Coal 29

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Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review
Jianglong Yua, John A. Lucasb, Terry F. Wallb,
Faculty of Energy and Power Engineering, Shenyang Institute of Aeronautical Engineering, 52 Huanghe Bei Avenue, Shenyang, 110034, PR China b Department of Chemical Engineering, School of Engineering, University of Newcastle, Callaghan, NSW 2308, Australia Received 21 July 2005; accepted 25 July 2006
a
Abstract The paper provides an overview of current studies on the behaviour of coal during devolatilization, especially the experimental studies and modelling efforts on the formation of char structure of bituminous coals in the open literature. Coal is the most abundant fossil fuel in the world. It dominates the energy supply in the future and plays an increasing role particularly in the developing countries. Coal utilization processes such as combustion or gasication generally involve several steps: i.e., the devolatilization of organic materials, homogeneous reactions of volatile matter with the reactant gases and heterogeneous reactions of chars with the reactant gases. The devolatilization process exerts its inuence throughout the life of the solid particles from the injection to the burnout, therefore is the most important step which needs to be understood. When volatile matter is generated, the physical structure of a char changes signicantly during the devolatilization, some accompanying a particles swelling. The complexity of a chars structure lies in the facts that the structure of a char itself is highly heterogenous inside an individual particle and between different particles and the chemistry of a char is strongly dependent on the raw coal properties. A chars structure is strongly dependent on the heating conditions such as temperature, heating rate and pressure. Understanding the swelling of coal and the formation of chars pore structure during the devolatilization of pulverized coal is essential to the development of advanced coal utilization technologies. During combustion and gasication of pulverized coal, the behaviour of individual particles differs markedly due to the variation of their maceral composition. Particles with different maceral constituents generate different types of char structure. The structure of a char has a signicant impact on its subsequent heterogeneous reactions and ash formation. The review also covers the most recent studies carried out by the authors, including the experimental observations of the thermoplastic behaviour of individual coal particles from the density fractions using a single-particle reactor, the experimental analysis on chars prepared in a drop tube furnace using the density-separated coal samples, the development of a mathematical model for the formation of chars pore structure based on a simplied multi-bubble mechanism and the investigation on the effect of pressure on char formation in a pressurized entrained-ow reactor. r 2006 Elsevier Ltd. All rights reserved.
Keywords: Char structure; Devolatilization; Pulverized coal; Coal swelling; Thermoproperty
Corresponding author. Tel.: +61 2 49 216179; fax: +61 2 49 216920.
E-mail address: Terry.Wall@newcastle.edu.au (T.F. Wall). 0360-1285/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.pecs.2006.07.003 Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003
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2 J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]]
Contents 1. 2. 3. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Coal and its heterogeneity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Devolatilization of coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3.1. Mechanism of coal pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 3.2. Relation between the yield of products and heating conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 3.2.1. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 3.2.2. Effect of heating rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.2.3. Effect of pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.2.4. Effect of particle size. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.3. Devolatilization models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 3.4. Changes in physical properties of coal during heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Formation of char structure from pulverized coal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.1. Importance of char structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 4.2. Classication of char structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 4.2.1. Pore system in coal and char . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 4.2.2. Classication of char structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 4.3. Relation between char structure and coal properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 4.4. Relation between char structure and heating conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 4.4.1. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 4.4.2. Effect of heating rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 4.4.3. Effect of pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 4.4.4. Char characteristics and gas environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 4.5. The relationship between char structure and coal swelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 4.6. Studies on transient coal swelling using single-particle reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 4.7. Application of density-separation techniques in studies of char structure . . . . . . . . . . . . . . . . . . . . . . . 23 Modelling the swelling and the formation of chars structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.
5. 6.
1. Introduction Coal is the most abundant fossil fuel in the world [1]. Worldwide, coal continues to dominate the energy supply in the future and play an increasing role particularly in developing countries. Coal utilization processes such as combustion or gasication generally involve several steps [2]: i.e., the devolatilization of organic materials leaving char behind, homogeneous reactions of volatile matter with the reactant gases and heterogeneous reactions of the char with the reactant gases during which ash is formed. The devolatilization process exerts its inuence throughout the life of the solid particles from the injection to burnout [3], therefore is the most important step which needs to be considered in modelling coal combustion [4]. While volatile matter is generated during the devolatilization, the physical structure of a char changes signicantly, some accompanied by the particles swelling [5]. The
complexity of chars structure lies in the facts that the structure itself is highly heterogenous within one individual particle and between different particles; the chemistry of a char is strongly dependent on the raw coal properties and a chars structure is strongly dependent on heating conditions such as the temperature, heating rate and pressure. Understanding of the swelling of coal and the formation of a chars pore structure during the pyrolysis of pulverized coal is crucial to the development of advanced technologies for coal utilization. During the combustion and gasication of pulverized coal, the behaviour of individual particles in a given coal varies markedly due to the variation of their maceral composition. Particles with different maceral constituents generate different types of char structure [6]. The char structure has a signicant inuence on the subsequent char reactions and ash formation [712]. These have attracted wide research interests over the past decades. This paper
Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003
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provides an overview of current studies on the behaviour of coal pyrolysis, particularly the experimental studies and modelling efforts on the formation of chars structure of bituminous coals in the open literature. 2. Coal and its heterogeneity As a sediment rock, coal varies remarkably in its chemical and physical properties depending on its maturity and geological environment of the coalication. In standard systems, coal is generally classied by its rank with xed carbon content and caloric value as the major indicators [1316] and is termed as lignite, sub-bituminous coal, bituminous coal and anthracite. The major transformations in coals properties with increasing the coal rank can be summarized as [17]: (1) a drop in moisture and a marked decreases in the oxygen content due to the loss of hydroxyl, carbonyl and carboxyl groups; (2) a removal of aliphatic and alicyclic groups which causes an important reduction in the volatile matter content with a parallel increase in the aromaticity during the bituminous coal stage; (3) the anthracite stage is characterized by a rapid fall of hydrogen (H2) content and a strong increase in both the reectance and the optical anisotropy. An increase in the aromaticity of coal with increasing the rank was reported by Whitehurst et al. [18]. The aromatic carbon content increases from 40% to 50% for sub-bituminous coal to over 90% for anthracite. Owing to the changes in its properties, the behaviour of a coal of different rank varies drastically during combustion and gasication [2]. Coal is well known as a heterogenous substance with a mixture of organic material (i.e., the coal matrix) and inorganic material (i.e., the mineral matter) [14,19,20]. Macroscopically, coal has a pronounced banded feature recognized as bright, predominantly bright or dull in the appearance [14,21]. The identiable banded components are termed as lithotypes. Microscopically, the organic material of coal consists of complex maceral constituents classied as three groups, i.e., liptinite, vitrinite and inertinite [19,2123]. Since different macerals are derived from different original plant tissues or coalied in different geological environment, there are remarkable distinctions in their chemical and physical properties between different maceral groups. In general, the volatile matter content, H2 content and H/C ratio appear in the
order: liptinite4vitrinite4inertinite. However, the reectance changes in the order: liptiniteovitriniteoinertinite. With increasing the coal rank, the change in its properties such as chemical composition and reectance of each maceral group follows its own path, as shown in Fig. 1(a) and (b). For most of the world coals, vitrinite group is the most abundant constituent. There is a tendency that the reectance of vitrinite is used as the indicator of coal rank [24]. For pulverized coal, remarkable variations in the maceral composition exist between individual particles from the same coal [6,7]. During
Fig. 1. Hydrogen content (a) and reectance (b) of macerals as a function of coal rank [14,19].
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heating, particles with different maceral constituents behave differently including the swelling, the yield of volatile matter, char structure, the reactivity and ash chemistry. Therefore, the microscopic heterogeneity of coal has attracted wide scientic interests in pulverized coal combustion and gasication [6]. However, the variation in the property of the different maceral groups diminishes at high rank. Therefore, it may be expected that maceral components of different groups from high rank coals may behave similarly during combustion [25,26]. The chemical structure, i.e., the macromolecular network of a coal is extremely important in terms of its devolatilization behaviour [16]. In the meantime, coal has a complex pore structure system which plays an important role during pyrolysis or gasication [27]. Upon heating, the pore structure of a coal changes dramatically. The physical structure of the solid residue generated during devolatilization is signicantly different from that of the feed coal. For softening coals (in bituminous rank), the original pore structures of a coal may be blocked due to the high uidity when it is heated [16]. The char structure is therefore determined by the devolatilization process (e.g., thermoplastic properties of the coal and heating conditions) rather than by its original pore structure. 3. Devolatilization of coal Coal devolatilization is referred to as pyrolysis when coal is devolatilized in an inert gas. Devolatilization and pyrolysis are usually not distinguished from each other due to the similar behaviour of coal in the two processes in terms of char chemistry and the composition of volatile matter [28]. The behaviour of coal during pyrolysis under different heating conditions has been extensively studied and reviewed over the past few decades [3,5,6,14,2838]. During heating, coal particles experience very complex physical and chemical transformations while yielding volatile matter and generating solid residues. Early review provided summaries of the kinetics of coal pyrolysis [31]. The experimental processes, kinetic rates and mechanisms of coal pyrolysis were reviewed by Solomon et al. [36]. Products resulting from the coal pyrolysis include gases, tar and solid char. The denition of pyrolysis products has also been summarized. Gas components can be dened straightforward, including some sulphur- or nitrogen-containing gases. Tar is dened as room temperature condensable compo-
nents which separate from the solid products during pyrolysis. The remaining solid is char which includes extractables of large molecular weights. Experimental investigations involve a variety of either captive or non-captive techniques such as wire mesh reactors or heating grids (screens), drop tube furnaces (DTFs) or gas ow reactors, TGA or uidized bed reactors. A summary of experimental conditions for different techniques has been provided by Solomon et al. [36] and Gavalas [33]. Apart from the particle size used in the different experimental techniques, heating conditions such as the heating rate, temperature and pressure of different reactors vary signicantly. Therefore, one should be very careful when comparing the experimental data by different researchers. 3.1. Mechanism of coal pyrolysis The mechanism of pyrolysis has been summarized in the literature [5,16,31,33,36,38]. Pyrolysis reactions are complex, broadly involving bond breaking, vaporization and condensation or cross-linking, accompanying changes in the density of aliphatic group and aromaticity. Saxena [38] summarized that pyrolysis reactions commence with the rupture of weak bonds. Since a minimum amount of energy is required to overcome the CC bond energy, pyrolysis reactions do not commence until the temperature is close to 670 K. The CC bonds at the bridge between the ring systems are much weaker than other CC bonds, particularly the ones in the aromatic ring structures. Therefore, the pyrolysis begins with the cracking of bridges between the ring systems, resulting in the formation of free radical groups such as CH2, O, etc. These free radicals are highly reactive and readily combine in the gas phase to produce the aliphatics (mainly methane, CH4) and water. Since the polynuclear aromatic compounds diffuse slowly even at high temperatures, they start to condense with the elimination of H2. The ultimate product due to the condensation reaction is coke/char. In addition, at high temperature, CO is also produced through the cracking of heterocyclic oxygen groups. The following typical reactions take place in stages as the temperature is increased [38]. Cracking: Saturation: Tar production: RCH2R0 -RR0 +CH2. CH2+2H0 -CH4, OH+H0 -H2O. RCH2+H0 -RCH3.
