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Energy & Fuels 2005, 19, 453-458 453

Coal Blending with Petroleum Coke in a Pulverized-Fuel


Power Plant
Katia S. Milenkova, Angeles G. Borrego,* Diego Alvarez, and Rosa Menéndez
Instituto Nacional del Carbón, CSIC, Apartado 73, 33080 Oviedo, Spain

Henrik I. Petersen and Per Rosenberg


Geological Survey of Denmark and Greenland (GEUS), Øster Voldgade 10,
DK-1350 Copenhagen, Denmark

Received July 28, 2004. Revised Manuscript Received November 5, 2004

The current work investigates the performance of petroleum coke (PC) as a blended fuel under
pulverized-fuel combustion conditions. Three full-scale combustion experiments were carried
out: a pure Carboniferous, high volatile bituminous coal and two blends of this coal with different
proportions of PC. The samples studied included feed fuels and blends, fly ashes, chars taken at
different positions of the combustion chamber, and chars prepared in a drop tube reactor to test
the performance of the individual fuels. The addition of PC led to a substantial increase in the
unburned carbon of the fly ashes. The petrographic analysis of the granulometric fractions of
the fuels revealed that this increase cannot be attributed to an enrichment in coke of the coarser
fractions, as reported in the literature. On the contrary, the finer fraction contained slightly
more coke than the raw blend. The petrographic analysis of the chars collected with the suction
probe and the fly ashes showed that the two blended fuels were strongly enriched in PC-derived
material, indicating a poorer combustibility compared to the high volatile bituminous coal. It is
concluded that the reactivity of the blends in the later stages of combustion is related with the
contents of PC-derived chars and the burnout itself.

Introduction quite different behaviors when submitted to conditions


similar to those occurring in pulverized-fuel boilers.4
Fuel-grade petroleum coke (PC) is the major product Only a few studies have considered the behavior of
resulting from petroleum refining and also the one PC under large-scale pulverized-fuel combustion, and
having the lowest added value.1 This is because, al- these have shown that PCs tend to increase the carbon-
though it is a cheap fuel that typically contains few in-ash content5-7 when cofired with bituminous coals.
volatiles and ashes, it also has a high sulfur content, This was attributed to their somewhat lower reactivity6,8
which has prevented its utilization at large scale. On and to the fact that they tend to concentrate in the
the other hand, the environmental concern on SOx larger size fractions.6
emissions has led to the installation of flue-gas desulfu- In this study, the performance of PC as a blended fuel
rization units on an increasing number of power plants, under pulverized-fuel combustion conditions is investi-
where PC has become a firm candidate to steaming fuel. gated through the study of a highly volatile bituminous
Indeed, a number of power plants are nowadays includ- coal and two blends containing different proportions of
ing PC as an additional component of their feed blends.2,3 PC, which were fired in a power plant. Both the feed
The behavior of PCs in a given process is difficult to fuels and their collected combustion chars were exten-
predict because their characteristics depend on the sively studied, mainly using optical microscopy tech-
delayed coking conditions, which is a continuous process niques, to obtain insight into the fate of the PC in the
where large differences occur within the drum and, boiler. All of the samples collected from the boiler were
particularly, on the feedstock composition. Although extensively burned (over 90%), and therefore some
most PCs seem to be fairly similar when looking at their laboratory-scale combustion tests were also performed,
proximate characterization data, they also have shown
(4) Milenkova, K. S.; Borrego, A. G.; Alvarez, D.; Xiberta, J.;
Menendez, R. Fuel 2003, 82, 1883-1891.
* To whom correspondence should be addressed. Phone: +34 (5) Hower, J. C.; Robertson, J. D.; Roberts, J. M. Fuel Process.
985119090. Fax: +34 985297662. E-mail: angeles@incar.csic.es. Technol. 2001, 74, 125-142.
(1) Adams, H. A. In Introduction to Carbon Technologies; Marsh, (6) Yu, J.; Külaots, I.; Sabanegh, N.; Gao, Y.; Hurt, R. H.; Suuberg,
H., Heintz, E. A., Rodriguez-Reinoso, F., Eds.; Universidad de Ali- E. S.; Mehta, A. Energy Fuels 2000, 14, 591-596.
cante: Alicante, Spain, 1997; pp 491-517. (7) Milenkova, K. S.; Petersen, H. I.; Rosenberg, P.; Borrego, A. G.;
(2) Hall, M. L.; Livingston, W. R. J. Chem. Technol. Biotechnol. 2002, Alvarez, D.; Menendez, R. Proceedings of the 12th International
77, 234-239. Conference on Coal Science; The Australian Institute of Energy:
(3) Gao, Y. M.; Kulaots, G.; Chen, X.; Suuberg, E. M.; Hurt, R. H.; Toukley, New South Wales, Australia, 2003; p CD-9.
Veranth, J. M. Proc. Combust. Inst. 2003, 29, 475-483. (8) Bryers, R. W. Fuel Process. Technol. 1995, 44, 121-141.

