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.     

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.     

Stabilization/solidification of waste ferrous sulphate from titanium dioxide production by fluidized bed combustion product

A treatment procedure to allow the disposal of waste ferrous sulphate was developed. This waste contains sulphuric acid and originates from titanium dioxide production. The process is based on simultaneous neutralization and stabilization/solidification (S/S) of the waste by means of fluidized bed combustion product (FBC-P). The prepared stabilized waste specimens have a solid matrix and their batch leachates display practically neutral pH and also satisfactory conductivity values. The leachate composition is notable in its absence of toxic metals and even iron.     

Vitrification of electric arc furnace dusts

Electric arc furnace baghouse dust (EAFD), a waste by-product of the steelmaking process, contains the elements that are volatilized from the charge during the melting (Cr, Pb, Zn, Cu and Cd). The results of leaching tests show that the concentration of these elements exceeds the regulatory limits. Consequently, EAFD cannot be disposed of in ordinary landfill sites without stabilization of the heavy metals. In this work, the vitrification of EAFD, from both carbon and stainless steel productions, were studied. The vitrification process was selected as the inertizing process because it permits the immobilization of the hazardous elements in the glass network and represents an environmentally acceptable method for the stabilization of this waste. Classes of various compositions were obtained by mixing EAFD with glass cullet and sand. The EAFD and the glass products were characterized by DTA, TG, X-ray analysis and by the TCLP test. The results show that the stability of the product is influenced by the glass structure, which mainly depends on the Si/O ratio. Secondary crystallization heat-treatment were carried out on some samples. The results highlighted the formation of spinel phases, which reduced the chemical durability in acid media. The possibility to recover Zn from carbon steel production EAFD was investigated and about 60-70% of metal recovery was obtained. The resulting glass show higher chemical stability than glasses obtained without metal recovery.     

Prediction of unconfined compressive strength of cement paste containing industrial wastes

Neural network analysis was used to construct models of unconfined compressive strength (UCS) as a function of mix composition using existing data from literature studies of Portland cement containing real industrial wastes. The models were able to represent the known non-linear dependency of UCS on curing time and water content, and generalised from the literature data to find relationships between UCS and quantities of five waste types. Substantial decreases in UCS were caused by all wastes; except for EAF dust, the effect was nonlinear with the greatest decrease caused initially by approx. 12% plating sludge, 40% foundry dust, 58% other ash, and 72% MSWI fly ash by mass of dry product. It appears that the maximum waste additions used in modelling may approximate the practical limits of waste additions used in modelling may approximate the practical limits of waste addition to Portland cement, i.e., 50% plating sludge or EAF dust, 64% foundry dust, 92% other ash, and 85% MSWI fly ash by mass of dry product. The laboratory was found to be a key predictive variable and acted as a surrogate for laboratory-specific variables related to cement composition, strength and hardening class, product mixing and preparation details, laboratory conditions, and testing details. While the neural network modelling approach has been shown to be feasible, development of better models would require larger data sets with more complete information regarding laboratory-specific variables and waste composition.     

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.     

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.     

有色金属行业含砷废弃物处置技术的研究进展

介绍了有色金属行业中含砷废弃物的两种处理技术——资源化和稳定化-固化的研究进展。从含砷的烟灰、废水及废渣3个方向对资源化处理技术的研究进展进行了介绍,含砷废弃物经资源化处理后可得到As2O3和砷酸盐产品,但砷产品品种有限,应开发新的资源化途径和砷产品。此外,综述了含砷废弃物的稳定化-固化处置技术的研究进展,指出铁盐稳定化优于钙盐稳定化,特别是臭葱石形式的沉淀具有稳定性高、堆存时间长和无需再固化的优点;对比了包胶固化、火法固化及熔融固化3种固化技术的特点,其中水泥包胶固化法的成熟度较高,但仍有改进空间。     

Laboratory study on solidification/stabilization of unwanted medications using asphalt as a binder

The rise in discarded or unwanted medications (UMs) is becoming an issue of great concern, as it has the potential to harm the components of the environment where it is discarded: particularly air, water and soil. To combat this problem, many researchers have investigated the best approach for the collection and proper disposal of UMs. This paper intends to elaborate upon a safe solution for treating this waste, specifically through a process of solidification/stabilization (S/S) that involves mixing UMs with asphalt cement and asphalt concrete mixtures. Volumes of 5, 10, 15 and 20 % of a mixture of UMs were mixed with asphalt cement and the analyzed properties of the mixture of UMs–asphalt included: softening point, ductility, penetration, flash and fire points, specific gravity and rotational viscosity. Marshal stability, flow, air voids, unit weight, voids in mineral aggregate (VMA) and voids filled with binder (VFB) of asphalt concrete mixture were also investigated. Results showed that this approach of S/S is a promising method for dual achievements to solve an environmental problem and to use the waste for road construction.     

