤灰和电石渣都使裂解产物中的轻质部分（汽油和裂解气）增加、重油降低；粉煤灰比电石渣更能加快反应的进行，而且加入量越多，反应越快，需时越短；粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果。     

改性粉煤灰及其处理废水的机理

应用正交设计的基本理论,研究了PDMDAAC(聚二甲基二烯丙基氯化铵)改性粉煤灰的最佳条件,并将改性粉煤灰用于模拟印染废水的处理,探索了改性粉煤灰处理废水的机理。结果表明,在原PDMDAAC的pH下．控制PDMDAAC的浓度为40g／L,恒温30℃．反应1h为最佳改性工艺,改性粉煤灰处理废水的机理以吸附电中和为主。     

Comparison of CaO’s effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023–1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)₂ and CaCO₃ in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO₄. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO₄ formation and lowered Cr leaching concentration.     

A comparative study on the recovery of polycyclic aromatic hydrocarbons from fly ash and lignite coal

The recovery of polycyclic aromatic hydrocarbons (PAHs) from lignite coal burnt in Greek power stations and the fly ash produced is examined comparatively using Soxhlet, ultrasonic and accelerated solvent extraction procedures with various organic solvents. Soxhlet using toluene/methanol mixture and accelerated solvent extraction/toluene were found to be the most efficient methods for fly ash PAHs, yielding average recoveries of about 80%. The accelerated solvent extraction/toluene procedure was superior for lignite PAHs, yielding 96% average recovery, whereas ultrasonic and Soxhlet extraction yielded relatively lower recoveries (75% and 67%, respectively).     

粉煤灰资源化特性及路面工程应用技术研究

对粉煤灰的各项技术参数进行了试验研究,揭示出粉煤灰的不同成分和形貌对其资源化特性的影响规律,初步完成了消除不利于粉煤灰资源化的有害成分炭的优化实验工作,进行了脱炭粉煤灰混凝土配合比等试验研究,并在路面修复工程中予以应有,结果表明,经脱炭处理的粉煤灰应用于混凝土工程可以明显改善混凝土的工作性能,实际道路运营和技术性能符合路面工程的要求,具有重大的经济效益和环境效益。     

Reaction of arsenic vapor species with fly ash compounds: kinetics and speciation of the reaction with calcium silicates

In coal combustion systems, the partitioning of arsenic between the vapor and solid phases is determined by the interaction of arsenic vapors with fly ash compounds under post-combustion conditions. This partitioning is affected by gas–solid reactions between the calcium components of the ash particles and arsenic vapors. In this study, bench scale experiments were conducted with calcium compounds typical of coal-derived fly ash to determine product formation, the extent of reaction and reaction rates when contacted by arsenic oxide vapors. Experiments conducted with arsenic trioxide (As₄O_6(g)) vapors in contact with calcium oxide, di-calcium silicate and mono-calcium silicate over the temperature range 600–1000 °C indicated that these solids were capable of reacting with arsenic vapor species in both air and nitrogen. Calcium arsenate was the observed reaction product in all the samples analyzed. Maximum capture of arsenic occurred at 1000 °C with calcium oxide being the most effective of the three solids over the range of temperatures studied. Using a shrinking core model for a first order reaction and the results from intrinsic kinetic experiments conducted in air, the reaction rate constants were found to be 1.4×10⁻³exp(−2776/T) m/s for calcium oxide particles, 7.2×10⁻³exp(−3367/T) m/s for di-calcium silicate particles and 5.5×10⁻³exp(−3607/T) m/s for mono-calcium silicate particles. These results therefore suggest that any calcium present in fly ash can react with arsenic vapor and capture the metal in water-insoluble forms of the less hazardous As(V) oxidation state.     

Edaphological characteristics of unweathered and weathered fly ashes from Gondwana and lignite coal

Naturally weathered and unweathered samples of fly ashes produced from Gondwana and lignite coals were characterized for their edaphological properties. The particle size distribution in these fly ashes varied widely, and the percentage of [Formula: see text] size particles governed their water holding capacity. All fly ashes were noncoherent in the dry state and had lower particle density than quartz and mulite. The fly ashes were low in available N, but were sufficient in available P, K, Ca, Mg, S, Cu, Fe, Mn, Zn and B. Among the fly ashes, unweathered lignite fly ash was the richest source of K, Ca, Mg, S and Fe, while weathered lignite fly ash had the highest amounts of Mn, Zn and B. The pH of the fly ashes was closely related to the ratio of exchangeable Ca to exchangeable Al. The fly ashes were high in soluble salt, but were poor in cation exchange capacity. As an amendment to correct soil pH, the fly ashes had a poor buffering capacity. Weathering decreased the total Fe, available S and exchangeable Na percentages, but increased the organic C content of the fly ashes. Invariably, an excess of soluble salts and exchangeable Na could limit plant growth on fly ash dumps. Toxic levels of B and Al existed in only some fly ashes.     

