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.     

Performance evaluation of cement stabilized fly ash-GBFS mixes as a highway construction material

Fly ash and granulated blast furnace slag (GBFS) are major by-products of thermal and steel plants, respectively. These materials often cause disposal problems and environmental pollution. Detailed laboratory investigations were carried out on cement stabilized fly ash-(GBFS) mixes in order to find out its suitability for road embankments, and for base and sub-base courses of highway pavements. Proctor compaction test, unconfined compressive strength (UCS) test and California Bearing Ratio (CBR) test were conducted on cement stabilized fly ash-GBFS mixes as per the Indian Standard Code of Practice. Cement content in the mix was varied from 0% to 8% at 2% intervals, whereas the slag content was varied as 0%, 10%, 20%, 30% and 40%. Test results show that an increase of either cement or GBFS content in the mixture, results in increase of maximum dry density (MDD) and decrease of optimum moisture content (OMC) of the compacted mixture. The MDD of the cement stabilized fly ash-GBFS mixture is comparably lower than that of similarly graded natural inorganic soil of sand to silt size. This is advantageous in constructing lightweight embankments over soft, compressible soils. An increase in percentage of cement in the fly ash-GBFS mix increases enormously the CBR value. Also an increase of the amount of GBFS in the fly ash sample with fixed cement content improves the CBR value of the stabilized mix. In the present study, the maximum CBR value of compacted fly ash-GBFS-cement (52:40:8) mixture obtained was 105%, indicating its suitability for use in base and sub-base courses in highway pavements with proper combinations of raw materials.     

Optimization for solidification of low-level-radioactive resin using Taguchi analysis

Solidification of low-level-radioactive (LLW) resin was optimized using Taguchi analytical methodology. The ingredients in LLW mortar which caused the solidification of cement were evaluated through consecutive measurements of the effects of various concentrations of ingredients. Samples selected according to Taguchi's method were separated into 18 different categories and measured at the 7th, 21st, and 28th day after fabrication on developing effects. Evaluations of the various samples focused on whether the compressive and bending strength fulfilled the special criteria of the Taiwan Power Company (TPC). Similar results indicated that both furnace slag and fly ash were the dominant material resulting from the solidification of LLW mortar. The superior combination was obtained as furnace slag 24 wt.%, fly ash 24 wt.%, and cement 8 wt.% to mix 24 wt.% of resin with 20 wt.% of water, to fulfill the contemporary requirements of TPC.     

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.     

Sustainable alkali-activated binders with municipal solid waste incineration ashes as sand or fly ash replacement

The present study investigates the feasibility of using two types of municipality solid wastes incineration ashes, namely, fly ash and bottom ash in the production of sustainable alkali-activated binder. The ashes are collected from the incineration plant and characterized to determine their particle size distribution, specific gravity, chemical composition, and heavy metals content. The ashes are then used as either fly ash or sand replacement with five replacement ratios 0%, 5%, 10%, 15%, and 20% to produce the binder. The produced binder are characterized in terms of strength, workability, density, water absorption, thermal conductivity and stability, chemical composition, and heavy metals content. The results reflect the ability of producing sustainable alkali-activated binder with small dosage of MSWI ashes as either fly ash or sand replacement without negatively affecting its strength, workability, density, and water absorption. The ashes enhance the thermal insulation capability of the binder.

     

Improvements of nano-SiO2 on sludge/fly ash mortar

Sewage sludge ash has been widely applied to cementitious materials. In this study, in order to determine effects of nano-SiO(2) additives on properties of sludge/fly ash mortar, different amounts of nano-SiO(2) were added to sludge/fly ash mortar specimens to investigate their physical properties and micro-structures. A water-binding ratio of 0.7 was assigned to the mix. Substitution amounts of 0%, 10%, 20%, and 30% of sludge/fly ash (1:1 ratio) were proposed. Moreover, 0%, 1%, 2%, and 3% of nano-SiO(2) was added to the mix. Tests, including SEM and compressive strength, were carried out on mortar specimens cured at 3, 7, and 28 days. Results showed that sludge/fly ash can make the crystals of cement hydration product finer. Moreover, crystals increased after nano-SiO(2) was added. Hence, nano-SiO(2) can improve the effects of sludge/fly ash on the hydration of mortar. Further, due to the low pozzolanic reaction active index of sludge ash, early compressive strengths of sludge/fly ash mortar were decreased. Yet, nano-SiO(2) could help produce hydration crystals, which implies that the addition of nano-SiO(2) to mortar can improve the influence of sludge/fly ash on the development of the early strength of the mortar.     

