Removal of boron from coal fly ash by washing with HCl solution

Boron as an environmentally regulated substance is well known to condense in the coal fly ash generated from coal combustion plants. Since boron in the coal fly ash tends to elute into the soil easily, a technology for its stabilization or removal from fly ash is required. An acid washing process is proposed and studied as one of the candidate technologies for the removal of boron from coal fly ash. A laboratory-scale investigation is conducted on the dissolution behavior of boron in the coal fly ash in a diluted HCl solution. The dissolution of boron and alkaline species is considerably fast and exhibits a behavior different from that of aluminum and silicon, which are major components of the ash. From the kinetic model, it is expected that boron in the ash may mainly be in the form of alkaline or alkaline earth borates that are deposited on the surface of relatively large ash particles of alumino-silicate or may be precipitated as fine particles during coal combustion. This acid washing process is extended to a bench-scale plant and boron is successfully removed from the coal fly ash until its content is less than the regulation limit.     

Application of B MAS-NMR to the characterization of boron in coal fly ash generated from Nantun coal

Boron and its compounds are environmentally hazardous substance and are well-known condensed products that appear in coal fly ash during combustion of coal in coal-fired electric power stations. In a previous study, we suggested that boron in coal fly ash obtained from Nantun coal in China, identified as Ash-N, may exist on the surface of relatively large coal fly ash particles or as very fine particles generated by homogeneous nucleation. Although the characterization of boron in coal fly ash is important for its effective stabilization or removal, its detection is quite difficult because of its low concentration in coal fly ash and its light atomic weight. In the present work, solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) technique has been applied to reveal the local chemical structures of boron in Ash-N. In the ¹¹B MAS-NMR spectrum of Ash-N, two peaks which are attributed to a three-oxygen coordinated boron unit (BO₃) and a four-oxygen coordinated boron unit (BO₄) were observed with high resolution. We have estimated quadrupole parameters of the BO₃ unit in Ash-N using computer simulation, and we have fingerprinted these moieties with the parameters of borates. The result of the present analysis shows that calcium- or magnesium-bearing orthoborate or pyroborate are the most likely forms of boron in Ash-N.     

A comparative study for boron removal from seawater by two types of polyamide thin film composite SWRO membranes

In this paper, field performance of a small-scale seawater reverse osmosis unit installed in Urla Bay-Izmir, Turkey was analyzed and presented. The design of SWRO system in Urla consists of two types of FilmTec polyamide thin film composite spiral wound seawater reverse osmosis membranes (high rejection FILMTEC XUS SW30XHR-2540 RO membrane and FILMTEC SW30-2540 RO membrane) which could be operated in parallel. To make a comparative study between two types of membranes regarding their desalination performances and boron rejections, each membrane was operated individually for each set of experiments. This comparison was made via investigation of the effects of feed seawater temperature (10–16 °C), operating pressure (55, 60 and 62 bar), and pH adjustment on the feed side (pH 7.0–7.5).     

Ge extraction from gasification fly ash

Water-soluble germanium species (GeS₂, GeS and hexagonal-GeO₂) are generated during coal gasification and retained in fly ash. This fact together with the high market value of this element and the relatively high contents in the fly ashes of the Puertollano Integrated Gasification in Combined Cycle (IGCC) plant directed our research towards the development of an extraction process for this element. Major objectives of this research was to find a low cost and environmentally suitable process. Several water based extraction tests were carried out using different Puertollano IGCC fly ash samples, under different temperatures, water/fly ash ratios, and extraction times. High Ge extraction yields (up to 84%) were obtained at room temperature (25 °C) but also high proportions of other trace elements (impurities) were simultaneously extracted. Increasing the extraction temperature to 50, 90 and 150 °C, Ge extraction yields were kept at similar levels, while reducing the content of impurities, the water/fly ash ratio and extraction time. The experimental data point out the influence of chloride, calcium and sulphide dissolutions on the Ge extraction.     

