High capacity cation exchanger by hydrothermal zeolitization of coal fly ash

During; hydrothermal treatment in NaOH medium coal fly ash partially transformed to zeolite P and/or hydroxysodalite, while quartz slowly dissolved and mullite remained stable. Residual coal favored the formation of zeolite P. The relative proportion of the two zeolites could be changed by seeding. During fusion of fly ash with NaOH an endothermic reaction at 170–180°C occurred, resulting in formation of an unreported Na aluminosilicate with approximate composition Na₁₅Si₄Al₃0₂₀ and major XIRD reflections at 4.793, 3.828, 3.000, 2.854, 2.578, and 2.524 Å. The product of fusion interacted with water giving aluminosilicate gel, which yielded zeolite P upon hydrothermal treatment at 100°C without aging and zeolite X after aging in water for 12 hours at room temperature. Cation exchange capacity was 420 and 400 meq/ 100 g for zeolite P and zeolite X respectively.     

Preparation of Na‐P1‐Type Zeolite and its Composite Material with Nanosized Magnetite

The Na‐P1‐type zeolite having a high cation‐exchange capacity (CEC) was obtained using the waste coal fly ash from thermal power stations and a 2M NaOH solution at 100°C. The Na‐P1‐type zeolite was formed with the reaction time of 6 h at 100°C, and its CEC value increased with an increase in the reaction time. The addition of a suitable amount of NaAlO₂ to the fly ash was also effective for improving the CEC value. A new composite material consisting of the Na‐P1‐type zeolite and magnetite was synthesized from the fly ash and iron chlorides because the magnetic collection was possible using this composite material after radioactive Cs⁺ ion adsorption. The existence of nanosized magnetites in the polycrystalline zeolite (several micrometers) was confirmed by TEM observations. The CEC and magnetic property of these composite materials were characterized.     

Properties and potential applications of zeolitic materials produced from fly ash using simple method of synthesis

Very low energy-consuming procedure is proposed for synthesis of zeolitic materials from fly ash. Three different zeolite materials (X, P and S), rich in zeolite phases, Na-X (FAU), NaP1 (GIS) and sodalite (SOD) were produced from F-class fly ash, using NaOH and NaCl solutions under atmospheric pressure at temperature below 110 °C.Obtained zeolitic products were analysed for their composition and physicochemical properties then compared to the raw fly ash and commercial adsorbents. The zeolitization results in a significant increase of CEC (from 5.5 up to 239 meq 100 g^− 1), and the high ability to adsorb heavy metal ions (over 40 mg g^− 1) and retain complex and organic molecules (EGME), mostly evident for material X. Adsorptive purification of waste and working lubricating oils using zeolitic products allow to provide their commercial applications in petroleum industry. Leachability of toxic elements after standard post-reaction washing is environmentally safe.     

Microwave-assisted zeolite synthesis from coal fly ash in hydrothermal process

Coal fly ashes, which include much amount of silica and alumina, can be converted into zeolite by hydrothermal alkaline treatment. In the present work, the effect of microwave irradiation on the zeolite formation was investigated with emphasis on the change in yield of zeolite during the reaction. The fly ash was mixed with 2 M NaOH solution and heated by oil bath or microwave for 2 h. Zeolite Na-P1 formed after the conventional treatment using oil bath, but no zeolitic product was obtained by microwave heating. When microwave was applied in the course of hydrothermal treatment, zeolitization was promoted by the early-stage irradiation. This is due to the stimulated dissolution of SiO₂ and Al₂O₃ from coal fly ash. On the other hand, the microwave irradiation in the middle to later stage retarded the crystallization of zeolite. The microwave is effective to produce the zeolite from coal fly ash in a short period by control of irradiation schedule in the early stage.     

Breakthrough analysis of carbon dioxide adsorption on zeolite synthesized from fly ash

Zeolite (FAZ) was synthesized by the fusion method using coal fly ash to adsorb carbon dioxide. The experimental adsorption was operated batchwise in a laboratory-scale packed-bed adsorber to obtain the breakthrough curves of CO₂ under conditions such as adsorption temperatures (20–80 °C), flow rates of gaseous mixture of carbon dioxide and nitrogen (40–100 cm³/min), and concentration of CO₂ (3000–10000 ppmv) at atmospheric pressure of 101.3 kPa. The influence of the experimental conditions, such as the gas flow rate, concentration of CO₂ and adsorption temperature on adsorption behavior, was discussed. The deactivation model, combined the adsorption with the deactivation of adsorbent, was used to analyze the physicochemical properties, such as the adsorption kinetics, capacity and heat of adsorption, by fitting the experimental data of the breakthrough curves to this model. The adsorptive activity and capacity of FAZ were as almost same as those of the commercial zeolite of Wako 4A.     

