Waste Management 23 (2003) 291305 www.elsevier.

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Release of salts from municipal solid waste combustion residues

Zareen Abbasa,*, Azadeh Partovi Moghaddama, Britt-Marie Steenarib
b a Department of Chemistry, Go teborg University, SE-412 96 Go teborg, Sweden Department of Environmental Inorganic Chemistry, Chalmers University of Technology, SE-412 96 Goteborg, Sweden

Accepted 9 May 2002

Abstract Residues from uidized 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 SO2 along with the total dis4 solved solids of bottom, hopper, cyclone and bag house lter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The eect 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 lter 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: lter 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 SO2 from the cyclone as well as from the lter ashes. The leached amounts 4 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 lter ashes as well as from unwashed lter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of lter ashes. # 2003 Elsevier Science Ltd. All rights reserved.

1. Introduction Combustion of municipal solid waste (MSW) oers a reduction in both the mass and volume of the waste subjected to nal disposal, as well as the possibility of energy recovery. Earlier it has been common to re MSW on a stationary or moving grate at about 1000  C, in so called mass burn (MB) facilities. In recent years uidized bed combustion (FBC) has been introduced as an alternative technique for MSW combustion (Rhyner et al., 1995). The combustion technique itself is well known since FBC boilers have been utilized for many years in energy production based on coal and biomass, and it has now been adjusted to suit also the inhomogeneous and sometimes troublesome fuel MSW. In an FBC boiler the fuel is burned in a bed of inert material (usually quartz sand) that is uidized by a stream of combustion air entering through the bottom
* Corresponding author. Tel.: +46-31-772-2886; fax: +46-31-7722853. E-mail address: zareenabbas56@hotmail.com (Z. Abbas).

of the combustion chamber. The combustion temperature in FBC is usually around 850  C and the boilers can either be of the bubbling uidized bed (BFB) type or of the circulating uidized bed (CFB) type (Rhyner et al., 1995). These two combustor types are shown schematically in Fig. 1. In the BFB the velocity of the air ow through the bed is rather low and the bed material remains in the combustion chamber (Fig. 1a). In the CFB, on the other hand, the velocity of the air is much higher which results in a circulation of bed material, ash and burning fuel in a loop consisting of the combustion chamber and a primary cyclone (Fig. 1b). The main advantages of the FBC technique are the exibility in choice of fuel, low NOx and SOx emissions and an ecient heat transfer from the sand bed to the heat exchanger walls. The amount of unburned matter in the ash residues is often low. However, the rather large volume of ash residues that is produced can be considered as a draw back. The ows of residues produced in FBC are bottom ash, cyclone ash and lter ash. Materials removed from the ue gases in dierent gas cleaning systems are generally called y ashes but

0956-053X/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved. PII: S0956-053X(02)00154-X

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Fig. 1. A schematic representation of (a) a bubbling uidized bed boiler (BFB) and (b) a circulating uidized bed boiler (CFB).

according to the recommendations of the international ash working group (IAWG) these materials should be referred as air pollution control (APC) residues (IAWG, 1997). The physical and chemical nature of the APC residues produced from MSW combustion mainly depends on the type of combustion system and ue gases treatment system used (Alba et al., 1997). Since FBC is relatively new in the eld of MSW combustion, only a few studies regarding the physical and chemical nature of its residues have been published. Recently Blondin et al. (1997) and our group (Abbas et al., 1999; 2001) have investigated the chemical composition and leaching behavior of bottom ash and APC residues from BFB boilers. The results showed that the bottom ash was mainly composed of aluminumsilicate minerals and that its leaching of salts and heavy metals was low. Coarse material removed from the ue gases in the cyclone also contained aluminumsilicate minerals together with soluble salts of alkali and alkaline earth metals. The leaching of alkali and alkaline earth metal salts was considerable, but, generally, only small

amounts of heavy metals were released. In the most nely sized ash fractions collected in a bag house lter, on the other hand, the dominant crystalline compounds were salts of alkali and alkaline earth metals and of various transition metals. These components were easily released in leaching tests. This indicates that the deposition of lter ash, and in some cases also of cyclone ash, will pose environmental problems due to their high content of soluble substances. Thus, some type of stabilization, which reduces the leaching of salts will be required to ensure a safe disposal of these ashes. Stabilization in the present context means a treatment that transforms the ash components into less soluble forms or removes the most soluble components. Stabilization of ashes can be achieved by various treatment methods such as weathering, solidication, thermal treatment or by applying a suitable liquid extraction method (Sakai et al., 1996; Wiles, 1996). Weathering is suitable for ashes with low contents of soluble salts and heavy metals such as bottom ash (Lamers and Born, 1994; Steketee, 1997; Chimenos et al.,

