Treatment process for MSW combustion fly ash laboratory and pilot plant experiments

Fly ash from combustion of municipal solid waste sometimes contains large amounts of soluble salts, such as NaCl, even though the content of soluble toxic metal compounds is relatively low. Removal of the salts by washing with water has been suggested as a method to increase the stability of this type of ash. In the work presented here, a simple washing process was studied and evaluated. The process includes three steps: leaching with water, filtration and displacement washing. Basic data were obtained in laboratory experiments and used in the construction of pilot plant equipment at a full size fluidized bed boiler, where a side-stream of the cyclone ash was treated. The process was designed to minimize the water consumption while obtaining an effective removal of salts and a stable ash residue. In order to achieve this, recirculation of leaching liquor was used and the displacement washing was adjusted to become close to ideal. The results showed that an ash/water slurry with a liquid to solid ratio as low as 3 could be handled without difficulty in the mixing, pumping and filtration units. Washing of the filter cake at a liquid to solid ratio of 0.5 removed the major part of the remaining dissolved salts in the pore liquid. About 90% of the chloride content was removed from the ash, whereas the contents of Na, K, Ca, Cd, Pb and a number of other minor elements were removed by 10-30%. Before treatment, the results of ash leaching tests were sometimes too high for chloride (2003/33/EC), but the treatment reduced the amount of soluble chlorides to far below the limit values. The leachability of most metals was reduced or unaffected by the ash treatment. For Na, K and Cl, it was less than 10% of the value for the untreated ash. However, the results showed that some ash components may be mobilized by the washing. Antimony is the most important due to its toxicity.     

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.     

Water extraction with CO2 bubbling as pretreatment of melting-furnace fly ash for metal recovery

In Japan, melting-furnace fly ash (MFA) generated from ash melting and gasification/melting plants is considered an “urban mine” due to its high metal content. This study aimed to develop a novel approach to pretreating MFA for metal recovery. Water extraction with CO₂ bubbling was investigated because MFA mainly consists of water-soluble salts containing elements such as Cl, Ca, Na, and K. Instead of acid addition, CO₂ bubbling was applied to maintain the optimal pH for minimizing the release of target metal elements and maximizing the removal of undesirable elements during water extraction. The results revealed that CO₂ bubbling effectively decreased the release of Pb, Zn, and Cd into the treatment water. This was mainly due to coprecipitation with CaCO₃, which was primarily formed by the reaction of Ca²⁺ from the MFA with CO₃ ²⁻ from the CO₂ gas. The bubbling process also helped accelerate the removal of Cl from MFA. Furthermore, the study showed that it is possible to lower the water-to-solid ratio to 5 with only a slight reduction in water extraction effect. Finally, approximately four times the concentration of target metals (rare metals and Cu, Pb, and Zn) was achieved by removing 90% of Cl, 70%–90% of Na and K, and 30%–40% of Ca through water extraction with CO₂ bubbling, resulting in a concentration of target metals that was nearly equal to that of ore.     

Metal leaching from MSWI bottom ash as affected by salt or dissolved organic matter

In order to manage municipal solid waste incineration (MSWI) bottom ash safely, risk assessments, including the prediction of leaching under different field conditions, are necessary. In this study, the influence of salt or dissolved organic matter (DOM) in the influent on metal leaching from MSWI bottom ash was investigated in a column experiment. The presence of salt (0.1M NaCl) resulted in a small increase of As leaching, whereas no impact on leachate concentration was found when lakewater DOM (35.1mg/l dissolved organic carbon) was added. Most of the added DOM was retained within the material. Further, X-ray spectroscopy revealed that Cu(II) was the dominating form of Cu and that it probably occurred as a CuO-type mineral. The Cu(2+) activity in the MSWI bottom ash leachate was most likely determined by the dissolution of CuO together with the formation of Cu-DOM complexes and possibly also by adsorption to (hydr)oxide minerals. The addition of lake DOM in the influent resulted in lower saturation indices for CuO in the leachates, which may be due to slow CuO dissolution kinetics in combination with strong Cu-DOM complexation.     

