Viscosity predictions of the slag composition of gasified coal, utilizing FactSage equilibrium modelling

Agglomeration of ash particles provides the desired porosity of the ash bed for adequate agent (steam and oxygen) flow and distribution, whereas excessive slagging inside the gasifier can cause channel burning, pressure drop problems or unstable operation, resulting in cut backs on gasifier load, which implies a direct loss in gas production. The ash flow temperature (AFT) is one property that specifically gives more information on the suitability of a coal source for combustion or gasification purposes. However, normal AFT analyses give an average flow property and do not indicate exactly at what temperature the first melt/slag is occurring or what the properties of the slag is at a specific temperature. Operating experience indicates that even when the gasifiers are operated at temperatures above the flow temperature as given by AFT analysis, a low percentage of slag is formed.In this study, the focus will be on the application of viscosity determinations together with FactSage modelling. Conventional AFT analyses take the bulk chemical composition of the mineral phase into account, and does not differentiate between the composition in the slag-liquid phase and the composition of the crystalline phase. It is therefore important to describe the viscosity of not only the completely molten phase, but also the partly crystallised slag and liquid portion. The combination of viscosity predictions together with FactSage modelling will result in viscosity predictions of the actual liquid component, rather than just an average or pseudo-viscosity prediction of the total mineral system at a specific temperature.Based on the fact that the Urbain model assumes the composition as 100% liquid or molten, which is not the case for example during fixed bed gasification where the mineral structure is of a heterogeneous nature with partial melting and crystalline material, viscosity predictions of the slag or molten portion can be more accurately determined by using the FactSage results. The viscosities, as determined from specific slag compositions at specific temperatures between 1000 °C and 1250 °C, differ from the average viscosity prediction and is highly likely to be a more accurate prediction of the slag viscosity than just based on the average mineral composition. The viscosity of the actual slag composition also remains fairly constant up to temperatures >1200 °C. This can also be related back to the initial deformation temperature onset of the coal, where the slag properties are cumulative enough for the onset of deformation to start. The specific decrease of the viscosity at the temperature between 1200 °C and 1250 °C correlates with the slag formation trend as obtained with FactSage modelling.During the gasification process the viscosity of the slag portion decreases to ±3.5 cp, which is on the border between a weak deposit and strong deposit. With increasing temperature above 1250 °C, for this specific coal source the viscosity moved into the strong deposit region. After the gasification zone, the viscosity increased again as the material crystallised in the combustion process. For a specific coal source, the viscosity of the slag portion can thus be calculated. The major source of glass is derived from included minerals in carbon rich particles. It is clear that a focus on the modification of the unclassified/amorphous phase, to increase the viscosity (decrease slag formation or have a higher concentration of crystalline phases) at a certain temperature, is important.An AFT analyses only supplies information on the temperature where a mass of material, enough to deform the structure of the cone, starts to slag and does not give information on the properties of the slag below that point. The use of viscosity predictions together with FactSage modelling supplies a better understanding of slag and ash properties at specific temperatures.     

Fundamental ash deposition characteristics in pulverized coal reaction under high temperature conditions

Three types of coal with the different melting temperature and ash content were burned under the condition of high-temperature air pulverized coal reaction. A water-cooled tube was inserted into the furnace to make the ash adhere. Particle size and composition distributions of ash particles in both reacting coal particles and depositing layer were analyzed, using a Computer Controlled Scanning Electron Microscope, to study the deposition behaviors of ash particles. As a result, quantity of the ash deposition on the tube surface increases with a decrease of the melting temperature of coal ash. Index of fraction of the ash deposition depended on the coal type. For structure of the deposit layer, fine particles of size less than 3 μm mainly consisted of the initial layer for three types of coal, and the thickness was about 30 μm. Deposition of fine particulates of about 3 μm became a trigger of initial deposition at the stagnation point of tube even if irrespective of coal type is burned. The chemical compositions of ash particles in the reacting particles differed from those in the initial deposition layer. The deposition phenomenon relates to the particle size distribution of ash formed, the flow dynamics surrounding the probe, the chemical compositions in each ash particle and so forth.     

