Experimental study on the activation of coal gasification fly ash from industrial CFB gasifiers

Coal gasification fly ash(CGFA)is an industrial solid waste from the coal circulating fluidized bed(CFB)gasification process,and it needs to be effectively disposed to achieve sustainable development of the environment.To realize the application of CGFA as a precursor of porous carbon materials,the physicochemical properties of three kinds of CGFA from industrial CFB gasifiers are analyzed.Then,the activation potential of CGFA is acquired via steam activation experiments in a tube furnace reactor.Finally,the fluidization activation technology of CGFA is practiced in a bench-scale CFB test rig,and its advantages are highlighted.The results show that CGFA is characterized by a high carbon content in the range of 54.06%–74.09%,an ultrafine particle size(d50:16.3–26.1 μm),and a relatively developed pore structure(specific surface area SSA:139.29–551.97 m^(2)·g^(-1)).The proportion of micropores in CGFA increases gradually with the coal rank.Steam activation experiments show that the pore development of CGFA mainly includes three stages:initial pore development,dynamic equilibrium between micropores and mesopores and pore collapse.The SSA of lignite fly ash(LFA),subbituminous fly ash(SBFA)and anthracite fly ash(AFA)is maximally increased by 105%,13%and 72%after steam activation;the order of the largest carbon reaction rate and decomposition ratio of steam among the three kinds of CGFA is SBFA>LFA>AFA.As the ratio of oxygen to carbon during the fluidization activation of LFA is from 0.09 to 0.19,the carbon conversion ratio increases from 14.4%to 26.8%and the cold gas efficiency increases from 6.8%to 10.2%.The SSA of LFA increases by up to 53.9%during the fluidization activation process,which is mainly due to the mesoporous development.Relative to steam activation in a tube furnace reactor,fluidization activation takes an extremely short time(seconds)to achieve the same activation effect.It is expected to further improve the activation effect of LFA by regulating the carbon conversion ratio range of 27%–35%to create pores in the initial development stage.

Ash Detection of Coal Slime Flotation Tailings Based on Chromatographic Filter Paper Sampling and Multi-Scale Residual Network

The detection of ash content in coal slime flotation tailings using deep learning can be hindered by various factors such as foam,impurities,and changing lighting conditions that disrupt the collection of tailings images.To address this challenge,we present a method for ash content detection in coal slime flotation tailings.This method utilizes chromatographic filter paper sampling and a multi-scale residual network,which we refer to as MRCN.Initially,tailings are sampled using chromatographic filter paper to obtain static tailings images,effectively isolating interference factors at the flotation site.Subsequently,the MRCN,consisting of a multi-scale residual network,is employed to extract image features and compute ash content.Within the MRCN structure,tailings images undergo convolution operations through two parallel branches that utilize convolution kernels of different sizes,enabling the extraction of image features at various scales and capturing a more comprehensive representation of the ash content information.Furthermore,a channel attention mechanism is integrated to enhance the performance of the model.The combination of the multi-scale residual structure and the channel attention mechanism within MRCN results in robust capabilities for image feature extraction and ash content detection.Comparative experiments demonstrate that this proposed approach,based on chromatographic filter paper sampling and the multi-scale residual network,exhibits significantly superior performance in the detection of ash content in coal slime flotation tailings.

