The effect of accelerated carbonation on the properties of cement-solidified waste forms

Ordinary Portland cement blended with blast furnace slag and pulverised fuel ash was used to solidify two industrial wastes containing large amounts of metals. The solidified mixes were carbonated using an accelerated regime previously established and compared for strength development, leaching characteristics and phase development against their non-carbonated analogues. A significant difference in the immobilisation of metals such as Zn, Ni and As was recorded for samples in which carbonation was optimised. The work has shown that by controlling mix parameters it is possible to improve the immobilisation of specific metals. Electron microanalysis showed that this is partly due to the precipitation of calcite in the solidified waste pore structure. Carbonation was also found to accelerate C₃S hydration in all carbonated samples and to modify the morphology of residual cement grains through the formation of a calcite coating over de-calcified hydration rims. Some metals appear to be incorporated in both of these zones.     

Stabilization of chloro-organics using organophilic bentonite in a cement-blast furnace slag matrix.

The application of cement-based stabilisation/solidification treatment to organic-containing wastes is made difficult by the adverse effect of organics on cement hydration. The use of organophilic clays as pre-solidification adsorbents of the organic compounds can reduce this problem because of the high adsorption power of these clays and their compatibility with the cementitious matrix. This work presents an investigation of the effect on hydration kinetics, physico-mechanical properties and leaching behaviour of cement-based solidified waste forms containing 2-chlorophenol and 1-chloronapthalene adsorbed on organophilic bentonites. These were prepared by cation exchange with benzyldimethyloctadecylammonium chloride and trimethyloctadecylammonium chloride. The binder was a 30% pozzolanic cement, 70% granulated blast furnace slag mixture. Several binder-to-bentonite ratios and different concentrations of the organics on the bentonite were used. Kinetics of hydration were studied by measurement of chemically bound water and by means of thermal and calorimetric analyses. Microstructure and other physico-mechanical properties of the solidified forms were studied by means of mercury intrusion porosimetry, scanning electron microscopy and unconfined compressive strength measurement. Leaching was checked by two different leaching tests: one dynamic, on monolithic samples, and the other static, on powdered samples. This study indicates that the incorporation of the organic-loaded bentonite in the binder matrix causes modifications in the hardened samples by altering cement hydration. The effects of the two organic contaminants are differentiated.     

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique.     

Treatment of organic-contaminated industrial wastes using cement-based stabilization/solidification—II. Microstructural analysis of the organophilic clay as a pre-solidification adsorbent

In the preceding paper detailed microstructural studies were presented of some fundamental aspects of the interactions of two organic compounds on a cement matrix. Organophilic clays are now attracting increasing attention as potential presolidification adsorbents to reduce adverse organic-cement interactions in solidification/stabilization (S/S) systems. This paper presents extensive microstructural studies of interactions between an organophilic clay, containing adsorbed organic wastes, and a cement matrix. Such interactions must be as fully understood as possible if the long-term integrity of the organophilic clay/cement mixes, in whatever formulation, is to be assured in S/S applications.A range of mixes was made up with the objective of characterizing the interaction of the organophilic clay with phenolic compounds and cement using microstructural methods. This approach was adopted in order to enable essential comparisons to be made between clay-containing and clay-free S/S mixes, using the same organics in both cases. Microstructural studies of organic-free cement/clay mixes showed that the presence of the clay caused an inhibition of the initial ettringite formation, up to seven days, but once ettringite had begun to form it increased to 140% of that in OPC paste at 28 days. Scanning electron microscopy (SEM) micrographs showed that the whole fracture surface was covered with a mat of needle shaped crystals approximately 1 μm in length. These results indicated that the incorporation of clay into the cement matrix may cause the strength reduction observed in macrostructural studies by altering the cement hydration reaction. Microstructural analysis of the solidified (post-adsorption) 3-chlorophenol showed that its detrimental effects on the cement hydration reaction were minimized, provided that the maximum adsorption capacity of the clay was not exceeded.     

