Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

PHYSICO-CHEMICAL CHARACTERIZATION AND LEACHING OF DESULPHURIZATION COAL FLY ASH

Fly ash produced by coal combustion using two types of desulphurization process were studied: a conventional pulverized coal boiler equipped with lime injection (PCL ash), and a circulating fluidized bed combustion boiler with limestone injection (CFBC ash). The ashes were characterized completely: granulometry, morphology, mineralogy, chemical composition and behaviour to water contact. Both PCL ash and CFBC ash present similar features: fine granulometry, presence of anhydrite phase and sulphate content. However, PCL ash also shows lots of spherical particles, unlike CFBC ash, and a much higher lime content, due to the lower desulphurization rate in PC boilers. Unlike CFBC ash, most of the trace elements in PCL ash show an inverse concentration–particle size dependence. Leachates obtained from both samples are rich in soluble salts [CaSO₄and Ca(OH)₂] and arsenic and selenium are prevented from solubilizing by high lime content. In wetted PCL ash, the formation of ettringite crystals stabilizes calcium and sulphate ions. Simultaneously, arsenate, selenate and chromate anions are trapped in the crystal. CFBC ash does not really harden because the lime content is too low. However, the leached selenium concentration is cut down in wetted CFBC ash samples.     

Leaching characteristics of woody biomass ash after low-temperature combustion

The leaching properties of trace elements in wood ash were examined to evaluate the safety of using woody biomass ash. Boron and selenium were detected in high concentrations not only in ash collected from an electric furnace but also in combustion ash from a small wood stove. As for the leaching of trace elements, the influence of calcium compounds on boron and selenium in wood ash is proposed. The leaching of trace elements is enhanced when calcium carbonate is the calcium compound in ash, although it is inhibited in the case of portlandite. There is little information in the literature that can be used to determine the effective use of wood biomass ash, thus limiting the development of woody biomass for applications such as thermal power generation.     

Metal distribution in incineration residues of municipal solid waste (MSW) in Japan

This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.     

Removal of unburned carbon from municipal solid waste fly ash by column flotation

Unburned carbon (UC) is the major source of organic contaminants in municipal solid waste (MSW) fly ash. So most organic contaminants can be removed by the removal of the UC from the MSW fly ash. In this paper, we first used a technique of column flotation to remove UC from MSW fly ash. The influences of column flotation parameters on the recovery efficiency of UC were systematically studied. It was found that the UC recovery efficiency was greatly influenced by the gas flow rate, pH value, collector kerosene's concentration and the types of fly ash. By optimizing the above parameters, we have successfully removed 61.2% of the UC from MSW fly ash having 5.24% UC content. The removal mechanism was well accounted for the kinetic theory of column flotation and surface-chemistry theory. The results indicate that the column flotation technique is effective in removing the UC from MSW fly ash, and show that there is a strong possibility for practical application of this technique in removing the organic contaminants from MSW fly ash.     

Characterization of PCDD/Fs and heavy metals from MSW incineration plant in Harbin

The characterization of PCDD/Fs and heavy metals in the flue gas and fly ash of Harbin municipal solid waste (MSW) incineration plant, located in the northeast of China, was investigated in this study. The MSW was treated in a twin internal fluidized (TIF) bed incinerator. The results indicate that the emission of PCDD/Fs into the environment is 0.02 ng I-TEQ/m3 and the level of PCDD/Fs in the fabric filter fly ash is 0.7982 ng I-TEQ/g. The leachability levels of Pb, Cd and Hg in the fly ash are below the limits of environmental protection standard in China. However, the contents of Cu, Zn, and Hg are high in the fly ash. This suggests that the fly ash is a hazardous waste that requires special treatment and disposal. The practice of more than four years of operation shows that the TIF bed incinerator is very suitable and practical for China.     

