Hydration reactions of cement combinations containing vitrified incinerator fly ash

One treatment option for municipal solid waste incinerator fly ash (IFA) is vitrification. The process yields a material containing reduced levels of trace metals relative to the original ash. The material is glassy and potentially suitable as a cement component in concrete. This paper examines the vitrification of an IFA and studies the hydration reactions of combinations of this vitrified material and Portland cement (PC). Isothermal conduction calorimetry, powder X-ray diffraction (XRD), thermogravimetry (TG) and scanning electron microscopy were employed to study the hydration reactions. As the levels of vitrified ash increase, the quantities of AFt phase produced decrease, whilst quantities of AFm phase increase, due to the reduced levels of sulfate in the vitrified ash. The levels of calcium silicate hydrate (CSH) gel (inferred from estimates of quantities of gel-bound water) remain constant at 28 days regardless of vitrified ash content, indicating that the material is contributing toward the formation of this product.     

Effects of Al2O3 on the hydration activity of municipal solid waste incinerator fly ash slag

This study investigates the effects of slag composition on the hydration activity of slag-blended cement (SBC) pastes. Synthetic slag samples were prepared by melting Al₂O₃-modified, municipal solid-waste incinerator (MSWI) fly ash. In addition to the original slag (containing 25.0% CaO and 17% Al₂O₃), two other synthetic slag types, A1 and A2 slag, were prepared, having a 15% or 5% Al₂O₃ content, respectively. These synthetic slags were blended with ordinary Portland cement (OPC) at weight ratios ranging from 10% to 40%. The results indicate that the incorporation of 10% A1 slag tended to enhance the degree of hydration in SBC pastes during the early ages (3-28 days), but at later ages, significant difference in the degree of hydration between the OPC and SBC pastes with 10% A1 slag was not observed. The tendency of the 10% A2 slag case was similar, but with a limited enhancement during the early ages (3-28 days). However, samples that incorporated the Al₂O₃-modified slag (AMS) showed decreased degrees of hydration. The degree of hydration of the 40% blend ratio sample decreased significantly.     

Compressive strength and hydration of wastepaper sludge ash-ground granulated blastfurnace slag blended pastes

Compressive strength and hydration characteristics of wastepaper sludge ash-ground granulated blastfurnace slag (WSA-GGBS) blended pastes were investigated at a water to binder (w/b) ratio of 0.5. The strength results are compared to those of normal Portland cement (PC) paste and relative strengths are reported. Early relative strengths (1 day) of WSA-GGBS pastes were very low but a marked gain in relative strength occurred between 1 and 7 days and this increased further after 28 and 90 days. For the 50% WSA-50% GGBS blended paste, the strength achieved at 90 days was nearly 50% of that of the PC control paste. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric (TG) analysis were carried out to identify the mineral components in the WSA and the hydration products of WSA and WSA-GGBS pastes. The principal crystalline components in the WSA are gehlenite, calcium oxide, bredigite and α′-C₂S (stabilised with Al and Mg) together with small amounts of anorthite and calcium carbonate and traces of calcium hydroxide and quartz. The α′-C₂S and bredigite, which phase separate from liquid phase that forms a glass on cooling, are difficult to distinguish by XRD. The hydration products identified in WSA paste are CH, C₄AH₁₃, C₃A.0.5CC?.0.5CH.H_11.5 and C-S-H gel plus possible evidence of small amounts of C₂ASH₈ and C₃A.3CS?.H₃₂. Based upon the findings, a hydration mechanism is presented, and a model is proposed to explain the observed strength development.     

Pozzolanic properties of reject fly ash in blended cement pastes

Low-grade fly ash (reject fly ash, r-FA), a significant portion of the pulverized fuel ash (PFA) produced from coal-fired power plants and rejected from the ash classifying process, has remained unused due to its high carbon content and large particle size. But it may be used in certain areas, such as in solidification and stabilization processes of hazardous waste and materials for road base or subbase construction, which require relatively lower strength and reactivity. It is therefore necessary to extend research on the properties of r-FA and explore its possible applications. This paper presents experimental results of a study on the mechanical and hydration properties of cementitious materials prepared by blending r-FA with ordinary Portland cement (OPC). Parallel mixes were also prepared with the good ash [i.e., classified fine fly ash (f-FA)] for comparison. Selective chemical activators were added to the mix to study the effects of the activators on the properties of the blend system. The results show that r-FA generally has a lower rate of hydration than f-FA particularly at the early stage of hydration. Adding Ca(OH)₂ alone almost had no effect on accelerating the hydration of r-FA. But adding a small quantity of Na₂SO₄ or K₂SO₄ together with Ca(OH)₂ significantly accelerated the hydration reaction. The results of the compressive strength measurement correlated nicely with the degree of hydration results. It was also found that water-to-binder ratio (w/b) was an important factor in affecting the strength development and the hydration degree of r-FA pastes.     

