Mechanism study of selenium retention by iron minerals during coal combustion

The interactions between selenium vapors and coal accessory Ca/Fe-minerals favor selenium emission control by transferring selenium into fly ash during coal combustion. Considering the complicated effects of iron transformation on selenium retention, iron species in fly ashes from seven coal-fired power plants were distinguished and the associations between selenium and iron minerals were assessed. Iron oxides (including Fe₃O₄, γ-Fe₂O₃ and ɑ-Fe₂O₃) were determined as the main form of iron minerals in fly ash. The adsorption of selenium vapors by different iron oxides was conducted at temperatures ranging from 300 to 900 °C and the species of captured selenium were identified. Furthermore, reaction sites on the surfaces of fresh and reacted iron oxides were compared to investigate the mechanism regarding selenium adsorption over these iron oxides, which were further clarified through density functional theory study. The results showed that iron oxides were surely to play a significant role in selenium retention mainly through chemisorption and the reactions probably occurred at temperatures below 900 °C. At 300 °C, ɑ-Fe₂O₃ had better selenium adsorption performance than Fe₃O₄/γ-Fe₂O₃. Regardless of iron species, Fe atoms on iron oxides participated in the selenium adsorption by forming a Se–O–Fe Structure. With temperature increasing, selenium adsorption by Fe atoms was suppressed, which caused a drop off in selenium capture capacity of Fe₃O₄ and ɑ-Fe₂O₃. Differently, increasing temperature promoted selenium adsorption over γ-Fe₂O₃, which owned a high selenium adsorption capacity even at 700 °C. Further analysis confirmed that the presence of O₂/H₂O(g) in the flue gas contributed to the formation of oxygen vacancies on the surface of γ-Fe₂O₃ at high temperatures and facilitated selenium vapors to react with Fe atoms.     

Insight of arsenic transformation behavior during high-arsenic coal combustion

The release of arsenic vapors (As³⁺) during high-arsenic coal combustion not only raises serious environmental concerns, but also causes catalyst deactivation in selective catalytic reduction (SCR) systems. To illuminate the mechanisms involved in the transformation of arsenic vapors towards less troublesome arsenates (As⁵⁺) during coal combustion, the accessory minerals in the high-arsenic coal were identified and the association relationship of these compounds with arsenic in fly ash was estimated. The results showed that Si/Al were the main inorganic elements in high-arsenic coal while the content of Ca was quite low. Ca was mostly transformed into sulfates during coal combustion and the effect of Ca on the arsenic transformation was limited. Al/Fe played a more significant role in arsenic speciation transformation and arsenic in the fly ash was predominantly bound with Al/Fe-oxides as arsenates. It was further confirmed that Al in kaolin/metakaolin showed good capacity on arsenic capture. In addition, few arsenic vapors were captured through the physical adsorption mechanism and the large fraction of As³⁺ in some fine particles was mostly attributed to the chemical reactions between arsenic vapors and Al-compounds. Meanwhile, a certain amount of arsenic vapors were converted into As₂O₅(s) under the influence of SCR catalyst and then carried by flue gas to participate in fly ash. Besides, part of arsenic distributed in the fly ash was through the stabilization of ash matrix in high temperature conditions. The transformation of arsenic from vapors towards particulate arsenic favored arsenic emission control by particulate matter control devices.     