Vitrification of bottom ash from a municipal solid waste incinerator

During incineration of municipal solid waste (MSW), various environmentally harmful elements and heavy metals are liberated either into bottom ash, or carried away with the off-gases and subsequently trapped in fly-ash. If these minor but harmful elements are not properly isolated and immobilized, it can lead to secondary environmental pollution to the air, soil and water. The stricter environmental regulations to be implemented in the near future in The Netherlands require a higher immobilization efficiency of the bottom ash treatment. In the present study, MSW incinerator bottom ash was vitrified at higher temperatures and the slag formed and metal recovered were examined. The behaviour of soluble elements that remain in the slag is evaluated by standard leaching test. The results obtained can provide a valuable route to treat the ashes from incinerators, and to make recycling and more efficient utilization of the bottom ash possible.     

Characteristics of element distributions in an MSW ash melting treatment system

Thermal treatment of municipal solid waste (MSW) has become a common practice in waste volume reduction and resource recovery. For the utilization of molten slag for construction materials and metal recovery, it is important to understand the behavior of heavy metals in the melting process. In this study, the correlation between the contents of elements in feed materials and MSW molten slag and their distributions in the ash melting process, including metal residues, are investigated. The hazardous metal contents in the molten slag were significantly related to the contents of metals in the feed materials. Therefore, the separation of products containing these metals in waste materials could be an effective means of producing environmentally safe molten slag with a low hazardous metals content. The distribution ratios of elements in the ash melting process were also determined. The elements Zn and Pb were found to have a distribution ratio of over 60% in fly ash from the melting furnace and the contents of these metals were also high; therefore, Zn and Pb could be potential target metals for recycling from fly ash from the melting furnace. Meanwhile, Cu, Ni, Mo, Sn, and Sb were found to have distribution ratios of over 60% in the metal residue. Therefore, metal residue could be a good resource for these metals, as the contents of Cu, Ni, Mo, Sn, and Sb in metal residue are higher than those in other output materials.     

Behavior of metals in ash melting and gasification-melting of municipal solid waste (MSW)

In this study, metal behavior in ash-melting and municipal solid waste (MSW) gasification-melting facilities were investigated. Eight ash-melting and three MSW gasification-melting facilities with a variety of melting processes and feedstocks were selected. From each facility, melting furnace fly ash (MFA) and molten slag were sampled, and feedstock of the ash-melting processes was also taken. For the ash melting process, the generation rate of MFA was well correlated with the ratio of incineration fly ash (IFA) in feedstock, and this was because MFA was formed mostly by mass transfer from IFA and a limited amount from bottom ash (BA). Distribution ratios of metal elements to MFA were generally determined by volatility of the metal element, but chlorine content in feedstock had a significant effect on Cu and a marginal effect on Pb. Distribution ratio of Zn to MFA was influenced by the oxidizing atmosphere in the furnace. High MFA generation and distribution ratio of non-volatile metals to MFA in gasification-melting facilities was probably caused by carry-over of fine particles to the air pollution control system due to large gas volume. Finally, dilution effect was shown to have a significant effect on metal concentration in MFA.     

Thermodynamic estimation of minor element distribution between immiscible liquids in Fe-Cu-based metal phase generated in melting treatment of municipal solid wastes

Waste electrical and electronic equipment (WEEE) has become an important target in managing material cycles from the viewpoint of not only waste management and control of environmental pollution but also resource conservation. This study investigated the distribution tendency of trace elements in municipal solid waste (MSW) or incinerator ash, including valuable non-ferrous metals (Ni, Co, Cr, Mn, Mo, Ti, V, W, Zr), precious group metals (PGMs) originated from WEEE (Ag, Au, Pd, Pt), and others (Al, B, Pb, Si), between Fe-rich and Cu-rich metal phases by means of simple thermodynamic calculations. Most of the typical alloying elements for steel (Co, Cr, Mo, Nb, Ni, Si, Ti, V, and W) and Rh were preferentially distributed into the Fe-rich phase. PGMs, such as Au, Ag, and Pd, were enriched in the Cu-rich phase, whereas Pt was almost equally distributed into both phases. Since the primary metallurgical processing of Cu is followed by an electrolysis for refining, and since PGMs in crude copper have been industrially recovered from the resulting anode slime, our results indicated that Ag, Au, and Pd could be effectively recovered from MSW if the Cu-rich phase could be selectively collected.     

