Experimental study on ash deposition of Zhundong coal in oxy-fuel combustion

To facilitate the large-scale utilization of high-alkali and -alkaline earth metals (AAEMs) coals in power generation, the ash deposition behaviors of a typical Zhundong coal in oxy-fuel combustion were experimentally investigated using a drop tube furnace. A wall-temperature-controlled ash deposition probe by which the bulk gas temperature could be measured simultaneously was designed and employed in the experiments. The deposition tendencies, ash morphologies, chemical compositions of deposited ash particles were studied respectively under various oxygen concentrations, bulk gas temperatures, probe surface temperatures and probe exposure times. The experimental results revealed that the oxygen concentration had a significant influence on the deposition behavior during oxy-fuel combustion of high-alkali coal. Compared with air case, more fine ash particles were generated during the combustion of Zhundong coal in 21% O₂/79% CO₂ atmosphere but the deposition tendency was weaker. However, a higher oxygen concentration could aggravate the tendency of ash deposition. The high contents of iron (Fe), calcium (Ca), sulfur (S), and sodium (Na) in Zhundong coal could result in the generations of low-melting point compounds. Calcium in flue gas existed as CaO and was captured prior to SO₃ by the probe surface during the ash deposition process. At the initial 30 min of the ash deposition process, the dark spherical fine ash particles rich in Fe, Na, oxygen (O), and S were largely produced, while in the range of 60–90 min the light spherical fine ash particles with high contents of Ca, barium (Ba), O, and S were generated on the other hand. The deposition mechanisms at different stages were different and the melted CaO (BaO)/CaSO₄ (BaSO₄) would give rise to a fast growth rate of ash deposit.     

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.     

Ash deposition behaviors during combustion of raw and water washed biomass fuels

Biomass-fired boilers have the tendency to suffer from severe problems of fouling and slagging due to the high potassium content of biomass fuel. The troublesome potassium, however, can be removed efficiently by water washing pretreatment. In this study, the ash deposition behaviors during combustion of raw and water washed biomass fuels were investigated by a one-dimensional furnace and a deposition probe. Two biomass fuels (corn stalk and wheat straw) were used, and deposition mass, deposition efficiency, composition and morphology of the deposit were studied. The ash deposition while firing raw biomass exhibits a “fast?slow?fast?slow” trend with the sampling time. After water washing, the deposition mass decreases dramatically, and the deposition efficiency reduces gradually as the sampling time increases. The analyses of elemental composition, morphology and chemical composition on the deposit from raw biomass imply that the condensation/thermophoresis is quite significant in the earlier deposition stage, whereas the chemical reaction is remarkable in the later stage. After water washing, the potassium content of the deposit decreases significantly. Morphology and chemical composition analyses indicate that the deposit from water washed biomass ascribes to the physical accumulation of non-viscous fly ash particles. The deposition mass can easily approach a maximum value. The ash fusion temperatures of deposits increase remarkably after water washing. In addition, ash deposition mechanisms during biomass combustion are discussed.     

Effects of oxy-fuel condition on morphology and mineral composition of ash deposit during combustion of Zhundong high-alkali coal

Zhundong coalfield is a super-large coal reserve, with high-alkali feature exacerbating ash deposition. Oxy-fuel combustion technology could propel the clean utilization of Zhundong high-alkali coal. While the ash deposition behavior of high-alkali coal under oxy-fuel condition has yet to be sufficiently investigated. The present study compared the differences of ash deposits between oxy-fuel and air combustion, and also examined the effects of oxygen content on ash deposition mechanism, employing a drop-tube furnace equipped with a specially designed sampling probe and some analysis methods, such as X—ray diffraction equipment, simultaneous thermal analyzer, etc. Experimental results indicated that ash deposition was weaker, with fewer contents of sodium chloride, calcium sulphate and less agglomeration ash in oxy-fuel atmosphere compared to the air case with same oxygen content. The content of the ash particle distributed in the range of 0–40 μm was up to 60% under oxy-fuel condition. The first weight loss of ash deposits, around 850 °C, was put down to the decomposition of carbonate and the second one, about 1150 °C, was ascribed to the decomposition of the sulphate minerals in the thermal process. Ash deposition worsened with more large particles (>120 μm), as the oxygen content rose. Sodium chloride content reached 9.7% with 50% oxygen content. The present study not only focuses on the morphology and chemical components, but also probes into the thermal volatility of ash deposits, which benefits the further understanding of the ash deposition mechanism and utilization of Zhundong high-alkali coal during oxy-fuel combustion.     