Predicted mineral melt formation by BCURA Coal Sample Bank coals: Variation with atmosphere and comparison with reported ash fusion test data

The thermodynamic equilibrium phases formed under ash fusion test and excess air combustion conditions by 30 coals of the BCURA Coal Sample Bank have been predicted from 1100 to 2000 K using the MTDATA computational suite and the MTOX database for silicate melts and associated phases. Predicted speciation and degree of melting varied widely from coal to coal. Melting under an ash fusion test atmosphere of CO₂:H₂ 1:1 was essentially the same as under excess air combustion conditions for some coals, and markedly different for others. For those ashes which flowed below the fusion test maximum temperature of 1773 K flow coincided with 75-100% melting in most cases. Flow at low predicted melt formation (46%) for one coal cannot be attributed to any one cause. The difference between predicted fusion behaviours under excess air and fusion test atmospheres becomes greater with decreasing silica and alumina, and increasing iron, calcium and alkali metal content in the coal mineral.     

Development of a modeling approach to predict ash formation during co-firing of coal and biomass

The scope of this paper includes the development of a modelling approach to predict the ash release behaviour and chemical composition of inorganics during co-firing of coal and biomass. In the present work, an advanced analytical method was developed and introduced to determine the speciation of biomass using pH extraction analysis. Biomass samples considered for the study include wood chips, wood bark and straw. The speciation data was used as an input to the chemical speciation model to predict the behaviour and release of ash. It was found that the main gaseous species formed during the combustion of biomass are KCl, NaCl, K₂SO₄ and Na₂SO₄. Calculations of gas-to-particle formation were also carried out to determine the chemical composition of coal and biomass during cooling which takes place in the boiler. It was found that the heterogeneous condensation occurring on heat exchange surfaces of boilers is much more than homogeneous condensation. Preliminary studies of interaction between coal and biomass during ash formation process showed that Al, Si and S elements in coal may have a ‘buffering’ effect on biomass alkali metals, thus reducing the release of alkali–gases which act as precursors to ash deposition and corrosion during co-firing. The results obtained in this work are considered to be valuable and form the basis for accurately determining the ash deposition during co-firing.     

Effect of Chemical Compositions on Ash Fusibility Characterization of a Jincheng Anthracite during Combustion and Gasification

The ash melting temperature of coal ash has an important effect during the fluidized bed combustion and gasification process, which affects the slagging and deposition characteristics of the boiler. Experiments on the effects of chemical components on the ash fusion behaviors have been completed on the ash fusion temperatures (AFTs) analyzer under typical gasification and combustion atmospheres. Meanwhile, calculations on the variation of minerals in ash with ash composition were conducted using the FactSage software. The results indicated that the AFTs under gasification were a little higher than those under the combustion atmosphere. On increasing the Fe₂O₃, CaO, and Na₂O contents under the combustion and gasification atmospheres, the four temperatures deformation temperature (DT), softening temperature (ST), hemispherical temperature (HT), and flow temperature (FT) decreased dramatically and the generation and transformation of minerals occurred. The iron-containing minerals, such as hercynite and fayalite, formed with increase in the content of Fe₂O₃; the Ca-bearing feldspar minerals, like gehlenite and anorthite, started appearing on increasing the CaO content, and the Na-containing feldspar minerals, like carnegieite, were detected as the Na₂O was increased. These three minerals can form low-temperature eutectics, decreasing the fusion temperature.     

Submicron ash formation from coal combustion

In recent years, fine particles have been found to be the cause of various harmful effects on health, and many countries have imposed restrictions on emission of these particles. Fine ash particles are formed during coal combustion in power stations and, if not collected in the air pollution control devices, are emitted into the atmosphere. The fine ash particles can remain airborne for long periods and can result in deleterious health effects when inhaled and deposited in the lungs.Previous studies have shown that combustion of coals of different rank can result in differences in the amount and chemistry of the submicron ash particles. This study examines the variability occurring between the submicron ashes formed from coals of similar rank. Five Australian bituminous coals were burned in a laminar flow drop tube furnace in two different oxygen environments to determine the amount and composition of submicron ash formed. The experimental setup is described and the repeatability of the experiments is discussed. The variability in the submicron ash yield as a percentage of the total ash collected and the submicron ash composition are presented and discussed. This paper presents experimental results rather than a detailed discussion on its interpretation. However, the results indicate that the condensation of evaporated species is responsible for the formation of ash particles smaller than 0.3 μm.     

