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.

Incorporating empirical knowledge into data-driven variable selection for quantitative analysis of coal ash content by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy(LIBS)has become a widely used atomic spectroscopic technique for rapid coal analysis.However,the vast amount of spectral information in LIBS contains signal uncertainty,which can affect its quantification performance.In this work,we propose a hybrid variable selection method to improve the performance of LIBS quantification.Important variables are first identified using Pearson's correlation coefficient,mutual information,least absolute shrinkage and selection operator(LASSO)and random forest,and then filtered and combined with empirical variables related to fingerprint elements of coal ash content.Subsequently,these variables are fed into a partial least squares regression(PLSR).Additionally,in some models,certain variables unrelated to ash content are removed manually to study the impact of variable deselection on model performance.The proposed hybrid strategy was tested on three LIBS datasets for quantitative analysis of coal ash content and compared with the corresponding data-driven baseline method.It is significantly better than the variable selection only method based on empirical knowledge and in most cases outperforms the baseline method.The results showed that on all three datasets the hybrid strategy for variable selection combining empirical knowledge and data-driven algorithms achieved the lowest root mean square error of prediction(RMSEP)values of 1.605,3.478 and 1.647,respectively,which were significantly lower than those obtained from multiple linear regression using only 12 empirical variables,which are 1.959,3.718 and 2.181,respectively.The LASSO-PLSR model with empirical support and 20 selected variables exhibited a significantly improved performance after variable deselection,with RMSEP values dropping from 1.635,3.962 and 1.647 to 1.483,3.086 and 1.567,respectively.Such results demonstrate that using empirical knowledge as a support for datadriven variable selection can be a viable approach to improve the accuracy and reliability of LIBS quantification.

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.

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.

Extraction of aluminum by pressure acid-leaching method from coal fly ash

Aluminum was leached out from coal fly ash by pressure acid-leaching method. The effects of coal fly ash size, sulfuric acid concentration, reaction time and reaction temperature on extraction efficiency of aluminum were investigated comprehensively. The phase and morphology of coal fly ash and solid residues after reaction were analyzed by XRD, SEM and IR. The optimal technological conditions for extracting aluminum from coal fly ash were eventually confirmed that coal fly ash with size of 74 μm and sulfuric acid with concentration of 50% are mixed in pressure reaction kettle to react for 4 h at 180 ℃. Under the optimal conditions, the extraction efficiency of aluminum can reach 82.4%.

Reaction behaviour of Al_2O_3 and SiO_2 in high alumina coal fly ash during alkali hydrothermal process

The reaction behaviours of A1203 and SiO2 in high alumina coal fly ash under various alkali hydrothermal conditions were studied. The means of XRD, XRF, FTIR and SEM were used to measure the mineral phase and morphology of the solid samples obtained by different alkali hydrothermal treatments as well as the leaching ratio of SiO2 to A1203 in alkali solution. The results showed that with the increase of the hydrothermal treating temperature from 75 to 160 ~C, phillipsite-Na, zeolite A, zeolite P, and hydroxysodalite were produced sequentially while the mullite and corundum phase still remained. Zeolite P was massively formed at low-alkali concentration and the hydroxysodalite was predominantly obtained at high-alkali concentration. By the dissolution of aluminosilicate glass and the formation of zeolites together, the leaching efficiency of SiO2 can reach 42.13% with the mass ratio of A1203/SIO2 up to 2.19：1.

Microstructure and properties of mullite-based porous ceramics produced from coal fly ash with added Al_2O_3

Using coal fly ash slurry samples supplemented with different amounts of Al2O3, we fabricated mullite-based porous ceramics via a dipping-polymer-replica approach, which is a popular method suitable for industrial application. The microstructure, phase composition, and compressive strength of the sintered samples were investigated. Mullite was identified in all of the prepared materials by X-ray diffraction analysis. The microstructure and compressive strength were strongly influenced by the content of Al2O3. As the Al/Si mole ratio in the starting materials was increased from 0.84 to 2.40, the amount of amorphous phases in the sintered microstructure decreased and the compressive strength of the sintered samples increased. A further increase in the Al2O3content resulted in a decrease in the compressive strength of the sintered samples. The mullite-based porous ceramic with an Al/Si molar ratio of 2.40 exhibited the highest compressive strength and the greatest shrinkage among the investigated samples prepared using coal fly ash as the main starting material. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

Microwave digestion and alkali fusion assisted hydrothermal synthesis of zeolite from coal fly ash for enhanced adsorption of Cd(Ⅱ) in aqueous solution

