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.     

Sorption of aqueous phosphorus onto bituminous and lignitous coal ashes

Aiming at the development of a phosphorus removal technology for waste water, phosphate (PO(4)(3-)) retention behavior of bituminous and lignitous coal ashes was investigated using a batch reactor. Ash samples, including fresh and weathered fly and bottom ashes, were studied for their sorption isotherms and reversibility. Fly ashes had a much higher phosphate retention capacity (4000-30,000mgP/kg) than bottom ashes (15-600mgP/kg). Lignitous coal ashes were more capable of retaining phosphate than bituminous coal ashes. The retention process was largely irreversible, and the irreversibility increased with the increase in the retention capacity. Weathering enlarged the retention capacity of the bituminous bottom ash, but substantially lowered that of the fly ash, likely due to the difference in the weather-induced changes between the fly and bottom ashes. Sorption isotherms of fly ashes were found to be adequately represented by the Langmuir model while those of bottom ashes fitted better to the Freundlich model. Concentrations of Ca(2+) and PO(4)(3-) in the aqueous phase were measured at the end of sorption and desorption experiments, and were compared with solubilities of three calcium phosphate minerals. The aqueous solutions were saturated or super-saturated with respect to tricalcium phosphate (Ca(3)(PO(4))(2)) and hydroxyapatite (Ca(5)(PO(4))(3)OH), and slightly under-saturated with respect to amorphous calcium phosphate. It is concluded that precipitation of calcium phosphate is the predominant mechanism for phosphate retention by coal ash under the conditions studied. There is a strong and positive correlation between alkalinity and phosphate sorption capacity. Consequently, acid neutralization capacity (ANC) can be used as an indicator of phosphate sorption capacity of coal ashes.     

The behaviour of Al in MSW incinerator fly ash during thermal treatment

Fly ash from municipal solid waste (MSW) incinerators contains leachable metals, including potentially hazardous heavy metals. The metal content of the fly ash can be reduced by thermal treatment, which vaporizes the volatile metal compounds. After heat treatment of fly ash at 1000 degrees C for 3 h, less metal was able to be leached from the thermally treated ash than from the ash without thermal treatment. Al and Cr were the exceptions. These metals were more soluble in the ash that had been thermally treated. This paper focuses on the leaching behaviour of Al only. Both simple and sequential extraction leaching tests showed that the leachable Al for the heat-treated fly ash is about twice that of the untreated fly ash. The sequential test further revealed that (i) the majority of the leachable Al is associated with Fe-Mn oxides in the fly ash, and (ii) most of the unleachable Al resides in the silicate matrices of the heat-treated and untreated fly ash. Pure chemicals, Al(2)O(3), CaO and CaCl(2), simulating the relevant ingredients in the fly ash, were used for studying their reactions at 1000 degrees C. The aluminum compounds were identified by X-ray Diffraction (XRD). Two new chemical phases produced by the thermal treatment were identified; Ca(AlO(2))(2) and 12CaO.7Al(2)O(3). Their formation suggests a mechanism whereby thermal treatment of fly ash would produce more soluble Al.     

醋酸钙/飞灰复合脱硫脱硝剂热解性能实验研究

为了提高脱硫脱硝效率同时合理利用火电厂产生的飞灰,研究了醋酸钙中加入飞灰制备的复合脱硫脱硝剂的热解性能。对不同条件下制得的醋酸钙/飞灰复合脱硫脱硝剂的热重特性、X射线衍射图谱、比表面积、扫描电镜结果等进行了分析,结果表明:利用醋酸钙和飞灰水合制备的脱硫脱硝剂具有比单纯的醋酸钙和飞灰更大的比表面积;经过900℃煅烧后脱硫脱硝剂孔隙结构最好;脱硫脱硝剂经过900℃煅烧后的热解产物(SiO2、Al2O3、Fe2O3和CaO)有助于脱除烟气中的硫氧化物和氮氧化物。     

Phosphorus sorption and fraction characteristics in the upper, middle and low reach sediments of the Daliao river systems, China

