The char structure characterization from the coal reflectogram

Coal is a heterogeneous substance and its heterogeneity is identified and characterized by variation in reflectance. The main objective of this paper is to characterize the heterogeneity of char and to correlate it with the coal reflectogram, which accounts for both rank and maceral composition effects. Chars from two density fractions in a set of coals were obtained in a Drop Tube Furnace (DTF) at 1400 °C in N₂ environment. The chars were examined under a Scanning Electron Microscope (SEM) and the morphology information was obtained from the image-processing technique. The average porosity of char changes systematically with the FMR of its parent coals (defined as the summation of each reflectance multiplied with its frequency). The char porosity increased with an increase in FMR up to a critical value around 98. With further increase in FMR, the corresponding char becomes dense. The char macro porosity distribution was found to be related to the coal reflectogram. In general, the char porosity distribution shows two peaks, which corresponds to the inertinite and vitrinite peaks in reflectogram. The intensity depends on the maceral content. The relationship between the char porosity and coal reflectance for this set of sample has been found, which is strongly dependent on the coal rank. However, these findings cannot be applied to coals with a strong maceral association (microlithotype).     

The estimation of char reactivity from coal reflectogram

Measurements of the intrinsic reactivity of chars to oxygen are increasingly being sought as an indicator of the combustion potential of fuels. The coal reflectogram has been used to characterize the chemical properties of coal and its resultant char structure. In this study, six Australian coals varying in rank were separated using density separation technique to obtain vitrinite and inertinite rich fractions. Chars were obtained from these density fraction samples in a Drop Tube Furnace (DTF) at 1673 K. The reactivity of the chars was measured non-isothermally in a Thermal Gravimetric Analysis (TGA) in the temperature range of 573–1073 K. The results suggested that with the increase in the coal rank, the maximum reactivity of chars derived from vitrinite rich fractions decreases, while the reactivity of chars derived from inertinite rich fractions decreases with the increase in the inertinite content in samples and has no obvious relationship with rank. The kinetic parameters were derived using data from non-isothermal TGA after accounting for changing in surface area with conversion. The frequency factor is found to decrease with increasing coal FMR, defined as the summation of each reflectance value multiplied by its frequency, for a constant activation energy (E=146 kJ/mol). This suggests that the behavior of a maceral is characterized primarily by its reflectance distribution instead of the type of its parent coal.     

Study on the structure and gasification characteristics of selected South African bituminous coals in fluidised bed gasification

The gasification characteristics of three South African bituminous coals were investigated in a bubbling fluidised bed reactor. The three coals are similar in rank, but two are inertinite-rich coals and the third has a high vitrinite content. The microstructural characteristics of the parent coals and their resultant chars were determined using XRD, FT-IR, Raman and petrographic analysis. The microstructural changes that occurred in the organic (maceral) and the inorganic (mineral) fractions of the selected coals were evaluated. The change in the carbon structure was correlated to the proportions of inertinite and vitrinite macerals in the coals. High vitrinite content resulted in an increase in the order of the disordered carbon structure after gasification and this leads to greater graphitised ordered carbon structures. While a high inertinite content resulted in low or no structural transformation of the chemical structure. The transformation of inorganic mineral constituents of the coal was correlated to the amount of inertinite present in the selected coals. Higher proportions of inertinite macerals and inertinitic chars resulted in higher proportions of melted minerals. Char samples with low proportions of organic matter resulted in higher proportion of melted minerals covering the char surface.     

Pyrolysis behavior of vitrinite and inertinite from Chinese Pingshuo coal by TG-MS and in a fixed bed reactor

The pyrolysis behaviors of vitrinite and inertinite from Chinese Pingshuo coal were investigated by using the thermogravimetry coupled with mass spectrometry (TG-MS) and in a fixed bed reactor, respectively. The results showed that inertinite has lower pyrolysis reactivity, lower tar and gas yields, but higher water yield than vitrinite. At 650 °C, the tar and gas yield of vitrinite is 22.4% and 14.4%, respectively, obviously higher than 13.4% and 10.2% of inertinite. The TG-MS analysis also showed much difference of vitrinite and inertinite in gas evolution profile. The ultimate and XRD analyses of chars indicated that the difference in element composition of vitrinite char and inertinite char decreases with the increase of temperature, and have similar element composition and structure characteristic at 650 °C. The total sulfur removal of both vitrinite and inertinite increases with the pyrolysis temperature, and reaches to 60% at 650 °C, but the organic sulfur in inertinite seems more stable than that in vitrinite.     

