Leaching Behavior of Fly Ashes from Power Plants

The Yanzhou mine district, located in southwestern Shandong Province, is about 1300 km2 with more than 8×109tons of proved coal reserves and there are 10 big power plants in this area. A large amount of coal ashes, which are regarded as waste materials, have been stockpiled in the area and have influenced the environment of the mine district. In this paper, analysis of fly ash samples from three power plants is carried out, the enrichment and concentration of trace elements, Pb, Zn, Cu and As, in coal ashes are analyzed, and petrological and mineralogical characteristics and chemical compositions of coal ashes are studied. The aim of this work is to provide basic scientific data for utilization of ashes and reduction of environmental pollutions.

Surface Modification of Fly Ashes with Carbide Slag and Its Effect on Compressive Strength and Autogenous Shrinkage of Blended Cement Pastes

Surfaces of grade III fly ashes were modified through mixing with carbide slag and calcining at 850 ℃ for 1 h. Mineralogical compositions and surface morphology of fly ashes before and after modification were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）, respectively. Effect of surface-modified fly ashes on compressive strength and autogenous shrinkage of blended cement pastes was investigated. Microstructures of cement pastes were examined by backscattered electron （BSE） imaging and mercury intrusion porosimetry （MIP）. The experimental results showed that β-C2S was formed on the surfaces of fly ashes after modification. Hydration ofβ-C2S on the surface-modified fly ashes densified interface zone and enhanced bond strength between particles of fly ashes and hydrated clinkers. In addition, surface modification of fly ashes tended to decrease total porosity and 10-50 nm pores of cement pastes. Surface modification of fly ashes increased compressive strength and reduced autogenous shrinkage of cement pastes.

Extraction of aluminium as aluminium sulphate from thermal power plant fly ashes

Valuable metal extraction technology from thermal power plant fly ash is limited.In the present study,aluminium is extracted from fly ash as highly pure aluminium sulphate(>99.0%)by leaching with sulphuric acid,followed by pre-concentration and successive crystallization.Two types of fly ashes from different sources,i.e.,Talcher Thermal Power Station(TTPS)and Vedanta Aluminium Company Limited(VAL)were chosen for comparative study on the extraction of aluminium as aluminium sulphate.The product is characterized by powder X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR)and thermogravimetric analysis(TGA).Purity of aluminium sulphate was also investigated by inductively coupled plasma?optical emission spectrometry(ICP?OES).The extraction efficiency of aluminium depends on the varied solid-to-liquid ratio(fly ash:18mol/L H2SO4,g/mL)and particle size of fly ashes.Physico-chemical analysis indicates that the obtained product is Al2(SO4)3·18H2O,having low iron content(0.08%).

Microstructure of ferrospheres in fly ashes: SEM, EDX and ESEM analysis

Ferrospheres in fly ashes from a coal-fired power plant were extracted by a magnetic separation technique and their microstructure was studied by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and environmental scanning electron microscopy (ESEM). Ferrospheres in fly ashes show significant iron enrichment compared to their respective fly ashes. Iron oxides in ferrospheres mainly occur as minerals magnetite (Fe3O4) and hematite (α-Fe2O3), which are derived mainly from the decomposition and oxidation of iron-bearing minerals in coal during combustion. EDX data indicate that ferrospheres also contain Si, S, Al and Ca resulting from quartz, mullite, anhydrite and amorphous materials. A large percentage of ferrospheres are commonly 5～50 μm in size. The microstructure of ferrospheres includes smooth, polygonal, dendritic, granular and molten drop characteristics. SEM coupled with EDX provided fast and accurate results of the microstructure and chemical composition of ferrospheres, and helped us to assess environmental issues related to the disposal and utilization of fly ashes.

