Latent Hydraulic Reactivity of Blended Cement Incorporating Slag Made from Municipal Solid Waste Incinerator Fly Ash

Abstract

The reactivity of cement pastes made by blending Portland cement with slag from municipal solid waste incinerator (MSWI) fly ash was investigated to assess the potential of recycling MSWI fly ash slag. The slag, prepared by melting MSWI fly ash at 1400 °C for 30 min, was pulverized and ground, then blended with ordinary Portland cement (OPC), using various substitution levels to make slag-blended cement (SBC). The pozzolanic reactivity of the ecocement was then characterized by determining variations in the compressive strength, degree of hydration, microstructure, speciation, and mineralogical crystalline phases. The results suggest that the strength of the pastes at an early age decreased with increasing substitution levels, whereas the strength at a later age of the tested pastes (with substitution levels less than 10%) outperformed OPC paste because of typical SBC properties. The development of strength at a later age was also confirmed by X-ray diffraction and scanning electron microscopy techniques. This implies that active silica (Si) and alumina (Al) react with the hydration product, calcium hydroxide (Ca(OH)₂), to form calcium silicate hydrate (C-S-H), which contributed to strength development at a later age by the filling up of pores in the SBC pastes. The pozzolanic activity of the SBC pastes indicates that it is suitable for use as a substitute for OPC in blended cement.     

Pozzolanic reactivity of the synthetic slag from municipal solid waste incinerator cyclone ash and scrubber ash

This study investigates the pozzolanic reactions and compressive strength of the blended cement manufactured using synthetic slag obtained from municipal solid waste incinerator (MSWI) cyclone ash and scrubber ash as partial replacement of portland cement. The synthetic slag was made by co-melting the MSWI scrubber ash and cyclone ash mixtures at 1400 degrees C for 30 min. Following pulverization, the different types of slag were blended with cement as cement replacement at ratios ranging from 10 to 40 wt %. The synthetic slag thus obtained was quantified, and the characteristics of the slag-blended cement pastes were examined. These characteristics included the pozzolanic activity, compressive strength, hydration activity, crystal phases, species, and microstructure at various ages. The 90-day compressive strength developed by slag-blended cement pastes with 10 and 20 wt % of the cement replaced by the synthetic slag outperformed ordinary portland cement by 1-7 MPa. X-ray diffraction species analyses indicated that the hydrates in the slag-blended cement pastes were mainly portlandite, the calcium silicate hydrate gels, and calcium aluminate hydrate salts, similar to those found in ordinary portland cement paste. Differential thermal and thermogravimetric analysis also indicated that the slag reacted with portlandite to form calcium silicate hydrate gels.     

Hydration properties of eco-cement pastes from waste sludge ash clinkers

Three types of hydraulic cements have been developed by incorporating sludge ash from a primary sewage treatment plant and a water purification plant, as well as slag from steelworks (ferrate), as a partial replacement for clay, silica, alumina, and iron oxide in raw cement meal. The raw meal for the pre-determined recipes was prepared by heating it to 1400 degrees C for 6 hr in a clinkerization process, using a simulated incinerator and smelter. The major components of ordinary Portland cement, C3S, C2S, C3A, and C4AF, were all found in the clinkers. Of the three types of eco-cements, the eco-cement A paste was most similar to ordinary Portland cement in terms of composition and compressive strength development, while the eco-cement B paste showed early strength development. The differential thermal analysis species analyses indicated that the hydrates in the eco-cement pastes were mainly calcium hydroxide and CSH gels, like those found in ordinary Portland cement paste. Moreover, the degree of hydration, as determined by nuclear magnetic resonance, increased in all eco-cement pastes with an increasing curing age. The results indicate that it indeed is feasible to use sludge ash and ferrate to replace up to 20% of the mineral components of raw materials for cement.     

水泥对垃圾焚烧飞灰的固化处理试验研究

对垃圾焚烧飞灰的化学成分、重金属物质的含量及浸出浓度进行测试分析.结果表明,飞灰中Pb和Cr等重金属物质浸出量超过浸出毒性标准,因而被认为是危险废物,必须进行固化处理.还考察了水泥对焚烧飞灰中重金属物质固化的效果,研究表明当飞灰掺量适当时,重金属物质的固化效果良好.重金属物质通过物理固封、替代,沉淀反应和吸附等形式可固化进水泥水化产物结构中.     