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Condensation (cross-linking) reactions: R2OH H2R ! R2R H2 O: R2H H2R0 ! R2R0 coke H2 : The R radical is obtained from benzene, naphthalene or phenantherene, etc. Oxides of carbon are produced by the following reaction: R2COOH ! R2H CO2 : Obviously, H2 is a key elemental composition in terms of pyrolysis reactions, particularly for the evolution of tars [38]. H2 in coal is used up partly to produce hydrocarbons and water and partly is liberated as molecular H2. The hydro-aromatic H2 is consumed in three different reactions, i.e., (i) in saturating the OH and O radicals to produce water; (ii) by the CH2 radicals to produce the aliphatics; and (iii) in saturating the larger radicals to produce tar molecules. The aromatically bonded H2 is liberated as molecular H2 during the condensation of aromatic nuclei to produce char. During gasication process, the objective is to use the H2 in coal as efciently as possible by devolatilization. But the structure of coal is such that it preferentially evolves H2 as chemical water and light aliphatics depleting the remaining carbon of much needed H2 during pyrolysis. Hence pyrolysis always produces char due to the inefcient use of the intrinsic H2. Excess H2 during hydro-pyrolysis signicantly enhances the production of tars and hydrocarbons [5,31,37]. During pyrolysis, Td is commonly identied as the active thermal decomposition temperature of coal beyond which massive weight loss takes place. Signicant thermally induced structural changes may occur without generating major amounts of volatile matter below Td [14]. These structure changes have important association with the pyrolysis reactions occurring later on. The overall decomposition process is therefore viewed as three successive stages: (i) limited thermal alterations of the original molecular structures (mostly by condensation reactions) at temperatures below Td; (ii) active decomposition leading to the generation and discharge of the bulk of volatile matter, primarily in the form of tars and light oils between Td and $820 K; and (iii) secondary degasication resulting in the formation and evolution of a variety of hydrocarbon gases, elemental H2 and oxides of carbon over an extended temperature range above $820 K.
An important concept in coal pyrolysis may be the functional group [18]. Gavalas [33] summarized functional groups and their roles in the thermal decomposition of coal. The reactivity of coal in pyrolysis can be characterized by the following functional groups, i.e., the aromatic nuclei, hydroaromatic structure, alkyl chains, alkyl bridges and oxygen containing groups. The thermal reactions such as bond dissociation, H2 abstraction and H2 addition were also described accordingly. Nine steps of the pyrolysis reactions were proposed to interpret the evolution of volatile matter by Solomon et al. [36]. As coal is heated, three processes occur in the temperature range of 470670 K. These processes are the disruption of H2 bonds (Step1), the vaporization and the transport of the non-covalently bonded molecular phase (Step 2) and low-temperature cross-linking in coals with more than 10% oxygen (Step 3) which coincides with CO2 or H2O evolution. During primary pyrolysis, the weakest bridges can break by producing molecular fragments (depolymerization) (Step 4). The fragments abstract H2 from the hydroaromatics or aliphatics, thus increasing the aromatic H2 concentration (Step 5). These fragments will be released as tar if they are small enough to vaporize and be transported out of the char particle (Step 6) under conventional pyrolysis conditions and do not undergo moderate temperature cross-linking reactions before escaping from the particle. The moderate temperature cross-linking reactions (Step 7) are slightly slower than the bridge breaking reactions and appear to correlate with CH4 evolution. The other event during primary pyrolysis is the decomposition of functional groups to release gases (Step 8), mainly CO2, light aliphatic gases and some CH4 and H2O. The release of CH4, CO2 and H2O may produce cross-linking, e.g., CH4 by a substitution reaction in which the attachments of a larger molecular weight release the methyl group, CO2 by condensation after a radical is formed on the ring when a carboxyl is removed, and H2O by the condensation of two OH groups or an OH group and a COOH group to produce an either link. The cross-linking is important to determine the release of tar and the visco-elastic properties of the char. The primary pyrolysis completes when the donatable H2s from hydro-aromatic or aliphatic portion of the coal are depleted. During secondary pyrolysis, there is additional gas formation (Step 8), i.e., CH4 evolving from methyl groups, HCN from ring nitrogen compounds and CO from
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ether links. And nally H2 evolves by ring condensation (Step 9). Another comprehensive reaction mechanism of pyrolysis was proposed by Ju ntgen [39,40] and overviewed by Smith [16]. This mechanism includes the desorption of water at 390 K, distillation of the mobile phase beginning at 520620 K forming an aliphatic tar, the formation of tar and gases by the degradation of the macromolecule beginning up to 620 K and the formation of char by condensation reaction with simultaneous evolution of H2 and CO at high temperature. This overall picture provides interpretations to some low heating rate experimental data. Pyrolysis of lignite is comprised of ve principal devolatilization phases according to the study by Suuberg et al. [41]. Pyrolysis behaviour of softening coals has been described as three stages [42], as illustrated in Fig. 2. Coal undergoes a reduction of H2 bonding during stage I. Sufcient labile bond breaking of the macromolecular network also occurs to form primary gas and liquid components which are often referred to as metaplast. The metaplast is generally recognized to be responsible for the uidity of coal upon heating [4347]. Bond breaking competes with bond stabilization to form char during stage I. Much of the material that is associated with the mobile phase and extractable with suitable solvents is released in this stage. Stage II is featured by bulk evolution of tar which is considered to be the low-molecular-weight component of metaplast. The remaining high-molecularweight components in the metaplast re-attach to the char structure by cross-linking reactions. In FGDVC model [36,48,49], tar forms as a result of the combined depolymerization and vaporization processes. The formation of gases is correlated with the decomposition of the functional groups. Thus coals with different functional group compositions will behave differently during pyrolysis. During stage
III, char evolves CO and H2 while continuing to cross-link with further ring condensation. Fig. 3 shows the experimental results of evolution rate and cumulative weight loss of volatile species of a bituminous coal analysed on a TG-FTIR [36]. During the pyrolysis at slow heating rates (o1 K s1) [16,38], the occluded carbon dioxide (CO2) and CH4 are driven off at about 470 K. Above this temperature, internal condensation occurs among the macromolecular structure of low-rank coals with the evolution of CO2 and water. In the range 470770 K, CH4 begins to evolve with its higher homologues and olens; most of the oxygen in coal structure is eliminated as water and oxides of carbon. The decomposition of both nitrogen structure and organic sulphur species begins in this temperature range. The evolution of H2 begins at 670770 K with a critical point at about 970 K characterized by a rapid evolution of H2 and carbon monoxide (CO). In the temperature range 770970 K, the volume of gases such as H2, CO, CH4 and nitrogen increases with increasing the temperature while most hydrocarbons decrease. Tar formation begins at around 570670 K with a maximum yield occurring at approximately 770820 K. For some bituminous coals, the tar evolution rate curves often show a small peak or shoulder at a lower temperature before the main peak due to the non-covalently bonded guest molecules [16]. The main peak is due to the release of coal fragments during the break-up of the macromolecular coal structure by bonds breaking, evaporation and transport. The character and composition of tars vary with the temperature and coal type. The proportion of the gases and tars vary widely with coal rank [16,50,51]. In general, low-rank coals generate a high yield of gases and a low yield of tar. High volatile bituminous coals generate a high yield of tar and a moderate yield of gases while high-rank
Fig. 2. Pyrolysis process of softening coal [42]. Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003
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Fig. 3. Evolution rates and cumulative yields of Illinois No. 6 coal during pyrolysis, from TG-FTIR analysis [36].
coals generate a moderate or low yield of tar and a low yield of gases. 3.2. Relation between the yield of products and heating conditions In practice, devolatilization of coal is a kinetic process. Experimental data show that the yield of pyrolysis products is strongly dependent on heating conditions, e.g., the temperature, heating rate, particle size, pressure and the presence of H2 [37,41,5262] and have been extensively reviewed in literature [5,14,31,33,36,38]. 3.2.1. Effect of temperature The trend that the amount of ultimate weight loss of a coal during pyrolysis increases with increasing the peak temperature observed by earlier work [37,52,54,55] has continuously been conrmed by later investigations [56,57,59,61]. Most of the above observations were conducted at high heating rates. The residence time needs to be considered when comparing the data. In the early review, Anthony et al. [31] summarized the effect of temperature on weight losses at different residence times by comparing the data from different workers, as shown in Fig. 4. The weight losses at different temperatures were normalized with the observed weight loss at 1270 K as 100%. A later review by Howard [5] provided additional informative data suggesting further devolatilization occurs beyond
Fig. 4. Effect of temperature on weight losses during pyrolysis at different residence times [31].
1270 K on short residence time based on results from US coals by a number of investigators. Data from the DTF [56,61] showing an increase in the weight loss when the furnace temperature increased from 1070 to 1670 K also supported this point. Additional information of the yields of pyrolysis products, e.g. H2O, CO, CO2, tar and H2 from a
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bituminous coal with increasing the temperature were illustrated by Gavalas [33] based on the experimental data for the Ohio No. 2 coal investigated by Solomon et al. [55]. An increase in the yield of tar from bituminous coal has been reported [59] as the peak temperature increases below 1100 K during pyrolysis at a heating rate of 1000 K s1 using a heating-screen reactor during investigating the effect of pressure. Fig. 5 presents the yield of products from a sub-bituminous coal measured by Suuberg [37] at a heating rate of 1000 K s1. 3.2.2. Effect of heating rate The effect of heating rate on weight losses during pyrolysis have been proved to be signicant in the past studies [5,14,31,37,41,52,54,58]. Anthony [31,54] investigated and compared the yields of volatile matter from a bituminous coal in a wide range of heating rates using different type of reactors such as crucibles, wire-mesh reactors and electrical strip furnace and found that when the heating rate increased from 1 to 104 K s1, the total yield of volatile matter increased around 11%. A high heating rate may shift the pyrolysis reactions to
a much higher temperature range. Therefore, the devolatilization takes place at a much higher rate [5,37]. A high heating rate results in a more extensive thermal fragmentation of coals molecule structure and suppresses secondary reactions [14] and the loss of xed carbon [52]. Critical observations are the excess yield of volatile matter over the proximate volatile matter content at high heating rates, leading to a Q factor (i.e., the ratio of the yield of volatile matter during devolatilization to the volatile matter content by standard proximate analysis) greater than 1 due to some of the xed carbon being carried into the gas phase [52]. An experimental comparison of the yield of volatile matter to the proximate volatile matter content was provided by Howard [5]. The Q value ranges from 1.3 to 1.5 for weakly swelling coals and from 1.4 to above 1.8 for highly swelling coals [53]. This effect has been the strongest for the medium rank coals, i.e. the bituminous coal where the yield of tar exhibits the maximum [5]. Other experimental evidences also show that higher heating rates result in higher a weight loss during devolatilization, particularly for intermediate rank coals, as presented in Fig. 6 [63]. It may be concluded from the current experimental data that excess volatile yield is primarily due to a higher yield of tar at when the heating rate increases. In the meantime, the maximum rate of devolatilization increases almost linearly with increasing the heating rate for some coals [64,65] because the pyrolysis reactions take place at a higher temperature range. However, the experimental data that bear on this mater are not without ambiguity [14]. Some of the data contain a
60
Devolatilization, wt%
50
40
30 -1 0 1 2 3 4 Heating rate (lg, F/sec) 5 6
Fig. 5. Product yield from Pittsburgh Seam bituminous coal during pyrolysis when heated to different peak temperatures [37].
Fig. 6. The effect of heating rate on the weight loss during devolatilization of a sub-bituminous coal [14,63].
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mixture of the effects of the temperature and the heating rate. Some experimental data also showed Q factors less than 1 at high heating rates [5] possibly due to the incomplete pyrolysis of the coal.
