Synthesis of zeolite Li-ABW from fly ash by fusion method

The zeolite Li-ABW was synthesized by fusion method using fly ash as raw material. It comprised alkaline fusion followed by hydrothermal treatment in LiOH·H₂O medium. Crystallinity of zeolite as high as 97.8% was attained under the following conditions: LiOH·H₂O concentration, 3 M; hydrothermal temperature, 180 °C; the corresponding aging time, 12 h. The content of Li-ABW increased at the expense of lithium aluminum silicate or quartz with an increase of LiOH·H₂O concentration. With increasing hydrothermal temperature and aging time, the soluble species re-crystallized and crystalline phase transformation between different zeolites was observed. Scanning electron microscopy (SEM) observation revealed that the obtained zeolite Li-ABW was a rod-like crystal. The pore size distribution curve indicated the presence of mesopores.     

Influence of NaOH concentrations on synthesis of pure-form zeolite A from fly ash using two-stage method

Synthesis of pure-form zeolite A were investigated using four concentrations of NaOH solution to dissolve Si source form fly ash, and with the addition of Al source, to prepare initial gel. Experimental results demonstrated, for two-stage method, that NaOH concentrations in initial gel played an important role in synthesis of pure-form zeolite A using fly ash as raw materials. Generally, pure-form zeolite A could be synthesized when following conditions were used: NaOH concentrations, 1.67, 5 and 6.67 M; the synthesis temperature, 100 °C; the corresponding crystallization time, 340, 250 and 190 min. However, a mixture phases of zeolites A and X were obtained at the condition of 3.33 M NaOH solution during various crystallization times. It was found that the higher NaOH concentration was used, the shorter crystallization time of zeolite A was required and the narrower particle size distribution of zeolite A was achieved. In addition, zeolite A submicron-crystals were first synthesized from fly ash using two-stage method in our study.     

Adsorption of herbicides on coal fly ash from aqueous solutions

Development of low cost adsorbent for pesticide retention is an important area of research in environmental sciences. The present study reports the sorption potential of coal fly ash, a waste from power stations, for removal of metribuzin, metolachlor and atrazine from water. Batch sorption method was used to study the sorption of herbicides from water. The amount of herbicides sorbed increased with increase in the amount of fly ash in the suspension. The maximum capacity of the fly ash to adsorb metribuzin, metolachlor and atrazine was found to be 0.20, 0.28 and 0.38 mg/g by Freundlich equation and 0.56, 1.0 and 3.33 mg/g by Langmuir equation. Freundlich adsorption equation better explained the results of herbicides sorption in fly ash as regression coefficient (R²) values were higher from Freundlich equation than the Langmuir equation. Adsorption isotherms were L-type suggesting that the herbicide sorption efficiency of fly ash depend on the initial concentration of herbicide in the solution and maximum removal of herbicide was observed at concentrations less than 10 μg/ml. The results of this study have implications in using the fly ash for removal of these herbicides from industrial and agricultural waste water and can find use as a material in the preparation of biobeds to minimize environmental contamination from pesticide use.     

Dielectric properties of fly ash

This paper reports the dielectric properties of fly ash. The dielectric measurements were performed as a function of frequency and temperature. The sample of fly ash shows almost similar behaviour in the frequency and temperature range studied. The large value of dielectric constant in the typical frequency range is because of orientation polarization and tight binding force between the ions or atoms in the fly ash. The sample of fly ash is of great scientific and technological interest because of its high value of dielectric constant (10⁴).     

Alkali-activated fly ash-based geopolymers with zeolite or bentonite as additives

Geopolymers were synthesized by using fly ash as the main starting material, zeolite or bentonite as supplementary materials, and NaOH and CaO together as activator. An orthogonal array testing protocol was used to analyze the influence of the mix proportion on the properties of the geopolymers. The results indicate that the concentration of NaOH solution and the CaO content play an important role on the strength of the materials. Especially, with zeolite as additive, the fly ash-based geopolymer shows the highest strength and the best sulfate resistance. Infrared spectroscopy, X-ray, and SEM–EDX demonstrate that supplementary zeolite may involve the process of geopolymerization to form a stable zeolitic structure and improve the properties of the geopolymer. Bentonite simply acts as a filler to make the geopolymer more compact, but shows no improvement on the compositions and the microstructures of the geopolymer.     