Effect of industrial by-products containing electron acceptors on mitigating methane emission during rice cultivation

Three industrial by-products (fly ash, phosphogypsum and blast furnace slag), were evaluated for their potential re-use as soil amendments to reduce methane (CH₄) emission resulting from rice cultivation. In laboratory incubations, CH₄ production rates from anoxic soil slurries were significantly reduced at amendment levels of 0.5%, 1%, 2% and 5% (wt wt⁻¹), while observed CO₂ production rates were enhanced. The level of suppression in methane production was the highest for phosphogypsum, followed by blast slag and then fly ash. In the greenhouse experiment, CH₄ emission rates from the rice planted potted soils significantly decreased with the increasing levels (2–20 Mg ha⁻¹) of the selected amendments applied, while rice yield simultaneously increased compared to the control treatment. At 10 Mg ha⁻¹ application level of the amendments, total seasonal CH₄ emissions were reduced by 20%, 27% and 25%, while rice grain yields were increased by 17%, 15% and 23% over the control with fly ash, phosphogypsum, and blast slag amendments, respectively. The suppression of CH₄ production rates as well as total seasonal CH₄ flux could be due to the increased concentrations of active iron, free iron, manganese oxides, and sulfate in the amended soil, which acted as electron acceptors and controlled methanogens’ activity by limiting substrates availability. Among the amendments, blast furnace slag and fly ash contributed mainly to improve the soil nutrients balance and increased the soil pH level towards neutral point, but soil acidity was developed with phosphogypsum application. Conclusively, blast slag among the selected amendments would be a suitable soil amendment for reducing CH₄ emissions as well as sustaining rice productivity.     

Strength properties of concrete incorporating coal bottom ash and granulated blast furnace slag

Coal bottom ash (CBA) and fly ash (FA) are by-products of thermal power plants. Granulated blast-furnace slag (GBFS) is developed during iron production in iron and steel plants. This research was conducted to evaluate the compressive strength property and some durability characteristics of concrete incorporating FA, CBA, and GBFS. FA is used as an effective partial cement replacement; CBA and GBFS are used as partial replacement for fine aggregate without grinding. Water absorption capacity, unit weight and compressive strengths in 7, 28, and 90-day ages were assessed experimentally. For these experiments, concrete specimens were produced in the laboratory in appropriate shapes. The samples are divided into two main categories: M1, which incorporated CBA and GBFS; and M2, which incorporated FA, CBA, and GBFS. Remarkable decreases are observed in compressive strength and water absorption capacity of the concrete; bulk density of the concrete is also decreased. It can be concluded that if the content of CBA and GBFS is limited to a reasonable amount, the small decreases in strength can be accepted for low strength concrete works.     

STABILIZATION OF RESIDUE CONTAINING HEAVY METALS BY MEANS OF MATRICES GENERATING CALCIUM TRISULPHOALUMINATE AND SILICATE HYDRATES

Two binding matrices based on blast furnace slag or fly ash/lime mixtures were studied in relation to the stabilization/solidification of a residue from a municipal solid waste incinerator. Their use is of interest because of the formation of calcium trisulphoaluminate and silicate hydrates. Mixtures of the above matrices with up to 80% of the incinerator residue were paste-hydrated and cured for 28 days at 25°C and 100% relative humidity. The effect of added waste on the hydration phenomena was studied by means of differential thermal analysis and X-ray diffraction analysis. The effectiveness of these systems as stabilization/solidification matrices was checked by means of mechanical and leaching tests. Cured samples with up to 20–40% of added waste gave compressive strengths sufficiently high for reuse as building materials. The U.S. Environmental Protection Agency leaching test has shown that disposal in a landfill in which no facilities for collecting and treating percolating waters are provided, is possible with 40–60% of waste content. Finally, the American Nuclear Society dynamic leaching test has shown that the entrapment is mainly dependent on the physical binding potential of the matrices.     

