Diopside-based glass-ceramics from MSW fly ash and bottom ash

By utilising MSW fly ash from the Shanghai Yuqiao municipal solid waste (MSW) incineration plant as the main raw material, diopside-based glass-ceramics were successfully synthesized in the laboratory by combining SiO(2), MgO and Al(2)O(3) or bottom ash as conditioner of the chemical compositions and TiO(2) as the nucleation agent. The optimum procedure for the glass-ceramics is as follows: melting at 1500 degrees C for 30 min, nucleating at 730 degrees C for 90 min, and crystallization at 880 degrees C for 10h. It has been shown that the diopside-based glass-ceramics made from MSW fly ash have a strong fixing capacity for heavy metals such as lead (Pb), chromium (Cr), cadmium (Cd) etc.     

The potential of SO2 for reducing corrosion in WtE plants

Due to the high-temperature boiler corrosion induced by chloride-rich fly ash deposits, steam generation in today’s Waste-to-Energy (WtE) plants is typically designed only for 40 bar/400 °C as an economic compromise between acceptable corrosion rate and maximum power generation. The high-corrosive metal chlorides in the fly ash can react with SO₂ forming low-corrosive sulfates. The sulfation efficiency is enhanced by high SO₂ levels and sufficient residence time of the flue gas at high-temperatures (700–900 °C). The fly ash sulfation was tested in full scale in a Swedish WtE plant by applying the economic sulfur recirculation method. Probes of several alloys (16Mo3, Inconel 625, Sanicro 28) were exposed for 1000 h at controlled material temperatures in the superheater position, at normal and during sulfating operation respectively. Analyses of the fly ash showed that the molar Cl/S was decreased to values well below 1 and the corresponding corrosion rates of the individual material samples were less than half when sulfur recirculation was in operation. These positive findings demonstrate that the sulfur recirculation process has high potential for low-corrosive high-temperature steam generation (T ≈ 500 °C) and improved electricity production. Further steam superheating can be realized by staged superheating using small amounts of secondary fuel.     

Environmental impact of fly ash utilization in roadway embankments

The leaching potential of heavy metals from a roadway embankment constructed of fly ash and soil mixture was studied. Leaching of eight environmentally concerned metals Ag, As, Ba, Cd, Cr, Hg, Pb, and Se from the fly ash–soil mixtures was examined through batch leaching test and column leaching test. The batch leaching test results showed that the fly ash meets the local regulatory standards for beneficial use of nonhazardous wastes. The column leach test revealed that only Ba, Cr, and Se were detectable in the effluents. The peak concentration of Ba in the effluents was much lower than the US EPA Primary Drinking Water Regulations’ maximum contaminant level (MCL). The peak concentrations of Cr and Se exceeded the MCLs only in the initial flush stage and quickly decreased to below the MCLs. Results of this study suggest a great potential for fly ash to be used in roadway embankments to enhance their mechanical properties, reduce the use of soil, and avoid the disposal of fly ash as waste.     

碱激发粉煤灰对Cs~+的吸附行为

将粉煤灰进行碱激发改性,运用XRD和SEM技术对碱激发粉煤灰进行了表征,通过静态平衡吸附实验研究了碱激发粉煤灰对Cs+的吸附动力学和热力学特性,并对吸附前后的碱激发粉煤灰进行了FTIR分析。表征结果显示,碱激发处理后,粉煤灰的晶相发生了改变,且粉煤灰表面密实的硬壳层被破坏。实验结果表明:在初始Cs+质量浓度为200 mg/L、吸附温度为25℃、溶液pH为10、碱激发粉煤灰投加量为12.0 g/L的条件下,碱激发粉煤灰对Cs+的平衡吸附率可达80%以上,其吸附能力比碱激发前提高了3倍以上;吸附过程可用准二阶动力学方程来描述,并较好地符合Langmuir等温吸附模型;碱激发粉煤灰对Cs+的吸附是吸热过程,且能自发进行;该过程以物理吸附为主,并伴随化学吸附。     

Accelerated carbonation of municipal solid waste incineration fly ashes

As a result of the EU Landfill Directive, the disposal of municipal solid waste incineration (MSWI) fly ash is restricted to only a few landfill sites in the UK. Alternative options for the management of fly ash, such as sintering, vitrification or stabilization/solidification, are either costly or not fully developed. In this paper an accelerated carbonation step is investigated for use with fly ash. The carbonation reaction involving fly ash was found to be optimum at a water/solid ratio of 0.3 under ambient temperature conditions. The study of ash mineralogy showed the disappearance of lime/portlandite/calcium chloride hydroxide and the formation of calcite as carbonation proceeded. The leaching properties of carbonated ash were examined. Release of soluble salts, such as SO4, Cl, was reduced after carbonation, but is still higher than the landfill acceptance limits for hazardous waste. It was also found that carbonation had a significant influence on lead leachability. The lead release from carbonated ash, with the exception of one of the fly ashes studied, was reduced by 2-3 orders of magnitude.     

