BENCH-SCALE BIOMASS/COAL

COFIRING STUDIES

Deirdre Belle-Oudry and David C. Dayton

National Renewable Energy Laboratory

1617 Cole Boulevard
Golden, CO 80401-3393

1. INTRODUCTION

The threat of increased global warming has subjected the use of fossil fuels to
increasing scrutiny in terms of greenhouse gas and pollutant emissions. As a result, the
use of renewable and sustainable energy resources, such as biomass, for electricity pro-
duction has become increasingly attractive. The use of dedicated biomass feedstocks for
electricity generation could help reduce the accumulation of greenhouse gases because
carbon dioxide is consumed during plant growth. The agricultural and wood products
industries generate large quantities of biomass residues that could also provide fuel for
electricity production. Increasing the use of these waste biomass fuels could alleviate the
burdens of waste disposal in the agricultural and wood products industries.
One solution to increasing the use of biomass to produce electricity is to build ded-
icated biomass power plants that use 100% biomass fuel. As of July 1995, there were 360
biomass plants and approximately 1% of the grid connected electricity in the United
States was generated from renewables [Cogen, 1995]. The initial capital investment to
build new biomass power plants to increase this percentage is high. Another scenario for
increasing the use of biomass to produce electricity is to cofire biomass and coal in extant
coal-fired power plants.
Coal-fired power plants are used to produce most of the electricity in the United
States and if biomass were cofired at low percentages in a small number of coal-fired power
plants, the use of biomass for power production could dramatically increase. Cofiring
biomass and coal can increase the use of sustainable fuels without large capital investments
and take advantage of the high efficiencies obtainable in extant coal-fired power plants.
Fuel diversity is another advantage of biomass/coal cofiring. Cofiring reduces the need for
a constant supply of biomass that would be required in a biomass power plant. Cofiring
biomass and coal is therefore a viable way to manage the increasing emissions of green-
house gases and may also reduce other pollutants from power-generating facilities.
Biomass and coal have fundamentally different fuel properties. For instance, biomass
is a more volatile fuel than coal and has a higher oxygen content. Coal, on the other hand,

Impact of Mineral Impurities in Solid Fuel Combustion, edited by Gupta et al.

Kluwer Academic / Plenum Publishers, New York, 1999. 569
570 D. Belle-Oudry and D. C. Dayton

has more fixed carbon than biomass. In general, biomass contains less sulfur than coal,
which translates into lower sulfur emissions as higher blending ratios of biomass are used.
Wood fuels tend to contain very little ash (on the order of 1 % ash or less) and consequently
increasing the ratio of wood in biomass/coal blends can reduce the amount of ash that
needs to be disposed. A negative aspect of biomass is that it can contain more potassium
and chlorine than coal. This is particularly true for some grasses and straws.
Several utilities have tested biomass/coal cofiring in utility boilers [Boylan, 1993;
Gold and Tillman, 1993]. Several issues, however, remain regarding how blending
biomass and coal will affect combustion performance, emissions, fouling and slagging
propensities, corrosion, and ash saleability [Tillman and Prinzing, 1995]. Many of these
issues have been highlighted in a comprehensive, multi-laboratory study known as the
European Commission’s APAS Clean Coal Technology Programme [Bemtgen, Hein, and
Minchener, 1995] that was formed to study the feasibility and technical challenges
associated with replacing coal partially by biomass and converting wastes (such as sewage
sludge) to energy in coal-fired power plants. In an effort to further address issues
that face biomass/coal cofiring, representatives from the National Renewable Energy
Laboratory, Sandia National Laboratories Combustion Research Facility, and the
Federal Energy Technology Center have embarked on a collaborative effort to study
many of the fireside issues that face biomass/coal co-combustion such as ash behavior,
particle capture efficiency, carbon burnout, and emissions, and reactivity.
This paper describes bench-scale biomass/coal cofiring experiments in support of this
collaborative effort.

