基于粒度分级的煤气化细渣特性分析及利用研究

煤气化过程中产生大量含碳量较高的气化细渣,目前主要以填埋方式处理,不仅占用大量土地,污染土壤和水体,同时造成能源浪费,对气化细渣进行高效环保的资源化利用是目前的研究热点。气化细渣中的残碳与灰组分分离是实现其高值化、减量化、无害化利用的关键,煤气化细渣粒度特性分析表明,各粒级产品灰分基本随粒级减小呈增大趋势,通过分级工艺可实现碳灰的分离与富集。榆林煤气化细渣固定碳含量随粒级减小均呈下降趋势,各粒级产品中均含有较多的SiO_2、Al_2O_3、Fe_2O_3、CaO,微观形貌主要由多孔基体、不规则颗粒、黏附小颗粒及圆球颗粒组成。煤气化细渣孔隙结构发达,比表面积丰富,75μm粒级产品可直接作为优质的吸附材料;与气化燃料煤相比,气化细渣各粒级产品燃烧的特征温度均显著提高,从着火温度看,除45 um颗粒外,着火特征温度都高于作为参照的无烟煤;由于气化细渣中丰富孔隙率的存在,增大了颗粒与氧气的接触面积,使燃烧中后阶段燃烧峰值温度低于无烟煤,且燃尽温度明显低于无烟煤。     

石油焦气化固态产物形成机理及对生产的影响

"粗渣"在气化反应以及灰分的双重影响下,其外观较煤气化装置所产生的"粗渣"有着较为明显的差别;"细渣"较煤气化装置的细渣粒径更细.针对石油焦气化装置产生"粗渣"和"细渣"与煤气化装置产生"粗渣"和"细渣"的问题,进步一探讨"粗渣"和"细渣"形成机理,对如何及时应对灰水水质的变化有着尤为重要的指导意义.     

煤气化渣特性分析及资源化利用研究进展

我国能源结构特点为富煤、贫油、少气,煤化工行业发展充满机遇和挑战。煤气化技术是现代煤化工的前端支柱,是实现煤炭清洁、高效、绿色、低碳利用的有效途径,具有重要的国家战略意义。煤气化技术规模化应用产生的大量固体废弃物(煤气化渣)的处置,是煤化工基地当前迫切需要解决的问题。分别从国内具代表性煤化工基地的气化灰渣粒度组成、矿物构成、微观形貌、表面性质和持水特性等理化性质入手,对比分析不同炉型、产地、气化工艺等条件下的灰渣特点。灰渣物性特点的差异化与气化工艺、炉型、煤种等因素均相关。灰渣主要组分为硅铝矿物等,其中粗渣粒度普遍偏大;细渣残炭质量分数一般在20%左右,且其表面含氧官能团丰富。此外,细渣因其孔隙率高,含水率较高。基于气化灰渣理化性质,系统归纳了目前报道的气化灰渣提质方法,提出炭-灰分离是实现气化灰渣减量化与资源化利用的重要前提。从高效回收微细粒矿物角度考虑,浮选是最合适的炭-灰分离方法,但由于残炭发达的孔隙结构与含氧亲水性基团的存在导致可浮性差,目前生产成本较高;从降低生产成本、提高处理量角度考虑,重力分选方法是首选,但存在分选下限高的问题;而磁力分选则对铁磁性矿物含量高的灰渣更具有针...     

多喷嘴对置式水煤浆气化炉炉渣特性研究

为实现多喷嘴对置式水煤浆气化炉炉渣资源化、减量化、无害化利用,对兖矿集团陕西未来能源化工有限公司气化炉粗渣和细渣进行分析,研究气化渣的粒度分布、烧失量、化学组成、显微结构、残碳分布、表面形态等特性,并对其综合利用方向提出建议。结果表明,气化细渣、粗渣烧失量均较高,粗渣为18.79%,细渣为30.57%,未燃碳是烧失量的主要成分,细渣未燃碳高于粗渣。未燃碳在粗、细渣中的分布具有一定规律性,细渣的碳含量随粒径增大而增加,粗渣碳主要分布在0.500~0.125 mm中等粒径。SEM结果表明,气化残渣中的物质由多孔不规则颗粒、黏结球形颗粒和孤立的大球形颗粒组成。其中,多孔不规则颗粒的主要成分为碳,球形颗粒主要成分为硅铝矿物。粗渣、细渣孔隙以4~10 nm介孔为主,细渣的孔结构和比表面积优于粗渣。试验炉渣可作为循环流化床掺烧燃料、废水处理吸附材料、建材掺混材料使用。     