Influences of sodium species with different occurrence modes on the thermal behaviors and gas evolution during pyrolysis of a sodium-rich Zhundong subbituminous coal

The Zhundong coal (ZDC) with a huge proven reserve is featured by high abundance of sodium species which behaves actively in the thermal conversion of it. In this work, to better understand the multiple roles of sodium species in coal pyrolysis, influences of sodium species with different occurrence modes on the thermal behaviors and gas evolution during pyrolysis of a sodium-rich ZDC were investigated. Raw coal was initially demineralized by dilute hydrochloric acid. Subsequently, sodium species was reloaded into the demineralized sample by ion-exchanged or immersed method. For quantitative analyses, a thermo-gravimetric analyzer coupled with a mass spectrometer was used to record the weight loss of different samples and the ever-changing amount of gaseous products in pyrolysis. The results show that the structural change induced by demineralized and ion-exchanged treatment is mainly reflected in the band intensity of carboxyl groups. In pyrolysis of ZDC, total volatile matters yield has a close relation with the occurrence modes of sodium species. It is proved that water-soluble sodium species has catalytic effects on the thermal-cracking reactions, whereas exchangeable sodium species tends to facilitate char-formed reactions. Compared with exchangeable ones, water-soluble sodium species can be also volatilized more easily in pyrolysis. As for gas evolution, exchangeable sodium species can obviously affect formation of CO through char gasification and it is also favorable to formation of hydrogen radicals. Moreover, due to the low sulfur content in ZDC, the intensity of H₂S released from all samples is extremely weak, which suggests that ZDC is a suitable feedstock for clean coal utilization.     

不同采矿深度准东煤物化特性和燃烧性能研究

选取天池能源浅层和深层煤样进行研究,以大同烟煤作为对比,了解采矿深度对煤质及燃烧特性的影响,为准东煤的勘探和燃烧提供必要的理论依据。研究发现,随着采矿深度的增加,煤中水分减少、灰分降低、发热量增加、含硫量减少,煤质更加接近烟煤;煤灰中Fe2O3明显减少,煤的结渣趋势减轻;煤的着火温度略有降低,燃烧速率提高,燃烧特性变好。与大同烟煤相比,准东煤高水分、低发热量、低氮含量,燃烧时着火温度显著降低且燃烧速率低。     

Effects of leaching and additives on the ash fusion characteristics of high-Na/Ca Zhundong coal

Considering the intensive application of Zhundong coal and its serious slagging during combustion in pulverized coal fired boilers, the effects of water leaching and different dosages of additives (Na₂CO₃, CaO, SiO₂, and kaolin) into the leached coal on ash fusion characteristics were studied using sintering tester, X-ray Fluorescence, and X Ray Powder Diffraction. After leaching, the contents of Na₂O, K₂O, CaO, MgO, SO₃, and Cl decreased, whereas the contents of SiO₂ and Fe₂O₃ increased. As a result, the slagging and fouling index of Basic/Acid ratio decreased from 1.6 in the raw coal ash to 1.1 in the leached coal ash, and alkali-induced slagging was reduced. However, the decreased ash fusion temperatures (AFTs) of the leached coal worsen the melt-induced slagging. Detailed analysis on the effects of ash compositions on the AFTs by additions of Na₂CO₃, CaO, SiO₂, and kaolin additives into the leached coal showed that Na₂CO₃ and SiO₂ improved the formation of low-melting Na₂SO₄ and Na₂SiO₃, and thus decreased the AFTs; However, overdosed Na₂CO₃ (for instance 9 wt%) improved the formation of relative high-melting Na₄Al₂Si₂O₉ and thus increased the AFTs. Overdosed SiO₂ as a high-melting contaminant also increased the AFTs. Similar with the function of overdosed SiO₂, CaO in the ash of leached coal was excess, and the AFTs increased with increased CaO dosage. Kaolin, which decomposed as high-melting mullite and cristobalite, caused an elevation of the AFTs. Therefore, water leaching decreased the AFTs of Zhundong coal and consequently worsen melt-induced slagging, lime and kaolin additives increased the AFTs effectively, but Na₂CO₃ and SiO₂ additives showed ‘V’ shaped functions on the AFTs. These general results are useful for the pretreatment of Zhundong coal during combustion and alleviating slagging.     

