Accelerated carbonation treatment of industrial wastes

The disposal of industrial waste presents major logistical, financial and environmental issues. Technologies that can reduce the hazardous properties of wastes are urgently required. In the present work, a number of industrial wastes arising from the cement, metallurgical, paper, waste disposal and energy industries were treated with accelerated carbonation. In this process carbonation was effected by exposing the waste to pure carbon dioxide gas. The paper and cement wastes chemically combined with up to 25% by weight of gas. The reactivity of the wastes to carbon dioxide was controlled by their constituent minerals, and not by their elemental composition, as previously postulated. Similarly, microstructural alteration upon carbonation was primarily influenced by mineralogy. Many of the thermal wastes tested were classified as hazardous, based upon regulated metal content and pH. Treatment by accelerated carbonation reduced the leaching of certain metals, aiding the disposal of many as stable non-reactive wastes. Significant volumes of carbon dioxide were sequestrated into the accelerated carbonated treated wastes.     

Effect of carbon dioxide injection on production of wood cement composites from waste medium density fiberboard (MDF)

The possibility of recycling waste medium density fiberboard (MDF) into wood-cement composites was evaluated. Both new fibers and recycled steam exploded MDF fibers had poor compatibility with cement if no treatment was applied, due to interference of the hydration process by the water soluble components of the fiber. However, this issue was resolved when a rapid hardening process with carbon dioxide injection was adopted. It appears that the rapid carbonation allowed the board to develop considerable strength before the adverse effects of the wood extractives could take effect. After 3-5 min of carbon dioxide injection, the composites reached 22-27% of total carbonation and developed 50-70% of their final (28-day) strength. Composites containing recycled MDF fibers had slightly lower splitting tensile strength and lower tensile toughness properties than those containing new fibers especially at a high fiber/cement ratio. Composites containing recycled MDF fibers also showed lower values of water absorption. Unlike composites cured conventionally, composites cured under CO(2) injection developed higher strength and toughness with increased fiber content. Incorporation of recycled MDF fibers into wood cement composites with CO(2) injection during the production stage presents a viable option for recycling of this difficult to manage waste material.     

Leaching of heavy metals from solidified waste using Portland cement and zeolite as a binder

This study investigated the properties of solidified waste using ordinary Portland cement (OPC) containing synthesized zeolite (SZ) and natural zeolite (NZ) as a binder. Natural and synthesized zeolites were used to partially replace the OPC at rates of 0%, 20%, and 40% by weight of the binder. Plating sludge was used as contaminated waste to replace the binder at rates of 40%, 50% and 60% by weight. A water to binder (w/b) ratio of 0.40 was used for all of the mixtures. The setting time and compressive strength of the solidified waste were investigated, while the leachability of the heavy metals was determined by TCLP. Additionally, XRD, XRF, and SEM were performed to investigate the fracture surface, while the pore size distribution was analyzed with MIP. The results indicated that the setting time of the binders marginally increased as the amount of SZ and NZ increased in the mix. The compressive strengths of the pastes containing 20 and 40wt.% of NZ were higher than those containing SZ. The compressive strengths at 28 days of the SZ solidified waste mixes were 1.2-31.1MPa and those of NZ solidified waste mixes were 26.0-62.4MPa as compared to 72.9MPa of the control mix at the same age. The quality of the solidified waste containing zeolites was better than that with OPC alone in terms of the effectiveness in reducing the leachability. The concentrations of heavy metals in the leachates were within the limits specified by the US EPA. SEM and MIP revealed that the replacement of Portland cement by zeolites increased the total porosity but decreased the average pore size and resulted in the better containment of heavy ions from the solidified waste.     

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.     

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.     

Modelling the effects of waste components on cement hydration

Ordinary Portland Cement (OPC) is often used for the solidification/stabilization (S/S) of waste containing heavy metals and salts. These waste components will precipitate in the form of insoluble compounds on to unreacted cement clinker grains preventing further hydration. In this study the long term effects of the presence of contaminants in solidified waste is examined by numerically simulating cement hydration after precipitation of metal salts on the surface of cement grains. A cement hydration model was extended in order to describe pore water composition and the effects of cement grain coating. Calculations were made and the strength development predicted by the model was found to agree qualitatively with experimental results found in literature. The complete model is useful in predicting the strength and leaching resistance of solidified products and developing solidification recipes based on cement.     