煤粉掺烧气化细渣的燃烧特性研究

为有效地对气流床煤气化细渣进行资源化利用,研究了高活性神华煤和低活性宁夏煤掺混气化细渣的燃烧特性,探究了煤粉掺烧气化细渣燃烧反应的协同机理.结果表明:煤粉中气化细渣添加量的增加会导致燃烧过程灰渣出现不同程度的熔融现象,表明气化细渣内Ca和Mg等碱金属降低混合样品的灰熔融温度.在非等温及空气气氛的燃烧条件下,宁夏煤粉/气...     

煤气化细渣特性对其浮选脱碳过程的影响

含残炭量高严重影响煤气化细渣的处理和应用。煤气化细渣灰分容易黏附,但灰分和残炭之间并不发生灰熔融聚合,残炭以絮状无定型形态存在,并不和灰分形成小球体,这使得煤气化细渣中的残炭有可能通过浮选方法脱出。煤气化细渣的灰分亲水疏油,而残炭疏水亲油,有利浮选。煤气化过程中,残炭表面反应活性增大,零电位变化,因此煤气化细渣浮选适合的p H值与普通煤泥和粉煤灰不同。由于煤气化细渣的平均粒度一般小于40μm,不适合直接采用普通浮选机进行浮选,应采取改善微细粒浮选的有效途径,如保持微细粒悬浮体、增强残炭的疏水性、通过选择性聚团增大残炭的有效浮选粒径以及采用高效的微细粒浮选设备等方法。煤气化细渣浮选研究,需要针对具体的煤种和气化工艺。     

煤泥粒度组成与浮选工艺效果探讨

实验研究了某选煤厂入浮煤泥的粒度、密度组成以及浮选特性,提出只对小于0.25 mm粒级细煤泥进行浮选,将浮选精煤与大于0.25 mm粒级粗煤泥混合作为最终浮选精煤;采用改进后的工艺,浮选精煤灰分变化不大,但精煤产率可提高近4百分点。     

西北地区气流床煤气化细灰理化特性研究

气化细灰是气流床气化炉的出口粗煤气经过洗涤后黑水沉淀得到的产物,是一种煤基固体废弃物,尚无大规模资源化处置方案。为了开发气化细灰高效脱碳技术,利用激光粒度仪、元素分析仪、扫描电子显微镜及能谱仪、X射线衍射仪、X射线荧光光谱仪、BET比表面积分析仪、热重分析仪等分析设备针对我国西北地区3种气流床煤气化细灰(DSG、HL、SH)的化学成分、粒径、微观形貌、孔隙结构、熔融特性和燃烧特性进行分析。结果表明:气化细灰水分较高均在40%以上,热值均低于10 MJ/kg,挥发分低,且孔隙结构差,表面存在熔融渣层。较差的孔隙结构阻碍未燃碳与氧气接触,制约了气化细灰的脱碳反应。热重分析中DSG、HL、SH的失重率分别为13%、29%和17%,相比3种气化细灰中原本的残碳16%、37%和48%,DSG气化细灰残碳消耗81%,HL气化细灰残碳消耗78%,SH气化细灰残碳消耗35%。氧气浓度由21%升至30%,一定程度上提高了气化细灰反应活性。目前常规的燃烧脱碳技术无法实现气流床煤气化细灰的高效脱碳,因此需开发新型的燃烧脱碳技术,为气化细灰的资源化利用提供支撑。     

基于视密度的煤气化渣水介质旋流炭-灰分离

煤气化利用过程中会产生大量气化渣,造成很大的环境污染,其综合利用势在必行。本文系统分析了煤气化渣不同密度组分的特性,明确了炭-灰分离是煤气化渣分质综合利用的前提与基础,并提出了基于视密度差异的炭-灰分离方法。以水介质旋流器为分选设备,通过单因素试验确定了主要工艺参数对炭-灰分离效果的影响规律,验证了水介质旋流分选对煤气化渣>0.074mm粒级炭-灰分离的可行性。借助Box-Behnken试验设计分析了旋流器锥体角度、底流口直径、溢流管插入筒体深度与产品灰分、产品产率及分选综合效率的定量关系,为煤气化渣炭-灰分离效果的预测及旋流器结构参数的选择提供了数据支持。本文研究内容对实现煤气化渣分质资源化利用具有指导意义。     