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2000). Solidication is generally achieved by using pozzolanic materials or cement. The disadvantage of this process is that the volume of the residue increases and the method may not be suitable for ashes containing large amounts of chlorides (IAWG, 1997; Mangialardi et al., 1999; Alba et al., 2001). Thermal methods are ecient in removing volatile heavy metals from the ash residues but are energy requiring and thus expensive (Sakai and Hiraoka, 1997). Recently it has also been reported that the leaching of Al (Chan et al., 2000) and Cr (Kirk et al., 2002) was enhanced from the thermally treated MSW y ash when compared with the untreated ash. An alternative stabilization method is liquid extraction. Hitherto extraction methods have been developed for ashes from MB techniques and have mainly been directed towards the extraction of heavy metals with acidic (Katsuura et al., 1996; Sreenivasarao et al., 1997; van der Bruggen et al., 1998; Yang et al., 1998) or alkaline solutions (Nilsson et al., 1995; Stegemann et al., 1995; Mizutani et al., 1996). However, less attention has been paid to developing a full-scale method for the extraction of alkali and alkaline earth salts with water. Water extraction can be a useful method because only the soluble salts are removed and the solid matrix of ash particles remains intact. Kirby and Rimstidt (1994) have investigated the possibility of water extraction of a mixture of bottom and y ash from a MB boiler. They found the method quite useful at lab scale. Dietler (1990) has developed a process for removing of salts from MB ashes by a water washing process. Liquid to solid ratio 2 and water extraction for 30 min was found to be suitable for the removal of soluble salts from the y ashes. However, the leaching behavior of washed ashes was not investigated. For a full-scale water extraction process to be economically feasible the amount of water used should be low and the extraction time should be as short as possible without seriously lowering the eciency. The present work was carried out as a pre-study to the development of a washing process for ashes from BFB and CFB boilers red with MSW. The extraction medium chosen was water and dierent parameters aecting the washing process were studied and optimized experimentally. This work was especially concentrated on the release of Na, Ca, K, Cl, Br, F and sulfates. In addition, an operationally dened measure i.e., the total dissolved solids (TDS) was used to characterize the ashes. The eect of washing was investigated by applying a two-step batch-leaching test on original as well as on the washed ashes.

The rst boiler is a BFB facility where ash samples were collected twice. This plant burns 69,000 tones of waste annually. At this facility bulky items are removed from the waste by a grab crane. The waste is then fed to a hammer mill. Approximately 85% of the ferrous metal is removed from the waste with a magnetic separator before waste is fed to the boiler. On the sampling dates, the municipal solid waste combusted had the following composition: 46.6% household waste, 26.4% sorted waste (household and light industry, burnable fraction), 16.2% business waste (mainly from paper and packaging) and 10.8% RDF (well sorted household waste). The ash samples were collected during a 2-week period. All four outgoing ows of residues from the plant (bottom ash, hopper ash, cyclone ash and lter ash) were sampled. Each day eight incremental samples of every residue were collected at a random time. The eight incremental samples of the ashes were mixed every day and saved in airtight plastic containers. The gross samples used in this study were prepared by mixing the daily samples taken during a 2-week sampling period. The ashes sampled at the rst occasion are all identied by the denotation (BFB1). A schematic representation of the boiler and sampling points are given in Fig. 1a. More details of the sampling procedure have been given elsewhere (Abbas et al., 1999). At a later date another sample of cyclone ash was collected. This sample is denoted cyclone ash BFB2. The second boiler is a CFB plant. This plant burns 39,000 tones of refused derived fuel (RDF). The RDF is produced from a mixture of 75% MSW and 25% light industrial waste. The ferrous metals are separated by a magnetic separator and then waste is shredded to produce RDF. During the ash sampling 100% RDF was combusted. The ash samples used in this study are the gross samples made by mixing the samples taken at different times of a day. A schematic representation of the plant and sampling points are illustrated by Fig. 1b. The cyclone beside the main combustion chamber is used to collect the bed material entrained in the ue gases. This bed material is then reintroduced into the main combustion chamber. An electrostatic precipitator (which is not in operation) is simply used as a particle collector. Hydrated lime is injected to neutralize the acidic gases and the particulate matter along with the products of this ue gases treatment process are collected in a bag house lter. The material sampled from the bag house lter of this boiler is denoted as lter ash CFB.

3. Methods 2. Material The ash materials used in the present study came from two boilers in Sweden: 3.1. X-ray diraction analysis The mineralogy of the ash samples was studied using X-ray diraction spectrometry after drying and crushing