2. EXPERIMENTAL APPROACH

The combustion behavior, gaseous emissions, and alkali metals released during the
combustion of several biomass/coal blends were investigated with a direct sampling, mol-
ecular beam mass spectrometer (MBMS) system [Evans and Milne, 1987] in conjunction
with a high-temperature quartz-tube reactor that has been described in detail in the lit-
erature [Dayton, French, and Milne, 1995; Dayton and Milne, 1996].
The biomass and coal samples, including the blends, were received from L. Baxter
of the Sandia Combustion Research Facility. For this study, results are presented for
blends of Eastern Kentucky coal with Red Oak wood chips, Danish Wheat Straw, and
Imperial Wheat Straw (from California). The proximate, ultimate and ash analyses for
the pure fuels are presented in Table 1. Blends are reported as a percentage on an energy
input basis, based on the higher heating value of the feedstock. The blends investigated
during this study consisted of 5%, 15%, and 25% biomass, on an energy input basis, with
the Eastern Kentucky coal.
Twenty to fifty milligrams of the pure fuels and blended samples were loaded into
hemi-capsular quartz boats that were placed in a platinum mesh basket attached to the
end of a ¼-in. diameter quartz rod. This quartz rod can be translated into a heated quartz-
or alumina-tube reactor enclosed in a two-zone, variable-temperature furnace. Furnace
temperatures were maintained at 1,100°C and a mixture of 20% in He was flowed
through the reactor at a total flow rate of 3.0 standard liters per minute. The residence
time of the combustion products in the reactor before sampling was 0.7–0.9 second. Gas
temperatures near the quartz boat were measured with a type-K thermocouple inserted
through the quartz rod. The actual boat temperature and the flame temperature were not
measured.
Bench-Scale Biomass/Coal Cofiring Studies 571

3. RESULTS AND DISCUSSION

The MBMS results for the pure fuels and the blends were similar to results obtained
in the past for biomass and coal combustion [Dayton and Milne, 1996]. All the samples
exhibited multiple phases of combustion, including the devolatilization and char com-
bustion phases. The char combustion phase for coal was generally longer than the char
combustion phase during biomass combustion. Combustion of the blends showed a sim-
ilarly longer char combustion phase compared to combustion of the pure biomass
samples. Triplicate samples of the pure fuels and blends were studied to establish exper-
imental reproducibility. After identifying the combustion products of interest, ion
intensity-versus-time profiles were integrated to determine the total relative amount of a
given product released during the combustion event. In this way, relative amounts of
several products measured during combustion of the pure fuels and blends could be com-
pared. These results were normalized to the signal intensity measured before the
sample was inserted into the hot zone of the reactor and the sample weight. Relative
species concentrations represent the averages of the triplicate samples, and the reported
error bars are one standard deviation.
572 D. Belle-Oudry and D. C. Dayton

3.1. Biomass/Coal Blends with Eastern Kentucky Coal

Summaries of the MBMS results for combustion of Eastern Kentucky coal, the
pure biomass fuels, and the blends of the biomass fuels with Eastern Kentucky coal in
the above mentioned ratios in 20% in He at 1,100°C are shown in Figs. 1 and 2. These
figures display the relative amounts of 7 combustion products as determined by inte-
grating the time-versus-intensity profiles for ions measured during the combustion event.
The main isotope of carbon dioxide at was not measured during these
cofiring studies because the signal saturated the detector at the sensitivity required to
detect the minor combustion products. Carbon dioxide production could be monitored
by measuring the signal intensity at which corresponds to the isotope.
This isotopic species accounts for 1.17% of the total carbon dioxide based on the natural
abundance of the carbon and oxygen isotopes.
Figure 1 displays the relative amounts of the species detected at
and during the combustion of the pure
fuels and the coal/biomass blends in 20% in He at 1,100 °C. The most was detected
during the combustion of the wheat straws and the most and was released
during combustion of the coal and the coal blends. In this study, blends of Red Oak and
Imperial Wheat Straw with Eastern Kentucky coal were studied in two different ratios to
investigate the possible effect of blending ratio on the combustion products. The data in
Fig. 1 suggest that varying the blending ratio has little effect on the amount of CO(g),
and released during combustion. The sulfur release is consistent with the
fact that the Eastern Kentucky coal has the highest sulfur content of the pure fuels inves-
tigated. Except for the Red Oak, the amount of NO(g) released during combustion of
Bench-Scale Biomass/Coal Cofiring Studies 573