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.     

Chemical changes in different types of coal ash during prolonged,large scale,contact with seawater

In this study, we followed the chemical changes occurring in coal ash exposed to prolonged (300 days), large scale, contact with running seawater. Four major components (Al, Ca, Mg, Fe) and seven minor and trace elements (Cd, Cr, Cu, Mn, Zn, Pb, Hg) were measured in four coal ash types: fly and bottom ash freshly obtained from coal-fired power plant, and old ash (crushed and blocks) recovered from the sea after 3-5 years contact with seawater. Changes occurred in the chemical composition of the coal ash along the experiment: Fe increased in fresh ash, Al increased in old ash and Ca increased in all ash types except old ash blocks. Cu and Hg decreased in fresh fly ash while Cr increased, Cd decreased in all ash types except bottom ash, and Mn decreased in bottom ash. Most of the changes occurred in the fresh fly ash, and not in the old ash, indicating equilibrium after prior exposure to seawater. In addition, more changes occurred in fresh fly ash than in bottom ash, emphasizing the differences between the two ash types. While the changes in the concentrations of the major elements may be an indication of the integrity of the ash matrix, the only elements of environmental significance released to the environment were Hg and Cd. However, calculated seawater concentrations were much lower than seawater quality criteria and therefore the coal ash was considered suitable for marine applications concerning seawater quality.     

Analyses of incinerated ash of paper sludge: comparison with incinerated ash of municipal solid waste

Fourteen paper sludge samples were collected at seven representative pulp and paper mills in Japan, and were analyzed to obtain fundamental data on the reuse of paper sludge-incinerated ash as papermaking material. For comparison, incinerated ashes of municipal solid waste (MSW) were collected at MSW incineration plants in Tokyo, and analyzed by similar methods. Elementary and X-ray diffraction analyses revealed that the predominant elements in paper sludge samples are calcium, silicon, aluminum, and magnesium, which are derived from paper fillers, coating pigments, and coagulants used in papermaking and process effluent treatments. Similar results were also obtained for the MSW-incinerated ashes, indicating that major components in the collected MSW are paper-related materials. Incineration of paper sludge around 800°C is recommended in terms of high brightness of the incinerated ash, which has about 60% brightness. Calcium, silicon, and aluminum components in the paper sludge are fused or sintered by heating. Although paper-sludge-incinerated ashes have irregular shape and large particle size distributions, they may be used as papermaking materials after pulverization using a ball mill. The MSW-incinerated ashes have 5%–30% water-soluble fractions and low brightness, and thus incineration conditions must be changed to reuse the MSW-incinerated ash as a papermaking material.Part of this paper was presented at the 68th Research Conference of Japan Tappi, Tokyo, 2001     

Municipal solid waste source-separated collection in China: A comparative analysis

A pilot program focusing on municipal solid waste (MSW) source-separated collection was launched in eight major cities throughout China in 2000. Detailed investigations were carried out and a comprehensive system was constructed to evaluate the effects of the eight-year implementation in those cities. This paper provides an overview of different methods of collection, transportation, and treatment of MSW in the eight cities; as well as making a comparative analysis of MSW source-separated collection in China. Information about the quantity and composition of MSW shows that the characteristics of MSW are similar, which are low calorific value, high moisture content and high proportion of organisms. Differences which exist among the eight cities in municipal solid waste management (MSWM) are presented in this paper. Only Beijing and Shanghai demonstrated a relatively effective result in the implementation of MSW source-separated collection. While the six remaining cities result in poor performance. Considering the current status of MSWM, source-separated collection should be a key priority. Thus, a wider range of cities should participate in this program instead of merely the eight pilot cities. It is evident that an integrated MSWM system is urgently needed. Kitchen waste and recyclables are encouraged to be separated at the source. Stakeholders involved play an important role in MSWM, thus their responsibilities should be clearly identified. Improvement in legislation, coordination mechanisms and public education are problematic issues that need to be addressed.     