Calcium phosphate stabilization of fly ash with chloride extraction

Municipal solid waste incinerator by products include fly ash and air pollution control residues. In order to transform these incinerator wastes into reusable mineral species, soluble alkali chlorides must be separated and toxic trace elements must be stabilized in insoluble form. We show that alkali chlorides can be extracted efficiently in an aqueous extraction step combining a calcium phosphate gel precipitation. In such a process, sodium and potassium chlorides are obtained free from calcium salts, and the trace metal ions are immobilized in the calcium phosphate matrix. Moderate calcination of the chemically treated fly ash leads to the formation of cristalline hydroxylapatite. Fly ash spiked with copper ions and treated by this process shows improved stability of metal ions. Leaching tests with water or EDTA reveal a significant drop in metal ion dissolution. Hydroxylapatite may trap toxic metals and also prevent their evaporation during thermal treatments. Incinerator fly ash together with air pollution control residues, treated by the combined chloride extraction and hydroxylapatite formation process may be considered safe to use as a mineral filler in value added products such as road base or cement blocks.     

Chloride extraction for quality improvement of municipal solid waste incinerator ash for the concrete industry.

Coal ash from power stations has long been used successfully in the cement industry as binders in several Portland formulations. This is not the case for municipal solid waste (MSW) ash as chloride concentrations, ranging from 10 to 200 g kg(-1) dry weight in the bottom and fly ash, respectively, exceed the maximum allowable concentration in most cement mixtures. To reduce chloride content in MSW bottom ash, a laboratory investigation was carried out based on the exhaustive washing in tap water. The influence of operative parameters such as temperature, granulometric properties and solid/liquid ratio of extraction was evaluated. In addition to optimization of the mentioned operative parameters for full-scale application, the paper gives preliminary indications on mechanistic aspects of the washing operation.     

Characterization of metal concentration,heavy metal elution,and desalination behavior of municipal solid waste incineration bottom and grate sifting deposition ash based on particle size

Resource and environmental safety protocols of incineration residues were evaluated by analyzing the metal concentration, heavy metal elution, desalination behavior, and chlorine removal ratio owing to particle size differences between bottom ash (BA) and grate sifting deposition ash (GA). In the total content test, Cl, Zn, and Cr in the incinerator BA exceeded the cement acceptance standard (Cl: 1000 mg/kg; Zn: 1700 mg/kg, and Cr: 170 mg/kg) at almost all of the particle sizes, while Au, Ag, Pd, and Zn had high contents in the GA. When using BA as a construction material, heavy metal elution values and contents are restricted as per the product quality standards based on the Japanese soil pollution control law. Lead within the BA and GA exceeded the standard values for most particle sizes. We predicted that there would be a limit on the elution of K by only washing with water. The removal ratio of total chlorine by particle size was approximately 20–70%, where the effect of the particle size on the removal ratio was small, suggesting that the elution of chlorine was complete in approximately 6 hours. These results contribute to information on the recycling of BA and GA.

     

Demobilisation of critical contaminants in four typical waste-to-energy ashes by carbonation

Two bottom ashes, one air pollution control (APC) residue and one fly ash from three different Swedish municipal solid waste incineration (MSWI) plants were characterised regarding the leaching of environmentally relevant components. Characterisation was performed using a diffusion tank leaching test. The impact of carbonation on the release of eight critical components, i.e., Cl(-), Cr, Cu, Mo, Pb, Sb, Se, SO(4)(2-) and Zn, was assessed at a lab-scale and showed carbonation to have a more pronounced demobilising effect on critical components in bottom ashes than in APC residue and fly ash. From grate type incinerator bottom ash, the release of Cr decreased by 97%, by 63% for Cu and by 45% for Sb. In the investigated APC residue, the releases of Cr, Se and Pb were defined as critical, although they either remained unaffected or increased after carbonation. Cl(-) and SO(4)(2-) remained mobile after carbonation in all investigated residues.     

Solidification and recycling of incinerator bottom ash through the addition of colloidal silica (SiO2) solution

The possibility of using incinerator bottom ash as a substitute for natural aggregates was investigated. Rough, porous surface of bottom ash, which diminishes the strength of solidified products, was improved by colloidal silica solution. As a result, a significant increase of mechanical strength was accomplished by a slight amount of silica (<1 wt% to total). Moreover, pozzolanic reaction was induced in initial cement hydration due to the nano-particle size of about 20 nm in colloidal silica solution. Cylindrical specimens and bricks were prepared from bottom ash added to a colloidal silica (SiO2) solution and cement, and then their compressive strengths were evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive strength when colloidal solution containing 4 wt% silica particles was sprayed onto the bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which meets the requirement of construction materials. Results of leaching tests based on Toxicity Characteristic Leaching Procedure (TCLP) proved that the solidified bottom ash possessed good chemical stability.     