Chemical modification of coal fly ash for the removal of phosphate from aqueous solution

This study investigated the chemical modifications of coal fly ash treated with HCl and NaOH. Sorption behavior of phosphate from water solution on treated fly ash was examined. Results showed that the HCl-treated fly ash (TFA-HCl) had a greater specific surface area (SSA) than the NaOH-treated fly ash (TFA-NaOH) and untreated fly ash (FA). The XRF, XRD patterns, and SEM images revealed the decreased CaO content in the TFA-HCl and observed the presence of NaP1 and sodalite zeolites in the TFA-NaOH. The P sorption capacity of all studied fly ashes increased with increasing initial P concentration and mechanisms of P sorption were influenced by the equilibrium pH. Maximum phosphate immobilization capacity obtained from Langmuir model was in the following manner, TFA-NaOH > FA > TFA-HCl (57.14, 23.20, and 6.90 mg P g⁻¹, respectively). The decreased CaO content and acidic pH in the TFA-HCl were responsible for the lowest capacity of phosphate immobilization, because of unfavorable condition for calcium phosphate precipitation. In contrast, due to alkaline condition and relatively high calcium content, the precipitation of calcium phosphate was a key mechanism for phosphate removal in the FA and TFA-NaOH. The TFA-NaOH had a greatest phosphate immobilization, due to high CaO content and an increased SSA after the conversion of fly ash to zeolite. Both Langmuir and Freundlich models were good fitted for the TFA-NaOH, while was only Langmuir model for the FA and Freundlich model for the TFA-HCl. Results suggested that treating fly ash with alkaline solution was a promising way to enhance phosphate immobilization.     

Leaching characteristics of boron and selenium for various coal fly ashes

The leaching characteristics of B and Se for coal fly ash (CFA) were examined. Twenty-one CFA samples were subjected to a leaching test, in which CFA was shaken with pure water in a liquid to solid ratio (L/S) of 100 for 24 h at room temperature. The correlation between the leaching amount and the concentration of element in CFA was investigated. The leaching amounts of B, Ca, S, and Se were essentially dependent upon their concentrations in CFA. As the degree of % leaching was higher, the leaching amount was more dependent upon the concentration. Also, the leaching test was performed under constant pH conditions. The leaching of Se tended to increase as the pH in the aqueous phase was raised. For CFA samples, which gave large degree of Ca leaching amount, the leaching of B and Se was decreased especially under high alkaline conditions. The effects of pH and the presence of leached Ca ion in the aqueous phase upon the leaching behavior were discussed.     

Preparation of zeolitic adsorbents from waste coal fly ash

Power plants burning coal generate a large amount of fly ash as waste matter. The objective of this study is to produce zeolitic adsorbents that possesses high adsorptive capacity for toxic cations. The sample was first pretreated with a High Intensity Magnetic Separator for the removal of iron and magnetic materials (mainly Fe₂O₃ and TiO₂). The zeolitic adsorbents were prepared under the various conditions of NaOH concentration (1–5 N), reaction time from 3 to 96 hours and at the various temperatures of 60, 80 and 100°C. The results of the experiment showed that the coal fly ash should be synthesized with 4 N NaOH for 48 hours at 100°C in order to have good adsorptive capacity. The zeolitic adsorbents showed higher cation exchange capacity values than the natural zeolite in removing NH ₄ ⁺ , Pb²⁺, Ca²⁺and Cd²⁺ions.     

Phosphate removal in marine electrolytes by zeolite synthesized from coal fly ash

The aim of this study was to examine the influence of seawater electrolytes on removal of phosphate by zeolite synthesized from fly ash (ZFA). A low-calcium ZFA was initially saturated with Na⁺, Mg²⁺, Ca²⁺, Al³⁺, and Fe³⁺. Al- and Fe-ZFA showed nearly complete removal of phosphate regardless of the major seawater electrolytes, pH, and salinity. This result was explained primarily on the basis of the adsorption mechanism through the formation of inner-sphere complexes. The remaining ZFAs showed lower phosphate removal performance, in general with the order of Ca-ZFA > Mg-ZFA > Na-ZFA. Compared with pure water, increase of electrolyte concentration or salinity initially enhanced phosphate uptake but then reduced phosphate removal. The individual presence of major seawater electrolytes all facilitated the retention of phosphate, with CaCl₂ being the most effective. The mechanism for phosphate removal by Na-, Mg-, and Ca-ZFA was due mostly to precipitation. Repeated batch equilibration experiments indicated that, compared with pure water, ZFA had greater sorptive capacity for phosphate (except for Ca-ZFA, whose capacity decreased slightly) and had lower reversibility for sorbed phosphate in marine electrolytes. In conclusion, our results suggest that presence of seawater electrolytes had roughly no effect, or even positive effects, on the removal of phosphate by ZFA.     