A reactivity study of chars obtained at different temperatures in relation to their petrographic characteristics

This study reports on the reactivity of chars obtained at 1000°C and 1300°C (within the range of temperatures reached by coal particles in the near-burner zone of pulverised fuel boilers) from three different coals. The coals were selected according to petrographic criteria: two of them are high volatile bituminous coals differing in maceral composition and the third one is a vitrinite-rich low volatile bituminous coal.The morphology and optical texture of the chars were studied by optical microscopy. The kinetic parameters for the combustion of the high temperature chars under Regime I (combustion controlled by chemical kinetics) have been obtained and related to the optical texture and reflectance of the chars. The intrinsic reactivity of the high temperature chars was found to be lower than that of the low temperature chars, whereas the enhanced porosity observed in the high temperature chars had a positive effect on their combustion reactivity under Regime II (combustion controlled by oxygen pore diffusion). The intrinsic reactivities of the chars decreased following the sequence: vitrinite-rich low rank char>inertinite-rich char>vitrinite-rich high rank char. As the combustion temperature increases, the reactivity of the inertinite-rich char approaches that of the low rank vitrinite-rich char, which justifies the good performance observed for high volatile bituminous inertinite-rich coals in power plants.     

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.     

Properties of high ash char particles derived from inertinite-rich coal: 1. Chemical,structural and petrographic characteristics

An investigation was undertaken to determine the properties of high ash coal–chars derived from South African discards rich in inertinites, for the development of suitable overall reaction rate models at low temperatures (<900 °C). Detailed characterisation results of the parent coal and chars prepared at 700 °C and 900 °C obtained from standard coal analytical methods, petrographic techniques, CCSEM image analysis and a surface adsorption method are presented. The parent coal consisted of 32% by volume of inertite (“pure” inertinite), 7% of vitrite (pure “vitrinite”), and 13% of bi- and tri-macerite, 30% of maceral/mineral mixtures (carbominerite) with 18% of mineral-rich material. Reflectances obtained from measurements taken on vitrinites and total maceral reflectance scans increased dramatically on charring at 900 °C and were accompanied by an extension of vitrinite reflectance class distributions indicating higher molecular ordering. Volatiles were liberated essentially from the original parent vitrinites, creating fine gas pores. Inertinites increased in reflectance but not in porosity and were characterised as dense char fractions in the final charred product, according to a coal form analysis. Structural change due to low temperature thermal stress fracturing (passive deflagration) occurred early on in the temperature regimes, creating increased surface areas and porosity. The chars consist of a high proportion (52%) of extraneous rock fragments together with minerals mainly as fine inclusions in carbon rich particles (13%). The chars had very low porosities and surface areas. These were created by the devolatisation of reactive maceral associations and deflagration. Such materials could introduce intra-particle diffusional effects during gasification and combustion of millimetre size particles at low temperatures.     

The CO2-gasification and kinetics of Shenmu maceral chars with and without catalyst

The CO₂ gasification of maceral chars was performed using CAHN TG-151 pressurized thermobalance under different conditions. The effect of mineral in macerals and catalyst on the gasification reactivity of maceral chars and the gasification kinetics were systematically investigated. The results showed that the apparent gasification rate of maceral chars depends on the temperature, pressure, BET surface area of chars and the gasification extent. With increasing temperature and pressure, the gasification rate of maceral chars all increase. After demineralization, the gasification reactivity of maceral chars all decrease. The gasification reactivity of maceral chars greatly increases with loading catalyst. And the loading method of catalyst has great effect on the gasification reactivity. The maceral chars loaded with catalyst by ultrasonic treatment have higher gasification reactivity than that by impregnation. The comparison of gasification reactivity of maceral charas demineralized maceral chars and maceral chars with and without catalyst showed that vitrinite chars always have higher gasification reactivity than inertinite chars. The kinetic results by distributed activation energy model showed that inertinite char has higher activation energy than vitrinite char, and the addition of catalyst greatly minimizes the activation energy and enhances the gasification rate.     