Conversion of Fly Ash to Swelling Mica: A New Approach for Recycling Fly Ash

Swelling mica exhibits unique characteristics for purification of drinking water contaminated by heavy metals and for selective removal of Sr²⁺ and Ba²⁺ ions from nuclear waste solution. As a new approach to recycle fly ash, conversion of fly ash to swelling mica has been attempted and ion-exchange properties of fly ash-derived swelling mica (referred to hereinafter as FA-swelling mica) were examined in this study. Thermal treatment of fly ash with MgO in the presence of excess NaF led to the formation of swelling mica along with trace quantities of impurities. A swelling mica of good quality was obtained from the reactant ratio of fly ash 1 g : MgO 0.75 g : NaF 1.75 g. Unlike gel or kaolinite-derived synthetic Na-4-micas, FA-swelling mica exhibited heterogeneity in its framework. Its uptake capacity for Sr²⁺ ions was estimated to be 17.4 meq/100 g from 0.1 mM SrCl₂ aqueous solution and 5.0 meq/100 g from 0.5 N NaCl solution containing the same Sr²⁺ concentration. These capacities are less than that of metakaolin-derived Na-4-mica. However, its ion exchange capacity for divalent transitional metal ions was estimated to be 284 meq/100 g from their inaqueous solutions and 206 meq/100 g from the 0.5 N NaCl solution containing the mixed metal ions of Cd²⁺, Co²⁺, Mn²⁺, Ni²⁺ and Zn²⁺ each at 1 mN concentration. These capacities are comparable to that of metakaolin-derived Na-4-mica. Its selectivity for transition metal ions is as follows: Zn²⁺ > Ni²⁺ Co²⁺ Cd²⁺ > Mn²⁺ and this is consistent with the G° values from Gibbs-Duhem equation. These results clearly showed that fly ash could be converted to swelling mica with high uptake capacity for divalent transitional metal ions. Therefore, conversion of fly ash to highly pure swelling mica will lead to a resource from waste.     

Resource Recovery of Waste Incineration Fly Ash: Synthesis of Zeolites A and P

The conversion of waste incineration fly ash to zeolitic compounds by hydrothermal treatment in the presence of NaOH solution has been investigated. An acid pretreatment of fly ash in addition to water washing and heating at 800°C was found to be an important process to prepare reproducible zeolitic compounds. Treatment with a low-concentration NaOH solution at 60°C and 100°–120°C successfully produced zeolites A and P, respectively, as major products. At increased concentrations of NaOH, sodalite was generated. The hydrothermal products showed uptake behavior for NH₄⁺ ions.     

Zeolites-containing geopolymers obtained from biomass fly ash: Influence of temperature,composition, and porosity

In this research, compositional and processing parameters were varied to obtain zeolites-containing geopolymers using mainly biomass fly ash wastes. In addition to curing temperatures, another primary factor affecting the typologies of the resulting zeolites was composition. The mixture composition used in the synthesis crucially affects the nature of the zeolitic crystalline phases in the geopolymeric matrix. Using 10 mol/L NaOH solution, faujasite-type zeolites produced in geopolymers show a surface area of ~100 m²/g (BET), while those prepared by 8 mol/L NaOH solution have a much lower surface area of ~19 m²/g.     

Zeolitization of mineral wastes by molten-salt method: NaOH–KNO3 system

Salt-thermal method exhibits several features such as high production yield, large-scale conversion, low elemental loss, and environmentally benign nature. This study has investigated the optimization of the NaOH–KNO₃ system for the zeolitization of fly ash and elucidated the characteristics of the resulting zeolitic materials. The following are the optimal reaction conditions for zeolitization of fly ash in NaOH–KNO₃ system: a temperature of 250 °C, 0.3–0.5 weight ratio of NaOH/KNO₃ and 0.7–1.4 weight ratio of KNO₃/fly ash. The NaOH–KNO₃ system is also confirmed for facile zeolitization of anthracite briquette, kaolinite, and pumice. The NaOH–KNO₃ system is likely to result in KNO₃ occlusion or/and trapping. Because KNO₃ supplies two plant nutrients, the zeolitic materials synthesized by the NaOH–KNO₃ system could be used in agriculture as soil conditioners and fertilizer additives. It is clearly shown in this study that KNO₃ could be employed in place of NaNO₃ in the salt-thermal method with a potential use of the product as soil conditioner and fertilizer.     