Effects of Xinjiang high calcium coal co-firing on melting characteristics of Ca-bearing minerals in ash

In this study, a high-calcium coal, a high-silicon-aluminum Xinjiang coal and their blends were burnt in a drop tube furnace. The computer-controlled scanning electron microscope (CCSEM) was used to analyze the total ash mineral composition and particle size distribution after combustion. Based on CCSEM analysis, the composition data of single particle ash was obtained. The thermodynamic equilibrium method was used to calculate the liquid phase ratio of minerals in the ash, and the effect of coal blending on the melting characteristics of calcium-containing minerals in the ash was analyzed. The results show that the organically bound Ca easily interacts with other minerals in the coal. The mineral species of Ca-bearing minerals in the bulk ash mainly depend on the included minerals in coal. Co-firing will promote the conversion of calcium-containing aluminosilicate in the ash to calcium-containing complex aluminosilicate, and at the same time promote the melting of calcium-containing minerals. Under low temperature conditions, the particle size distribution of molten calcium-containing minerals in co-fired coal ash is affected by the particle size distribution of the alkali metal; however, under high temperature conditions, co-firing promotes the migration of molten calcium-containing minerals to large particle size ash.     

A mathematical model of ash formation during pulverized coal combustion

A mathematical model of ash formation during high-rank pulverized coal combustion is reported in this paper. The model is based on the computer-controlled scanning electron microscope (CCSEM) characterization of minerals in pulverized coals. From the viewpoint of the association with coal carbon matrix, individual mineral grains present in coal particles can be classified as included or excluded minerals. Included minerals refer to those discrete mineral grains that are intimately surrounded by the carbon matrix. Excluded minerals are those liberated minerals not or at least associated with coal carbon matter. Included minerals and excluded minerals are treated separately in the model. Included minerals are assumed to randomly disperse between individual coal particles based on coal and mineral particle size distributions. A mechanism of partial-coalescence of included minerals within single coal particles is related to char particulate structures formed during devolatilization. Fragmentation of excluded minerals, which is important particularly for a coal with a significant fraction of excluded minerals, is simulated using a stochastic approach of Poisson distribution. A narrow-sized sample of an Australian bituminous coal was combusted in a drop-tube furnace under operating conditions similar to that in boilers. The particle size distribution and chemical composition of experimental ash were compared to those predicted with the model. The comparisons indicated that the model generally reflected the combined effect of coalescence of included minerals and fragmentation of excluded minerals, the two important mechanisms governing ash formation for high-rank coals.     

Main mineral melting behavior and mineral reaction mechanism at molecular level of blended coal ash under gasification condition

The main mineral melting behavior and mineral reaction mechanism at molecular level of Chinese blended coal ash under gasification condition (30% H₂, 66% CO, 4% CO₂) from 1073 K to 1573 K were studied through the ASTM test, X-ray diffraction (XRD), ternary phase diagram system and quantum chemistry calculation with ab-initio calculations. The results show that with increasing blending mass fraction of low ash fusion temperature (AFT) ash (ash B), the location of blended ash in ternary systems is transferred from the mullite region to the anorthite region, as the dominant crystal mineral of blended ash at around DT (XRD analysis) is also transferred from mullite to anorthite. The calcium-bearing minerals, such as anhydrite, calcite etc., can react with mullite and the precursors of mullite (metakaolinite etc.), which is one of the main refractory minerals in high AFT ash (ash A), and is converted into low-melting minerals (anorthite, gehlenite, and fayalite etc.) in the temperature range between 1273 K and 1403 K. The reaction between mullite and CaO to form anorthite plays a significant role in decreasing AFTs of blended coal ash A/B. It is because the chemical activity of the highest occupied molecular orbits (HOMO) in mullite cluster is stronger than that of the lowest unoccupied molecular orbits (LUMO) in mullite cluster, the Ca²⁺ as electron acceptor can easily enter into the crystal lattice of mullite mainly through O (7) and O (12) and cause the rupture of bonds Al (1)-O (13) (in the [AlO₆]⁹⁻-octahedron) and Al (8)-O (13) (in the [AlO₄]⁵⁻-tetrahedron), which are weaker than any other bonds in crystal lattice of mullite. Finally, the entrance of Ca²⁺ can force mullite to transform to anorthite by the effect of Ca²⁺, and the entered Ca²⁺ is located in the center of [SiO₄]⁴⁻-tetrahedron ring in the anorthite crystal lattice. Taking the [SiO₄]⁴⁻-tetrahedron, which is composed of Si (70), O (78), O (48), O (91), O (86) as an example, the Ca²⁺ can capture the partial electronics of O (86) and cause the bond length (B.L.) of bond Si (70)−O (86) to become longer and unstable.     