垃圾焚烧飞灰处置技术研究进展

系统介绍了垃圾焚烧飞灰处理技术和最新研究成果,阐述了垃圾焚烧飞灰处理技术一般可分为固化/稳定化技术和分离萃取技术两大类。其中固化/稳定化技术主要为水泥固化、热处理、化学药剂稳定化及水热处理技术;分离萃取技术主要为生物/化学提取和超临界流体萃取技术。分析了各项技术的优缺点,认为:水泥固化技术成本低,但增容过大;热处理技术有一定的减容效果,但能耗成本过高;化学药剂稳定化技术稳定化程度高,但较难实现多种重金属的同步固化;生物/化学提取技术反应条件温和,但成本较高;超临界流体萃取技术虽能有效实现重金属的回收利用,但其对设备要求过高;而水热处理技术的反应条件虽对设备有一定要求,但其无害化程度高,而且反应产物可以再利用。最后指出,水热法应该是未来具有较大应用潜力的飞灰处理方法。     

粉煤灰矿渣复合水泥强度协同效应的研究

研究了由粉煤灰、矿渣、钢渣与一定量熟料组成的粉煤灰矿渣复合水泥中各组分对水泥的强度协同效应以及影响协同效应的主要因素。并利用SEM和MIP等技术研究了粉煤灰矿渣复合水泥的水化硬化过程、水化产物相组成及硬化浆体结构,以此来论证各组分间协同效应的作用机理。研究结果表明:当各组分比例适当时,通过石膏和添加剂的有效作用,采取合理的粉磨工艺和制度,粉煤灰矿渣复合水泥各组分可以产生强度协同效应。     

Examination of the jarosite-alunite precipitate addition in the raw meal for the production of portland cement clinker

The aim of the present research work was to investigate the possibility of adding a jarosite-alunite chemical precipitate, a waste product of a new hydrometallurgical process developed to treat economically low grade nickel oxides ores, in the raw meal for the production of Portland cement clinker. For that reason, two samples of raw meals were prepared, one with ordinary raw materials, as a reference sample ((PC)_Ref) and another with 1% jarosite-alunite precipitate ((PC)_J/A). Both raw meals were sintered at 1450 °C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the jarosite-alunite precipitate did not affect the mineralogical characteristics of the so produced Portland cement clinker. Furthermore, both clinkers were tested by determining the grindability, setting time, compressive strength and expansibility. The hydration products were examined by XRD analysis at 2, 7, 28 and 90 days. The results of the physico-mechanical tests showed that the addition of jarosite-alunite precipitate did not negatively affect the quality of the produced cement.     

Replacement of raw mix in cement production by municipal solid waste incineration ash

The feasibility of municipal solid waste incineration (MSWI) ash utilized as the replacement of raw mix in cement production is investigated. Result shows that sieving, self-grinding, and magnet separation processes are necessary to remove the debris, salt, and metallic contents that existed in the MSWI ash. By using the pretreated MSWI ashes, the produced cement specimens were in compliance with the unconfined compression strength (UCS) standard in Taiwan at small replacement percentage (<5%). When ash replacement percentage is large (more than 10%), the strength development of specimens would be hindered due to the deficient formation of the calcium silicate. Calculation on lime saturation factor (LSF) also shows a descending trend in consequence of the increase in replacement percentage. Thus, compositional effect should be taken into consideration for promoting the calcium silicate formation at the case of large ash replacement. In this research, adjustment of chemical composition was achieved by adding 183 g calcium oxide per kilogram of cement raw mixture with 15% ash replacement. After adjustment, the produced cement could develop seven- and fivefold increase on UCS compared with those without calcium oxide supplement at 3 and 7 days of curing, respectively. Results concluded that the MSWI ash was suitable in reuse for cement production under a well-conditioned situation.     

Reactions of fly ash with calcium aluminate cement and calcium sulphate

The hydration processes in the ternary system fly ash/calcium aluminate cement/calcium sulphate (FA/CAC/C$) at 20 °C were investigated; six compositions from the ternary system FA/CAC/C$ were selected for this study. The nature of the reaction products in these pastes were analysed by X-ray diffraction (XRD) and infrared spectroscopy (FTIR). At four days reaction time, the main hydration reaction product in these pastes was ettringite and the samples with major initial CAC presented minor ettringite but calcium aluminates hydrates. The amount of ettringite developed in the systems has no direct relation with the initial components.     

