Characterization of alkali-activated thermally treated incinerator bottom ash

The fine fraction (<14mm) of incinerator bottom ash (IBA) obtained from a UK energy from waste plant has been milled and thermally treated at 600, 700, 800 and 880 degrees C. Treated materials have been activated with Ca(OH)(2) (10wt%) and the setting times and compressive strengths at different curing times measured. In addition to decomposition of CaCO(3) to CaO, thermal treatment increases the content of gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)). Thermally treated samples were significantly more reactive than milled IBA and heating to 700 degrees C produced a material which rapidly set. Silica, gehlenite and wollastonite were the main crystalline phases present in hydrated samples and a mixed sulphate-carbonate AFm-type phase (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33).11H(2)O) formed. Significant volumes of gas were generated during curing and this produced a macro-porous microstructure that limited strength to 2.8MPa. The new materials may have potential for use as controlled low-strength materials.     

Leaching from MSWI bottom ash: evaluation of non-equilibrium in column percolation experiments

Impacts of non-equilibrium on results of percolation experiments on municipal solid waste incineration (MSWI) bottom ash were investigated. Three parallel column experiments were performed: two columns with undisturbed percolation and one column with two sets of 1-month-long flow interruptions applied at liquid-to-solid (L/S) ratios of L/S 2L/kg and 12L/kg, respectively. Concentrations of Na, K, Cl(-), Ca, Si, SO(4)(2-), Al, Cu, Ni, Mo, Ba, Pb, Zn, and dissolved organic carbon (DOC) were monitored throughout the entire leaching period; geochemical modeling was used to identify non-equilibrium-induced changes in the solubility control. Despite both physical and chemical non-equilibrium, the columns were found to provide adequate information for readily soluble compounds (i.e., Na, Cl(-), and K) and solubility-controlled elements (i.e., Ca, SO(4)(2-), Ba, Si, Al, Zn, and Pb). The leaching of Cu and Ni was shown to depend strongly on DOC leaching, which was likely affected by physical non-equilibrium during flow interruptions. Consequently, the leaching of Cu and Ni in the undisturbed columns was shown to be by about one order of magnitude lower compared with the interrupted column. The results indicate that the leaching of DOC-related metals in laboratory column experiments may be considerably underestimated compared with full-scale scenarios in which the impacts from non-equilibrium may be significantly lower. The leaching of Mo (or MoO(4)(2-)) may be controlled solely by its availability in the mobile zone, which in turn appeared to be controlled by diffusion from the stagnant zone; no Mo controlling minerals were predicted by the geochemical modeling.     

Ceramic processing of incinerator bottom ash

The <8 mm fraction of aged incinerator bottom ash from a commercial incinerator (energy from waste) plant has been collected at regular intervals, characterised and processed to form ceramic materials. Ashes were sieved, wet ball milled, dried, compacted and sintered at temperatures between 1080 and 1115 degrees C. Variations in the chemical composition and mineralogy of the milled ash, and the mineralogy, physical properties and leaching of sintered products have been assessed. Milling produces a raw material with consistent chemical and mineralogical composition with quartz (SiO(2)), calcite (CaCO(3)), gehlenite (Ca(2)Al(AlSi)O(7)) and hematite (Fe(2)O(3)) being the major crystalline phases present. Different batches also milled to give consistent particle size distributions. Sintering milled incinerator bottom ash at 1110 degrees C produced ceramics with densities between 2.43 and 2.64 g/cm(-3) and major crystalline phases of wollastonite (CaSiO(3)) and diopside (CaMgSi(2)O(6)). The sintered ceramics had reduced acid neutralisation capacity compared to the as-received ash and exhibited reduced leaching of Ca, Mg, Na and K under all pH conditions. The leaching of heavy metals was also significantly reduced due to encapsulation and incorporation into glassy and crystalline phases, with Cu and Al showing greatly reduced leaching under alkali conditions.     

