Environmental impacts of coal combustion: A risk approach to assessment of emissions

This paper summarises some of the work performed in the Cooperative Research Centre for Coal in Sustainable Development (CCSD) on emissions from current power generation. A comprehensive approach was taken in the CCSD program to assessing environmental issues of concern for the power, and by implication the coal, industries. Here results of sampling on full scale operating plants are described, and detailed data on emission fluxes, particle size distributions, trace element concentrations as a function of particle size, and speciation of the trace elements are illustrated. The results show that particle capture in electrostatic precipitators (ESPs) is significantly less efficient than in fabric filters (FFs), particularly for submicron material, and that significant enrichment is observed in the finer particle sizes emitted from both ESPs and FFs. Results for the speciation of chromium, arsenic and selenium in coals, bottom ash and fly ash are also presented. The majority of chromium in fly ash is present in the less toxic Cr³⁺ form. Speciation of arsenic in feed coals is variable but the dominant form of As in fly ash is the less toxic As⁵⁺.     

Speciation of major and selected trace elements in IGCC fly ash

The speciation of Ga, Ge, Ni, V, S and Fe in fly ash from IGCC power plant were investigated for possible further extraction process by combining conventional mineral and chemical analysis, leaching tests, wet sequential extraction, Mössbauer and XAFS spectroscopies. The results shown that Ge occurs mainly as water-soluble species, GeS and/or GeS₂ and hexagonal GeO₂. Ga is present as an oxide, Ni occurs mainly as nickeline (NiAs), with minor proportions of Ni arsenates and vanadium as V(III) with minor amounts of V(IV) in the aluminosilicate glass matrix. Pyrrhotite and wurtzite-sphalerite are sulfide species containing Fe and Zn, but an important fraction of iron is also present in the aluminosilicate glass. These clear differences between the speciation of the above elements in this material and those reported for fly ash from conventional PC combustion.     

Trace element partitioning during the firing of washed and untreated power station coals

The effect of coal washing on trace element content and combustion behaviour of four world-traded coals has been studied at rig scale. The inputs and process outputs from a 1 MW combustion test facility, including coal, bottom ash, suspended fly ash, retained ash and flue gas, have been analysed for a standard suite of 17 trace elements. The results suggest that although coal cleaning significantly reduces the total ash content of the coal, the concentrations of individual trace elements are not reduced proportionately. Combustion of the washed coals resulted in increased concentrations of trace elements in the fly ash, although total fly ash loadings were reduced. Cleaning appeared to have little effect on concentrations of gaseous trace elements in the flue gas. The partitioning of the more volatile trace elements such as mercury and selenium between the vapour and solid phase was influenced by the amount of excess oxygen in the furnace, presumably affecting carbon-in-ash levels.The results suggest that the coal cleaning undertaken for these experiments did not significantly reduce the emissions to atmosphere of trace elements. The ultimate emissions will be determined by the efficiency of the dust capture systems.     

Characterization of unburned carbon from ash after bituminous coal and lignite combustion in CFBs

This paper deals with the characterisation of carbon (UC) from bottom ash (BA) and fly ash (FA) samples from two fluidised-bed power stations burning bituminous coal and lignite. The laboratory results for the carbon determinations and its mass balances are evaluated. Chemical and mineral analyses and textural characteristics (specific surface area and pore-size distribution) are presented. Depletion/enrichment of selected elements (S, Cl, V, Cr, Ni, Cu, Zn, As, Se, Sb, Hg, and Pb) in carbon from the bottom ash are compared with both ash compostions. The strong positive relationships between the concentrations of some trace element contents (Hg, Se, As, Cu, Ni, V and Cl) in fly ash with the content of carbon and the specific surface area of FA are presented and expressed by regression equations with very high correlation coefficients. Laser ablation-ICP-MS has been used to obtain an insight into element distributions within carbon grains from the bottom ash.     