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.     

Ash transformation and deposition characteristic during straw combustion

The main objective of this study was to determine ash transformation and deposition characteristic for three types of straw (corn straw, oat straw, and rice straw) combustion at temperatures between 500 and 1000°C. The collected deposits on the sampling probe were characterized with X-ray diffraction and scanning electron microscopy combined with energy dispersive X-ray analysis. The results indicated that the ash forming processes of straw were influenced by fuel composition and temperature. The quantity of corn straw ash collected from deposition probe was noticeably lower than that of oat straw and rice straw due to different contents of K, S, and Si in fuels. The deposition amounts of corn straw and oat straw followed a linear pattern at temperatures below 800°C, while rice straw followed a nonlinear pattern as a function of temperature. Corn straw was an ideal fuel compared to oat straw and rice straw from the points of deposition amounts and appearance. It also can be found that silicon, calcium, potassium, and sulfur were key points in the forming process of ash deposits.     

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.     

Transformation characteristics of Na and K in high alkali residual carbon during circulating fluidized bed combustion

In this study, the transformation characteristics of sodium (Na) and potassium (K) during combustion of Zhundong coal gasification fly ash in circulating fluidized bed (CFB) reactors were investigated by examining gasification fly ash (TCf) from a 0.1-MW CFB test system. Experimental results indicated that TCf was rich in Na and K, with water-soluble and insoluble Na the main Na forms. Insoluble K was the major K form in TCf, accounting for 70.6% of total K. Reactor bed temperature exerted important effects on Na release during combustion such that, as bed temperature increased, the proportions of Na in bottom and circulating ash decreased while the Na in fly ash increased. Hydrochloric acid-soluble and insoluble Na in ash accounted for a large fraction of total Na. However, insoluble K was the principle K form in ash and bed temperature showed little influence on K release and distribution in ash during combustion. With decreased flue gas temperature, the Na content in deposition ash initially increased, then decreased, and eventually stabilized, while the K content in deposition ash was basically unchanged. Agglomeration of ash particles occurred during combustion, being more apparent at higher gas temperatures, and the agglomerates were rich in Na, K, sulfur (S), chlorine (Cl), and calcium (Ca). Deposition ash Na was mainly contained NaCl and Ca/Na sulfates. The enrichment of these salts as well as of Ca sulfate in ash was the main cause of ash agglomeration and deposition.     

准东煤中钠元素赋存形态及洗煤对气化特性影响

为探究准东煤中钠元素赋存形态及洗煤对准东煤气化特性的影响,采用逐级洗煤法对准东煤进行洗煤处理。利用电感耦合等离子体质谱仪、离子色谱仪和X 射线衍射仪研究了准东煤中钠元素赋存形态及含量。利用热重分析仪研究了煤样的气化特性,并采用等转化率法计算气化反应动力学参数。结果表明：准东煤中钠元素主要以水溶钠为主,但并非以钠盐化合物晶体的形式存在于煤中。洗煤对煤样孔结构特性和矿物质含量均产生影响,矿物质含量较低时,气化特性主要由煤样的孔结构特性决定。随着洗煤程度加深,煤焦碳转化率达到90 %时所需的时间由5.35 min延长至12.02 min,气化反应活性指数逐渐降低,气化反应活化能由177.7～214.8 增大至203.5～252.4 kJ.mol-1。     

