准东煤碱金属赋存形态及对燃烧特性的影响

实验研究了准东煤碱金属赋存形态以及不同萃取处理方式对其燃烧特性的影响.结果表明,准东煤的碱金属钠含量明显高于其他煤种,而钾的含量低于其他煤种.准东煤碱金属赋存形态与其他煤种差异很大,准东煤中的碱金属钠主要以水溶性钠形式存在.经过不同萃取方式处理后的准东煤样燃烧的DTG曲线均明显向高温区偏移,燃烧特性变差.萃取方式对准东煤样燃烧行为的影响存在显著差异,水溶性和有机形式的碱金属会对煤燃烧起到催化作用.     

不同灰化温度下准东煤碱/碱土金属的析出特性

实验考察了不同灰化温度下3种不同矿区的准东煤碱/碱土金属的析出特性。结果表明,随灰化温度升高,灰分含量减少,减少程度与煤灰成分有关;不同矿区准东煤灰中碱金属、碱土金属以及氯元素含量差别较大;灰化温度对碱金属 Na、K 元素析出的影响因煤样矿区不同而迥异,与碱金属的赋存形式有关;实验温度范围内(500～815,℃),碱土金属Ca、Mg元素的析出基本不受灰化温度的影响;煤灰中氯元素对碱金属的释放特性有影响。     

配煤对新疆准东高碱煤沾污结渣特性的影响

选用我国新疆准东地区某典型高碱煤和某低碱井工煤作为研究对象,研究了不同掺混比例对混煤灰熔融特性的影响,并应用相平衡理论对实验结果进行理论分析.结果表明:2种煤按不同比例混合后,由于混煤中的矿物质组成和煤灰化学成分发生变化,使得混煤灰的熔融特性也发生较大变化,混煤灰的熔融温度并不与2种煤的掺混比例呈线性变化关系,而与相应三元相图上的液相线温度具有一定的相似性;按照不同比例对不同煤样进行配比,可通过高温下煤中耐熔矿物质与助熔矿物质间的化学反应,改变混煤灰中的主要矿物质组成,减少高碱煤中Na、K等碱金属低温共熔物的生成,从而达到改变和调节煤灰熔融特性的目的.     

新疆高碱煤沾污结渣特性中试试验研究

为了深入研究新疆高碱煤沾污结渣特性,利用3 MW煤粉燃烧中试平台进行了典型新疆高碱煤燃烧过程中灰的生成及其沾污结渣特性研究。实验结果表明:在炉膛燃烧区域的渣样主要以含铁、钙矿物为主,如:磁铁矿(Fe3O4)、钙硅石(CaSiO_3)等;在高温对流受热面区域,由于煤中Na、K等碱金属的升华、冷凝作用以及沾污层与烟气中SO_2、飞灰颗粒之间的物理化学反应,其沾污层主要以熔点较低的无水石膏(CaSO_4)、无水芒硝(Na_2SO_4)以及Na-Al-Si和Ca-Al-Si的低温共熔体。这些低温共熔体在较低的温度下(850℃~1 150℃)具有较强的黏性,能够进一步捕捉烟气中的飞灰颗粒,加速沾污层厚度的增长,使得新疆高碱煤沾污层增长速度较其他易沾污煤要快得多。     

准东煤旋风燃烧过程碱金属迁移规律

为研究旋风燃烧过程对碱金属迁移的影响,对比研究了燃用准东煤的旋风炉和室燃炉内碱金属Na、K的迁移规律.结果表明:旋风燃烧条件下Na在渣中的存在形式为不可溶的硅铝复盐,而在灰中的存在形式为硫酸盐和硅铝酸盐;渣中不可溶的K被全部置换进入气相;与固态排渣的室燃炉相比,旋风炉具有较高的捕渣率,水平烟道飞灰中Na、K盐浓度会升高...     

温度对准东煤燃烧碱金属释放特性影响的激光测量研究

针对煤燃烧过程中释放的碱金属引起锅炉换热面沾污和腐蚀的问题,通过在线标定,利用激光诱导击穿光谱(LIBS)技术定量测量了准东煤燃烧过程中钠和钾随时间的动态释放特性;实验中利用一个自制的多射流燃烧器模拟真实火焰环境,在线测量得到准东煤燃烧过程中碱金属释放过程。实验发现煤燃烧过程的挥发分阶段、焦炭阶段、灰分阶段可以通过测得的碱金属释放曲线进行时间划分;随着温度升高,煤燃烧挥发分阶段、焦炭阶段、灰分阶段的Na、K释放速率均显著增加。     