The variation of structural characteristics of macerals during pyrolysis

Vitrinite and inertinite were separated by DGC from Chinese Shenmu bituminous coal and the structural characteristics of the macerals, before and after pyrolysis, were analyzed by ultimate analysis, FTIR and ¹³C NMR. The results showed that vitrinite chars always had higher H and lower C content than inertinite char at the same pyrolysis temperature. The FTIR and ¹³C NMR indicated that vitrinite had more aliphatic C-H, hydrogen bonding and lower aromaticity. With increasing temperature, the aliphatic C-H decreased, aromatic C-H, aromaticity and H_ar/H_al ratio increased. At the same temperature, inertinite always had higher H_ar/H_al ratio than vitrinite, which is consistent with that inertinite had higher aromaticity than vitrinite. And the H_ar/H_al ratio was also related to the remainder volatile matter. With increasing H_ar/H_al ratio, the remainder volatile matter in vitrinite and inertinite decreased. The higher aromaticity and H_ar/H_al ratio and lower H content of the inertinite in all temperature range were correlated with its higher thermal stability and lower volatile yield than vitrinite.     

陕北低阶烟煤显微组分结构特征及分子结构模型

为了更好地利用我国丰富的低阶煤资源,以变质程度较低的陕北低阶烟煤镜质组、惰质组富集物作为研究对象,采用常规的煤质分析、傅立叶变换红外光谱、高分辨固体13C核磁共振、X射线衍射等分析表征手段,对样品结构进行全面分析,得到了陕北低阶烟煤显微组分分子结构特征及结构参数,建立了镜质组和惰质组的部分分子结构模型。结果表明,陕北低阶烟煤镜质组和惰质组氧含量均较高,硫含量很低,所选镜质组的芳碳率为0.634,平均缩合环数约为2.98个;惰质组的芳碳率为0.734,平均缩合环数约为3.15个;相对于镜质组,惰质组的缩合程度更高,芳核尺寸更大,排列也更加规则有序。今后低阶烟煤加工转化工艺的研究应从分子层面揭示其不同显微组分结构特征的差异性,为低阶烟煤清洁高效利用新工艺的开发奠定基础。     

Exploring the possibilities of using Brazilian subbituminous coals for blast furnace pulverized fuel injection

The current study investigates the combustion and blast furnace injection performance of three Brazilian subbituminous coals (Mina do Recreio) and their beneficiation products using laboratory scale combustion tests. The coals have relative high ash yields (up to 40 wt%) that were reduced stepwise to levels as low as 12 wt%, dry basis. The reduction of ash yields is paralleled by a significant decrease in sulphur and inertinite contents.The combustion tests were performed in a drop tube reactor operating at 1300 °C using two different atmospheres (2.5 and 5% O₂). The chars exhibited preferentially rounded shapes with thick walls and abundant secondary porosity for the 2.5% O₂ chars, whereas the 5% O₂ chars showed very thin walls as a consequence of extensive burnout. The intrinsic reactivities of both set of chars were similar. The differences in conversion between the two working atmospheres were 24-37% and roughly tend to increase with increasing mineral matter content. Conversions as high as 76-81% were reached operating under 5% O₂ indicating that the coals are easy to burn. The small differences in burnout among the coals and their beneficiation products cannot be clearly attributed neither to mineral matter or inertinite content. A rough inverse relationship was found between the intrinsic reactivity of the chars and the inertinite content of the parent coal indicating that the char material derived from inertinite was intrinsically less reactive than that derived from vitrinite. These differences were no longer relevant at high temperature.Blast furnace injection performance was studied through thermobalance experiments using CO₂ atmosphere and 1050 °C temperature. It is apparent that the beneficiation process has no effect on the reactivity of the coals from Recreio Mine. The only exception is the low ash coal-2-LabB (11.5 wt%), for which a higher reactivity is indicated. The reactivity tests show also that the coals have adequate properties to be used together with imported coal blends in pulverized coal injection in the blast furnace (PCI).     