新疆高钙煤混烧对灰中含钙矿物熔融特性影响

选用一种高钙和一种高硅铝新疆煤,在沉降炉中进行不同比例的混煤和单煤燃烧实验。采用计算机控制扫描电镜(CCSEM)分别对燃烧后总灰矿物成分和粒径分布进行分析。基于CCSEM分析获取单颗粒灰成分数据,采用热力学平衡方法对灰中矿物液相比例进行计算,分析混煤燃烧对灰中含钙矿物熔融特性影响。结果表明,煤中有机结合态Ca极易与煤中其他矿物元素发生交互反应,交互反应后含钙矿物种类取决于煤中内在矿种类。混煤燃烧会促进灰中含钙硅铝酸盐向含钙复杂硅铝酸盐转化,同时促进含钙矿物的熔融。在低温条件下,混烧煤灰中熔融含钙矿物粒径分布受碱金属粒径分布影响;但是高温条件下,混烧促进熔融含钙矿物向大粒径煤灰迁移。     

The effect of oxygen-to-fuel stoichiometry on coal ash fine-fragmentation mode formation mechanisms

Ash particles smaller than 2.5 μm in diameter generated during pulverized coal combustion are difficult to capture and may pose greater harm to the environment and human health than the discharge of larger particles. Recent research efforts on coal ash formation have revealed a middle fine-fragment mode centered around 2 μm. Formation of this middle or fine-fragment mode (FFM) is less well understood compared to larger coarse and smaller ultrafine ash. This study is part of an overall effort aimed at determining the key factors that impact the formation of FFM. This work examined the effects of oxygen-to-fuel stoichiometry (OFS).Pulverized Illinois #6 bituminous coal was combusted and the ash generated was size segregated in a Dekati low pressure inertial impactor. The mass of each fraction was measured and the ash was analyzed using scanning electron microscopy (SEM) and X-ray microanalysis. The FFM ash types were classified based on the SEM images to evaluate the significant fine-fragment ash formation mechanisms and determine any possible link between stoichiometry and formation mechanism.From the particle size distributions (PSDs), the coarse mode appears unaffected by the change in OFS, however, the OFS 1.05 lowered the fraction of ultrafine ash in relation to the higher OFS settings, and appears to increase the portion of the FFM. An intermediate minimum was found in the FFM at 1.3 μm for the 1.20 and 1.35 OFS tests but was not observed in the 1.05 OFS. SEM analysis also suggests that OFS may contribute to changing formation mechanisms.     

