煤燃烧过程中汞、砷、硒反应机理研究

本文以三种典型煤为对象,测定了煤及灰中汞,砷,硒的浓度,了解了元素的挥发性。对钱家营褐煤进行了不同温度的燃烧实验。测定了在不同温度下燃烧灰中汞,砷,硒的含量变化。将所得实验结果与化学热力平衡分析工具F~*A~*C~*T2.1模拟系统结果相比较。推测了其中可能发生的反应。     

PM2.5和PM10排放的一维炉煤燃烧实验研究

我国煤烟污染十分严重。燃煤排放的PM10和PM2.5表面富集了大量的有毒痕量元素,进入大气后,对环境的危害极大。本文在一维炉中对不同煤种分别在650℃,850℃,950℃下燃烧PM的排放进行实验研究,发现PM10和PM2.5的排放量随温度升高有增加的趋势;随煤种含S量的增加,其排放量也增加;随着煤灰分的增加,PM10和PM2.5的排放量也有增大的趋势,煤中矿物质的种类和形态对其排放有明显的控制作用。     

煤中汞,砷,硒赋存形态的研究

本文利用连续化学浸提法对三种典型煤进行连续浸提,根据不同形态的溶解度,将煤中的汞,砷,硒分为可交换态,硫化物形态,有机物结合态及残渣态四种形态。结果表明不同的煤有不同的形态分布特征。但总体来看,汞主要以硫化物形态和残渣态存在。砷主要以硫化物形态存在。硒赋存在硫化物,有机物及残渣态中。     

Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres

The use of two activated carbon fibres, one laboratorial sample prepared from a commercial acrylic textile fibre and one commercial sample of Kynol^®, as prepared/received and modified by reaction with powdered sulfur and H₂S gas in order to increase the sulfur content were studied for the removal of mercury from aqueous solution and from flue gases from a fluidized bed combustor. The sulfur introduced ranged from 1 to 6 wt.% depending on the method used. The most important parameter for the mercury uptake is the type of sulfur introduced rather than the total amount and it was found that the H₂S treatment of ACF leads to samples with the highest mercury uptake, despite the lower sulfur amount introduced. The modified samples by both methods can remove HgCl₂ from aqueous solutions at pH 6 within the range 290-710 mg/g (ACF) which can be favourably compared with other studies already published. The use of a filter made with an activated carbon fibre modified by powdered sulfur totally removed the mercury species present in the flue gases produced by combustion of fossil fuel.     

燃煤黄铁矿迁移转化模拟的研究

基于已有的动力学数据对单颗粒黄铁矿迁移转化进行了全过程模拟,分析讨论了各种因素对黄铁矿氧化过程和S释放率的影响,结果表明:随着颗粒尺寸的减小和炉膛温度的升高,黄铁矿颗粒的分解氧化过程加快,颗粒在炉内停留很短时间内温度即升高到共融点以上,使颗粒呈混熔态,进而导致灰沉积、结渣.颗粒氧化过程中S的释放主要受扩散控制,其释放速率与颗粒粒径成反比,与氧气浓度和炉膛温度成正比.     

煤粉锅炉燃烧产物中汞,砷分布特征研究

对某300 MW燃煤电厂锅炉进行煤、渣、飞灰取样后,测定煤和燃烧产物中汞和砷的含量,研究了电除尘四个电场飞灰中汞与砷的分布特点。结果表明飞灰中砷的浓度随着粒度的降低而升高。在底渣中含量较低。通过飞灰粒度与砷浓度的拟合,初步得出砷的富集并不是只由物理凝结造成的,也有外部表面反应(或孔扩散)控制的过程。汞在电除尘1,2,3电场中是预料中的随着粒度的减小浓度增加。但在四电场中汞的浓度又降低了。通过分析得出飞灰含碳量也是影响汞吸附量的重要因素。     

Application of pressurized circulating fluidized bed technology for combined cycle power generation