Influence of waste input and combustion technology on MSWI bottom ash quality

The waste input and the process technology of waste incineration plants appear to have a great influence on bottom ash quality. To better understand how these parameters can affect the characteristics of residues, bottom ash from six plants were tested and compared in this study. Bottom ash physico-chemical characteristics were investigated by chemical analyses, and leaching tests. In order to understand their long-term behavior, accelerated ageing experiments and biodegradation tests were also performed. The whole analyses gave complementary information. It was shown that the six samples do have different properties. Waste inputs have a great influence on Cl and S content in bottom ash, as well as on the Ca/Si ratio. The importance of this ratio on the carbonation process has been demonstrated. Combustion parameters have an influence on the quantity and mobility of the residual organic matter.     

Recycling MSWI bottom and fly ash as raw materials for Portland cement

Municipal solid waste incineration (MSWI) ash is rich in heavy metals and salts. The disposal of MSWI ash without proper treatment may cause serious environmental problems. Recently, the local cement industry in Taiwan has played an important role in the management of solid wastes because it can utilize various kinds of wastes as either fuels or raw materials. The objective of this study is to assess the possibility of MSWI ash reuse as a raw material for cement production. The ash was first washed with water and acid to remove the chlorides, which could cause serious corrosion in the cement kiln. Various amounts of pre-washed ash were added to replace the clay component of the raw materials for cement production. The allowable limits of chloride in the fly ash and bottom ash were found to be 1.75% and 3.50% respectively. The results indicate that cement production can be a feasible alternative for MSWI ash management. It is also evident that the addition of either fly ash or bottom ash did not have any effect on the compressive strength of the clinker. Cement products conformed to the Chinese National Standard (CNS) of Type II Portland cement with one exception, the setting time of the clinker was much longer.     

纯碱生产废水的综合治理

介绍了纯碱生产过程中产生的蒸氨废清液和生产下水的综合治理情况。将废清液晒盐回收ＮａＣｌ,然后从母液中回收ＣａＣｌ２。在雨季等情况下对废清液的治理措施是,将其两次兑海水,使其各项指标达到国家排放标准。     

Mobility of organic carbon from incineration residues

Dissolved organic carbon (DOC) may affect the transport of pollutants from incineration residues when landfilled or used in geotechnical construction. The leaching of dissolved organic carbon (DOC) from municipal solid waste incineration (MSWI) bottom ash and air pollution control residue (APC) from the incineration of waste wood was investigated. Factors affecting the mobility of DOC were studied in a reduced 2(6-1) experimental design. Controlled factors were treatment with ultrasonic radiation, full carbonation (addition of CO2 until the pH was stable for 2.5h), liquid-to-solid (L/S) ratio, pH, leaching temperature and time. Full carbonation, pH and the L/S ratio were the main factors controlling the mobility of DOC in the bottom ash. Approximately 60 weight-% of the total organic carbon (TOC) in the bottom ash was available for leaching in aqueous solutions. The L/S ratio and pH mainly controlled the mobilization of DOC from the APC residue. About 93 weight-% of TOC in the APC residue was, however, not mobilized at all, which might be due to a high content of elemental carbon. Using the European standard EN 13 137 for determination of total organic carbon (TOC) in MSWI residues is inappropriate. The results might be biased due to elemental carbon. It is recommended to develop a TOC method distinguishing between organic and elemental carbon.     

Preparation of activated carbons from heavy-oil fly ashes

The use of heavy oil fly ash with high ash content (45 wt.%) as a precursor for the preparation of activated carbons has been investigated. The raw fly ash and the fly ash with lower ash content, obtained by a HCl/HF washing treatment, have been pyrolyzed at 900 degrees C and then activated with CO(2) in the temperature range of 800-900 degrees C for different times. The activated carbons have been characterised as regards the surface area and the pore volume. The evolution of the porosity has been related to the burn-off degree.     

An investigation of halogens in Izmit hazardous and clinical waste incinerator

In the combustion facilities, halogens (Cl, F, Br, I) should be considered with regard to the control of the compounds such as polychlorinated dibenzodioxins (PCDD), polychlorinated dibenzofurans (PCDF), halogenated polyaromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and volatile heavy metals formed as a result of incomplete combustion and caused adverse environmental effects. In this study halogens were observed in Izmit Hazardous and Clinical Waste Incinerator (IZAYDAS). Halogen contents of the combustion menu, flue gas, fly ash, bottom ash and filter cake were measured and their distributions in these exit streams were determined. Results showed that the major part of the halogens was partitioned to solid residues, i.e., bottom ash and filter cake which represents the removal by wet scrubbers. Fly ash and flue gas fractions of halogens were much lower due to the reduced formation of volatile compounds.     