Mechanical Properties of Cement Mortar Containing Fine-Grained Fraction of Fly Ashes

This paper presents the effect of fly ash grain-size fractions on Portland-fly ash cement hydration and its properties. Siliceous fly ashes of size fraction of 0 - 16 and 16 - 32 μm, separated from initial fly ash samples from 1st, 2nd and 3rd hopper in ESP system, were analysed. Cement hydration was investigated by determination of hydration heat and content of Ca(OH)2 and C3S in cement samples. Water to cement ratio and initial setting time of cement pastes as well as compressive strength and microstructure of cement mortars were also analyzed. Results showed that the same amount of the same size ash fraction can give cement of lower or higher early strength and its lower or higher increase with time. Incorporation of 20 wt% of ash fraction of 0 - 16 μm can produce Portland-fly ash cement CEM II/A-V of strength class 42.5R (from 2nd hopper) or 52.5N (from 3rd hopper). Cement containing 40 wt% of ash fraction of 0 - 16 μm from 2nd and 3rd hopper can be classified as pozzolanic cements CEM IV/A-V of strength class 42.5 and normal or rapid early strength, respectively. Different development of strength of cement with addition of the same size ash fraction separated from the initial ash sample from the next hopper in ESP system is connected with higher depolymerization degree of SiO4 units in ash glass, resulting from the greater amount of AlO4 units replacing SiO4 units. Ash fraction of 16 - 32 μm shows lower depolymerisation of glass network and as a consequence lower hydration degree of C3S to portlandite and calcium silicate hydrates (C-S-H).

Solvothermal synthesis and adsorption performance of layered boehmite using aluminum chloride and high-alumina fly ash

High alumina fly ash(FAHAl)is a kind of bulk solid waste unique to China,whose availability of high-value aluminum and the threat to the environment makes its high-value utilization urgent.In this work,the alumina containing leaching solution obtained from Na_(2)CO_(3) roasting and HCl leaching of FAHAl was used as the mother liquor to prepare layered boehmite in situ.The preparation process with AlCl_(3) as the raw material was also compared.The formation process and mechanism of boehmite,the choice of solvent,along with the adsorption capability of Congo red were analyzed by X-ray diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,Brunauer-Emmett-Teller method and adsorption experiments.Results showed that during the preparation of layered boehmite,the precursor Al(OH)_(3) from the reaction of Al^(3+) and OH-is transformed into boehmiteγ-AlOOH.The existence of ethanol is beneficial to regulate and promote the growth of boehmite crystal effectively.When water and ethanol are mixed with a volume ratio of 2:1 and used as the solvent,the maximum specific surface area of the boehmite is obtained at 135.7 m^(2)·g^(-1),and 99.16%of Congo red can be absorbed after 10 min when AlCl3 is used as a raw material.As purified leaching solution is used as the mother liquid,the crystallinity of boehmite decreases slightly when the pH value decreases from 12.5 to 11.When pH is 11,the removal efficiency of Congo red reaches a maximum of 72.25%.This process not only achieves the extraction of aluminum and high-value utilization of FAHAl but also provides a thought to prepare layered boehmite with adsorption properties.

Experimental study on the activation of coal gasification fly ash from industrial CFB gasifiers

Coal gasification fly ash(CGFA)is an industrial solid waste from the coal circulating fluidized bed(CFB)gasification process,and it needs to be effectively disposed to achieve sustainable development of the environment.To realize the application of CGFA as a precursor of porous carbon materials,the physicochemical properties of three kinds of CGFA from industrial CFB gasifiers are analyzed.Then,the activation potential of CGFA is acquired via steam activation experiments in a tube furnace reactor.Finally,the fluidization activation technology of CGFA is practiced in a bench-scale CFB test rig,and its advantages are highlighted.The results show that CGFA is characterized by a high carbon content in the range of 54.06%–74.09%,an ultrafine particle size(d50:16.3–26.1 μm),and a relatively developed pore structure(specific surface area SSA:139.29–551.97 m^(2)·g^(-1)).The proportion of micropores in CGFA increases gradually with the coal rank.Steam activation experiments show that the pore development of CGFA mainly includes three stages:initial pore development,dynamic equilibrium between micropores and mesopores and pore collapse.The SSA of lignite fly ash(LFA),subbituminous fly ash(SBFA)and anthracite fly ash(AFA)is maximally increased by 105%,13%and 72%after steam activation;the order of the largest carbon reaction rate and decomposition ratio of steam among the three kinds of CGFA is SBFA>LFA>AFA.As the ratio of oxygen to carbon during the fluidization activation of LFA is from 0.09 to 0.19,the carbon conversion ratio increases from 14.4%to 26.8%and the cold gas efficiency increases from 6.8%to 10.2%.The SSA of LFA increases by up to 53.9%during the fluidization activation process,which is mainly due to the mesoporous development.Relative to steam activation in a tube furnace reactor,fluidization activation takes an extremely short time(seconds)to achieve the same activation effect.It is expected to further improve the activation effect of LFA by regulating the carbon conversion ratio range of 27%–35%to create pores in the initial development stage.