烟气激冷对准东煤沾污特性的影响

在3 MW煤粉锅炉试验台和循环流化床(CFB)锅炉试验台上研究了烟气激冷对准东煤沾污积灰的影响,并用X射线衍射(XRD)和X射线荧光检测(XRF)对沾污物质进行了分析。结果表明:无论是煤粉锅炉还是CFB锅炉,烟气激冷均可减轻受热面的沾污;准东煤的初始沾污积灰主要是由Na2SO4造成的,而CaSO4被尚未凝结的Na2SO4捕捉,引起沾污加剧;烟气激冷使Na2SO4在接触沾污测试管之前就已凝结固化,从而起到减缓沾污的作用。     

还原条件下准东煤煤灰的凝结特性研究

本文使用灰熔融特性实验台,对还原性气氛下降温过程中准东煤煤灰的熔融特性进行实验研究,通过使用SEM(Scanning Electron Microscopy)、EDS(Energy Dispersive Spectrometer)和XRD(X-Ray Diffraction)等实验仪器,考察了不同温度激冷条件下的准东煤高温灰和低温灰凝结特性的差距,并对碱金属影响熔融态灰渣样品的凝结过程,进行了相应研究。研究结果表明,受晶体成核速率和晶体生长速率的影响,准东煤样品在降温激冷过程中,晶体成分的含量先增加再减少;准东煤样品晶体析出主要集中在800～1 200℃,出现了较为规则的图案和孔隙、棱角结构,元素出现了富集的情况;在灰渣降温过程中,析出的高温晶体类物质在熔融态玻璃体内形成了骨架结构,同时低温共熔物质填充了晶体骨架之间的孔隙结构。     

羧酸钠对五彩湾煤热解及煤焦热反应性的影响

针对准东煤中高含量有机钠对煤热解燃烧会产生不利影响的问题,通过向酸洗脱除碱金属后的五彩湾煤定向加载羧酸钠的方法,对比分析加钠煤和再次脱钠二次酸洗煤的热重曲线、气体产物及不同温度热解焦在低温下的热反应性,研究羧酸钠对五彩湾煤热解和焦反应活性的影响。结果表明:羧酸钠会显著促进五彩湾煤热解挥发分的释放及煤羧基官能团的热分解,在600℃以下抑制CO的生成,600℃以上时则相反,同时高温下会抑制脂肪侧链的分解及煤的缩聚反应;羧酸钠对煤焦的热反应性具有催化作用,主要由两条路径实现:在煤焦表面形成"C-O-Na"基团或钠团簇进行催化。     

洗煤对高碱煤碱金属迁移及灰熔融特性的影响

针对燃用某高碱煤种遇到的强沾污、结渣难题,对典型高碱煤种分别用去离子水、1 mol/L硝酸和1 mol/L醋酸铵进行了洗煤,并用电感耦合等离子体发射光谱仪(ICPOES)、X射线荧光仪(XRF)、和X射线衍射仪(XRD)等分析测试仪器对不同溶剂洗煤前后煤中的碱金属元素、矿物质组成进行了分析与测试。研究结果表明:3种洗煤介质对煤中Al和Si几乎没有脱除效果。但去离子水对煤中Na、K、S、Fe的脱除率在50%左右;硝酸和醋酸铵能对煤中Ca和Na的脱除率达到90%左右;洗煤后煤灰的熔融温度虽然变化不大(DT升高11~42℃),但洗煤后由于Na、S等碱金属的脱除,使得在灰的熔融过程中,初始液相析出温度由原煤的700℃升至900℃(硝酸)和1 100℃(醋酸铵);且初始液相析出的质量百分比也由17wt%降低至5.38wt%(去离子水)/5.09wt%(硝酸),这对降低高碱煤的沾污程度起着至关重要的作用。     

Impacts of alkali or alkaline earth metals addition on reaction intermediates formed in methanation of CO2 over cobalt catalysts

Additives affect the physiochemical properties of the catalyst as well as the evolution of the reaction intermediates produced during the reaction process such as the methanation of CO₂. In this study, Co/Al₂O₃ catalysts modified with Na, K, Mg or Ca were prepared and the reaction intermediates formed during CO₂ methanation were investigated. The results showed that Na, K or Mg species reacted with alumina, forming Al(OH)₃ or MgAl₂O₄ spinel structure, leading to the re-structure of the catalysts and a remarkable decrease of the specific surface area. The increased alkalinity of the catalyst did not promote the catalytic activity for methanation but promoted CO formation. The addition of Na or K enhanced the affinity of the catalyst to the reaction intermediates of HCOO* and CO₃²⁻, slowing down their further reduction to CH₄ and leading to the lower catalytic activity. The evolution of HCOO* and CO₃²⁻ species strongly correlated with the catalytic activity, while the direct correlation between the capability for the absorbance of CO₂* as well as the C–O functionality and the catalytic activity was not found. In addition, the addition of Na or K to Co/Al₂O₃ could also induce the formation of a significant amount of the coke species in the nanotube form.     