Immobilization of radioactive waste by cementation with purified kaolin clay

A study is undertaken to determine the waste immobilization performance of low-level wastes in cement-clay mixtures. Liquid low-level wastes are precipitated using chemical methods, followed by solidification in drums. Solidification is done using cementation processes. Long-term leaching rates of the radionuclides are used as indicators of immobilization performance of solidified waste forms. In addition to evaluating the effects of kaolin clay on the leaching properties of the cemented waste forms, the effect of addition of kaolin on the strength of the cemented waste form is also investigated. The long term leaching tests show that inclusion of kaolin in cement reduces the leaching rates of the radionuclides significantly. However, clay additions in excess of 15 wt.% causes a significant decrease in the hydrolytic stability of cemented waste form. It is found that the best waste isolation, without causing a loss in the mechanical strength, is obtained when the kaolin content in cement is 5%.     

Study of the treatment effectiveness of a solidification/stabilization process for waste bearing heavy metals

The sludge from a steel processing unit bearing zinc, lead, iron, and manganese was solidified with ordinary Portland cement. The waste was stabilized in the specimens with a waste/binder ratio range of 0.16–4.0. On the basis of the available leaching and unconfined compressive strength, the performance of the solidified/stabilized waste was compared for different numbers of curing days. It was found that curing up to 28 days resulted in a performance improvement, as shown by less leaching of heavy metals and the increased unconfined compressive strength of the specimen. The treatment effectiveness of the solidification/stabilization process was assessed for the metals Pb, Zn, Fe, and Mn, and was found to be 89%, 95%, 74%, and 90%, respectively, for an optimum ratio of 4.0 after 28 days of curing.     

An alternative method for the treatment of waste produced at a dye and a metal-plating industry using natural and/or waste materials.

The aim of this study was to develop cost-effective, appropriate solidification technologies for treating hazardous industrial wastes that are currently disposed of in ways that may threaten the quality of local groundwater. One major objective was to use materials other than cement, and preferably materials that are themselves wastes, as the solidification additives, namely using wastes to treat wastes or locally available natural material. This research examines the cement-based and lime-based stabilization/solidification (S/S) techniques applied for waste generated at a metal-plating industry and a dye industry. For the lime-based S/S process the following binder mixtures were used: cement kiln dust/ lime, bentonite/lime and gypsum/lime. For the cement-based S/S process three binder mixtures were used: cement kiln dust/cement, bentonite/cement and gypsum/cement. The leachability of the wastes was evaluated using the toxicity characteristic leaching procedure. The applicability and optimum weight ratio of the binder mixtures were estimated using the unconfined compressive strength test. The optimum ratio mixtures were mixed with waste samples in different ratios and cured for 28 days in order to find the S/S products with the highest strength and lowest leachability at the same time. The results of this work showed that the cement-and lime-based S/S process, using cement kiln dust and bentonite as additives can be effectively used in order to treat industrial waste.     

Treatment of organic-contaminated industrial wastes using cement-based stabilization/solidification—I. Microstructural analysis of cement-organic interactions

The major deficiencies in cement-based stabilization/solidification (S/S) processes are their inability to treat inorganic wastes contaminated with organic material or organic wastes. In general, organic compounds are poorly retained in a cement matrix and frequently have a detrimental, poorly understood, effect upon cement hydration and strength development. These interactions need to be understood as fully as possible, however, if S/S processes are to be developed in ways which will assure the long-term integrity of the resultant products.The work presented in this paper investigates some fundamental aspects of the interactions of two organic compounds, 3-chlorophenol and chloronaphthalene, with a cement matrix. Phenolic compounds have previously been shown to have a detrimental effect upon the macrostructural properties of ordinary Portland cement (OPC), for example, the strength, setting rate and leachability (Montgomery et al. 1988). Microstructural studies in this work have shown that 3-chlorophenol inhibits the hydration of tricalcium silicate (C₃S in cement chemists' notation), with up to 90% of the C₃S remaining after 28 days for highly dosed 3-chlorophenol/OPC samples. The formation of ettringite was found to be increased by the presence of 3-chlorophenol and its conversion to monosulphate inhibited. Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis of the samples showed that 3-chlorophenol crystallized in the cement matrix to form discrete crystals containing calcium and phenol. In contrast, chloronaphthalene had no observable effect on hydration reactions. In a subsequent paper, detailed studies will be presented showing how these deleterious effects can be minimized by the use of organophilic clays as a pre-solidification adsorbent.     