Arsenate removal from water by an alumina-modified zeolite recovered from fly ash

A cancrinite-type zeolite was synthesized from Class C fly ash by molten-salt method. The product (ZFA) was used as the adsorbent for the arsenate removal from water. The adsorption equilibriums of arsenate are investigated on various adsorbents. ZFA showed a higher adsorption capacity (5.1 mg g(-1)) than activated carbon (4.0 mg g(-1)), silica gel (0.46 mg g(-1)), zeolite NaY (1.4 mg g(-1)), and zeolite 5A (4.1 mg g(-1)). The relatively higher adsorption capacity of ZFA than zeolite NaY and 5A was attributed to the low Si/Al ratio and the mesoporous secondary pore structure of ZFA. However, it was found that the adsorption capacity of zeolites were generally lower than activated alumina (16.6 mg g(-1)), which is ascribed to the small pores in zeolite frameworks. The adsorption capacity of ZFA was significantly improved after loaded by alumina via a wet-impregnation method. The modified ZFA (ZFA-Al(50)) with the optimum alumina loading showed an adsorption capacity of 34.5 mg g(-1), which was 2.1 times higher than activated alumina. The Toxicity Characteristic Leaching Procedure (TCLP) leachability tests indicated that the spent ZFA and alumina-modified ZFA complied with the EPA regulations for safe disposal.     

Green activating silica-alumina insoluble phase of fly ash to synthesize zeolite P with high adsorption capacity for Pb(II) in solution

Using fly ash as a raw material to synthesize zeolite is an effective way to obtain cheap adsorbent. However, the high energy consumption of activating the insoluble silica-alumina phase of fly ash limits its practical application. In this study, a low-energy, wet-grinding hydrothermal method was used to activate the insoluble phase of fly ash to synthesize zeolite P, and the adsorption capacity of zeolite for lead ion in solution was studied. Wet-grinding can reduce fly ash particle size to nanometer scale and break long-chain Q⁴(Al) into short-chain low-polymer. Without aging, the activated material could directly synthesize zeolite P with a relative crystallinity of 89.37 %. Compared with the common alkali-fusion method, the wet-grinding method reduced energy consumption by 45.93 % and increased synthetic zeolite relative crystallinity by 7.51 %. The synthesized zeolite P could effectively remove Pb²⁺ ions from solution through ion exchange and hydroxyl reaction, and the adsorption capacity reached 497.01 mg/g.     

Phosphate removal from aqueous solutions using raw and activated red mud and fly ash

The effect of acidification and heat treatment of raw red mud (RM) and fly ash (FA) on the sorption of phosphate was studied in parallel experiments. The result shows that a higher efficiency of phosphate removal was acquired by the activated samples than by the raw ones. The sample prepared by using the RM stirred with 0.25 M HCl for 2h (RM0.25), as well as another sample prepared by heating the RM at 700 degrees C for 2h (RM700), registered the maximum removal of phosphate (99% removal of phosphate). This occurred when they were used in the phosphate sorption studies conducted at pH 7.0 and 25 degrees C with the initial PO(4)(3-) concentration of 155 mg P/l. The FA samples treated in the same way described above can achieve 7.0 and 8.2 mg P/l phosphate removal for FA0.25 and FA700 respectively, corresponding to 45.2% and 52.9% removal. The activated materials performed higher phosphate removal over broader pH range compared with the raw ones. The influences of various factors, such as initial pH and initial phosphate concentration on the sorption capacity were also studied in batch equilibration technique. Solution pH significantly influenced the sorption. Each sample achieved the maximal removal of phosphate at pH 7.0. The amount of phosphate removal increased with the solute concentration. The Freundlich and Langmuir models were used to simulate the sorption equilibrium. The results indicate that the Langmuir model has a better correlation with the experimental data than the Freundlich model.     

Removal of trivalent chromium from aqueous solution by zeolite synthesized from coal fly ash

The capability of 14 zeolites synthesized from different fly ashes (ZFAs) to sequestrate Cr(III) from aqueous solutions was investigated in a batch mode. The influence of pH on the sorption of Cr(III) was examined. ZFAs had a much greater ability than fly ash to remove Cr(III), due to the high cation exchange capacity (CEC) and the high acid neutralizing capacity (ANC) of ZFAs. The mechanism of Cr(III) removal by ZFAs involved ion exchange and precipitation. A high-calcium content in both the fly ashes and ZFAs resulted in a high ANC value and, as a result, a high immobilization capacity for Cr(III). The pH strongly influenced Cr(III) removal by ZFAs. Inside the solubility range, removal of chromium increased with increasing pH. Hydroxysodalite made from a high-calcium fly ash had a higher sorptive capacity for Cr(III) than the NaP1 zeolite from medium- and low-calcium fly ashes. On the other hand, at pH values above the solubility range, the efficiency of chromium removal by the ZFAs approached 100% due to the precipitation of Cr(OH)3 on the sorbent surfaces. It is concluded that ZFAs and high-calcium fly ashes may be promising materials for the purification of Cr(III) from water/wastewater.     

