Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Utilization of gold tailings as an additive in Portland cement.

Mine tailings are formed as an industrial waste during coal and ore mining and processing. In the investigated process, following the extraction of gold from the ore, the remaining tailings are subjected to a two-stage chemical treatment in order to destroy the free cyanide and to stabilize and coagulate heavy metals prior to discharge into the tailings pond. The aim of this study was the investigation of the feasibility of utilization of the tailings as an additive material in Portland cement production. For this purpose, the effects of the tailings on the compressive strength properties of the ordinary Portland cement were investigated. Chemical and physical properties, mineralogical composition, particle size distribution and microstructure of the tailings were determined by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), particle size analyzer (Mastersizer) and scanning electron microscope (SEM). Following the characterization of the tailings, cement mortars were prepared by intergrinding Portland cement with dried tailings. Composition of the cement clinkers were adjusted to contain 5, 15, 25% (wt/wt) dried tailings and also silica fume and fly ash samples (C and F type) were added to clinker in different ratios. The mortars produced with different amounts of tailings, silica fume, fly ashes and also mixtures of them were tested for compressive strength values after 2, 7, 28 and 56 days according to the European Standard (EN 196-1). The results indicated that gold tailings up to 25% in clinker could be beneficially used as an additive in Portland cement production. It is suggested that the gold tailings used in the cement are blended with silica fume and C-type fly ash to obtain higher compressive strength values.     

Evaluation of a lime-mediated sewage sludge stabilisation process. Product characterisation and technological validation for its use in the cement industry

This paper describes an industrial process for stabilising sewage sludge (SS) with lime and evaluates the viability of the stabilised product, denominated Neutral, as a raw material for the cement industry. Lime not only stabilised the sludge, raised the temperature of the mix to 80-100 °C, furthering water evaporation, portlandite formation and the partial oxidation of the organic matter present in the sludge.Process mass and energy balances were determined. Neutral, a white powder consisting of portlandite (49.8%), calcite (16.6%), inorganic oxides (13.4%) and organic matter and moisture (20.2%), proved to be technologically apt for inclusion as a component in cement raw mixes. In this study, it was used instead of limestone in raw mixes clinkerised at 1400, 1450 and 1500 °C. These raw meals exhibited greater reactivity at high temperatures than the limestone product and their calcination at 1500 °C yielded clinker containing over 75% calcium silicates, the key phases in Portland clinker. Finally, the two types of raw meal (Neutral and limestone) were observed to exhibit similar mineralogy and crystal size and distribution.     

Hydration and leaching characteristics of cement pastes made from electroplating sludge

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the ²⁹Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability.     

Utilization of municipal solid waste incineration fly ash for sulfoaluminate cement clinker production

The feasibility of partially substituting raw materials with municipal solid waste incineration (MSWI) fly ash in sulfoaluminate cement (SAC) clinker production was investigated by X-ray diffraction (XRD), compressive strength and free expansion ratio testing. Three different leaching tests were used to assess the environmental impact of the produced material. Experimental results show that the replacement of MSWI fly ash could be taken up to 30% in the raw mixes. The good quality SAC clinkers are obtained by controlling the compositional parameters at alkalinity modulus (C(m)) around 1.05, alumina-sulfur ratio (P) around 2.5, alumina-silica ratio (N) around 2.0~3.0 and firing the raw mixes at 1250 °C for 2h. The compressive strengths of SAC are high in early age while that develop slowly in later age. Results also show that the expansive properties of SAC are strongly depended on the gypsum content. Leaching studies of toxic elements in the hydrated SAC-based system reveal that all the investigated elements are well bounded in the clinker minerals or immobilized by the hydration products. Although some limited positive results indicate that the SAC prepared from MSWI fly ash would present no immediate thread to the environment, the long-term toxicity leaching behavior needs to be further studied.     