Burning and physico-chemical characteristics of carbon in ash from a coal fired power plant

The paper addresses the relationship between the chemico-physical properties and the residual combustion reactivity of fly ashes from a full-scale front fired PF coal boiler. Ashes collected at different rows of electrostatic precipitators (EP) have been characterized for their particle size distribution, morphology, chemical composition and combustion reactivity. The combustion time of carbon in ash has been estimated for a wide range of temperatures using a thermobalance and a heated strip reactor.Results showed the existence of marked differences in the content of both carbon and inorganic elements according to the row of EP and the granulometric size of the samples. In contrast with this, the combustion reactivity of all ash samples was similar regardless of their collection point and particle size. Ash reactivity resulted to be approximately 100 times lower than that of the parent coal.The role of thermal annealing on the low reactivity of fly ashes and their propensity to undergo additional thermodeactivation upon further heat treatment has also been investigated. To this end coal and fly ashes have been heated under inert conditions up to 2000 °C and then characterised for their residual combustion reactivity. These tests showed that heat treatment does reduce the reactivity of coal but does not reduce any further the already low reactivity of fly ashes.     

Volatility and chemistry of trace elements in a coal combustor

The volatility of 16 trace elements (TEs) (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, Te, Tl, V, Zn) during coal combustion has been studied depending on the combustion conditions (reducing or oxidizing) and type of coal (high- or low-ash coal), together with their affinities for several active gaseous atoms: Cl, F, H, O, and S.

The elements can be divided into three groups according to their tendencies to appear either in the flue gases or in the fly ashes from a coal combustor:

Group 1: Hg and Tl, which are volatile and emitted almost totally in the vapor phase.

Group 2: As, Cd, Cu, Pb and Zn, which are vaporized at intermediate temperature and are emitted mostly in fly ashes.

Group 3: Co, Cr, Mn and V, which are hardly vaporized and so are equally distributed between bottom ashes and fly ashes. In addition, Sb, Sn, Se and Te may be located between Groups 1 and 2, and Ni between 2 and 3.

At 400 and 1200 K, the 16 TEs behave differently in competitive reactions with Cl, F, H, O and S in a coal combustor.     

Numerical study of coal particle cluster combustion under quiescent conditions

Behavior of ignition and combustion of coal particle cluster under a quiescent condition was numerically simulated by solving balance equations of mass and enthalpy with combustion kinetic models of volatiles and char. Two-flame structure, one flame penetrating into the cluster and the other moving out of the cluster, was predicted during the combustion of coal particle cluster. Effects of radiative heat transfer, group number, ambient temperature, coal particle size, and oxygen concentration on ignition and combustion of coal particle clusters were also analyzed. Simulations indicated that the gas volume fraction of coal particle cluster increases with time after devolatilization. Gas velocity passing through the cluster surface varied significantly at volatile liberation. The ignition time delay was reduced with the increase of ambient temperature. The cluster devolatilization rate and char burning rate increased while the ignition time delay decreased with the increase of ambient oxygen concentration.     

原子荧光光度法应用于湖泊底泥中汞和砷的形态分析

采用五步连续萃取和原子荧光光度法分析湖泊底泥中Hg和As的形态。结果表明：Hg主要以生物可利用性较强的三种形态（可交换态、碳结合态和铁锰氧化物结合态）存在,占总量的71．48％,而As则主要以残渣态存在,占总量的95．2％。采用原子荧光光谱法同时测定砷和汞,其检出限As为0．015ng／mL、Hg为0．006ng／mL;RSD为：0．33—4．26％;回收率为：97．7～100．6％。     

Mobilisation of trace elements from as-supplied and additionally cleaned coal: Predictions for Ba, Be, Cd, Co, Mo, Nb, Sb, V and W

The partitioning of the elements antimony, barium, beryllium, cadmium, cobalt, molybdenum and vanadium between the products of combustion of coals containing them burnt as pulverised fuel in excess air has been modelled using the MTDATA thermodynamic equilibrium package with data from the MTOX silicate melt model added to the standard database and trace element data added where necessary. The coals examined were Gascoigne Wood, ElCerrejon and Harworth coals as normally supplied (washed) and after additional washing, and Binungan low ash coal only as normally supplied, represented by the analyses for coal, coal mineral and trace elements obtained in a study of the partitioning carried out in a pilot scale pf combustor by PwerGen on behalf of the United Kingdom DTI. Excess air levels were 1% for all coals and 3% in addition for Harworth. The equilibrium amount of silicate melt was predicted to fall more rapidly with falling temperature for additionally washed than for normally washed coals. It was also predicted that Ba and Co would be almost immobile, Be and V would be relatively immobile, and Sb, Cd and Mo would be mobile. Additional calculations were carried out for niobium and tungsten as trace elements in the coals, and Nb was found to be relatively immobile and W mobile. The mobilities of Ba, Be, Co, Cd, Mo, Sb and V were in agreement with those implied by the ratio of bottom ash to fly ash concentrations found in experimental investigation.     