3.2.3. Effect of pressure The effect of pressure on the behaviour of coal during devolatilization have attracted wide interests in the recent years because of the development of pressurized facilities for coal utilization such as IGCC [66,67] and pressurized uidized bed combustion (PFBC) [68]. Wall et al. [11,12] provided a recent review on the impact of pressure on a variety of aspects of coal reactions during pulverized coal conversion. In general, pressure signicantly inuences the yield of volatile matter, coal particle swelling and the structure of the char residue. This further inuences the char reaction rate [9] and the ash formation mechanism [10]. A pronounced reduction of the total weight loss and the yield of tar at elevated pressures and high temperatures has been observed using different types of reactors [34,37,54]. The early investigations carried out using the Pittsburgh bituminous coal [54] showed that the total yield of volatile matter decreased with increasing the pressure and the effect was more distinguishable at high temperatures. Measurements on Pittsburgh No. 8 coal by Suuberg et al. [37] revealed that when the pressure increased the total yield of volatile matter and the yield of tar decreased while the total gas production increased, as is shown in Fig. 7. The published data regarding the pressure effect on the total yield of volatile matter under various conditions have been summarized in the literature [69], as is shown in Fig. 8. It has been clear that high pressure suppresses the formation and release of tar and shifts the molecular weight of tar to a lighter fraction. On the other hand, high pressure promotes secondary reactions, hence increases the total yield of light gases. Because tar is the predominant product of volatile matter, the total yield of volatile matter decrease signicantly when pressure is increased [5,14]. In general, the effect of pressure is to increase the yields of solid and gases at the expense of tar production [65]. The effect of secondary reactions may not be signicant for non-plastic coals according to Lewellens study [70] on the Montana lignite. His results showed that total yield of volatile matter did not vary over a wide range of pressures and heating rates.
Fig. 7. The yields of volatile species vs. pressure during the pyrolysis of Pittsburgh No. 8 coal at 1270 K [37].
3.2.4. Effect of particle size Very little experimental data have been accumulated regarding the effect of particle size of coal during devolatilization [5]. Badzioch et al. [53] found that particle size had no signicant effect on the weight loss based on rather limited observation of coals with the mean size of 20, 40 and 60 mm and attributed the results to that the heating rate of the particle was controlled mainly by the heating rate of the carrier gas, so that the coarser particles heated only at slightly lower rates than the ne particles. Mathews and co-workers [71] concluded that the particle size dependence of the measured volatile matter after correction for effect of mineral matter is due almost entirely to differences in maceral composition based on the observations of two pure bituminous coal vitrinite in the size range of 60400 US mesh (37250 mm). However, Anthony [54,70] found the yields of volatile matter somewhat fell with increasing particles size over the size range 531000 mm for Pittsburgh Seam bituminous coal during pyrolysis. Gavalas [33] observed signicant
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Fig. 8. The yield of volatile matter as a function of pressure [69].
particle size effect during the pyrolysis of a subbituminous coal. The yield of gases showed a substantial increase with increasing the particle size while the yield of tar generally decreased. This observation is also consistent with Suubergs results [37]. The effect of particle size on the total yield of volatile matter may be interpreted by the mass transfer and secondary reactions. Larger particle sizes restrain the transport of volatile matter out of a particle and promote secondary reactions which increase the yield of light gases and decrease the yield of tar. Overall, the effect of particle size is similar to that of pressure [5]. 3.3. Devolatilization models The kinetics of devolatilization deals with how fast the volatile matter evolves and is discharged from the coal under certain conditions [14]. An earlier review by Gavalas [33] summarized the kinetic modelling efforts on describing coal pyrolysis including the rst order reaction [5,31], the competing reactions [41,72] and the detailed Chemical Models [33]. The rst-order reaction models describe the total weight loss using one set of kinetic rates, i.e., the rate constant k and the activation energy E. The yield of individual volatile matter is also described with several independent rst-order reactions. The competing reactions are based on the experimental observations showing a negative cor-
relation between the ultimate yields of tar and gases which are generated by the competition between purely chemical steps or secondary reactions in conjunction with mass transfer limitations. The detailed chemical model developed by Gavalas et al. [33] describes the pyrolysis on the basis of functional groups and their elementary reactions. The distributed activation energy model has been widely applied to predict the overall conversion and the yield of given components during coal reactions and a simple method was developed to estimate f(E) and k0(E) from experimental data [73,74]. The model was employed [75] to investigate the pyrolysis and gasication reactions of hydrothermally and supercritically upgraded low-rank coal, and their results suggested that some changes in the rate-controlling step or in the physical structure of coal might have taken place during gasication. Many studies have suggested that the chemical structure of coal can be considered as a macromolecular network to which the concepts of crosslinked polymers may be applied [58]. A number of researchers have applied statistical methods to predict how the network would behave when coal is subjected to thermally induced bridge-breaking, cross-linking and mass transport processes and have developed network models with different features. The macromolecular network models are the functional group-depolymerization, vaporization and cross-linking (FG-DVC) model [42,48,49,76,77],
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the distributed-energy chain (FLASHCHAIN) model [7880] and the chemical percolation model for devolatilization (CPD) [50,51,8183]. Network models of coal thermal decomposition approximating the breaking-down of the macromolecular network have demonstrated success in modelling the devolatilization behaviour of coal [16,49,69]. The network code for devolatilization has been incorporated in the modelling of coal combustion to improve the design of combustion plants [4]. 3.4. Changes in physical properties of coal during heating When coal is subjected to heating, two physical properties, i.e., the viscosity and pore structure of coal during the plastic stage are extremely important because they govern the rate of mass transport [33] and further determine the yield of volatile matter. Some coals such as coking coals develop signicant uidity [14,84] and may be considered to behave as a Newtonian uid [85]. These coals are also referred to as softening or plastic coals which are in the medium rank. The thermoplastic properties of a coal determine the size and pore distribution of char particles [3]. During devolatilization, coal particles swell to different extents and therefore generate solid residues with different physical structures. Another important physical property which is not yet understood is the surface tension of coal during the plastic stage [46]. The mechanism and experimental measurements of the thermo-plasticity of coal has been a subject of discussion for long time because of its importance in coke production [84]. Thermoplastic phenomena are obviously associated with thermal decompositions of coal. However, the uidity is very difcult to be correlated to other individual associated plastic phenomena such as dilatation, softening, contraction or swelling [14]. Crossing-linking reactions are critically important to the development of uidity and tar formation [16,86]. The occurrence of lowtemperature cross-linking reactions provides interpretations to the absence of uidity in lignites [86,87]. Some evidences show that the uidity of a coal has a direct correlation to its cross-linking density during heating. Different theories for softening such as physical melting, thermo-bitumen and physico-chemical process are hypothesized to interpret the thermoplastic behaviour of softening coal [14,65]. The metaplast pre-exists in coal and that developed during thermal decomposition are re-
sponsible for coals thermo-plasticity during heating [19,43,46,47,88]. The thermal decomposition of coal upon heating is therefore conceptually simplied as a two-step reaction, i.e., coal-metaplast-coke [41,44,48]. A number of viscosity models have been developed based on the metaplast theory to predict coals viscosity which is generally a function of metaplast fraction under different heating conditions [47,8890]. On the basis of the macromolecular theory, Lynch et al. [91] described the transient nature of thermo-plasticity of bituminous coals as three overlapping processes, i.e., a physical mobilization of aromatic-rich structure, thermochemical decomposition of the macromolecular structure and a rapid condensation to produce a rigid semi-coke. The thermoplastic properties of coal are complicated functions of coal properties such as the rank and petrographic compositions as well as pyrolysis conditions such as the heating rate, particle size and pressure [65]. The petrographic composition is a critical property which governs the thermoplastic behaviour of a coal [19,9295]. Sung [96] concluded that the plasticity of bituminous coal was primarily attributed to the presence of exinite and vitrinite maceral components. This coincides with earlier observations by van Krevelen et al. [19,44]. Inertinites exhibit little plasticity upon heating at conventional heating rate of 3 K min1 whereas exinites become extremely uid while vitrinites take an intermediate position. Both vitrinites and exinites develop the highest uidity at the medium coal rank where the carbon content of vitrinites is around 8688% (as shown in Fig. 9). An additive relation is found when vitrinites and exinites are mixed. Inertinites have a strong suppressing effect on the uidity of a coal [19]. Nomura and Kidena [9395,97] studied the nature of plastic phenomena of vitrinite- and inertinite-rich fractions of two bituminous coals using a number of techniques. They reported that the inertinite-rich fractions exhibited little uidity in the plastic temperature range. 13C NMR analysis suggests they had a larger size of aromatic clusters, a less amount of substituents (alkyl- and oxygen functional groups) on aromatic rings and a higher density of cross-linking than the vitrinite-rich fractions. The vitrinite-rich fractions of the same coal exhibited a higher uidity due to relatively higher a concentration of aliphatic chains and bridges and branched aliphatic moieties and alicyclic parts, along with a low aromaticity and much more transferable H2.
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Heating rate has a crucial impact on the coal uidity [16,44,98]. At slow heating rates (o10 Kmin1), both the maximum uidity and the temperature range of the plastic region increase with increasing the heating rate [19], as shown in Fig. 10(a). Fong et al. [88] developed a fast plastometer to measure the viscosity of coal under rapid heating conditions (40800 K s1). The results demonstrated signicant impacts of heating rates on
Fig. 9. Maximum Gieselar plasticity of vitrinites and exinites as a function of carbon content (with the heating rate 3 K min1) [19].
the temperature range, the duration of the plastic region and the temperature of the maximum uidity, as shown in Fig. 10(b). It may be noted that the maximum uidity decreased with increasing the heating rate. This implies that the coal plasticity will not increase innitely when the heating rate is increased. An optimal value of the heating rate for the maximum uidity may exist. Smith [16] suggests that plastic properties become more pronounced at higher heating rates up to a point. If the heating rate becomes too high, coals cannot plasticize or uidize because the cross-linking reaction temperature is attained and the cross-linking reactions are initiated before diffusion processes can manifest a uid-like behaviour. However, the heating rate range for the optimum uidity is not clear. On the other hand, low rank coals (lignites) which do not exhibit uidity at conventional heating rates may develop a uidity if they are heated at extremely high heating rates (42 104 K s1) when the low temperature cross-linking becomes signicantly reduced [16,99]. Chan et al. [98] studied the thermo-plastic behaviour of a range of coals under the pressurized carbonization conditions and found that, at slow heating rates ($20 K min1), the plastometry torque decreased with increasing the heating rate for all coals investigated while the effect of pressure is more complicated. It may be noted that the rheological properties of coal may also play an
Fig. 10. Fluidity of coal during plastic stage as a function of heating rate: (a) slow heating rates [19], and (b) fast heating rates [88]. Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003
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Fig. 11. Gieseler uidity as a function of pressure in N2 gas [65,101].
important role in coals thermoplastic properties at fast heating rates [64,65,100]. An increased Gieseler uidity under elevated pressures at the heating rate of 3 K min1 has been observed by Lancet et al. [101] and the effect appears to be stronger in the low-pressure range up to 1.5 MPa, as presented in Fig. 11. Although Fong et al. [88] reported a decrease in the uidity under the pressure of 3.5 MPa at 350 K s1 and an enhanced repolymerization reactions resulting in an increased resolidication rate were believed to be responsible for the decrease in the uidity under elevated pressures, it is generally expected that pressure has a strong enhancement to the uidity of coal during devolatilization. 4. Formation of char structure from pulverized coal The change in the internal structure of a char is one of the most important issues during coal devolatilization and is closely associated with the swelling phenomenon of coal during plastic stage. The extent to which the pore structure changes is dependent on the coal type and is strongly affected by the conditions under which coal is devolatilized. 4.1. Importance of char structure The importance of chars structure arises from the following three aspects: (i) The change of the internal structure of a char during pyrolysis determines the mass transport of the volatile matter. During devolatilization,