煤气化细渣浮选脱碳分析

对煤气化细渣的浮选脱碳进行了研究。因煤气化细渣含残炭量高,制约了煤气化细渣的应用;而煤气化细渣的矿物组成和润湿性能与粉煤灰的指标大体相似,粉煤灰浮选已经工业化,气化细渣也具有浮选脱碳的可行性。通过分析论证发现,浮选脱碳是煤气化细渣脱碳的合适方法;气化细渣粒度微细,分布范围广,应采用分级浮选方法脱碳;对于40μm以下的颗粒,适合采用旋流-微泡浮选柱,而对于40μm以上的颗粒,适合采用机械搅拌式浮选机进行浮选。     

多喷嘴对置式气化炉中飞灰性质

On a laboratory scale opposed multi-burner gasifier (OMBG), the fly ashes at different sampling mouths are collected and analyzed by SEM, EDS, XRF and Malvern mastersizer. Most fly ash particles produced in the gasification are irregular, aggregate or spherical. As for the composition of the particles, carbon is the main content, while S, Fe and Na get enriched. At the same time, the concentration of Al and Si in the fly ash particles is lower than that in the original slag. From the nozzle plane to the exit of gasification chamber, the carbon content of particles decreases along the axes of gasifier. The carbon content of particles decreases rapidly from the nozzle plane to No. 7 sampling mouth and declines slowly from No. 7 sampling mouth to the chamber exit. The size of particles generated in the gasification appears a triple-humped-distribution with peaks at 0.1—0.2 μm, 2 μm and 14 μm. The particle size distribution in different sampling places is different. Above the impact plane, more ultra-fine particles are found and coarse particles are larger in location near the impact plane. In symmetrical up and down locations of the impact plane, the particle size distributions are similar, but there are more coarse particles below the impact plane. The coarse particle size decreases and the proportion of fine particles increases below the impact plane, while the proportion of coarse particles increases at the chamber exit.     

煤粉粒径对HNCERI气化炉碳转化率与固/液渣层分布的影响

以中国华能集团清洁能源技术研究院（Huaneng Clean Energy Research Institute,HNCERI）两段干粉加压气化炉为研究对象,采用考虑了焦炭颗粒表面气体组分扩散效应的随机孔模型计算焦炭气化反应速率以评估碳转化率。同时,耦合熔渣子模型计算气化炉一段壁面固液渣层分布特性和热损失,研究了煤粉粒径对HNCERI气化炉碳转化率和固液渣层分布特性的影响。结果表明所构建的模型可以准确预测气化炉出口主要气体组分组成、碳转化率和气化炉一段壁面热损失;气化炉一段碳转化率受固有气化速率和停留时间控制,二段主要受颗粒停留时间控制;因此,通过减小煤粉粒径可以减小气体在颗粒表面扩散阻力,有利于提高气化炉一段碳转化率,而适量增加煤粉粒径可以增加煤粉颗粒在气化炉二段的停留时间,有利于提高二段碳转化率。模拟结果显示煤粉颗粒粒径从20μm增加到200μm,一段碳转化率从99.68%降低到了95.06%,二段碳转化率从69.03%增加到了89%。煤粉粒径对气化炉上缩口和直段壁面液态渣层分布影响很小,但显著影响固态渣层厚度的发展。     

An understanding of lump coal physical property behaviour (density and particle size effects) impacting on a commercial-scale Sasol-Lurgi FBDB gasifier