煤矿采动影响体微生物采残煤与CO_(2)-粉煤灰协同充填关键技术

煤矿采空区是我国实现“双碳”目标的重要突破口,煤炭开采形成的、能够富集煤层气、为后期微生物活动和矿化充填提供底物和空间的地质体定义为采动影响体。以采动影响体为研究对象,提出了采动影响体微生物采残煤与CO_(2)-粉煤灰协同矿化充填关键技术,并从必要性和可行性2个方面阐述了该技术在采动影响体资源二次开发、CO_(2)安全封存以及燃煤电厂粉煤灰固废高效处置等的广阔前景。其总体思路是将采动影响体作为一个厌氧发酵“工厂”,高产高效产甲烷菌群作为“劳动者”对“工厂”已有的原材料——残煤、薄煤层和分散有机质以及注入的CO_(2)进行加工,其“产品”是甲烷,进而实现微生物采残煤和CO_(2)资源化。同时,CO_(2)与碱性的粉煤灰结合,在实现了CO_(2)矿化封存的同时,也实现了采动影响体的充填。该技术涉及的关键科学问题包括采动影响体类型划分与有机质特征、采动影响体原位条件下厌氧发酵产甲烷机制、微生物-CO_(2)-粉煤灰协同矿化/固化机制以及微生物采残煤与充填关键技术示范工程建设。实验室物理模拟采动影响体原位条件实验表明其中残煤和富含有机质的泥页岩能够在微生物作用下生成生物甲烷,且添加少量的粉煤灰能够进一步强化甲烷的产出。物理模拟地下水补给的动态实验表明营养物质的补给对厌氧发酵系统的影响尤为重要,补给循环周期为14 d的厌氧发酵系统恰与产甲烷菌群繁殖的周期一致,能够保证厌氧发酵系统的持续高效运行。高钙粉煤灰-CO_(2)-矿井水协同胶结的试件经过28 d的养护后抗压强度为12.31 MPa,其矿化封存潜力约为21.99 m3 CO_(2)/t(粉煤灰),说明粉煤灰在实现采空区固化的同时能够实现CO_(2)减排。此外,基于微生物采残煤与粉煤灰充填目的对工程试验靶区进行优选,地下水滞留区是CO_(2)矿化和粉煤灰充填的最佳场所,因采掘活动自然形成的自然圈闭和人工充填形成的圈闭是较有利的工程试验靶区之一。针对这些靶区提出了微生物采残煤与CO_(2)-粉煤灰协同充填关键技术,旨在为中国碳减排和采空区生态环境治理提供一条新的技术路径。

超声空化-流体剪切协同强化油团聚分选煤气化细渣

煤气化细渣(CGFS)具有较高的利用价值,但残炭回收率低极大地制约了其资源化利用。油团聚分选法在CGFS分选过程中具有明显优势,但炭灰共生结构严重限制了油团聚分选效率。为突破油团聚法分离富集残炭技术的瓶颈问题,考察了超声时间、超声功率、流体剪切时间及其交互作用对油团聚分选效果的影响,并结合BET、粒度分布、FT-IR、XPS以及SEM-EDS等分析手段,揭示了超声空化-流体剪切(UC-FS)协同预处理对油团聚分选效果的强化机理。结果表明:当超声功率为270 W、超声处理时间29 min、流体剪切时间23 min时,能分选得到灰分为9.55%的精矿、灰分为91.51%的尾矿,可燃体回收率可提高至90.54%。超声空化作用使原本致密的炭灰结构逐渐松散,与流体剪切的冲刷作用协同促进CGFS的孔隙结构的发展,使炭灰颗粒解离度增加,从而降低了精矿灰分。UC-FS协同预处理能够有效增加残炭表面C—C、C=C以及C—H等疏水基团的比例,使其接触角由110.34°增加到121.16°,扩大了炭和灰颗粒表面疏水性差异,提高了油团聚分选的效果。UC-FS协同预处理使炭灰颗粒高效分离的强化作用主要归因于超声空化气泡与细粒微球耦合产生的微磨料效应。可为实现CGFS分质资源化利用提供理论基础和技术指导。