Differential behaviour of combustion and gasification fly ash from Puertollano Power Plants (Spain) for the synthesis of zeolites and silica extraction

Coal gasification (IGCC) and pulverised coal combustion (PCC) fly ashes (FAs), obtained from two power plants fed with the carboniferous bituminous coal from Puertollano (Spain), were characterised and used as raw materials for zeolite synthesis by direct conversion (DC) and by alkaline fusion (Fu), and SiO₂ extraction (Si-Ex) at laboratory scale. The Puertollano FAs are characterised by a high SiO₂ content (59%) with respect to EU coal FAs. High zeolite synthesis yields were obtained from both FAs by using conventional alkaline activation. However, the Si extraction yields were very different. The results of the zeolite synthesis from the Si-bearing extracts from both FAs demonstrated that high purity zeolites with high cation exchange capacity (CEC, between 4.3 and 5.3 meq/g) can be produced. The solid residue arising from Si-Ex is also a relatively high NaP1 zeolite product (CEC 2.4–2.7 meq/g) equivalent to the DC products. The zeolitic materials synthesised from both FAs by Fu showed an intermediate (between the high purity zeolites and the DC products) zeolite content with CEC values from 3.4 to 3.7 meq/g. Low leachable metal contents were obtained from high purity A and X zeolites and zeolite material synthesised by Fu for PCC FA.     

Efficiency of fly ash belite cement and zeolite matrices for immobilizing cesium

The efficiency of innovative matrices for immobilizing cesium is presented in this work. The matrix formulation included the use of fly ash belite cement (FABC-2-W) and gismondine-type Na-P1 zeolite, both of which are synthesized from fly ash of coal combustion. The efficiency for immobilizing cesium is evaluated from the leaching test ANSI/ANS 16.1-1986 at the temperature of 40 degrees C, from which the apparent diffusion coefficient of cesium is obtained. Matrices with 100% of FABC-2-W are used as a reference. The integrity of matrices is evaluated by porosity and pore-size distribution from mercury intrusion porosimetry, X-ray diffraction and nitrogen adsorption analyses. Both matrices can be classified as good solidify systems for cesium, specially the FABC-2-W/zeolite matrix in which the replacement of 50% of belite cement by the gismondine-type Na-P1 zeolite caused a decrease of two orders of magnitude of cesium mean Effective Diffusion Coefficient (D(e)) (2.8e-09 cm(2)/s versus 2.2e-07 cm(2)/s, for FABC-2-W/zeolite and FABC-2-W matrices, respectively).     

Treatment of radioactive liquid waste by sorption on natural zeolite in Turkey

Liquid radioactive waste has been generated from the use of radioactive materials in industrial applications, research and medicine in Turkey. Natural zeolites (clinoptilolite) have been studied for the removal of several key radionuclides ((137)Cs, (60)Co, (90)Sr and (110m)Ag) from liquid radioactive waste. The aim of the present study is to investigate effectiveness of zeolite treatment on decontamination factor (DF) in a combined process (chemical precipitation and adsorption) at the laboratory tests and scale up to the waste treatment plant. In this study, sorption and precipitation techniques were adapted to decontamination of liquid low level waste (LLW). Effective decontamination was achieved when sorbents are used during the chemical precipitation. Natural zeolite samples were taken from different zeolite formations in Turkey. Comparison of the ion-exchange properties of zeolite minerals from different formations shows that Gordes clinoptilolite was the most suitable natural sorbent for radionuclides under dynamic treatment conditions and as an additive for chemical precipitation process. Clinoptilolite were shown to have a high selectivity for (137)Cs and (110m)Ag as sorbent. In the absence of potassium ions, native clinoptilolite removed (60)Co and (90)Sr very effectively from the liquid waste. In the end of this liquid waste treatment, decontamination factor was provided as 430 by using 0.5 mm clinoptilolite at 30 degrees C.     