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the samples into powder form. The X-ray powder diraction apparatus used in this work was a computer-controlled Siemens D5000 powder diractometer. The measurements were carried out applying Cu characteristic radiation and either a position sensitive detector or a scintillation detector. The Joint Committee of Powder Diraction Standards database was used for identication of crystalline compounds (PDF-1 S, 1995). This method allows the identication of crystalline components present in amounts larger than 12% (w/w). 3.2. Determination of total contents of Na, K and Ca Total contents of Na, K, and Ca in these ashes were determined according to the standard method ASTM E 886-94. 0.1 g of ash sample was melted with 1 g of Li2B4O7 in a platinum dish at 1000  C for 15 min. The melt was dissolved in 150 ml of dilute HCl and stirred for 30 minutes at a temperature near the boiling temperature. The solution was cooled and diluted to a nal volume of 200 ml with dilute HCl. The Ca, Na and K contents were determined using ame atomic absorption spectroscopy (F-AAS). Total contents of K, Na and Ca in lter ash from BFB1 were also determined after acid digestion according to the method ASTM E 886-94. In this method 0.1 g of ash is digested in a Teon bomb with 3 ml of 2.5 N aqua regia at 100  C for 2 h. Finally the mixture is diluted to 100 ml with deionized water. The reason why we tested the two methods for lter BFB1 ashes was due to our previous observation that the leached amounts of K in CEN test from lter BFB1 ash were higher than the total contents of K determined by borate melt method. This discrepancy was removed by using the bomb digestion method (Abbas et al., 1999). Apparently there is a loss of K during the melting of lter BFB1 ash with borate at 1000  C. Thus borate melting method may not be suitable for determining the total content of K in materials rich in chloride salts such as lter ash BFB1. 3.3. Total water extractable contents The procedure for the determination of total water extractable contents of Na, K, Ca, sulfates, chloride, bromide and uoride was adopted from the method used by the Swedish National Testing and Research Institute (SP), Boras, Sweden. An appropriate amount of ash and water was mixed to obtain a certain liquid to solid (L/S) ratio. This mixture was boiled for 5 min and then ltered through a 0.45-mm membrane lter. The concentration of interesting species was then determined in the ltrate. Due to dierences in ash characteristics a single method, i.e., a constant L/S ratio could not be applied to all ashes. The extraction method was optimized for

each ash type. The L/S ratio was increased until the extracted amounts of the above mentioned components became independent of the L/S ratio. The ranges of L/S ratio tested are given below. Bottom and Hopper ashes (BFB1): L/S range 10 ! 50. Cyclone ash (BFB1): L/S range 100 ! 200. Filter ash (BFB1): L/S range 100 ! 400. Cyclone ash (BFB2): L/S range 100 ! 200. Filter ash (CFB): L/S range 100 ! 300. In order to study specically the eect of boiling on the release of dierent species, ashwater mixtures (at the highest L/S ratios given above) were agitated at room temperature for 15 min. The mixtures were ltered and analyzed. Sulfate, chloride, bromide and uoride concentrations were determined by ion chromatography, whereas the concentrations of Ca, Na and K were determined by FAAS. 3.4. Determination of total dissolved solids (TDS) TDS is an operationally dened measure of the water soluble weight fraction of a waste, e.g. an ash. For an ash, the TDS value includes mainly soluble salts, such as NaCl, KCl, CaCl2 and CaSO4. In this work, samples for the determination of TDS were prepared by mixing ash and de-ionized water to obtain a certain L/S ratio. Due to dierences in ash characteristics the L/S ratio had to be optimized for each sample type. After agitating the mixture for 24 h in an air-tight plastic bottle on an orbital shaker, the solution was ltered o using a 0.45-mm membrane lter. The ltrate was then boiled till dryness in a glass beaker. In order to ensure the dryness of the sample, the beaker was weighed after 30 and 60 min of drying at 105  C. Weighing was carried out after cooling the samples in a desiccator. The ash remaining after extraction was also dried at 105  C and weighed. The weight loss of dried ash and the weight of dissolved material was compared to the original ash weight. The results were calculated as TDS % of the total ash. 3.5. Stabilization experiments, leaching test and associated analytical methods A stabilization method based on washing the ash residue with water seems simple enough, but there are some parameters that may inuence the result of the washing. These parameters are temperature, agitation method (e.g. mixing eciency), L/S ratio, contact time, and the number of extraction steps. Temperatures of 25, 40 and 60  C have been tested in initial experiments (Abbas et al., 1999; Gard, 2000). The results obtained showed that the salt extraction eciency was independent on temperature in this range. Therefore, the

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experiments in the present study were carried out at room temperature. L/S ratios of 1, 2, and 4 and extraction times of 5, 10, 30, 60 and 120 min were used. The ash mixtures were agitated in air-tight plastic containers on an orbital shaker. In earlier tests this mixing method has been shown to be equally eective as mixing by means of a magnetic stirrer (Gard, 2000). The number of extraction steps was varied (1 and 3, respectively) while keeping the contact time and mixing method the same (15 min and orbital shaker). These experiments were carried out using both L/S 1 and L/S 2. The ash remaining after each washing test was evaluated with respect to its stability towards leaching of salts using the CEN leaching test. It is a two-stage serial batch-leaching test. The material is milled until 90% of the total sample has a particle size < 4 mm. The material (100 g) is mixed with 200 ml de-ionized water to attain a L/S ratio 2 and the mixture is agitated for 6 h in air-tight plastic bottles. The mixture is ltered through a 0.45-mm membrane lter and the ltrate is saved for analysis. In the second step, the ash remaining from the rst step is leached for 18 h at L/S 8, with fresh deionized water. The results of the CEN test are presented as released amounts based on dry ash weight (mg/kg ash) at L/S 2 and at accumulated L/S 10. The pH values of the leachates were determined by acidometric titration. Concentrations of Cl, Br, SO42 and F in the leachates were determined by ion chromatography, whereas the concentrations of Na, K and Ca were determined by FAAS.