电解锰渣-赤泥-粉煤灰路面砖的力学性能及浸出毒性研究

针对大宗工业固废回收利用难的问题,实现多种固废减量化、无害化、资源化的目标,通过利用取自中国西南地区企业的石膏类、碱性及硅铝质三类典型大宗固废中的电解锰渣、赤泥、粉煤灰协同处理的无害化渣制备环保型透水混凝土路面砖(permeable concrete paving bricks,PCB),研究了水洗、掺渣量对所制备PCB的力学性能与浸出毒性的影响,并通过X射线衍射(XRD)和扫描电子显微镜(SEM)对最佳性能PCB的物相组成与微观形貌结构进行分析.结果表明:①随着无害化渣与水洗无害化渣掺入量的提升,路面砖的劈裂抗拉强度、线性破坏荷载发生明显变化,总体呈下降趋势.当无害化渣掺入量为6%、水洗无害化渣掺入量为14%时,经28 d养护,所制备砖体的劈裂抗拉强度分别为4.09和3.46 MPa,达到了《透水路面砖和透水路面板》(GB/T 25993-2010)中规定的f_(ts)4.0与f_(ts)3.0等级.②路面砖的重金属与NH_(4)^(+)-N的浸出毒性均低于《水泥窑协同处置固体废物技术规范》(GB 30760-2014)的要求.路面砖的主要物相中方解石、石英与钙矾石是主要支撑性物质.研究显示,电解锰渣、赤泥、粉煤灰协同处理的无害化渣可替代部分原材料制备透水混凝土路面砖,满足力学性能与浸出毒性相关标准,能有效促进固体废弃物的减量化与资源化,建议进一步开展砖体在实际应用场景中的环境风险试验,以期为电解锰渣、赤泥、粉煤灰的综合利用技术发展提供更明确的支撑.

Alkali desilicated coal fly ash as substitute of bauxite in lime-soda sintering process for aluminum production

By desilication treatment,the Al2O3/SiO2 molar ratio of coal fly ash could be improved to the range of 1.63-2.0.The desilicated coal fly ash(DSCFA)was enriched in alumina extraction.A processing technology was developed for alumina extraction from the DSCFA with the lime sintering process.Ca/(SiO2+TiO2)molar ratio,and NaO/Al2O3 molar ratio,sintering time,and temperature were the most significant parameters impacting on the aluminum extraction efficiency.The optima aluminum extraction efficiency was obtained under conditions of Ca/(SiO2+TiO2)molar ratio of 2.0,NaO/Al2O3 molar ratio of 0.98,and sintering at 1 200 ℃for 60 min.Astandard industrial dissolution method was used under conditions of caustic ratio(αk=n(NaO)/n(Al2O3)of 2.0,Al2O3 concentration of 50 g/L,sodium hydroxide concentration(Nk)of 60.78 g/L,Na2CO3 concentration of 10 g/L,temperature of 85℃, and dissolution duration of 10 min.The final aluminum extraction efficiency was 90%.

Lowering ash slagging and fouling tendency of high-alkali coal by hydrothermal pretreatment

High-alkali species in coal are notorious for causing ash slagging and fouling incidents.In this paper,four high-alkali coals were individually subject to hydrothermal pretreatment(HTP),within a batch-type autoclave at 300 -C for 1 h,and the treated coals were analyzed,along with the oxygen-containing functional groups determined by Fourier transform infrared spectrometer(FT-IR).Then the alkali species and other components in the coal ash were quantified by X-ray fluorescence(XRF)for evaluating the ash slagging and fouling tendency.Apart from this,FactSage was adopted to simulate the occurrence and transformation of alkali species during coal thermal conversion ending at various temperatures.The findings indicate that the treated coals are superior to the parent ones in terms of certain remarkable changes via HTP.The moisture,oxygen and sulfur of the hydrothermally treated coals decline obviously,while the calorific value rises sharply.HTP could reduce the alkali species to less than 2%(%,by weight,equivalent to Na2O in dry ash),with a maximum removal ratio of 88.9%,lowering the ash slagging and fouling tendency.The proposed mechanism of HTP was that the alkali species in coal matrix became released due to the breakage of the coal functional groups and micropores during HTP.