Strength properties of fly ash based controlled low strength materials

Controlled low strength material (CLSM) is a flowable mixture that can be used as a backfill material in place of compacted soils. Flowable fill requires no tamping or compaction to achieve its strength and typically has a load carrying capacity much higher than compacted soils, but it can still be excavated easily. The selection of CLSM type should be based on technical and economical considerations for specific applications. In this study, a mixture of high volume fly ash (FA), crushed limestone powder (filler) and a low percentage of pozzolana cement have been tried in different compositions. The amount of pozzolana cement was kept constant for all mixes as, 5% of fly ash weight. The amount of mixing water was chosen in order to provide optimum pumpability by determining the spreading ratio of CLSM mixtures using flow table method. The shear strength of the material is a measure of the materials ability to support imposed stresses on the material. The shear strength properties of CLSM mixtures have been investigated by a series of laboratory tests. The direct shear test procedure was applied for determining the strength parameters Phi (angle of shearing resistance) and C(h) (cohesion intercept) of the material. The test results indicated that CLSM mixtures have superior shear strength properties compared to compacted soils. Shear strength, cohesion intercept and angle of shearing resistance values of CLSM mixtures exceeded conventional soil materials' similar properties at 7 days. These parameters proved that CLSM mixtures are suitable materials for backfill applications.     

Transport properties of high volume fly ash roller compacted concrete

This paper describes research on the transport properties of high-volume fly ash roller compacted concrete (RCC). The mixes were developed through incorporating 50–260 kg/m³ cement and high volumes of fly ash ranging from 40% to 85% by mass of the total cementitious material. The concretes were investigated for permeability, absorption, sorption and chloride diffusion. The study showed that RCCs of moderate cement and moderate fly ash contents had lower values of permeability, absorption, sorption and chloride diffusivity.     

Removal mechanism of phosphate from aqueous solution by fly ash

This work studied the effectiveness of fly ash in removing phosphate from aqueous solution and its related removal mechanism. The adsorption and precipitation of phosphate by fly ash were investigated separately in order to evaluate their role in the removal of phosphate. Results showed that the removal of phosphate by fly ash was rapid. The removal percentage of phosphate in the first 5min reached 68-96% of the maximum removal of phosphate by fly ash. The removal processes of phosphate by fly ash included a fast and large removal representing precipitation, then a slower and longer removal due to adsorption. The adsorption of phosphate on fly ash could be described well by Freundlich isotherm equation. The pH and Ca2+ concentration of fly ash suspension were decreased with the addition of phosphate, which suggests that calcium phosphate precipitation is a major mechanism of the phosphate removal. Comparison of the relative contribution of the adsorption and precipitation to the total removal of phosphate by fly ash showed that the adsorption accounted for 30-34% of the total removal of phosphate, depending on the content of CaO in fly ash. XRD patterns of the fly ash before and after phosphate adsorption revealed that phosphate salt (CaHPO4 x 2H2O) was formed in the adsorption process. Therefore, the removal of phosphate by fly ash can be attributed to the formation of phosphate precipitation as a brushite and the adsorption on hydroxylated oxides. The results suggested that the use of fly ash could be a promising solution to the removal of phosphate in the wastewater treatment and pollution control.     

Characterization of alpha-cordierite glass-ceramics from fly ash

Batches of alpha-cordierite glass-ceramics, designated as GC-I and GC-II, containing 68 and 64 wt.% fly ash, respectively, were crystallized in the temperature range of 1125-1320 degrees C. The XRD (X-ray powder diffractometer) of the glass-ceramics show that alpha-cordierite became the dominant phase in GC-I and GC-II at 1200 degrees C. GC-I and GC-II, whose solid parts contain 74 and 78 vol.% alpha-cordierite and whose compressive strengths are 35 and 50 MPa, respectively, have the respective linear thermal expansion coefficients of 1.51x10(-6) and 1.43x10(-6)/ degrees C. The fly ash alpha-cordierite glass-ceramics can be employed as kiln furniture, honeycomb substrates for catalysts, and heat exchangers.     