Impact of the modification method of Ni/ZrO2 catalyst by alkali and alkaline earth metals on its activity in thermo-chemical conversion of cellulose

The goal of this work is to determine an impact of the modification method of Ni/ZrO₂ catalyst by alkali and alkaline earth metals on its activity in thermo-chemical conversion of cellulose to hydrogen-rich gas. Me_xO-ZrO₂ supports (where Me = Ca, Mg, Na or K) were prepared by impregnation, precipitation and sol-gel methods. The obtained results reveal that an introduction of dopants to the zirconia support considerably enhances the H₂ yield in comparison to unmodified catalyst. An increase in the hydrogen formation is accompanied by a rise in the total volume of the produced gases. It is demonstrated that the highest amount of hydrogen is formed in the presence of the catalysts containing CaO-ZrO₂ support followed by Na doped materials. This phenomenon can be attributed to more efficient incorporation of Ca²⁺ and Na⁺ cations in the zirconia lattice making it more stable in the reaction conditions. Moreover, it is observed that an activity order of the investigated catalysts is consistent with the changes in the basic character of their surface.     

Investigation on PM formation from combustion of lignite with high contents of AAEMs (alkali and alkaline earth metals) and Fe: Effect of the reaction temperature

Coal-fired power plants require higher flexibility and a broader range of the operating temperature than before to accommodate the load regulation of the power grid. The relationship between the reaction temperature and the characteristics of particulate matter (PM) need to be better understood. In this study, Zhundong coal combustion was conducted in a drop tube furnace at different reaction temperatures in air. The PM characteristics and elemental contributions are investigated in detail. The experimental results show that the mass yields of PM_0.4 and PM_0.4-10 are non-monotonic with the reaction temperature. The competition between the generation of inorganic fumes and the removal of inorganic fumes by Si–Al-bearing minerals governs the mass yield of PM_0.4. At higher reaction temperature, generation of Ca, Mg, Fe-containing fumes increases, contributing most to the increment of PM_0.4; while the sulfation of chlorides is inhibited, resulting in more Cl in PM_0.4. The S content in PM_0.4 is mainly affected by the sulfation of AAEMs (alkali and alkaline earth metals) oxides. The mass yield of PM_0.4-10 is controlled by the competition between the fragmentation of char or mineral particles and the coalescence of mineral particles. For Zhundong coal combustion, the reaction temperature is recommended to be 1273K–1373K to control PM emission.     

Numerical analysis on combustion process and sodium transformation behavior in a 660 MW supercritical face-fired boiler purely burning high sodium content Zhundong coal

CHEMKIN software was used to optimize the reaction mechanism of sodium in flue gas to study the influence of targeted design for purely burning Zhundong (ZD) coal on boiler characteristics. Then, the optimized 32-step elemental reaction was combined with CFD software. An eddy-dissipation concept model considering detailed chemical reactions was used to simulate the transformation behavior of sodium-containing substances. The combustion characteristics of the 660 MW face-fired boiler under various loads were also simulated. The field distribution in the furnace and the migration path of sodium along the track of pulverized coal particles were obtained. The results show that the interference between each burner in the furnace is small at the BMCR load, and the phenomenon of “wind wrapping fire” is distinctly clear. The temperature at furnace outlet is approximately 970.98 °C. At a low load, the combustion in the furnace is stable, and the temperature at the furnace outlet reaches the design value. The sodium present in ZD coal is involved in the reaction after it is released in the form of Na and NaCl. Sodium is present in different forms in the main burner zone, mainly NaCl (67%), NaOH (12%), Na (9%), and Na₂SO₄ (7%). The forms of sodium at the furnace outlet are NaCl (50%), Na₂SO₄ (37%), Na₂Cl₂ (9%) and NaHSO₄ (4%). A small amount of Na₂SO₄ is formed by NaHSO₄ reaction in the main burner zone. It then reacts to form NaSO₄, wherein NaHSO₄ is formed by path 2. Na₂SO₄ is mainly generated in the burnout zone through path 1, and paths 2, 3, and 4 are hardly observed. The findings of this research can provide reference for the design of a purely fired ZD coal boiler and further studies on slagging observed on the heating surface.     