Immobilization of Cs,Cd, Pb and Cr by synthetic zeolites from Spanish low-calcium coal fly ash

This report describes a study of the immobilization of Cs⁺, Cd²⁺, Pb²⁺ and Cr³⁺ by synthetic zeolites formed as a result of the hydrothermal treatment of Spanish class F coal fly ash in a 1 M solution of NaOH. The majority zeolite formed at 150 °C was a gismondine-type P1-Na species (Na₆Al₆Si₁₀O₃₂·12H₂O), which at 200 °C transformed into analcime-C zeolite (Na(Si₂Al)O₆H₂O). The shift in pore size distribution towards pores with diameters of about 2.2 nm observed after the zeolites were washed entailed an increase in the specific surface area, to values nearly double the figures recorded prior to washing. With a high selectivity for Cs, the gismondine type Na zeolite P was found to be the best candidate for immobilizing radioactive waste. Gismondine and analcime-C zeolites also exhibited high Cd selectivity.     

Synthesis and adsorption performance of fly ash/steel slag-based geopolymer for removal of Cu (II) and methylene blue

In order to realize the value-added resource utilization of solid waste, geopolymer particle adsorbents were prepared at low temperatures using silica-aluminum-rich fly ash and steel slag powders as raw materials. In order to investigate the mechanism of their adsorption of dyes and heavy metal ions from wastewater, the effects of steel slag/fly ash ratio, adsorbent dosage, initial concentration of methylene blue (MB) and Cu²⁺ solution, adsorption time and temperature on the adsorption performance of the fly ash/steel slag-based geopolymer adsorbents were investigated, systematically. Results presented that the adsorption capacities of MB and Cu²⁺ were 33.30 and 24.15 mg/g, and the removal efficiencies were 99.90% and 96.59% with the dosages of 3 and 4 g/L geopolymer adsorbents (steel slag/fly ash ratio of 20 wt.%), respectively. The adsorption processes of MB and Cu²⁺ on the adsorbents were in accordance with the proposed pseudo-second-order and Langmuir isotherm models, which mainly included physical and chemical adsorption mechanisms. The adsorption was a spontaneous endothermic process. The fly ash/steel slag-based geopolymer had good removal ability for dyes and heavy metal ions, and it could maintain good adsorption performance after three cycles of regeneration. It had potential application in wastewater treatment.     

Adsorption of heavy metal ions from aqueous solution by fly ash

The removal characteristics of lead and copper ions from aqueous solution by fly ash were investigated under various conditions of contact time, pH and temperature. The influence of pH of the metal ion solutions on the uptake levels of the metal ions by fly ash were carried out between pH 4 and 12. The level of uptake of Pb²⁺ and Cu²⁺ ions by the fly ash generally increased, but not in a progressive manner, at higher pH values. The effect of temperature on the uptake of Pb²⁺ and Cu²⁺ ions was investigated between 30 °C and 60 °C, the adsorption of being enhanced at the lowest temperature. Rate constants were evaluated in terms of a first-order kinetics. The rate constant, k for uptake of Pb²⁺ and Cu²⁺ ions were 1.77 × 10⁻² s⁻¹ and 2.11 × 10⁻² s⁻¹, respectively. The experimental results underline the potential of coal fly ash for the recovery of metal ions from waste water. The main mechanisms involved in the removal of heavy metal ions from solution were adsorption at the surface of the fly ash and precipitation.     

Adsorptive removal of thiophene and benzothiophene over zeolites from Mae Moh coal fly ash

Zeolites have been hydrothermally synthesized using Thai coal fly ash from Mae Moh Power Plant as silica and alumina sources. The synthesis conditions, i.e., SiO₂/Al₂O₃ ratio, amount of water, amount of base, and aging temperature, were varied to prepare different topologies of zeolitic products. The zeolites attained were sodalite (SOD), gismondine (GIS), and cancrinite (CAN). The zeolites have been applied to adsorption of thiophene and benzothiophene in n-hexane solution. It was found that GIS with higher specific surface area and average pore volume had superior performance to other synthesized materials. Adsorption capacity of our developed zeolites was compared to those of commercial zeolites, i.e. NaY, HUSY, beta, and ZSM-5 obtained via the conventional synthesis methods. The results suggested a potential of zeolites derived from Mae Moh coal fly ash for removal of refractory sulfur compounds, such as benzothiophene.     

