Speciation and thermal transformation of sulfur forms in high-sulfur coal and its utilization in coal-blending coking process:A review

The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.

Influence of coal blending on mineral transformation at high temperatures

Transformation of mineral matter is important for coal utilization at high temperatures.This is especially true for blended coal.XRD and FTIR were employed together to study the transformation of mineral matter at high temperature in blended coals.It was found that the concentration of catalytic minerals, namely iron oxides, increases with an increasing ratio of Shenfu coal, which could improve coal gasification.The transformation characteristics of the minerals in blended coals are not exactly predictable from the blend ratio.This was proved by comparing the iron oxide content to the blending ratio.The results from FTIR are comparable with those from XRD.FTIR is an effective method for examining variation in mineral matter.

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.

Matter Composition and Two Stage Evolution of a Liangshan Super High-Sulfur Coal Seam in Kaili,Eastern Guizhou

Super-high sulfur coal resultes in serious coal-derived pollution but might have a particular genesis. Thus,a columnar section of an Early Permian Liangshan Formation coal seam. weight average sulfur content 5.80%,from Kaili,eastern Guizhou,was studied using the methods of coal petrology and geochemistry. The results show that the seam was apparently formed in seawater-effected peat bogs that developed in two distinct stages. During the first stage various layers were formed in a supratidal bog and have a composition characteristic of a bog with a gradually decreasing sea-water effect,decreasing water dynamics,and an increasingly reductive environment. Layers in the upper seam formed during a second stage in an intertidal bog. These layers are very high in total and inorganic sulfur,the ratios of or-ganic/inorganic sulfur and V/I drop,they are high in coal ash yield and have a high ash component index,considerable barkinite,oxidized and detrital macerals,have a porphyroclatic micro-structure and are rich in pyrite,all of which indi-cate the coal-forming environment had higher oxidation potential,strong and roiling water dynamics,and intermittent exposure to a sulfur rich environment.

Experimental Research on Spontaneous Combustion Tendency of High Volatile Blended Coals

Experiment of oxidation characteristics with slow velocity of high volatile blended coals was investigated in the surroundings of low oxygen conditions, which gives three kinetic factors in the step of low temperature through the methods of thermo gravimetric analysis, the Coats-Redfern integration and Achar-Brindley-Sharp-Wendworth. The results of calculation show that activation energy and pre-exponential factor increase with the reaction process, and tendency of spontaneous combustion of the blended coal have changed. The experimental results show that the type of absorbing oxygen is mainly physical adsorption and calorific value is very small during increasing weight. Volatile of blended coal releases before single coal and combustion temperature of blended coal is between one and other single coals. If the oxygen content is below 16% in the milling system, explosion-proof effect on high volatile blended coal can be obtained.

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.

Characterization and Desulfurization Possibilities of High Sulfur Gediz-Turkey Coal

Coal is one of the important energy sources, but it causes serious environmental problems such as air pollution, acid rain and greenhouse effects. Sulfur in coal is one of the responsibilities of these negative effects. Coal includes two types of sulfur： organic and inorganic. While inorganic sulfur can be completely removed with physical desulfurization methods, organic sulfur can be removed only by chemical desulfurization methods. But chemical methods are not only expensive but also difficult processes. Firstly in desulfurization, types of the sulfur content in coal should be well characterized. High sulfur Gediz-Turkey coal has been chosen to this study. This coal basin is located in the centre of the Turkey. In this study, characterization and desulfurization possibilities of high sulfur Gediz coal were investigated. For this purpose, several physical and chemical characterization methods such as proximate and ultimate coal analysis （ash, calorific value, volatile matter, moisture and sulfur analysis）, mineralogical and petrographic analysis, fourier transform infrared spectroscopy, scanning electron microscope were used. Results of these analysis are shown that Gediz coals include 3.15% pyritic sulfur and 2.89% organic sulfur. Removing pyritic sulfur from Gediz-Turkey coal with physical methods such as gravity and sink-float separation is not possible because pyrite particle has 1-2 micron liberation size in coal.

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。

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。

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。

高挥发分气煤在配煤炼焦中的应用探究

为扩展炼焦用煤资源范围,合理高效利用不同类型煤炭资源,开发新的可用于炼焦生产的煤炭资源,以山西焦化股份有限公司炼焦生产配煤方案为基础,选取一种高黏结性、高流动度、高挥发分的气煤,分析其与基础配煤中气煤、中黏煤的煤质特性差异,通过40 kg焦炉炼焦试验,考察了高挥发分气煤对配煤焦炭质量的影响。结果表明:高挥发分气煤以适宜比例替代配煤中部分气煤或中黏煤,配煤焦炭质量明显高于基础焦炭,且配煤成本降低。