Kinetics study for sodium transformation in supercritical water gasification of Zhundong coal

Zhundong coal (ZDC) has attracted much attention due to its high alkali metal content which can lead to a series of problems such as furnace slagging and ash fouling. Supercritical water gasification (SCWG) become a better choice for ZDC coal utilization because of its unique chemical and physical properties. The transformation mechanism of alkali metals during SCWG process was different from conventional ways of coal utilization. Systematic research about it could hardly be found. In this study, ZDC was used to explore sodium transformation mechanism and kinetics during supercritical water gasification under typical conditions. We got four kinds of sodium including the water-soluble fraction (L1), the carboxylic matrix-associated fraction (L2), the macromolecular organic group-associated fraction (L3), and the inorganic silicate mineral fraction (L4) through sequential extraction method after SCWG. A reaction pathway of sodium transformation in supercritical water gasification was proposed. A quantitative kinetic model for describing sodium transformation mechanism was developed. Finally, it was found that, L1 played an important role in catalytic process and mineral in coal weaken the catalytic process by combining with L1. L2 and L3 served as the two important intermediate products in the coal gasification, which explained the catalytic mechanism of sodium. L3 showed better reactivity. Sodium finally tended to deposit in the form of NaSiAlO₄ (L4) which was stable and environmentally friendly. All of these could provide basis for high-efficiency utilization of ZDC and the design of a reactor.     

煤/石油焦共气化过程中AAEM的催化转化行为

以富含碱金属及碱土金属的准东煤和石油焦为原料,在热重反应器上分别进行了水蒸气及CO2条件下的共气化实验,探究了AAEM的赋存形态对其转化行为及燃料气化特性的影响规律.研究表明,准东煤与石油焦在水蒸气条件下的共气化反应速率明显快于CO2条件,来自煤中的AAEM促进了石油焦的气化.在CO2气氛中,不同赋存形态矿物的催化作用存在较大差异,盐酸溶态的Ca起主要催化作用,并在气化过程中生成CaS.而在水蒸气气氛中,不同赋存形态矿物的催化作用差异较小,气化过程中含Ca组分主要生成CaO.     

Characterization and performance of common alkali metals and alkaline earth metals loaded Mn/TiO2 catalysts for NOx removal with NH3

The influence of four common alkali metals and alkaline earth metals (Na, K, Mg and Ca) on Mn/TiO₂ catalysts for selective catalytic reduction of NO_x with NH₃ was investigated. K, Na and Ca deactivated the catalysts and the deactivation effects were shown in sequence as K > Na > Ca, while Mg improved the capability of the catalysts. Furthermore, physical and chemical properties of catalysts were characterized by XRD, H₂-TPR, NH₃-TPD, BET, FESEM, XPS, TG and in situ DRIFTS analyses. Characterization results suggested that the obvious decrease of NH₃ adsorption and surface redox ability and the formation of inactive compounds could take credit for the deactivation caused by alkali metals and alkaline earth metals except Mg. The atomic concentrations of Mn³⁺ and relative concentration ratios of O_α/(O_α+O_β) on the surfaces were also important factors for SCR activities of Mn/TiO₂ catalysts doped with the main group IA elements (Na and K). The in situ DRIFTS tests further confirmed that the alkaline size resulted in the considerable changes in the desorption strength of ammonia which was in accordance with the NH₃-TPD results. Meanwhile, the slight decrease of NH₃ adsorption and surface redox ability and the formation of MgMn₂O₄ appeared to be directly correlated with the better SCR performance of the catalysts doped with Mg. Moreover, acid site and redox site played important roles in the catalytic cycle for Mn/TiO₂ catalysts during the NH₃-SCR reaction.     

生物质热化学转化过程中碱金属问题的相关研究

介绍了生物质中碱金属元素的存在形态及其测定方法,分析了生物质热化学转化过程中碱金属的析出、迁移规律及其影响因素。最后提出了几种减轻碱金属问题的措施,指出了今后的研究方向,为生物质的开发利用提供有价值的参考。     

Release and transformation characteristics of Na/Ca/S compounds of Zhundong coal during combustion/CO2 gasification

Zhundong (ZD) coal from northwest China is a high quality steam coal with reserves of more than 390 billion tons. However, the utilization of ZD coal is limited due to the high content of alkali and alkaline earth metals. This study aimed at revealing the release and transformation mechanism of Na/Ca/S compounds during combustion/gasification of ZD coal. The results demonstrate that Na was primarily influenced by temperature, mostly releases at 600–800 °C. The transformation of Ca compounds was affected by both temperature and atmosphere. The high temperature of the combustion process could accelerate the decomposition of CaCO₃ and CaSO₄, and the high content of CO₂ during gasification prolonged the decomposition of CaCO₃. The transformation of S was primarily influenced by atmosphere. SO₂ could react with CaO and form CaSO₄ during the combustion process. While S compounds were mainly released as S (g) and H₂S (g) during gasification process. There was a significant interaction among Na/Ca/S compounds during combustion, original CaSO₄ in coal could adsorb Na compounds with SO₂ at 600–800 °C and then reacted with aluminosilicates, by this reaction, Na could be fixed above 1000 °C.