Hydration Properties of Eco-Cement Pastes from Waste Sludge Ash Clinkers

Abstract

Three types of hydraulic cements have been developed by incorporating sludge ash from a primary sewage treatment plant and a water purification plant, as well as slag from steelworks (ferrate), as a partial replacement for clay, silica, alumina, and iron oxide in raw cement meal. The raw meal for the pre-determined recipes was prepared by heating it to 1400 °C for 6 hr in a clinkerization process, using a simulated incinerator and smelter. The major components of ordinary Portland cement, C₃S, C₂S, C₃A, and C₄AF, were all found in the clinkers. Of the three types of eco-cements, the eco-cement A paste was most similar to ordinary Portland cement in terms of composition and compressive strength development, while the eco-cement B paste showed early strength development. The differential thermal analysis species analyses indicated that the hydrates in the eco-cement pastes were mainly calcium hydroxide and CSH gels, like those found in ordinary Portland cement paste. Moreover, the degree of hydration, as determined by nuclear magnetic resonance, increased in all eco-cement pastes with an increasing curing age. The results indicate that it indeed is feasible to use sludge ash and ferrate to replace up to 20% of the mineral components of raw materials for cement.     

高铝粉煤灰提取氧化铝后硅钙渣用作水泥混合材

为了使高铝粉煤灰提取氧化铝后所产生的硅钙渣被大量的用作水泥混合材,通过水泥强度、水化放热和干缩性实验研究了原状硅钙渣和脱碱硅钙渣对水泥强度和稳定性的影响。结果表明,当硅钙渣掺量达30%时,硅钙渣水泥强度仍可满足P·C 32.5水泥要求。且随硅钙渣掺入量的增加,水泥早期水化放热速率增加的同时水泥累计水化放热量和干缩率还会显著降低。与原状硅钙渣相比,在同等掺量的情况下,脱碱硅钙渣更有利于保持水泥强度,降低其水化热和改善干缩性。     

垃圾焚烧飞灰浸出特性及固化试验的研究

垃圾焚烧飞灰残留有重金属元素和二恶英等物质而被认为是危险废物,必须对之进行稳定化处理.通过试验研究分析了国内首家自主开发成功的广东省东莞市某回转窑垃圾焚烧发电厂垃圾焚烧飞灰的化学成分及矿物组成,研究了飞灰的浸出毒性,考察了水泥固化焚烧飞灰的效果,并与熔融/玻璃固化进行了比较.研究表明,该焚烧飞灰中重金属Cd的浸出毒性严重超标,并且随pH值的减小而增大,水泥固化效果随龄期的增大而更加显著.熔融/玻璃固化的效果优于水泥固化,但其经济性有待提高.     

垃圾焚烧飞灰综合利用研究进展

焚烧处理是解决日益增长生活垃圾的有效方法。垃圾焚烧产生的飞灰因含有大量的重金属等污染物而属危险废物 ,目前常采用的处理方法是填埋。本文就垃圾飞灰的综合利用研究现状进行了论述。从环境和技术的角度看 ,垃圾飞灰的预处理、水泥固化和玻璃化是目前飞灰综合利用的主要研究方向     

流化床锅炉飞灰活性激发与建材利用的试验研究

流化床锅炉飞灰活性较差,常规的粉煤灰活性激发方法对该飞灰效果不佳.本研究采用了加入适当激发剂的方法激发其活性,结果表明,加入激发剂后水泥胶砂的早期抗折、抗压强度均有100%的增长,后期抗折强度提高约100%、抗压强度提高60%以上,凝结时间和安定性均符合要求.水泥中飞灰掺量达40%时,其胶砂各龄期强度均达到甚至超过了42.5R水泥的强度;飞灰掺量65%～75%时,胶砂强度显示仍可生产一些低强度要求的建材产品,如砌筑水泥、建筑砂浆等.采用XRD、SEM等微观测试手段对飞灰活性激发机理进行了探讨.     

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.     