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.     

Production of lightweight aggregate from industrial waste and carbon dioxide

The concomitant recycling of waste and carbon dioxide emissions is the subject of developing technology designed to close the industrial process loop and facilitate the bulk-re-use of waste in, for example, construction. The present work discusses a treatment step that employs accelerated carbonation to convert gaseous carbon dioxide into solid calcium carbonate through a reaction with industrial thermal residues. Treatment by accelerated carbonation enabled a synthetic aggregate to be made from thermal residues and waste quarry fines. The aggregates produced had a bulk density below 1000 kg/m³ and a high water absorption capacity. Aggregate crushing strengths were between 30% and 90% stronger than the proprietary lightweight expanded clay aggregate available in the UK. Cast concrete blocks containing the carbonated aggregate achieve compressive strengths of 24 MPa, making them suitable for use with concrete exposed to non-aggressive service environments. The energy intensive firing and sintering processes traditionally required to produce lightweight aggregates can now be augmented by a cold-bonding, low energy method that contributes to the reduction of green house gases to the atmosphere.     

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.     

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.     

Effects of carbonation and leaching on porosity in cement-bound waste

Porosity is possibly an important parameter with respect to leaching of constituents from cement monoliths. During its lifetime, the pore structure of cementitious matrices changes due to carbonation and leaching. This paper discusses the effects of both accelerated carbonation and continuous leaching on the porosity, and, conversely, how porosity affects leaching properties. Two sample types are investigated: a mortar with MSWI-bottom ash substituting the sand fraction and a cement paste with 30 wt% of the cement substituted by a flue gas cleaning residue. The samples have been intensively carbonated in a 20% CO(2) atmosphere for up to 60 days and were subsequently leached. The porosity was investigated by mercury intrusion porosimetry. Accelerated carbonation decreases total porosity by 12% in the case of 60 days of treatment of bottom ash mortars, whereas continuous leaching during 225 days increases it by 16%. Both carbonation and leaching decrease the amount of smaller capillary pores. Carbonation decreases both porosity and pH. Decreasing porosity diminishes leaching of sodium and potassium, while the decrease in pH increases leaching. However, the former process dominates the latter, resulting in a net decreasing effect of carbonation on the release of sodium and potassium from these cement matrices.     

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.     

Hybrid cement-assisted dewatering,solidification and stabilization of sewage sludge with high organic content

Sewage sludge with high organic content is particularly difficult to dewater before disposal in landfill. In this study, different hybrid cement binders were investigated to evaluate their ability to dewater the sewage sludge with high organic content. After 7 days of stabilization, the CASC (Mayenite/Sulfoaluminate cement) hybrid binder showed an excellent efficiency on both water content reduction and strength development; the water content and unconfined compressive strength value of solidified sludge reached 52.43 % and 109.55 kPa, respectively, at 8 % binder/sludge mass rate. The horizontal vibration leaching test (HJ 557-2009) indicated that leachability of heavy metals of the CASC-solidified sludge was far lower than that of non-solidified sludge and CAPC-solidified sludge. Furthermore, SEM and XRD analyses suggested that certain hydrates formed in the solidification process might have accelerated the depletion of interstitial water and strength development in the CASC-solidified sludge.     

Utilization of bottom ash from the incineration of separated wastes as a cement substitute.

Waste incineration is still an essential technology in the concept of integrated waste management. Most of the combustion residues are incinerator bottom ash. It has been discovered that incinerator bottom ash from the incineration of separated waste in the primary chamber of the modular two-stage incinerator mainly consists of metal oxides, especially SiO2 and CaO, in proportions that are quite similar to those in cement and so the feasibility of its application as a substitute for cement in concrete was investigated. It was found that after 28 days, the flexural and compressive strengths of the binder using bottom ash were practically comparable with those of a pure cement mixture. The results show that it is reasonable to use a binder containing incinerator bottom ash for applications in which an early-stage lower strength of concrete element is acceptable.     