Comparison of two types of municipal solid waste incinerator fly ashes with different alkaline reagents in washing experiments

In this study, we propose a "washing-calcination-conversion of washed fly ash into cement material with bottom ash" (WCCB) system to reduce the amount of fly ash that must be specially treated so it can be used as raw cement material. Calcium hydroxide (Ca(OH)2) is widely used in air-pollution control devices of incinerators while sodium bicarbonate (NaHCO3) is not. We conducted single-, double-, and triple-washing experiments to compare the washing characteristics of two types of fly ash. Unlike NaHCO3 fly ash, Ca(OH)2 fly ash has almost twice as much washed residue and almost 2.5 times more chlorine after the same washing procedure. After washing once, the washing frequency is also important for NaHCO3 fly ash, while the mixing time and liquid/solid ratio are more critical for Ca(OH)2 fly ash. The use of NaHCO3 is more suitable for the WCCB system.     

Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes

In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.     

Preparation and characterization of sorbents prepared from ash (waste material) for sulfur dioxide (SO2) removal

Sorbents synthesized from various types of ash (coal fly ash, coal bottom ash, oil palm ash, and incinerator ash) for flue gas desulfurization were investigated. The sorbents were prepared by mixing the ashes with calcium oxide and calcium sulfate using the water hydration method. The effects of various sorbent preparation variables, such as the hydration period, the ratio of calcium oxide to ash, and the amount of calcium sulfate, on the Brunauer-Emmett-Teller (BET)-specific surface area of the resulting sorbent were studied using a two-level full factorial design. The surface area of the sorbents obtained range from 15.4 to 122.1m²/g. Regression models were developed to correlate the significant variables to the surface area of the sorbents. An analysis of variance (ANOVA) showed that the model was significant at a confidence level of 95%. It was found that apart from all the individual variables studied, interactions between variables also exerted a significant influence on the surface area of the sorbent. From the activity test results, it was found that sorbents prepared from coal fly ash and oil palm ash have the highest SO₂ absorption capacity. Scanning electron microscope (SEM) analysis showed that the sorbent was composed of a compound with a high structural porosity, while an X-ray diffraction spectrum showed that calcium aluminum silicate hydrate compounds are the main products of the hydration reaction.     

Water washing effects on metals emission reduction during municipal solid waste incinerator (MSWI) fly ash melting process

This study investigated that water washing effects on the metals emission reduction in melting of municipal solid waste incinerator (MSWI) fly ash. Experimental conditions were conducted at liquid-to-solid (L/S) ratio 10, 20, and 100 for water-washing process and its subsequent melting treatment at 1450 °C for 2 h. The simple water-washing process as a pre-treatment for MSWI fly ash can remove most of the chlorides, leachable salts, and amphoteric heavy metals from the MSWI fly ash, resulting in the washed ash having lowered chlorine content. MSWI fly ashes washed by L/S ratio 10 and above that were melted at 1450 °C produced slag containing relatively high vitrificaton ratio of Cu and Pb. Besides, the vitrification ratios of Na, K, Ca, and Mg in washed MSWI fly ash were also higher than that of MSWI fly ash. The results indicated that washed MSWI fly ash can reduce the emission of metallic chlorides during its subsequent melting treatment.     

Recovery of zinc and lead from fly ash from ash-melting and gasification-melting processes of MSW--comparison and applicability of chemical leaching methods

Fly ash generated from MSW ash-melting and gasification-melting plants, known as Melting Furnace Fly Ash (MFA), contains considerable amounts of heavy metals such as Pb and Zn. These metals can be recovered using a smelting furnace after "pre-treatment" for removal of unnecessary elements such as Cl, Sn and Si. Chemical methods have been studied for pretreatment in the past. However, they have been discussed only with regard to treatment cost and the concentration of Pb and Zn recovered, but neither applicability to various types of MFA nor the environmental impact have been considered. In this study, acid, alkaline and ammonia/chloride leaching methods were compared from the standpoints of: (1) applicability to MFA, (2) concentration of Pb and Zn recovered, (3) treatment cost, and (4) environmental impact. Twenty-three samples of MFAs were collected and classified into 4 types based on element contents. A Pb and Zn recovery experiment was conducted for the representative MFA of those types. The results showed: (1) MFA from gasification-melting plants cannot be treated by chemical methods; (2) the other MFA can be treated to an acceptable quality by existing smelting furnaces; (3) only MFA from electric resistance ash-melting plants can be treated easily by the water washing method; and (4) alkaline and ammonia/chloride leaching methods were more effective than acid leaching.