Properties of biomass vs. coal fly ashes deposited in electrostatic precipitator

This paper presents comparative experimental studies of the morphology and elemental composition of fly ash particles from coal- and biomass-fired boilers, deposited in each stage of 3-stage electrostatic precipitators (ESPs). It was shown that fly ash morphology, its physical properties, and the percentage of elements in the fly ash taken from each stage of ESP depend on the kind of fuel. The biomass fly ash contains many irregular large particles, which are pieces of unburned wood. Bulk density of biomass fly ash is on average lower than that of coal fly ash, and drastically decreases in the second and third stages of ESP. The resistivity, measured at electric field of 4 kV/cm, of fly ash from biomass-fired boilers is much lower than that from coal, and can be below 10² Ω m, whereas from coal, except the first stage, varies in the range from 10⁷ to 10¹⁰ Ω m. The low resistivity of coal fly ash in the first stage of ESP results from high carbon content, and of biomass is probably an effect of additional high percentage of potassium, calcium and sodium sulfates. The percentage of Si, Al, Na, Fe, and Ti in fly ash from coal-fired boilers is much higher than from biomass, and in the opposite, the percentage of Mg, K, Ca, Mn, Mo, S, Cl, and P in biomass ash exceeds that in coal fly ash. Potential detrimental effects of biomass combustion products (salts, acids, tar) leaving the boiler on the construction elements of the electrostatic precipitator, including electrodes and HV insulators have been discussed in this paper. It was concluded that the long-term effects of biomass co-firing on the electrostatic precipitator performance, including the collection efficiency, have not been sufficiently studied in the literature and these issues require further detailed investigations.     

煤粉低尘燃烧器热态试验研究

以液排渣旋风燃烧技术为基础的煤粉低尘燃烧器可在燃烧过程实现捕渣,为工业加热提供含尘浓度低的高温火焰,是工业加热过程实现以煤代油的先进燃烧技术。本论文介绍了新型煤粉低尘燃烧器的热态燃烧试验研究结果,该燃烧器采用端面旋流进风,煤粉和一次风在旋转气流外层送入,分级燃烧等技术。热态试验研究表明,采用上述技术的煤粉低尘燃烧器具有燃烧完全,捕渣率高,NOx排放浓度低等特点。     

分光光度法研究粉煤灰对亚甲基蓝的吸附及其机理研究

以龙岩雁石火电厂粉煤灰对亚甲基蓝进行吸附实验,探讨了改性粉煤灰、粉煤灰用量、吸附时间、温度对亚甲基蓝吸附的影响。当粉煤灰投加量为4g/L,亚甲基蓝浓度15mg/L,常温条件下,在60min左右,亚甲基蓝降解率达到了98%以上。结果表明,利用粉煤灰处理亚甲基蓝,具有处理效果好、简单,经济等特点。利用Freundlich等温式和Langmuir等温式对其吸附行为进行描述,表明粉煤灰易于吸附亚甲基蓝,吸附属于化学吸附;用颗粒内扩散方程和准二级吸附动力学方程对实验数据进行回归分析,更好地描述亚甲基蓝在粉煤灰上的吸附。准二级吸附动力学方程能够反映亚甲基蓝在粉煤灰上的吸附机理,准二级吸附速率常数k2=0.5758g/(mg.min)。本研究为粉煤灰处理印染废水提供了理论依据和实践依据。     

Oxy-coal combustion in a 30 kWth pressurized fluidized bed: Effect of combustion pressure on combustion performance,pollutant emissions and desulfurization

Oxy-coal combustion with pressurized fluidized beds has recently emerged as a promising carbon capture and storage (CCS) technology for coal-fired power plants. Although a large number of energy efficiency analyses have shown that an increase in combustion pressure can further increase the net plant efficiency, there are few experimental studies of pressurized oxy-coal combustion conducted on fluidized bed combustors/boilers with continuous coal feeding. In this study, oxy-coal combustion experiments with lignite and anthracite were conducted with a 30 kW_th pressurized fluidized bed combustor within the pressure range of 0.1 MPa to 0.4 MPa. The investigation focused on the elucidation of the impacts of combustion pressure on the combustion performance, pollutant emissions and desulfurization of oxy-coal combustion in fluidized beds. The results showed that an increase in pressure increased the combustion efficiency and combustion rate of coal particles, and the promoting effect of pressure increase was more significant for the high rank coal with smaller particle size and the high O₂ concentration atmosphere. For both coals, NO_x emissions decreased with pressure but N₂O emissions increased with pressure and accounted for a considerable part of the nitrogen oxide pollutants under high pressure oxy-coal combustion conditions. The pressure had insignificant impact on the SO₂ emissions of oxy-coal combustion but an increase in pressure enhanced the direct desulfurization of limestone.     