Effect of Na_(2)CO_(3)Roasting Activation on Acid Leaching Property of Fly Ash

By using high-alumina fly ash as raw material,a process was proposed for activating the fly ash with Na_(2)CO_(3)calcination and extracting aluminum from activated clinker with sulfuric acid leaching.The feasibility of roasting process of activated fly ash by Na_(2)CO_(3)was discussed based on thermodynamic analysis.The experimental results showed that Na_(2)CO_(3)gradually reactes with mullite over 700 K to produce NaAlSiO_(4).The optimal process conditions for the activation stage are:a material ratio of 1:1 between sodium carbonate and fly ash,a calcination temperature of 900℃,and a calcination time of 2.5 hours.Under these conditions,the leaching rate of aluminum is 90.3%.By comparing the SEM and XRD analysis of raw and clinker materials,it could be concluded that the mullite phase of fly ash is almost completely destroyed and transformed into sodium aluminosilicate with good acid solubility.

Mechanism study of Cu(Ⅱ) adsorption from acidic wastewater by ultrasonic-modified municipal solid waste incineration fly ash

High concentrations of copper ions(Cu(Ⅱ)) in water will pose health risks to humans and the ecological environment. Therefore, this study aims to utilize ultrasonic-cured modified municipal solid waste incineration(MSWI) fly ash for Cu(Ⅱ) adsorption to achieve the purpose of “treating waste by waste.” The effects of p H, adsorption time, initial concentration, and temperature on the modified MSWI fly ash’s adsorption efficiency were systematically studied in this article. The adsorption performance of the modified MSWI fly ash can be enhanced by the ultrasonic modification. At pH = 2, 3 and 4, the adsorption capacity of the modified MSWI fly ash for Cu(Ⅱ) increased by 2.7, 1.9 and 1.2 times, respectively. Furthermore, it was suggested that the adsorption process of the modified MSWI fly ash can be better simulated by the pseudo-second-order kinetic model, with a maximum adsorption capacity calculated by the Langmuir model of 24.196 mg.g-1. Additionally, the adsorption process is spontaneous,endothermic, and chemisorption-dominated from the thermodynamic studies(ΔH and ΔS > 0, ΔG < 0).Finally, the enhanced adsorption performance of the modified MSWI fly ash for Cu(Ⅱ) may be attributed to electrostatic interaction and chelation effects.

Combined use of fly ash and silica to prevent the long-term strength retrogression of oil well cement set and cured at HPHT conditions

The long-term strength retrogression of silica-enriched oil well cement poses a significant threat to wellbore integrity in deep and ultra-deep wells, which is a major obstacle for deep petroleum and geothermal energy development. Previous attempts to address this problem has been unsatisfactory because they can only reduce the strength decline rate. This study presents a new solution to this problem by incorporating fly ash to the traditional silica-cement systems. The influences of fly ash and silica on the strength retrogression behavior of oil well cement systems directly set and cured under the condition of 200°C and 50 MPa are investigated. Test results indicate that the slurries containing only silica or fly ash experience severe strength retrogression from 2 to 30 d curing, while the slurries containing both fly ash and silica experience strength enhancement from 2 to 90 d. The strength test results are corroborated by further evidences from permeability tests as well as microstructure analysis of set cement. Composition of set cement evaluated by quantitative X-ray diffraction analyses with partial or no known crystal structure(PONKCS) method and thermogravimetry analyses revealed that the conversion of amorphous C-(A)-S-H to crystalline phases is the primary cause of long-term strength retrogression.The addition of fly ash can reduce the initial amount of C-(A)-S-H in the set cement, and its combined use with silica can prevent the crystallization of C-(A)-S-H, which is believed to be the working mechanism of this new admixture in improving long-term strength stability of oil well cement systems.