Physical and mechanical properties of cement-based products containing incineration bottom ash

This paper presents the results of a wider experimental programme conducted in the framework of the NNAPICS ("Neural Network Analysis for Prediction of Interactions in Cement/Waste Systems") project funded by the European Commission and a number of industrial partners under Brite-EuRamIII. Based on the fact that bottom ashes from waste incineration are classified as non-hazardous wastes according to the European Waste Catalogue, the aim of the present work was to investigate the feasibility of addressing the potential use of such residues in cement-based mixtures. This issue was suggested by the analysis of the properties of different bottom ashes coming from Italian municipal and hospital solid waste incinerators, which showed a chemical composition potentially suitable for such applications. Different mixes were prepared by blending bottom ash with ordinary Portland cement in different proportions and at different water dosages. The solidified products were tested for setting time and bulk density, unconfined compressive strength and evaporable water content at different curing times. The results of the experimental campaign were analysed through a statistical procedure (analysis of variance), in order to investigate the effect of mixture composition (waste replacement level and water dosage) on the product properties.     

Use of flue gas desulphurisation (FGD) waste and rejected fly ash in waste stabilization/solidification systems

Stabilization/solidification (S/S) processes have been used as the final treatment step for hazardous wastes prior to land disposal. Fly ash is a by-product of coal-fired power generation; a significant proportion of this material is low-grade, reject material (rFA) that is unsuitable as a cement replacement due to its high carbon content and large particle size (>45 microm). Flue gas desulphurization (FGD) sludge is a by-product from the air pollution control systems used in coal-fired power plants. The objective of this work was to investigate the performance of S/S waste binder systems containing these two waste materials (rFA and FGD). Strength tests show that cement-based waste forms with rFA and FGD replacement were suitable for disposal in landfills. The addition of an appropriate quantity of Ca(OH)2 and FGD reduces the deleterious effect of heavy metals on strength development. Results of TCLP testing and the progressive TCLP test show that cement-rFA-Ca(OH)2 systems with a range of FGD additions can form an effective S/S binder. The Leachability Index indicates that cement-based waste forms with rFA replacement were effective in reducing the mobility of heavy metals.     

Accelerated carbonation of steel slags in a landfill cover construction

Steel slags from high-alloyed tool steel production were used in a full scale cover construction of a municipal solid waste (MSW) landfill. In order to study the long-term stability of the steel slags within the final cover, a laboratory experiment was performed. The effect on the ageing process, due to i.e. carbonation, exerted by five different factors resembling both the material characteristics and the environmental conditions is investigated. Leaching behaviour, acid neutralization capacity and mineralogy (evaluated by means of X-ray diffraction, XRD, and thermogravimetry/differential thermal analysis, TG/DTA) are tested after different periods of ageing under different conditions.Samples aged for 3 and 10 months were evaluated in this paper. Multivariate data analysis was used for data evaluation. The results indicate that among the investigated factors, ageing time and carbon dioxide content of the atmosphere were able to exert the most relevant effect. However, further investigations are required in order to clarify the role of the temperature.     

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%.     

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.     

The effects of accelerated carbonation on CO2 uptake and metal release from incineration APC residues

This work presents the results of a study on accelerated carbonation of incinerator air pollution control residues, with a particular focus on the modifications in the leaching behaviour of the ash. Aqueous carbonation experiments were carried out using 100% CO₂ at different temperatures, pressures and liquid-to-solid ratios, in order to assess their influence on process kinetics, CO₂ uptake and the leaching behaviour of major and trace elements. The ash showed a particularly high reactivity towards CO₂, owing to the abundance of calcium hydroxides phases, with a maximum CO₂ uptake of ～250 g/kg. The main effects of carbonation on trace metal leaching involved a significant decrease in mobility for Pb, Zn and Cu at high pH values, a slight change or mobilization for Cr and Sb, and no major effects on the release of As and soluble salts. Geochemical modelling of leachates indicated solubility control by different minerals after carbonation. In particular, in the stability pH range of carbonates, solubility control by a number of metal carbonates was clearly suggested by modelling results. These findings indicate that accelerated carbonation of incinerator ashes has the potential to convert trace contaminants into sparingly soluble carbonate forms, with an overall positive effect on their leaching behaviour.