粉煤灰的改性及对刚果红的吸附

分别采用沸水浸泡、酸浸、碱浸和加热的方法对粉煤灰进行改性处理，利用FTIR仪和XRD仪对改性粉煤灰的成分和官能团进行了分析，并利用改性粉煤灰对模拟刚果红废水进行脱色。实验结果表明：碱改性粉煤灰中含有大量官能团，以及NaPl型沸石类物质，能够明显提高粉煤灰对刚果红的吸附性能；与活性炭相比，碱改性粉煤灰具有更高的性价比；在初始刚果红质量浓度为20mg/L、碱改性粉煤灰加入量为50g/L的条件下，废水的脱色率可达87.52%；碱改性粉煤灰对刚果红的吸附过程遵循二级反应动力学，较好地符合Langmuir等温式和Freundlich等温式。     

粉煤灰及其制备沸石对高浓度氨氮的去除比较

以粉煤灰为原料,采用改进的水热合成法制备了粉煤灰沸石,并将粉煤灰和粉煤灰沸石用于高浓度氨氮的吸附去除。实验结果表明:在粉煤灰和粉煤灰沸石的投加量分别为0.10 g/m L和0.04 g/m L、反应体系p H为5~7、初始氨氮质量浓度为500 mg/L的条件下,分别吸附660 min和60 min,粉煤灰和粉煤灰沸石对氨氮的去除率分别约为20.1%和50.7%左右,粉煤灰沸石对高浓度氨氮的去除效果明显优于粉煤灰;粉煤灰和粉煤灰沸石对氨氮的吸附动力学行为符合准二级动力学方程;Langmuir和Freundlich等温吸附模型能较好地描述粉煤灰对氨氮的等温吸附过程,而粉煤灰沸石对氨氮的等温吸附过程则更适宜用线性模型和Freundlich模型描述。     

Effect of the milling solution on lead stabilization in municipal solid waste incinerator fly ash during the milling processes

The wet milling process had been found to effectively stabilize lead in fly ash. This study adopts this method and looks at the effect of different milling solutions to improve the efficiency of lead stabilization. Different milling solutions (water, phosphoric acid and ethanol) and different milling times (1, 24, 48 and 96 h) were selected as parameters. Since lead oxide can be identified by XRD in this experiment’s samples, 5% lead oxide was added to the extracted mixed fly ash to make instrumental analysis easier. The experimental results indicate that the effect of stabilization of lead after milling could exceed 96%. During milling with water, considerable lead leached into the water in the initial stage (1 h) of the process, but a stable level was reached as the milling time increased. After milling with ethanol and 0.2 M phosphoric acids, the efficiency could exceed 93% after 1 h of milling time. The results of the sequential extraction procedure (SEP) results show that the residual fraction could be increased from 8.93% to 56.16% when a 0.2 M phosphoric acid solution was used. Clearly the choice of an appropriate milling solution can enhance lead stabilization in the fly ash.     

CuCl2改性飞灰吸附气相零价汞

采用CuCl₂对循环流化床锅炉飞灰进行改性,在固定床反应器上对CuCl₂改性飞灰进行了气相零价汞（Hg⁰）吸附实验。考察了CuCl₂负载量和吸附温度对改性飞灰Hg⁰吸附能力的影响,并结合颗粒内扩散模型、准一阶动力学模型、准二阶动力学模型和耶洛维奇模型拟合结果分析该过程的控制步骤。结果表明： CuCl₂改性飞灰的Hg⁰穿透时间远大于未改性飞灰,对Hg⁰的吸附量随CuCl₂负载量的增加而增加;CuCl₂改性飞灰的Hg⁰吸附能力随吸附温度的升高先增大后减小,150 ℃为最佳吸附温度;准二阶动力学模型的拟合值与实验值相关系数最高,且该模型初始吸附速率与实验值最为接近,即准二阶动力学模型更适合于描述CuCl₂改性飞灰的Hg⁰吸附过程。     