Effects of NaOH concentrations on physical and electrical properties of high calcium fly ash geopolymer paste

The effects of sodium hydroxide (NaOH) concentration on setting time, compressive strength and electrical properties at the frequencies of 100 Hz–10 MHz of high calcium fly ash geopolymer pastes were investigated. Five NaOH concentrations (8, 10, 12, 15 and 18 molar) were studied. The liquid to ash ratio of 0.4, sodium silicate to sodium hydroxide ratio of 0.67 and low temperature curing at 40 °C were selected in making geopolymer pastes. The results showed that NaOH concentration had significant influence on the physical and electrical properties of geopolymer paste. The pastes with high NaOH concentrations showed increased setting time and compressive strength due to a high degree of geopolymerization as a result of the increased leaching of silica and alumina from fly ash. The dielectric constant and conductivity increased with NaOH concentration while tan δ decreased due to an increase in geopolymerization. At the frequency of 10³ Hz, the dielectric constants of all pastes were approximately 10⁴ S/cm and decreased with increased frequency. The relaxation peaks of tan δ reduced with an increase in NaOH concentration and ranged between 2.5 and 4.5. The AC conductivity behavior followed the universal power law and the values were in the range of 3.7 × 10⁻³–1.5 × 10⁻² at 10⁵–10⁶ Hz.     

Shrinkage behavior of structural foam lightweight concrete containing glycol compounds and fly ash

Shrinkage behavior of the structural foam lightweight concrete with density of 1600 kg/m³ was investigated. Owing to high drying shrinkage of the lightweight concrete, glycol compounds were used in the concrete mixture to study their effect on shrinkage behavior. Propylene glycol (PG), triethylene glycol (TEG) and dipropylene glycol tert-butyl ether (DPTE) were selected for testing of drying shrinkage of the lightweight concrete. Partial replacement of cement and sand with fly ash was also used to reduce the shrinkage. Results indicated that PG, TEG and DPTE were effective in reducing the shrinkage of lightweight concrete through reduction of surface tension of water. However, DPTE significantly reduced the surface tension and caused the foam instability and early stiffening of mixture. The partial replacement of cement and sand with fly ash could also reduce the shrinkage of the lightweight concrete. In this case, the compressive strength was also enhanced owing to the additional pozzolanic reaction.     

Biotoxicity evaluation of fly ash and bottom ash from different municipal solid waste incinerators

Different types of municipal solid waste incinerator (MSWI) fly and bottom ash were extracted by TCLP and PBET procedures. The biotoxicity of the leachate of fly ash and bottom ash was evaluated by Vibrio fischeri light inhibition test. The results indicate the following: (1) The optimal solid/liquid ratio was 1:100 for PBET extraction because it had the highest Pb and Cu extractable mass from MSWI fly ash. (2) The extractable metal mass from both fly ash and bottom ash by PBET procedure was significantly higher than that by TCLP procedure. (3) The metal concentrations of fly ash leachate from a fluidized bed incinerator was lower than that from mass-burning and mass-burning combined with rotary kiln incinerator. (4) The TCLP and PBET leachate from all MSWI fly ash samples showed biotoxicity. Even though bottom ash is regarded as a non-hazardous material, its TCLP and PBET leachate also showed biotoxicity. The pH significantly influenced the biotoxicity of leachate.     

Sorption properties of the activated carbon-zeolite composite prepared from coal fly ash for Ni(2+), Cu(2+), Cd(2+) and Pb(2+)

Composite materials of activated carbon and zeolite have been prepared successfully by activating coal fly ash (CFA) by fusion with NaOH at 750 degrees C in N(2) followed by hydrothermal treatments under various conditions. Uptake experiments for Ni(2+), Cu(2+), Cd(2+) and Pb(2+) were performed with the materials thus obtained from CFA. Of the various composite materials, that were obtained by hydrothermal treatment with NaOH solution (ca. 4M) at 80 degrees C (a composite of activated carbon and zeolite X/faujasite) proved to be the most suitable for the uptake of toxic metal ions. The relative selectivity of the present sorbents for the various ions was Pb(2+)>Cu(2+)>Cd(2+)>Ni(2+), with equilibrium uptake capacities of 2.65, 1.72, 1.44 and 1.20mmol/g, respectively. The sorption isotherm was a good fit to the Langmuir isotherm and the sorption is thought to progress mainly by ion exchange with Na(+). The overall reaction is pseudo-second order with rate constants of 0.14, 0.17, 0.21 and 0.20Lg/mmol min for the uptake of Pb(2+), Cu(2+), Cd(2+) and Ni(2+), respectively.