10.1021/ef049817u CCC: $30.25 © 2005 American Chemical Society


Published on Web 12/30/2004
454 Energy & Fuels, Vol. 19, No. 2, 2005 Milenkova et al.

Table 1. Proximate and Ultimate Analyses of Single Fuels and Blends and Petrographic Analysis of the Coala
vol mmf % ash CV daf %
code Rr (%) V L I (db %) (db kcal/kg) VM C H N O S
PF 0.84 58.4 11.2 30.4 15.05 7210 35.3 83.3 5.3 1.5 9.2 0.8
PC 3.33 6581 13.8 84.7 3.9 1.0 4.5 5.3
M1 13.53 7014 33.1 83.6 5.4 1.4 8.8 1.4
M2 13.76 6999 32.8 83.5 5.4 1.3 9.0 1.5
a Rr ) random reflectance, V ) vitrinite, L ) liptinite, I ) inertinite, CV ) calorific value, VM ) volatile matter, vol ) volume, mmf

) mineral-matter-free basis, db ) dry basis, and daf ) dry-ash-free basis.

aimed at getting some additional information about the microscope equipped with oil immersion objectives and a 1λ
behavior of the fuels in the earlier stages of combustion. retarder plate.
Combustion Tests. PC was injected into the full-scale
facility only as a blend component together with coal PF, and
Experimental Section
therefore no information about its individual performance is
Samples. The feed fuels considered in this study are a available. To fill this gap, combustion experiments using only
Polish high volatile bituminous coal (PF; 0.84% Ro) of Carbon- the isolated fuels were carried out at laboratory scale. The tests
iferous age and a fuel-grade PC. The full-scale combustion tests included (i) combustion at programmed temperature in a
were carried out at the Energi E2 power plant Stignaes Unit2 thermobalance to estimate the fuel combustibility, where
(Denmark) and comprised the combustion of the pure PF coal samples (13 mg) were heated at 10 °C min-1 under air from
and of two blends, both premixed before grinding and com- 30 to 1000 °C, and (ii) combustion at high temperature in a
posed of coal PF plus 8% (M1) and 11% (M2) PC, respectively. drop tube reactor (DTR) described elsewhere.4 The reactor was
Samples from the individual fuels, the pulverized blends, the operated at 1300 °C with a gas flow of 750 L h-1, an injection
corresponding fly ashes, and chars collected at different flow of 150 L h-1, and a fuel feed rate of 1 g min-1. Previous
locations in the flame zone in the boiler were obtained. The studies9 demonstrated that a combustion temperature of 1300
285 MWe Stigsnaes Unit2 boiler has four burner levels, each °C ensures that the obtained chars will be comparable to chars
supporting six burners. Full-scale experiments were carried derived from full-scale combustion, in regards to their mor-
out during normal commercial operation of the power plant phology. The oxygen content in the reacting atmosphere was
and with the three upper burner levels (18 burners) in 5% O2 in N2, and the estimated residence time of the particles
operation. The full-scale char samples were taken from three in the reactor was 0.3 s. The burnouts of PC and PF were also
positions along the rear wall, which is opposite to the burners, studied under highly overstoichiometric conditions, to better
and from one location in each of the two side walls at a distance simulate the high conversions achieved in the boiler. This was
of about 2 m from the burner wall. The char samples were done by raising the oxygen content in the reacting atmosphere
collected using a 3-m-long water-cooled lance (suction pyrom- to 21% (air).
eter), which was inserted about 1.5 m into the furnace through Conversion was calculated using the ash tracer as a mass
small openings in the furnace walls. The probe was held 5-10 balance between the ashes entering and leaving the reactor,
min inside the furnace, and the char particles were collected using the following expression:
with a filter attached to the cold outlet of the pyrometer. A
total of nine char samples were collected during the test runs.
Preparation of Size Fractions for the Assessment of
Fuel Grindability. As coal and PC were mixed before
conversion ) 1 -[ ( ashcoal
100 - ashcoal )(
100 - ashchar
ashchar )] × 100