Microstructure and properties of mullite-based porous ceramics produced from coal fly ash with added Al_2O_3

Using coal fly ash slurry samples supplemented with different amounts of Al_2O_3,we fabricated mullite-based porous ceramics via a dipping-polymer-replica approach,which is a popular method suitable for industrial application.The microstructure,phase composition,and compressive strength of the sintered samples were investigated.Mullite was identified in all of the prepared materials by X-ray diffraction analysis.The microstructure and compressive strength were strongly influenced by the content of Al_2O_3.As the Al/Si mole ratio in the starting materials was increased from 0.84 to 2.40,the amount of amorphous phases in the sintered microstructure decreased and the compressive strength of the sintered samples increased.A further increase in the Al_2O_3 content resulted in a decrease in the compressive strength of the sintered samples.The mullite-based porous ceramic with an Al/Si molar ratio of 2.40 exhibited the highest compressive strength and the greatest shrinkage among the investigated samples prepared using coal fly ash as the main starting material.

Simultaneous Measurements of Coal Ash Composition by Laser-induced Breakdown Spectroscopy in Different Optical Collection

针对燃煤组分分布不均匀的特性，研究不同收光模式对激光诱导击穿光谱技术同步测量灰成分的影响。选用具有不同灰成分含量梯度的燃煤样品作为检测对象，对比分析同向收光和侧向收光下灰成分组成元素谱线信号探测的强度和稳定性及SiO2、Al2O3、Fe2O3、CaO、MgO和TiO2含量定量分析的精确度。研究结果表明，相同实验条件下同向收光模式的光谱信号稳定性和定量分析精确度更好，检验样品中各灰成分的预测值和参考值之间的拟合度均在0．986以上。而侧向收光模式下探测到的光谱信号强度更强，光谱探测下限可以达到190nm。

Catalytic spectrophotometric determination of trace vanadium in fly ash and coal gangue by Triton X-100 enhancing effect

Trace Ⅴ(Ⅴ) catalyzes mightily the decolorization reaction of arsenazo Ⅲ(AsA Ⅲ) by oxidizing with H_2O_2 in a pH 4.0 HAc-NaAc buffer solution, and the addition of TritonX-100 can further increase the sensitivity of the reaction and its catalytic extent is linear withthe content of Ⅴ(Ⅴ). A catalytic spectrophotometric procedure for determining trace Ⅴ(Ⅴ)wasdeveloped. The results show that the maximun absorption of the color solution is at 560 nm and thedetection limit of the method for Ⅴ(Ⅴ) is 0.014 mg·L^(-1). Beer's law is obeyed for Ⅴ(Ⅴ) in therange of 0.00-0.20 mg·L^(-1). The recoveries are 99.0%-104.6%, and the relative standarddeviations (RSD) are 2.7%-3.7%. Combined with ion-exchange resin, the method has been applied to thedetermination of trace vanadium in fly ash and coal gangue with satisfactory results.

The Future Resources for Eco-building Materials:Ⅱ. Fly Ash and Coal Waste

To use fly ash and coal waste effectively, the current technologies for reprocessing and recycling these wastes into eco-building materials were reviewed, such as utilizing fly ash as the component of fly ash cement and low heat cement after the processes of separation, removal of carbon remains and fine comminution, calcining coal waste into kaolin and meta-kaolin with suspension technology, and preparing clinkerless alkali-activated geopolymer materials with fly ash and meta-kaolin.

Hydrothermal synthesis of zeolites-calcium silicate hydrate composite from coal fly ash with co-activation of Ca(OH)_(2)-NaOH for aqueous heavy metals removal