Industrial wastes derived solid adsorbents for CO2 capture: A mini review

Coal combustion in thermal power plants throughout the world produces large amounts of fly ash. Disposal of fly ash is a serious threat to the environment and hence is a worldwide concern for conversion of these wastes into useful products. Synthesis of mesoporous silica materials from coal fly ash has already been proposed as an option which can be utilized as an adsorbent. Adsorption is considered to be one of the more promising technologies for capturing CO₂ from flue gases. This paper reviews the recent development of solid adsorbents from industrial waste materials with special reference to fly ash for post-combustion capture of CO₂.     

Zeolite synthesis from coal fly ash for the removal of lead ions from aqueous solution

Fly ash samples from the Bayswater and Eraring power plants, located in New South Wales, Australia, were used in a preliminary study on zeolite synthesis by hydrothermal treatment with sodium hydroxide under various conditions. The treated fly ash was tested for the ability to remove lead ions from aqueous solution. Both fly ashes were partially converted to zeolite. The zeolites formed under the experimental conditions were zeolite Na‐P1 and sodalite octahydrate for the Bayswater ash and phillipsite, zeolite X, zeolite Na‐P1 and sodalite octahydrate for the Eraring ash. The type of zeolite formed was dependent on the treatment time and sodium hydroxide concentration. In the case of the Bayswater ash, zeolite Na‐P1 was formed by treatment with 4 mol dm^?3 NaOH for 48 h while treatment with 5 mol dm^?3 NaOH for 96 h produced sodalite octahydrate at the expense of zeolite Na‐P1. In the case of the Eraring ash, phillipsite was formed following treatment with 3 mol dm^?3 NaOH, zeolite X and zeolite Na‐P1 were formed following treatment with 4 mol dm^?3 NaOH and sodalite octahydrate was formed following treatment with 5 mol dm^?3 NaOH. A maximum cation exchange capacity of ～400 meq/100 g was achieved by both treated ash samples. Treatment of a solution with a lead ion concentration of 120 ppm using 0.5 g of both treated ash samples (S/L ratio = 0.25 g/100 cm³) achieved complete removal in 5 min, whereas treatment with 0.1 g of each material (S/L ratio = 0.05 g/100 cm³) achieved complete lead ion removal after 24 h. © 2001 Society of Chemical Industry     

Preparation and characterization of mullite whisker reinforced ceramics made from coal fly ash

Ceramics with mullite whiskers were prepared from coal fly ash and Al₂O₃ raw materials, with AlF₃ used as an additive. The phase structures and microstructures of the ceramics were identified via X-ray diffraction and scanning electron microscopy, respectively. The results show that pickling of coal fly ash is an effective method for enhancing the flexural strength of ceramics. Sintering temperature and AlF₃ addition were also key factors influencing the creation of ideal ceramics. The ceramic made from pickled coal fly ash, 6?wt% AlF₃, and sintered at 1200?°C, exhibited the highest flexural strength of 59.1?MPa, and had a bulk density of 1.32?g/cm³ and porosity of 26.8%. The results show that ceramic materials made under these conditions are ideal candidates for manufacturing ceramic proppants for the exploitation of unconventional oil and gas resources.     

Low cost adsorbents obtained from ash for copper removal

We investigated the utilization of ash and modified ash as a low-cost adsorbent to remove copper ions from aqueous solutions such as wastewater. Batch experiments were conducted to determine the factors affecting adsorption of copper. The influence of pH, adsorbent dose, initial Cu²⁺ concentration, type of adsorbent and contact time on the adsorption capacity of Cu²⁺ from aqueous solution by the batch adsorption technique using ash and modified ash as a low-cost adsorbent were investigated. The optimum pH required for maximum adsorption was found to be 5. The results from the sorption process showed that the maximum adsorption rate was obtained at 300 mg/L when a different dosage of fly ash was added into the solution, and it can be concluded that decreasing the initial concentration of copper ion is beneficial to the adsorption capacity of the adsorbent. With the increase of pH value, the removal rate increased. When the pH was 5, the removal rate reached the maximum of over 99%. When initial copper content was 300 mg/L and the pH value was 5, the adsorption capacity of the zeolite Z 4 sample reached 27.904 mg/g. The main removal mechanisms were assumed to be the adsorption at the surface of the fly ash together with the precipitation from the solution. The adsorption equilibrium was achieved at pH 5 between 1 and 4 hours in function of type of adsorbent. A dose of 1: 25 g/mL of adsorbent was sufficient for the optimum removal of copper ions. For all synthesized adsorbents the predominant mechanism can be described by pseudo-second order kinetics.     