Evaluation of the homogeneity of stabilised/solidified wastes by a video imaging technique

A video imaging technique is described for the homogeneity assessment of wastes that have been treated by stabilisation/solidification (S/S). The method incorporates a fluorescent tracer into the S/S reagent. A test “waste” consisting of an artificial soil was stabilised/solidified with varying degrees of mixing using Portland cement as the S/S reagent. The tracer distribution was monitored with a video camera, and the cement distribution was determined by chemical analysis for calcium. Measurement of the homogeneity of the products by the video imaging technique gave results comparable to those obtained by the chemical analysis. The results warrant use of the video imaging technique in field applications since it is easier, cheaper and faster than traditional chemical methods.     

铬渣水泥固化体稳定性研究

采用水泥固化的方法对铬渣进行处理。在水泥与铬渣、砂、水、硅酸钠的质量比为1：0．6：0．45：0．15：0．1时固化效果较好。固化体经28d的养护后,表面Cr^6 的浸出率为10^-5数量级,即使破碎至5mm以下的粒度,其Cr^6 的浸出质量浓度仍在国家标准以下。模拟酸溶试验和固化体抗压强度测试结果表明,固化体用于填埋是长期安全的。     

Solidification/stabilisation of air pollution control residues using Portland cement: Physical properties and chloride leaching

Portland cement (CEMI) was used to solidify air pollution control (APC) residues from an energy-from-waste plant burning municipal solid waste. APC residue/CEMI mixes were prepared with CEMI additions ranging from 0 to 50 weight% (wt%) of total dry mass and water/solids ratios between 0.40 and 0.80. Isothermal conduction calorimetry was used to assess the effect of APC residues on the hydration of CEMI. Although up to 30wt% additions of APC residues accelerated CEMI hydration, the total heat of hydration during the initial 98h was significantly reduced. Higher levels of APC residues severely inhibited CEMI hydration. The consistence, setting time, compressive strength, porosity and chloride leaching characteristics of the solidified products were determined. As might be expected, increasing the CEMI addition and reducing the water content resulted in increased compressive strengths. All mixes achieved compressive strengths greater than 1MPa at 7 and 28days but only 50wt% samples did not show significant strength reduction when tested after immersion in water. Monolithic leaching tests indicated low physical immobilisation of chloride in the CEMI solidified APC residues, with chloride leaching in excess of relevant UK landfill waste acceptance criteria (WAC). The results of this study show that greater than 50% CEMI additions would be required to effectively treat APC residues to meet current WAC limits.     

Examination of the influence of dissolved halite (NaCl) on the leaching of lead (Pb) from cement-based solidified wastes

The leaching of lead from cement-based solidified waste forms mixed at different water/cement ratios was studied by conducting equilibrium and semi-dynamic leaching tests using deionized water and sodium chloride solutions. The results suggest that leaching of the primary constituents of the cement (calcium, silicon and sulfate) is controlled by solubility equilibria, with increased leaching into chloride solutions due to ionic strength effects. The original porosity of the waste forms increased with water/cement ratio and chloride solutions further increased it as a result of decalcification. Lead leaching was generally low, and appears to be a transport-controlled process, such that leaching correlates positively with porosity.     

