生活垃圾焚烧中重金属行为的研究进展

垃圾中的金属以氧化物、氮化物、碳化物及其它形态转移到焚烧产物如烟气、飞灰和底灰中，需严格控制焚烧过程中重金属的排放，故清楚了解金属在焚烧中的行为是很必要的。经研究发现，飞灰中重金属含量远远大于底灰中的含量，因此以垃圾焚烧飞灰中重金属的稳定化处理为目标，分析了目前国内外处理垃圾焚烧飞灰的方法和重金属在各种影响因素下的行为，并进行了比较，为飞灰的无害化和资源化处理提供参考。     

垃圾焚烧飞灰处置与资源化利用研究进展

随着生活垃圾焚烧处理方式的不断推广，焚烧飞灰的产生量也不断增加。按照我国固体废物分类方法，焚烧飞灰属于危险废物，必须进一步处置才能进入填埋场或资源化利用。本文分析了飞灰物理化学特性，论述了常规处置技术（水泥固化、化学药剂稳定化、酸溶剂提取和熔融固化等）存在的问题。将原始飞灰直接应用于水泥、混凝土或路基材料，飞灰中高含量的重金属和盐类会产生新的环境问题。飞灰水洗可以高效去除其中的可溶性盐类，水洗飞灰在焙烧后重金属的浸出浓度远低于原始飞灰烧结后的相应浓度，飞灰水洗-焙烧技术具有很好的应用前景。     

分子键合TM技术在垃圾焚烧飞灰治理中的应用

结合国内垃圾焚烧飞灰的治理现状,对分子键合TM技术治理垃圾焚烧飞灰的原理、工艺进行了介绍分析,并通过实验研究对分子键合TM技术在垃圾焚烧飞灰治理中的应用进行了探讨。     

我国南方某城市垃圾焚烧飞灰特性及固化/稳定化处置实验

我国南方某城市主要采用焚烧法处理生活垃圾,已建7个焚烧厂日产生飞灰量为101.62 t/d。文章分析了各个垃圾焚烧厂飞灰的化学组成和重金属浸出毒性,其主要成分为CaO、SiO2、MgO、Al2O3、Fe2O3、Na2O、SO3和Cl,所有焚烧飞灰都有至少一种重金属浸出浓度超标,属于危险废物。在飞灰处置出路亟待解决的背景下,实验探讨了飞灰稳定化工艺,结果表明10%的水泥添加量可以使飞灰中超标重金属(Cd、Pb和Zn)的浸出浓度满足危险废物鉴别浓度限值和安全填埋场入场浓度限值。同时,通过人体健康风险评价分析了飞灰豁免管理的可行性,并对近期和远期该城市焚烧厂飞灰的处理处置及管理提出建议。     

Characterization of MSWI fly ash through mineralogy and water extraction

This paper investigates the mineralogical characteristics of fresh, aged and hot water extracted MSWI fly ash for providing the baseline information of minerals stability which controls the released heavy metals into the environment. Quantitative determination of bulk phase abundance in the fresh fly ash by the XRD Rietveld refinement method provided composition levels for amorphous and crystalline phases such as potassium tetrachlorozincate (K₂ZnCl₄), gehlenite, halite, quartz, anhydrite, and feldspar. The minerals association in the fly ash is clearly unstable and subject to mineralogical reactions. The phases of K₂ZnCl₄, halite and anhydrite in the fresh fly ash were involved in hydration and dissolution/precipitation processes to form new minerals such as the Zn-bearing mineral gordaite, syngenite, gypsum and hydrocalumite. The solubility-controlling phases and extractability of heavy metals were examined in a Soxhlet hot water-extractor. Here the soluble salts were simply removed from fly ash while Ca-, Al-, Si- and SO₄²⁻-bearing hydrate minerals were precipitated from the extraction solution. Furthermore, a low release of heavy metals Zn, Pb and Cd in hot water was noticed, indicating a strong retention of the trace metals in the mineral phases remaining in the insoluble fly ash residues.     

湿法预处理对垃圾焚烧飞灰中重金属的形态及风险影响研究

以某典型城市生活垃圾焚烧飞灰为研究对象,采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）和电感耦合等离子体光谱仪（ICP）测定了焚烧飞灰的主要成分、矿物学组成和重金属含量,探讨了湿法预处理工艺对飞灰的化学组成、矿物学形态、化学形态及风险水平的影响.结果表明,飞灰的主要化学组成为O、Ca、Cl、Na、K等,占飞灰总质量的93.54％,其次含有0.04％ ～0.68％的Zn、Pb、Cu、Cr等微量重金属元素;经过湿法预处理,飞灰中可溶性氯盐具有较好的去除效果,且几乎所有重金属元素的不稳定形态（弱酸提取态和可还原态）比例都有一定程度的减少,有效降低了重金属的毒性、生物有效性及环境风险水平.本研究有助于降低焚烧飞灰的环境风险和探寻其资源化的有效途径.     