the pore openings of a softening coal will be blocked at the onset of the plastic stage due to the high uidity contributed by the metaplast. Therefore, the volatile matter will be trapped in the coal particles to form bubbles. The release of volatile matter and the ultimate structure of a char will be largely determined by the behaviour of the bubbles [16,46,89] rather than by the original pore structure of the feed coal [70]. According to the multi-bubble mechanism [46], the volatile matter is transported through the movements of bubbles during the plastic stage. When a large number of bubbles exist in the coal uid, the volatile matter diffuses into bubbles instead of diffusing directly out of the particles surface. This causes the growth of bubbles and swelling of the coal particle. When bubbles reach the surface of the particle, they overcome the force balance to burst and release the volatile matter. This mechanism has been generally accepted to interpret the swelling phenomena of bituminous coals during heating. The observation by Yu et al. [102] conducted on a single particle reactor conrmed that the growth and rupture of bubbles was the dominant phenomenon during the plastic stage. (ii) The ultimate structure of a char plays a signicant role in its reactivity during the subsequent char oxidation to devolatilization, particularly during char gasication [9,103]. Based upon the analysis on three British bituminous coals, Koranyi [104] found that a good correlation exists between a chars reactivity and its micro-porosity. Hurt et al. [105] studied the roles of micro-porosity and concluded that CO2 gasication reactions took place primarily outside the micro-pore network, i.e., on the surfaces of larger pores. The distribution of pores determines the diffusion of the reactants in the particle which is often the rate-limiting step for the chars oxidation [3]. The morphology of the char formed during pyrolysis will affect the overall combustion efciency [106,107]. Hampartsoumian et al. [108] studied the effect of the porous structure of char on its rate of gasication and proposed an estimated effectiveness factor during investigating the inuence of the pore diffusion under different conditions. Menendez et al. [109] listed the most important char characteristics with increasing combustion temperature successively as follows: (i) the surface area and
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the surface structure, i.e., the total surface which may be accessible to the reacting gases; (ii) the porosity which inuences the rate of access of the reacting gas to the surface; and (iii) the size of a char particle. These parameters are crucial in modelling of pf combustions and gasication. Highly porous chars have experienced much more extensive devolatilization during heating resulting in a loss of its most materials. Therefore, during the char oxidation, these chars will burnout at a rather early stage compared to solid ones, even they burn at a similar rate [10,11]. (iii) Char structure has a signicant impact on ash formation and pollutant emission during coal conversion. Porous char particles are easily fragmented during combustion. Kantorovich et al. [110] investigated the role of pore structure in the fragmentation of highly porous char particles and claimed that the reason for local fragmentation under non-uniform oxidation is the increase in the local macro-porosity. The tendency of fragmentation of different types of chars has a major impact on the chemistry of the nal ash particles, therefore is crucial to the performance of a furnace [10,111]. Kang et al. [112] studied the effect of chars structure on ash formation during pf combustion and concluded that the fragmentation of a char induced by macro-pores can inuence the particle size distribution (PSD) of the nal ash due to less occurrence of the ash coalescence. Using a pressurized drop tube furnace (PDTF), Wu et al. [10,113] reported that ner ash particles were generated under elevated pressures due to a higher yield of highly porous chars. The textural properties (i.e., the size distribution of pores and the active surface area) of a char from bituminous coals are also found to have some important effect on the NOx emissions [114].
The pore size of a porous solid system is generally expressed by either the diameter of the opening (assuming cylindrical) or the width of the slit [115]. Pores with a diameter (or slits with a width) less ) are referred to as microthan 20 Angstrom units (A are pores. Pores with a diameter larger than 500 A referred to as macro-pores. Those with dimensions are meso-pores [27,115]. in between 20 and 500 A This description applies to both parent coal and char, although the conguration of the pore structure of a char from softening coals after devolatilization is signicantly different from that of the feed coal. As the major parameters of a chars structure, the porosity and the surface area are usually of the most concern. Micro-pores account for the major portion (490%) of the internal surface area and consequently provide most of the surface reaction sites [9,116]. On the contrary, the meso-pores and macro-pores which are important for the mass transport of gaseous phases account for the major portion of total pore volume [117]. A number of techniques are available to measure the porosity and the surface area of coal and chars including the mercury intrusion porosimetry (MIP) and gas adsorption [115]. In recent years, the characterization of a chars structure extensively involves image-processing techniques [6,107,109, 111,118125] mainly due to their practical applications in describing chars morphological parameters. Image-processing techniques can provide a number of geometric parameters of individual char particles such as mean particle diameter, twodimensional macro-porosity and particle sphericity [6]. These parameters are crucial in the char structure classication systems to determine the structure type of individual chars. 4.2.2. Classication of char structure Extensive efforts have been made in the past decades to classify morphologically complicated char structures [25,26,103,106,109,118,119, 124130]. These classication systems largely rely on image-processing techniques to obtain char morphological parameters including macro-porosity, the wall thickness, particle shape, etc. [6,9,10, 129]. Benfell [6] provided a recent summary of different char classication systems after Cloke et al. [129], as shown in Table 1. These systems are based upon a combination of the structural parameters, e.g., the external dimensions of particles, macro-porosity, size distribution of macropores, wall thickness and anisotropy. The detailed
4.2. Classication of char structure 4.2.1. Pore system in coal and char The pore structure is a rather complex system and highly heterogeneous in terms of their dimensions and spatial congurations in both coal and char. Pores are described to have a random spatial distribution in the carbon matrix with linkages and intersections existing between each other [27].
Table 1 Summary of various char morphology classication systems, after Benfell [6,129] C D E F G H I J
Char type
Cenosphere Network Cenosphere with ribs Tenuinetwork Network (Type II) Plastic/porous Penuinetwork Inertoid Solid (Type III) Inertoid Mesosphere Inertoid Solid Solid (Type III) Inertoid Fusinoid/ solid Unfused block Unfused block Non-reacted
Cenosphere
Honeycomb
Unfused
Unfused
Unfused Skeleton Fusinite Microdisrupted Fragment
Thin-walled balloon Thin-walled cenosphere
Thick-walled balloon Thick-walled cenosphere
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Tenuisphere
Crassisphere
Fusinoid
Mixed porous
Mixed dense
Fragment
Cenosphere (Type I) Plastic/porous
Cenosphere (Type I) Plastic/porous
Fusinoid Fusinoid/ solid Variable density type Variable density type
J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]]
Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003 Network (Type II) Plastic/ porous Variable density type 15
Jones et al. (1985) Oka et al. (1987) Goodarzi and Vleeskens (1988) Bailey et al. (1990) ndez et al. Mene (1993) Vleeskens et al. (1993) Rosenberg et al. (1996)
Tenuisphere
Crassisphere
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16 J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]] Table 2 Summary of the three-fold char structure classication system by Bailey and Benfell [118,125], after Benfell [6] and Liu [9] Char groups Group I Group II Group III
Char subtypes
Cenosphere tenuisphere, tenuinetwork Spheroidal 480% Spheroidal o5 mm Vitrinite 41.3
Char particle shape Porosity Pore shape Wall thickness Dominant maceral components Swelling ratio
Crassisphere, crassinetwork, mesosphere, mixed porous (mixed dense) Spheroidal to irregular 450% Variable Variable Vitrinite and inertinite o1.0
Inertoid, solid, fusinoid (mixed dense) Subspheroidal, rectangular or irregular $50% Spheroidal to elongate and angular 45 mm Inertinite o0.9
description of the characteristics of each char group can be found in the literature [6,129]. A three-group classication system suggested by Benfell and Bailey [6,125] based upon Baileys earlier work [118] has demonstrated its practicability in the assessment of combustion characteristics of chars [6,7,118,125] and has been adopted by a number researchers [7,9,111,113,131]. The characteristics of the three groups of chars are presented in Table 2. The feasible parameters to dene a chars structure type are porosity, sphericity and wall thickness because they can be easily quantied through image analysis. 4.3. Relation between char structure and coal properties Previous studies show that the structure of a char is strongly dependent on coal rank and is certainly associated with thermoplastic properties of the coal during heating. Low rank coals such as lignites usually generate network-type to solid char structure. As the rank increases up to low volatile bituminous rank, there is an increase in coals aromaticity and fusibility [118]. Therefore, the proportion of network-type chars decreases while the proportion of cenospheric chars increases [6,106,118,129,130]. Further increase in the coal rank results in an increase in the wall thickness of chars while the population of thin-walled cenospheric char decreases [103,128]. The maceral composition of coal plays a dominant role in the morphology of char during the
Fig. 12. The yields of volatile matter of maceral components as a function of coal rank [19,21].
devolatilization [6,26,118,124,129], although vitrinites and inertinites from coals ranking above semianthracites may be expected to behave similarly during combustion [25,26]. Vitrinite-containing particles from bituminous coals commonly produce cenospheric chars while the inertinite produces a higher proportion of relatively solid chars with a low porosity [6,9,25,26,106,118,122,124,132]. The difference in the morphology of a char from different maceral components may be attributed to the difference in their thermo-plasticity and the extent to which a coal is devolatilized [19,44]. The thermo-plasticity of macerals as a function of coal
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rank has been shown in Fig. 9. Fig. 12 demonstrates the yields of volatile matter of different macerals as a function of the coal rank. Signicant differences exist in the yields between different macerals in medium to low rank coals [19,21]. The presence of inertinites signicantly reduces the thermo-plasticity of a coal during heating [19] and promotes the formation of thick-walled cenospheric chars [133135]. Inertinites can also make major contribution to the population of cenospheric chars when suitably fusible under certain heating conditions [6,118]. At conventional heating rates, it is possible to correlate a chars structure to the maceral composition of coal under the assumption that porous chars are derived from liptinites and vitrinites which develop uidity and experience a large extent of devolatilization. An empirical equation [9] has been proposed to correlate the population of Group I chars to vitrinite (including liptinite) content and pressure based on the experimental results: nGrpI % 0:6 Pt 0:53 vitr 37, (1) where nGrpI is the number percentage of Group I char, Pt is the total pyrolysis pressure (atm), and vitr is the vitrinite (including liptinite) content (%). The correlation has been applied in predicting ash formation [136]. 4.4. Relation between char structure and heating conditions For softening coals, the formation of different types of char structures is closely associated with their thermoplastic behaviour such as uidity and swelling during heating. Therefore, the heating conditions that inuence the thermo-plasticity of a coal will strongly inuence its char morphology. 4.4.1. Effect of temperature The temperature history plays a signicant role during the evolution of a chars morphology [32,57,59,88,118,124,137,138]. As the temperature increases, sub-bituminous coals produce less amount of heavy-density and thick-walled chars [118]. Similar observations by Grifn et al. [59] showed that char morphology changed to structures with larger central pores and network voids at an increased temperature. A decrease of the char micro-porosity at a higher temperature at 1770 K was measured compared to chars from the same coal prepared at 1270 K [32]. This is consistent with
the observation by Jenkins et al. [139] which indicated that the intrinsic reactivity of char decreased when the pyrolysis temperature increased. Lewellen [70] measured the surface area of chars from softening coal with increasing the temperature and found that a sharp decrease of accessible surface area started at the softening points. The porosity of chars from non-plastic coal increased steadily with increasing the carbonization temperature. 4.4.2. Effect of heating rate Limited data by Cai et al. [140] showed that chars prepared at fast heating rates contained more micro-pores and meso-pores and had a greater internal surface area, resulting in a higher reactivity. Fast heating rates lead to a greater anisotropy in a char [141]. Gale et al. [142,143] compared their results to others [144] and found that the overall porosity and swelling ratio of char increased with increasing the heating rate up to 103 K s1, then levelled off. A further increase in the heating rate above 2 104 K s1 resulted in a decreased porosity and swelling, as shown in Fig. 13. This is attributed to the faster generation rate of volatile matter than the relaxation time for expanding the char particle. The temperature gradient in a particle at a very fast heating rate may also take some effect. 4.4.3. Effect of pressure There have been wide research interests in the effect of pressure on char structure. The development of efcient power generation technologies
Fig. 13. The porosity and swelling ratio as a function of heating rate [142,143].
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such as PFBC and integrated gasication combined cycle (IGCC) [6,9,10,66,68] provide several potential advantages over the conventional coal ring processes including an increased coal throughput, a reduced pollutant emission and an enhancement of coal reactions. Recent previous work on coal pyrolysis [34,57,59,62,125,140,145147], coal swelling and char structure [6,10,125,148151] and char reactivity [7,140,147,152154] have revealed that the pressure has a critical impact on coal swelling during the devolatilization. In the meantime, the reactivity of a char is changed at high pressures and the pressure signicantly inuences the ash formation through its effect on the structure of chars. The effect of pressure on ash formation and coal reactions has been recently reviewed by Wall et al. [11,12]. A high swelling ratio of chars under elevated pressures under a variety of heating conditions [6,59,111,125,146150] implies that a higher porosity may result under pressurized pyrolysis conditions. The opponent factors, i.e., the decrease in the yield of tar and the increase in the yield of gases and uidity result in a maximum swelling ratio at an optimum pressure range, as is show in Fig. 14 [65]. A measurement by Wu et al. [111] on chars collected from a PDTF showed that both the porosity and the
1.0
1.0
Macro-porosity (%)
