Fuel 79 (2000) 13791388 www.elsevier.

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Char porosity characterisation by scanning electron microscopy and image analysis

H.S. Srensen a, P. Rosenberg b,*, H.I. Petersen b, L.H. Srensen c
b

Danfoss A/S, L7-S38, 6430 Nordborg, Denmark Geological Survey of Denmark and Greenland (GEUS), Thoravej 8, 2400 Copenhagen NV, Denmark c ReaTech, Frederiksborgvej 399, 4000 Roskilde, Denmark

Received 10 March 1999; received in revised form 25 November 1999; accepted 29 November 1999

Abstract No signicant change in either the morphotype composition or the macroporosity (pores 5 mm) in the 030 wt.% char burnout interval were revealed by reected light microscopy or image analysis. Two high temperature char series from a Tertiary South American coal (C1) and a Permian Gondwana coal (C2) were therefore examined by scanning electron microscopy to provide information on the combustion process up to 60 wt.% char burnout. This study documents a signicant mesopore (0.15 mm) development on the fused chars in the burnout interval studied. A method to quantify the size and amount of the mesopores is described and both the parameters increased with increasing char burnout. Above a char burnout of 30 wt.% an increase in macroporosity was detected and ascribed to coalescence of mesopores to form larger pores. Although the measurement of mesoporosity is restricted to fused chars, i.e. pores in fragments and the char morphotypes inertoid, fusinoid and solid could not be measured, the consideration of mesoporosity seems to be fundamental in understanding, evaluating and modelling combustion processes in the char burnout interval studied. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Pulverised fuel combustion; Char porosity; Mesopores; Scanning electron microscope

1. Introduction Pulverised coal combustion is widely used in power plants for the generation of electricity and heat. It is essential that a burnout close to 100% is reached during the combustion process for two main reasons: (1) as much energy as possible should be extracted from the coal; (2) a too high proportion of unburned char may render an ash product unsuitable for construction purposes etc. and, consequently, must be disposed of. Combustion of coal can be subdivided broadly into two distinct stages. The rst stage, pyrolysis, lasts in the order of 30100 ms, whereas the second, char combustion, takes a considerably longer time, in the range of a second. The parent coal petrography and the processes during pyrolysis control the chars macroscopic morphology, which can have important consequences for subsequent char combustion [14]. It has been shown that in some cases the porous tenuisphere and crassisphere chars can be correlated with the microlithotypes vitrite, clarite and vitrinertite V,
* Corresponding author. Tel.: 45-3814-2000; fax: 45-3814-2050. E-mail address: pro@geus.dk (P. Rosenberg).

whereas the more thick-walled char morphotypes, i.e. the crassinetwork/mixed/mixed network morphotype group, can be correlated with the microlithotypes inertite, durite, vitrinertite I, duroclarite, and clarodurite [2,3]. However, in some cases the reected light microscopic methods of char morphotype and macroporosity characterisation fail to explain the mass transport in the char burnout interval below 30 wt.% burnout (middle coal burnout interval, 5070 wt.% coal burnout) [4]. This has encouraged more detailed studies of chars by scanning electron microscopy (SEM), as a means to understand the combustion process. The present paper focuses on a comparison of the results obtained from the SEM study with the results obtained from reected light microscopic studies of the same char samples, and it describes a newly developed SEM method to characterise chars.

2. Sample material Two char series produced in a laminar ow reactor, at temperatures in the range 15321692 K (12591419C), heating rates of 10 4 10 5 K, and an oxygen concentration of

0016-2361/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S0016-236 1(99)00282-3

1380 Table 1 Various parameters for the selected char series Coal C1 Sample no. 4201A 4202A 4203A 4204A 2933A 2934A 2935A 2936A

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Coal burnout (d.a.f, wt.%) 59 70 79 84 49 62 66 71

Char burnout (d.a.f, wt.%) 0 27 49 61 0 26 33 49

Gas temperature (K) 1692 1645 1591 1532 1682 1642 1593 1536

Sample position (residence time) 64 mm (47 ms) 129 mm (72 ms) 191 mm (95 ms) 254 mm (117 ms) 64 mm (47 ms) 129 mm (72 ms) 191 mm (95 ms) 252 mm (117 ms)