4. Results and discussion 4.1. Mineralogy and total contents The combustion residues studied in this work were all produced at 850  C in uidized bed boilers. At such a low temperature the ash does not melt to any signicant extent. Thus, the content of glassy material is low (Steenari et al., 1999). The crystalline compounds found

in these ash samples are given in Table 1. As has been discussed elsewhere (Abbas et al., 1999, 2001), the abundance of silicate and aluminumsilicate minerals is very high in the bottom ash as well as in the hopper ash. In Table 2, the total contents of Na, K and Ca are compared with the contents of major soluble salts (chloride, bromide, uoride, sulfate) of the same elements. It is evident that Na, K and Ca in bottom and hopper ashes are mainly present in low solubility compounds, such as silicates. The two cyclone ash samples (BFB1 and BFB2), taken about a year apart, are similar in mineral composition and have similar contents of Na, K, Ca and associated salts (Tables 1 and 2). A signicant part of the cyclone ashes consist of silicates, aluminum-silicates and iron oxides. These are all low solubility compounds and can be expected to remain in the residue after washing. However, the relative abundance of soluble salts in cyclone ashes is higher than the bottom and hopper ashes. Soluble compounds of calcium and alkali salts with addition of minor amounts of quartz dominate the composition of bag house lter BFB1 ash samples. The lter CFB ash is also rich in soluble compounds of Ca and alkali metals but the abundance of these soluble salts is lower than in the lter BFB1 ash and higher than in the cyclone and bottom ashes. In order to assess the environmental impact of a waste material it is important to determine the total leachable content of the material. This information for MSW ash can be obtained by performing an availability test (Fallman, 1997) on the ash. In availability test the total leachable amount is determined by extracting the material at pH 7 with high water to solid ratio and also by extracting the ash in acidic solution of pH 4. The amounts released at pH 7 along with the amounts released by the dissolution of solid ash particles at pH 4 are considered as total leachable contents. Similarly the information about the total water extractable contents of ash residues is also important for the development and evaluation of simple water washing processes as well as for the assessment of leaching behavior of ashes.

Table 1 Crystalline components of dierent ashes as determined by X-ray diraction analysis Alkali metal salts Bottom and hopper ashes BFB1 Cyclone ash BFB1 Cyclone ash BFB2 Bag house lter ash BFB1 NaCl NaCl, KCl NaCl, KCl, KCaCl3 NaCl, KCl Ca compounds CaCO3, Ca3Al2O6 CaCO3, CaO, CaSO4, Ca3Al2O6 CaCO3, CaSO4 CaCO3, Ca(OH)2, CaClOH, CaSO4, Ca3Al2O6 CaCO3, CaSO4, Quartz and silicates SiO2, Ca2Al2SiO7, KAlSi3O8, (Na,Ca)AlSi3O8 SiO2, Ca2Al2SiO7, KAlSi3O8, (Na,Ca)AlSi3O8 SiO2, Ca2Al2SiO7 SiO2 Iron oxides Fe3O4, Fe2O3 Fe3O4, Fe2O3, MgFe2O4 Fe3O4, Fe2O3, MgFe2O4 Other compounds Al (in the hopper ash) Al Al, Ca5(PO4)3OH

Bag house lter ash CFB

SiO2, Ca2Al2SiO7

Al, MgO

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Table 2 Total contents (Na, K, Ca) and total water extractable contents of ashes from bubbling (BFB) and circulating uidized bed (CFB) boilers Ash sample Total content Na (mg/kg) Bottom ash (BFB1) Hopper ash (BFB1) Cyclone ash (BFB1) Cyclone ash (BFB2) Filter ash (BFB1) Filter ash (CFB)
a

Water extractable contents Ca (mg/kg) 43,300 54,920 120,000 148,000 363,000 213,000 Extraction methoda Cold Hot Cold Hot Cold Hot Cold Hot Cold Hot Cold Hot L/S ratio 25 25 50 50 200 200 200 200 400 400 300 300 Cl (mg/kg) 198 327 1231 1473 15,830 22,000 17,590 21,990 175,900 202,300 82,500 108,800 Br (mg/kg) 0 9 18 20 176 247 211 299 528 704 132 230 F (mg/kg) 1 6 6 12 179 120 671 200 289 376 174 206 SO 4 (mg/kg) 354 574 2227 3577 10,800 22,270 10,800 20,250 46,975 49,270 7695 7692 Na (mg/kg) 108 248 1860 2473 10,960 17,060 12,320 15,160 32,000 37,600 23,100 25,590 K (mg/kg) 68 60 600 985 5840 8940 8080 9444) 32,000 36,800 16,440 20,250 Ca (mg/kg) 488 632 1610 1740 16,372 25,246 21,028 22,890 326,080 356,080 75,210 83,400

K (mg/kg) 24,860 19,800 17,200 16,700 22,800 19,100

37,530 25,480 25,370 20,300 31,800 28,400

Cold means ash extracted with water at room temperature; hot means ash extracted with boiling water.