The composition of size-fractionated pulverised coal and the trace element associations

Major and trace element analyses have been performed on size fractions of a pulverised coal from Eggborough Power Station (UK). Minerals are concentrated in the fractions less than 10 μm in size and there is relative enrichment of pyrite in the fractions greater than 50 μm. Because of the compositional variation with size it is possible to proportion statistically the elements between, in this case, organic matter, silicates and pyrite. Germanium, Br and V are dominantly organic associated and Cr, Cu, Ni, Zn, Sr, Ba and Pb are also present in the organic matter, although concentrations are lower than in other fractions of the coal. These elements are either in the organic structures or contained within pore fluids. Chromium, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Sm, Th and U are dominantly associated with the silicate fraction, as are V, Ni and Zn, but other coal fractions contribute more to the total coal composition. Concentrated in pyrite are Mo, Se, As, Pb, Sb, and to a lesser extent Ni, Cu and Zn in that these elements are sufficiently concentrated in other fractions that pyrite is not the major location in the coal. Validation for the method is achieved by summing element concentrations in the three fractions and comparing with the bulk composition. Previous calculations on a related coal have been extended and close agreement observed for the composition of the three fractions. The calculated values for the fractions apply specifically to one coalfield, although some of the values may have more general application.     

Biodesulphurization of coal: behaviour of trace elements

The purpose of this study is to show how the different size fractions of coal are affected during a process of biodesulphurization in a packed column and to examine the repercussions of the process on the elimination of certain heavy and trace elements. The total desulphurization obtained in 51 days is about 25 wt%, as only pyritic sulphur is attacked. The greatest reduction in sulphur content was for the 1-0.5 mm fraction although the lowest actual sulphur content was found in particles of under 0.125 mm, where it dropped from 1.76 to 1.17 wt%. The most important changes in the metal content were decreases in Ni, Cu, Zn, As, Cr, Co and Sr, mainly in the smaller sizes.     

Characterization and re-use potential of by-products generated from the Ohio State Carbonation and Ash Reactivation (OSCAR) process

Two novel sorbents (i.e. “regenerated sorbent” and “supersorbent”) for dry flue gas desulfurization were tested, and by-products characterized, using a pilot-scale version of the Ohio State Carbonation and Ash Reactivation (OSCAR) process. The main elements of the process consisted of sorbent production, a riser reactor, cyclone and baghouse. Trace elements, including As, Se and Hg, were found at higher levels in the OSCAR solid by-products (in both the cyclone and baghouse) compared to traditional lime spray dryer (LSD) ash. Polycyclic aromatic hydrocarbons (PAHs) detected on solid by-products were primarily small molecular weight compounds at low concentration (e.g., μg/kg). Small particulates (?3 μm) that escaped from the cyclone and were captured by the baghouse showed higher trace element concentrations, possibly due to the lower operating temperature and greater specific surface area of solids in the baghouse. Operating conditions including flue gas flow rate and sorbent injection rate influenced the levels of trace elements and PAHs in OSCAR by-product material. Capture of PAHs was observed to increase with Ca concentration in experiments using supersorbent injection. However, possible release of PAHs occurred with regenerated sorbent injection. The concentrations of trace elements in leachate for all OSCAR cyclone samples tested were below Resource Conservation and Recovery Act limits. The concentrations of most trace elements in OSCAR by-product were also below the limits regulated in the EPA 503 Rule except As and Se. The similarity in the physical and engineering properties of OSCAR cyclone samples to natural cohesive soils suggests that this material can be utilized in a variety of construction, reclamation, and agricultural applications.     