A novel microwave digestion and alkali fusion assisted hydrothermal method was proposed to synthesize zeolite from coal fly ash and the zeolite product was studied for removal of Cd(II)from aqueous solution through batch experiments.The adsorbent was characterized by X-ray diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,surface area analyzer and zeta potential measurement.The results show that the synthetic zeolite was identified as faujasite.The optimum conditions for removal of Cd(II)are found to be:adsorbent dose of0.5g/L,pH6,contact time of90min and initial concentration of20mg/L,the removal rate of Cd(II)is98.55%.The experimental kinetic data agree well with the pseudo second-order equation;the Langmuir isotherm model is found to be more suitable to explicate the experimental equilibrium isotherm results than Freundlich,Dubinin-Radushkevich and Temkin models,and the maximum adsorption capacity of Cd(II)is found to be86.96mg/g.The thermodynamic parameters such asΔGΘ,ΔHΘandΔSΘwere evaluated and the results show that the adsorption of Cd(II)onto the as-synthesized zeolite is spontaneous,endothermic and feasible under studied conditions.

Alkali desilicated coal fly ash as substitute of bauxite in lime-soda sintering process for aluminum production

By desilication treatment,the Al2O3/SiO2 molar ratio of coal fly ash could be improved to the range of 1.63-2.0.The desilicated coal fly ash(DSCFA)was enriched in alumina extraction.A processing technology was developed for alumina extraction from the DSCFA with the lime sintering process.Ca/(SiO2+TiO2)molar ratio,and NaO/Al2O3 molar ratio,sintering time,and temperature were the most significant parameters impacting on the aluminum extraction efficiency.The optima aluminum extraction efficiency was obtained under conditions of Ca/(SiO2+TiO2)molar ratio of 2.0,NaO/Al2O3 molar ratio of 0.98,and sintering at 1 200 ℃for 60 min.Astandard industrial dissolution method was used under conditions of caustic ratio(αk=n(NaO)/n(Al2O3)of 2.0,Al2O3 concentration of 50 g/L,sodium hydroxide concentration(Nk)of 60.78 g/L,Na2CO3 concentration of 10 g/L,temperature of 85℃, and dissolution duration of 10 min.The final aluminum extraction efficiency was 90%.

Recovery of metals and other beneficial products from coal fly ash： a sustainable approach for fly ash management

Increasing production and disposal of coal fly ash （CFA） is a matter of serious environment concern. However, CFA contains various beneficial metals and mineral matters whose demand is increasing in the industrialized world, while natural supplies are diminishing. Therefore, recovery of these potential resources from CFA can be an alternative way to save mineral resources, as well as to reduce the environmental burden of CFA disposal. There are numerous methods developed for the recovery of beneficial products from CFA. Based on the US patents and journal literatures, the present review describes the recovery status and technologies of major elements such as Al, Si, Fe and Ti, and trace elements such as V, Ga, Ge, Se, Li, Mo, U, Au, Ag, Pt groups and rare earth elements （REEs） and other beneficial products such as magnetic materials, cenospheres, and unburned carbon from CFA. It also highlights the recovery efficiency and drawbacks for their extraction, and suggests future research to develop satisfactory results in terms of selective recovery and purification.

Recovering germanium from coal ash by chlorination with ammonium chloride

A new process of enriching germanium from coal ash was developed. The processinvolves in mixing the coal ash and ammonium chloride and then roasting the mixture to producegermanium chloride that is then absorbed by dilute hydrochloric acid and hydrolyzed to germaniumoxide. The germanium recovery reached to 80.2% at the optimum condition: mass ratio of NH_4Cl/coalash is 0.15, roasting temperature 400℃ and roasting time 90 min.

Hydrothermal synthesis of zeolites-calcium silicate hydrate composite from coal fly ash with co-activation of Ca(OH)_(2)-NaOH for aqueous heavy metals removal