In this study we have determined the total water extractable contents of Na, K, Ca, Cl, F, Br, and SO2, by hot and cold extraction methods and the 4 results are given in Table 2. In nearly all the cases the extracted amounts were higher in the hot extraction when compared to the cold extraction. This indicates that heating has enhanced the dissolution of solid phases. Moreover, the dierences in the water extractable contents of ashes are in accordance with the mineralogical characteristics of these ashes. For example lter ash BFB1 is predominantly composed of soluble salts and has the highest water extractable contents. On the other hand, the bottom ash BFB1, which is mainly composed of aluminumsilicate minerals and has the lowest water extractable contents. The total percentage of soluble salts obtained by summation in Table 2 is 25% for lter ash CFB and as high as 68% for lter ash BFB1. It is important to note that two dierent ash types may have similar total contents of an element but still the water extractable amounts can be very dierent. For example, bottom ash BFB1 and lter ash CFB have nearly the same total contents of Na and K but much larger amounts of these elements were released from lter CFB ash as compared to the bottom ash (Table 2). This indicates that the mineral phase in which an element exists is the controlling factor for the release of that element. 4.2. Total dissolved solids

TDS level was considered as the maximum. The results are presented in Fig. 2. The bottom ash, hopper ash and the two cyclone ashes lost only minor weight portions, i.e. 1, 2 and 5%, respectively. On the other hand CFB lter ash has 18% of its dry weight as TDS and the lter BFB1 ash has 54% of its weight as TDS. Ontiveros et al. (1989) have also reported similar TDS values for bottom and y ashes from MSW combustion with MB techniques. In their work, ashes were extracted with water in three serial extractions at L/S ratio 20. The concentrations of cationic and anionic species in the leachates were determined and TDS was assumed to equal to the sum of the mass of the ionic species in solution. The TDS values for the bottom ashes were in the range 2.54.2% of the weight of the dry ash, whereas for electrostatic precipitator and bag house lter ashes the TDS values were 24 and 13.8%, respectively. In standard tests for comparison with limit values the measurements of total dissolved solids (TDS) are carried out at L/S ratios of 10 to 30 (DIN 38414 S4, 1984; Dechets: Essai de lixiviation X 31-210, 1986). The limiting values associated with these tests are 10% for TA Sonderabfall and 3% for TA Siedlungsabfall in Germany, whereas it is 5% for Type V waste or nonhazardous waste in France. Thus, the results obtained in this study indicate that lter ashes and some cyclone ashes would be considered as hazardous waste according to these limiting values. 4.3. CEN leaching test

In the present study TDS values were determined at a number of L/S ratios in order to investigate the correlation between L/S and TDS for dierent ash types. The L/S was increased until the dierence between two consecutive TDS values became less than 5% and then, that

The CEN test is a two-stage serial batch-leaching test that is being recommended in the European Union as standard leaching test for granular wastes (prEN 12457, 1996). This test is also one of the standard methods

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Fig. 2. Total dissolved solids (TDS) as % of the dry mass of ve dierent ashes are given at increasing L/S ratios.

proposed for Nordic leaching tests for granular waste materials (Wahlstrom, 1996). The CEN test is designed for use as a compliance test where quick assertion of the environmental impact of a granular waste material is required. It is easy to apply and the duration of the test is short, i.e. maximum 24 h. In the rst step of the CEN test short-term leaching behavior of granular waste material is simulated whereas the long term leaching behavior is simulated in the second step of the CEN test. It is also assumed that chemical equilibrium is attained during the test time and thus, the leaching of

waste constituents is solubility controlled. These assumptions have not been fully veried yet. In order to facilitate the component release, the waste material is milled until 90% of the total sample has a particle size < 4 mm. Moreover, agitation of the ash water mixtures decreases the boundary layer around the particles, hence increasing the rate of leaching. Thus, the small size of waste particles and the agitation procedure help to attain the equilibrium or near equilibrium conditions during the CEN test (Fallman and Aurell, 1996).

Fig. 3. Extraction of cyclone BFB2 ash with water at L/S 2 for dierent time periods. At each time interval new ash material was used.

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The leaching behavior of MSW ash disposed in a landll may be best depicted by column test. In column test the liquid moves through a column (packed with granular waste material) very slowly, e.g. it takes 20 days to attain an accumulated L/S 2. Principally the results of the CEN and column tests at a certain L/S ratio should be comparable because the basic leaching process in both the tests is assumed to be the equilibrium controlled release (Fallman and Aurell, 1996). Recently, Eline et al. (1997) have compared the results of column and the CEN tests for bottom ash from coal combustion. They concluded that the CEN test is a possible short test to replace the column test. In our previous article (Abbas et al., 1999) we have also shown that the CEN test and column test gave similar results for cyclone and lter BFB1 ashes at L/S 2. Thus, due to the above mentioned reasons the CEN test was used in this and previous studies to assess the short- and long-term leaching behavior of original and washed ashes. The CEN test results of original cyclone and lter BFB1 ashes have already been presented in previous article (Abbas et al., 1999). The released amounts of Cl, SO2, Na, K and Ca from cyclone BFB2 ash in 4 the second step of CEN test are 19000, 120, 7160, 5440 and 4660 mg per kg of dry ash, respectively. Thus, the leaching behaviors of two cyclone ashes, i.e., BFB1 and BFB2 in the CEN test are very similar. On the other hand, large amounts of Na, K, Ca, sulfates and chlorides were released from the lter BFB1 ash. Note that, the CEN test for lter BFB1 ash was repeated in this study. The major dierence from the

