Particles fly ash

The proposed mechanism by which chlorinated dioxins and furans form has shifted from one of incomplete destmction of the waste to one of low temperature, downstream formation on fly ash particles (33). Two mechanisms are proposed, a de novo synthesis, in which PCDD and PCDF are formed from organic carbon sources and Cl in the presence of metal catalysts, and a more direct synthesis from chlorinated organic precursors, again involving heterogeneous catalysis. Bench-scale tests suggest that the optimum temperature for PCDD and PCDF formation in the presence of fly ash is roughly 300°C. 

Both CI2 and HCl have been shown to chlorinate hydrocarbons on fly ash particles. Pilot-scale data involving the injection of fly ash from municipal waste combustion (33) show that intermediate oxygen concentrations (4—7%) produce the highest levels of PCDD and PCDF. These data also show significant reductions in PCDD and PCDF emissions with the upstream injection of Ca(OH)2 at about 800°C. 

Lambert, A.L., et al., Enhanced allergic sensitization by residual oil fly ash particles is mediated by soluble metal constituents, Toxicol. Appl. Pharmacol. 165, 1, 84, 2000. 

PCDD/F and other chlorinated hydrocarbons observed as micropollutants in incineration plants are products of incomplete combustion like other products such as carbon monoxide, polycyclic aromatic hydrocarbons (PAH), and soot. The thermodynamically stable oxidation products of any organic material formed by more than 99% are carbon dioxide, water, and HCl. Traces of PCDD/F are formed in the combustion of any organic material in the presence of small amounts of inorganic and organic chlorine present in the fuel municipal waste contains about 0.8% of chlorine. PCDD/F formation has been called the inherent property of fire. Many investigations have shown that PCDD/Fs are not formed in the hot zones of flames of incinerators at about 1000°C, but in the postcombustion zone in a temperature range between 300 and 400°C. Fly ash particles play an important role in that they act as catalysts for the heterogeneous formation of PCDD/Fs on the surface of this matrix. Two different theories have been deduced from laboratory experiments for the formation pathways of PCCD/F ... 

More than 90% of the coal used by electric utilities is burned in pulverized coal boilers. In these boilers, 65-80% of the ash produced is in the form of fly ash. This fly ash is carried out of the combustion chamber in the flue gases and is separated from these gases by electrostatic precipitators and/or mechanical collectors. The remainder of the ash drops to the bottom of the furnace as bottom ash. While most of the fly ash is collected, a small quantity may pass through the collectors and be discharged to the atmosphere. The vapor is that part of the coal material that is volatilized during combustion. Some of these vapors are discharged into the atmosphere others are condensed onto the surface of fly ash particles and may be collected in one of the fly ash collectors. 

The principal limitations of ESCA include the inability to detect elements present at trace concentrations within the analytical volume, and insufficient lateral resolution to characterize single micrometer-sized particles. The inability to characterize trace species is illustrated in Figure 10 for a sample of coal fly ash particles (11). The fly ash results from the noncombustible mineral components of the coal and consists largely of fused iron oxides and aluminosilicates (42). In addition, most elements are present in at least trace concentrations (22, 42), and many of these elements are highly enriched in the surface region of the particles (evidence for this will be discussed in the next section). However, the ESCA spectrum acquired over several hours of counting time indicates only the presence of detectable surface S and Ca in addition to the fly ash matrix constituents. 

The surface layer composition may influence the effectiveness of pollution control devices. For example, it is apparent that a surface region highly enriched is alkali-alkaline earth sulfates may enhance the fly ash particle collection efficiency of electrostatic precipitators (11, 12, 51-53). 

Hansen LD, Fisher JL. 1980. Distribution in coal fly ash particles. Environmental Science and Technology 14 1111-1117. 

The replacement of Portland cement by fly ash class F (ASTM C 618) has been found to reduce the rate of slump loss in a prolonged mixed concrete, and the extent of the reduction is greater with increased cement replacement (Fig. 7.37). Fly ash also was found to be beneficial in reducing slump loss in concretes with conventional water-reducing and retarding admixtures [95], The effect of fly ash on reducing slump loss can be attributed to chemical and physical factors. It was found that the surface of fly ash particles may be partly covered with a vapor-deposited alkali sulfate that is readily soluble [103, 104], Thus the early hydration process of Portland cement is effected because sulfate ions have a retarding effect on the formation of the aluminates. Indeed, fly ash was found to be a more effective retarder than an... 