Effect of coal type on gasification in pressurized drop tube furnace

In order to understand the effect of coal type on coal gasification process at 15 atmospheric pressure of pressurized drop tube furnace (PDTF), a numerical study was conducted. Eulerian approach is used for the gas phase, whereas Lagrangian approach is used for the solid phase. Turbulence is modelled using the standard k–ε model. The turbulent gas‐phase combustion model incorporates the eddy dissipation model. One‐step two‐reaction model is employed for the devolatilization. Effect of coal type on carbon conversion at the same coal feed rate and gas flow rate cannot be verified due to the variation of equivalence ratio according to coal composition. Therefore, the same equivalence ratio is chosen to evaluate the effect of coal type on gasification. It is found that the volatile release based on experimental results should be taken in computations to predict accurate carbon conversion, especially in coal gasification due to the low gasification reaction. Even at over 1500 K and 15 atmospheric pressure, at which reactions are primarily diffusion‐controlled, the exit carbon conversion varies with the coal type. The temperature gradient in near‐burner region becomes gentle with increasing proximate volatile and moisture contents, but the volatiles released can make the temperature gradient steep by means of the fast reaction with oxygen. Copyright © 2001 John Wiley & Sons, Ltd.     

Migration and transformation of sodium and chlorine in high-sodium high-chlorine Xinjiang lignite during circulating fluidized bed combustion

The Xinjiang lignite mined from Shaerhu coalfield (SEHc) easily causes severe fouling and corrosion because of its high sodium and chlorine contents. Therefore, it is necessary to study the migration and transformation behavior of sodium and chlorine during combustion in order to reveal the mechanisms of fouling and corrosion, and propose the effective solutions of above problems. In this study, based on the 0.4 T/D circulating fluidized bed (CFB) test system, the migration and transformation behavior of sodium and chlorine in SEHc during combustion at 950 °C was explored. The migration and transformation paths of sodium and chlorine were proposed through the chemical characterization of ash samples along the flue gas flow direction, as well as the thermodynamic equilibrium calculation by the software of Factsage 6.1. The experimental studies show the sodium and chlorine mainly in the form of NaCl crystal in raw coal underwent a series of physical and chemical changes during combustion, and subsequently distributed in bottom ash/circulating ash, fly ash and gas phase in various forms including sodium aluminosilicates, chlorides and sodium oxides. Sodium was more inclined to be resided in ash in the form of aluminosilicates through the reactions with other minerals (SiO₂ and Al₂O₃), while chlorine was easily released into the flue gas in forms of HCl, Cl₂, NaCl, etc. The Cl-based species might result in the corrosion of metal heating surfaces because of the presence of corrosion products (metal chlorides) in fly ash. As temperature decreased, the sodium or chlorine vapors would successively deposit in fly ash via physical condensation or chemical reaction. At 840～570 °C, the sodium-based species (Na₂O and NaCl) would first deposit in fly ash, then gaseous chlorine species (NaCl, FeCl₃ and so on) primarily deposited at 570～180 °C.     

准东煤灰与液态排渣煤粉炉耐火材料的烧结特性

采用TGA-DSC分析确定了准东煤灰和其混合灰样(不同质量比的准东煤灰和耐火材料)燃烧过程中的特征温度,并分别采用XRD和FSEM-EDS对不同特征温度段灰样进行矿物识别和形貌、能谱分析,得到了原灰与混合灰的烧结温度、灰中主要矿物的转化和熔融过程,并对比了不同耐火材料含量的煤灰熔融温度;在此基础上提出了耐火材料构型的极...     