C2

12 mol%, were selected for the present study [3,5]. Four char samples at different burnout levels were available in each series (Table 1). The coal burnout and char burnout values were calculated on a dry, ash-free basis using the ash-tracer method [5]. The two char series were produced from the 106125 mm fraction of a Tertiary South American coal (C1) and a Permian Gondwana coal (C2), both of high-volatile bituminous C rank (Table 2). The C1 coal is rich in vitrinite (75 vol.%), and has a reectance of 0.59%Ro, whereas the C2 coal is rich in inertinite (54 vol.%) with subordinate vitrinite (37 vol.%) and has a reectance of 0.63%Ro. Petrographic and proximate analyses of the two coals are given in Table 2. 3. Experimental The selected chars were characterised with respect to morphotype composition and macroporosity by reected light microscopy, whereas ner structural details were studied both qualitatively and quantitatively by SEM. 3.1. Optical characterisation Polished blocks suitable for reected light microscopy were prepared by embedding the char samples in epoxy resin. Char classication was undertaken by counting 300 char particles in each sample at an overall magnication of 312.5 . Particles less than 25 mm and fragments were not counted. During the counting particles were counted both when the crosshairs fell on solid matter and when it fell on void spaces within the particle area. This means that the
Table 2 Petrographic and proximate analyses of the coals (after Rosenberg et al. [3]) Coal composition Vitrinite (vol.%) Liptinite (vol.%) Inertinite (vol.%) Minerals (vol.%) %Ro Moisture (wt.%) Ash (wt.%) Volatile matter (wt.%) Heating value (MJ kg 1) C1 coal 75 6 17 2 0.59 11.6 9.6 32.6 25.2 C2 coal 37 7 54 2 0.63 10.2 15.2 27.8 24.3

classication reects the composition based on volume percentage of morphotypes. Identication of the morphotypes follows the guidelines suggested by Bailey et al. [2] and at the ICCP annual meetings in 1993 and 1994 (Table 3). However, mineroid (50% inorganic matter) and unaltered coal particles were omitted and the rest normalised to 100%. The macroporosity was measured by optical image analysis on individual particles in the same polished blocks that were used for morphotype classication. The embedding material, and thus the internal pores, was distinguished from solid char material by differences in grey level. By dening the outer surface of the particles, and thereby eliminating external embedding material, the porosity was calculated as the ratio between the internal pores area and the total area of the char particles. The resolution of this technique is estimated to be around a pore diameter of 5 mm. Due to the time-consuming nature of this process only 100 particles were measured in each sample. 3.2. Qualitative scanning electron microscopy SEM photomicrographs were obtained for char particles dispersed evenly on conductive carbon tape, mounted on an aluminium sample stub, and covered with a thin carbon layer evaporated onto the sample. The fused chars studied
Table 3 Char classication Char type Tenuisphere Crassisphere Tenuinetwork Crassinetworkmixed networkmixed Inertoid Fusinoid-solid Mineroid Coal Description Spherical to angular, porosity 80%, 75% of wall area 5 mm Spherical to angular, porosity 60%, 75% of wall area 5 mm Internal network structure, porosity 70%, 75% of wall area 5 mm Char with internal network structure with 75% of wall area 5 mm or char with a fused and unfused part, porosity 4070% Dense, porosity 540%, 75% of wall area 5 mm Inherited cellular fusinite structure or solid particle with 5% porosity Particle with 50% inorganic matter Particle of unburned coal

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Fig. 1. Examples of two unfused chars surrounded by fused chars with a considerable mesoporosity. (a) Fusinoid (F) char particle (C2-derived char at 33 wt.% char burnout). (b) Solid (S) char particle (C2-derived char at 79 wt.% char burnout).

contained pores ranging in size between 0.1 and 5 mm, which hereafter are termed mesopores. 3.3. Quantitative scanning electron microscopy study The second part of the SEM study involved the development of a technique for the quantication of mesoporosity and size measurement of mesopores. To achieve this goal, image analysis of digital SEM photomicrographs was applied. The aim was to measure surface mesoporosity on a number of rounded, fused chars in each sample, so that a statistical representation could be achieved. A standard magnication of 4000 was chosen since this gives an adequate resolution of mesopores, and enables the operator to search out surface areas without too many y ash particles

or surface folds/irregularities. Ideally, the eld of view should be covered by a at smooth char surface without y ash. However, this is rarely the case and unwanted features must be removed during the subsequent image processing. In some cases, parts of macropores are present in the eld of view and must be omitted from the measurement. The selection of char particles is important for the results. The mesoporosity is well-developed in fused particles and, therefore, these were selected for analysis. Fusinoid, solid and inertoid chars do not develop any signicant mesoporosity in the studied burnout interval. In Fig. 1 two typical unfused char particles are shown. It is acknowledged that this subjective choice of particles induces a bias to the data when considering the whole range of char morphotypes.