Polycyclic aromatic hydrocarbon (PAH) emission from co-firing municipal solid waste (MSW) and coal in a fluidized bed incinerator

Polycyclic aromatic hydrocarbons (PAH) emissions from a commercial municipal solid waste incinerator (MSWI) were studied. A MSW–coal mixture and coal only were used as fuel for the fluidized bed incinerator. Seven sampling points were chosen according to the classified four PAH emission pathways: flue gas, residue, ash and water. The mixture of MSW and coal resulted in PAH emission more than that of coal only, and PAH emission increased with increasing MSW mass percentage. Calcium oxide (CaO) or calcium carbonate (CaCO₃) was added as a desulfurizer. PAH emission also changed with different desulfurizers because of their different influences on heat balance. The PAH toxic equivalent (TEQ) of all operating conditions was also examined, showing that total daily PAH emission from MSWI can be determined.     

Quantifying the availability and the stability of trace cationic elements in fly ash

For adsorption-desorption controlled leaching processes, the total leachable mass and the adsorption constant are parameters representing the availability and the stability of trace elements in solid media. With these parameters, one can predict the leaching behavior of trace elements from solids under various pH and solid-to-liquid ratio conditions. An approach was developed in this paper to determine these parameters for model elements Cu(II), Cd(II), and Ni(II) in fly ash. This approach consists of a batch equilibrium titration, a batch equilibrium leaching with and without target element addition, and mathematical modeling. Results indicated that the adsorption constant of a trace element can be determined by modeling the adsorption ratio of the added element to the system as a function of pH. Results also indicated that the trace element originally present in fly ash had similar adsorption-desorption behavior as that added externally. By modeling the batch leaching data with and without external element addition, the total leachable mass and adsorption constant of the target element can be determined simultaneously. The total leachable mass is in agreement with experimental data from 50mM EDTA extraction.     

Characterization and Leaching of Coal Fly Ash

Physical characteristics, chemical composition and leaching behaviour of a waste fly ash from a coal-fired power station are reported. Particle size distribution was studied by the following techniques: sedimentation in a liquid medium; sedimentation in an air flow; and Fraunhofer diffraction of a laser beam. Results obtained by the different methods are in good agreement. Mineralogical content and chemical composition were determined by X-ray diffraction, electronic microprobe and X-ray fluorescence. Acid leaching of the samples was investigated, using the following strong acids in sequence: HCl+ HNO₃, H₂F₂, HClO₄. Analysis of leachates by atomic absorption shows trace metals In, Tl, Ge, Cu, Ga, Pb, Ni, Co, Mn, Cd, Zn, Cr.In this work fly ashes from a Spanish power plant are characterized according to the type of particles, size distribution and chemical composition by means of physical methods. Three particle size fractions are leached by acids and analysis of trace elements in the leaching liquor is carried out. The concentration of trace metals is somewhat higher in the particles of smallest size.     

Impact of the use of waste on trace element concentrations in cement and concrete.

The results of model calculations carried out to identify and quantify the input pathways of trace elements into cement and concrete and to estimate the extent to which trace element concentrations in cement may change due to waste utilization are presented. As expected, primary raw materials represented the most important input pathway for trace elements into cement, but the contribution from wastes was not negligible. The use of waste led to a slight increase of the concentrations of cadmium, antimony and zinc in cement. For cobalt, lead and vanadium, this increase was less distinct and for all other trace elements considered, the effect of the use of wastes on trace element concentrations in cement could not be demonstrated clearly. The trace element content of concrete was governed by the aggregates for most elements considered. However, for arsenic, cadmium, lead and zinc, both cement and the additive coal fly ash contributed noticeably to the total trace element concentration in the concrete.     

燃煤飞灰中痕量元素的研究

综述了煤中痕量元素的含量分布、煤燃烧过程中痕量元素的分布转化规律,总结了痕量元素在飞灰中的富集规律和赋存状态,以及痕量元素的释放控制方法和技术,并探讨了今后的研究方向.