Ahlstrom Pyropower, Inc. (API) pioneered the development of atmospheric circulating fluidized bed (ACFB) technology. The sustained success with ACFB and continued research in ACFB systems has led Ahlstrom towards the development of pressurized circulating fluidized bed (PCFB) technology. Since the mid-1980s many components of the PCFB combined cycle power plant were developed. Based on the component development experience, a 10 MW_th PCFB pilot plant was built to support the design of commercial size PCFB units.The PCFB pilot plant has operated over 4500 hours since its commissioning in mid 1989. Five types of coals and five types of sorbents have been tested. Emissions and load following performance of the pilot plant have demonstrated that the PCFB performs significantly better than required under the current stringent environmental standards. The sulfur capture has been 95 to 98%; the NO_x level with SNCR is less than 25 mg/MJ; the ash generated from the PCFB is less basic than the ash from conventional system.API, under the U.S. Department of Energy's Clean Coal Technology III program, was awarded a contract to build a nominal 80 MW_e PCFB combined cycle repowering unit. The unit is scheduled for commissioning in early 1997. API has also performed design studies for larger capacity units in the range of 100 – 400 MW_e. These designs include a second generation PCFB technology combined cycle system for the use of high ash coals. The second generation PCFB technology involves partial gasification of coal and the use of the syngas to heat up the PCFB exhaust flue gas to 1300°C at the gas turbine inlet. This paper, in addition to presenting the pilot plant results, summarizes the salient features of PCFB combined cycle plants for various fuels including high ash Indian coals.     

新阳炼焦煤结构的FTIR和XPS谱学表征

认知煤中主要元素的结构与赋存是获取煤结构参数的基础,对构建煤结构模型,研究煤的反应特性,合理利用煤炭资源具有重要意义。目前煤结构研究多是针对中低变质程度煤的,对炼焦煤结构研究较少,炼焦煤的结构模型尚未见报道。应用FTIR对新阳炼焦煤中羟基基团、脂肪结构、芳香结构、含氧官能团及杂原子结构进行谱学表征,通过XPS解析煤中氮和硫的赋存形式,掌握炼焦煤中主要元素的禀赋特征。结果表明： 新阳煤中与芳香环上的π电子形成的羟基π氢键是羟基的主要存在形式,多聚体是煤结构中缔合结构的具体表现;次甲基、甲基、亚甲基的含量依次增加,亚甲基和次甲基含量占煤中脂肪烃总量的82.05%,煤中烷基侧链较多;苯环二取代、苯环三取代是煤中芳香烃的主要结构,占芳香烃总量的86.74%;含氧官能团中,羟基和羰基是主要组成基团,羧基和醚基含量不足10%。新阳煤中硅的含量比较丰富,主要以Si-O-Si和Si-O-C的形态赋存。吡啶、吡咯和氮氧化物为氮的主要存在形式,绝大多数氮分布于煤分子结构单元的边缘;噻吩硫是煤中有机硫最主要的赋存形式,超过有机硫总量的60%,砜和亚砜的含量次之,硫醇和硫醚的赋存最少。     

Investigation of sulfur speciation in particles from small coal-burning boiler by XANES spectroscopy

Sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy was employed to study the speciation of sulfur in raw coal, ash by-product and fine particulate matter from a small coal-burning boiler. By means of least square analysis of the XANES spectra, the major organic and inorganic sulfur forms were quantitatively determined. The results show that about 70% of the sulfur in raw coal is present as organic and a minor fraction of the sulfur occurs as other forms: 17% of pyrite and 13% of sulfate. While in bottom ash, fly ash, and PM_2.5, the dominant form of sulfur is sulfate, with the percentage of 80,79 and 94, respectively. Moreover, a number of other reduced sulfur including thiophenic sulfur, element sulfur and pyrrhotite are also present. During coal combustion, most of organic sulfur and pyrite were oxidized and released into the atmosphere as SO₂ gas, part of them was converted to sulfate existing in coal combustion by-products, and a small part of pyrite was probably reduced to elemental sulfur and pyrrhotite. The results may provide information for assessing the pollution caused by small boiler and developing new methods for the control of SO₂ pollution.     