The disposal of radioactive ferric floc

An iron hydroxide floc is used as treatment for adsorbing low amounts of actinides during nuclear fuel re-processing. This waste is cemented only after pre-treatment with Ca(OH)(2). Characterisation of all simulant material has been undertaken using XRD, TGA and SEM/EDS. The floc is a moderately alkaline colloidal slurry containing approximately 15wt% solids, with the main particulate being an amorphous hydrated iron oxide. The main phase formed during pre-treatment appears to be an X-ray amorphous hydrated calcium-ferrate phase. Embedded within this are small amounts of crystalline Ca(OH)(2), calcite, Fe(6)(OH)(12)(CO(3)), Ca(6)Fe(2)(SO(4))(3)(OH)(12).26H(2)O and Ca(3)B(2)O(6), and can form depending on concentrations of Ca(OH)(2) and time. Apart from Ca(OH)(2) and calcite, none of the crystalline phases detected during pre-treatment are detected when the floc is encapsulated in an OPC/PFA composite cement hydrated for 90 days. The main crystalline phase detected in the hardened wasteform is a solid solution hydrogarnet, Ca(3)AlFe(SiO(4))(OH)(8), known as C(3)(A,F)SH(4) in cement chemistry nomenclature.     

Role of aluminous component of fly ash on the durability of Portland cement-fly ash pastes in marine environment

The durability, of mixtures of two kinds of Spanish fly ashes from coal combustion (ASTM class F) with 0, 15 and 35% replacement of Portland cement by fly ash, in a simulated marine environment (Na(2)SO(4)+NaCl solution of equivalent concentration to that of sea water: 0.03 and 0.45 M for sulphate and chloride, respectively), has been studied for a period of 90 days. The resistance of the different mixtures to the attack was evaluated by means of the Koch-Steinegger test. The results showed that all the mixtures were resistant, in spite of the great amount of Al(2)O(3) content of the fly ash. The diffusion of SO(4)(2-), Na+ and Cl- ions through the pore solution activated the pozzolanic reactivity of the fly ashes causing the corresponding microstructure changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

Effects of competitive ions,humic acid,and pH on removal of ammonium and phosphorous from the synthetic industrial effluent by ion exchange resins

The removal of the ammonium and phosphorous from the synthetic industrial effluent by the ion exchange resins was studied in this paper, aiming at the determination of the effects of competitive ions, humic acid, pH and resin amount. The kinetic experiments show that the equilibrium time for the removal of both contaminants in the absence and presence of the competing matters was 4 h. Na+ and K+ significantly reduced the ammonium removal percentage, while the existence of Mg2+, Ca2+ and humic acid also had a negative influence. Adsorption of ammonium ions in both absence and presence of Na+ and K+ observed the linear isotherm, however, it did not follow commonly used isotherms in the presence of Na+, K+, Mg2+, Ca2+ and humic acid. The phosphorous removal decreased in the presence of the competitive matters, such as Cl-, CO3(2-), SO4(2-) and humic acid. Higher pH can cause higher phosphorous removal percentage. A decrease in the solution pH was observed in the phosphorous removal experiments, possibly due to the ion exchange and the adsorption of OH-. Uptake of humic acid by the resins was observed. Finally, a series of fixed-bed experiments were performed, showing that the performance was dependent on the empty bed contact time (EBCT). Higher EBCT would cause higher bed volumes of both treated ammonium and phosphorous.     

湿法烟气脱硫石膏制备硫酸铵

采用湿法烟气脱硫石膏为原料,与( NH4)2CO3反应,制备(NH4)2SO4.通过X射线衍射仪表征可知:脱硫石膏的主要成分为CaSO4,反应后CaSO4中的Ca2+大部分以CaCO3形式存在于固体沉淀物中,CaCO3粉末平均粒径为80 nm;而原先CaSO4中的不溶性SO2-4则与NH+4结合生成(NH4)2SO4,...     