Thermal expansion of slag and fly ash from coal gasification in IGCC power plant

Integrated gasification in combined cycle (IGCC) is an electrical power generation system which is characterized to be a clean coal technology different than conventional process in combustible treatment. IGCC process gives rise to inorganic solid wastes in the form of vitreous slag and fly ashes with singular thermal properties. The gasification of the fuel takes place at high temperature and pressure in reducing atmosphere. Under that conditions, gases such as H₂, N₂ or CO, which are the main components of the gas mixture in the gasifier, show a high solubility in the melt and during the cooling remain enclosed in the vitreous slag. When these wastes are afterward thermal treated in oxidizing conditions, two phenomena occur. The development of a crystalline phase by devitrification of the glassy matrix and the releasing of the enclosed gas, which starts at temperatures nearly to the softening point. At higher temperatures the bubbles with increasing kinetic energy tend to ascent with difficult through the viscous liquid phase and promotes an expansive reaction, giving rise to a foam glass-ceramic product. This paper has been focused on the study of thermal expansion in slag and fly ash samples from the ELCOGAS IGCC power plant located in Puertollano (Spain).     

Mode of occurrence of arsenic in feed coal and its derivative fly ash, Black Warrior Basin, Alabama

An arsenic-rich (As = 55 ppm) bituminous feed coal from the Black Warrior Basin, Alabama and its derivative fly ash (As = 230 ppm) were selected for detailed investigation of arsenic residence and chemical forms. Analytical techniques included microbeam analysis, selective extraction, and As K-edge X-ray absorption fine-structure (XAFS) spectroscopy. Most As in the coal is contained in a generation of As-bearing pyrite (FeS₂) that formed in response to epigenetic introduction of hydrothermal fluids. XAFS results indicate that approximately 50% of the As in the coal sample occurs as the oxidized As(V) species, possibly the result of incipient oxidation of coal and pyrite prior to our analysis. Combustion of pyrite and host coal produced fly ash in which 95% of As is present as As(V). Selective extraction of the fly ash with a carbonate buffer solution (pH = 10) removed 49% of the As. A different extraction with an HCl-NH₂OH mixture, which targets amorphous and poorly crystalline iron oxides, dissolved 79% of the As. XAFS spectroscopy of this highly acidic (pH = 3.0) fly ash indicated that As is associated with some combination of iron oxide, oxyhydroxide, or sulfate. In contrast, a highly alkaline (pH = 12.7) fly ash from Turkey shows most As associated with a phase similar to calcium orthoarsenate (Ca₃(AsO₄)₂). The combined XAFS results indicate that fly ash acidity, which is determined by coal composition and combustion conditions, may serve to predict arsenic speciation in fly ash.     

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.     

Humidity-control assists high-efficient coal fly ash removal by PTFE membrane

In the present study, the effects of relative humidity on filtrating coal-fired fly ash with hydrophobic poly tetra fluoroethylene (PTFE) membranes were investigated. The intergranular force of particulate matter at different RH conditions was measured by analyzing the critical angle between particles. Effects of humidity (from 30% to 70%) on filtration pressure drop and membrane fouling conditions were characterized. It was found the membrane showed optimal filtration resistance of 530 Pa at RH of 60% and the gas permeance can be maintained at 1440 m³·m^-2·h^-1·kPa^-1. Moreover, to optimize the operation parameters for this filtration system, effects of fly ash concentration, diameter, membrane pore size, and gas velocities were systematically investigated.     

Nano-crystal glass-ceramics obtained from high alumina coal fly ash

Glass has been obtained by melting high alumina coal fly ash with fluxing additives. A thermal treatment was employed to convert the obtained glass into nano-crystal glass-ceramics. X-ray diffraction (XRD) patterns show that the main crystalline phases in both the glass-ceramics are anorthite (CaAl₂Si₂O₈) and wollastonite (CaSiO₃). The crystals are homogeneously dispersed within the parent glass. The average crystal size is below 200 nm. Physical and mechanical properties, such as density, thermal expansion coefficient, hardness, and bending strength, of the glass have been examined and the corresponding microstructures are discussed. The results demonstrate that the glass-ceramics have potential for a wide range of construction application.     

Mineralogy and geochemistry of Greek and Chinese coal fly ash

In this paper the mineralogy and geochemistry of Greek and Chinese coal fly ash are examined. Annual production of fly ash in China is around 160 Mt while in Greece lignite fly ash accounts around 10 Mt. Even though the mineralogical and chemical composition of the fly ashes coming from these two countries differs, there are common questions on the utilization of this material. The variation of the Greek fly ash’ chemical composition, from Ca-poor to Ca-rich fly ash, has resulted to applications such as dam construction, use in cement and possibly in concrete and road construction. The Chinese fly ash, which is rich in mullite, is broadly applied for brick making.     