煤质硫含量紫外差分吸收测量方法研究

快速准确地测定煤质硫含量,可为企业、环境监督部门提供重要的技术依据。国内外已有多种煤质硫含量分析仪器,但或多或少存在令操作人员不满意的地方。提出一种基于紫外(UV)差分吸收光谱(DOAS)的煤质硫含量测量方法。针对分子数分数测量范围宽、光程短等问题,在传统算法的基础上,提出基于有限脉冲响应(FIR)滤波和四阶多项式非线性补偿的改进DOAS算法。搭建了实验测量系统,对5种标准煤样进行了实验研究。结果表明,测量系统的下限为0.014%,能够去除烟尘和背景气体的影响,降低系统的维护量,单次测量时间在4min左右,测量系统的重复性满足国家标准的要求。     

煤在燃烧过程中表面灰层内气体扩散传质特性的研究

煤在燃烧过程中表面灰层内气体扩散传质特性的研究严建华，倪明江，张宏焘，岑可法（浙江大学能源工程系杭州３１００２７）关键词：灰层扩散，煤燃烧，孔隙率一、引言就流化床燃烧锅炉通常燃用的较大粒度的煤而言，其焦碳的燃尽时间占了煤粒燃尽所需时间的绝大部分，粗略...     

不同来源煤灰激光诱导击穿光谱测量特性对比研究

飞灰含碳量的定量分析需要不同含碳量梯度的飞灰样品作为定标之用。通常做法是用煤粉按照快速灰化法的要求灼烧得到不同含碳量的灰样,用于定标分析。但是这与实际锅炉飞灰的成分存在一定差异,需要对光谱特性的差异进行研究来指导实际定标工作。因此,对比了快速灰化法制备的不同含碳量的煤灰样品与锅炉飞灰在特征谱线强度、等离子温度等等离子光谱特征方面的差异。实验证明快速灰化法制备的煤灰样品的Fe,Mg和Al谱线强度强于锅炉飞灰样品,飞灰等离子温度低于所制备的煤灰样品的等离子体温度,这可能是不同处理过程的物理化学特性差异造成的。用主成分分析法考察了导致光谱差异的主要原因,认为Fe,Mg,Al和Si等元素是导致二者在光谱特性差异的主要因素,这可能因为实验室内按照快速灰化法进行制样的飞灰相应矿物质组成不同所导致的。在用灼烧后的煤灰定标未燃碳时,应注意由于成灰过程不同所造成的Fe,Mg,Al和Si等元素含量和形态不同所带来的影响。     

陕北侏罗纪富镜煤和富惰煤分子结构的FTIR，XPS和13C NMR表征

侏罗纪优质煤炭资源为煤制油、制气等清洁高效利用提供了丰富的物质基础,其显微组分以富集惰质组为特征,而镜质组与惰质组大分子结构在很大程度上决定了煤的物理化学性质和工艺性能,进而决定了煤炭资源的综合利用效率及附加值。采集并制备了陕北侏罗纪煤田小保当煤矿和柠条塔煤矿的原煤(XR)、富镜质组煤(XV、NV)和富惰质组煤(XI、NI)样品,利用傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、固体13C核磁共振谱(13C NMR)等手段,结合煤质分析结果,定量表征了不同显微组分富集物分子结构的差异。研究结果表明：XI和NI煤中芳烃结构芳环取代程度低,主要以3个相邻、4~5个相邻的氢原子形式存在,苯环上氢原子较少被其他官能团取代,同时其结构中芳烃C═C骨架振动明显,脂肪结构中亚甲基伸缩振动强度较低,并且甲基含量略高于富镜煤,C═O基团相对含量略高,表明富惰煤有较多含氧桥键相连的芳香结构,其结构中脂族链、脂环基团脱落、断裂以及芳烃富集,支链相对较少且长度较短,芳碳率、芳香度、芳环缩合程度及成熟度较高。XV和NV煤中表面结构中碳的赋存形态“C—C,C—H”,“C—O”的相对含量高于富惰煤,反映其结构中应含较多的芳环取代的脂肪族侧链,XI和NI煤表面结构中氧的赋存形态以“C—O”为主,“C═O”和“COO—”明显高于富镜煤。XV和XI煤的芳碳率分别为57.91%和66.02%,脂甲基碳分别为10.02%和7.84%,质子化芳碳为非质子化芳碳的两倍,XV煤的羰基和羧基碳相对含量较高,两者桥碳和周碳之比分别为0.25和0.40,芳香核结构平均缩合环数分别为2.68和3.03,平均尺寸分别为0.448和0.676 nm,XI煤结构中芳香核以萘和蒽为主,支链化度L_γ分别为0.22和0.19,表明XV比XI存在较多脂肪侧链、饱和环结构,生烃(油)潜力大。     