Environmental assessment of sewage sludge as secondary raw material in cement production--a case study in China

A life cycle assessment was carried out to estimate the environmental impact of sewage sludge as secondary raw material in cement production. To confirm and add credibility to the study, uncertainty analysis was conducted. Results showed the impact generated from respiratory inorganics, terrestrial ecotoxicity, global warming, and non-renewable energy categories had an important contribution to overall environmental impact, due to energy, clinker, and limestone production stages. Also, uncertainty analysis results showed the technology of sewage sludge as secondary raw material in cement production had little or no effect on changing the overall environmental potential impact generated from general cement production. Accordingly, using the technology of sewage sludge as secondary raw material in cement production is a good choice for reducing the pressure on the environment from dramatically increased sludge disposal. In addition, increasing electricity recovery rate, choosing natural gas fired electricity generation technology, and optimizing the raw material consumption in clinker production are highly recommended to reduce the adverse effects on the environment.     

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.     

Determination of Cu and Ni incorporation ratios in Portland cement clinker

Cu and Ni are metals found in galvanic sludges; these sludges are considered hazardous due to their heavy metal content. The main objective of this work is to determine the incorporation amount of Cu and Ni in Portland clinker when a galvanic sludge containing these metals is added to the clinker raw-material. The influence of this addition on the clinkering reactions is evaluated as well as the possibility of co-incinerating galvanic sludges containing Cu and Ni in rotary cement kilns. This study also characterizes the galvanic sludge. Samples were prepared by additions from 0.25 to 5 wt.% of a galvanic sludge to an industrial clinker raw-material. The clinkering process was simulated in a laboratory device. The following techniques were applied to characterize the raw materials and the products of the tests: chemical analysis, differential thermal analysis (DTA) and thermogravimetric analysis (TG). Leaching tests were performed in the produced clinker samples in order to verify the incorporation of the studied metals in the clinker structure. The results led to the conclusion that additions of up to 2 wt.% of a galvanic sludge containing 2.4 wt.%Cu and 1.2 wt.% Ni to clinker raw-material do not affect the clinkering reactions and that these metals are totally incorporated into the clinker.     

Recycling and recovery routes for incinerated sewage sludge ash (ISSA): A review

The drivers for increasing incineration of sewage sludge and the characteristics of the resulting incinerated sewage sludge ash (ISSA) are reviewed. It is estimated that approximately 1.7 million tonnes of ISSA are produced annually world-wide and is likely to increase in the future. Although most ISSA is currently landfilled, various options have been investigated that allow recycling and beneficial resource recovery. These include the use of ISSA as a substitute for clay in sintered bricks, tiles and pavers, and as a raw material for the manufacture of lightweight aggregate. ISSA has also been used to form high density glass–ceramics. Significant research has investigated the potential use of ISSA in blended cements for use in mortars and concrete, and as a raw material for the production of Portland cement. However, all these applications represent a loss of the valuable phosphate content in ISSA, which is typically comparable to that of a low grade phosphate ore. ISSA has significant potential to be used as a secondary source of phosphate for the production of fertilisers and phosphoric acid. Resource efficient approaches to recycling will increasingly require phosphate recovery from ISSA, with the remaining residual fraction also considered a useful material, and therefore further research is required in this area.     

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.     

Recycling of combined coal-biomass ash from electric power plant waste as a cementitious material: characteristics and improvement

Combined coal-biomass ash has an enormous impact on environmental quality near electric power plants. This paper describes an alternative to disposal in which the ash is used to produce cementitious materials. Ash was obtained from combustion of coal and biomass containing four mass ratios of anthracite, bitumen, rice husks, and eucalyptus bark. The cement-forming properties were systematically characterized including compressive strength development, durability, and expansion in water. The ash samples were ground to increase the specific surface area, and then used to partially replace ASTM Type I Portland cement in mixtures containing 15, 30, or 45 % ash by mass. The water-binder material's (Portland cement with or without combined coal-biomass ash) ratios (w/c) were held constant at 45, 55, or 65 % by mass. Types A, B, and D ash behaved similarly, while the properties of type C ash were slightly different. Increasing the ash fraction in Portland cement mixtures increased the water requirement and resulted in lower compressive strength. Thorough mechanical grinding reduced the porosity and significantly enhanced the material properties.     