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Table 4 Char morphology composition for the selected char series (TS: tenuisphere; TN: tenuinetwork; CP: crassisphere; CN: crassinetwork/mixed network/ mixed; F/S: fusinoid/solid; I: inertoid. All values are volume percentage) Coal C1 Sample no. 4201A 4202A 4203A 4204A 2933A 2934A 2935A 2936A TS 8 8 10 12 0 0 1 1 TN 2 0 5 3 1 1 1 1 CP 41 45 43 51 15 13 18 15 CN 49 45 29 25 78 84 79 78 F/S 0 2 2 2 5 2 1 4 I 0 0 11 7 1 0 0 1

C2

However, the same morphological types of fused chars are searched for and measured at all char burnout stages. The corresponding char morphotypes are probably mainly crassispheres, tenuispheres, tenuinetwork, and crassinetwork/ mixed/mixed network. Therefore, the measured mesoporosity is representative of only the most fused morphotypes. These particles however represents in all instances more than 87% of the char particles.

4. Results and discussion In the studied burnout interval the C1-derived chars showed only a minor change in morphotype composition, while the C2-derived chars did not show any signicant change in morphotype composition (Table 4), i.e. it appears that the various morphotypes burn at similar rates in this interval. This is in agreements with the ndings of Vleeskens et al. [6], but not with Bailey et al. [2] who found that the thin-walled chars disappeared more rapidly than the thick-walled chars. The overall macroporosity (pores larger than 5 mm) of the C1-derived chars did not change below 27 wt.% char

burnout, but increased signicantly above this char burnout level (Fig. 2a). The C2-derived chars did not show any macroporosity change below 26 wt.% char burnout, whereas it increased from 3349 wt.% char burnout (Fig. 2b). In the C2-derived char samples the morphotypes crassisphere and crassinetwork/mixed/mixed network constituted the majority (Table 4). The macroporosity of these specic morphotypes was measured by optical image analysis, which allows a more detailed understanding of the macroporosity development. The macroporosity of the crassisphere chars was virtually unchanged from 026 wt.% char burnout, whereas it appeared to increase from 26 33 wt.% char burnout. From 3349 wt.% char burnout, it was again virtually unchanged (Fig. 3a). For the crassinetwork/mixed/mixed network group the macroporosity was virtually unchanged from 033 wt.% char burnout, whereas it increased from 3349 wt.% burnout (Fig. 3b). However, as the crassinetwork/mixed/mixed network group is the most dominant morphotype group in the C2-derived chars, constituting 7884% of all measured particles (Table 4), it determines the total macroporosity of the chars. Thus, in conclusion, the macroporosity did not change from 0 33 wt.% char burnout in the C2-derived chars, whereas it increased from 3349 wt.% char burnout. The constant macroporosity in the early char burnout interval is in agreement with the concept that the formation of macropores is caused by plastic deformation, swelling, and degassing during pyrolysis of the coal particles, and then ceases. Hence, below 30 wt.% char burnout, no change in macroporosity nor morphotype composition was detected by the applied optical method, which provides no answer as to how the combustion affects the char particles in this burnout interval. Above 30 wt.% char burnout, an increase in macroporosity was observed whereas the morphotype composition appeared unaltered. Evidently, optical characterisation of morphology and porosity is not adequate to describe the mass ow in the early char burnout interval.

a)
40 30

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0 wt. % 27 wt. % 49 wt. % 61 wt. % % particles
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0 0 0.2 0.4 0.6 0.8 1

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Porosity

Fig. 2. Macroporosity versus char burnout for: (a) the C1-derived char series; (b) the C2-derived char series.

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a)
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Fig. 3. Macroporosity of specic morphotypes in C2-derived char samples at various char burnout. Note the absence of a macroporosity increase in the studied burnout interval, and only a tendency to an increase in macroporosity at the highest burnout levels. (a) Crassisphere chars; (b) crassinetwork/mixed network/ mixed char morphogroup.