0.8 0.6 0.6 0.4 Porosity Sphericity 0.2 0.0 0.4 0.8 Pressure (MPa) 1.2 1.6 0.4
Fig. 15. Macro-porosity of chars from a DTF as a function of pressure [113].
Fig. 16. Char structure types of an Australian bituminous coal generated at different pressures [10].
Fig. 14. Swelling ratio as a function of pressure [65].
sphericity of a char increased with increasing the pressure up to 1.5 MPa, as shown in Fig. 15. This was accompanied by the increased swelling ratio at the same pressure range. Gadiou et al. [154] investigated the inuence of pressure on the structure and reactivity of millimetre sized single coal particles using a laser heating reactor and concluded that their results are consistent with the results of Wu et al. [111] in terms of the swelling. Results from Australian bituminous coals and maceral concentration coal samples [6,9,10], as shown in Figs. 16 and 17, indicate that a pressure increases the overall proportion of Group I chars. When the pressure increases from 0.5 to 1.5 MPa, the population of Group I chars increases from 38%
Particle sphericity
0.8
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to 72%. Chars with different structures tend to behave differently during the subsequent char combustion or gasication. Group I chars, due to their high porosity, are more readily fragmented leading to the formation of ner ash particles [10]. Wu et al. [10] found that a highly porous foam char structure tended to evolve during pyrolysis when the pressure increased in a PDTF. A mechanism for the evolution of the foam structure through bubble generation was also proposed, as shown in Fig. 18. However, this process has not been quantitatively modelled in their study. Their experimental results suggest that the population of chars with a foam structure appears to dominate the char sample. The char morphology under SEM (Fig. 19) is also distinctive from chars produced on an ordinary
DTF. More recently, Yu et al. [155] compared the structure and morphology of chars produced on a pressurized entrained ow reactor (PEFR) to the chars produced on an ordinary DTF, as shown in Fig. 20. It has been found that the surface texture of a char from a PEFR is similar to that of a char from a PDTF, but very different from that of a char produced from an ordinary DTF. This clearly indicates that the pressure plays the dominant role in the evolution of a chars structure and morphology. It has also been found that the population of porous chars increased substantially. The physical character and gasication reactivity of chars produced under different pressures were investigated by Matsuoka and co-workers [151]. They claimed that the lm material was preferentially gasied compared to the skeleton carbon. They also found that porous char was more graphitic therefore less reactive during gasication than a dense char.
Fig. 17. Percentages of Groups I, II and III chars for an inertinite-concentration sample as a function of the pressure (prepared at 1570 K in a PDTF) [6].
Fig. 19. SEM image of a char particle produced in a PDTF [10].
Fig. 18. The evolution of a highly porous foam char structure under pressurized conditions during devolatilization of a pulverized coal [10]. Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003
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Fig. 20. Comparison of surface textures of a char from the PEFR with the char from a DTF: (a) a char from PEFR (20 bar), and (b) a char from DTF (1 bar).
4.4.4. Char characteristics and gas environment Some comparisons have been made in the literature between the char morphologies in inert gas and in oxidizing environments. Bailey et al. [118] found that a solid residue from early combustion stage had the morphology similar to chars from pyrolysis produced at comparable temperatures, although the proportion of different types of chars may vary. Under combustion conditions at a burnout level of 5060 wt%, the vitrinite-dominated micro-lithotypes generate crassisphere and tenuisphere chars [124]. Inertinites fuse more readily in combustion than in pyrolysis, producing a larger quantity of tenuisphere chars [6,118]. Chars collected from industrial furnaces also demonstrate that inertinites may fuse more readily in boilers [133,134]. This may be due to a higher the heating rate in industrial boilers than in laboratory scale reactors such as a DTF or a wire mesh reactor. Fletcher [156] suggested that the difference in the swelling behaviour during devolatilization experiments from char combustion experiments is not due to the presence of oxygen, but because of the heating rate or post-ame gas species other than oxygen. The presence of H2 during pyrolysis signicantly increases the yield of tar and the uidity of coal [37,54,110], therefore may change a chars morphology signicantly due to the strong association between char structure and the thermoplastic properties and the evolution of volatile matter [110,148]. The solid residues from inertinites are less susceptible to a high-temperature loss of reactivity than vitrinites [133,134]. Overall, a char from pyrolysis is suitable for the study of chars morphologies developed under early-stage combustion conditions [6,118].
Fig. 21. Typical swelling curve measured by dilatometer of a caking coal [14].
4.5. The relationship between char structure and coal swelling The ultimate structure of a char from softening coals is strongly associated with its swelling history during plastic stage [5,14]. The extent to which coal swells determines not only the particle size of a char, but also its porosity and wall thickness. Apparently, the more a particle swells, the more porous the structure will be. The swelling ratio may be expressed as the volume difference between the char and the initial coal [14,149] or by comparing the diameter of the char particle to that of the initial particle of the feed coal (d/d0) [89,157]. The latter one has been widely used in pulverized coal combustions [3,6,9,58,89,111,131,150]. Fig. 21 shows the typical volume change of a caking coal measured by a dilatometer [14] at a slow heating rate of 15 K min1. It demonstrates that a
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caking coal follows quite complex swelling history during which contraction, dilatation and resolidication take place at different stage. The nal swelling ratio is referred to as the ratio of the volume of a char particle to the original coal particle. The dilatation is referred to as the maximum volume of the particle to its minimum volume at the contraction. The dilatation can be much higher than the swelling for a caking coal which develops a signicant uidity during heating. The transient physical structure change may not be reected by the ultimate structure of the solid residue. The maximum porosity and swelling ratio of a coal particle during devolatilization may be much higher than that measured from the nal char at the completion of the devolatilization. The nal swelling ratio of a char from softening coal is dependent on the coal type and the maceral composition is the determining factor [6,158]. At a heating rate between 102 and 104 K s1 [89], typical swelling of particles from Pittsburgh No. 8 coal exhibit three types: $10% shows virtually no sign of uidity, hence no swelling; the majority ($80%) experience swelling of about the same magnitude; the other $10% exhibits behaviour that can be associated with a much lower viscosity than the majority. These three types of behaviour are associated with maceral compositions, i.e., inertinites, vitrinites and exinites [89]. Recent studies [6,9] showed that the Group I chars had a larger particle size compared to solid chars. Cenospheric chars have the largest swelling and the highest porosity during devolatilization. Vitrinites and liptinites develop uidity during heating. Therefore, they are the major compositions contributing to the swelling of coal and the population of porous chars. Similar to a chars structure, the swelling ratio of coal is strongly inuenced by heating conditions through their effects on the uidity and the rate devolatilization. When heating rate is increased, both swelling ratio and maximum devolatilization rate increase, as is shown in Fig. 22 [65]. The peak swelling and porosity appear at heating rate range of 27 104 K s1 [142,159], as shown in Fig. 13. This heating rate range is believed to be the transition value between the heating rate of DTFs and that of a at-ame burner [142]. However, Solomon et al. [3] predicted a different heating rate range for the maximum swelling ratio after which a sharp drop in swelling took place during the pyrolysis of Illinois No.6 coal. Khan et al. [149] found that swelling may not be sensitive to the
Fig. 22. Swelling of two bituminous coals as a function of heating rate [65].
heating rate under pressurized conditions. The change in the thermoproperties especially the uidity of coal in presence of H2 will signicantly inuence the swelling of coal and further the char structure [110,148]. In the presence of H2, more porous chars will be generated. The effect of pressure on the swelling of a coal has been found to be signicant under a variety of conditions [6,59,111,141,149,160,161]. An optimum pressure range exists for the maximum increase in the swelling when the pressure increases, as shown in Fig. 14. Khan and Jenkins [149] investigated the swelling behaviour of 12 bituminous coals (from LVB to HVB) under elevated pressures with a particle size of 355 710 mm, among which nine presented an increased swelling with increasing the pressure. Solomon and Fletcher [3] compared the model predictions to the experimental results [146,150] on swelling of Illinois No. 6 coal and found that the peak appeared at 0.51.5 MPa, as shown in Fig. 23. That more volatile matter is trapped inside the coal particle due to the elevated external pressure has been believed to be the reason for the increase of the swelling. However, other factors such as viscous forces, the extent of secondary reactions and surface tension are obviously doing some work [3]. Wu et al. [10,111] reported an increased swelling of Australian bituminous coals under elevated pressures and attributed the formation of ner ash to the increased population of highly porous Group I chars.
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4.0
Swelling ratio (r/r0)
3.0
2.0
1.0
Experimental Predicted 0 10 20 Pressure (atm) 30 40
0.0
Fig. 23. Experimental results and model predictions on swelling ratio of Illinois No. 6 coal as a function of pressure (after Solomon and Fletcher [3]). Fig. 24. The burning time as a function of the maximum particle expansion rate [169].
4.6. Studies on transient coal swelling using singleparticle reactors In single-particle experiments, the laser heating technique has been extensively employed due to its unique capacity of simulating the ame heating uxes in conventional and high intensity combustion [160,162], particularly in investigations on the combustion characteristics [163168]. For instance, Shen et al. [169] investigated the combustion behaviour of single pulverized coal particles and found a good correlation between the maximum particle expansion rate, (VmaxV0)/V0, and the burning time. The burning time decreased linearly with increasing the maximum expansion rate, as shown in Fig. 24. By using a CO2 laser heating apparatus, Gao et al. [170] observed the transition of the surface structure of coal particles and concluded that there was an optimum range of heating rate for the increase in coals plasticity. In their further studies [160], the swelling and uidity of single coal particles heated with a CO2 laser were evaluated using image analysis. They linked the bubble behaviour to the coal plastic properties. Fig. 25 shows the transient swelling of a particle from Goonyella coal recorded using a high-speed camera [160]. Johnson et al. [171] studied the pyrolysis of single particles using several UK coals at a heating rate of 1001500 K s1. The onset of the melting and swelling was recorded. Their results showed that the maximum rate of devolatilization and the yield of hydrocarbon gases appeared within the same
4.0 1000 800 600 400 1.0 Swelling Temperature 0.0 0 100 200 300 Time (ms) 400 0 500 200 Temperature(C) Swelling (St/S0) 3.0
2.0
Fig. 25. Transient swelling of a coal particle from Goonyella coal at a fast heating rate using laser heating [160], laser intensity 2.22 MW m2, particle size 149 mm.
temperature range (7001000 K) for a vigorous swelling. Yu et al. [172] conducted experiments on a captive single-particle reactor using a densityseparated Australian coal at a heating rate of 10200 K s1 under the atmospheric pressure. Remarkable variations in the swelling took place between particles from different density fractions of the same coal. The light-density fraction exhibited a higher swelling and more intense bubbling, as is shown in Fig. 26. The images in Fig. 26(a) indicate that the particle grows larger during the plastic stage due to the growth of the bubbles while the particle shrinks as the bubbles burst. This
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Fig. 26. Transient swelling behaviour of the observed particles from different density-fraction samples of an Australian coal at the heating rate of 100 K s1: (a) F1.25; (b) S1.30F1.35; and (c) S1.35F1.50, scale bar130 mm [172].
process takes place repeatedly until the particle resolidies. At the later plastic stage, the particle looks almost transparent when the particle swells to a very large extent. This implies that the particle is highly porous and the outer liquid shell is very thin. The swelling and bubbling decrease signicantly as the coal density increases. The particle in Fig. 26(c) exhibits very little change in its morphology. The results of petrographic analysis showed that the liptinites and vitrinites contents decreased while the ash content increased with increasing the coal density. Therefore, particles observed in the case of gure (a) and (b) are most likely liptinites or vitrinites particles while the particle in gure (c) contains inertinites or mineral matter. Inertinites exhibit little uidity at conventional heating rates. Ash grains remain solid at the pyrolysis temperature and suppress the apparent uidity of the whole particle. Fig. 27 presents the transient swelling
ratios quantied through image analysis [172]. A large swelling ratio is obtained for the particle from the lightest density fraction (F1.25) and the swelling decreases drastically as the coal density increases. The maximum swelling ratio of the particle from F1.25 fraction is 3.2 while the nal swelling ratio is around 2.0. This implies that the swelling ratio of chars from a DTF is not able to reect the transient swelling and the chars structure change during the intermediate stage of the devolatilization process. 4.7. Application of density-separation techniques in studies of char structure The fact that different structures are derived from different pulverized coal particles is attributed to the variations in their maceral composition [6,9,122]. In general, particles containing liptinites or vitrinites generate a porous char while those containing
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3.5 3 Swelling ratio (d/d0 ) 2.5 2 1.5 1 0.5 1 2 3 4 Time (s)