C-Fe谱线干扰修正对飞灰含碳量LIBS测量的影响

在燃煤电厂,飞灰含碳量是直接反映锅炉燃烧效率的重要指标,控制含碳量水平和低氮燃烧之间的平衡要求实现含碳量的在线(或快速)检测。将激光诱导击穿光谱技术应用于飞灰含碳量的快速测量,针对测量中248 nm附近的C和Fe谱线干扰问题,提出了利用Fe谱线修正的方法以提取重叠峰中C谱线的积分强度,对比分析了Fe 248.33 nm, Fe 254.60 nm和 Fe 272.36 nm谱线分别作为Fe 247.98 nm的修正谱线时提取的C修正积分强度对飞灰含碳量定标曲线和未知样品重复测量精确度的影响。研究结果表明,对C和Fe谱线干扰进行强度修正可以提高含碳量定标曲线的拟合度,并且可以显著改善低含碳量样品重复测量的精确度。但同时需要注意用于修正的Fe谱线的合理选取,防止在对低含碳量样品中C谱线强度的过度修正。从定标曲线和重复测量精确度总体评价而言,Fe 254.60 nm谱线最适用于LIBS测量飞灰含碳量时的C和Fe谱线干扰的修正。     

分光光度法研究改性粉煤灰对有机磷的吸附性能

常温下,用硫酸铝为改性剂制得改性粉煤灰,以此作为有机磷废水的吸附剂,用分光光度法分析改性粉煤灰对有机磷的吸附性能,并通过XRD对其结构进行表征。结果表明:改性时,盐灰质量比为1∶12;吸附时,改性粉煤灰用量为35g/L、溶液的pH值为8、振荡时间为30min、吸附温度为30℃时,磷的去除率可达97.0%。     

Non-gray chemical composition based radiative property model of fly ash particles

Particle radiation has a spectral dependence and is closely related to the chemical composition of the material. Iron oxide, one of the main components of fly ash, observably affects the complex index of refraction of the particles. In this study, following the theory of the spectrum k-distribution based weighted sum of gray particles model (Guo et al. [4,13]), a non-gray fly ash radiative property model involving the chemical composition was developed. First, four typical fly ash particles with different iron oxide contents were selected, and the corresponding particle radiative parameters were obtained using the Mie theory. Then, the absorption efficiency and weighting factors of the non-gray model were directly obtained from the Gaussian integral points of the k-distribution. The scattering efficiency of the particles was obtained from the Planck mean. The accuracy of the newly developed model was evaluated in a one-dimensional plane-parallel slab system through comparison with the line-by-line (LBL) model and two commonly used gray radiative property models. The results show that the new non-gray model agrees well with the LBL solution and becomes more accurate as the iron oxide content increases. When the iron oxide content of the fly ash increased from 5.47% to 30.50%, the maximum relative error of the radiative heat flux and the radiative source term decreased from 12.50% to 5.68% and from 20.97% to 12.62%, respectively. The new model can improve the prediction accuracy of radiative heat transfer in pulverized coal-fired furnaces.     

Mercury speciation in air-coal and oxy-coal combustion: A modelling approach

In this study, a mechanism for mercury chlorination in flue gases resulting from the combustion of pulverised coal has been presented. Arrhenius parameters of the gas-phase elementary reactions in the Hg–Cl sub-mechanism have been updated and are mainly based on recent experimental and quantum mechanical rate determinations. The mechanism is validated by comparison to accurate experimental data that is unbiased by Hg oxidation in the impinger solutions of aqueous chemistry methods. Solid-phase retention of Hg⁰ has been studied in parallel to char combustion; the heterogeneous model describes condensation of mercury on fly ash particles. The combined homogeneous–heterogeneous model predictions show comparable trends to those of power plant data. This approach aims to provide an improved prediction of mercury speciation from coal-fired power plants and to shed light on the chemical kinetic changes encountered during oxy-coal operation.     

