Feasibility studies on cleaning of high sulfur coals by using ionic liquids

Coal has been used as an energy resource around the world, primarily for the generation of electricity. The cleaning of coal by removing its unwanted sulfur and mineral matter components is utmost essential before their gainful utilizations. The ionic liquids （ILs） are considered as non-toxic solvents for using in different industrial processes. The effect of two ILs namely, 1-n-butyl, 3-methylimidazolium tetrafluoro borate （ILl） and 1-n-butyl, 3-methylimidazolium chloride （IL2） in oxidative de-sulfurization and de-ashing of two industrially important high sulfur coal samples from Meghalaya （India） is discussed in this paper. The maximum removal of total sulfur, pyritic sulfur, sulfate sulfur and organic sulfur are observed to be 37.36 %, 62.50 %, 83.33 % and 31.63 % respectively during this oxidative process. The quantitative diffuse reflectance Fourier transform-infrared spectroscopy analysis supports the formation of sulfoxides （S--O） and sulfones （-SO2） and their subsequent removal during the oxidation of the coals in presence of ILs. The X-ray fluorescence combined with near edge X-ray absorption fine structure and scanning electron microscopic studies reveal the removal of mineral matters （ash yields） from the coal samples. The thermogravimetric analysis of the raw and clean coals indicates their high combustion efficiencies and suitability for using in thermal plants. The method is partially green and the ILs could be recovered and reused in the process.

Physico-chemical and elemental investigation of aqueous leaching of high sulfur coal and mine overburden from Ledo coalfield of Northeast India

Acid mine drainage （AMD） is one of the major problems in high sulfur coal mining areas generating acidic water. The acidic mine water generated contain hazardous elements in varying concentrations. The Northeastern Indian coalfield produces considerable amounts of AMD. The AMD and metal leaching from coal and mine over burden （OB） are the two important naturally occurring processes. In order to know the AMD potential, the aqueous leaching experiment of a few coal and OB samples from the Ledo colliery of the Northeastern coalfield, Mergherita （India）, at different time periods （1, 3, 5, and 8 h） and at different temperatures （25, 45, 65, and 90℃） were performed in the laboratory. The physico- chemical analysis of the aqueous leachates shows the pH, electrical conductivity （EC）, and total dissolved solid （TDS） in the range of 1.62-3.52, 106-2006 μs/cm, and 106-1003 ppm for the raw coal samples respectively. The OB samples produced pH, EC, and TDS in the range of 3.68-6.92, 48.6-480 μs/cm, and 69.5-240 ppm respectively. From the study, it was revealed that the concentrations of major （Si, A1, K, Na, Fe, Ca, Mg）, minor （Mn） and trace/hazardous elements （As, Ba, Cd, Co, Cr, Cu, Hg, Ni, Pb, Se, Zn） considerably change with leaching time as well as with leaching temperature. Out of these elements As, Cd, Hg, Pb, Cr, and Se are of greater environmental importance. Alteration of the physico-chemical structure of the coal and OB samples resulting from leaching was also studied by field emission scanning electron microscope- energy-dispersive X-ray spectroscopy method. The release of the potentially hazardous elements from the raw coal and OB during leaching time periods to the leachates was detected by inductively coupled plasma-atomic emission spectroscopy and ion-chromatographic analyses. The major minerals found in coal and OB are quartz （SiO2）, pyrite （FeS2）, hematite, marcasite, and kaolinite. The association of different functional groups in minerals and their mode of association were studied by Fourier-transform infrared spectroscopy and X-ray diffraction analytical techniques. The present laboratory study will be useful in relating the characteristics of aqueous leaching from coal and mine OB with the natural weathering condition at the coal mine area.