Thermal processes which utilize coarse coal, such as fixed-bed gasification and chain grate stoker boilers, are dependant on a stable particle size for stable operation. During coarse coal utilization, thermal fragmentation of lump coal (upon heating) produces hydrodynamic effects (pressure drop fluctuations) manifesting itself in a variety of ways, and include: channel-burning and solids elutriation. Primary thermal fragmentation occurring in the drying zone of a fixed-bed reactor is primarily a function of moisture content release with ensuing particle size reduction. Large particles tend to fragment more than finer particles, thus leading to hydrodynamic problems. From fragmentation studies it was elucidated that a thermal “stable size” is reached through the process of thermal fragmentation for optimum heat transfer and utilization during the drying and pyrolysis zone regions of the coarse coal utilization process.In this paper, the Sasol-Lurgi MK IV FBDB gasifier turn-out physical property profiles (bulk density and particle size distribution) results will be discussed. It was found that these profiles provided significant insight into the complex heterogeneous nature of the coal transformation processes occurring within the fixed-bed reactor. In the case of the bulk density profile, a shrinking core and flaking mechanism was proposed to explain the increase in density occurring in the bottom half of the gasifier.The +25 mm size fraction distribution profile was found to clearly show the fragmentation effects occurring within the reactor. Primary fragmentation was inferred as the mechanism responsible for causing breakage of this size fraction down to a remaining ca. 15% +25 mm fraction. The significant breakage of the coarse +25 mm fraction is expected to influence unstable gasifier conditions in the top part of the gasifier, due to pressure drop fluctuations caused by void packing. A good correlation was obtained for the relationship between bulk density versus the ?25 mm + 6.3 mm size fraction content, indicating that the bed-packing density is highly dependent on the relative abundance of this intermediate size fraction. The ?6.3 mm size fraction distribution profile was found to not be significantly different between the four reaction zones identified in the gasifier. Breakage of the coarser +6.3 mm sizes occurred continuously, and could possibly be related to breakage caused by the ash-grate when sampling.The Ergun Index was successfully used to profile the fragmentation zones identified and to show areas within the gasifier where pressure drop and resultant instability occurs. This is the first-ever identification of this phenomenon occurring within a fixed-bed gasifier and is expected to lead to significant optimization challenges to ensure better stability.     

Carbon particle type characterization of the carbon behaviour impacting on a commercial-scale Sasol-Lurgi FBDB gasifier

Char-form analysis, whilst not yet an ISO standard, is a relatively common characterization method applied to pulverized coal samples used by power utilities globally. Fixed-bed gasification coal feeds differ from pulverized fuel combustion feeds by nature of the initial particle size (+6 mm, −75 mm). Hence it is unlikely that combustion char morphological characterization schemes can be directly applied to fixed-bed gasifier chars. In this study, a unique carbon particle type analysis was developed to characterize the physical (and inferred chemical) changes occurring in the particles during gasification based on coal petrography and combustion char morphology. A range of samples sequentially sampled from a quenched commercial-scale Sasol-Lurgi fixed-bed dry-bottom (FBDB) Gasifier were thus analysed.It was determined that maceral type (specifically vitrinite and inertinite) plays a pivotal role in the changes experienced by carbon particles when exposed to increasing temperature within the gasifier. Whole vitrinite particles and vitrinite bands within particles devolatilized first, followed at higher temperatures by reactive inertinite types. By the end of the pyrolysis zone, all the coal particles were converted to char, becoming consumed in the oxidation/combustion zone as the charge further descended within the gasifier.The carbon particle type results showed that both the porous and carbominerite char types follow similar burn-out profiles. These char types formed in the slower pyrolysis region within the pyrolysis zone, increasing to around 10% by volume within the reduction zone, where 53% carbon conversion occurred. Both of these char forms were consumed by the time the charge reached the ash-grate at the base of the reactor, and therefore did not contribute to the carbon loss in the ash discharge. It would appear as if the dense char and intermediate char types are responsible for the few percent carbon loss that is consistently obtained at the gasification operations.The carbon particle type analysis developed for coarse coal to the gasification process was shown to provide a significant insight into the behaviour of the carbon particles during gasification, both as a stand alone analysis and in conjunction with the other chemical and physical analyses performed on the fixed-bed gasifier samples.     

Characterization of unburned carbon present in coarse gasification ash

Depending on the mode of operation and quality of the feed material, discrete unburned carbon particles are evident in coarse gasification ash emanating from a commercial gasifier. Black, partially reacted carbon particles in the size range −13 + 4 mm were randomly hand picked from grab sample following a gasifier shutdown. These particles were classified into three major categories namely: unburned carbon, carbonaceous shale, and “shrinking core” particles. The unburned carbon particles were further macroscopically subdivided into remnant “coal” particles, solid carbon, layered carbon, and porous carbon. The unburned carbon particles were characterized using a petrographic analysis, reflectance analysis, chemical analysis, TGA mass loss curves, pore volume and surface area, and mineral characterization. The carbon particles were compared to the feed coal. The petrographic-based characterization technique as developed for the characterization of coarse unburned carbon particles indicated that remnant coal, devolatilised coal, highly porous isotropic carbon, dense anisotropic carbon, and variations in-between occurred in the coarse gasification ash sample.     