Preparation and performance of arsenate (V) adsorbents derived from concrete wastes

Solid adsorbent materials, prepared from waste cement powder and concrete sludge were assessed for removal of arsenic in the form of arsenic (As(V)) from water. All the materials exhibited arsenic removal capacity when added to distilled water containing 10–700 mg/L arsenic. The arsenic removal isotherms were expressed by the Langmuir type equations, and the highest removal capacity was observed for the adsorbent prepared from concrete sludge with heat treatment at 105 °C, the maximum removal capacity being 175 mg-As(V)/g. Based on changes in arsenic and calcium ion concentrations, and solution pH, the removal mechanism for arsenic was considered to involve the precipitation of calcium arsenate, Ca₃(AsO₄)₂. The enhanced removal of arsenic for the adsorbent prepared from concrete sludge with heat treatment was thought to reflect ion exchange by ettringite. The prepared adsorbents, derived from waste cement and concrete using simple procedures, may offer a cost effective approach for arsenic removal and clean-up of contaminated waters, especially in developing countries.     

Recycling MSWI bottom and fly ash as raw materials for Portland cement

Municipal solid waste incineration (MSWI) ash is rich in heavy metals and salts. The disposal of MSWI ash without proper treatment may cause serious environmental problems. Recently, the local cement industry in Taiwan has played an important role in the management of solid wastes because it can utilize various kinds of wastes as either fuels or raw materials. The objective of this study is to assess the possibility of MSWI ash reuse as a raw material for cement production. The ash was first washed with water and acid to remove the chlorides, which could cause serious corrosion in the cement kiln. Various amounts of pre-washed ash were added to replace the clay component of the raw materials for cement production. The allowable limits of chloride in the fly ash and bottom ash were found to be 1.75% and 3.50% respectively. The results indicate that cement production can be a feasible alternative for MSWI ash management. It is also evident that the addition of either fly ash or bottom ash did not have any effect on the compressive strength of the clinker. Cement products conformed to the Chinese National Standard (CNS) of Type II Portland cement with one exception, the setting time of the clinker was much longer.     

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.     

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.     

Use of waste ash from palm oil industry in concrete

Palm oil fuel ash (POFA), a by-product from the palm oil industry, is disposed of as waste in landfills. In this study, POFA was utilized as a pozzolan in concrete. The original size POFA (termed OP) was ground until the median particle sizes were 15.9 microm (termed MP) and 7.4 microm (termed SP). Portland cement Type I was replaced by OP, MP, and SP of 10%, 20%, 30%, and 40% by weight of binder. The properties of concrete, such as setting time, compressive strength, and expansion due to magnesium sulfate attack were investigated. The results revealed that the use of POFA in concretes caused delay in both initial and final setting times, depending on the fineness and degree of replacement of POFA. The compressive strength of concrete containing OP was much lower than that of Portland cement Type I concrete. Thus, OP is not suitable to be used as a pozzolanic material in concrete. However, the replacement of Portland cement Type I by 10% of MP and 20% of SP gave the compressive strengths of concrete at 90 days higher than that of concrete made from Portland cement Type I. After being immersed in 5% of magnesium sulfate solution for 364 days, the concrete bar mixed with 30% of SP had the same expansion level as that of the concrete bar made from Portland cement Type V. The above results suggest that ground POFA is an excellent pozzolanic material and can be used as a cement replacement in concrete. It is recommended that the optimum replacement levels of Portland cement Type I by MP and SP are 20% and 30%, respectively.     