基于响应面法的污泥快速固化效能综合影响简

针对现有污泥固化技术存在的固化养护时间长、低温条件下固化效能低等问题。研究提出污泥快速（3 d）固化技术,采用响应曲面分析方法,重点考察了石灰、组分A、硅酸盐水泥、粉煤灰和温度等5因素对固化效能的综合影响,研究结果表明,石灰、组分A、硅酸盐水泥、粉煤灰和养护温度等因素对3 d固化体的无侧限抗压强度和含水率的线性效应显著,石灰和组分A、石灰和养护温度对无侧限抗压强度的交互影响显著,石灰和粉煤灰、组分A和养护温度、硅酸盐水泥和粉煤灰对含水率的交互影响显著;得出了5因素对固化体3 d无侧限抗压强度和含水率影响的定量模型,可对污泥快速固化进行优化和预测;并利用XRD和SED对污泥固化块的化学成分和微观结构进行了分析。     

Immobilization of antimony waste slag by applying geopolymerization and stabilization/solidification technologies

During the processing of antimony ore by pyrometallurgical methods, a considerable amount of slag is formed. This antimony waste slag is listed by the European Union as absolutely hazardous waste with a European Waste Catalogue code of 10 08 08. Since the levels of antimony and arsenic in the leachate of the antimony waste slag are generally higher than the landfilling limits, it is necessary to treat the slag before landfilling. In this study, stabilization/solidification and geopolymerization technologies were both applied in order to limit the leaching potential of antimony and arsenic. Different combinations of pastes by using Portland cement, fly ash, clay, gypsum, and blast furnace slag were prepared as stabilization/solidification or geopolymer matrixes. Sodium silicate–sodium hydroxide solution and sodium hydroxide solution at 8 M were used as activators for geopolymer samples. Efficiencies of the combinations were evaluated in terms of leaching and unconfined compressive strength. None of the geopolymer samples prepared with the activators yielded arsenic and antimony leaching below the regulatory limit at the same time, although they yielded high unconfined compressive strength levels. On the other hand, the stabilization/solidification samples prepared by using water showed low leaching results meeting the landfilling criteria. Use of gypsum as an additive was found to be successful in immobilizing the arsenic and antimony.

ImplicationsDespite the wide use of antimony for industrial purposes, disposal options for an antimony waste such as slag from thermal processing of antimony ore were not reported in the existing literature. This study aimed to develop a disposal strategy for the hazardous antimony waste slag. The findings of this study would contribute to understand the immobilization mechanisms of antimony and arsenic and will also be of interest to the owners of the antimony ore processing plants and to researchers investigating the efficiency of stabilization/solidification and geopolymerization technologies.     

添加垃圾焚烧飞灰冷固小球的工业烧结实验

将垃圾焚烧飞灰添加进烧结冷固球团配料进行造球,对冷固小球的成分及强度进行分析,结果表明,添加垃圾焚烧飞灰冷固小球化学组成稳定,重金属浸出毒性远低于危险废物鉴别标准,落下强度较基准期略微降低,但符合运输、贮存的要求.并对添加了飞灰的冷固小球对其后续烧结、冶炼工序的影响进行分析,结果表明,用添加飞灰的冷固小球进行烧结所得烧结矿的转鼓强度、落下强度及常规化学成分较基准期没有太大变化,添加飞灰进行造球、烧结,对其后续冶炼工序的顺行几乎没有影响,所带来的额外的环境污染微乎其微.     

One-part alkali-activated slag binder for cemented fine tailings backfill: proportion optimization and properties evaluation

In this study, a one-part alkali-activated slag (AAS) composed of ground-granulated blast furnace slag, desulfurized gypsum, and hydrated lime is proposed as alternative to cement for the production of cemented fine tailings backfill (CFTB), which is an environmentally friendly binder consisting of 93.72 wt.% industrial solid waste. Results show that AAS with 67.83 wt.% slag, 25.92 wt.% desulfurized gypsum, and 6.25 wt.% hydrated lime yields the highest strength, which is 1.7–3.2 times that of ordinary Portland cement (OPC). Aside from calcium silicate hydrate gel, appreciable quantity of ettringite characterized by interlocking needles structure and high bound water is also produced during the AAS hydration process. In addition, the hydration heat of the AAS binder is 48% less than that of OPC. Moreover, CFTB made of AAS provides better workability than that of CFTB with OPC up to 20 h. The findings of this study will contribute to the production of more cost-effective, durable, and environmental-friendly cemented fine tailings backfill.