Use of fly ash for the removal of phenol and its analogues from contaminated water

This work attempts to elucidate the effects of different operational variables affecting the mechanistic function of fly ash for removal of some priority organic pollutants viz. phenol and its analogues. Thermodynamic parameters like free energy change, enthalpy and entropy of the process, as well as the sorption isotherms for phenols on fly ash, were measured and the most suitable isotherm was determined. Results of the study indicate that the extent of solute removal is determined by the initial solute concentration, molecular size and molecular arrangement of the solute. At the fixed set of experimental conditions, a model equation can be developed from which the percent removal corresponding to the load of the particular solute is determined. It is assumed that the mechanism of adsorption is governed by the surface characteristics of fly ash; pH has a vital role in influencing the solute removal as both the ionizing power (acidity, pKa) of the solutes and the zero point charge of fly ash (pH(ZPC)) depend on the solution pH. Isotherm pattern and the free energy change indicate that the process is favorable, as well as spontaneous. The information gathered from the study will serve as a predictive modeling procedure for the analysis and design of the removal of organic pollutants and decontamination of water. The leaching experiment indicates that the retained solutes do not release from fly ash. The retained solutes can be recovered and utilized as industrial raw material.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Recycling of municipal solid waste incinerator fly ash by using hydrocyclone separation

The municipal solid waste incinerators (MSWIs) in Taiwan generate about 300,000 tons of fly ash annually, which is mainly composed of calcium and silicon compounds, and has the potential for recycling. However, some heavy metals are present in the MSWI fly ash, and before recycling, they need to be removed or reduced to make the fly ash non-hazardous. Accordingly, the purpose of this study was to use a hydrocyclone for the separation of the components of the MSWI fly ash in order to obtain the recyclable portion. The results show that chloride salts can be removed from the fly ash during the hydrocyclone separation process. The presence of a dense medium (quartz sand in this study) is not only helpful for the removal of the salts, but also for the separation of the fly ash particles. After the dense-medium hydrocyclone separation process, heavy metals including Pb and Zn were concentrated in the fine particles so that the rest of the fly ash contained less heavy metal and became both non-hazardous and recyclable.     

Lead immobilization in mechanochemical fly ash recycling

In previous studies, we focused on a mechanochemical process for recycling fly ash for use in cement; this process was expected to immobilize heavy metals in the fly ash, a desirable outcome in light of the fact that recycled fly ash is commonly used in the synthesis of inorganic materials. Here, we investigated the leaching of lead (Pb) from fly ash treated by a mechanochemical process and from cement prepared from the treated fly ash. We used lead oxide (PbO), a typical Pb compound in fly ash, as a model substance. Mechanochemical treatment of the fly ash inhibited Pb leaching by 93%, and further inhibition (more than 99.9%) was observed in cement produced from the treated fly ash. During the mechanochemical treatment, PbO was reduced to Pb by iron from the stainless-steel mill used for processing, and the lower solubility of Pb in water resulted in immobilization of the Pb.     

粉煤灰基吸附剂对模拟废水中Cd2+的吸附性能

以粉煤灰为原料、Na2CO3为助熔剂,采用盐熔融—水浴结晶法制备粉煤灰基吸附剂。探讨了吸附剂的最佳制备条件及其对模拟废水中Cd2+的最佳吸附条件、吸附动力学和吸附机理。实验结果表明:制备吸附剂的最佳工艺条件为m(粉煤灰)∶m(Na2CO3)为1∶2,焙烧温度为450℃;采用最佳制备工艺条件下制备的吸附剂(记作2-450℃-FA吸附剂),在初始Cd2+质量浓度为300 mg/L、初始溶液pH为7.7、振荡时间为120 min的条件下,对模拟废水中Cd2+的去除率为98.0%。2-450℃-FA吸附剂对Cd2+的吸附主要受颗粒内扩散控制,吸附过程可用准二级吸附动力学方程很好地描述。Ea为77.22 kJ/mol,吸附过程主要为化学吸附。     