Synergistic CO_(2) mineralization using coal fly ash and red mud as a composite system

CO_(2) mineralization plays a critical role in the storage and utilization of CO_(2).Coal fly ash(CFA)and red mud(RM)are widely utilized as CO_(2) mineralizers.However,the inert calcium species in CFA limit its carbonation capacity,meanwhile the substantial Ca^(2+)releasing of RM is hindered by a covering layer of calcium carbonate.In this study,CO_(2) mineralization in a composite system of CFA and RM was investigated to enhance the carbonation capacity.Multiple analyzers were employed to characterize the raw materials and resulting mineralization products.The results demonstrated that a synergistic effect existed in the composite system of CFA and RM,resulting in improving CO_(2) mineralization rate and efficiency.The produced calcium carbonate was ectopically attached the surface of CFA in the composite system,thus slowing down its coverage on the surface of RM.This phenomenon facilitated further releasing Ca^(2+)from the internal RM,thereby enhancing CO_(2) mineralization efficiency.Meanwhile,the inclusion of RM significantly improved the alkalinity of the composite system,which not only promoted the dissolution of Ca^(2+)of the inert CaSO_(4)(H_(2)O)_(2) in CFA,but also accelerated CO_(2) mineralization rate.The investigation would be beneficial to CO_(2) mineralization using industrial solid wastes.

A mini review on the separation of Al,Fe and Ti elements from coal fly ash leachate

The electricity demand is increasing rapidly with the development of society and technology.Coal-fired thermal power plants have become one of the primary sources of electricity generation for urbanization.However,coal-fired thermal power plants produce a great amount of by-product coal fly ash every year.Coal fly ash disposal in landfills requires a sizable space and has negative environmental impacts.Therefore,it is crucial to develop new technologies and methods to utilize this enormous volume of solid waste in order to protect the environment.In this review,the fundamental physical and chemical character-istics of coal fly ash are introduced,and afterward the disposal policies and utilization ways of coal fly ash are discussed to gain a comprehensive understanding of the various ways this waste.The leaching of valuable metals in coal fly ash and the extraction of metal elements in leachate under different conditions are also summarized.Furthermore,the possibility of coal fly ash to serve as a supplementary source for mineral resources is analyzed,providing a basis for its extensive use as a raw material in the metal industry in China and worldwide.

Study on Fly Ash Based Porous Ceramsite as Biological Filter Media

Using fly ash as a raw material,porous ceramic particles with an apparent density of 1.21 g/cm^(3),a visible porosity of 51.03%,and a specific surface area of 4.26 m^(2)/g were prepared and used as biofilter materials for wastewater treatment.Through SEM,XRD analysis,and heavy metal leaching analysis,it was found that porous ceramsite were porous materials with rough surfaces.After calcination,the newly formed mineral was silicate calcium feldspar.The heavy metal concentration in the leaching solution of porous ceramsite met the national surface water quality requirements.The treatment of domestic sewage showed that the volumetric loads of COD Cr,NH_(4)^(+)-N,and TN removed by the aerated biofilter were 5.23,0.98,and 0.35 kg/(m^(3)·d),respectively,with removal rates of 85.46%,96.13%,and 32.31%.

Chemical composition and physical properties of filter fly ashes from eight grate-fired biomass combustion plants