grinding, some size segregation due to the differences in


grindability of the two fuels might be expected. To study this The reactivity of the chars, assuming no diffusional con-
possibility, granulometric separations of the mill samples were straints, was isothermally recorded at 550 °C. Chars were
carried out, and the various size fractions thus obtained (>150, heated under N2 at 25 °C min-1 until 550 °C: After weight
150-100, 100-75, 75-45, 45-20, and <20 µm) were prepared stabilization, the gas flow was switched to air, and weight
for petrographic examination. losses upon combustion were recorded until constant weight.
Characterization of Fuels. Ultimate analysis of compo- The reactivity (ash-free basis) was calculated as R ) 1/m0 (dm/
nent fuels and blends were performed using a LECO CHN600 dt), where m0 is the initial sample weight.
for carbon, nitrogen, and hydrogen, a LECO SC132 for sulfur,
and a LECO VTF900 for oxygen. Proximate analyses were Results and Discussion
carried out on the same samples following the standard
procedures described in ISO-562/1981 for volatile matter and Fuel Characterization. Coal PF is a vitrinite-rich
ISO-1171/1981 for ash content. Standard petrographic (mac- high volatile bituminous coal with moderate ash content
eral ISO-7404-3/1994 and random reflectance ISO-7404-5/ (Table 1). The PC is a typical fuel-grade coke with low
1994) analyses were carried out on the coal. Size fractions of ash and high sulfur content. The relatively high ash
the blends were microscopically analyzed to determine the content of PC compared with a typical PC is due to
relative amounts of PC and PF in each fraction. A total of 500 contamination with 19% of a coal similar in character-
determinations were recorded by point counting on each
istics to PF. The presence of this coal also increases the
fraction.
Fly-Ash and Combustion Char Characterization. Fly proximate volatile matter content of PC (Table 1). This
ashes were analyzed for carbon and sulfur content. In addition, also has some implications for the blend compositions.
they were submitted to acid digestion with HF and HCl to Thus, the amount of PC in M1 decreases to ca. 6.5%
dissolve the inorganic material. The combustion chars taken and that in M2 to ca. 9%. This should be taken only as
from both the boiler and the carbon-concentrated fly ashes a rough estimate because the presence of the coal in PC
were prepared for petrographic analysis by embedding them was quantified by petrographic techniques, which yield
in an epoxy resin to make pellets suitable for reflected light volume percentages, whereas the nominal blend com-
microscopy. Samples were carefully polished to avoid damage
to the fragile walls of the combustion residues and then (9) Rosenberg, P.; Petersen, H. I.; Thomsen, E. Fuel 1996, 75, 1071-
analyzed using a point counter attached to a reflected light 1082.
Coal Blending with Petroleum Coke Energy & Fuels, Vol. 19, No. 2, 2005 455

Figure 1. Combustion at programmed temperature of the coal


(PF) and the PC. Figure 3. Variation of the char reactivity with conversion for
the chars prepared in a DTR.