Fig. 27. Transient swelling ratio of the observed particles from three density fractions of an Australian coal at heating rate 100 K s1 [172].
F1.25 F1.35 F1.50
inertinites generate relatively dense char structures. Therefore, samples of selective maceral concentrations are very useful in investigating the formation of chars structure during pyrolysis. This can be achieved by sampling from the different coal faces selectively [68,125]. An empirical correlation between chars structure and the vitrinite concentration has been established recently [6]. The reactivity of maceral concentrates was also investigated [32,173]. Density-separation techniques such as the sinkoat technique and centrifugation have been extensively employed to separate coal macerals [174,175]. Cloke et al. [120] characterized density-separated coal fraction samples using a FT-IR and petrographic analysis. It was concluded that the Aar/Aal ratios increased for heavier fractions, indicating a change in the aromaticity when the coal density was increased. Kawashima et al. [176] used the NMR technique to characterize the density-separated components during pyrolysis. They found that the lighter components underwent a greater structural change than the heavier components did. The elimination of aliphatic side chains took place to a greater extent in lower rank coals than in a high rank coal and the content of aliphatic moieties in each maceral group determines its reactivity. Gilllan et al. [122,132] examined the structure and reactivity of density-separated coal fractions of six world coals. The morphological analysis of the char clearly indicated that thin-walled chars were produced from the light density fractions while the proportion decreased with increasing the density.
The chemical structure investigations using a FT-IR and 13C NMR showed that aromaticity increased for heavier density fractions with the inertinite-rich fractions having the highest values. During a density-separation process, the particle size is usually reduced to below 38 mm (106 m) [122] by crushing down the raw coal. The raw coal particle sizes are even reduced to several microns to achieve effective liberation of the maceral components. Minerals are usually removed prior to the density separation [175] through acid washing. During investigating the heterogeneity of large pulverized coal particles, Gibbins et al. [177] found some synergic effect during the devolatilization and suggested that the ability of using relatively pure macerals (from hand-picking or by micronizing, demineralization and density separation) to represent actual pf combustion behaviour may be limited. In their study, a wide range of particle mineral content was also observed and the minerals were generally well dispersed and frequently associated with the inertinite maceral. By measuring the char intrinsic reactivity, they suggested that minerals may act as a catalyst for char oxidation, although the effect may be small. Instead, some decrease in the combustion rate of a particle during the later stage of a char burnout took place due to the increased resistance to oxygen transport and heat losses caused by a large quantity of mineral matter admixed with organic materials. It is therefore suggested that both the inertinite content and mineral matter should be included to explain the poor burnout of chars in some cases. Yu et al. [131] conducted a systematic study on the chemistry of chars prepared on an DTF using density fractions of an Australian coal which was not subjected to a demineralization. The density separation was carried out using ZnCl2 aqueous solutions. Petrographic analysis indicated that the light density fractions contained high liptinites and vitrinites while the heavy density fractions had a high content of inertinites and mineral matters. SEM images of the chars from DTF are shown in Figs. 28 and 29. The results indicate that the lightdensity fractions (i.e., F1.25 and F1.30) generated very porous char particles with a cenospheric structure. A cenospheric char has the conguration of a single central void surrounded by a thin outer shell ($5 mm) [123,126]. In these chars, the population of Group I chars were higher than 70%. Chars from the heavy-density fractions (i.e., F1.50 and S1.50) had a rather solid structure with a low
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Fig. 28. SEM images of cross-sections of chars prepared in a DTF at 1570 K using density-fraction samples of an Australian coal: (a) F1.25; (b) S1.30F1.35; (c) S1.35F1.50; and (d) S1.50 (Igroup I chars, IIgroup II chars, IIIgroup III chars, SGsolid carbon particle, SMsolid particle with included mineral grains, SCsmall cenospheric char particle, Mexcluded mineral grains, after Yu et al. [131]).
100 80 Percentage (%) 60 40 20 0 Group I Group II Char type