Fly ash as a liming material for cotton

A field experiment was conducted to determine the effect of fly ash from a coal combustion electric power facility on soil acidity in a cotton (Gossypium hirsutum L.) field. Fresh fly ash was applied to a Bosket fine sandy loam (fine-loamy, mixed, thermic Mollic Hapludalf) soil with an initial soil pH(salt) of 4.8. The fly ash was equivalent to 42 g kg(-1) calcium carbonate with 97% passing through a 60 mesh (U.S. standard) sieve. Fly ash was applied one day before cotton planting in 1999 at 0, 3.4, 6.7, and 10.1 Mg ha(-1). No fly ash was applied in 2000. Within 60 d of fly ash application in 1999, all rates of fly ash significantly increased soil pH above 6.0. Manganese levels in cotton petioles were reduced significantly by 6.7 and 10.1 Mg ha(-1) of fly ash. Soil boron (B) and sodium (Na) concentrations were significantly increased with fly ash. In 1999, B in cotton leaves ranged from 72 to 84 mg kg(-1) in plots with fly ash applications. However, no visual symptoms of B toxicity in plants were observed. In 1999, cotton lint yield decreased on average 12 kg ha(-1) for each Mg of fly ash applied. In 2000, cotton yields were significantly greater for the residual 3.4 and 6.7 Mg fly ash ha(-1) plots than the untreated check. Due to the adverse yield effects measured in the first year following application, fly ash would not be a suitable soil amendment for cotton on this soil at this time.     

PHOSPHATE IN WATERS: I. REDUCTION USING NORTHERN LIGNITE FLY ASH1

Fly ashes fiom lignite coal fixed steam electric plants contain appreciable amounts of materials that can, in principle, decrease the phosphorus concentration in surface waters. Typical samples of un-weathered fly ash were used to test efficacies of removal of phosphorus from standard phosphate solutions and actual lake water samples. The effects of changing parameters such as contact time, pH, fly ash/water ratios, and solution temperature are presented. Water soluble and insoluble factors in the ash both appear to be reactive constituents. Trials with municipal waste waters showed near quantitative removal of ortho-phosphate.     

垃圾焚烧飞灰中重金属的固化/稳定化处理实验研究

研究了城市生活垃圾焚烧-电灰的特性及飞灰中重金属的特性,对利用水泥作粘结剂进行飞灰固化/稳定化处理效果开展了系统的实验研究,分析了水泥固化/稳定化飞灰的工艺特点和最佳工艺参数,并讨论了粘结剂固化飞灰机理以及重金属浸出毒性,为进一步研究城市生活垃圾焚烧飞灰的无害化处理与利用提供了有重要价值的参考依据.     

The reuse of municipal solid waste incinerator fly ash slag as a cement substitute

The results of the treatment of fly ash from a municipal solid waste incinerator (MSWI) by melting are described, and the safety and the effectiveness of using the slag produced by this melting treatment are studied. The properties of the MSWI fly ash slag were analyzed, to evaluate the feasibility of its reuse as a substitute for part of the cement required in mortar preparation. This MSWI fly ash slag was found to be comprised mainly of SiO₂ and CaO, which can be substituted for up to 20% of the cement content in mortar, without sacrificing the quality of the resultant concrete. In fact, the concrete thus produced has greater compressive strength, 10% higher than that without the substitution. The setting time of the fresh mortar becomes lengthens as increasing amounts of cement are replaced; while the spread flow value increases with the increasing percentage of cement substitution. X-ray diffraction analysis reveals that when the W/C=0.38 and the curing AGE=28 days, the crystal patterns in the mortar samples, prepared with different amounts of cement having been replaced by MSWI fly ash slag are similar. According to the results of the toxic characteristic leaching procedure analysis, MSWI fly ash slag should be classified as general non-hazardous industrial waste, that meets the effluent standard. Therefore, the reuse of MSWI fly ash slag is feasible, and will not result in pollution due to the leaching of heavy metals.     

Modification Effect of Proton-Exchange Membrane on Methanol Permeation and Proton Conductivity for Direct Methanol Fuel Cell

Abstract

The Nafion membranes modified with a long chain counter ion, (C₈H₁₇)₄N⁺ or (CH₃)₄N⁺, and sandwich-type modified Nafion membranes were prepared as proton conducting membranes (PEM) for a direct methanol fuel cell (DMFC). We evaluated the methanol permeability, ionic conductivity, ion cluster diameter, ion exchange capacity and water content. The ion cluster diameter of the modified Nafion membranes was determined by small angle X-ray diffraction (SAXRD) measurements, and decreased in comparison with Nafion 117. The methanol crossover flux decreased to less than 10% that of Nafion 117 with the decreasing ion cluster diameter. For the sandwich-type membrane (Octyl-s1), the methanol crossover flux was 46% that of Nafion 117 and the ionic conductivity was 4.2 S/m.     