Ash formation and deposition during combustion of pulverized torrefied wood and coal in a 100 kW downflow combustor

Torrefied wood originating from beetle-killed trees is an abundant biomass fuel that can be co-fired with coal for power generation. In this work, pulverized torrefied wood, a bituminous coal (Sufco coal) and their blended fuel with a mixing ratio of 50/50 wt.%, are burned in a 100-kW rated laboratory combustor under similar conditions. Ash aerosols in the flue gas and ash deposits on a temperature-controlled surface are sampled during combustion of the three fuels. Results show that ash formation and deposition for wood combustion are notably different from those for coal combustion, revealing different mechanisms. Compared to the coal, the low-ash torrefied wood produces low concentrations of fly ash in the flue gas but significantly increased yields (per input ash) of ash that has been vaporized. All the mineral elements including the semi- or non-volatile metals in the wood are found to be more readily partitioned into the PM₁₀ ash than those in the coal. The inside layer deposits sticking to the surface and the loosely bound outside deposits exposed to the gas both show a linear growth in weight during torrefied wood test. Unlike coal combustion, in which the concentration of (vaporized) ash PM₁ controls the inside deposition rate, wood combustion shows that the formation of porous bulky deposits by the condensed residual ash dominates the inside deposition process. Co-firing removes these differences between the wood and coal, making the blended fuel to have more similar fly ash characteristics and ash deposition behavior to those of the bituminous coal. In addition, results also show some beneficial effects of co-firing coal with torrefied wood, including reduction of the total deposition rate and the minimization of corrosive alkali species produced by wood.     

Optical emission spectroscopy of point-plane corona and back-corona discharges in air

Results of spectroscopic investigations and current-voltage characteristics of corona discharge and back discharge on fly-ash layer, generated in point-plane electrode geometry in air at atmospheric pressure are presented in the paper. The characteristics of both discharges are similar but differ in the current and voltage ranges of all the discharge forms distinguished during the experiments. Three forms of back discharge, for positive and negative polarity, were investigated: glow, streamer and low-current back-arc. In order to characterize ionisation and excitation processes in back discharge, the emission spectra were measured and compared with those obtained for normal corona discharge generated in the same electrode configuration but with fly ash layer removed. The emission spectra were measured in two discharge zones: near the tip of needle electrode and near the plate. Visual forms of the discharge were recorded with digital camera and referred to current-voltage characteristics and emission spectra. The measurements have shown that spectral lines emitted by back discharge depend on the form of discharge and the discharge current. From the comparison of the spectral lines of back and normal discharges an effect of fly ash layer on the discharge morphology can be determined. The recorded emission spectra formed by ionised gas and plasma near the needle electrode and fly ash layer are different. It should be noted that in back arc emission, spectral lines of fly ash layer components can be distinguished. On the other hand, in needle zone, the emission of high intensity N₂ second positive system and NO _γ lines can be noticed. Regardless of these gaseous lines, also atomic lines of dust layer were present in the spectrum. The differences in spectra of back discharge for positive and negative polarities of the needle electrode have been explained by considering the kind of ions generated in the crater in fly ash layer. The aim of these studies is to better understand the discharge processes encountered in electrostatic precipitators.     

Experimental study on electrostatic removal of high-carbon particle in high temperature coal pyrolysis gas

A high-temperature electrostatic precipitator (ESP) presents a good solution for hot gas cleaning, which can remove fly ash from pyrolysis gas at temperatures higher than the tar dew point. In this paper, the characteristics of negative DC corona discharge in air and simulated coal pyrolysis gas were studied. The removal of coal pyrolysis furnace fly ash (ash A) was investigated and compared with that of coal-fired power plant fly ash (ash B) in ESP with a temperature ranging from 300?K to 900?K. The current density of simulated gas was higher than that of air under the same discharge voltage and at different temperatures. The simulated gas also had a higher spark voltage and a lower onset voltage compared with air. The fractional collection efficiency of ash A was lower for particles with diameters of larger than 0.1?µm at high temperature, compared with ash B. A lower collection efficiency in simulated gas was obtained for particles with diameters of less than 0.1?µm compared with air. The collection efficiency of submicron particles in simulated gas was usually higher than it in air, especially for particles with diameters of less than 0.04?µm. In simulated gas, the overall collection efficiency of ash A was obviously lower than that of ash B, especially at high temperature. From 300?K to 700?K, the collection efficiencies of both ash samples were as high as above 93%, but the collection efficiency of ash A in simulated gas decreased to 78.7% at 900?K.     