previous results is an increase in the amount of SO2 4 and Ca released from this ash. The released amounts of Ca and SO2 in the present case are 15,280 and 90,600 4 mg/kg in the second step of CEN test, respectively, whereas in the previous studies the corresponding released amounts were 5400 and 82,900 mg/kg. This dierence can be due to the variation in sample composition because the ash samples used in this study were prepared by combining the dierent ash samples taken in a period of 2 weeks (Abbas et al., 1999, 2001). The released amounts of Cl, SO4, Na, K and Ca from lter CFB ash in the second step of the CEN test are 97,000, 308, 26,800, 17,000 and 23,000 mg per kg of dry ash, respectively. Thus, the lter CFB ash has shown an intermediate leaching behavior, i.e., the leached amounts are higher than the cyclone ashes and are lower than the lter BFB1 ash. These results indicate that although, the released amounts of soluble salts from cyclone ashes are relatively low when compared with the lter ashes, they are high enough for these ashes to be considered as hazardous material in some European countries (Fallman and Hartlen, 1993). Filter ashes, on the other hand, will denitely pose environmental problems due to the large release of soluble salts. 4.4. Time and L/S ratio optimization A goal in the development of the washing process was that to utilize the lowest possible L/S ratio and shortest possible washing time. As it is rather easy to arrange a heating of the washing vessel by recovering waste energy at the boiler it was also considered interesting to study if

Fig. 4. Extraction of lter CFB ash with water at L/S 2 for dierent time periods. At each time interval new ash material was used.

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heating would improve the extraction eect. However, test results have shown that heating did not give any improvement (Abbas et al., 1999; Gard, 2000) at least at temperatures up to 60  C. Initial experiments with different L/S ratios showed that L/S 2 would be most suitable water to ash ratio, even though a higher L/S in some cases gave a more ecient washing. L/S 1 can also be used if the process can be designed in such a way that an eective mixing of ash and water is ensured. Figs. 3

and 4 display correlations between washing results at L/ S 2 for cyclone BFB2 and lter CFB ashes and contact time. Similar results for cyclone and lter BFB1 ashes have been given in our previous study (Abbas et al., 1999). In all cases the major part of the extracted species was released within 1020 min. An increase in contact time did not give any considerable improvement. Washing at L/S 1 gave the same trend but with lower extracted amounts. Thus, 15 min extraction time was

Fig. 5. (a) A comparison of the extraction eciency of a single water washing step (15 min) with the three washing steps (5 min in each step) for (a) cyclone BFB1 ash, (b) cyclone BFB2 ash, (c) lter BFBI ash, (d) lter CFB ash. Extracted amounts given as the percentage of total water extractable contents of original ash.

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Fig. 5. (continued)

chosen to be the most appropriate shortest extraction time for multistage extractions at L/S 1 and 2. 4.5. Multi-step extraction tests In this series of multi-step extraction experiments a total extraction time of 15 min was adopted at L/S 1 and 2. A one-step washing was carried out for 15 min, whereas in the three-steps extraction an extraction time of 5 min in the three consecutive steps was used. The

stability with respect to salts leachability of the ashes remaining after the washing procedure was evaluated by performing the CEN test on the washed ash. The results for the one and three steps extractions are presented in Fig. 5ad. It is clear from these results that a three step washing procedure gives a more ecient removal of salts, especially chlorides, than a one step extraction. An increase of the L/S ratio from 1 to 2 also enhances the eect of washing considerably. One example is the removal of chlorides

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from the cyclone ash BFB1 which was 30 and 50% using one step washing with L/S 1 and 2, respectively, whereas it was 64% in the three step procedure with L/S 1 and as much as 78% with L/S 2 (Fig. 5a). Generally, the percentage of extracted species was higher for the cyclone ash BFB 2 than for the BFB1 ash (Fig. 5a and b). The three step method removed as much as 90% of the chlorides from cyclone ash BFB2 at L/S 2. The same trends were noted for the lter ashes and in some cases an almost total removal of alkali metal chlorides was achieved (Fig. 5c and d). This would mean that a lter ash might loose about half of its initial weight in a washing process. Release of elements from these types of ash is evidently very dependent on the amount of water used. The total L/S ratio applied in the three-step method is 6 when an L/S of 2 is used in each step and

only 3 when an L/S of 1 is used. This means that one ton of ash would require 36 tons of water in a full-scale application of this washing process. However, the results given in Fig. 5ad are total amounts removed. It is also interesting to compare the eciency in each of the consecutive washing steps. Such data for the cyclone BFB1 and the lter CFB ashes are given in Figs. 6a and b, respectively. It is clear that a large part of the total extractable material was lost in the rst step and that only smaller amounts were released in the second and third extraction steps. Mostly chlorides, Na, and K were released in the rst extraction step. This indicates that the major soluble portion of these ashes is composed of salts such as NaCl and KCl. The data in these gs. also shows that the increase in L/S from 1 to 2 has a larger inuence on the rst