Investigation of MSWI fly ash melting characteristic by DSC-DTA

The melting process of MSWI (Municipal Solid Waste Incineration) fly ash has been studied by high-temperature DSC-DTA experiments. The experiments were performed at a temperature range of 20-1450 degrees C, and the considerable variables included atmosphere (O(2) and N(2)), heating rates (5 degrees C/min, 10 degrees C/min, 20 degrees C/min) and CaO addition. Three main transitions were observed during the melting process of fly ash: dehydration, polymorphic transition and fusion, occurring in the temperature range of 100-200 degrees C, 480-670 degrees C and 1101-1244 degrees C, respectively. The apparent heat capacity and heat requirement for melting of MSWI fly ash were obtained by DSC (Differential Scanning Calorimeter). A thermodynamic modeling to predict the heat requirements for melting process has been presented, and it agrees well with the experimental data. Finally, a zero-order kinetic model of fly ash melting transition was established. The apparent activation energy of MSWI fly ash melting transition was obtained.     

钛硅分子筛催化双氧水氧化水中间甲酚

探索催化双氧水氧化去除间甲酚对开发炼油厂碱渣废水处理新技术意义重大。采用钛硅分子筛催化双氧水氧化水中间甲酚,考察了反应时间、反应温度、双氧水加入量、催化剂加入量和初始溶液pH对间甲酚去除率的影响。实验结果表明：钛硅分子筛对双氧水氧化间甲酚具有显著的催化作用;在反应时间为90 min、反应温度为80 ℃、n（H₂O₂）∶n（间甲酚）为4、催化剂加入量为1.5 g/L、初始溶液pH为1.0~11.0的条件下,间甲酚去除率约为94%,间甲酚溶液的BOD₅/COD从氧化前的0.26提高到氧化后的0.38,可生化性显著提高。     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

改性粉煤灰的制备及其对分散蓝的吸附

以聚二甲基二烯丙基氯化铵(PDMDAAC)为改性剂,制备PDMDAAC改性粉煤灰。采用正交实验考察了制备条件对PDMDAAC在粉煤灰上的负载量的影响。实验结果表明:在反应温度为70℃、反应时间为3 h、PDMDAAC质量浓度为50 g/L、溶液pH为10的最佳条件下,PDMDAAC在粉煤灰上的负载量为0.98 mg/g;在吸附温度为30℃、初始分散蓝质量浓度为50 mg/L、PDMDAAC改性粉煤灰加入量为4 g/L的条件下,PDMDAAC改性粉煤灰对分散蓝的去除率可达98%。PDMDAAC改性粉煤灰对分散蓝的吸附符合Langmuir吸附模型。     

Water washing effects on metals emission reduction during municipal solid waste incinerator (MSWI) fly ash melting process

This study investigated that water washing effects on the metals emission reduction in melting of municipal solid waste incinerator (MSWI) fly ash. Experimental conditions were conducted at liquid-to-solid (L/S) ratio 10, 20, and 100 for water-washing process and its subsequent melting treatment at 1450 °C for 2 h. The simple water-washing process as a pre-treatment for MSWI fly ash can remove most of the chlorides, leachable salts, and amphoteric heavy metals from the MSWI fly ash, resulting in the washed ash having lowered chlorine content. MSWI fly ashes washed by L/S ratio 10 and above that were melted at 1450 °C produced slag containing relatively high vitrificaton ratio of Cu and Pb. Besides, the vitrification ratios of Na, K, Ca, and Mg in washed MSWI fly ash were also higher than that of MSWI fly ash. The results indicated that washed MSWI fly ash can reduce the emission of metallic chlorides during its subsequent melting treatment.     

Recycling MSWI bottom and fly ash as raw materials for Portland cement

Municipal solid waste incineration (MSWI) ash is rich in heavy metals and salts. The disposal of MSWI ash without proper treatment may cause serious environmental problems. Recently, the local cement industry in Taiwan has played an important role in the management of solid wastes because it can utilize various kinds of wastes as either fuels or raw materials. The objective of this study is to assess the possibility of MSWI ash reuse as a raw material for cement production. The ash was first washed with water and acid to remove the chlorides, which could cause serious corrosion in the cement kiln. Various amounts of pre-washed ash were added to replace the clay component of the raw materials for cement production. The allowable limits of chloride in the fly ash and bottom ash were found to be 1.75% and 3.50% respectively. The results indicate that cement production can be a feasible alternative for MSWI ash management. It is also evident that the addition of either fly ash or bottom ash did not have any effect on the compressive strength of the clinker. Cement products conformed to the Chinese National Standard (CNS) of Type II Portland cement with one exception, the setting time of the clinker was much longer.