Fig. 29. The char type distribution of chars from the density fractions of an Australian coal, as prepared in a DTF at 1570 K [131].
F1.25 F1.30 F1.35 F1.50 S1.50
Group III
porosity. Over 80% particles are Group III chars. Solid particles were either relatively pure carbon particles (marked as SG) or carbon particles with some included ash grains (marked as SM). In the S1.50 fraction, some excluded pure mineral grains were also observed (marked as M). The char from the medium-density fraction (i.e., F1.35) contained a mixture of different types of chars with a moderate porosity and wall thickness. A conclusion has been drawn that both maceral composition and mineral matter are playing roles in the formation of char structure. Yu et al. [131] also provided a systematic analysis on the surface morphology of char particles produced on a DTF using densityfraction samples. Table 3 lists the typical morphologies of group A to H and their characteristics and occurrence. Littlejohn et al. [127] carried out a
26
Table 3 Typical morphology of char particles prepared in a DTF under SEM [131] C D E F F H
Morphology
Image
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Occurrence
Low-density samples (F1.25 and F1.30) Char particles with pore opening on the surface Solid char particles with cracks on the surface
Low-density samples (F1.25 and F1.30)
Medium- to highdensity samples (F1.35, F1.50 and S1.50)
High-density samples (F1.50 and S1.50)
Low-density samples (F1.25 and F1.30) Small and round particles
Medium- and low-density samples (F1.35 and F1.30) Char particles with multiple component
Low-density sample (F1.25 of coal A) Char particles of high conversion
Heavy-density samples (F1.50 and S1.50) Solid char particles
J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]]
Description
Porus char with one blow hole, and ow patterns on surface
Porus char with closed surface and ow patterns
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similar study. The particles from heavy density fractions develop little uidity and generate much less amount of volatile matter. The volatile matter is released through the open pores or cracks on the particles surface. These particles will generate mostly group C, D, or H chars. Little change in the morphology takes place for these particles during pyrolysis. Some particles may develop local uidity so that they have some parts are liquidized, although the whole particle does not soften or swell. These particles are most likely to generate group C or F chars. Particles that develop high uidity during pyrolysis may have three pathways:
A particle may break up to form several small liquid drops during the plastic stage due to a very high uidity and intense generation of volatile matter. The small particles continue to undergo pyrolysis and swelling. These particles generate group E or B chars. Some particles may swell to a large extent to form a cenospheric char. During this process, bubbles may rupture. However, the holes may not be closed again due to the intense release of volatile matter through the holes. These particles will generate group A chars with a large blowhole on their surface. The particle may swell but the bubbles do not rupture or the blow hole is closed again after the bubble rupture. A group B char is then generated.
A coal particle with a mixture of two different maceral components may generate a group F char. group G chars evolve from coal particles consisted of liptinites. These particles experienced a high extent of swelling and a high conversion during pyrolysis. Overall, light-density fractions generate groups, A, B, E or G chars while heavy-density fractions produce groups, C, D or H chars. 5. Modelling the swelling and the formation of chars structure Signicant modelling efforts have been made to deal with the physical aspects of coal pyrolysis, i.e. the swelling and a chars structure. Early studies have been focused on providing mechanistic interpretations to the mass transport and swelling phenomena when coal is heated [46,70,96]. The mode of transport of volatile matter for a plastic coal differs radically from a non-plastic coal
[46,70,96]. Instead of using pore transport mechanism, Lewellen [70] proposed the concept of volatile matter transport via gas bubbles and used this mechanism to model the secondary reactions during pyrolysis of coal. Based on a number of assumptions, the physics of bubble generation, bubble growth and destruction was described. Sung [96] employed this mechanism to interpret the swelling phenomena of a coal during pyrolysis. A multi-bubble mechanism for the mass transport of volatile matter for plastic coal during devolatilization was proposed [46,90], as illustrated in Fig. 30. According to this mechanism, the metaplast is generated through a physical melting (those preexisting in the parent coal) and thermal decompositions upon heating. The primary gases and char are also formed simultaneously. The further decomposition of the metaplast generates tars, secondary gases and chars. Bubbles are initiated from macropores of the parent coal at the onset of the plastic stage or through nucleation mechanism. Volatile matter (i.e., tars and gases) may be transported into bubbles or to the surface of a particle through diffusion. However, time for a direct diffusion of gases to the particles surface is several magnitudes longer than that into the internal bubbles. Therefore, the physics of multi-bubble mechanism is summarized as: the volatile matter is carried by bubbles; the volatile matter is released through bubble movements rather than by the direct diffusion to the particles surface; the swelling of a particle is caused by the growth of bubbles due to the generation of volatile matter; the rupture of bubbles at the particles surface is determined by a force balance for which the viscous force is a major term. The change of the number of bubbles is described as Eq. (2): dnj K j 1 nj1 n1 K j nj n1 dt N j N X 1X Pi;j i ni nji Pi;j ni nj E j nj , 2 i2 i2
where nj is the number of the bubbles with size j, and N is the total number of bubbles. Ej is the escaping rate of bubbles, and Kj and Pi,j are the kinetic rates for the growth and coalescence of bubbles, respectively. This equation has a similar form to that for describing the behaviour of a colloid. Considering the uncertainty of the size distribution of bubbles at the onset of a plastic stage, this equation is a rather
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Fig. 30. The multi-bubble mechanism for mass transport of volatile matter in a plastic coal during devolatilization [46,90].
complicated and un-applicable. A number of simplied cases have been thereby considered, including the extreme case that the bubbles are uniformly spatially distributed with a uniform size [46]. The growth of a bubble is caused by the generation of volatile matter. The growth rate of a bubble determines the bubble escaping rate and coalescence rate. The volatile matter builds up the internal pressure and is restrained by the external pressure, surface tension and viscous force. The equation describing the growth rate of a bubble essentially describes the force balance, as shown in Eq. (3) [46]: Pb P 2s=rb dr 3 dr 2 4m dr , rb dt 2 dt rrb dt r (3)
changes of a char. The physics of the single-bubble model is based upon the assumptions that the liquidized coal particle forms a single centric void surrounded by a porous outer uid shell. Volatile matter is released through both the rupture of bubbles and the direct diffusion of volatile matters to the particles surface. The rupture of a bubble takes place when the internal pressure builds up and reaches the following criterion [89]: 1 :5 r 3 b Pb P P4Swc , 3 r3 p rb (4)
where dr/dt is the rate of a bubbles growth, rb is the bubbles radius, m is the viscosity, Pb is the internal pressure, P is the external pressure, s is the surface tension and r is the density of coal. A single-bubble model has been proposed by Solomon et al. [89] which is incorporated with the FG-DVC model [42,76] to predict a coals swelling. In this model, the viscosity is calculated from an empirical model by Solomon et al. [47]. The singlebubble model has been employed by Sheng et al. [178] to the transient swelling and morphology
where rb and rp are the radius of the bubble and the particle, respectively, Swc is the critical wall stress, Pb is the internal pressure and P is the external pressure. The diffusion term of the volatile matter through the porous shell is expressed as [89,178] 4pDv C b 1=rb 1=rp , (5) where Dv is the diffusivity of volatile matter in the porous liquid and Cb is the molar concentration of volatile matter in the bubble. DL is used in Solomons work [89] while the effective diffusivity term, De, has been used by Sheng et al. [178]. Sheng et al. also compared their model predictions with the experimental measurements in the literature [160].
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Yu et al. [179,180] combined the multi-bubble mechanism and the single-bubble model and proposed a simplied mechanism for the evolution of chars structure of softening coal during pyrolysis. According to this mechanism, devolatilization is divided into three stages, i.e., the pre-plastic stage (m4mc, ToTs), the plastic stage (mpmc, TspTpTd) and the resolidied stage (m4mc, T4Td). This division is based on the viscosity of coal calculated from the volume fraction of the metaplast during heating. The critical viscosity, mc, is from 4 104 to 2 105 Pa s. The plastic stage is the key step for the evolution of a chars structure. The change in the number of bubbles, the force balance and mass balance all need to be formulated carefully to describe the behaviour of a coal particle during the plastic stage. As illustrated in Fig. 31 [179], a large number of bubbles with a uniform size and spatial distribution exist in the molten coal particle at the onset of the plastic stage. The bubbles originate from those macro-pores which have survived the initial soft-
ening. The initial number density of bubbles at the onset of the plastic stage is estimated at 1013 g1 coal according to Oh [90]. Bubbles grow by the generation of volatile matter during the decomposition of a coal and diffusion of the volatile species into a bubble. When bubbles rupture at the surface of the particle, the gas inside those bubbles is released. The growth of these bubbles results in the particles swelling. In the meantime the internal physical structure of the particle changes to a different extent. The direct diffusion of volatile matter to the surface of the particle is also considered when a cenospheric char has formed. The ultimate structure of a char depends on when the coal particle resolidies. As such, a dense char (Group III), a foam structure (Groups II or III) or a cenospheric char (Group I) may evolve, depending on the properties of the coal. An important feature of this model is its capacity of predicting the distribution of a chars structure under different heating conditions in combination with the density-separation technique. Results in Fig. 32 demonstrated that the model
Fig. 31. The evolution of char structure of softening coal during coal pyrolysis [179]. Please cite this article as: Jianglong Yu et al., Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review, Progress in Energy and Combustion Science (2006), doi:10.1016/j.pecs.2006.07.003
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Char distribution (%)
predicts experimental trends for the behaviour of a bituminous coal during rapid heating, including the swelling, the porosity and the distribution of char structures. The decrease in the weight losses with increasing coals density by both predictions and measurements is apparent in Fig. 32(a). Fig. 32(b) shows that the swelling ratio predicted by the model and the measurement using a Malvern Sizer and through SEM image analysis on chars from the DTF decreases as coal density increases. However, the model predicts a higher swelling ratio than the measured value for the light fractions. During experiments, when the lightest density fraction coal sample was devolatilized at high heating rates in gas ow reactors, some particles may break up during the plastic stage due to a high uidity and a high rate of devolatilization. Although the fragmented liquid particles continue to swell, the nal swelling ratio of these chars may be much smaller than particles not experiencing fragmentation. This has not been included in the multi-bubble model. Fig. 32(c) demonstrates a good agreement of the predicted porosity of chars with measurements on chars from the DTF. Corresponding to a decrease in the swelling ratio, the porosity decreases remarkably as coal density increases. The porosity of a char is one of the major parameters determining its structure. Therefore, the decrease in the porosity virtually leads to a change in the chars structure. Group I chars have a porosity above 80%, Group II chars have a porosity of 5080% while Group III chars have a porosity below 50%. The model predicts different types of structures for chars from different density fractions by considering each density fraction as a homogeneous material. In combination with the yield of each density fraction from a density separation, the distribution of char structures of the full coal was obtained. Fig. 32(d) compares the models predictions with the measurements on chars from the DTF. The results agree reasonably well. 6. Concluding remarks In summary, the extensive experimental and modelling efforts made in the past have signicantly advanced our understanding of the mechanism and kinetics of the formation of char structure during devolatilization of pulverized coal. The mechanism of the evolution of volatile matter during pyrolysis has been well established. Network models for devolatilization have been developed to provide
60 50 Weight loss (wt.%) 40 30 20 Prediction 10 0 1.5 Experimental (a)
Swelling ratio (d/d0)
1.0 Prediction 0.5 Malvern Image Analysis 0.0 80 (b)
Porosity (%)
60 40 20 0 F1.25 F1.30 F1.35 F1.50 S1.50 Density fraction 60 50 40 30 20 10 0 Group I Group II Char type Group III Experimental Prediction (d) Experimental Prediction (c)
Fig. 32. Comparison of the models prediction with measurements on chars prepared from density fractions of an Australian coal in a DTF [179]: (a) weight loss; (b) swelling ratio; (c) porosity; and (d) distribution of char structures.
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quantitative predictions to the yields of volatile species. The swelling and structure of a char have been studied extensively using a variety of experimental techniques and have been classied using different systems based on morphological parameters of chars. Limited experimental observations on the transient swelling behaviour of individual coal particles during devolatilization improved our fundamental understanding of coals thermoplastic behaviour. Mathematical models have been developed based on bubble transport mechanism to predict the transient swelling behaviour of softening coals and provide a potential capability in describing the evolution of char structure. Acknowledgements The authors acknowledge the support provided by the Cooperative Research Centre for Coal in Sustainable Development (CCSD), which is funded in part by the CRC Program of Australia, to carry out the research mentioned in this paper. Thanks are also due to Dr. Vladmir Strezov, Dr. Guisu Liu, Dr. Hongwei Wu and Dr. Katharine E. Benfell for helpful discussion and communicating their information in this eld. The authors also acknowledge the support from the National Basic Research Program of China (2005CB221203). References
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36 J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]] [179] Yu JL, Lucas J, Wall T, Liu G, Sheng CD. Modelling the development of char structure during the rapid heating of pulverized coal. Combust Flame 2004;136:51932. [180] Yu JL, Lucas SJ, Liu GS, Wall T. A mechanistic study on char structure evolution during coal devolatilizationexperiments and model predictions. Proc Combust Inst 2003;29:46773. [177] Gibbins JR, Beeley TJ, Crelling JC, Scott AC, Skorupska NM, Williamson J. Observations of heterogeneity in large pulverized coal particles. Energy & Fuel 1999;13: 592601. [178] Sheng C, Azevedo JLT. Modelling the evolution of particle morphology during coal devolatilization. Proc Combust Inst 2000;28:222532.