THE APPLICATION OF REVERSE FLOCCULATION METHOD IN HIGH SULFUR COAL DESULFURIZATION

The reverse flocculation method for removing pyritic sulfur from high sulfor coals has been conceptually beveloped and investigated. The tentative tests on China high sulfur coals have shown that this advanced physical separation techaique can be very efficient in coal desulfurization, provided the process parameters are properly optimized. Under the circumsances of acquiring high coal recovery, the total sulfur rejection with four kinds of coal samples normally falls in tbe range 57% to 71 % by one-step reverse flocculation, and within the range 40% to 59% by one-step normal flocculation process.

REE Geochemistry of Moderate-and High-Sulfur Coals from North Shanxi, China

Contents of the rare-earth elements (REE) in two coal seams from North Shanxi Province, China, were determined using the instrumental neutron activation method. Based on the REE distribution patterns, and correlation analysis and cluster analysis, the main conclusions were drawn as follows. The REE contents are controlled mainly by the coal-forming environments, but might be affected by acidic solution leaching after peat sedimentation. The REE distribution patterns should be nearly the same in the sublayers of the same coal seam, and the occurrence of abnormal patterns might indicate the geological effect during post-sedimentation. The REE in coals are present mainly in the inorganic phase, and might be derived mainly from terrigenous detrital minerals. Some harmful elements, such as V, P, Mo, Cr, Cu, Mo, Th and Cd, might have cleaning potential during processing and dressing by washing because they are associated with REE.

Research on Factors Affecting Flotation and Desulfurization of Coal by Electrochemical Method

Influence of factors such as potential of electrolyte, electrolyzing time, concentration of electrolyte, and pH value on flotation and desulfurization of coal was researched. The result shows that the electrochemical reduction can enhance the desulfurization effect and increase the yield of clean coal under certain conditions. So it is an effective method.

STUDY ON REGULATIONS OF SULFUR OCCURRENCE AND PYRITE MAGNETISM OF LATE PERMIAN COALS IN SOUTHWEST CHINA

The Permian coal in southwest China contains highest sulfur among the Chinese coal .Compositional variations of sumir in coal are mainly controlled by palaogeographital environmentsduring peat accumulation. High organic sulfur coal is formed in peat swamp developing in tidal flat of limited carbonate platform, and it is provided with especial petrologital and geochemical characteristics, and its organoschr-containing compounds are mainly thiophene series. The macroscopitaland microscopical shapes or types of pyrites in Late Permisn coal are diversined. Bituminous coal and anthracite are diamagnetic, but the pyrites are paramagnetic. The magnetic susceptibility oftbe pyrites is depended on the content of paramagnatic elements associnted with pyrites.

Mechanism of sulfur capture during coal briquette combustion

The mechanisms of sulfur capturing during coal briquette combustion was discussed. Various factors affecting sulfur removal efficiency have been studied. Characterization of the slag left after combustion has been carried out by using X ray diffraction (XRD), Messbauer spectroscopy (MS), scanning electron microscopy (SEM), energy dispersion X ray analysis (EDAX), and electron spectroscopy for chemical analysis (ESCA). No other sulfur containing species besides CaSO 4 was found. Small amount of CaFe 3(SiO 4) 2OH, some complexes of CaO SiO 2 Fe 2O 3 and vitreous iron oxides were identified on the surface of CaSO 4 grains. This might explain the mechanism of sulfur fixation during coal briquettes combustion.