中国神木煤灰渣在高温下的流变特性

利用高温流变仪测定了中国神木煤灰渣在不同温度下的流变特性,并利用光学显微镜观察了煤灰渣在高温下冷激后的微观形貌,同时利用热力学软件FactSage预测了煤灰渣在不同温度下结晶粒子的相对含量与其均相熔体组成随温度的变化。实验结果表明:当实验温度为煤灰渣的全液相温度时,其流型表现为牛顿性流体;当温度低于其全液相温度时,随着温度的降低,其流型依次变为Bingham流型与Casson流型。同时随着温度的降低,由于煤灰渣中的固含量在不断增加,使得煤灰渣表现出明显剪切变稀的流变现象。最后利用Urbain模型与改进后的Einstein-Roscoe模型分别对煤灰渣中均相熔体黏度与实际黏度进行了模拟,其模拟值与实验值有良好的相关性。     

Study on the ash fusion temperatures of coal and sewage sludge mixtures

The coal, sewage sludge, water and chemical additives are milled to produce coal-sludge slurry as a substitute for coal-water slurry in entrained-flow gasification, co-gasification of coal and sewages sludge can be achieved. The ash fusion temperature is an important factor on the entrained-flow gasifier operation. In this study, the ash fusion temperatures (DT, ST, HT and FT) of three kinds of coals (A, B and C), two kinds of sewage sludges (W1 and W2) and series of coal-sewage blends were determined, and the mineral composition during the ash melting process was analyzed by X-ray diffraction (XRD). The results showed that the ash fusion temperatures of most coal-sewage blends are lower than those of the coals and sewage sludges. The ashes have different mineral composition at different temperature during the heating process. It was found that the mineral composition of AW1 blend ash is located in the low-temperature eutectic region of the ternary phase diagram of SiO₂-Al₂O₃-CaO. The minerals found in BW1 blend ash are almost the same as those in B coal ash. Kyanite is detected in CW1 blend ash, which results in the ash fusion temperatures of CW1 blend ash higher than those of C coal. We found that sodium mineral matters are formed because of NaOH added to W2, which can reduce the ash fusion temperature of coal-sewage blends.     

红外光谱分析淮南煤灰中矿物组成

选取淮南矿区HN115与HN119两种煤样,在氧化性气氛下,制成815℃煤灰。利用红外光谱研究了其矿物质组成以及煤中添加不同比例助熔剂CA后矿物组成的变化。结果表明:淮南煤灰中,矿物质组成为石英、硬石膏、方解石、高岭土和赤铁矿,其中硬石膏和方解石含量较低。煤中添加助熔剂CA后,煤灰中硬石膏含量增加,并且随着助熔剂CA量的不断增加,方解石含量在不断减少,硬石膏含量在不断增加。     

Manipulation of gasification coal feed in order to increase the ash fusion temperature of the coal enabling the gasifiers to operate at higher temperatures

Coal is a crucial feedstock for South Africa’s unique synfuels and petrochemicals industry and used by Sasol as a feedstock to produce synthesis gas via the Sasol-Lurgi Fixed Bed Dry Bottom (FBDB) gasification process. The ash fusion temperature (AFT) gives detail information on the suitability of a coal source for gasification purposes, and specifically to which extent ash agglomeration or clinkering is likely to occur within the gasifier. Ash clinkering inside the gasifier can cause channel burning and unstable operation.Sasol-Lurgi FBDB gasifiers are currently operated with the philosophy of adding an excess of steam to the process to control the H₂/CO ratio of the syngas produced, but indirectly also to control the maximum gasifier temperature below the AFT of the coal. An opportunity exists to increase the AFT of the coal fed to the gasifiers by adding AFT increasing minerals to the coal blend before it is fed into the gasification process. For the aim of this study a South African coal source was investigated, as being used by the gasification operations in Secunda.With the specific aim of this study, to increase the AFT, the determination of the AFT of the coal blends where acidic components such as silica (SiO₂), alumina (Al₂O₃) and titania (TiO₂) were added was conducted. The Al₂O₃ had the biggest and most significant effect on the AFT with the least addition to the coal blend. The effect of SiO₂ and TiO₂ were very similar, but the effect was much smaller and further Al₂O₃ was needed to increase the AFT to a similar AFT level in comparison to the SiO₂ used. Kaolinite, roof and floor components (containing mainly Al₂O₃ and SiO₂) were also added, also showing an increase in the AFT with up to 4 mass% addition. Another observation was that the AFT was non-additive (not a linear weighted calculated average) and not the weighted average AFT as was expected for the other coal properties such as the ash content, for example. The ash slagging characteristics is a non-additive property of individual coal sources in the blend and therefore difficult to predict.In general it can be concluded that the unique opportunity exists to increase the AFT, was tested, proven and mechanistically outlined in this study on the coal source fed to the Sasol-Lurgi FBDB gasifiers. The AFT can be increased to >1350 °C by adding AFT increasing minerals or species to the coal blend before it is fed into the gasification process. By increasing the AFT, the direct effect will be that steam consumption can be decreased, which in turn will improve carbon utilization.     