煤中痕量元素在低温燃烧下的分布规律

为了解流化床燃烧过程中痕量元素的分布与富集规律,以流化床燃煤过程为研究对象,在实验室的小型机理性试验台架上进行实验,研究了煤中痕量元素的排放特点。实验模拟流化床低温燃烧的特点, 6种典型煤分别在650℃、800℃、950℃三个工况下燃烧,分析得到Pb、Cr、Cd等痕量元素大部分留在灰中。Hg在灰中的富集规律不明显。     

Mechanism on the contribution of coal/char fragmentation to fly ash formation during pulverized coal combustion

In this paper, the correlations between coal/char fragmentation and fly ash formation during pulverized coal combustion are investigated. We observed an explosion-like fragmentation of Zhundong coal in the early devolatilization stage by means of high-speed photography in the Hencken flat-flame burner. While high ash-fusion (HAF) bituminous and coal-derived char samples only undergo gentle perimeter fragmentation in the char burning stage. Simultaneously, combustion experiments of two kinds of coals were conducted in a 25?kW down-fired combustor. The particle size distributions (PSDs) of both fine particulates (PM_1-10) and bulk fly ash (PM₁₀₊) were measured by Electrical Low Pressure Impactor (ELPI) and Malvern Mastersizer 2000, respectively. The results show that the mass PSD of residual fly ash (PM₁₊) from Zhundong coal exhibits a bi-modal shape with two peaks located at 14?µm and 102?µm, whereas that from HAF coal only possesses a single peak at 74?µm. A hybrid model accounting for multiple-route ash formation processes is developed to predict the PSD of fly ash during coal combustion. By incorporating coal/char fragmentation sub-models, the simulation can quantitatively reproduce the measured PM₁₊ PSDs for different kinds of coals. The sensitivity analysis further reveals that the bi-modal mass distribution of PM₁₊ intrinsically results from the coal fragmentation during devolatilization.     

The roles of added chlorine and sulfur on ash deposition mechanisms during solid fuel combustion

The focus of this paper is on effects of chlorine and sulfur on coal ash deposition rates, under practically relevant but systematically controlled combustion conditions. This problem is important, not so much for coal, but to understand and predict deposition rates for biomass combustion where chlorine contents can be high. To this end, ash deposition rates on a controlled temperature surface were measured for controlled amounts of chlorine and sulfur added to a pulverized coal, doped with potassium and burned in a 100 kW rated combustion rig. Previous work with 35 tests on 11 coal, biomass and petroleum coke fuels burned under a range of operating conditions had strongly suggested that the deposition rate of the tightly bound inside deposits was independent of the ash aerosol composition, and depended only on PM₁ in the flue gas. The loosely bound outside deposition rate was dependent primarily on the total alkali content in the flue gas. The new results using chlorine added to the fuel (in the form of ammonium chloride) required these previous conclusions to be drastically revised. They showed that chlorine, not alkali alone, had large effects on the deposition rate of the inside deposits, which now were orders of magnitude higher than without chlorine addition, and did not fit previous (multi-fuel) correlations with PM₁. Sulfur addition, together with chlorine, did not affect deposition rates much, although it did lower the chlorine content of the deposit. These results are interpreted in terms of the ash aerosol size segregated composition, which was also measured, and potential sulfation reactions within the deposit.     