电石渣和煤矸石对型煤固硫性能的影响及作用机制研究

研制高效低成本的耐高温固硫剂和添加剂有助于解决型煤高温燃烧环境下钙基固硫产物的分解问题。电石渣和煤矸石属于典型的工业固体废弃物,利用固废作为添加剂制备固硫型煤有助于降低固硫型煤成本和挖掘固废资源价值,发挥这两种固废中矿物组分协同作用可改善高温条件下型煤固硫效果。开展了电石渣和煤矸石分别作为固硫剂和添加剂制备环保型煤的研究,考察了固硫剂种类(碳酸钙、氧化钙、氢氧化钙和电石渣)、钙硫物质的量比(1.5~4.0)、燃烧温度(900℃~1300℃)、煤矸石用量(2%~7%)对型煤固硫效果的影响。通过型煤燃烧评价实验发现,仅用电石渣作为固硫剂,在钙硫物质的量比为3.0时制得的型煤在燃烧温度低于1000℃时固硫率能达到80%以上,燃烧温度提高到1300℃时型煤固硫率下降40%,结合分析表征数据发现主要原因是固硫产物硫酸钙的高温分解。添加的煤矸石在高温条件下被电石渣组分活化后起到辅助固硫作用,当添加的煤矸石的质量分数达到5%时型煤的固硫率能维持在60%以上,在此基础上增加煤矸石用量并不能明显提升型煤固硫率。通过固硫产物热稳定性研究并结合分析表征数据发现,高铝煤矸石灰渣活性组分发生高温反应生成硫铝酸钙、钙黄长石、硅酸三钙等耐高温稳定物相,在一定程度上抑制了CaSO_(4)的分解,从而提高了型煤的高温固硫率。

掺杂秸秆的高硫煤气化脱硫行为研究

通过热重分析法研究高硫肥煤与玉米秸秆混合物的热解动力学,并利用Coats-Redfern法计算混合物的活化能、指前因子。通过对其混合物的热解实验,发现掺杂玉米秸秆对高硫煤有明显的脱硫作用。

燃用高硫煤锅炉空预器选型分析

为有效解决2×660MW燃用高硫煤超超临界机组空预器堵塞问题,研究了回转式空预器和管式空预器特性,分析了机组特点,提出了回转式空预器和管式空预器两级换热器串联方案,并探究了该方案对机组锅炉效率的影响。研究表明,相比于常规回转式空预器方案,采用回转式空预器和管式空预器两级换热器串联方案时,回转式空预器的出口排烟温度高于烟气酸露点,有效解决了机组空预器腐蚀堵塞问题,同时在保证设备安全下使锅炉效率提高1%。

高硫煤基多孔碳材料的可控制备及其用于锂硫电池

高性能、低成本的多孔碳材料是理想的锂硫电池硫宿主材料,但利用廉价的原料实现其规模化制备仍面临巨大挑战。以资源丰富的高硫煤为原料,采用氧化镁和氢氧化钾作为模板剂和活性剂,制备了煤基多孔碳材料,并研究了其作为锂硫电池硫宿主材料的构效关系。研究发现,煤基碳材料制备过程中,模板剂MgO作用下产生介孔(占比74%);活性剂KOH主要导致微孔(占72%)生成;MgO和KOH共同作用制备的碳材料PCMgO+KOH比表面积大(1616 m^(2)/g)、孔容高(1.02 m^(3)/g)、孔结构丰富(介孔54%、微孔46%)。电化学性能测试结果表明,S@PCMgO+KOH具有良好的倍率性能和优异的循环稳定性,在1 C充放电倍率循环500圈后容量仍能保留553.2 mAh/g,容量保持率达65.5%,每个循环的衰减率低至0.069%;在2 C下,循环500圈后容量为484.0 mAh/g,容量保持率为63%,每圈衰减率仅0.075%,具有良好的倍率性能和优异的循环稳定性。PCMgO+KOH优异的电化学性能主要来自其较小的欧姆电阻和电荷转移电阻、快速的多硫化物氧化还原反应动力学及对多硫化锂优异的束缚能力。本研究为价廉性高的锂硫电池硫宿主材料的制备提供了可选择的路线。