利用钢铁酸洗废液生产三氯化铁

利用钢铁酸洗废液和钢铁厂的粉尘平炉灰生产三氯化铁试验结果表明，该工艺废治废，方法简单，其产品可用于饮用水净化，污水处理和工业生产，实现了利用，化害为利，具有较好的经济，社会和环境效益。     

Reuse of residues arising from lead batteries recycle: a feasibility study

The performance of products arising from the stabilization/solidification of slags from lead batteries recycle into a Portland cement matrix has been evaluated not only in order to get a stabilized waste to be disposed of according to the current legislation, but also to obtain a recyclable material, with both economic and environmental benefits. Under this respect a detailed characterization of raw slags has been performed and different slag-cement samples have been prepared by varying the slag content. The parameters related to the cementation process have been evaluated and a series of tests on the final waste forms have been carried out, aimed at assessing both mechanical performance and leaching behaviour. In spite of the acceptable values for flexural, compressive and tensile strength, however, the high release of lead from the solidification products seems to be a limiting factor for a reusable material. While explanations of such phenomenon are given (high alkalinity of Portland cement; early "doping" of cementitious components by lead in the amorphous state), the main conclusion of the research work is that further efforts should be addressed to the adoption of a different or a modified incorporation matrix.     

Manufacture of artificial aggregate using MSWI bottom ash

This paper reports the results of an investigation on material recovery by stabilization/solidification of bottom ash coming from a municipal solid waste incineration plant. Stabilization/solidification was carried out to produce artificial aggregate in a rotary plate granulator by adding hydraulic binders based on cement, lime and coal fly ash. Different mixes were tested in which the bottom ash content ranged between 60% and 90%. To avoid undesirable swelling in hardened products, the ash was previously milled and then granulated at room temperature. The granules were tested to assess their suitability to be used as artificial aggregate through the measurement of the following properties: density, water absorption capacity, compressive strength and heavy metals release upon leaching. It was demonstrated that the granules can be classified as lightweight aggregate with mechanical strength strongly dependent on the type of binder. Concrete mixes were prepared with the granulated artificial aggregate and tested for in-service performance, proving to be suitable for the manufacture of standard concrete blocks in all the cases investigated.     

Re-usage of waste foundry sand in high-strength concrete

In this study, the potential re-use of waste foundry sand in high-strength concrete production was investigated. The natural fine sand is replaced with waste foundry sand (0%, 5%, 10%, and 15%). The findings from a series of test program has shown reduction in compressive and tensile strengths, and the elasticity modulus which is directly related to waste foundry inclusion in concrete. Nevertheless the concrete with 10% waste foundry sand exhibits almost similar results to that of the control one. The slump and the workability of the fresh concrete decreases with the increase of the waste foundry sand ratio. Although the freezing and thawing significantly reduces the mechanical and physical properties of the concrete. The obtained results satisfies the acceptable limits set by the American Concrete Institute (ACI).     