As exhaust gases and fly ash particles are vented from the furnace, they quickly begin to cool, leading to the condensation and adsorption of volatilized elements onto the surfaces of fly ash particles entrained in the gas stream (Kaakinen etal. 1975). Under high-temperature combustion conditions certain elements, including S, are enriched on the surface of particles (Davison et al. 1974 Smith 1980). A vaporization-condensation process is the primary mechanism... 

Beyond similarities in bulk density, the physical properties of fly ash and bottom ash are very distinct (Table 3). The diameter of fly ash particles is generally several orders of magnitude smaller than that of bottom ash particles, leading to... 

The chemical composition of CCPs varies with coal origin and rank however, the major elemental constituents of all coal ash residues are O, Si, Al, Fe, and Ca, along with lesser amounts of Mg, S, and C. The relative abundance of constituents that typically make up more than 1 % of the total mass of fly ash and bottom ash are summarized in Table 4. These elements are found in the ash because of their lower volatility and the short time the particles actually remain in the furnace during combustion (Helmuth 1987). Both crystalline and non-crystalline compounds form on the surface of fly ash particles when elements react with oxygen in the flue gases, and through... 

Fig. 2. Scanning electron micrograph of typical coal fly ash particles.

Few comprehensive classification schemes for CCP exist. The American Society for Testing and Materials (ASTM 1994) classifies two catgories of fly ash (Class F and Class C) based upon chemical and physical properties of the fly ash (the total amount of Si + A1 + Fe, sulphate, loss on ignition). This classification system was developed for the use of fly ash as an admixture in concrete. More recently, new classification schemes have been developed that place emphasis on textural descriptions, the form of carbon (or char ), and the surface properties of fly ash (Hower Mastalerz 2001). These new classification schemes for fly ash may be the result of growing concern over mercury emissions from coal-fired boilers. Studies have shown that mercury adsorption onto the surface of fly ash particles is a function of both the total carbon content and the gas temperature at the point of fly ash collection (Hower et al. 2000). 

Fig. 8. Scanning electron micrograph of hydrated Class-C lignite fly ash (from Fort Union coal). Eltringite crystals are the small bumps seen on the surface of the fly ash particles.

As was previously mentioned, trace elements that sublime at temperatures below those attained during coal combustion (e.g., As, Se, Hg, Zn), and are associated with thermally unstable solid phases (in particular organic matter and sulphide minerals), are subject to vaporization into furnace gases. Once these gases, and fly ash particles entrained in the gases, are vented from the combustion furnace they quickly cool, leading to the condensation of volatilized elements onto the... 

Trace elements on the surfaces of fly ash particles that are accessible to humans through air, soil, water, can affect health in several ways. The pathways by which metals from CCP may cause harm include (1) soil deposition and resulting plant uptake of metals and subsequent movement into the food chain (2) direct ingestion of soil by animals or humans (3) leaching of metals from CCP to water systems and uptake by plants, animals, or humans and (4) inhalation of dust (from soil) or respirable ash particles (Ryan Bryndzia 1997). 

Bosbach, D. Enders, M. 1998. Microtopography of high-calcium fly ash particle surfaces. Advances in Cement Research, 10, 17-23. 

Mattigod, S. V. 1982. Characterization of fly ash particles. Scanning Electron Microscopy, 2, 611-617. 

Utilities using post-combustion SCR-supported ammonia injection for NOx control as well as those using ammonia conditioning to improve electrostatic precipitator performance will produce fly ash that contains ammonia compounds. The ammonia is primarily physically adsorbed onto the fly ash particles as sulphate and bisulphate species. In many cases, the residual ammonia levels are quite low (<50ppm) however, elevated concentrations can occur as the catalyst ages or due to mechanical problems with the ammonia injection system. While elevated ammonia concentrations in fly ash do not negatively impact pozzolanic properties, it can reduce ash marketability due to odour concerns. For this reason, several processes have been developed to remove or reduce the amount of ammonia in fly ash. 

Organic contaminants. The concentration of polynuclear aromatic hydrocarbons (PAH) in the particulate phase of flue gases of oil-shale-combusting thermal power plants has been estimated to range from 0.04 to 3.16 mg/m3 (Aunela et al. 1995). The solvent-extractable fraction (<1.5 wt%) from fly ash particles collected from Narva power plant smog chambers included several PAHs (phenanthrene,... 

Fig. 9. Scanning election microscope image of the typical fly ash particles. The samples were taken in a simulated experiment, 130 minutes after generation of the fly ash aerosol (Photo Courtesy Teinemaa el al. 2002) ( Elsevier).

---