红外和拉曼光谱的煤灰矿物组成研究

研究煤灰中矿物质的性质通常从矿物组成的表征入手。为了分析两种高硅铝煤灰的矿物成分,采用傅里叶变换红外光谱(FTIR)、拉曼光谱和X射线衍射(XRD)技术对煤灰样进行了测试和综合表征,将FTIR和拉曼光谱的分析结果与XRD进行了比较。FTIR结果表明,在1 100~1 000 cm-1范围内高硅铝煤灰出现最强的特征峰,例如石英峰(1 089 cm-1)和偏高岭石峰(1 042 cm-1),它们都归属于Si-O伸缩振动。对原始红外谱图进行二阶导数处理后,可获得重叠峰的峰位,有助于更完整的解析矿物吸收峰,从而获得更丰富的矿物组成信息。煤灰中硬石膏的红外和拉曼光谱发现,在1 157,1 126和674 cm-1的拉曼光谱峰与在1 151,1 120和678 cm-1的红外光谱峰振动模式分别相同且峰位接近,还存在一些完全不同的拉曼光谱与红外光谱峰,表明这两种光谱存在互补性。尽管煤灰中锐钛矿含量很低,但由于Ti-O的极化率很高,因此拉曼光谱显示锐钛矿的144 cm-1峰远远强于石英的461 cm-1峰。XRD结果表明,煤灰中主要存在石英、云母、赤铁矿、硬石膏和未知的无定形相矿物,FTIR和拉曼光谱综合分析的结果表明除了这些矿物,还存在偏高岭石、无定形氧化硅、长石、方解石和锐钛矿等。在定性分析方面,将FTIR和拉曼光谱结合起来比XRD单独获得的矿物组成信息更为详细。     

Phosphor thermometry at the surface of single reacting large-diameter spherical coke particles to characterise combustion for packed bed furnaces

Packed-bed furnaces fired with large-diameter coke are important in high-temperature material processing industries such as lime and iron production. The combustion conditions are complicated by the presence of an ash layer surrounding the coke particle that remains intact during passage through the furnace and alters oxygen diffusion and heat transfer to the reacting particle core. The objective of this study is to determine the surface temperature of this ash layer using lifetime-based phosphor thermometry during combustion of single spherical 38 mm diameter coke particles in a high temperature tube furnace. Time traces of the coke particle core temperature and mass conversion rate do not significantly differ between experiments performed with and without the phosphor layer, indicating that the presence of the phosphor particles does not alter the overall combustion behaviour. Surface temperatures of up to 950 °C are measured and correlated with the fuel mass conversion rate. When the coke particle starts to react the surface temperature is up to 100 °C higher than that of the core. As the reaction front progresses toward the centre, the core temperature exceeds the surface temperature by 200 °C due to the insulating effect of the ash layer. The surface temperature of the ash layer decreases with time due to the steadily decreasing fuel mass conversion rate. The method and results can be used to provide key validation data for shrinking-core combustion models, for example by constraining the unknown transport properties of the ash layer, thereby assisting the development of complete packed-bed furnace simulations for process optimisation.     

A new reaction: vacuum synthesis and characterization of IONO2 and IONO

The new reactions for preparing IONO₂ and IONO have been found. IONO₂ and IONO can be easily prepared in vacuum by the heterogeneous reactions of gaseous ICl over the solid powders AgNO₃(s) at the room temperature and AgNO₂(s) at 0(±1) °C which were loosely filled into the quartz inlet tube (about 1.5 cm inside diameter and 5 cm long) and supported on the quartz wool, respectively, and then are characterized well by the PES experiment and the ROVGF calculations.     