Reactivities of 34 coals under steam gasification

The reactivities of 34 coal chars of varying rank with H₂O have been determined to examine the effect of coal rank on the gasification rate of coal char. The reactivities of chars derived from caking coals and anthracites (carbon content > 78 wt%, daf) were very small compared with those from non-caking (lower-rank) coals. The reactivities of low-rank chars do not correlate with the carbon content of the parent coals. To clarify which factor is more important in determining the reactivity, the evolution of CO and CO₂ from char, the moisture content of char and the amount of exchangeable cations were determined for these low-rank coals or their chars. These values were considered to represent the amount of active carbon sties, the porosity and the catalysis by inherent mineral matters, respectively. It was concluded that the amount of surface active sites and/or the amount of exchangeable Ca and Na control the reactivity of low-rank chars in H₂O.     

Gasification kinetics of five coal chars with CO<Subscript>2</Subscript> at elevated pressure

For five coals, the reactivity of char-CO₂ gasification was investigated with a pressurized thermogravimetric analyzer (PTGA) in the temperature range 850-1,000 C and the total pressure range 0.5-2.0 MPa. The effect of coal rank, initial char characteristics and pressure on the reaction rate were evaluated for five coal chars. The reactivity of low lank coal char was better than that of high rank coal char. It was found that Meso/macro-pores of char markedly affect char reactivity by way of providing channels for diffusion of reactant gas into the reactive surface area. Over the range of tested pressure, the reaction rate is proportional to CO₂ partial pressure and the reaction order ranges from about 0.4 to 0.7 for five chars. Kinetic parameters, based on the shrinking particle model, were obtained for five chars.     

Coal lump devolatilization and the resulting char structure and properties

Lumps of six bituminous coals, from 20 to 40 mm in size, were devolatilized in a laboratory oven in nitrogen atmosphere at different final temperatures ranging from 300 to 800 °C. The structure and morphology of the resulting chars with different degree of devolatilization have been examined under an optical microscope in order to better understand the formation mechanism of different types of char. The swelling of the caking coals and the fissuring of the non-caking coals were characterised by image analysis and some correspondences between the distribution of lithotypes within the initial coal lumps and the char structure obtained were revealed. The relation between chars structure and properties was also investigated. The char lumps obtained from caking coal exhibit better resistance to breakage than their parent coal lumps while non-caking coals show the opposite behaviour. For both caking and non-caking coals, a significant decrease of resistance is observed in the intensive devolatilization temperature range from 400 to 600 °C.     

Char characterization and DTF assays as tools to predict burnout of coal blends in power plants

The aim of this study is to predict efficiency deviations in the combustion of coal blends in power plants. Combustion of blends, as compared to its single coals, shows that for some blends the behavior is non-additive in nature. Samples of coal feed and fly ashes from combustion of blends at two power plants, plus chars of the parent coals generated in a drop-tube furnace (DTF) at temperatures and heating rates similar to those found in the industrial boilers were used. Intrinsic kinetic parameters, burning profiles and petrographic characteristics of these chars correlated well with the burnout in power plants and DTF experiments. The blend combustion in a DTF reproduces both positive and negative burnout deviations from the expected weighted average. These burnout deviations have been previously attributed to parallel or parallel-series pathways of competition for oxygen. No deviations were found for blends of low rank coals of similar characteristics yielding chars close in morphology, optical texture and reactivity. Negative deviations were found for blends of coals differing moderately in rank and were interpreted as associated with long periods of competition. In this case, fly-ashes were enriched in material derived from the least reactive char, but also unburnt material attributed to the most reactive char was identified. Improved burnout compared to the weighted average was observed for blends of coals very different in rank, and interpreted as the result of a short interaction period, followed by a period where the less reactive char burns under conditions that are more favorable to its combustion. In this case, only unburned material from the least reactive char was identified in the fly-ashes.     