Influence of combustion temperature on the performance of sewage sludge ash as a supplementary cementitious material

The potential for using sewage sludge ash (SSA) as a supplementary cementitious material (SCM) has been investigated. Controlled combustion of sewage sludge collected in Croatia from two wastewater treatment plants produced SSA with different characteristics. These were used to substitute for cement in mortar samples. The chemical composition and physical properties of SSA depend on wastewater composition, the sludge treatment process and the combustion temperature. These factors influence the suitability of SSA to be used as a SCM. For three different combustion temperatures (800, 900 and 1000 °C), it was concluded that properties of fresh mortar were not affected while in the hardened state, the most favorable combustion temperature is 900 °C regarding mechanical properties. Regardless of combustion temperature, for all types of SSA used in mortars as cement replacement (up to 30%), the average decrease in both compressive and flexural strength values was less than 8% for every 10% of added SSA. The results presented indicate that using up to 20% replacement of cement by SSA produces mortars that meet the specific technical requirements analyzed in this work.     

Assessment of the leaching of metallic elements in the technology of solidification in aqueous solution

Results are presented of experiments performed to optimize the solidification/stabilization system for metallic elements in aqueous solution. This system involves mixing cement and a solution of metallic elements in a conventional mixer: the paste thus obtained is transferred drop by drop into a recipient filled with an aqueous solution of NaOH at 20% by weight, in which it solidifies immediately. The separate use of chloride solutions of Li+, Cr3+, Pb2+ and Zn2+ makes it possible to obtain granules displaying various levels of compressive strength. Three different inertization matrices were used in the experiments, the first consisting solely of Portland cement, the second of Portland cement and a superplasticizer additive, and the third of Portland cement partially replaced with silica-fume and superplasticizer. The results of the tests performed showed a very low level of leaching into the alkaline solidification solution for Cr3+, the quantity leached being under 2% as against higher levels for the other metallic elements. For all the considered elements, the best results were obtained by using silica-fume in the inertization matrix.     

Incorporation of sewage sludge in clay brick and its characterization.

This study reports the use of sewage sludge generated from sewage treatment plant (STP) as raw material in a clay brick-making process. The physico-chemical and mineralogical characterization of the sewage sludge and clay were carried out in order to identify the major technological constraints and to define the sludge pretreatment requirements if necessary. Moreover, the effects on processing conditions and/or on changes of typical final characteristics are also evaluated. Bricks were produced with sewage sludge additions ranging from 10 to 40% by dry weight. The texture and finishing of the surface of sludge-amended clay bricks were rather poor. As for the physical and chemical properties, bricks with a sludge content of up to 40 wt.% were capable of meeting the relevant technical standards. However, bricks with more than 30 wt.% sludge addition are not recommended for use since they are brittle and easily broken even when handled gently. A tendency for a general degradation of brick properties with sludge additions was observed due to its refractory nature. Therefore, sludge bricks of this nature are only suitable for use as common bricks, which are normally not exposed to view, because of poor surface finishing.     

Evaluation of leaching characteristics and environmental compatibility of solidified/stabilized industrial waste

An attempt was made to judge the environmental compatibility, the governing leaching mechanism, and mobility patterns in a waste–cement solidified/stabilized matrix after 21 days of curing. The mixed sludge from a steel pickling facility was stabilized by ordinary Portland cement. Iron was the major leachable metal, along with Pb, Zn, and Mn. To characterize the leaching behavior, the mobility and mechanism of leaching were determined by diffusion leaching tests. In the solidified/stabilized matrix, the mobility of all the elements studied was reduced, and average to low mobility was observed. Values for the negative log of the effective diffusion coefficient of more than 12.5 were obtained for the metals. The dominant leaching mechanisms were surface wash off in the initial stage, followed by diffusion. The environmental performance of the solidified/stabilized product when considered in terms of mass leached over 64 days was found to be satisfactory for consideration for the safe disposal and reuse of waste.