Utilization of Fly Ash Nanofluids in Two-phase Closed Thermosyphon for Enhancing Heat Transfer

This study investigates how fly ash nanofluids affect the thermal performance of a two-phase closed thermosyphon at various states of operation. The utilization of nanofluids obtained from X₂O₃-type oxides, such as Al₂O₃, Fe₂O₃, or CuO, on the improvement of two-phase closed thermosyphon performance was reported in a number of studies in the literature. The present study experimentally demonstrated the effect of using a nanofluid obtained from fly ash comprised of various types of metal oxides in varying ratios on improving the performance of a two-phase closed thermosyphon. The fly ash was obtained from the flue gas that was captured in the cyclones of the Yatagan thermal power plant (Turkey). Triton X-100 (Dow Chemical Company) dispersant was used in the study to produce the 0.2% (wt) fly ash/water nanofluid via direct synthesis. A straight copper tube with an inner diameter of 13 mm, outer diameter of 15 mm, and length of 1 m was used as the two-phase closed thermosyphon. The nanofluid filled 33.3% (44.2 ml) of the volume ofthe two-phase closed thermosyphon. Three heating power levels (200, 300, and 400 W) were used in the experiments with three different flow rates of cooling water (5, 7.5, and 10 g/s) used in the condenser for cooling the system. A increase of 26.39% was achieved in the efficiency of the two-phase closed thermosyphon when 4% (wt) fly ash containing nanofluid was used to replace deionized water at a heat load of 200 W and with a cooling water flow rate of 5 g/s.     

A Light Scattering Study of Coal Combustion in a Drop Tube Furnace

A light scattering method has been devised to discriminates between coal and fly ash and measure particle size. Sizing was performed by the measurement of forward scattered intensity, and discrimination was displayed by the ratio of the intensities of crossed to parallel polarisations at a scattering angle of 160°. The technique has been applied to a study of coal combustion in a variable length drop tube furnace. It has been demonstrated that the development of the size distribution can be followed as a function of residence time. Further, it is indicated that there is a simple correlation between the polarisation ratio and the carbon content of the ash. This leads to the possibility of monitoring combustion efficiency in industrial furnaces.     

New advanced in situ carbon monoxide sensor for the process application

Mixed potential solid electrolyte CO sensors with sensing electrodes based on composite with various semiconducting oxides were extensively studied in the temperature range 500–650 °C for sensitivity, stability and cross-sensitivity besides CO to other combustion components like CO₂, H₂O, O₂, and SO₂. The highest CO sensitivity was found for the CO sensor with composite electrode based on Au/Ga₂O₃ showing also good reproducibility and stability in hazardous combustion environment. CO sensor response behavior in non equilibrated oxygen containing gas mixtures is mainly determined by the catalytic activity of the measuring electrode and depends strongly on preparation and measuring conditions. Mixed oxides based on doped chromites show only a little sensitivity to CO. CO sensor based on Au/Ga₂O₃ composite electrodes was showing good CO selectivity in the presence of other combustion gas species and finally was tested in combustion environment at power plant. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

减少二氧化碳对LIBS检测飞灰中未燃碳含量影响的研究

通常热力发电厂将飞灰中未燃碳的含量作为评价锅炉燃烧效率的重要指标,通过测量飞灰中未燃碳的含量来评价煤粉燃烧的充分程度,进而实现优化燃烧、提高机组效率。基于激光诱导击穿光谱技术(LIBS)无接触、快速响应、高灵敏度、可以在线测量等特点,备用来测量飞灰中未燃碳的含量。由于烟气中CO₂气体的存在,碳谱线强度会随CO₂浓度的变化而改变。为了减少CO₂气体对飞灰未燃碳测量结果的影响,提出并设计了具有二级旋风分离器的LIBS测量飞灰未燃碳含量实验系统,飞灰从给粉机流出后通过二级旋风分离器进入测量腔体,脉冲激光经过透镜作用于飞灰样品进而产生等离子体。LIBS系统采用双中心波长光谱仪,可测得飞灰中C,Si,Mg,Fe,Ca和Al等主要元素谱线,同时高分辨率通道可分辨出相邻C和Fe的元素谱线,可以在获得充分的飞灰光谱信息的同时保证了测量的精度。实验结果表明该系统可有效分离和收集飞灰颗粒,减少CO₂气体对测量结果的干扰,为LIBS技术的工程应用提供了更准确的依据。