     

地聚合材料固化处理垃圾焚烧飞灰

以垃圾焚烧飞灰和高岭土为主要原料,氢氧化钾为碱激活剂制备了地聚合材料,当焚烧飞灰的掺加量在70%时,其28 d抗压强度可达19.36 MPa。重金属浸出实验表明,地聚合物材料对垃圾焚烧飞灰中的重金属有明显的固化效果,在28 d时基本无溶出。SEM结果表明,地聚合材料的断面结构与力学性能和固化效果相关,XRD和FTIR的分析结果表明,焚烧飞灰和高岭土在碱的激发下生成新的硅铝酸盐聚合物,所得地聚合材料为无定形态。     

基于响应面法的污泥快速固化效能综合影响

针对现有污泥固化技术存在的固化养护时间长、低温条件下固化效能低等问题。研究提出污泥快速（3d）固化技术,采用响应曲面分析方法,重点考察了石灰、组分A、硅酸盐水泥、粉煤灰和温度等5因素对固化效能的综合影响,研究结果表明,石灰、组分A、硅酸盐水泥、粉煤灰和养护温度等因素对3d固化体的无侧限抗压强度和含水率的线性效应显著,石灰和组分A、石灰和养护温度对无侧限抗压强度的交互影响显著,石灰和粉煤灰、组分A和养护温度、硅酸盐水泥和粉煤灰对含水率的交互影响显著;得出了5因素对固化体3d无侧限抗压强度和含水率影响的定量模型,可对污泥快速固化进行优化和预测;并利用XRD和SED对污泥固化块的化学成分和微观结构进行了分析。     

固体废弃物对新拌水泥浆体密实度与强度的影响

研究固体废弃物(石灰石粉、粉煤灰、赤泥和矿渣)作掺合料颗粒体系与新拌浆体填充密实性能的关系;分析了在水胶比为0.3时,以上4种固体废弃物以不同比例等质量取代水泥的净浆强度。实验结果表明,石灰石粉、粉煤灰、赤泥作为掺合料,能够改善胶凝材料的颗粒级配,填充新拌水泥浆体中的孔隙,使浆体更为密实,并且对其净浆的强度有利。     

Chlorobenzenes removal from municipal solid waste incineration fly ash by surfactant-assisted column flotation

The organic contaminants in municipal solid waste incineration (MSWI) fly ash, including chlorinated aromatic compounds and polycyclic aromatic hydrocarbons, have high toxicity and a potential negative impact on the environment. An effective and low energy consumption technique to remove the organic contaminants from MSWI fly ash is required urgently. Organic contaminants, such as chlorobenzenes (CBzs), in MSWI fly ash are known to become enriched in the unburnt carbon (UC) fraction. It is proposed that removal of UC from fly ash will result in the effective removal of most organic micropollutants. In this research, we use a technique of surfactant-assisted column flotation to decontaminate MSWI fly ash by removal of the CBzs-enriched UC from MSWI fly ash. We find that 39.8% of CBzs can be removed from fresh MSWI fly ash with 61.7% UC removal efficiency, whereas only 33.2% of CBzs can be removed from weathered MSWI fly ash with a low UC removal efficiency of 33.7%. By adding a mixture of two kinds of surfactants: sorbitan mono-oleate and polyoxyethylene (20) sorbitan mono-oleate to the weathered fly ash, 47.0% of CBzs were removed at the hydrophile lipophile balance value of 13.5, while the UC removal efficiency increased to 49.0%. The results show that surfactants can enhance CBzs and UC removal efficiencies during the column flotation process. Higher CBzs and UC removal efficiencies can be expected by further optimizing the conditions of surfactant-assisted column flotation.     

Strength development of solidified/stabilized organic waste and optimum treatment design

Artificially contaminated (spiked) natural soils were solidified/stabilized using various combinations of commonly used additives, such as lime, cement, fly ash, activated carbon, and silica fume. The effectiveness of the solidification/stabilization (S/S) processes was evaluated based on experimental findings from compaction testing, unconfined compressive shear strength, and X-ray diffraction (XRD). Correlations of limited reliability between unconfined compressive strength and penetrometer and torvane measurements were derived. Results from XRD experiments indicated that certain organic contaminants (i.e., naphthalene and pyrene) might impact the S/S processes for a given combination of additives. The type and amount of organic contaminants also affected the pozzolanic reactions. Specifically, the absence or small peak intensity of pozzolanic product XRD patterns for a given combination of additives was a good indication that the type and the amount of organic contaminant present inhibited pozzolanic reactions. This phenomenon was tested and confirmed for actual field-contaminated samples.     

Influence of thermally activated paper sludge on the behaviour of blended cements subjected to saline and non-saline environments

Background, aim and scope  One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods  Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results  Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion  SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions  The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives  Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.