particles, evidenced as a slight increase in the produc-


tion of fine particles in blend M2. This constitutes in
itself an advantage for combustion purposes because
smaller particles tend to burn better than larger ones,10
but it still has to be clarified whether the PC tended to
accumulate in the larger size fractions or not. The
results of the petrographic analysis of the size fractions,
given in Figure 2b, revealed that the amount of PC
increases as the particle size of the fractions decreases,
and this was observed, with only small differences, in
the two blends. Overall, the results shown in Figure 2
indicate that PC accumulates in the smallest size
fraction. This observation differs from the result ob-
tained by Yu et al.,6 who reported a certain increase in
the proportion of large PC particles at the outlet of the
mills. In any case, it is well-known4 that the character-
istics of PCs can substantially vary depending on their
provenance.
Laboratory-Scale Chars. Chars were prepared in
a DTF in an atmosphere containing 5% O2 in N2. Under
these conditions, the PC achieved a 17% burnout
whereas the coal burned by 56%. This large difference
Figure 2. (a) Size distribution of the mill samples fed in the in the rates of fuel consumption is due, in part, to the
full-scale combustion tests. (b) Amount of PC (vol %) in the difference in the volatile matter content between the two
various size fractions. fuels. In any case, when the burnouts are calculated on
a volatile-matter-free basis (discounting the volatiles
positions (8 and 11%) were expressed as weight percent- obtained by proximate analysis of the feed samples), the
ages of PC. The petrographic analysis of the PC not only differences in burnout are still obvious (5% for PC and
showed that it contained a certain amount of coal but 33% for PF), which confirms the lower combustibility
also allowed the assessment of the optical texture of PC char. The chemical reactivity of both chars was
characterizing this coke. Almost 60% of the coke exhib- measured in a thermobalance at a temperature (550 °C)
ited small domain optical texture (10-60 µm in size), where the reaction is known to occur under kinetic
30% was quantified as coarse mosaic (5-10 µm), and control. The results showed a very different profile for
the remaining 10% comprised semicokefied material both chars (Figure 3). The coal char showed a maximum
and particles exhibiting flow domain optical texture. in reactivity at about 10% conversion, with a sharp drop
Figure 1 shows the curves obtained from the combus- as combustion progressed, whereas the PC char dis-
tion at programmed temperature of the fuels (dif- played a lower reactivity, with a maximum placed at
ferential thermogravimetry). The curves indicate that about 50% conversion.
the maximum rate of weight loss is slightly higher for The petrographic analysis of both chars showed
the PC, which burns in a narrower temperature interval significant differences in morphotypes and also in the
than PF, although the characteristic thermogravimetric optical texture of the char-forming material. Around
analysis temperatures (initiation, peak, and burnout 40% of the PF char consisted of cenospheres, either
temperatures) are lower for the coal. isotropic or showing incipient anisotropy, derived from
Grinding Behavior. The grinding behavior of the the vitrinitic part of the coal. Figure 4a shows a
PC/PF blends can be described by the cumulative curves micrograph of a vitrinite-derived cenosphere. Most of
built after weighing of the amounts of sample recovered the inertinite remained isotropic after its passage
in each sieve. The plot in Figure 2a shows a larger through the reactor (56%) and showed little or no signs
amount of fine particles in the blends containing PC of melting. Finally, only 4% of the char material
than in the pure PF sample. The small difference in PC
contents between the blends (M1 ) 6.5%; M2 ) 9%) only (10) Liakos, H. H.; Theologos, K. N.; Boudovis, A. G.; Markatos, N.
had a minor effect on the particle size distribution of C. Appl. Therm. Eng. 1998, 18, 981-989.
456 Energy & Fuels, Vol. 19, No. 2, 2005 Milenkova et al.

Figure 4. Appearance of the coal-derived material (top) and the PC-derived material (bottom) in the fly ashes. Optical images
taken under incident light, crossed polars, and a 1λ retarder plate.