For the handling, treatment and utilization of fly ash from biomass combustion its chemical composition and physical properties are important. In this study eight filter fly ashes from different grate-fired biomass combustion plants were investigated. In fly ash from straw combustion high concentrations of（K） were found, whereas in the fly ash from wood combustion the concentrations of Ca and Mg were higher. The average concentration of PO3-4was similar in both types of fly ashes. In all wood fly ashes some measured heavy metal concentrations were above the limits for utilization. The straw fly ashes were much less contaminated and can be utilized. For wood fly ash most parameters showed little variation, except from one fly ash where the dust pre-separator is in poor condition. The average values were： mass median diameter 4.3 ± 0.8 μm, spread of particle size distribution19 ± 11, particle density 2620 ± 80 kg/m^3 and angle of repose 50°± 1°. The density of the straw fly ashes is lower（2260 ± 80 kg/m^3） and the spread of the size distribution is higher（72 ± 24）.For one straw combustion fly ash the values of the mass median diameter and the angle of repose were similar to the values of wood combustion fly ash, for the other straw fly ash the values differed considerably. While the particle size of this fly ash was much smaller,surprisingly the angle of repose was also lower. This can be attributed to the formation of small agglomerates in this fly ash, which were not disintegrated without a certain stress.

Enhancing fly ash utilization in backfill materials treated with CO_(2)carbonation under ambient conditions

The environmental concerns resulting from coal-fired power generation that produces large amounts of CO_(2)and fly ash are of great interest.To mitigate,this study aims to develop a novel carbonated CO_(2)-fly ash-based backfill(CFBF)material under ambient conditions.The performance of CFBF was investigated for different fly ash-cement ratios and compared with non-CO_(2)reacted samples.The fresh CFBF slurry conformed to the Herschel-Bulkley model with shear thinning characteristics.After carbonation,the yield stress of the fresh slurry increased significantly by lowering fly ash ratio due to gel formation.The setting times were accelerated,resulting in approximately 40.6%of increased early strength.The final strength decreased when incorporating a lower fly ash ratio(50%and 60%),which was related to the existing heterogeneous pores caused by rapid fluid loss.The strength increased with fly ash content above 70%because additional C-S(A)-H and silica gels were characterized to precipitate on the grain surface,so the binding between particles increased.The C-S(A)-H gel was developed through the pozzolanic reaction,where CaCO_(3)was the prerequisite calcium source obtained in the CO_(2)-fly ash reaction.Furthermore,the maximum CO_(2)uptake efficiency was 1.39 mg-CO_(2)/g-CFBF.The CFBF material is feasible to co-dispose CO_(2)and fly ash in the mine goaf as negative carbon backfill materials,and simultaneously mitigates the strata movement and water lost in post-subsurface mining.

A Study on the Effect of Low Calcium Ultra-fine Fly Ash as a Partial Sustainable Supplementary Material to Cement in Self-compacting Concrete

The aim and scope of the present study were to determine the efficacy of UFFA in evaluating the workability,static and dynamic stabilization properties,retention period,and slump loss of SCC systems in their fresh state,as well as their compressive strength at various ages.Microstructure(SEM and XRD)of blended SCC systems were studied.Also,the thermogravimetry behavior of blended SCC specimens were researched.According to the evaluated results,incorporating up to 20%UFFA into fresh concrete improved its performance due to its engineered fine particle size and spherical geometry,both of which contribute to the enhancement of characteristics.Blends of 25%and 30%of UFFA show effect on the water-binder ratio and chemical enhancer dosage,resulting in a loss of homogeneity in fresh SCC systems.The reduced particle size,increased amorphous content,and increased surface area all contribute to the pozzolanic reactivity of the early and later ages,resulting in denser packing and thus an increase in compressive strength.The experimental results indicate that UFFA enhances the properties of SCC in both its fresh and hardened states,which can be attributed to the particles’fineness and their relative effect on SCC.

Molecular mechanism of fly ash affecting the performance of cemented backfill material