The mesoporosity was studied using SEM and image processing for fused char particles for the two char series as a function of burnout. For the C1-derived chars it appeared that mesopores on the char surface increase in size and number throughout the studied burnout interval as indicated in Fig. 4. In the early char burnout interval only a few mesopores were present on the rather smooth surface of the char (Fig. 4a and e), whereas above 30 wt.% char burnout several mesopores, larger than those observed at lower char burnout, were distributed on the surface (Fig.4b and f). At 49 wt.% char burnout the mesopores increased in size (Fig.4c and g) and at 61 wt.% char burnout, many of the pores had grown to such an extent that they coalesced into larger composite openings on the surface, and the overall char structure appeared fragile and spongy (Fig.4d and h). Pores or bubbles in the same size range as those described here were also observed in combustion chars by Unsworth et al. [7] who ascribed them to pyrolysis after plastic swelling of the carbonaceous matter had ceased. This can hardly be the case for these chars, since the mesopores continued to form and grow in a char burnout interval reaching as high as 61 wt.%. At this burnout level degassing is likely to have ceased. Broken particles suggest that mesopores are also present in the interior char walls (Fig. 5). Similar features were observed for the C2-derived chars. At the initial char burnout only a few mesopores were present on the surface of the fused particles, whereas a signicant increase in mesoporosity was seen at 33 and 49 wt.% char burnout (Fig. 6). The qualitative correlation between mesopores and burnout indicates that the mesopores are related to the mass transfer in the studied char burnout interval (middle coal burnout interval), a feature which was not explained by the optical microscopy as the macroporosity measured by the optical image analysis system is limited to a resolution of 5 mm pore diameter.

The mesoporosity results for the two char series are plotted against char burnout in Fig. 6. Especially at high char burnout level a considerable scatter can be observed, however statistical considerations justify the application of a semi-quantitative interpretation. For a char burnout range between 061 wt.% the C1-derived chars showed an increase in average mesoporosity from 0.9 to 16.7% (Fig. 6a). A signicant increase in average mesoporosity from 0 27 wt.% char burnout can be observed, while no changes were observed in either macroporosity or morphotype distribution in this interval [4]. From 2749 wt.% char burnout both the macroporosity and average mesoporosity increased. For a char burnout range between zero and 49 wt.% the C2-derived chars increased in average mesoporosity from 1.220.7% (Fig. 6b). A gradual increase occurred from 033 wt.% char burnout, an interval in which no changes were observed in either macroporosity or in morphotype distribution [4]. Above 33 wt.% char burnout both the macroporosity and the average mesoporosity increased. Similar morphological types of fused particles were measured at each char burnout level and therefore, the SEM analysis measures the mesoporosity of the fused char types, i.e. fragments and the morphotypes fusinoid, solid, and inertoid are not measured. Therefore, to compare the development of macroporosity and mesoporosity, ideally, one should constrain the discussion to these morphotypes. However, it is not possible to perform a morphotype classication on the basis of SEM photomicrographs, since char classication is based on reected light microscopy on polished blocks (cross-sections of particles). Measurements of each mesopore by feature sizing characterise variations in pore size distributions. Fig. 7 illustrates these features for the C1-derived chars. Evidently, there is a change in pore size distribution with increasing burnout. At 0 wt.% char burnout the vast majority of pores

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Fig. 4. SEM photomicrographs of the C1-derived chars showing the development of mesoporosity at varying char burnout levels. Note the increasing amount and size of mesopores with increasing char burnout. At the highest char burnout level the mesopores have coalesced into larger composite openings. (a) and (e): 0 wt.% char burnout; (b) and (f): 27 wt.% char burnout; (c) and (g): 49 wt.% char burnout; (d) and (h): 61 wt.% char burnout.

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Fig. 5. SEM photomicrographs of C1-derived chars showing broken particles. Mesoporosity appears also to be present in the interior walls of the chars.

have an area below 0.5 mm 2. At increasing char burnout, the distribution moves towards larger pore-areas, both as a function of individual pore growth and of pores that have coalesced to form larger composite pores. The maximum pore sizes detected in the analysis were 20 mm 2, because larger pores will not usually be contained within the eld of view at 4000 magnication, and are therefore omitted from feature sizing. Fig. 8 illustrates pore size distributions for the C2-derived chars as a function of char burnout. The trend is similar to

that observed for the C1-derived chars (Fig. 7), with the smallest pores dominating at low char burnout, and gradually increasing in size with increasing char burnout. When evaluating the actual number of pores at different burnout levels it emerges that even though the relative number of small pores decreases with increasing char burnout (Figs. 7 and 8), actually the absolute number increases in the lower char burnout range (Fig. 9). For the C1-derived chars there is a marked increase in the average number of pores 1 mm 2 from 027 wt.% char burnout

40

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Mesoporosity (area %)
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Fig. 6. Mesoporosity at increasing char burnout for: (a) the C1-derived chars; (b) the C2-derived chars. Diamonds: mesoporosity for individual particles; solid line: average mesoporosity.