Characteristics and composition of fly ash from Canadian coal-fired power plants

Fly ashes were collected from the electrostatic precipitator (ESPs) and/or the baghouse of seven coal-fired power plants. The fly ashes were sampled from power plants that use pulverized subbituminous and bituminous feed coals. Fly ash from bituminous coals and limestone feed coals from fluidized-bed power plant were also sampled. The fly ashes were examined for their mineralogies and elemental compositions. The fly ashes from pulverized low sulfur coals are ferrocalsialic, those from high sulfur coals are ferrosialic and the fly ashes from the fluidized bed coals are ferrocalcic. The concentrations of As, Cd, Hg, Mo, Ni, and Pb in fly ash are related to the S content of the coal. Generally, those feed coals with a high S content contain higher concentrations of these elements. The concentrations of these elements are also greater for baghouse fly ash compared to ESP fly ash for the same station. The S content of fly ash from high S coal is 0.1% for pulverized ESP fly ash and 7% for baghouse fly ash from the fluidized bed, indicating that most of the S is captured by fly ash in the fluidized bed. The baghouse fly ash from the fluidized bed has the highest content of Cd, Hg, Mo, Pb, and Se, indicating that CaO, for the most part, captures them. Arsenic is captured by calcium-bearing minerals and hematite, and forms a stable complex of calcium or a transition metal of iron hydroxy arsenate hydrate [(M²⁺)₂Fe₃(AsO₄)₃(OH)₄·10H₂O] in the fly ash. Most elements in fly ash have enrichment indices of greater than 0.7 indicating that they are more enriched in the fly ash than in the feed coal, except for Hg in all ESP ashes. Mercury is an exception; it is more enriched in baghouse fly ash compared to ESP. Fly ash collected from a station equipped with hot side ESP has a lower concentration of Hg compared to stations equipped with cold side ESP using feed coals of similar rank and mercury content. Fly ash particles from fluidized bed coal are angular and subangular with cores of quartz and calcite. The quartz core is encased in layer(s) of calcium-rich aluminosilicates, and/or calcium/iron oxides. The calcite core is usually encased in an anhydrite shell.     

Volatility of fly ash and coal

The volatilization of fly ash has been examined by a number of techniques including TGA—DTA, Knudsen cell mass spectrometry, volatilization of neutron-activated fly ash, and X-ray fluorescence analysis of sized fly ash, low-temperature ash, and the parent coal. At low temperatures, H₂O, CO₂, SO₂, and a number of organic compounds are the primary volatile species as determined by mass spectrometry. Analysis of the volatiles collected from activated fly ash heated to temperatures up to 1400 °C shows that Hg, Se, As, Br, and I are nearly completely volatilized. The analysis of the bulk and size fractions of fly ash, and parent coal, is consistent with this and provides evidence for volatilization of 15 elements during coal combustion. Comparison of coal and fly ash compositions also shows that significant amounts of Se are still present in the gas phase at the precipitators and more than 50 wt % of the Se is contained in the stack emissions. The results are consistent with present models for fly ash formation and trace element enrichment.     

Thin fly ash/ ladle furnace slag geopolymer: Effect of elevated temperature exposure on flexural properties and morphological characteristics

The flexural properties and thermal performance of 10 mm-thin geopolymers made from fly ash and ladle furnace slag were evaluated before and after exposure to elevated temperatures (300 °C, 600 °C, 900 °C, 1100 °C and 1150 °C). Class F fly ash was mixed with liquid sodium silicate (Na₂SiO₃) and 12 M sodium hydroxide (NaOH) solution using aluminosilicate/activator ratio of 1:2.5 and Na₂SiO₃/NaOH ratio of 1:4 to synthesise thin fly ash (FA) geopolymers. 40 wt% of ladle furnace slag was partially replacing fly ash to produce fly ash/slag-based (FAS) geopolymers. Thermal treatment enhanced the flexural strength of thin geopolymers. In comparison to the unexposed specimen, the flexural strength of FA geopolymers at 1150 °C and FAS geopolymers 1100 °C was increased by 161.3% to 16.2 MPa and 208.9% to 24.1 MPa, respectively. A more uniform heating was achieved in thin geopolymers which favoured the phase transformation at high temperatures and contributed to the substantial increase in flexural strength. The joint effect of elevated temperature exposure and the incorporation of ladle furnace slag further improved the flexural strength of thin geopolymers. The calcium-rich slag refined the pore structure and increased the crystallinity of thin geopolymers which aided in high strength development.