Stream sediments play an important role in the transport and storage of phosphorus in the stream ecosystems. This research investigated the sorption and fraction of P in the sediments of a long-term seriously contaminated river, the Daliao river system, using isotherm sorption and selective sequentially extraction tests. Results indicated that the total content of P in the sediments was 479–1202 mg kg⁻¹, depending on iron content in the sediments. The content of potential bioavailable P, including soluble and loosely bound P, Al bound P, Fe bound P, and reductant soluble P was only 10–20% of total P in the sediments of the Hun river and Taizi river, while it was 40–55% in the sediments of the Daliao river, the downstream of the river system. Equilibrium phosphorus concentration without net P sorption (EPC₀) was from 0.05 to 0.54 mg L⁻¹, with an increasing trend from upstream to downstream, indicating increasingly release potential. On the other hand, the upstream sediment generally sorbed more P than the downstream sediment for each river at the same equilibrium P concentration. The binding energy constant of P on the strong sites of the sediments generally decreased from 2.24 to 2.65 L mg⁻¹ at upstream to 0.41 L mg⁻¹ at downstream or estuary, suggesting that the strong binding sites have been occupied and partly saturated by the phosphate added by point and diffuse sources along the river. On the other hand, molar ratio of Fe to TP contents in the sediments showed sorption capacity of the sediments to P might be under-saturated. The added or sorbed P by the isotherm test was primarily bound to Fe oxides and secondly to Al oxides. Long-term pollution of the river lead to the decrease of P sorption capacity of the river sediment and the increase of P release potential.     

Leaching behaviour of major and trace elements from concrete: Effect of fly ash and GGBS

The leaching of major and trace elements from concrete made with Portland cement, fly ash and GGBS (ground granulated blast-furnace slag) was studied using pH static availability and tank leach tests. The release of substances during the tank leach test occurs by surface dissolution of phases at the concrete surface and diffusion inside the concrete, the amounts depending on the phases controlling solubility and concrete porosity. Alkali release is controlled by diffusion and is thus reduced by lower water/binder ratios and the replacement of Portland cement by fly ash. Ca, Al and S release occurs mainly by surface dissolution of portlandite and AFt/AFm, respectively. The release of V is determined by surface dissolution of V substituted ettringite and/or calcium vanadate. Although fly ash can increase the total V content of concrete, enhancing release, only 2% of the total V content in concrete was available for release.     

Trace elements partitioning during co-firing biomass with lignite in a pilot-scale fluidized bed combustor

This study describes the partitioning of 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and 9 major and minor elements (Al, Ca, Fe, K, Mg, Na, S, Si, Ti) during co-firing of olive residue, hazelnut shell and cotton residue with high sulfur and ash content lignite in 0.3 MW(t) Middle East Technical University (METU) Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) test rig with limestone addition. Concentrations of trace elements in coal, biomass, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission and mass spectroscopy (ICP-OES and ICP-MS). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Tl, V and Zn) are recovered in fly ash when firing lignite only. Co-firing lignite with biomass enhances partitioning of these elements to fly ash. Co-firing also shifts the partitioning of Cd, P, Sb and Sn from bottom to fly ash.     

Partitioning behavior of trace elements during pilot-scale fluidized bed combustion of high ash content lignite

This study describes the partitioning of 20 trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and eight major and minor elements (Al, Ca, Fe, K, Mg, Na, Si, Ti) during the combustion of high ash content lignite. The experiments were carried out in the 0.3 MW(t) Middle East Technical University (METU) atmospheric bubbling fluidized bed combustor (ABFBC) test rig with and without limestone addition. Inert bed material utilized in the experiments was bed ash obtained previously from the combustion of the same lignite without limestone addition in the same test rig. Concentrations of trace elements in coal, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Cr, Hg, Li, Mo, Ni, Sn, V, Zn) are recovered in fly ash. Limestone addition shifts the partitioning of Ba, Cr, Mo, Ni, Sn, V, Zn from bottom ash to fly ash.     

Simultaneous uptake of ammonium and phosphate ions by compounds prepared from paper sludge ash

Al-containing CaO-SiO(2)-H(2)O phases were prepared by hydrothermal treatment of mixtures of paper sludge ash (PSA) with various silica and calcia sources and their properties were determined with particular reference to the simultaneous uptake of ammonium and phosphate ions, which are implicated in the eutrophication of lakes and ponds. After examination of various silica and calcia sources, Ca(OH)(2) and SiO(2) sol were selected as the most appropriate starting materials. Dry milling was found to be superior to wet milling in avoiding contamination from the milling media during mixing. Nine samples with three different Ca/Si ratios and Al(2)O(3) contents were prepared with various mass ratios of Ca(OH)(2), PSA and SiO(2). The chemical compositions of the hydrothermal products of these mixtures moved towards the tieline of CaSiO(3)-PSA, with respect to the starting compositions. The major phase formed in all samples was poorly crystalline C-S-H(I), with hydroxysodalite also formed in the Al-containing mixtures. All the products showed a capacity for the simultaneous uptake of ammonium and phosphate ions. The saturated sorption capacities calculated from the Langmuir equation ranged from 0.9 to 2.4mmol/g for the ammonium ion and from 3.3 to 5.2mmol/g for the phosphate ion. Since the sorption capacities for both ions increased with increasing Ca contents of the product, substitution of Ca(2+) for NH(4)(+) and the formation of calcium phosphate phases such as apatite and brushite by precipitation are thought to be the main sorption mechanisms.     