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Progress in Energy and Combustion Science ] (]]]]) ]]] ]]] www.elsevier.com/locate/pecs

Corresponding author. Tel.: +61 2 49 216179; fax: +61 2 49 216920.

30 -1 0 1 2 3 4 Heating rate (lg, F/sec) 5 6

Fig. 8. The yield of volatile matter as a function of pressure [69].

Fig. 11. Gieseler uidity as a function of pressure in N2 gas [65,101].

Unfused Skeleton Fusinite Microdisrupted Fragment

Thin-walled balloon Thin-walled cenosphere

Thick-walled balloon Thick-walled cenosphere

Cenosphere (Type I) Plastic/porous

Cenosphere (Type I) Plastic/porous

Fusinoid Fusinoid/ solid Variable density type Variable density type

J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]]

Cenosphere tenuisphere, tenuinetwork Spheroidal 480% Spheroidal o5 mm Vitrinite 41.3

Fig. 15. Macro-porosity of chars from a DTF as a function of pressure [113].

Fig. 14. Swelling ratio as a function of pressure [65].

Fig. 19. SEM image of a char particle produced in a PDTF [10].

Swelling ratio (r/r0)

Experimental Predicted 0 10 20 Pressure (atm) 30 40

3.5 3 Swelling ratio (d/d0 ) 2.5 2 1.5 1 0.5 1 2 3 4 Time (s)

F1.25 F1.35 F1.50

100 80 Percentage (%) 60 40 20 0 Group I Group II Char type

F1.25 F1.30 F1.35 F1.50 S1.50

Low-density samples (F1.25 and F1.30)

Medium- to highdensity samples (F1.35, F1.50 and S1.50)

High-density samples (F1.50 and S1.50)

Low-density samples (F1.25 and F1.30) Small and round particles

Low-density sample (F1.25 of coal A) Char particles of high conversion

Heavy-density samples (F1.50 and S1.50) Solid char particles

J. Yu et al. / Progress in Energy and Combustion Science ] (]]]]) ]]] ]]]

Porus char with one blow hole, and ow patterns on surface

Porus char with closed surface and ow patterns

Char distribution (%)

60 50 Weight loss (wt.%) 40 30 20 Prediction 10 0 1.5 Experimental (a)

Swelling ratio (d/d0)

1.0 Prediction 0.5 Malvern Image Analysis 0.0 80 (b)

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