Table 2. Fly-Ash Composition


developed anisotropic optical texture in network struc-
sample burnout (%) PC (vol %) C (db %) S (db %)
tures, as illustrated in Figure 4b. All of the morpho-
types, even those derived from inertinite and containing FPF 98.6 6.89 0.19
FM1 97.9 59.2 10.03 0.57
anisotropic material, were clearly distinguishable from FM2 97.7 56.8 12.14 0.57
the particles generated by PC. The petrographic analy-
sis of the PC char revealed the existence of two different the adscription of the char material in the industrial
behaviors, as shown by the two well-defined structural samples to their parent fuels.
types formed: (i) material yielding massive anisotropic Full-Scale Combustion. The fly-ash analysis data
particles with shrinking cleats (75 vol %), of the type given in Table 2 show that the addition of PC led to
illustrated in Figure 4d, and (ii) material yielding reduced performances in the boiler. This is more clearly
devolatilization voids surrounded by relatively thin seen in the figures of carbon-in-ash. The burnouts are
walls with well-developed anisotropy indicating the also lower in the two blends than in the coal, although
passage through a plastic stage (25 vol %). This struc- this parameter is less sensitive to variations in the
tural type is shown in Figure 4c. The massive particles combustion efficiency when high conversions are in-
were similar to those reported previously in PC-derived volved.
unburned material in fly ash5,6 and displayed a network Figure 4 shows the appearance of both the PC-derived
of cleats similar to that found in calcined PCs. The cleats and coal-derived material in the fly ashes. The particles
in the particles with mosaic optical texture were more were similar to those found in the chars prepared in
randomly oriented, whereas those of the small-domain the laboratory, confirming the utility of the DTF to
or flow-domain chars had their cracks parallel to the reproduce the time-temperature history of the par-
ticles. The main difference between the two sorts of
domain orientation. About two-thirds of these massive
chars was found in the optical appearance of the
particles exhibited small-domain optical texture. Mosa-
vitrinite-derived material, which showed thicker yet
ics and flow domain accounted for the rest of the
more porous walls in the full-scale samples. This is
massive structures. attributed to a faster heating rate than that in the
Particles of both the dense and porous type have also laboratory-scale facility.11 The ratio of porous PC to total
been identified in other PC chars, and their relative PC-derived material in the chars prepared in the DTF
proportions seem to be related to the size of the optical was 0.4, in the range of values recorded for the full-
texture of the parent coke. Thus, the smaller the optical scale samples (0.2-0.5), indicating that the plastic
texture of the parent coke, the higher the amount of behavior of the PC is more affected by the characteris-
vesiculated particles in the pyrolisis/combustion prod- tics of the parent material than by the differences in
ucts.4 the operation parameters in the DTF and the boiler. In
The description given above about the texture and (11) Alonso, M. J. G.; Borrego, A. G.; Alvarez, D.; Parra, B.;
morphology of the blend components will be used for Menendez, R. J. Anal. Appl. Pyrol. 2001, 58-59, 887-909.
Coal Blending with Petroleum Coke Energy & Fuels, Vol. 19, No. 2, 2005 457