Thermal activation on calcium silicate slag from high-alumina fly ash: a technical report

The fly ash with alumina composition from 45 to 55 % has been found in China in last 10 years, which attracts great attention from Chinese government and related alumina industry. Chinese government and its state-owned enterprises have successfully extracted the Al as alloy product from the high-alumina fly ash. However, to recycle the calcium silicate slag as residue from the Al industry is still undetermined. In this report, an innovative process is introduced to achieve the regional sustainability for the high-alumina fly ash industry, and it is found that the cementitious material composed of calcium silicate slag met with the mechanical requirements of 32.5 cement for road pavement. The chemical and mineral analysis show that the calcium silicate slag has high CaO content, which reaches up to 48.64 %. C₂S and C₃A are the dominant mineral phases by XRD analysis indicating its potential pozzolanic activity during the hydration process. Thermal activation from 200 to 900 °C was applied to enhance its pozzolanic activity for the calcium silicate slag and it proved that 600 °C is the optimal calcination temperature due to the decomposition of calcite and clay minerals. Also the mineral phase amorphization was also observed during the XRD analysis, which might also contribute to the enhanced pozzolanic properties at 600 °C. Although the designed cementitious material contains a large quantity of solid waste, none of the hazardous heavy metals exceed the EPA limits. This short article originally reported a promising direction for managing solid waste for Al industry and enhancing utilization efficiency for the enterprise internal solid wastes.     

Antimony leaching from uncarbonated and carbonated MSWI bottom ash

The recycling potential of municipal solid waste incinerator (MSWI) bottom ash may be limited by the leaching of antimony (Sb). Therefore, treatment methodologies need to be developed. The pH-dependent leaching behaviour of this oxyanion-forming element in fresh and weathered bottom ash is, however, not understood. Sb leaching was investigated in a wide range of both pH and extent of carbonation. Sb came close to equilibrium with calcium antimonate (Ca[Sb(OH)(6)](2)) at acid and neutral pH. Therefore, adsorption experiments with synthetic calcite (CaCO(3)), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12) x 26H(2)O), gypsum (CaSO(4) x 2H(2)O), and portlandite (Ca(OH)(2)) and adsorption modelling to hydrous ferric oxides (HFO) and amorphous aluminium minerals (AAM) were conducted to investigate which minerals decrease Sb leaching below equilibrium with calcium antimonate. At pH>12, calcium antimonate comes into solution due to portlandite formation, but the subsequent increase in Sb leaching is reduced due to strong interaction of Sb with portlandite and ettringite. Ettringite appears to be an important host mineral for Sb at the natural pH of mildly weathered bottom ash (11.8) because a minimum in leaching is observed. When pH is decreased below 10.5, ettringite dissolves and Sb comes into solution, approaching equilibrium with calcium antimonate near pH 9. Gypsum showed no affinity for Sb. The interaction of calcite with Sb was not clear. Adsorption modelling suggested that HFO, rather than AAM, control Sb leaching when pH<9. During carbonation, Sb leaching first increased, most likely due to dissolution of ettringite. Then, Sb leaching decreased, since the pH became low enough to allow sorption by HFO.     

Synthesis of calcium phosphate hydrogel from waste incineration fly ash and bone powder

Waste incineration fly ash and bone powder could be successfully recycled into calcium phosphate hydrogel, a type of fast proton conductor. Various properties of the intermediate and calcium phosphate hydrogel from them were characterized and compared with that from calcium carbonate reagent. It was found that the intermediate from the incineration fly ash and calcium phosphate glass was more brittle than that from bone powder and calcium carbonate reagent. The electric conductivity of crystallized hydrogel obtained from all raw materials increases exponentially with temperature. However, the crystallized hydrogel from incineration fly ash has lower electric conductivity and lower crystallinity than that from bone powder and the reagent. Moreover, the difference in electric conductivity between these crystallized hydrogels decreases with temperature. Compared with using the reagent as a raw material, bone powder provides a 25% reduction in the usage of H(3)PO(4) to acquire the crystallized hydrogel which has the highest conductivity. These experimental results suggest that the incineration fly ash and bone powder are useful calcium sources for the synthesis of calcium phosphate hydrogel.     