Balancing durability and environmental impact in concrete combining low-grade recycled aggregates and mineral admixtures

This paper investigated the effect of various amounts of low-grade recycled aggregates in concrete containing mineral admixtures at three different water-binder ratios on mechanical and environmental performance. The balance between durability and environmental impact for a given strength level similar to normal-use concrete was also examined using analytic hierarchy process. Results showed that increasing the water-binder ratio and volume of recycled aggregates reduced compressive strength and increased air permeability and drying shrinkage relative to normal aggregates. However, compared to normal-use concrete similar or better performance could be achieved, which was attributed to improvement of low-grade recycled aggregate performance when combined with fly ash. Similarly, CO₂ emissions and volume of raw materials were lower than the normal-use concrete for all mixes. Concrete mixes with low air permeability and low CO₂ footprint had the best balance of durability and environmental impact, as decreasing raw material volume tended to more greatly reduce durability.     

Adsorption of basic dye from aqueous solution onto fly ash

The fly ash treated by H₂SO₄ was used as a low-cost adsorbent for the removal of a typical dye, methylene blue, from aqueous solution. An increase in the specific surface area and dye-adsorption capacity was observed after the acid treatment. The adsorption isotherm and kinetics of the treated fly ash were studied. The experimental results were fitted using Langmuir and Freundlich isotherms. It shows that the Freundlich isotherm is better in describing the adsorption process. Two kinetic models, pseudo-first order and pseudo-second order, were employed to analyze the kinetic data. It was found that the pseudo-second-order model is the better choice to describe the adsorption behavior. The thermodynamic study reveals that the enthalpy (ΔH⁰) value is positive (5.63 kJ/mol), suggesting an endothermic nature of the adsorption.     

Ash and deposit formation from oxy-coal combustion in a 100 kW test furnace

Ash deposition is still an unresolved problem when retrofitting existing air-fired coal power plants to oxy-fuel combustion. Experimental data are quite necessary for mechanism validation and model development. This work was designed to obtain laboratory combustor data on ash and deposits from oxy-coal combustion, and to explore the effects of oxy-firing on their formation. Two bituminous coals (Utah coal and Illinois coal) and one sub-bituminous coal (PRB coal) were burned on a down-fired combustor under both oxy- and air-firing. Two oxy-fired cases, i.e., 27 vol% O₂/73 vol% CO₂ and 32 vol% O₂/68 vol% CO₂, were selected to match the radiation flux and the adiabatic flame temperature of air combustion, respectively. Once-through CO₂ was used to simulate fully cleaned recycled flue gas. The flue gas excess oxygen was fixed at 3 vol%. For each case, both size-segregated fly ash and bulk fly ash samples were obtained. Simultaneously, ash deposits were collected on an especially designed un-cooled deposition probe. Ash particle size distributions and chemical composition of all samples were characterized. Data showed that oxy-firing had insignificant impacts on the tri-modal ash particle size distributions and composition size distributions in the size range studied. Bulk ash compositions also showed no significant differences between oxy- and air-firing, except for slightly higher sulfur contents in some oxy-fired ashes. The oxy-fired deposits were thicker than those from air-firing, suggesting enhanced ash deposition rates in oxy-firing. Oxy-firing also had apparent impacts on the deposit composition, especially for those components (e.g., CaO, Fe₂O₃, SO₃, etc.) that could contribute significantly to ash deposition. Based on these results, aerodynamic changes in gas flow and changes in combustion temperature seemed more important than chemical changes of ash particles in determining deposit behavior during oxy-coal combustion.     

Treatment and toxicity evaluation of methylene blue using electrochemical oxidation,fly ash adsorption and combined electrochemical oxidation-fly ash adsorption

Treatment of a basic dye, methylene blue, by electrochemical oxidation, fly ash adsorption, and combined electrochemical oxidation-fly ash adsorption was compared. Methylene blue at 100 mg L^?1 was used in this study. The toxicity was also monitored by the Vibrio fischeri light inhibition test.When electrochemical oxidation was used, 99% color and 84% COD were removed from the methylene blue solution in 20 min at a current density of 428 A m^?2, NaCl of 1000 mg L^?1, and pH₀ of 7. However, the decolorized solution showed high toxicity (100% light inhibition).For fly ash adsorption, a high dose of fly ash (>20,000 mg L^?1) was needed to remove methylene blue, and the Freundlich isotherm described the adsorption behavior well.In the combined electrochemical oxidation-fly ash adsorption treatment, the addition of 4000 mg L^?1 fly ash effectively reduced intermediate toxicity and decreased the COD of the electrochemical oxidation-treated methylene blue solution. The results indicated that the combined process effectively removed color, COD, and intermediate toxicity of the methylene blue solution.     