Trace elements in coal: Associations with coal and minerals and their behavior during coal utilization - A review

Trace elements such as mercury, arsenic and selenium present in coal are known to be of concern for public health. Coal-fired power plants have resulted in emission of several tons of TEs in environment. These elements mostly evaporate during combustion and condense either homogeneously as sub-micron ash or heterogeneously onto already existing fine ash. The coal-mineral and mineral-mineral associations play an important role in the formation of fine particles and in subsequent condensation of trace elements in various phases. Any retention of these elements in fly ash particles is strongly influenced by their association with other minerals in individual coal and mineral grains. Clean coal technology development is, therefore, a priority area for research and needs continuous improvements in increased efficiency and decreased pollutant emission. The paper will include trace elements in different coals from around the world. It will consider different modes of occurrences present in coals, the ash formation and evaporation of trace elements and emissions. The typical emissions from typical power stations will be presented. The paper will also review different approaches adopted in estimating the deportment of these elements. The paper at the end would discuss control strategies for reducing emissions and future directions.     

Behavior of trace elements during pyrolysis of coal in a simulated drop-tube reactor

Release behavior and chemical form distribution of As, Pb, Cr, Cd and Mn in Datong coal during pyrolysis was studied in a simulated drop-tube reactor at a heating rate of about 1000 °C/s, including effects of temperature (300-1000 °C), atmosphere (N₂ and H₂), and holding time (0.3-10 min). Results show that the bleeding ratios of As, Pb, Cr, Cd and Mn increase with increasing pyrolysis temperature and holding time. Reductive environment results in higher emission of the elements. Among the five trace elements, As, Pb and Cd show similar behavior with volatilities higher than that of Cr and Mn at 1000 °C. The five trace elements in the coal and coal-derived chars are separated into five fractions through an extraction procedure. Ion exchangeable form of the elements is not found in the coal and the chars, and the elements remained in the residue fraction is the most dominant occurrence form in the coal and the chars for As, Pb, Cd and Cr. All the forms for all the elements undergo transformation in the pyrolysis resulting in reduced content in the chars.     

Mercury transformation across particulate control devices in six power plants of China: The co-effect of chlorine and ash composition

This paper presents the results of field measurements on mercury speciation in six power plants of China by applying the Ontario hydro method. During the tests, flue gas was sampled simultaneously before and after particulate control devices (electrostatic precipitator and fabric filter baghouse) along with the pulverized coal, bottom ash and fly ash sampling. The amount of oxidized mercury in gas phase before and after ESP/FF suggests that mercury oxidation after combustion is a kinetically controlled process. The comparison of mercury speciation in different power plant indicates a clear relationship with coal type, especially the chlorine concentration and the basic ash compositions in coal. Both of the factors are analyzed quantitatively in this study. A new parameter C (ratio of chlorine in coal to base/acid ratio) has been introduced to evaluate the co-effect of the two factors above on mercury speciation.     

Dynamics of trace elements release in a coal pyrolysis process

Samples of coal and solid carbonization product obtained at four temperatures: 400, 600, 850 and 1000 °C were tested on account of the contents of trace elements. The following hazardous trace elements were considered: arsenic, beryl, cadmium, manganese, nickel, lead, mercury and selenium. The release curves for the elements tested were determined.     

火力发电厂燃煤飞灰润湿性能

化学团聚是控制燃煤电厂细微颗粒排放最有效的方法之一。颗粒物被团聚剂润湿是化学团聚的首要步骤。以小龙潭电厂燃煤飞灰为对象,采用激光粒度仪研究了燃煤飞灰在十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)和Triton X 100(TX100)三种润湿剂溶液中的润湿性能,考察了润湿剂浓度、温度对燃煤飞灰润湿性能的影响。结果表明：水仅能将飞灰颗粒中的PM^₁₀+部分全部润湿,0.25%的SDS溶液中PM_2.5⁺可全部润湿,1%的SDS及0.4%的SDBS溶液中PM₁⁺可全部润湿;TX100溶液在低浓度条件下具有较强的润湿飞灰颗粒的能力,且0.1%的TX100溶液对细微颗粒的润湿性能较好;温度从20℃上升到60℃,润湿剂溶液表面张力降低,飞灰的润湿性能增强。鉴于飞灰在三种润湿剂中良好的润湿性能,三种润湿剂均可作为团聚剂组分以促进燃煤飞灰中的细微颗粒润湿进而被团聚成为容易脱除的大颗粒。     