Coal fly ash is a typical secondary aluminum/silicon resource.The preparation of zeolite-type absorbent is a potential way for its value-added utilization,while the purity and adsorption property of zeolite are limited due to the occurrence of side reactions in the synthesis process.In this study,a designated composite consisted of crystalline zeolites and amorphous calcium silicate hydrate was selected,which was direct synthesized from fly ash under conditions of a Ca/Si molar ratio of 0.8,an initial NaOH concentration of 0.5 mol/L,a hydrothermal temperature of 170℃and a liquid–solid ratio of 15 mL/g.The results indicated that this composite had superior adsorption property for a variety of heavy metals,which was based on the exchange of calcium and sodium ions in zeolites and calcium silicate hydrate.Its adsorption capacities for Pb^(2+),Ni^(2+),Cd^(2+),Zn^(2+),Cu^(2+)and Cr^(3+)attained 409.4,222.4,147.5,93.2,101.1 and 157.0 mg/g,respectively,in single solution with a pH of 4.5.After regulating the synthesis conditions,the transformation of amorphous calcium silicate hydrate into crystallized tobermorite weakened the adsorption capacity of the composite.Besides,due to the competitive adsorption in a multiple ions solution,the adsorption capacities for these heavy metals had a reduction.

Application of response surface methodology(RSM) for optimization of leaching parameters for ash reduction from low-grade coal

Coal is the world's most abundant energy source because of its abundance and relatively low cost. Due to the scarcity in the supply of high-grade coal, it is necessary to use low-grade coal for fulfilling energy demands of modern civilization. However, due to its high ash and moisture content, low-grade coal exerts the substantial impact on their consumption like pyrolysis, liquefaction, gasification and combustion process. The present research aimed to develop the efficient technique for the production of clean coal by optimizing the operating parameters with the help of response surface methodology. The effect of three independent variables such as hydrofluoric acid(HF) concentration(10–20% by volume), temperature(60–100 °C), and time(90–180 min), for ash reduction from the low-grade coal was investigated. A quadratic model was proposed to correlate the independent variables for maximum ash reduction at the optimum process condition by using central composite design(CCD) method. The study reveals that HF concentration was the most effective parameter for ash reduction in comparison with time and temperature. It may be due to the higher F-statistics value for HF concentration, which effects to large extent of ash reduction. The characterization of coal was evaluated by Fourier transform infrared spectroscopy(FTIR) analysis and Field-emission scanning electron microscopy with energy-dispersive X-ray(FESEMEDX) analysis for confirmation of the ash reduction.

Determination of trace multi-elements in coal fly ash by inductively coupled plasma mass spectrometry

The contents of Cr, Cu, Ni, As, Cd and Pb in coal fly ash were determined by a high resolution inductively coupled plasma mass spectrometry method. The sample digestions were performed in closed microwave vessels with HNO3, HClO4 and HF. The optimum conditions for the determination were obtained. The applicability of the proposed method was validated by the analysis of coal fly ash reference material (NIST SRM 1633a). The results show that most of the spectral interferences can be avoided by measuring in the high resolution mode (maximum mass resolution R=9 000). The detection limit is from 0.05 to 0.21 μg/g, and the precision is fine with relative standard deviation less than 4.3%.

Triboelectrostatic Separation-an Efficient Method of Producing Low Ash Clean Coal

At present, coal is mainly consumed as fuel. In fact, coal is also a kind of precious raw material in chemical industry on the premise that some harmful minerals should be removed from coal. The paper presents the results of the research on producing low ash (<2%) coal with triboelectrostatic separator used for producing high-grade active carbon. The test is conducted in bench-scale system, whose capacity is 30～100 kg/h. The results indicate that: 1) the ash content of clean coal increases with the increase of solid content of feedstock, on the contrary, the yield of clean coal is declining; 2) a high velocity may result in a good separation efficiency; 3) for the same solid content, the reunion caused by intermolecular force makes the separation efficiency drop down when the ultra-fine coal is separated; 4) the separation efficiency is improved with the increase of electric field intensity, but there is a good optimized match between the electric field intensity and yield of clean coal; 5) a low rank coal is easy-to-wash in triboelectrostatic separation process; 6) the yield of clean coal can be enhanced and the ash decreased through adapting optimized conditions according to various coals.