从含铬铝泥中回收铝的新工艺

采用"打浆水洗除Cr(Ⅵ)—电渗析除Cr(Ⅵ)—碱浸提铝—碳酸化分解法精制Al_2O_3"的新工艺处理含铬铝泥(以下简称铝泥),并回收Al_2O_3。实验结果表明:铝泥在70℃下经3次打浆水洗后,w(Na_2CrO_4)(以干铝泥计)降至5.0%;采用电渗析除Cr(Ⅵ)工艺可有效去除铝泥中以结合态和结晶态形式存在的Na_2CrO_4,在55 V直流电压下电渗析6h后铝泥中的w(Na_2CrO_4)降至0.98%;在碱浸温度为100℃、碱浸时间为3 h、NaOH质量浓度为150 g/L的优化碱浸条件下,铝浸出率(以Al_2O_3计)高达90.0%;经3次碳酸化分解处理后,Al_2O_3产品的纯度达98.65%,满足GB/T 24487-2009《氧化铝》中的一级标准,Al_2O_3回收率为96.37%。     

Leachability of municipal solid waste ashes in simulated landfill conditions

In Japan the volume of municipal solid waste is reduced by incineration, with fly ash and bottom ash disposed in controlled landfills. The leachability of anions and heavy metal cations, Zn, Cu and Pb, from MSW fly ash and bottom ash at different pHs was examined using batch- and column-leaching tests. The MSW ashes had a high capacity for neutralizing acids. Behaviour during leaching depended on the pH of the solution. For the volumes applied, the leachabilities of MSW fly ash were very similar at pHs from 3 to 6. Due to its amphoteric nature, Pb is leachable at pHs of approximately 10 or more, with leachate concentrations of about 3 and 3-10mg/L for the fly ash and bottom ash, respectively, much higher than for Zn and Cu. Pb concentrations for most leaching solutions were 1 and 3mg/L for the fly ash and bottom ash, respectively. Zn, and Cu leached at low concentrations for solutions of pH 3-6. Na and K ions leached at high concentrations of approximately 5000 mg/L in the first batch leaching test, decreasing to 10mg/L by the fourth leach. Ca and Mg ions leached more gradually than Na and K. Cl(-) and SO(4)(2+) ions were the major anions in the MSW ash. The high pH and cation leaching are expected to have negative impacts on the performance of clay liners.     

The use of 'exotic' framework structures in waste management

The use of porous framework materials in waste management applications has the potential to be a powerful tool in toxic metal remediation. The properties that these materials possess, including high surface area and ion-exchange capacity, are theoretically valuable. Furthermore, the flexibility of many of these frameworks allows the potential for immobilisation of waste materials with the framework of the material, in addition to the traditional capture in the pore structure. However, for either of these routes to be useful for waste management purposes, these structures must also be stable in any proposed storage media. This study examines the stability of a range of porous materials whose frameworks are made out of zinc and arsenic, both considered toxic minesite wastes, when exposed to aqueous media. The three frameworks examined (sodalite analogue Na(6)(H(2)O)(8)(ZnAsO(4))(6), open framework K(3)Zn(4)O(AsO(4))(3).3.5H(2)O, and an ABW type framework NH(4)ZnAsO(4)) all have similar hydrothermal synthetic routes and bulk framework compositions, but differ in counter ion used, pore size and complexity of structure. The phases were examined before and after storage in an aqueous environment, and their crystallinity and leaching were determined. All phases prepared were found to be extremely unstable outside their original synthetic environment, and very soluble when exposed to water, calling into question their practical use in any environment.     

Evaluation of Air Quality over the Black Sea: Major Ionic Composition of Rainwater

This article attempts to put the light on the air quality of the Black Sea region of Turkey. In addition to that, it endeavors to locate the possible sources of the different pollutants at local, regional and long range transported scales. About 196 rainwater samples were collected over the Black Sea region of Amasra between 1995 and 1999, and analyzed for major ions and trace elements using spectrophotometric techniques. Andersen wet only rain samples were used to collect rain events, where the rain sample was filtered inline using 0.45 m cellulose acetate filters. Major anions (SO₄ ^2-, NO₃ ^- and Cl^-) were determined using ion chromatography, whereas metals (Ca, Mg, Al, Fe, Na, K), werequantified using ICP-AES. This study shows that, the Black Sea region receives different amounts and types of anthropogenic pollutants via long-range transport according to trajectory models. Although the pH of rain water is not considered acidic (pH = 5.21) yet the neutralizing species are lower than other sites around Europe.     

Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed under vacuum (3.5-10kPa) conditions, and the effects of temperature and basic additives (Na(2)CO(3), NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50wt% was achieved at 480 degrees C by adding 3wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na(2)CO(3) addition. Pyrolysis gas was mainly composed of H(2), CO, CH(4), CO(2), C(2)H(4) and C(2)H(6). Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5wt%) was much higher.     

Modelling of long-term dynamic leaching tests applied to solidified/stabilised waste

The paper aims at simulating the closed-system dynamic leaching of a cement-based monolith containing lead with the numerical reactive transport code HYTEC in a 3D-cylindrical geometry. The model considers, simultaneously, the chemical evolution of pore water, the progression of mineralogical alteration fronts, and the concomitant release of elements from the S/S waste. In good agreement with the experiment, element releases were found to be mainly controlled by either diffusion (Na, K, and, to a lesser extent, Cl), by surface dissolution (Ca, Si) or by a mixed evolution (Pb, SO4). All of the calculated mineralogical transformations take place in a thin layer beyond the monolith surface. Consequently, modelling of Ca, Si and SO4 releases was quite sensitive to the node size of the simulation grid and was improved by taking into account the increase of porosity and effective diffusion coefficient due to mineral dissolution in the leached layer. In agreement with experimental results, the deepest front corresponds under closed-system conditions to portlandite dissolution and calcium silicate hydrates CSH 1.8 transformation into CSH of lower Ca/Si ratio. A second, distinct and intermediate, front is made by ettringite dissolution. The network of CSH is globally preserved in the leached layer, complete dissolution occurring over a very small thickness only. Finally, hydrotalcite precipitation in the leached layer is expected by modelling due to pH drop.     

Crystalline phase analysis and phosphorus availability after thermochemical treatment of sewage sludge ash with sodium and potassium sulfates for fertilizer production

Phosphorus rich sewage sludge ash is a promising source to produce phosphorus recycling fertilizer. However, the low plant availability of phosphorus in these ashes makes a treatment necessary. A thermochemical treatment (800–1000 °C) with alkali additives transforms poorly plant available phosphorus phases to highly plant available calcium alkali phosphates (Ca,Mg)(Na,K)PO₄. In this study, we investigate the use of K₂SO₄ as additive to produce a phosphorus potassium fertilizer in laboratory-scale experiments (crucible). Pure K₂SO₄ is not suitable as high reaction temperatures are required due to the high melting point of K₂SO₄. To overcome this barrier, we carried out series of experiments with mixtures of K₂SO₄ and Na₂SO₄ resulting in a lower economically feasible reaction temperature (900–1000 °C). In this way, the produced phosphorus potassium fertilizers (8.4 wt.% K, 7.6 wt.% P) was highly plant available for phosphorus indicated by complete extractable phosphorus in neutral ammonium citrate solution. The added potassium is, in contrast to sodium, preferably incorporated into silicates instead of phosphorus phases. Thus, the highly extractable phase (Ca,Mg)(Na,K)PO₄ in the thermochemical products contain less potassium than expected. This preferred incorporation is confirmed by a pilot-scale trial (rotary kiln) and thermodynamic calculation.

     

Properties of mortars made by uncalcined FGD gypsum-fly ash-ground granulated blast furnace slag composite binder

A series of novel mortars were developed from composite binder of uncalcined FGD gypsum, fly ash (FA) and ground granulated blast furnace slag (GGBFS) for the good utilization of flue gas desulphurization (FGD) gypsum. At a fixed ratio (20%) of GGBFS to the composite binder, keeping consistency of the mortar between 9.5 and 10.0 cm, the properties of the composite mortar were studied. The results show that higher water/binder (W/B) is required to keep the consistency when increasing the percentage of FGD gypsum. No obvious influences of the W/B and content of FGD gypsum on the bleeding of paste were observed which keeps lower than 2% under all experimental conditions tried. The highest compressive and flexural strengths (ratio is 20% FGD gypsum, 20% GGBFS and 60% FA) are 22.6 and 4.3 MPa at 28 days, respectively. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicate that massive ettringite crystals and C-S-H gels exist in the hydration products. At 90 days the mortars with FGD gypsum is dramatically smaller drying shrinkage (563-938 micro strain) than that without FGD gypsum (about 2250 micro strain). The release of the SO(4)(2-) from the mortar was analyzed, indicating that the dissolution of sulfate increases with FGD gypsum. The concentration of SO(4)(2-) releasing from the mortar with 10% FGD gypsum is almost equal to that obtained from the mortar without FGD gypsum. The release of SO(4)(2-) from the mortar with 20% FGD gypsum is 9200 mg·m(-2), which is lower than that from the mortar with 95% cement clinker and 5% FGD gypsum.     