Development of a fuel cell propulsion system for the existing Mercedes B-Class 160 of petrol driven car

This paper presents a theoretical comparison between fuel cell (FC) power train and conventional petrol driven propulsion system. FC has potential to reduce the CO₂-emissions from road. However, FC power trains require energy storing device, to meet the peak power during extreme drive situations and also able to recover the kinetic energy of the vehicle during break operation. The proposed system includes a polymer electrolyte membrane fuel cell (PEMFC) based drive train and a super capacitor connected in parallel. The system is designed and dimensioned for a conventional petrol driven propulsion system of the Mercedes B-Class160. The feasibility study also includes comparison between the existing conventional systems. It is shown that although FC power train is heavier compared to existing system, urban performance is better and produces no CO₂ and other harmful emissions.     

Novel lithium-based sorbents from fly ashes for CO2 capture at high temperatures

In this work several Li₄SiO₄-based sorbents from fly ashes for CO₂ capture at high temperatures have been developed. Three fly ash samples were collected and subjected to calcination at 950 °C in the presence of Li₂CO₃. Both pure Li₄SiO₄ and fly ash-based sorbents were characterised and tested for CO₂ sorption at different temperatures between 400 and 650 °C and adding different amounts of K₂CO₃ (0–40 mol%). To examine the sorbents performance, multiple CO₂ sorption/desorption cycles were carried out. The temperature and the presence of K₂CO₃ strongly affect the CO₂ sorption capacity for the sorbents prepared from fly ashes. When the sorption temperature increases by up to 600 °C both the CO₂ sorption capacity and the sorption rate increase significantly. Moreover when the amount of K₂CO₃ increases, the CO₂ sorption capacity also increases. At optimal experimental conditions (600 °C and 40 mol% K₂CO₃), the maximum CO₂ sorption capacity for the sorbent derived from fly ash was 107 mg CO₂/g sorbent. The Li₄SiO₄-based sorbents can maintain its original capacity during 10 cycle processes and reach the plateau of maximum capture capacity in less than 15 min, while pure Li₄SiO₄ presents a continual upward tendency for the 15 min of the capture step and attains no equilibrium capacity.     

Investigation of the uptake ability of fly ashes produced after lignite combustion

Fly ash samples from the five steam electric power stations of the Lignite Center of Western Macedonia were used in this study. They consisted mainly of anhydrite, lime, quartz and amorphous material as well as feldspars, calcite, micas + clays, portlandite and gehlenite which were all present in minor amounts. Anhydrite, lime and portlandite in the fly ash samples diminished upon treatment with ammonium acetate aqueous solution, whereas quartz, feldspars, gehlenite and amorphous material were enriched. The uptake ability of the fly ash samples ranged from 89 to 101 mequ./100g. The uptake ability of the samples was mainly attributed to the amorphous material and the microporous minerals, micas + clays. The amorphous material content was estimated at between 17 and 20 wt% in the treated fly ashes and may be unburned organic matter and amorphous inorganic material that resulted during the combustion of the lignite. A positive correlation was observed between the uptake ability and the total percentage of amorphous material and micas + clays. The relatively high uptake ability of the fly ash samples could lead to additional industrial and environmental uses of the fly ashes. The environmental advantage of fly ash exploitation will be particularly important for large electric power centers, such as the LCWM.     

Separation and recovery of carbon dioxide by a membrane flash process

A novel process for carbon dioxide (CO₂) separation, which was named a membrane flash process, was developed to realize an energy-saving technology and to substitute it for a conventional regenerator. The electric energy for CO₂ recovery in a membrane flash process using aluminum oxide and diethanolamine was lower than the thermal energy of the conventional chemical absorption process. Flashing at elevated temperature by the low temperature energy significantly reduced the electric energy and required much less membrane area. This process has potentiality of low cost capture of CO₂ when the low temperature energy, which is not available for other purposes, can be utilized to elevate flashing temperature.     

Direct methanol fuel cell bubble removal mechanism using magnetic actuation

This article develops a direct methanol fuel cell (DMFC) with a magnet-actuated bubble removal mechanism. A micro-DC motor is used to control the bubble removal mechanism. The lower magnetic device is operated to extrude a Polydimethylsiloxane (PDMS) runner to compress the liquid fuel in the anode flow channel, forcing the CO₂ bubbles in the runner to flow toward the outlet end. The bubble retention in the anode flow channel is thereby improved, enhancing the cell performance. The proposed mechanism stability and performance and Polymethylmethacrylate (PMMA) runner are also discussed.