Coal fly ash is a typical secondary aluminum/silicon resource.The preparation of zeolite-type absorbent is a potential way for its value-added utilization,while the purity and adsorption property of zeolite are limited due to the occurrence of side reactions in the synthesis process.In this study,a designated composite consisted of crystalline zeolites and amorphous calcium silicate hydrate was selected,which was direct synthesized from fly ash under conditions of a Ca/Si molar ratio of 0.8,an initial NaOH concentration of 0.5 mol/L,a hydrothermal temperature of 170℃and a liquid–solid ratio of 15 mL/g.The results indicated that this composite had superior adsorption property for a variety of heavy metals,which was based on the exchange of calcium and sodium ions in zeolites and calcium silicate hydrate.Its adsorption capacities for Pb^(2+),Ni^(2+),Cd^(2+),Zn^(2+),Cu^(2+)and Cr^(3+)attained 409.4,222.4,147.5,93.2,101.1 and 157.0 mg/g,respectively,in single solution with a pH of 4.5.After regulating the synthesis conditions,the transformation of amorphous calcium silicate hydrate into crystallized tobermorite weakened the adsorption capacity of the composite.Besides,due to the competitive adsorption in a multiple ions solution,the adsorption capacities for these heavy metals had a reduction.

Kinetics of decomposition of mullite and corundum in coal fly ash under highly alkaline condition

Decomposition kinetics of mullite and corundum in coal fly ash with highly alkaline solution was studied.The effects of the reaction temperature and reaction time on decomposition rates of mullite and corundum and alumina extraction efficiency were investigated.The results show that increasing reaction temperature and reaction time increases the decomposition rates of mullite and corundum and alumina extraction efficiency,with the decomposition temperature of mullite lower than that of corundum.After 90 min reaction at 220℃,more than 100 g alumina was extracted when recycling 1 L of alkaline solution.The decomposition processes of mullite and corundum corresponded with the shrinking unreacted core model,and the reaction rate was under chemical reaction control,with the activation energies of mullite and corundum being 67.46 and 161.82 kJ/mol,respectively.

Character of the Si and Al Phases in Coal Gangue and Its Ash

Analysis of the Si and AI phases in coal gangue fuel and its ash is important for use of coal gangue ashes. A comprehensive study by theoretical and experimental analyses with differential thermal analysis, X-ray diffraction and Infrared Spectroscopy has been made in the present article to explore the diagram of the Si and Al phases in coal gangue fuel and its ashes. It is found that kaolinite and quartz are the main phases in coal gangue fuel. The ratio of moles A1203 to SiO2 （i.e., Al2O3 （mole） / SiO2 （mole）） is usually no more than 0.5 in most coal gangue fuel and its ashes. The kaolinit at about 984℃ releases a large quantity of SiO2, which makes calcine coal gangue more active than coal gangue itself. The relationship between the ratio A1203 （mole）]SiO2（mole）and the components of coal gangue ash is analyzed, resulting in a formula to calculate the quantity of each phase. Applying the formula to the testing samples from an electric plant in north China supports the above conclusions.

Determination of trace multi-elements in coal fly ash by inductively coupled plasma mass spectrometry

The contents of Cr, Cu, Ni, As, Cd and Pb in coal fly ash were determined by a high resolution inductively coupled plasma mass spectrometry method. The sample digestions were performed in closed microwave vessels with HNO3, HClO4 and FIE The optimum conditions for the determination were obtained. The applicability of the proposed method was validated by the analysis of coal fly ash reference material （NIST SRM 1633a）. The results show that most of the spectral interferences can be avoided by measuring in the high resolution mode （maximum mass resolution R=9 000）. The detection limit is from 0.05 to 0.21 μg/g, and the precision is fine with relative standard deviation less than 4.3%.

Adsorption of residual amine collector HAY from aqueous solution by refined carbon from coal fly ash and activated carbon

Refined carbon(RC) derived from coal fly ash(CFA) as well as powdered activated carbon(PAC) was investigated as adsorbent to remove residual amine collector HAY from aqueous solution.The RC and PAC were characterized by scanning electron microscopy(SEM),surface area measurement,Zeta potential measurement and Fourier transform infrared(FTIR) spectroscopy.The effect factors and mechanisms of HAY adsorption onto RC and PAC were studied in detail.The results show that the experimental kinetic data agree well with the pseudo second-order equation,and the Langmuir isotherm model is found to be more appropriate to explicate the experimental equilibrium isotherm results than the Freundlich model.The adsorption capacities of PAC and RC increase with pH.It is found that alkaline condition is conducive to the adsorption of HAY onto PAC and RC and the adsorption efficiency of RC is close to PAC at pH near 11.Zeta potential variation of adsorbents suggests that HAY generates electrostatic adsorption onto RC and PAC.FTIR analysis shows that the adsorption is dominantly of a physical process.The Box-Behnken design optimization conditions of process are RC 1 g/L,pH 11,temperature 302 K and initial HAY concentration 100 mg/L.Under these conditions,the measured adsorption ratio and adsorption capacity are 87.91%and 87.91 mg/g,respectively.Thus,the RC is considered to be a potential adsorbent for the removal of residual amine from aqueous solution.