Leaching of ashes and chars for examining transformations of trace elements during coal combustion and pyrolysis

One sub-bituminous coal and two bituminous coals were subjected to the combustion and pyrolysis by slow heating to a temperature ranging 550-1150 °C. Leaching of raw coals, ashes and chars with dilute HCl and HNO₃ was carried out, and leachate concentrations of major and trace elements were determined. Such a comparative leaching method was validated for characterizing the modes of occurrence of trace elements in coal and their transformations upon heating. Leaching results suggested that Be, V, Co, Cr and Ni were partially associated with organic matter, and As was partially associated with pyrite. During the ashing at 550-750 °C, the organically associated trace elements in coal formed some acid-soluble species. After the ashing at 1150 °C, Be, Co, Cr and Ni, together with Mn, Zn, and Pb, were immobilized in ash against leaching, whereas As was not immobilized. After pyrolysis, the organically associated trace elements in chars remained insoluble in both acids, and some HNO₃-soluble As in coal turned to a HNO₃-insoluble species.     

Occurrence and volatilization behavior of Pb, Cd, Cr in Yima coal during fluidized-bed pyrolysis

The volatilization behavior of Pb, Cd, Cr and the influence of coexisting mineral matters were investigated during pyrolysis of Yima coal in a fluidized-bed reactor at temperatures ranging from 500 to 900 °C. The modes of occurrence of Pb, Cd, Cr in Yima raw coal and two char samples were determined using density fractionation, demineralization and sequential chemical extraction methods. Lead in Yima coal is mostly associated with mineral matter in various forms, mainly pyrite, sulfates and monosulfides. Large part of cadmium is associated with pyrite. Chromium in Yima coal is mainly associated with organic matter. Different trends are observed for various forms of trace metals during pyrolysis. Lead associated with pyrite, sulfates and carbonates, lead in water soluble and ion exchangeable forms, and cadmium associated with pyrite are all unstable under pyrolysis conditions. During Yima coal pyrolysis, the volatilities of lead and cadmium vary greatly with pyrolysis temperature, while chromium volatility in Yima raw coal only has slight changes over the temperature range (500-900 °C) studied. The volatility of Pb, Cd, Cr in demineralized Yima coal (YimaD) is much higher than that of Yima coal during pyrolysis. New thermally stable forms of Pb, Cd and Cr are formed during pyrolysis of Yima, whereas the sources of them are different. The interactions between chromium and its coexisting mineral matters in Yima coal retard its vaporization during pyrolysis.     

Petrography and geochemistry of the Middle Devonian coal from Luquan, Yunnan Province, China

Coals from Luquan, Yunnan Province, China, have high contents of cutinite and microsporinite, with an average of 55 and 33.5 vol%, respectively, (on a mineral-free basis). The coals are classified as cutinitic liptobiolith, sporinite-rich durain, cutinite-rich durain, and sporinitic liptobiolith. These four liptinite-rich coals are often interlayered within the coal bed section and vary transversely within the coal bed. The vitrinite content varies from as low as 1.6-20.5% (mineral-free basis), and it is dominated by collodetrinite, collotelinite, and corpogelinite. The maceral composition may be attributed to the type of the peat-forming plant communities. Moreover, the Luquan coals are characterized by high contents of volatile matter, hydrogen, and oxygen, and the high values of the atomic hydrogen to carbon ratio as a result of the maceral composition. As compared with the common Chinese coals and the upper continental crust, the Luquan coals are enriched in Li, B, Cu, Ga, Se, Rb, Mo, Ba, Pb, Bi, and U, with averages of 99.9, 250, 111, 24.4, 4.55, 130, 58.8, 1276, 162, 3.85, and 34.1 μg/g, respectively. The SEM-EDX results show that V, Cr, Ga, and Rb occur mainly in clay minerals, and Cu and Pb are associated with clay minerals and pyrite, and Mo and U are mainly in clay minerals and organic matter. Barite and clay minerals are the main carrier of barium. The high B and U contents are probably resulted from deep seawater influence during coal formation.