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.     

Fabrication of bulk materials with zeolite from coal fly ash

After packing a compact of coal fly ash mixed with 3.5?M (mol/L) sodium hydroxide solution into a cylindrical plastic mold at 80?°C and 50?% relative humidity for 24?h, the plastic mold was released and the compact was immersed in 3.5?M sodium hydroxide solution at 80?°C for 48?h. When the resultant compact was removed from the solution and cured at 80?°C and 50?% relative humidity for 7?days, a bulk material with zeolite was formed. The strength of the resultant bulk material was a result of the formation of geopolymer (alkali-activated cement). The specific surface area and the compressive strength of the bulk body sample were 21.4?m²/g and 29.0?MPa, respectively. According to a quantitative analysis conducted using the X-ray diffraction (XRD) technique, the content of the formed Na-P type zeolite was estimated to be approximately 28.2?% in mass ratio. The pore size of the resultant bulk materials with zeolite ranges from sub-nanometer to several tens of nanometers, so the resultant bulk material with zeolite exhibited excellent water vapor retention characteristics.     

Evaluation of the use of a sequential extraction procedure for the characterization and treatment of metal containing solid waste

Metal containing wastes like MSWI fly ashes and blast furnace sludge form a major environmental problem as they are polluted with heavy metals. The ash has to be landfilled or can be used as a construction material, but a pretreatment is in general necessary. Washing of the ashes with water in order to dissolve soluble salts or extracting the heavy metals with chemicals are possibilities. Blast furnace sludge contains large quantities of iron and carbon and could be recycled in the blast furnace, if the zinc content were not that high. Using a hydrometallurgical process the zinc can be removed from the sludge particles. In order to evaluate such treatment methods knowledge of the leaching behaviour of the studied material is very important. One of the factors influencing the leaching behaviour is the composition and mineralogy of the solids. A sequential extraction procedure, whereby the material is sequentially leached with different leaching solutions, can be used as an aid to characterize the material and to determine which chemical conditions are needed to obtain a sufficient extraction efficiency. To verify the accuracy of the sequential extraction procedure, a method is tested on MSWI fly ash and evaluated by comparing the results with those of leaching experiments whereby the final pH of the leaching solutions is varied over a wide range. Based upon this evaluation some suggestions for the use of the sequential extraction procedure are made and an adapted procedure is suggested, and applied to a blast furnace sludge.     

Vitrification for reclaiming spent alkaline batteries

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.     

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.     

Effects of fly ash addition on physical properties of porous clay-fly ash composites via polymeric replica technique

The porous composites of clay and fly ash have the potential to be used in many fields, such as catalyst support and gas adsorbents. In this study, various ratios of fly ash (1–2) with different percentage of suspension (50–70 wt%) were applied to produce porous clay-fly ash composites via polymeric replica technique. Fabrication process starts by mixing clay and fly ash in distilled water to form slurry. The process is followed by fully immersing polymer sponge in slurry. The excess slurry is then removed through squeezing. Finally, the sponge coated with slurry is sintered at 500 and 1250 °C for 1 h. It is found that the compressive strength of porous composites improves significantly (0.178–1.28 MPa) when the amount of clay-fly ash suspension mixture (50–70 wt%) increases. The compressive strength of porous composites is mainly attributed to the mullite, quartz and amorphous phase formations. These results are supported by X-ray diffraction analysis. On the other hand, increase in the amount of suspension reduces the apparent density (from 2.44 to 2.32 g/cm³) and porosity (from 97 to 85 %). The reduction in apparent density is believed to be caused by the presence of high fly ash content in porous composites. The melted fly ash cenospheres have closed the internal pores and increased density of samples. Higher suspension level not only reduces porosity, but also increases close pores of the porous composites. The results are justified through the observation from the structures of porous clay-fly ash composites.     