The great challenge of cemented tailings backfill(CTB)is difficult simultaneously maintaining its excellent mechanical properties and low cost.Fly ash(FA)can potentially address this problem and further replace cement in favor of low carbon development.However,its mechanism on CTB with low cement dosage and low Ca system remains unclear.Consequently,this study conducted uniaxial compression,Xray diffraction(XRD),and scanning electron microscopy(SEM)-energy dispersive spectrometer(EDS)tests to investigate the effect of FA dosage on the mechanical property and microstructure of CTB.A molecular model of FA-CSH was constructed to reproduce the molecular structure evolution of CTB with FA based on the test results.The influences of FA dosage and calcium/silica molar ratio(Ca/Si ratio)on the matrix strength and failure model were analyzed to reveal the mechanism of FA on calcium silicate hydrated(C-S-H).The results show that the strength of CTB increases initially and then decreases with FA dosage,and the FA supplement leads to a decrease in Ca(OH)_(2) diffraction intensity and Ca/Si ratio around the FA particles.XRD and SEM-EDS findings show that the Ca/Si ratio of C-S-H decreases with the progression of hydration.The FA-CSH model indicates that FA can reinforce the silica chain of C-S-H to increase the matrix strength.However,this enhancement is weakened by supplementing excessive FA dosage.In addition,the hydrogen bonds among water molecules deteriorate,reducing the matrix strength.A low Ca/Si ratio results in an increase in water molecules and a decrease in the ionic bonds combined with Ca^(2+).The hydrogen bonds among water molecules cannot withstand high stresses,resulting in a reduction in strength.The water absorption of the FA-CSH model is negatively correlated with the FA dosage and Ca/Si ratio.The use of optimal FA dosage and Ca/Si ratio leads to suitable water absorption,which further affects the failure mode of FA-CSH.

An Experimental Investigation on Workability and Bleeding Behaviors of Cement Pastes Doped with Nano Titanium Oxide (n-TiO 2) Nanoparticles and FlyAsh

In this study,the workability of cement-based grouts containing n-TiO 2 nanoparticles and fly ash has been investigated experimentally.Several characteristic quantities(including,but not limited to,the marsh cone flow time,the mini slump spreading diameter and the plate cohesion meter value)have been measured for different percentages of these additives.The use of fly ash as a mineral additive has been found to result in improvements in terms of workability behavior as expected.Moreover,if nano titanium oxide is also used,an improvement can be obtained regarding the bleeding values for the cement-based grout mixes.Using such experimental data,a multi-layer perceptron artificial neural network model has been developed(5 neurons in the hidden layer of the network model have been developed using a total of 42 experimental data).70%of the data employed in this model have been used for training,15%for validation and 15%for the test phase.The results demonstrate that the artificial neural network model can predict Marsh cone flow time,mini slump spreading diameter and plate cohesion meter values with an average error of 0.15%.

REMEDIATION OF POLLUTED SOILS BY UTILIZING HYDROTHERMALLY TREATED CALCAREOUS FLY ASHES

This paper investigates a treated fly ash to act as a synthetic zeolite to remediate soils polluted with heavy metals and metalloids （As, Pb, Cu, Zn, Fe, Cd and Mn）. Four types of such ＇zeolites＇ were synthesized by hydrothermal treatment of a calcareous fly ash derived from Greek lignite-fired power plants： two with excess of sodium hydroxide in a solid/liquid ratio of 50 g·L^-1, and two with excess of fly ash in a solid/liquid ratio of 100g·L^-1. Soil samples were obtained from a former mining site at Lavrion, Greece. Mobilization and transfer of metals to the retention agents was effected by using HCI aq 1M, with satisfactory results with respect to As, Pb, Cu, Mn and Cd. The great variety of metal complexes in soil was found to be of major importance for the effectiveness of the overall process. The final products were solidified either on their own, or by using additives such as lime and cement.

Bulk flow properties of fly ashes at ambient and high temperature

The bulk flow properties of four different fly ashes were assessed at ambient temperature and at 500 ~C, using a high temperature annular shear cell. These powders all resulted from industrial processes and had similar chemical compositions but different particle size distributions. Applying a high temperature was found to increase the powder cohesion, with this effect being more significant in the case of the sample with the highest proportion of fines. To better understand the effect of temperature on the bulk flow properties of these materials, a model previously proposed by some of the authors was used to correlate the powder isostatic tensile strength with the interparticle forces and microscale particle contact struc- ture. This model combines the continuum approach with description of particle-to-particle interactions. A comparison with experimental data indicated that the effects of consolidation and temperature on the tensile strength of the fly ashes were correctly described by the model. This theoretical approach also elucidates the mechanism by which the temperature affects the bulk flow properties of fly ashes through modifications of the microscale intemarticle contacts.