高硫煤矸石协同飞灰制备多孔玻璃物相转变机理

采用高硫煤矸石协同垃圾焚烧飞灰制备多孔玻璃,同时利用玻璃体固定垃圾焚烧飞灰中的Pb、Cd、Zn、Cr、Cu、Mn等重金属,实现多源固废、危废协同无害化处置和资源化利用。针对多孔玻璃轻质和高强度难以兼顾的问题,一方面,通过还原气氛抑制残碳在中低温氧化反应,使高硫煤矸石中残碳在1000℃以上与Fe_(2)O_(3)反应生成CO_(2)气体,促进熔体发泡,多孔玻璃容重由900 kg/m^(3)降低至300 kg/m^(3);另一方面,通过在配合料中添加高岭土,使多孔玻璃孔壁的主要晶相由长石转变为莫来石,莫来石独特的交联结构使多孔玻璃具有较高强度。当容重在500 kg/m^(3)时,多孔玻璃强度提升了80%。多孔玻璃重金属浸出毒性分析结果表明,各种重金属的浸出浓度远远低于规定的标准限值(5.0 mg/L),多孔玻璃中重金属Pb的浸出浓度降低至1.1×10^(-2)mg/L,其它重金属的浸出浓度也普遍呈现出显著的下降趋势,说明多孔玻璃对多元重金属具有良好的固定效果。

高硫无烟煤制备柱状活性炭对Cu^(2+)的吸附规律及影响机制

高硫无烟煤燃烧时会产生大量硫氧化物,破坏大气环境,随着环保要求日益严格,需寻求高硫无烟煤由传统燃料向高端材料发展的途径。由于活性炭制备与应用在特定领域尚无技术指标,造成制备目标模糊,活性炭定向制备问题亟需解决。采用晋城地区高硫无烟煤,通过物理活化法制备,并采用磷酸浸渍处理,得到了比表面积1066.42 m^(2)/g(AC-1)和1568.79 m^(2)/g(AC-2)的2种活性炭。采用FTIR、XPS、SEM等方法进行表征。结果表明,AC-1的最几可孔径为1.688 nm,AC-2的最几可孔径为0.718 nm,前者具有更发达的介孔结构。以Cu^(2+)为吸附质研究2种活性炭的吸附性能。结果表明,AC-1的吸附性能显著优于AC-2,吸附行为由孔径分布和表面官能团含量2个因素共同决定。最佳吸附条件为pH=4,温度35℃,活性炭投加量0.30 g,吸附时间2 h。动力学研究表明2种活性炭对Cu^(2+)的吸附过程均由化学吸附而不是颗粒内扩散控制。吸附等温线拟合结果表明Langmuir等温模型不适用于AC-2,这可能与其以物理吸附为主导有关。本研究讨论活性炭孔隙分布和表面官能团含量对其吸附性能的影响,为高硫无烟煤定向制备具有良好水相重金属离子去除能力的活性炭提供指导。

红沙岗高硫煤循环流化床富氧气化炉内脱硫试验研究

为进一步拓宽兰石金化首套千吨级循环流化床加压煤气化示范项目原料来源,解决甘肃省武威市民勤县红沙岗2号煤矿高硫煤(以下简称“红沙岗高硫煤”)使用下游脱硫成本过高的问题,在5 t/d的新型循环流化床富氧气化中试试验平台上,进行了红沙岗高硫煤气化炉内石灰石干法脱硫试验,考察了在气化温度为920~980℃、钙硫摩尔比为1∶1~1.5∶1的工况条件下煤气脱硫效果。结果表明,在温度为950℃、钙硫比为1∶1、富氧浓度为35.46%条件下,气化炉内脱硫效率达75.30%,脱硫效果显著,可减少下游脱硫装置投资和运行成本,综合效益明显。

燃烧高硫煤对冲锅炉水冷壁高温腐蚀研究

针对某电厂哈尔滨锅炉厂设计制造的HG1021/18.2-YM3型亚临界自然循环锅炉水冷壁高温腐蚀问题进行了研究,在检修期间了解到水冷壁存在较为突出的腐蚀问题,并针对问题提出风向调整和假想切圆直径改造方案,了解改造后水冷壁高温腐蚀问题的改善效果。分析认为与低氮改造后空气分级燃烧技术、四角切圆燃烧器直径过大有关;通过改造后炉内速度场、温度场、CO浓度场和O_(2)浓度场、H_(2)S浓度场观察,证实改造方案可改变火焰冲刷问题、缩小高温区域、提升氧化性气氛,调节炉内H_(2)S浓度。最后通过实际工程验证,改造后方案可有效改变水冷壁重点区域高温腐蚀问题。