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.     

The hydration characteristics and utilization of slag obtained by the vitrification of MSWI fly ash

This study investigated the effects of slag composition on the hydration characteristics of slag blended cement (SBC) pastes. Synthetic slag samples were prepared by melting CaO-modified and Al(2)O(3)-modified municipal solid waste incinerator (MSWI) fly ash. MSWI fly ash was mixed with 5% CaO and 5% Al(2)O(3) (by weight), respectively, resulting in two fly ash mixtures. These mixtures were then melted at 1400 degrees C for 30 min to produce two types of slag with different contents, designated at C-slag and A-slag. Both the C-slag and A-slag samples exhibited a pozzolanic activity index higher than the unmodified slag sample. The results show that the synthetic slags all met the Taiwan EPA's current regulatory thresholds. These synthetic slags were then blended with ordinary Portland cement (OPC) at various weight ratios ranging from 10 to 40%. The 28-day strength of the C1 paste was higher than that developed by the OPC paste, suggesting that the C-slag contributed to the earlier strength of the SBC pastes. At curing times beyond 28 days, the strength of the A1 paste samples approached that of the OPC paste samples. It can be seen from this that increasing the amount of calcium and aluminum oxide increases the early strength of SBC. The C-slag blended cement paste samples showed an increase in the number of fine pores with the curing time, showing that the C-slag enhanced the pozzolanic reactions, filling the pores. Also, the incorporation of a 10% addition of C-slag also tended to enhance the degree of hydration of the SBC pastes during the early ages (3-28 days). However, at later ages, no significant difference in degree of hydration between the OPC pastes and the SBC pastes was observed with the 10% C-slag addition. However, the incorporation of A-slag did decreased the degree of hydration. A slag blend ratio of 40% significantly decreased the hydration degree.     

Investigating mechanical properties and durability of concrete containing recycled rubber ash and fibers

This article investigates the suitability of utilizing end of life rubber tyre particles in concrete as fine aggregate. Rubber ash and rubber fibers were used to develop two series of rubber ash concrete (series I) and hybrid concrete (series II) mixes. The natural fine aggregate was replaced by rubber ash (by volume of 5%, 10%, 15% and 20%) in series I; whereas in series II, the amount of rubber ash was kept constant at 10% and rubber fiber was introduced as replacement of fine aggregate (by volume of 5%, 10%, 15%, 20% and 25%). The concrete mixes were evaluated for compressive strength, flexural strength, resistance to impact loading, fatigue loading, water penetration and shrinkage strain was evaluated. It was observed that inclusion of rubber ash resulted in the improvement of impact resistance of concrete. The results also show that up to 10% rubber ash and rubber fibers can be utilized as fine aggregate to develop feasible and durable rubberized concrete pavements, crash barriers and paver blocks.

     

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.     

Foamed lightweight materials made from mixed scrap metal waste powder and sewage sludge ash.

The porous properties and pozzolanic effects of sewage sludge ash (SSA) make it possible to produce lightweight materials. This study explored the effects of different metallic foaming agents, made from waste aluminium products, on the foaming behaviours and engineering characteristics, as well as the microstructure of sewage sludge ash foamed lightweight materials. The results indicated that aluminium powder and mixed scrap metal waste powder possessed similar chemical compositions. After proper pre-treatment, waste aluminium products proved to be ideal substitutes for metallic foaming agents. Increasing the amount of mixed scrap metal waste by 10-15% compared with aluminium powder would produce a similar foaming ratio and compressive strength. The reaction of the metallic foaming agents mainly produced pores larger than 10 microm, different from the hydration reaction of cement that produced pores smaller than 1 microm mostly. To meet the requirements of the lightweight materials characteristics and the compressive strength, the amount of SSA could be up to 60-80% of the total solids. An adequate amount of aluminium powder is 0.5-0.9% of the total solids. Increasing the fineness of the mixed scrap metal waste powder could effectively reduce the amount required and improve the foaming ratio.