Field-scale leaching of arsenic, chromium and copper from weathered treated wood

Earlier studies documented the loss of wood preservatives from new wood. The objective of this study was to evaluate losses from weathered treated wood under field conditions by collecting rainfall leachate from 5 different wood types, all with a surface area of 0.21 m². Wood samples included weathered chromate copper arsenate (CCA) treated wood at low (2.7 kg/m³), medium (4.8 kg/m³) and high (35.4 kg/m³) retention levels, new alkaline copper quat (ACQ) treated wood (1.1 kg/m³ as CuO) and new untreated wood. Arsenic was found to leach at a higher rate (100 mg in 1 year for low retention) than chromium and copper (<40 mg) in all CCA-treated wood samples. Copper leached at the highest rate from the ACQ sample (670 mg). Overall results suggest that metals' leaching is a continuous process driven by rainfall, and that the mechanism of release from the wood matrix changes as wood weathers.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.     

Fly and bottom ashes from biomass combustion as cement replacing components in mortars production: Rheological behaviour of the pastes and materials compression strength

In the present research mortar pastes obtained by replacing a commercial cement with the equivalent mass of 5, 10, 20 and 30 wt.% of fly ash or bottom ash from fir chips combustion, were prepared and rheologically characterized. It was observed that the presence of ash modifies their rheological behaviour with respect to the reference blend due to the presence, in the ashes, of KCl and K₂SO₄ which cause precipitation of gypsum and portlandite during the first hydration stages of the pastes. Hydrated materials containing 5 wt.% of ash display compression strength and absorption at 28 d of same magnitude as the reference composition; conversely, progressive increase of ash cause a continuous decline of materials performances. Conversely, samples tested after 180 d display a marked decline of compression strength, as a consequence of potassium elution and consequent alkali-silica reaction against materials under curing.     

The internal microstructure and fibrous mineralogy of fly ash from coal-burning power stations

Coal fly ash (CFA) is a significant environmental pollutant that presents a respiratory hazard when airborne. Although previous studies have identified the mineral components of CFA, there is a paucity of information on the structural habits of these minerals. Samples from UK, Polish and Chinese power stations were studied to further our understanding of the factors that affect CFA geochemistry and mineralogy. ICP-MS, FE-SEM/EDX, XRD, and laser diffraction were used to study physicochemical characteristics. Analysis revealed important differences in the elemental compositions and particle size distributions of samples between sites. Microscopy of HF acid-etched CFA revealed the mullite present possesses a fibrous habit; fibres ranged in length between 1 and 10 μm. Respirable particles (<10 μm) were frequently observed to contain fibrous mullite. We propose that the biopersistence of these refractory fibres in the lung environment could be contributing towards chronic lung diseases seen in communities and individuals continually exposed to high levels of CFA.     

Leaching of PCDD/F from fly ash and soil with fire-extinguishing water

Leaching experiments from fly ash and soil with fire-extinguishing water result in significant amounts of PCDD/F in the related leachates. In contrast to the water solubilities the higher chlorinated congeners are leached more easily than the low chlorinated tetra- and penta-congeners. Obviously, the cosolvents present in the fire-extinguishing water enhances PCDD/F solubilities.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

粉煤灰制备混凝剂及其砸黄河水的处理效果

以粉煤灰和铁泥为原料、加入一定量NaCl作助溶剂室温下制备粉煤灰混凝剂,考察酸灰比与酸浓度对Fe3＋、Al“溶出率及混凝剂对黄河水处理效果的影响。结果表明,Fe3＋、A13＋的最佳溶出条件为酸灰比3mL／g、HCl浓度4mol／L,此时Fe“溶出率为28．1％,浓度为11．81g／L;A13＋溶出率为5．2％,浓度为1．86g／L。粉煤灰混凝剂对黄河水的处理效果在投加量2．38mL／L、沉降时间30min、pH6．2～7．5时最佳,对浊度、ss和COD。。平均去除率分别为89．7％、83．6％和62．3％,优于传统市售混凝剂PAC和Fc,Fe3＋、AI3＋同时存在有利于各自优势的发挥从而提高混凝效果。     

火电灰渣场自然恢复下灰渣养分及重金属含量研究

对自然恢复下4类不同年代样地的灰渣养分含量及重金属含量进行研究,通过对比分析发现,有机质、全氮、全钾、全磷含量随着自然恢复时间的增加呈现递增的趋势,全磷含量在各恢复阶段与对照样地之间并不存在显著差异(P0.05)。pH随着恢复时间的增加呈现递减的趋势。对灰渣综合质量指数进行研究发现,自然恢复长期、中期、短期与自然恢复初期对比均有显著提高(P0.05),且随着自然恢复时间的增加灰渣综合质量指数逐渐提高。对灰渣场锌、铅、铜3种重金属研究后发现,在自然恢复下随着时间的增加,灰渣中重金属含量均呈现递减的趋势。