基于高效解离-选择性絮凝耦合作用的煤气化渣提炭实验研究

煤气化渣是由煤气化工艺产生的一种富含铝硅酸盐、灰组分及残炭的大宗工业固体废弃物,其规模化生产对生态环境造成了严重的影响。因此,将煤气化渣进行炭-灰分离是实现其减量化、无害化和资源化利用的关键。以煤气化渣为研究对象,采用高效解离-选择性絮凝耦合作用的工艺,为实现煤气化渣更为合理、高效的资源化利用,减少煤气化渣带来的土壤、空气、水体资源等污染问题,对煤气化渣进行提炭实验研究。首先分析了煤气化渣的理化性质,其次采用单因素变量法探究了磨矿时间、pH、絮凝剂种类、絮凝剂用量、高速剪切转速对煤气化渣提炭实验的影响,以实现残余炭产品的高度富集。结果表明:原煤气化渣灰分质量分数为67.19%,普通湿筛筛上物料灰分质量分数为54.3%,当煤气化渣磨矿时间为5 s, pH为7,絮凝剂聚氧化乙烯用量为0.4 kg/t,在转速为4 000 r/min高速剪切15 min的条件下提炭效果最佳,最终可获得产率为26.6%、湿筛筛上灰分质量分数为43.3%的残炭产品。对比普通湿筛法,基于高效解离-选择性絮凝实验方法在普通湿筛的基础上灰分质量分数降低了11%,降灰效果明显。

Removal of lead(Pb(Ⅱ))and zinc(Zn(Ⅱ))from aqueous solution using coal fly ash(CFA)as a dual-sites adsorbent

Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with unique properties.This work focused on the adsorption of Pb(Ⅱ)and Zn(Ⅱ)from binary system,a mixture containing two metal ion solutions present simultaneously,onto NaOH-modified CFA(MCFA).Several adsorption tests were conducted to evaluate the effect of several parameters,including pH and contact times.The experiment results indicated that chemical treatment of CFA with NaOH increased pore volume from 0.021 to 0.223 cm^3·g^(-1).In addition,it could also enhance the availability of functional groups on both minerals and unburned carbon,resulting in almost 100%Pb(Ⅱ)and 97%Zn(Ⅱ)adsorbed.The optimum pH for adsorption system was pH=3 and quasi-equilibrium occurred in 240 minutes.Equilibrium data from the experimental results were analyzed using Modified Extended Langmuir(MEL)and Competitive Adsorption Langmuir-Langmuir(CALL)isotherm models.The analysis results showed that the CALL isotherm model could better describe the Pb(Ⅱ)and Zn(Ⅱ)adsorption process onto MCFA in binary system compared with MEL isotherm model.

An Evaluation on the Physical and Chemical Composition of Coal Combustion Ash and Its Co-Placement with Coal-Mine Waste Rock

In the last few decades, the utilization of coal to generate electricity was rapidly increasing. Consequently, the production of coal combustion ash (CCA) as a by-product of coal utilization as primary energy sources was increased. The physical and geochemical characteristics of CCA were site-specific which determined by both inherent coal-source quality and combustion condition. This study was intended to characterize the physical, chemical and mineralogical properties of a coal-combustion ash (CCA) from a site specific power plant and evaluate the leachate characteristic of some scenario on the co-placement of CCA with coal-mine waste rock. The physical properties such as specific gravity, dry density, porosity and particle size distribution were determined. Chemically, the CCA sample is enriched mainly in silica, aluminum, iron, and magnesium along with a little amount of calcium and sodium which includes in the class C fly ash category. Moreover, it is found that the mineral phases identified in the sample were quartz, mullite, aragonite, magnetite, hematite, and spinel. Co-placement experiment with mudstone waste rock shows that the CCA, though it has limited contribution to the decreasing permeability, has important contributed to increase the quality of leachate through releasing higher alkalinity. Moreover, addition of CCA did not affect to the increase of the trace metal element in the leachate. Hence, utilization of CCA by co-placement with coal mine waste rock in the dumping area is visible to be implemented.