Conversion of coal fly ash into zeolite and heavy metal removal characteristics of the products

Fly ash obtained from a power generation plant was used for synthesizing zeolite. Zeolites could be readily synthesized from the glassy combustion residues and showed potential for the removal of heavy metal ions. By the use of different temperatures and NaOH concentration, five different zeolites were obtained: Na-P1, faujasite, hydroxy sodalite, analcime, and cancrinite. The synthesized zeolites had greater adsorption capabilities for heavy metals than the original fly ash and natural zeolites. Na-P1 exhibited the highest adsorption capacity with a maximum value of about 1.29 mmole Pb g^-1 and had a strong affinity for Pb²⁺ ion. The metal ion selectivity of Na-P1 was determined as: Pb²⁺> Cu²⁺> Cd²⁺> Zn²⁺, consistent with the decreasing order of the radius of hydrated metal ion. The adsorption isotherm for lead by Na-P1 fitted the Freundlich rather than the Langmuir isotherm.     

The application of molecular simulation in ash chemistry of coal

One of the crucial issues in modern ash chemistry is the realization of efficient and clean coal conversion. Industrially, large-scale coal gasification technology is well known as the foundation to improve the atom economy. In practice, the coal ash fusibility is a critical factor to determine steady operation standards of the gasifier, which is also the significant criterion to coal species selection for gasification. Since coal behaviors are resultant from various evolutions in different scales, the multi-scale understanding of the ash chemistry is of significance to guide the fusibility adjustment for coal gasification. Considering important roles of molecular simulation in exploring ash chemistry, this paper reviews the recent studies and developments on modeling of molecular systems for fusibility related ash chemistry for the first time. The discussions are emphasized on those performed by quantum mechanics and molecular mechanics, the two major simulation methods for microscopic systems, which may provide various insights into fusibility mechanism. This review article is expected to present comprehensive information for recent molecular simulations of coal chemistry so that new clues to find strategies controlling the ash fusion behavior can be obtained.     

碱性氧化物对煤灰熔融特征行为的影响

利用分析纯试剂制备了酸碱比为0.82,但Na₂O、CaO、MgO和Fe₂O₃含量不同的合成灰,并在815℃下在马弗炉中进行灼烧后,对其熔融温度进行测定。同时利用扫描电子显微镜-能谱仪（SEM-EDS）和X射线衍射仪（XRD）对样品微观形貌和矿物组成进行表征。结果表明：随着Na₂O质量分数从4%升高到12%,合成灰变形温度（DT）、软化温度（ST）、半球温度（HT）和流动温度（FT）分别从1225℃、1233℃、1255℃和1297℃下降为1162℃、1174℃、1181℃和1189℃,意味着Na₂O对合成灰具有较强的助熔效果;随着CaO和MgO含量在合成灰中分别增加,DT、ST和HT均单调上升,而FT则呈先下降后上升趋势,说明二者含量变化与合成灰熔融温度呈非线性关系;随着Fe₂O₃质量分数由5%增加至30%,FT由1215℃上升至1308℃,而其他3个熔融特征温度并无显著变化。通过SEM-EDS和XRD表征发现,合成灰中耐熔矿物（SiO₂和CaAl₂Si₂O₈等）和助熔矿物（CaMgSi₂O₆和NaAlSiO₄等）的比例变化和含钠矿物、含钙矿物之间低温共熔反应程度是影响其熔融温度的主要原因。综合对比所有合成煤灰熔融特征温度和化学组成发现,对于具有相同酸碱比的煤灰,DT主要与样品中Na₂O含量和碱土金属总量（CaO+MgO）密切相关影响,而FT主要受Na₂O和Fe₂O₃含量影响。