煤中汞、矿物、灰分的相关性研究

本文以阿尔伯塔次烟煤为研究对象,对煤样进行密度段划分,测定了个密度段的汞含量,用低温灰化仪对各密度段煤样进行低温灰化,对低温灰进行XRD(X-Ray Diffractometers)分析,研究其中矿物成分及含量.分析了该煤样中汞、矿物及其灰分的相关性,提出了汞赋存于阿尔伯塔次烟煤中一种特殊矿物-赵击石(Chaoite)中的可能性.     

燃煤飞灰物理化学特性及其润湿机理研究

以小龙潭电厂燃煤飞灰及其不同粒径范围的分级灰为对象,采用X射线荧光光谱、X射线衍射、离子色谱、Zeta电位、扫描电镜等实验方法研究了飞灰的物理化学特征.同时采用沉降实验、表面张力实验研究了三种不同润湿剂对飞灰的润湿性能.研究发现,溶液对飞灰的润湿能力不仅取决于其气液界面张力,还与飞灰的组成、表面电位以及形貌特征密切相关.亲水性物质含量的增加,颗粒表面电荷与润湿剂分子间的静电吸引,颗粒表面的棱角孔隙等均可以促进其润湿;温度越高飞灰润湿性能越好,且温度对飞灰润湿过程影响较大,温度较高(60℃)时润湿剂种类及浓度对飞灰润湿过程的影响不明显.     

Enhanced desulfurizing flotation of coal using sonoelectrochemical method

Enhanced desulfurizing flotation of low sulfur coal was investigated using sonoelectrochemical method. The supporting electrolyte used in this process was sodium chloride and the additive was anhydrous ethanol. The effects of treatment conditions on desulfurization were studied by a single-factor method. The conditions include anhydrous ethanol concentration, sodium chloride concentration, sonoelectrolytic voltage, sonoelectrolytic temperature, sonoelectrolytic time and coal sample granulometry. The optimal experimental conditions achieved for anhydrous ethanol concentration, sodium chloride concentration, sonoelectrolytic voltage, sonoelectrolytic temperature and sonoelectrolytic time are 1.7 mol L^?1, 5.1 × 10^?3 mol L^?1, 10 V, 70 °C, 50 min achieved for a ?0.18 mm coal sample. Optimal conditions cause a sulfur reduction of up to 69.4%. The raw and treated coals were analyzed by infrared spectroscopy and a chemical method. Pyritic sulfur, organic sulfur, ash as well as moisture are partially removed. The combination of high sulfur reduction, high yield, as well as high ash reduction was obtained in the newly developed method of enhanced flotation by sonoelectrochemistry. Ultrasound irradiation promotes electron transfer efficiency and increases clean coal yield.     

Experimental and modeling study of H2S formation and evolution in air staged combustion of pulverized coal

High-concentration H₂S formed in the reduction zone of pulverized coal air-staged combustion can result into the high temperature corrosion of water wall tube of boiler, so it is of great importance to accurately predict H₂S concentration for the safe operation of boilers and burners. H₂S formation and evolution depends on two steps: the sulfur release from coal conversion and gas-phase reactions of sulfur species. In this study, the sulfur release characteristics from the pyrolysis of 17 coals, including 5 lignite, 9 bituminous coals and 3 anthracites, are investigated in a drop tube furnace (DTF). Sulfur release model is developed to describe the relationship between sulfur release and coal types. A global gas-phase reaction mechanism of sulfur species composed of ten reactions is used to calculate and predict the formation and evolution of H₂S, COS and SO₂ in the reduction zone of pulverized coal air-staged combustion. A wide range of air-staged combustion experiments of 17 coals are conducted in the DTF at different temperatures and stoichiometric ratios to validate the developed model. The results show that the prediction errors of sulfur species, including SO₂, H₂S and COS, are within ± 30%, which indicates that the developed prediction model of sulfur species is of great assistance for CFD modeling of actual engineering application.