Electrokinetic remediation of bottom ash from municipal solid waste incinerator

The electrokinetic remediation was studied to verify the possibility to reclaim the bottom ash from municipal solid waste incineration (MSWI). In Italy, a production of 1 million tons per year of this kind of residue has been estimated, 90% of which is still landfilled. This work shows the results of four electrokinetic remediation tests for the removal of Pb, Cu, Zn, Cd and chlorides, using an open cell with graphite electrodes and without enhancing agents. The four tests have, respectively, been performed at a constant current density of 0.89, 1.67, 2.04 and 2.48 mA cm⁻², with duration of 42, 68, 47 and 40 h. Heavy metals occur in ashes in various forms, such as exchangeable, adsorbed, precipitated, organically complexed and residual phases. In order to determine the nature of any given system, in terms of specific chemical species and pertaining mobilities, sequential extraction analyses have been performed. The release of pollutants was investigated for treated and untreated ash. After treatment, the concentration of pollutants in the leachate was reduced by 31-83%, better results being obtained for chlorides. Both the low amount of heavy metal extracted and the increase of ash pH during the electrokinetic tests, suggest to use enhancing agents or a cation exchange membrane at the cathode, to prevent the precipitation of metals as hydroxides.     

利用城市垃圾焚烧飞灰煅烧水泥熟料初探

针对垃圾焚烧飞灰化学组成上的特点,进行了利用垃圾焚烧飞灰烧制水泥熟料的探索研究,通过试验研究了其对水泥生料的易烧性、烧制的水泥熟料的力学性能和水化速率等的影响规律。研究结果表明,垃圾焚烧飞灰可以用作水泥原料从而有效地降低其处置成本,减少其对环境造成的二次污染,硬化水泥浆体水化28d时各重金属浸出量低于鉴别标准规定的指标,是一种有待开发的潜在的水泥原料资源。     

Use of municipal solid waste incineration fly ash in concrete

With a view of reducing the quantities to be landfilled, the Solvay Company has been working on the development of a new physicochemical treatment for municipal solid waste incineration (MSWI) fly ashes: the Revasol process. This process allows reducing the soluble fraction, fixing heavy metals and eliminating dioxins. This article reports on the characteristics of a treated ash and on its use in concrete. For the latter point, three characteristics were chosen: the compressive strength and the durability of the hardened concrete and its behavior to leaching. From mechanical and durable points of view, the ash incorporated in the concrete behaves like ordinary sand. The leaching tests carried out on the concrete confirm that the process makes it possible to obtain materials without major risks for the environment. Also, these results as a whole suggest that the use of waste in concrete constitutes a potential means of adding value.     

The influence of initial water curing on the strength development of ordinary portland and pozzolanic cement concretes

The effect of initial water-curing period on the strength properties of concretes was investigated. Three types of cement, one ordinary Portland cement (OPC) and two natural pozzolanic cements (blended and trass cements), were used in the concrete mixtures. Six different curing regimes were applied to the specimens, the first of which was continuous water storing, and the second continuous air storing. In the remaining four regimes, the specimens were stored under varying initial water-curing periods of 3, 7, 14, and 28 days, respectively. The compressive strength tests were carried out on the cubic specimens at the ages of 7, 14, 28, 90, and 180 days. The variation of compressive strength with time was evaluated by using a semilogarithmic function and the strength-gaining rates were calculated by using this equation for different curing conditions. It was found that poor curing conditions are more adversely effective on the strength of concretes made by pozzolanic cements than that of OPC, and it is necessary to apply water curing to the former concretes at least for the initial 7 days to expose the pozzolanic activity. However, when the pozzolanic cement concretes have sufficient initial curing, they can reach the strength of OPC concretes in reasonable periods of time.     

Hydration mechanisms of super sulphated slag cement

The hydration and the strength evolution of supersulphated cements (SSC) produced by the activation of two different ground granulated blast furnace slags with anhydrite and small amounts of an alkaline activator have been investigated. The main differences between the two mixtures are found to be the strength development, the dissolution rate of the slags, the amount and volume of the individual hydration products formed and the growth mechanisms of the ettringite. The chemical composition of the slag had a large influence on the amount of the hydrates formed and thus on the volume of the hydrated slag.Advancement of the amount of hydrates of a slag with low reactivity by adding aluminium sulphate and calcium hydroxide did increase the amount of ettringite. Nevertheless, the early compressive strength was not increased, but late strength shows a slow increase. It was concluded that the early compressive strength of an SSC using low reactive slag cannot be overcome by adding stoichiometric amounts of constituents which are used for the formation of a specific hydration product. The best way to increase early compressive strength is to increase the intrinsic dissolution rate.     