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Fig. 7. Pore size distribution of mesopores in C1-derived chars with increasing char burnout. With increasing char burnout the pore size increases signicantly. (a) 0 wt.% burnout; (b) 27 wt.% burnout; (c) 49 wt.% burnout; (d) 61 wt.% burnout.

whereas the number decreases above 27 wt.% char burnout. For the C2-derived chars a similar pattern emerges as the number of pores 1 mm 2 increases from 026 wt.% char burnout, but decreases drastically in number at higher char burnout. The initial increase is explained by continuing formation of pores at the lower char burnout levels in the two char series, whereas the decrease at higher char burnout is less conclusive. It can be partly explained by individual pore growth, but may also be a consequence of smaller pores being incorporated in larger growing pores. However, it is still possible that small pores could be forming, but this effect could have been overwhelmed, by the presence of two processes mentioned above.

5. Conclusions Mesopores (dened as pores between 0.15 mm) have been identied in highly fused combustion chars in the studied char burnout interval (061 wt.%). A measurement

technique has been developed to quantify surface mesoporosity in the combustion chars on an area basis, and to determine the size distribution of the mesopores. However, the method is extremely time consuming and needs to be further developed to make measurements of many more particles possible and thus improving the analytical uncertainty. The mesoporosity was measured in two experimentally produced combustion char series, and was documented to increase signicantly with increasing char burnout in the early burnout interval. The mesoporosity was in the same magnitude in the two char series at similar char burnout, although the parent coals differed signicantly, in both petrographic compositions, origin and age. In the early char burnout interval (030 wt.%), the morphotype composition and macroporosity as measured by reected light microscopy cannot explain the mass transport during combustion. Morphotype composition was unchanged, indicating that all morphological types burn at the same rate. If this was the case, then changes in macroporosity would be expected to occur, but the macroporosity

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Fig. 8. Pore size distribution of mesopores in C2-derived chars with increasing char burnout. With increasing char burnout the pore size increases signicantly. (a) 0 wt.% burnout; (b) 26 wt.% burnout; (c) 33 wt.% burnout; (d) 49 wt.% burnout.

a)
70 60 50 40 30 20 10 10 0 0 20 40 60 80 0 50

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Fig. 9. The average number of pores (seen in a frame of the SEM-image) in specic size intervals (mm 2) and for different char burnout. The relative number increase up to a char burnout of 2530 wt.%, about which the relative number of mesopores decreases, probably due to coalescence of the mesopores to form larger pores. This coincides with the detection of an increase in macroporosity at a char burnout level of 30 wt.% (cf. Figs. 2 and 6). (a) Cl-derived chars; (b) C2-derived chars.

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was virtually unchanged. However, the SEM study showed that mesoporosity increased signicantly in the actual char burnout interval, both by pore formation and pore growth. At the lower levels of the studied burnout intervals, the actual numbers of small mesopores (1 mm 2) increased, showing that mesopores were being formed continually. With increasing char burnout the size distribution of mesopores changed towards larger pore areas. For both the C1-derived and the C2-derived chars, an increase in the overall macroporosity was detected in the upper part of the studied burnout interval (above 30 wt.% char burnout). This increase is ascribed largely to coalescence of mesopores to form larger composite macropores that are detectable by the optical image analysis system. It is suggested that the formation and growth of mesopores contribute signicantly to mass transport, perhaps initiated by initial oxygen attack at active sites in the carbonaceous structure. This study shows that the mesopores should be taken into consideration when evaluating and modelling combustion processes in the char burnout interval studied.

Acknowledgements Elkraft A.m.b.a. is thanked for the nancial support to this project. S. Slberg (GEUS) is thanked for technical assistance. This paper is published with the permission of the Geological Survey of Denmark and Greenland. References
[1] [2] [3] [4] Cloke M, Lester E. Fuel 1994;73:315. Bailey JG, Tate A, Diessel CFK, Wall TF. Fuel 1990;69:225. Rosenberg P, Petersen HI, Thomsen E. Fuel 1996;75:1071. Rosenberg P, Petersen HI, Srensen HS, Thomsen E, Guvad C. Combustion Char Characterisation, Final Report. Energy Research Project No. 1323/91-0012 and 1323/93-0018, Danmarks og Grnlands Geologiske Undersgelse Rapport, 1996/51, Copenhagen. [5] Jensen PT, Mitchell RE. High temperature char reactivity measurements in the Sandia laminar ow reactor. Energy Research Project No. 1323/87-16, 1993, Copenhagen. [6] Vleeskens JM, Menendez RM, Roos CM, Thomas CG. Fuel Process Technol 1993;36:91. [7] Unsworth JF, Barratt DJ, Robert PT. Coal quality and combustion performance: Part B, Coal science and technology, 19. Amsterdam: Elsevier, 1991.