Optimization of cement-based stabilization/solidification of organic-containing industrial wastes using organophilic clays

The treatment of organically contaminated industrial wastes by cement-based stabilization/solidification has, in the past, been restricted by the detrimental effect of organic compounds on cement hydration. This work investigates the use of organophilic clays as adsorbents for the organic components of industrial wastes prior to conventional cement-based solidification. Three industrial wastes containing between 2–12% organic carbon and trace heavy metal contamination were treated with a quaternary ammonium salt exchanged clay. The organic component of all three wastes was well adsorbed by the clay. Solidification of the waste/clay mixes produced a monolithic mass with adequate strength and very low leaching of either the organic compounds or the metals. This study has shown that organophilic clays can act as successful adsorbents for the organic contaminants of industrial wastes and enable them to be treated by cement-based solidification.     

Stabilization/solidification of MSW incineration residues from facilities with different air pollution control systems. Durability of matrices versus carbonation

This paper discusses the stabilisation/solidification process with Portland cement applied to municipal solid waste incineration residues. Two types of residues were considered: fly ash (FA) produced in an electrostatic precipitator, and air pollution control (APC) residues from a semi-dry scrubber process. Cement pastes with different percentages of FA and APC residues were characterised according to their physical properties, the effect of the hydration products and their leaching behaviour. Portland pastes prepared with APC residues showed a rapid setting velocity in comparison with setting time for those pastes substituted with FA residues. Portland cement hydration was retarded in FA pastes. Leaching test results showed that heavy metals (such as Zn, Pb and Cd) and sulphates are immobilised within the paste, whereas chlorides are only partially retained. The carbonation process increases the leachability of S04(2-) and heavy metals such as Zn and Cr.     

Cement-clay pastes for stabilization/solidification of 2-chloroaniline

Immobilization of a model liquid organic pollutant, i.e. the 2-chloroaniline (2-CA), into a cement matrix using organoclays as pre-sorbent agents was investigated. Five cement-clay pastes were prepared with different nominal water-to-cement ratios (w/c=0.40, 0.25 and 0.15 wt/wt) and various amounts of waste (waste-to-cement o/c=0.20, 0.60 and 1.00 wt/wt); for comparison, a neat cement paste was also prepared. Dynamic leach tests were performed on solidified monoliths in order to assess the successful immobilization of the 2-CA. In monoliths at constant w/c ratio (0.40) the total amount of pollutant released increases with its initial content, and ranges from 15 to 35% with respect to it. By lowering w/c from 0.40 to 0.15 at constant o/c, the performances improved (<25% released). The microstructure of the hardened cement-clay pastes was characterized by quantitative X-ray diffraction (QXRD) and electronic microscopy (SEM-EDS) techniques; hydration degree was estimated by means of thermogravimetric analysis (TGA) in addition to QXRD. No evidence of any chemical reaction between 2-CA and cement phases was found. Moreover, it was shown that the most important factors affecting the cement hydration process were the total water content, i.e. the one taking also into account the water contained in the wet polluted clay, and the amount of 2-CA not firmly sorbed by the organoclay, and then freely dispersed in the paste.     

The influence of mix parameters and binder choice on the carbonation of cement solidified wastes

This paper explores the kinetics of carbonation of cement-based solidified hazardous waste. This study is part of a wide investigation into the effects of carbonation on solidified waste forms. Two commercially produced heavy metal wastes were solidified with three different types of Portland cement and two mineral admixtures and carbonated under controlled conditions. Measurements of the uptake of carbon dioxide were made for the different mixes and areas showing the degree of carbonation for each cement system were defined. The effects of water/binder ratio, waste and binder type on both total uptake of carbon dioxide and rate of carbonation were investigated and are discussed.     