Fig. 6. Amounts of dierent species released during the three-step extraction procedure are given as the % of total water extractable content of (a) the original cyclone BFB1 ash and (b) the original lter CFB ash.

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extraction than on the following steps. For example 50 and 80% of the total water extractable contents of chlorides from lter CFB ash were extracted at L/S 1 and at L/S 2, respectively (Fig. 6b). The amounts of chlorides released at the corresponding L/S ratios in the second washing step are approximately 20%. This enhancement in the released amounts at L/S 2 is more prominent for Cl, Na and K than for Ca (Fig. 6b). These results could also indicate that secondary reactions or physical changes occur in the ash particles, thus decreasing the surface area available for leaching. The results for cyclone BFB2 and lter BFB1 ashes showed similar trends as those discussed above. The second step of the CEN test is designed to simulate the long-term leaching behavior of granular materials. Thus, a comparison of the leaching behavior of washed and original (unwashed) ashes will indicate the relative stability of the washed ashes. If the leaching of ash components from the washed ashes decreases con-

siderably as compared to the original ash, the washed ash should be considered as more stable. At present there is no denitive criteria or limiting values for the released amounts of dierent substances in the CEN test but work in this direction is in progress (Fallman, per sonal communication). In Fig. 7ad, the released amounts of dierent species during the second stage of the CEN test performed on washed and original ashes are compared. The leaching of most species from the ashes washed one time at L/S 1 and 2 had been reduced. In some cases, i.e. cyclone BFB1 and cyclone BFB2, the leached concentrations of Ca are even higher than for the untreated ash (Figs. 7a and b). The reason may be that washing has exposed new mineral surfaces in the ash particles in such a way that leaching of certain species is enhanced. On the other hand, the released amounts from ashes washed three times are considerably lower than from the original and also from the one time washed ashes. Particularly the released amounts from the three times washed cyclone BFB1 and

Fig. 7. Comparison of the CEN test results (at accumulated L/S ratio 10) for the original, one and three times water washed (a) cyclone BFB1 ashes, (b) cyclone BFBZ ashes, (c) lter BFB1 ashes and (d) lter CFB ashes.

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303

Fig. 7. (continued)

lter CFB ashes decreased signicantly (Fig. 7a c). However, in the case of three times washed lter BFB1 ash there was still considerable release of chlorides and Ca. This indicates that three washings have removed most of the soluble salts from the cyclone and lter CFB ashes and that the washed ashes can be considered as stable with respect to the leaching of these substances. The X-ray diraction analysis of washed ashes revealed that the soluble crystalline phases such as NaCl and KCl were absent from cyclone as well as from the bag house lter ashes. In the washed cyclone ashes Ca2Al2SiO7, SiO2, CaCO3, Al, and CaSO4 were the major crystalline phases. Calcium minerals such as CaCO3, CaSO4 2H2O, CaSiO3, Ca(OH)2, Ca5(PO4)3Cl

and CaSO4 were the dominant crystalline components of washed BFB1 lter ash. Goethite was found in the washed CFB lter ash, which was not detected in the original ash. These X-ray diraction results on washed ashes show that most of the soluble salts have been dissolved from the cyclone ash during the three stage washing procedure. In the evaluation of the washing process as a stabilization method for ash residues one has also to take into consideration the amount of washing liquid produced and the amount of dissolved material. The liquid and its constituents have to be handled in an ecologically and economically feasible way. This aspect has not been covered experimentally in this study but some ideas will be tested in the continued work.