Sulfur polymer solidification/stabilization of elemental mercury waste

Elemental mercury, contaminated with radionuclides, presents a waste disposal problem throughout the Department of Energy complex. In this paper we describe a new process to immobilize elemental mercury wastes, including those contaminated with radionuclides, in a form that is non-dispersible, will meet EPA leaching criteria, and has low mercury vapor pressure. In this stabilization and solidification process, elemental mercury is combined with an excess of powdered sulfur polymer cement (SPC) and sulfide additives in a mixing vessel and heated to approximately 40 degrees C for several hours, until all of the mercury is converted into mercuric sulfide (HgS). Additional SPC is then added and the temperature of the mixture raised to 135 degrees C, resulting in a molten liquid which is poured into a mold where it cools and solidifies. The final treated waste was characterized by powder X-ray diffraction and found to be a mixture of the hexagonal and orthorhombic forms of mercuric sulfide. The Toxicity Characteristic Leaching Procedure was used to assess mercury releases, which for the optimized process averaged 25.8 microg/l, with some samples being well below the new EPA Universal Treatment Standard of 25 microg/l. Longer term leach tests were also conducted, indicating that the leaching process was dominated by diffusion. Values for the effective diffusion coefficient averaged 7.6x10(-18) cm2/s. Concentrations of mercury vapor from treated waste in equilibrium static headspace tests averaged 0.6 mg/m3.     

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.     

A new way to stabilize fly ash from municipal incinerators

Heavy metals and toxic chlorinated organics, added to very low grain-size distributions, make fly ashes from municipal incinerators a very hazardous waste. For their disposal, the present general trend is, not only to stabilize chemically the ashes, i.e. to reduce the leachability of the toxic substances, but also to stabilize them mechanically, i.e. to convert them into massive, resistant, and unleachable solids. This paper describes various stabilization methods used on representative European fly ash samples, which led to the development of a new stabilization technique taking place in four stages: elimination of the alkali chlorides by dissolution; addition of a moderate quantity of phosphoric acid; calcination; and solidification with Portland clinker or cement. The principal advantages of the process are as follows: the polychlorodibenzodioxins-polychlorodibenzofurans are destroyed, the reactivity of the heavy metals is reduced drastically, the final solids have satisfactory mechanical properties, and the increase in weight of the waste to be disposed of does not exceed one fourth. Comparative results of TCLP extraction tests are presented.     

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.     

Chemical stability of geopolymers containing municipal solid waste incinerator fly ash

Municipal solid waste incinerators every year produce tons of fly ashes which, differently from coal fly ashes, contain large amounts of toxic substances (heavy metals, dioxins, furans). The stabilization/solidification (S/S) technology known as geopolymerization is proposed with the purpose to bond physically and chemically incinerator fly ashes (IFA) in a solid matrix, in order to reduce pollutant mobility. The chemical stability of geopolymers with Si/Al ratio of 1.8–1.9 and Na/Al ratio of 1.0, synthesized by alkali activation of metakaolin and the addition of 20 wt% of two different kinds of IFA, is presented. The concentration of the alkaline solution, water to solid ratio and curing process have been optimized. The room temperature consolidation of IFA containing geopolymers has been tested for leachability in water for 1 day, accordingly to EN 12457 regulation and extended to 7 days to increase the water attack on solid granules. Leachable metals in the test solution, determined by ICP_AES, fall within limit values set by regulation for non-dangerous waste landfill disposal. Geopolymeric matrix evolution with leaching time has been also evaluated in terms of pH and electrical conductivity increase in solution.     

Efficiency analysis of reduction and stabilization of biodegradable waste using an aerobic stabilization system

The reduction and stabilization of biodegradable waste were studied using three operational stages in an aerobic stabilization system. The system used for mechanical/biological treatment utilized two-shaft screws in multiple box reactors. In the first operational stage, 50-kg batches of biodegradable waste were charged in each of the three reactors, with peat moss used as a bulking agent. Analysis revealed that peat moss can be used at this initial stage, based on the observed increase in temperature and carbon dioxide levels. The second stage of operation involved adding 100 kg/day of biodegradable waste to the first reactor. It was confirmed that a continuous reaction is possible by the addition of more waste. In the third stage of operation, 20 kg/day of the 100 kg/day of biodegradable waste feed was replaced with material fed back from the third reactor. At this stage, final product was also removed from the third reactor. The temperature was not controlled, and up to 8%–9% carbon dioxide was formed, enabling normal activation of decomposition. This three-stage operational test confirmed the expected decomposition of organic matter and biodegradable materials. The rate of mass reduction calculated for the final product compared with the input amount was 94.3%, which confirmed that this system would be a useful means for the reduction and stabilization of biodegradable waste. This study also measured the water content of the material in the reactors: the water content decreased as the reaction progressed. This indicated that the activation of microorganisms did not occur sufficiently in the second and third reactors. Future studies of methods to control the internal water content of each reactor should improve the decomposition efficiency.