升温速率及水蒸气分压改变对神华煤焦及其显微组分焦气化反应性的影响

用非等温热重法考察了神华煤焦及其显微组分富集物焦的水蒸气气化反应,分析了升温速率、水蒸气分压改变对煤焦及其显微组分富集物焦气化反应性的影响。利用最大反应速率和半衰期两种方法评价了所选样品的气化反应性。结果表明：对神华煤而言,在相同的气化反应条件下,当升温速率和水蒸气分压发生改变时,其气化反应性顺序均为,镜质组富集物焦〉原煤焦〉惰质组富集物焦。     

平顶山高灰熔融性温度煤的气化反应性研究

介绍了平顶山地区有代表性的7种煤样在800℃～1 200℃下,其脱灰煤焦-CO2气化反应活性的实验,主要考察了煤种、灰含量及粒径对煤焦反应性的影响,实验结果表明:煤种对煤焦-CO2气化反应有明显影响;煤中灰分对煤焦气化反应的影响主要表现在两个方面,一是灰成分对煤焦气化反应的催化作用,二是灰熔融性影响煤焦气化排渣行为。脱灰既可以除去煤焦中具有催化作用的矿物质,又可以增大煤焦的内表面积。     

Reactivity of heat-treated coals in air at 500 °C

Twenty one US coals, of widely ranging rank, have been carbonized under controlled conditions to 1000 °C, and the reactivity in air at 500 °C of the resulting chars or cokes has been measured by a gravimetric method. The reactivities lie within a well-defined band when plotted against rank of the parent coal. The lower-rank coal chars are more reactive than those prepared from high-rank coals. In extreme cases, the reactivity found for a Montana lignite char is some 100 times as great as that obtained for a char produced from a Pennsylvania low-volatile coal. Variation of reactivity with heat-treatment temperature (600 to 1000 °C) has been studied for three coals. As heat-treatment temperature increases, there is a decrease in reactivity. Some results are reported on the effects which mineral matter and pore structure have on the reactivity parameter. Chars containing high concentrations of magnesium and calcium impurities are most reactive. The amount of macro and transitional porosity in a char has a marked influence on reactivity.     

Thermogravimetric determination of the carbon dioxide reactivity of char from some New Zealand coals and its association with the inorganic geochemistry of the parent coal

Thermogravimetrically-determined carbon dioxide reactivities of chars formed from New Zealand coals, ranging in rank from lignite to high volatile bituminous, vary from 0.12 to 10.63 mg/h/mg on a dry, ash-free basis. The lowest rank subbituminous coal chars have similar reactivities to the lignite coal chars. Calcium content of the char shows the strongest correlation with reactivity, which increases as the calcium content increases. High calcium per se does not directly imply a high char reactivity. Organically-bound calcium catalyses the conversion of carbon to carbon monoxide in the presence of carbon dioxide, whereas calcium present as discrete minerals in the coal matrix, e.g., calcite, fails to significantly affect reactivity. Catalytic effects of magnesium, iron, sodium and phosphorous are not as obvious, but can be recognised for individual chars. The thermogravimetric technique provides a fast, reliable analysis that is able to distinguish char reactivity differences between coals, which may be due to any of the above effects.     

Optical image analysis of fine coal particles as an aid in optimizing combustion in a fluidized bed

The performance of a fluidized bed combustor is adversely affected by the entrainment of fine coal and char particles. The size distribution of the entrained particles is an indicator of the combustor's performance. Size analysis data may be helpful for optimizing the operating conditions.

An optical image analysis system (TAS, Leitz) was used to analyze the size distribution of char particles elutriated from a small fluidized bed after one single pass. The TAS system discriminates between highly reflecting char particles and low-reflectance ash. The maximum size of the chars produced in these experiments was about 50 μm, almost independent of the type of coal.