Evaluation of sodium content and sodium hydroxide molarity on compressive strength of alkali activated low-calcium fly ash

Activation of low calcium fly ash is investigated using activating solutions of sodium hydroxide (NaOH) and sodium silicate (Na₂SiO₃). The oxide ratio of Na₂O relative to the total reactive silica in the activated mix provides consistent results in achieving the highest ultimate strength. The total reactive silica used for calculating the ratio consists of the reactive silica contributed by fly ash and the silica from the activating solution. There is an increase in the ultimate compressive strength on increasing the total sodium content relative to the total reactive silica content in the activated system. Increasing the sodium content beyond a certain limit does not provide additional gain in the ultimate compressive strength. The ratio of total reactive SiO₂ to Na₂O in the activated system equal to 4.72 is shown to provide the highest compressive strength and there is no further increase in the ultimate strength on increasing the sodium content. A N-A-S-H type gel with reaction products containing Si, Al and Na, is formed in the activated system. The ultimate strength achieved is directly related to the reaction product content in the system and is dependent on the extent of glassy phase dissolution from fly ash. The extent of glassy phase dissolution and the quantity of reaction product formed in the system increases with an increase in the molarity of NaOH, which also contributes to an increase in the sodium content in the activating solution. The decrease in the unreacted glassy phase content of fly ash is sensitive to temperature at a lower molarity of NaOH. The Al/Na ratio in the reaction product approaches a value of 0.9 on increasing the sodium content in the activated system. The Si/Al ratio in the reaction product varies within a range of 2.3–2.8.     

Degradation of PCDD/Fs by mechanochemical treatment of fly ash from medical waste incineration

The potential of mechanochemical treatment (MC) to degrade PCDD/Fs contained in fly ash was tested via grounding with and without calcium oxide (CaO) under atmospheric pressure. Three types of fly ash collected from medical waste incineration were compared, originating either from rotary kiln fluidized bed multi-stage incinerator using activated carbon spray (FA1, FA2), or a simple stoker incinerator without activated carbon spray (FA3). In test I: CaO to FA1 mixed at ratio of 6-60% was milled at rotational speed of 350 rpm; in test II: FA2 and FA3 without CaO were milled at rotational speed of 400 rpm. The duration of the tests was 2h. The results from the present study indicate that (1) under two test conditions of with and without CaO, PCDD/Fs contained in real fly ash both can be degraded by mechanochemical treatment, (2) under condition of blending with CaO, the degradation efficiency of PCDD/Fs increased with increasing ratio of CaO, (3) the degradation efficiency of PCDD/Fs may increase with rotational speed increasing and (4) the destruction and dechlorination are major mechanism for PCDD/Fs degradation. These results show that mechanochemical treatment is a high potential technology for PCDD/Fs degradation in fly ash.     

Mineralogical and microstructural characterisation of alkali-activated fly ash/slag pastes

A mechanical, mineralogical and microstructural characterisation of the cement pastes obtained by alkaline activation of fly ash/slag mixtures cured at different temperatures has been carried out. The pastes obtained were characterised by XRD, FTIR, MAS NMR, SEM/EDX, atomic absorption and ion chromatography, also the insoluble residue in HCl was determined.The results obtained have proved the existence of two different reaction products in those activated pastes. The average atomic ratios in the main reaction product were Ca/Si∼0.8, Al/Ca∼0.6, Si/Al∼2–3. Such analysis corresponds to calcium silicate hydrate rich in Al, which includes Na in its structure. Other reaction product which was detected in the pastes as result of fly ash activation, was an alkaline aluminosilicate hydrate with a three-dimensional structure.     