Coal and coal ash characteristics to understand mineral transformations and slag formation

A knowledge of the composition and structure of minerals in coal is necessary in order to understand the mineral transformations and agglomerate or slag formation during combustion or gasification. Coal ash fusibility characteristics are difficult to determine precisely, partly because the ash contains many components with different chemical behaviours, and may vary from coal source to coal source.The first objective of this study was to determine if the most relevant characteristics of coal were representative of the typical coal from the South African Highveld region. Secondly, a detailed understanding of the coal and coal ash are needed in order to explain slag formation and mineral transformations.Based on standard coal properties, such as the ash content, volatile content, carbon content and maceral composition, it can be concluded that the coal sample used for this study was representative and comparable with the coal from the Highveld region.From the results obtained and the analysis done on the coal samples, it was observed that the mineral grains showed a wide range of types that ranged from pure coal to pure minerals. The types of mineral particles within the coal range from large irregular minerals to small irregular minerals on the edge of coal particles. Kaolinite and quartz can occur as fine inclusions in carbon rich particles or associated with mudstone, siltstone or sandstone, together with kaolinite infillings. The main minerals present in the coal feed are kaolinite, quartz, dolomite, calcite, muscovite, pyrite and microline. An abundance of calcium-rich particles, which are probably calcite and dolomite, were observed. These minerals are present throughout the coal structure and are not specific to one type of mineral grain or structure. An increase in Si and Al abundance in three different prepared coal fractions with increasing particle size distribution was observed the high density fractions are mainly situated in the coarser particles.After combustion or gasification, the major source of glass is derived from included minerals in carbon rich particles. It is clear that focus on the modification of the unclassified/amorphous phase, to increase viscosity (decrease slag formation or have a higher concentration of crystalline phases) at a certain temperature, or in general terms the ash fusion temperature of the coal, is important. Altering the ash chemistry involves the addition of a material to the coal to increase the viscosity.     

水煤浆气化炉内飞灰的形成机理

基于实验室规模的多喷嘴对置式水煤浆气化炉,利用SEM、马尔文激光粒度仪和XRD表征气化炉内飞灰的粒径分布和组成,并分析了气化炉内飞灰的形成机理。结果表明,喷嘴平面处飞灰与气化炉出口处飞灰的粒径分布及化学组成存在显著差异,不同气化阶段飞灰的形成机理也不同。气化燃烧阶段飞灰的形成机理为部分固定碳燃烧和外在矿物转化,而在焦炭气化反应阶段,飞灰的形成机理为焦炭破碎和内在矿物释放及转化。     

气化对煤质的要求

介绍了气流床气化对煤质的要求,论述了煤的水分、反应活性、粒度和灰分对气化的影响。研究表明,煤的内水含量是决定煤浆性能的主要因素,灰渣的黏温曲线比灰熔点对气化炉的操作更具指导意义,选择在操作温度区间灰渣黏度变化平缓的煤种有利于气化炉的安全、平稳运行。     

德士古煤气化工艺运行方式总结

在全面总结德士古气化炉试运行经验的基础上,进行了优化煤种配比和降低气化操作温度等新尝试。经过一段时间的摸索和考察,肯定了高、低灰熔点煤种的混配可降低入炉煤的灰熔点,保证气流床熔融排渣气化工艺的稳定运行;在低于煤灰熔融温度下进行气化并实施固态排渣工艺是可行和有效的,经十余年的运行,其经济效益明显。     

The effect of coal particle size on pyrolysis and steam gasification

For future power generation from coal, one preferred option in the UK is the air-blown gasification cycle (ABGC). In this system coal particles sized up to 3 mm, perhaps up to 6 mm in a commercial plant, are pyrolysed and then gasified in air/steam in a spouted bed reactor. As this range of coal particle sizes is large it is of interest to investigate the importance of particle size for those two processes. In particular the relation between the coal and the char particle size distribution was investigated to assess the error involved in assuming the coal size distribution at the on-set of gasification. Different coal size fractions underwent different changes on pyrolysis. Smaller coal particles were more likely to produce char particles larger than themselves, larger coal particles had a greater tendency to fragment. However, for the sizes investigated in this study ranging from 0.5 to 2.8 mm, the pyrolysis and gasification behaviour was found not to vary significantly with particle size. The coal size fractions showed similar char yields, irrespective of the different char size distributions resulting from pyrolysis. Testing the reactivity of the chars in air and CO₂ did not reveal significant differences between size fractions of the char, nor did partial gasification in steam in the spouted bed reactor. From the work undertaken, it can be concluded that pyrolysis and gasification within the range of particle sizes investigated are relatively insensitive to particle size.