Removal of lead(Pb(Ⅱ))and zinc(Zn(Ⅱ))from aqueous solution using coal fly ash(CFA)as a dual-sites adsorbent

Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with unique properties.This work focused on the adsorption of Pb(Ⅱ)and Zn(Ⅱ)from binary system,a mixture containing two metal ion solutions present simultaneously,onto NaOH-modified CFA(MCFA).Several adsorption tests were conducted to evaluate the effect of several parameters,including pH and contact times.The experiment results indicated that chemical treatment of CFA with NaOH increased pore volume from 0.021 to 0.223 cm^3·g^(-1).In addition,it could also enhance the availability of functional groups on both minerals and unburned carbon,resulting in almost 100%Pb(Ⅱ)and 97%Zn(Ⅱ)adsorbed.The optimum pH for adsorption system was pH=3 and quasi-equilibrium occurred in 240 minutes.Equilibrium data from the experimental results were analyzed using Modified Extended Langmuir(MEL)and Competitive Adsorption Langmuir-Langmuir(CALL)isotherm models.The analysis results showed that the CALL isotherm model could better describe the Pb(Ⅱ)and Zn(Ⅱ)adsorption process onto MCFA in binary system compared with MEL isotherm model.

Demineralization mechanism and influence of parameters on high ash Indian coal by chemical leaching of acid and alkali solution

The current research was investigated the mechanism of coal demineralization and the effect of leaching parameters on high ash coal and study the characterization of pre and post-treated coal. The two high ash Indian coal selected from Mahanadi Coalfield Limited, Odisha, pulverized to 375, 230 and 180 gm particle size were undergone simultaneous acid and alkali treatment at a different concentration, temperature and time. The percent demineralization was increased with decrease the size of the particle and rises with leaching parameters. The investigation suggested 180 μm particle size offers efficient demineralization for both coals at 30% NaOH and 30% H2SO4 concentration. The alkali leaching leads to obtaining the demineralization 46% and 42% whereas acid treatment resulted in 34% and 32% of the original coal samples. The extent of demineralization was improved the calorific value of coal. Besides, the degree of demineralization was proved from the FTIR, XRF and FESEM-EDX analysis results. FTIR analysis result showed that the peak intensity of mineral band decreased by the leaching effect and the degree of demineralization was significantly obtained to large extent by the X-ray Fluorescence spectrometer; which elucidates major minerals removed from coal by the leaching effect of acid and alkali solution.

Main influencing factors and coal fly ash characteristics of gasoues fuel reburning process

The unburned carbon concentration in fly ash and the influence of main factors on the reduction of nitrogen oxides during gaseous fuel reburning process were experimentally studied in a 36 kW down-fired furnace when five typical coals with different qualities were served as the primary fuel. It is found that the higher nitrogen oxide reduction efficiency can be obtained by reburning process when the coal used as the primary fuel contains more volatile matter. But under the optimizational operating conditions, both above 50% nitrogen oxide reduction and low carbon loss can be achieved by reburning process even though the primary fuel is the low-volatile coal. The experimental results show that the reasonable residence time in reburn zone is 0.6-0.9 s, the appropriate gaseous reburn fuel percentage is 10%-15% and the optimal average excess air coefficient in reburn zone is 0.8-0.9. These results extend the ranges of the key parameter values for reburning process with respect to that the low-volatile coals are used as the primary fuel.

Study on structural and compositional transitions of coal ash by using NMR

Structural and compositional transitions of Datong coal ash and its CaCO3 additional effects were carefully exam- ined at a temperature range of 300 to 1 600℃ by using XRD and solid state NMR. The quantitative estimation of amorphous structures of ashes can be successfully obtained through the analyses of solid state NMR spectra. Viscosity of molten ash and its changes with CaCO3 addition were also evaluated up to 1 700 ℃ by using a rotary type viscometer. Glasses with poor crystalline and amorphous phase were continuously formed through the eutectic reaction of silica above fusing temperature （FT〉1 500 ℃） that caused broadening and shift of 29Si and 27A1 peaks in NMR results. With the additional amount of CaCO3 increasing, the peaks shifted to downfield obviously; the fraction of Si（OA1）0（OSi）4 decreased, while that of Si（OA1）l（OSi）l at 84.3 x 10-6 increased apparently. These transitions indicated the destruction of large alumina-silicate framework into small segments by the addition of Ca ion.