Characterization of geopolymers from compositionally and physically different Class F fly ashes

The alkali-activation technology of coal fly ash is one of several potential solutions to minimize the harmful disposal of fly ash. This study reports high-resolution characterization of the alkali-activated reaction products for two representative Korean Class F fly ashes, which are significantly different in compositional and physical characteristics. The analysis confirms that differences in the network modifying element content, the amorphous phase content, and the particle size lead to large differences in compressive strength. Chabazite-Na and Al-rich chabazite-Na are identified as major crystalline phases in the high strength samples, supporting the favoring formation of ABC-6 family of zeolitic precursors for the higher mechanical strength while the C–S–H formation from the high CaO content (or crystalline CaO) is not a major source of the strength. The XRD analysis shows that the presence of amorphous humps located at 27–29° 2θ is not a sufficient indicator of geopolymeric gel formation. In the ²⁹Si MAS NMR, some portion of −108 ppm Q₄(0Al) peak is not related to quartz, implying that this portion of Si atoms actively participate in geopolymerization. The ²⁷Al MAS NMR spectra exhibit more conversion of Al(V) and Al(VI) aluminum atoms into Al(IV) units in the higher strength sample, which can be an indication of more geopolymeric reaction.     

Solid state compatibilities in CaO–CaO.Al2O3–CaSO4–CaF2 system

The determination of the phases assemblages in equilibrium in the CaO–CaO.Al2O3–CaSO4–CaF2 system at 1100°C has been performed. Four assemblages are found and one more is deduced. 3CA.CaSO4 appears in all compatibility tetrahedra in solid state or in melt presence. It is compatible with C3A, C12A7ss, CA, C11A7.CaF2 and the aluminate formed depends on Al2O3 and CaF2 proportion, (cement chemistry abbreviations: C=CaO, A=Al2O3). © 1998 Kluwer Academic Publishers     

Fixation of alkyl phosphate using waste incineration fly ash

Waste incineration fly ash (Fa), pretreated by washing with distilled water and heating at 1000°C in air, was treated with various concentrations of octyl phosphate [C₈H₁₇OPO₃H₂(OP)] aqueous solution by stirring at 25°C for 3 h and aging at 85°C for 24 h. X-ray fluorescence and X-ray diffraction measurements indicated that the major element of Fa is Ca which exists as CaO and gehlenite (2CaO · Al₂O₃ · SiO₂). Treating Fa in OP solutions dissolved the CaO and gehlenite to form calcium octyl phosphate (C₈H₁₇OPO₃Ca.nH₂O), which is composed of a multilayer alternating dicalcium phosphate dihydrate (CaHPO₄ · 2H₂O)-like phase and a bimolecular layer of octyl groups of the phosphates. Increasing the OP concentration increased the fixed amount of OP and amount of recovery after the treatment. The fixed amount and amount of recovery steeply increased during stirring at 25°C, and were almost unchanged by aging. These facts allow us to infer that Fa is available to fix alkyl phosphate ions such as OP.     

The importance of the network-modifying element content in fly ash as a simple measure to predict its strength potential for alkali-activation

Six different Class F fly ashes were examined to identify the material properties that determine the strength development in geopolymerization. All of the fly ashes displayed typical features of Class F fly ash in chemical and mineral composition, amorphous phase (glass) content, and X-ray diffraction pattern profile; however, the strength developments of the ashes were quite different from each other. The results suggest that the strength is higher under the following configuration: greater content of network modifying elements, greater glass content, lower silicon content, lower intensity of quartz-related ²⁹Si NMR peak, and higher fraction of Al(IV) in the ²⁷Al NMR spectrum. Among the possibilities, the network-modifying elemental content may be the simplest and most accurate measure for strength development of alkali activation of fly ash.     

Sintering of MSWI fly ash by microwave energy

This study presents the sintering of municipal solid waste incineration (MSWI) fly ash assisted by microwave energy. The composition of fly ash was investigated by chemical sequential extraction and modified microwave digestion method. Effects of process time, container materials, aging time and salt contents were also discussed. The major elements of fly ash are Ca, Cl, Na, Si, K, Al, Mg, and Zn, and the metal species, Zn, Cr, Pb, Ca, and Cu, are mainly in the oxide phase. Under microwave processing, the fly ash was sintered into a glass-ceramics and the leaching concentrations of heavy metals were restrained. The stabilization efficiency increased with an increase in processing time in most of the cases. Better stabilization efficiency of fly ash was discovered by using the SiO(2) or Al(2)O(3) container than by using the graphite plate/SiC plate. The presence of salt in the fly ash could enhance the sintering and stabilization of fly ash. During the aging time of 0-30 days, negligible Pb in the sintered fly ash was leached out, and the leaching concentration was lower than the criterion.