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Z. Abbas et al. / Waste Management 23 (2003) 291305 Alba, N., Gasso, S., Lacorte, T., Baldasano, J.M., 1997. Characterization of municipal solid waste incineration residues from facilities with dierent air pollution control systems. Journal of Air and Waste Management Association 47, 11701179. Alba, N., Vazquez, E., Gasso, S., Baldasano, J.M., 2001. Stabilization/solidication of MSW incineration residues from facilities with dierent air pollution control systems. Durability of matrices versus carbonation. Waste Management 21, 313323. Blondin, J., Iribarne, A.P., Anthony, E.J., 1997. Study of ashes from municipal wastes incinerated in classical grate boilers and FBC units: solidication of MWIR with FBC coal ashes for disposal. In: Proceedings of 14th International Conference on Fluidized Bed Combustion, ASME. Chan, C.C.Y., Kirk, D.W., Marsh, H., 2000. The behavior of Al in MSW incinerator y ash during thermal treatment. Journal of Hazardous Materials. B76 103111. Chimenos, J.M., Fernandez, A.I., Nadal, L., Espiell, F., 2000. Shortterm natural weathering of MSWI bottom ash. Journal of Hazardous Materials. B79 287289. Anon., 1986. Dechets: Essai de Lixiviation X 31-210.. Association Francaise de Normalisation (AFNOR), Paris. Dietler, U., 1990. Auslagverfahren mit nachgeschalteter Verfestigung gemass TVA-Scheweiz, Reststoe aus der Rauchgasreinigung. Bei hefte zu Mull und Abfall 29, 8894. DIN 38414 S4, 1984. German Standard Procedure for Water, Wastewater and Sediment Testing-Group S (Sludge and Sediment): Determination of Leachability (S4). Institut fur Normung, Berlin. Eline, E., van der Hoek, Frans, J.M.L., 1997. Short leaching test compared to a column leaching test for internal quality control of coal bottom ash. In: Goumans, J.J.J.M., Senden, G.J., Van der Sloot, H.A. (Eds.), Waste Materials in Construction: Putting Theory into Practice. Elsevier Science, Amsterdam, pp. 327337. Fallman, A.M., Hartlen, J., 1993. Karakterisering och klassicering av avfall. Genomgang av olika landers system (Characterization and Classication of Waste. Survery of the Systems in Dierent Coun tries) Rapport 4226. Naturvardsverket, Solna, Sweden (in Swedish). Fallman, A.M., Aurell, B., 1996. Leaching tests for environmental assessment of inorganic substances in wastes, Sweden. Science of the Total Environment 178, 7184. Fallman, A.M., 1997. Performance and design of the availability test for measurement of potentially leachable amounts from waste materials. Environmental Science and Technology 31, 735744. Gard, C., 2000. Stabilicering av cyclone aska fran FB forbranning av avfall-forstudie till design av pilotanlaggning (Diploma work). Department of Forest Products and chemical engineering: Chalmers University of Technology, Sweden. IAWG (International Ash Working Group; Chandler, A.J., Eighmy, T.T., Hartlen, J., Hjelmar, O., Kosson, D.S., Sawell, S.E., van der Sloot, H.A., Vehlow, J), 1997. Municipal Solid Waste Residues. Studies in Environmental Science 67. Elsevier Science, Amsterdam, Netherlands. Katsuura, H., Inoue, T., Hiraoka, M., Sakai, S., 1996. Full-scale plant study on y ash treatment by acid extraction process. Waste Management 16, 491499. Kirby, C.S., Rimstidt, D.J., 1994. Interaction of municipal solid waste ash with water. Environmental Science and Technology 28, 443451. Kirk, D.W., Chan, C.C.Y., Marsh, H., 2002. Chromium behavior during thermal treatment of MSW y ash. Journal of Hazardous Materials B90 3949. Lamers, F.J.M., Born, G.P., 1994. Upgrading techniques for the quality improvment of municipal waste incineration residues materials. In: Goumans, J.J.J.M., van der Sloot, H.A., Aalbers, Th.G. (Eds.), Environmental Aspects of Construction with Waste. Elsevier Science, Amsterdam, pp. 645654. Mangialardi, T., Paolini, A.E., Polettini, A., Sirini, P., 1999. Optimization of solidication/stabilization process of MSW y ash in cementitious matrices. Journal of Hazardous Materials B70, 5370.

5. Conclusions The ash residues studied in this work were all from uidized bed combustion of MSW. The bottom ash samples were mainly composed of silicates and aluminumsilicate minerals with low solubility. The fractions of soluble salts were low and thus, bottom ash with respect to the salts leachability can be considered as stable. On the other hand the particulates collected in bag house lter contained considerable amounts of soluble salts of alkali and alkaline earth metals. The soluble portion of the textile lter ash from the BFB plant had been further enhanced by the addition of lime for absorption of acidic species in the ue gas. When the proposed ash stabilization process based on washing with water was applied to the lter ashes up to half of the initial ash weight was dissolved. Extraction of such a large amount of material is not practical thus washing is not a suitable stabilization method or lter ashes of these types. However, using either one or more washing steps with a liquid to solid ratio of 12 at room temperature for the cyclone ashes resulted in a signicant reduction in ash leachability with a reasonable amount of liquid to handle. A sequence with three washing steps using L/S 2 gave the best result but the complexity and economy of the method has also to be considered. These aspects will be covered in future work. In addition the choice of the best washing process will dependent on the level of the legislative requirements. Generally it can be concluded that for cyclone ashes this washing method can be a cheap and simple stabilizing method for the reduction of salts leachability.

Acknowledgements This project has received nancial support from the following research foundations: Angepanneforeningen Forskningstiftelsen, Stiftelsen J Gust Richert and Stiftelsens Wilhem och Martina Lundgrens, which is gratefully acknowledged. Authors are also thankful to Margareta Lundberg and Bengt Ake Andersson, Kvaerner Pulping AB, Goteborg for providing the ash samples and other relevant information.

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