Hydrothermal synthesis of zeolites from coal fly ash

The fly ash, from the combustion of coal to produce energy and heat, is an industrial waste, in which large accumulations represent a serious environmental threat. To reduce the environmental burden and improve the economic benefits of energy production, the science and industry focus on the transformation of coal combustion byproducts into new functional materials. The fly ash was studied by modern analytical methods. As a result of the hydrothermal reaction, several types of zeolites were synthesised from the fly ash: analcime, faujasite (zeolite X) and gismondine (zeolite P). It was shown that the experimental conditions (temperature, reaction time and alkali concentration) have a significant influence on the type of zeolite and its content in the reaction products. The series of experiments resulted in building approximate crystallisation field of zeolites and other phases as the first stage of the formation of ceramic membrane and other materials.     

Synthesis of pure zeolites from supersaturated silicon and aluminum alkali extracts from fused coal fly ash

In this study, the silicon and aluminum in fly ash was activated by fusion with sodium carbonate. The fused product was treated by a method involving a desilicification and hydrothermal process. From the supersaturated silicon and aluminum extracted from fly ash, different pure zeolites were synthesized. The structure-directing agents and crystal seeds made a promoting effect on the type of crystallization achieved. The zeolites were characterized in terms of mineralogical composition and cation exchange capacity (CEC). The results showed that the pure zeolites exhibited high CEC ranged from 3.2 to 4.6 meq/g, and the yield ratio reached to 70%.     

Mineralogy and microstructure of sintered lignite coal fly ash☆

Lignite coal fly ash from the ‘Nikola Tesla’ power plant in Yugoslavia has been characterised, milled, compacted and sintered to form monolithic ceramic materials. The effect of firing at temperatures between 1130 and 1190 °C on the density, water accessible porosity, mineralogy and microstructure of sintered samples is reported. This class C fly ash has an initial average particle size of 82 μm and contains siliceous glass together with the crystalline phases quartz, anorthite, gehlenite, hematite and mullite. Milling the ash to an average particle size of 5.6 μm, compacting and firing at 1170 °C for 1 h produces materials with densities similar to clay-based ceramics that exhibit low water absorption. Sintering reduces the amount of glass, quartz, gehlenite and anhydrite, but increases formation of anorthite, mullite, hematite and cristobalite. SEM confirms the formation of a dense ceramic at 1170 °C and indicates that pyroplastic effects cause pore formation and bloating at 1190 °C.     

Boron removal from saline water: A comprehensive review

Boron is an essential micronutrient for plants and animals as well as a useful component for numerous industries. It is necessary to produce low boron containing water from RO desalination plants for both human consumption and for agriculture. For plants, a small amount of boron is necessary for their growth and development, but boron becomes toxic if the amount is slightly greater than required. Desalinated seawater from RO plants often contains high boron content and, when used for irrigation, has been proven to be damaging to crops including blackberry, lemon, and grapefruit. Apart from the toxic effects of boron on plants, boron should be removed from RO desalination plants to comply with the current guideline value, 0.5 mg/L, for potable water issued by the World Health Organisation (WHO). Currently there is no simple method to remove boron from saline water. The use of multi-pass reverse osmosis membrane (RO) with pH modification and the use of ion exchange using boron selective resins (BSRs) have both been considered as effective methods for the removal of boron. A hybrid process, Adsorption Membrane Filtration (AMF), has received attention as an emerging technology for boron removal with a high efficiency and low operating costs. The purpose of this review is to give an overview on boron in general and to discuss its toxicity. The problems of boron in the MENA (Middle East and North Africa) region are discussed as well as technologies, current and future, for the removal of boron from seawater. The focus is placed on current RO and ion exchange methodologies using BSRs as well as the future for the AMF method. The fundamentals of each process, the effects of experimental parameters, and findings are discussed.     

粉煤灰合成人造沸石除磷效果的研究

以粉煤灰为原料,在微波场下水热合成人造沸石,可缩短结晶时间.将这种人造沸石应用于污水处理实验,处理城市景观用水,控制水体富营养化的氮、磷指标.氨氮的去除机理主要为离子交换,而磷的去除机理的研究目前尚缺乏相关资料.合成沸石中含磷量较低时,不影响在污水处理中的应用.     

Production of glass from coal fly ash

The coal fly ash from a Chinese thermal power plant was vitrified after the addition of ∼10 wt% Na₂O. The glass products have suitable viscosity at 1200 °C and displayed a good chemical durability. The heavy metals of Pb, Zn, Cr and Mn were successfully immobilized into the glass as determined by the toxicity characteristic leaching procedure method. Results indicate an interesting potential for the coal fly ash recycling to produce useful materials.