closely reproduces the behavior of the two fuels in the


boiler, given the different operating conditions and
scales of both facilities, but are clear proof that the two
fuels studied here have substantially different perfor-
mances when burned under the same conditions. The
results obtained from the two facilities indicate that the
PC tends to accumulate in the burnout products of the
blends.
The reactivity of full-scale chars hardly changes
between M1 and M2 samples taken from equivalent
sampling spots (Table 3), which is not surprising, given
the relatively minor compositional differences between
the two blends. A rough inverse relationship can be seen
(Table 3) between the reactivity of the samples and their
PC char contents. This is due to the low surface areas
Figure 5. Evolution of the isotropic coal-derived material with and reactivities of PC fly ashes6 and also to the well-
burnout assessed by optical microscopy. known effect of char deactivation at high burnouts,12
which in this work was accompanied by an enrichment
Table 3. Burnout, Reactivity, and Petrographic
Composition of the Samples (Prefix B Samples Taken
in the PC material. Indeed, if the evolution of char
with a Water-Cooled Probe, Prefix F Fly Ashes, mmf ) reactivity with conversion under kinetic control is
Mineral Matter Free) considered, the variation of the PC char reactivity was
coal-derived very small, whereas the coal char reactivity strongly
R (×104) burnout coke-derived (vol % mmf) decreased with the progress of combustion, to reach even
sample (s-1) (%) (vol % mmf) isotropic anisotropic lower values than those of the PC char at high conver-
sions (Figure 3).
BPF 10.78 94.3 82.3 17.7
FPF 3.71 98.6 84.4 15.2 An attempt was made here to merge those two effects,
BM1-1 7.85 93.2 26.2 58.6 15.2 the PC char content and char deactivation, for the
BM1-2 7.82 93.3 38.8 57.5 3.8 samples studied here. As the reactivity of the combus-
BM1-3 4.97 96.1 46.2 49.2 4.6 tion chars decreases with both the burnout and the PC
FM1 1.36 97.9 59.2 32.8 8.0
BM2-1 9.20 90.6 39.3 44.9 15.7 char content, an empirical expression is proposed that
BM2-2 4.66 91.9 45.6 39.7 14.7 takes these two variables into account. Thus, the
BM2-3 4.14 91.4 32.2 53.0 14.8 reactivity of the samples is assumed to be proportional
FM2 1.88 97.7 56.8 34.4 8.8 to the coal-derived char content, whereas an inverse
exponential dependence is formulated for the burnout.
addition, no indications of substantially different com- The best-fit equation found is as follows:
bustion efficiency between the two PC-derived materials
(massive and porous) were found because both seem to Rcal ) R[100 - PC] × 10-βbo
be consumed at comparable rates during the combustion
of the blends. where Rcal is the calculated reactivity, PC is the volume
According to the data of Table 3, the burnouts at percentage of PC in the samples, as measured by point
equivalent sampling spots were typically higher for the counting, bo is the percentage of burnout, and R and β
blend containing the lowest proportion of PC, although are fitting parameters (0.8965 and 0.0527, respectively).
this difference became smaller in the case of the fly The comparison between the experimental and calcu-
ashes. The amount of isotropic material in the samples lated reactivities is plotted in Figure 6. Two extra data
did not vary significantly with burnout when coal PF were included in this graph, which were obtained in a
was burned alone, as can be seen in the plot of Figure fourth location in the boiler but only for the M1 blend,
5, indicating a similar consumption rate for coal-derived so that no equivalent data were available from M2 or
isotropic and anisotropic materials. When the blends PF samples. The graph shows only a rough agreement
were fired, the relative amount of isotropic material, of the calculated data with the experimental results,
undoubtedly derived from the coal, decreased as com- although the correlation notably improves compared
bustion progressed, and this consumption rate was with the calculations based on a single parameter, either
higher for the blend with the lowest proportion of PC the PC content or burnout. In any case, given the
(Figure 5). A similar result was observed when the blend extreme complexity of these industrial samples and the
components were combusted alone in the DTF. Thus, uncertainties inherent to the point-counting procedure
the combustion of PF in the DTF under air raised its for char analysis and especially to the ash-tracer
burnout to 97.4%, in good agreement with the perfor- technique, the correlation seems to offer a satisfactory
mance achieved in the full-scale boiler (98.6%). On the description of the later stages of combustion of coal/coke
other hand, the combustion of PC under the same blends.
conditions led to 85.8% burnout, substantially lower
than PF and also in good agreement with estimates of Conclusions
the combustion of this fuel when blended with PF in
The addition of PC to a highly volatile bituminous coal
the industrial boiler (86.2 and 89.4% in M1 and M2
led to a marked increase in the carbon-in-ash content
blends, respectively). These similarities in burnout,
although being quite remarkable, do not mean that the (12) Hurt, R.; Sun, J. K.; Lunden, M. Combust. Flame 1998, 113,
course of combustion in the laboratory-scale facility 181-197.
458 Energy & Fuels, Vol. 19, No. 2, 2005 Milenkova et al.

because the PC did not accumulate in the coarser size


fractions, but precisely the opposite. The results suggest
that it is the low reactivity of the PC char that is
responsible of the poor performance of this fuel. It was
found that the drop of reactivity in the later stages of
combustion can be explained in terms of two combined
factors: the increased coke-derived contents and the
deactivation undergone by highly combusted chars.
Overall, the addition of PC to a low-rank coal in-
creases the carbon-in-ash content, but this does not
mean that they should not be used in pulverized-fuel
combustion. In fact, the degree of burnout of the coke
in the two blends studied here (8 and 11% PC) was as
high as 86.2 and 89.4%, respectively, as estimated by
the coke contents of the fly ashes. The co-combustion of
PC with a higher rank coal would probably lead to a
substantial improvement of its combustibility.

Acknowledgment. Financial support through the


Figure 6. Calculated reactivity vs experimental values for European Project ECSC-PR071 is gratefully acknowl-
the full-scale chars. edged. K.S.M. thanks the Spanish Agency for Interna-
tional Co-operation for a predoctoral fellowship. L.
when fired in a full-scale pulverized-fuel boiler. Micro-
Vagtholm and the staff at the Energi E2 Power Plant
scopic examination of the fly ashes revealed that they
Stigsnaes, Denmark, are thanked for their cooperation
were strongly enriched in PC-derived material, com-
during sampling of full-scale combustion chars.
pared with the feed blends. The poor combustibility of
the PC could not be attributed to its larger particle size EF049817U

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