Hydration and properties of novel blended cements based on cement kiln dust and blast furnace slag

The aim of the present paper is to address the key technical issues pertaining to the utilization of cement kiln dust (CKD) as an activator for ground granulated blast furnace slag (GGBFS) to create nonconventional cementitious binders for concrete. The relatively high alkaline content of CKD is the predominant factor preventing its recycling in cement manufacture. However, it was observed that depending on the water-soluble alkali and sulfate compounds, CKD could provide the environment necessary to activate latent hydraulic materials such as GGBFS. Binary blends containing slag and CKDs from different sources were characterized and compared in terms of the rates of heat evolution and strength development, hydration products, and time of initial setting. A study of the effects of the influencing factors in terms of soluble alkali content, particle size, and free lime content was undertaken. The results confirm the dependence of the dissolution rate of slag on the alkalinity of the reacting system, and the importance of the optimum lime content on the rate of strength gain.     

医疗垃圾焚烧飞灰处理研究进展

介绍了水泥固化、熔融、氯化焙烧及分步浮选等几种飞灰处理技术,着重分析了各项技术应用于医疗飞灰的可行性及局限性。水泥固化法因飞灰中高含量的活性炭和氯盐会阻碍水泥的水化作用,使水泥掺量过高,该方法不适合;熔融处理因飞灰量小、高氯、高碳会引起耐火材料的侵蚀及石墨电极的烧损等不利影响,不适合采用电弧炉熔融处理。医疗垃圾焚烧飞灰适宜采用残余炭式熔融炉;鉴于医疗垃圾焚烧飞灰中氯含量较高,直接焙烧处理是分离重金属的有效方法;分步浮选法是针对飞灰中碳组分含量高且二英在碳组分中富集的特性,通过两步浮选分离医疗垃圾焚烧飞灰中二英和重金属等毒害物,同时可脱氯。     

A simple semiempiric model for NMR relaxometry data of hydrating cement pastes

In this contribution, results from NMR relaxometry experiments on hydrating white cement pastes are presented. Nonexponential effects are discussed and quantified by stretched-exponential analysis. From the magnetization decay curves in transverse relaxation experiments, the degree of hydration is estimated and a semiempiric model is proposed describing the relationship between the microstructure development in the hydrating cement and the degree of hydration.     

Liquid-phase self-diffusion in hydrating cement pastes — results from NMR studies and perspectives for further research

The changes in the pore structure of hydrating cement are accompanied by changes in the dynamics of liquid phases contained in the pore system of the hydrating matrix. Dynamic NMR methods (relaxometry, diffusometry) allow the non-destructive observation of these changes. Relaxometry can be performed using quite simple equipment and has been widely used in studies of the kinetics of cement hydration. Diffusion studies, by contrast, require much more sophisticated equipment. On the other hand, the diffusion coefficient has a direct relevance for the transport of moisture or contaminants in the cement matrix while relaxation time measurements provide more indirect information. The purpose of the present paper is to review the possibilities of field gradient NMR in diffusion studies on hydrating cement and to provide an outlook on how this information can be used for improving our understanding of the properties and microstructure of hydrating cement. As an example, new results on the relationship between the diffusive exchange length in the sample and non-exponential relaxation in cement are discussed at the end of the contribution.     

The influences of siliceous waste on blended cement properties

The influences of siliceous waste on the properties of fly ash and blast furnace slag cement were studied, and its optimum mixing amount in blended cement was determined. The strength, setting time, resistance to chemical attack, dry shrinkage, and impermeability of blended cement mixed with siliceous waste were also investigated by different experiments. The measurement of pore size distribution for hardened cement pastes made by Poremaster-60 was recorded and analyzed in this article.     

The leachability of heavy metals in hardened fly ash cement and cement-solidified fly ash

The effect of mix proportion, leachant pH, curing age, carbonation and specimen making method etc. on the leaching of heavy metals and Cr(VI) in fly ash cement mortars and cement-solidified fly ashes has been investigated. In addition, a method for reducing the leaching of Cr(VI) from cement-solidified fly ashes is proposed. The results mainly indicate that: (1) either Portland cement or fly ash contains a certain amount of heavy and toxic metals, and the leaching of them from hardened fly ash incorporated specimens exists and is increased with fly ash addition and water to cement ratio; (2) the leachability of some heavy metals is greatly dependent on leachant pH; (3) when carbonation of cement mortars occurs the leaching of chromium ions is increased; (4) the amount of heavy metals leached from cement-solidified fly ashes depends more on the kind of fly ash than their contents in fly ash; and (5) with ground granulated blast furnace slag addition, the leaching of Cr(VI) from solidified fly ashes is decreased.