Reuse of municipal solid wastes incineration fly ashes in concrete mixtures

This study is aimed at assessing the feasibility of concrete production using stabilized m.s.w. (municipal solid waste) incineration fly ashes in addition to natural aggregates. The tested fly ashes were washed and milled, then stabilized by a cement-lime process and finally were reused as a "recycled aggregate" for cement mixture production, in substitution of a natural aggregate (with dosage of 200-400 kg m(-3)). These mixtures, after curing, were characterized with conventional physical-mechanical tests (compression, traction, flexure, modulus of elasticity, shrinkage). In samples containing 200 kg(waste) m(-3)(concrete), a good compressive strength was achieved after 28 days of curing. Furthermore, concrete leaching behavior was evaluated by means of different leaching tests, both on milled and on monolithic samples. Experimental results showed a remarkable reduction of metal leaching in comparison with raw waste. In some cases, similar behavior was observed in "natural" concrete (produced with natural aggregates) and in "waste containing" concrete.     

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville,Colorado

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.     

The hydration characteristics and utilization of slag obtained by the vitrification of MSWI fly ash

This study investigated the effects of slag composition on the hydration characteristics of slag blended cement (SBC) pastes. Synthetic slag samples were prepared by melting CaO-modified and Al(2)O(3)-modified municipal solid waste incinerator (MSWI) fly ash. MSWI fly ash was mixed with 5% CaO and 5% Al(2)O(3) (by weight), respectively, resulting in two fly ash mixtures. These mixtures were then melted at 1400 degrees C for 30 min to produce two types of slag with different contents, designated at C-slag and A-slag. Both the C-slag and A-slag samples exhibited a pozzolanic activity index higher than the unmodified slag sample. The results show that the synthetic slags all met the Taiwan EPA's current regulatory thresholds. These synthetic slags were then blended with ordinary Portland cement (OPC) at various weight ratios ranging from 10 to 40%. The 28-day strength of the C1 paste was higher than that developed by the OPC paste, suggesting that the C-slag contributed to the earlier strength of the SBC pastes. At curing times beyond 28 days, the strength of the A1 paste samples approached that of the OPC paste samples. It can be seen from this that increasing the amount of calcium and aluminum oxide increases the early strength of SBC. The C-slag blended cement paste samples showed an increase in the number of fine pores with the curing time, showing that the C-slag enhanced the pozzolanic reactions, filling the pores. Also, the incorporation of a 10% addition of C-slag also tended to enhance the degree of hydration of the SBC pastes during the early ages (3-28 days). However, at later ages, no significant difference in degree of hydration between the OPC pastes and the SBC pastes was observed with the 10% C-slag addition. However, the incorporation of A-slag did decreased the degree of hydration. A slag blend ratio of 40% significantly decreased the hydration degree.     

用生物滴滤床处理H2S和挥发性有机物混合废气

用生物滴滤床（BTF）处理某化工厂污水站的H2S和挥发性有机物（VOCs）混合废气,当废气中H2S质量浓度为120～400mg／m^3、VOCs质量浓度为115～340mg／m^时,运行稳定后H2S和VOCs的去除率为95％和85％。考察了影响BTF运行的循环水水质情况,试验结果表明：加入Na2CO3可使循环水pH控制在3～6;循环水中含盐量、Cl^-质量浓度和SO4^2-质量浓度分别为2200～3300,600～800,1200～1400mg／L,均未达到抑制微生物的水平。