韦州矿区煤中硫分布特征及形成机制研究

为提高对韦州矿区煤中硫的系统认识,促进煤炭资源的高效利用为目的,从平面上分析了矿区煤中硫的分布特点及垂直上的分异机理,对韦州矿区煤中硫的形成机理进行了探讨。分析认为:韦州矿区含硫等级低至中等偏高,高硫煤呈间或分布状态;各主采煤层的硫分与成煤时代密切相关。

3×135MW循环流化床锅炉湿法脱硫工程改造设计研究

自备电厂燃煤锅炉实际使用燃煤特性与设计值偏离,尤其是入炉煤的低位发热量降低和含硫量升高,导致烟气中二氧化硫排放浓度大幅度增加。而环保要求更为严格,烟气中二氧化硫的排放浓度限制从之前的400mg/m^(3)降低到50mg/m^(3)。由于以上两个原因,原先安装的炉内脱硫系统无法满足锅炉的大气环保排放要求。需要采用效率更高、技术更成熟的石灰石-石膏湿法脱硫工艺对自备电站三台锅炉进行脱硫工程改造,以实现锅炉烟气的SO2达标排放。

气化无烟煤高效助熔剂研究与实践

研究了晋城矿区高硫无烟粉煤的煤灰特性,特别是灰熔点和黏温特性。针对这些特性,通过大量基础分析和试验,采用添加助熔剂的方法,成功将入炉煤灰熔点降低至1300℃左右,保证了气化炉的稳定运行。

高硫分燃煤电厂超低排放颗粒物排放特性分析

某高硫分燃煤锅炉在经过超低排放改造后,颗粒物排放浓度仍较高,检测发现锅炉脱硫装置出口颗粒物存在较多亚微米级颗粒物,主要包含飞灰、SO_(3)胶体、硫酸钙结晶体以及少量含碳物质,通过进一步分析,烟气温度会影响电除尘器去除粉煤灰、SO_(3)的能力,控制电除尘器入口烟气温度低于120℃,能有效提升细小飞灰、SO_(3)去除效率。

介孔氧化硅分子筛负载金属氧化物高温煤气脱硫剂结构调控与脱硫过程放硫的研究进展

煤气化是煤炭清洁高效利用的核心技术,但气化粗煤气中所含硫化氢(H_(2)S)会腐蚀设备并污染环境,因此需要对煤气进行净化脱硫。介孔氧化硅分子筛具有大比表面积、大孔容和有序的介孔结构等特性,将其作为金属氧化物的载体可促进金属氧化物的分散,并为脱硫反应提供大量的反应活性位点,减少传质阻力。脱硫剂构效关系是煤气脱硫技术的关键科学难题之一,然而对于负载型高温煤气脱硫剂而言,上述关系受介孔氧化硅分子筛、脱硫活性组分种类、脱硫剂改性手段和脱硫条件等多因素叠加影响,因而要明晰其本质极具挑战。为此,首先探讨了不同介孔氧化硅分子筛的孔道结构特性,剖析了介孔氧化硅分子筛负载活性组分后的脱硫行为差异,发现拥有丰富孔结构及较厚孔壁的载体的脱硫剂在高温脱硫过程中表现更优。同时,分析了近年来针对锌基、锰基和铁基等金属氧化物负载型脱硫剂的结构调控策略及其对脱硫性能的影响规律,认为通过金属掺杂复合改性可提高活性组分脱硫活性;并对脱硫过程中的放硫机制、放硫规律及抑制手段进行了探讨,认为在脱硫剂中引入催化羰基硫(COS)氢解助剂可有效抑制放硫行为。本综述内容可为高性能高温脱硫剂结构设计与功能化构筑提供理论依据。