Heavy metal leaching from hydroxide, sulphide and silicate stabilised/solidified wastes

A synthetic, mixed-metal solution has been stabilised by treatment with sodium hydroxide, sodium sulphide, and sodium silicate, respectively. The three stabilised filter cakes have subsequently been solidified using additions of ordinary Portland cement and pulverised fuel ash (PFA) which are typically used in UK solidification operations. Both the stabilised filter cakes and the solidified wastes have been subjected to an equilibrium extraction test, a modified TCLP test, and a series of single-extraction, batch leach tests using an increasingly acidic leachant. Metal release was found to be primarily dependent on the pH of the leachate. Under mildly acidic conditions, the percentages leached from the stabilised and the stabilised/solidified wastes were comparable for most metals. A high-volume fraction of these solidified wastes is occupied by the stabilised filter cake. When they are broken up and tested in single-extraction leach tests, the primary effect of the cementitious additives is to increase the pH of the leachate so that most heavy metals remain insoluble. When tested under acidic leachate conditions, copper, lead, and mercury were found to be particularly well retained within sodium sulphide stabilised wastes. Under similar test conditions, cadmium was leached at very low levels from the sodium silicate stabilised waste.     

Cement solidification of simulated off-gas condensates from vitrification of low-level nuclear waste solutions

Solidification in a cementitious matrix is a viable alternative for low-level nuclear waste management; it is therefore important to understand the behavior and properties of such wasteforms. We have examined the cementitious solidification of simulated off-gas waste streams resulting from the vitrification of low-level nuclear waste. Different possible methods for scrubbing the off-gasses from a vitrifier give rise to three possible types of waste compositions: acidic (from aqueous dissolution of volatile NOx and POx carried over from the vitrifier), basic (from neutralizing the former with sodium hydroxide), and fully carbonated (arising from a direct-combustion vitrifier). Six binder compositions were tested in which ordinary Portland cement was replaced at different proportions by fly ash and/or ground granulated blast furnace slag. A high solution to binder ratio of 1l/1 kg was used to minimize the volume of the wasteform and 10% attapulgite clay was added to all mixes to ensure that the fresh mix did not segregate prior to setting. The 28-day compressive strengths decreased when a high proportion of cement was replaced with fly ash, but were increased significantly when the cement was replaced with slag. The heats of hydration at early age for the various solids compositions decreased when cement was replaced with either fly ash or slag; however, for the fly ash mix the low heat was also associated with a significant decrease in compressive strength. High curing temperature (60 degrees C) or the use of extra-fine slag did not significantly affect the compressive strength. Recommendations for choice of binder formulations and treatment of off-gas condensates are discussed.     

Strength, leachability and microstructure characterisation of Na2SiO3-activated ground granulated blast-furnace slag solidified MSWI fly ash.

The chemical composition and the leachability of heavy metals in municipal solid waste incinerator (MSWI) fly ash were measured and analysed. For the leachability of unstabilized MSWI fly ash it was found that the concentrations of Pb and Cr exceeded the leaching toxicity standard. Cementitious solidification of the MSWI fly ash by Na2SiO3-activated ground granulated blast-furnace slag (NS) was investigated. Results show that all solidified MSWI fly ash can meet the landfill standards after 28 days of curing. The heavy metals were immobilized within the hydration products such as C-S-H gel and ettringite through physical encapsulation, substitution, precipitation or adsorption mechanisms.     

Microstructure of Portland cement pastes containing metal nitrate salts

In recent years, Backscattered Scanning Electron microscopy techniques (BSE), coupled with an image analysis system have been recognised as a powerful tool for quantitative analysis. This paper investigates the effect of metal additions (Ba, Cu, Ni, Zn, Cr(III), Pb and Cd) to Portland cement to produce a solidified product which meets the durability criteria quantified by the ratio of hydrated products and porosity. In addition, other indicators of the progress of cement hydration such as the bulk density and evaporable water of the solidified products were also measured. Metal concentrations of 0.1 and 1% per weight of cement at a constant water/cement ratio of 0.4 were examined. The same measurements were conducted on control samples of different water/ cement ratio. The results have shown that the control samples at different W/C ratio showed consistent trend in residual cement porosity, density and evaporable water content. It also showed that low dosage of metal nitrate additions can reduce cement hydration by up to 50% and at the same time reduce the observable porosity. Overall, this work has shown that Scanning Electron Microscopy (SEM) and image analysis are powerful tools and could be used to quantify the observable porosity and cement hydration in solidified systems.