Pulverized coal burnout in blast furnace simulated by a drop tube furnace

Reactions of pulverized coal injection (PCI) in a blast furnace were simulated using a drop tube furnace (DTF) to investigate the burnout behavior of a number of coals and coal blends. For the coals with the fuel ratio ranging from 1.36 to 6.22, the experimental results indicated that the burnout increased with decreasing the fuel ratio, except for certain coals departing from the general trend. One of the coals with the fuel ratio of 6.22 has shown its merit in combustion, implying that the blending ratio of the coal in PCI operation can be raised for a higher coke replacement ratio. The experiments also suggested that increasing blast temperature was an efficient countermeasure for promoting the combustibility of the injected coals. Higher fuel burnout could be achieved when the particle size of coal was reduced from 60–100 to 100–200 mesh. However, once the size of the tested coals was in the range of 200 and 325 mesh, the burnout could not be improved further, resulting from the agglomeration of fine particles. Considering coal blend reactions, the blending ratio of coals in PCI may be adjusted by the individual coal burnout rather than by the fuel ratio.     

Simulation of ash deposition in different furnace temperature with a 2D dynamic mesh model

Ash deposit on the heat exchangers reduces the heat transfer efficiency and even threatens the operation of the equipment. The tool of computational fluid dynamics (CFD) allows for better understanding of the deposit formation and the prediction of the process. This paper presents an improved CFD model to reproduce the growth of ash deposition on a temperature-controlled probe in a pilot-scale furnace with the commercial software Fluent16.0. Dynamic mesh technique is included to investigate the shape variation of the ash deposit during the deposit growth. The model is improved by taking the changing surface temperature of the deposition into consideration. The deposition efficiency, surface temperature and heat flux through the deposit are monitored as the iteration. Three cases are presented to investigate the influence of furnace temperature (1473 K, 1523 K and 1573 K). The results show that the deposition efficiency increases with the increasing surface temperature of the deposit while the mass flow of impaction decreases with the changing flow field. The growth rates of the deposit for the three cases are 0.064, 0.079 and 0.103 mm/min within the simulation time which is consistent with experiment results. The simulated surface temperature shows the same trend of the experimental values. The heat flux in the simulation decreases with a range of 38.2%, 50.3% and 50% for the three cases, respectively. This method of modelling can be used to predict the growth of deposit accurately.     

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。     

High-temperature pyrolysis behavior of two different rank coals in fixed-bed and drop tube furnace reactors

In order to explore the high-temperature pyrolysis behavior and mechanism, two different rank coals (Shenhua bituminous coal and Baiyinhua lignite coal) were pyrolyzed in fixed-bed and drop tube furnace (DTF) reactors. Pyrolysis gas production was online quantified by a drainage method while the gas composition was detected by the gas chromatography. The physical and chemical characteristics of pyrolysis char were observed by N₂ absorption and FTIR. Results show that pyrolysis gas release rate and total production increase with the higher temperature. The gas production of SH coal (618–749 ml/g) is always higher than that of BYH coal (418–510 ml/g) due to its higher volatile content. The main high-temperature pyrolysis gas products are H₂ (∼50% vol), CO, CH₄ and CO₂. Carbon-reduction reaction at high temperatures can further form H₂ and CO while the rupture of aromatic heterocyclic ring can generate CH₄. High-temperature pyrolysis can greatly remove the coal moisture, develop their pore structures, crack the chemical functional groups (O–H, –CH₃, CO, C–O, etc.) and upgrade the coal rank. Different coal structures and pyrolysis heating rates result in various gas evolution and char formation behaviors. Higher heating rate can help to quickly generate large amounts of free radicals and change the pyrolysis behaviors.     

The peculiar influence of the mineral impurities content in coal-water fuel on the regularities of fuel drop ignition and combustion

This paper presents the results of the comparative research of combustion specifics of coal-water fuel produced from low-ash and high-ash Ukrainian flame coal. The analysis shows that the effect of the ash content in the coal-water fuel on the duration of the burning of a fuel drop depends on the drop size. The full combustion time of CWF drop based on the low-ash coal can be both less and longer than that of high-ash coal under the identical conditions for different equivalent diameters of the fuel drop. This specific is explained with the domination of different physical factors during the fuel combustion process.The results of this research extend significantly our knowledge of coal-water fuel, allow understanding some issues of its combustion and are important for the design of the specialized energy facility which is used coal-water fuel as an energy source.