the fuels and blends was similar. The most NO(g) was released during the combustion
of the 85% Eastern Kentucky coal/15% Imperial Wheat Straw blend.
Figure 2 shows the relative amounts of various chlorides detected at
and during combustion of the pure fuels and
the Eastern Kentucky coal/biomass blends. The most HCl(g) was detected during com-
bustion of the wheat straws. The most I and were detected
during combustion of the Imperial Wheat Straw. This is consistent with the fact that the
Imperial Wheat Straw has the highest levels of potassium (2.75 wt% dry basis), sodium
(1.66 wt% dry basis), and chlorine (2.17 wt% dry basis) of the pure fuels investigated in
this study.
Figures 3 to 6 display the relative amounts of NO(g), HCl(g), and KCl(g),
respectively, detected during the combustion of the Eastern Kentucky coal/biomass
blends compared to the expected amounts of these products based on the combustion
results for the pure fuels. Figure 3 shows that any decrease in the amount of
observed because of blending biomass with coal was merely caused by diluting the
amount of sulfur in the fuel blend compared to the pure coal. The Eastern Kentucky
coal contains 0.89 wt% (dry basis) sulfur, the biomass samples contain, on a dry basis,
0.33 wt% (Imperial Wheat Straw), 0.17 wt% (Danish Wheat Straw), and 0.02 wt (Red
Oak) sulfur, respectively. Therefore, blending any one of the biomass fuels with the coal
reduces the amount of sulfur in the fuel blend. The amount of detected during
combustion of the blends was consistent with expectations based on the values calcu-
lated from the amount of detected during combustion of the pure fuels. The
overall amount of detected was greater for those blends with higher ratios of coal,
but these levels of were consistent with the expected amount.
574 D. Belle-Oudry and D. C. Dayton

These results appear to be inconsistent with previous studies published in the liter-
ature [Nordin, 1995; Nordin and Ohman, 1996] where significant (up to 95%) sulfur
retention by alkali metals in the biomass in coal/biomass blends was observed. A closer
examination of these previous studies suggests that the results for emissions during
combustion of biomass/coal blends are consistent. The previous studies were conducted
in various fluidized bed combustors where the gas/solid interaction times are cosiderably
longer than those in the quartz-tube flow reactor used in this study. The bed tempera-
tures established in the previous studies (550–850°C) were also lower than the 1,100°C
furnace temperature established in the experiments presented in this study. The earlier
studies [Nordin, 1995] clearly show that sulfur retention by the biomass ash decreases
sharply with temperature above 850°C. In addition, the earlier studies [Nordin and
Ohman, 1996] claim that in large scale biomass/coal cofiring in a pulverized
fuel boiler, sulfur emissions were reduced according to the percentage of biomass used
in the fuel blend. The gas/solid interaction times are considerably shorter in pulverized
fuel boilers compared to fluidized bed combustors. Therefore, these observations from
earlier work are consistent with emissions measured for the residence times and
temperatures established in the present study.
Figure 4 displays similar data for the amount of NO(g) released during combus-
tion of the Eastern Kentucky coal/biomass blends. All of the NO(g) measured in these
studies came from the conversion of fuel-bound nitrogen to NO(g) since He was used as
a diluent in the reactor atmosphere instead of Therefore, the amount of NO(g) mea-
sured in these laboratory experiments does not contain a contribution from thermal
which can be substantial in commercial-scale pulverized fuel systems. Within the errors
of the measurements, the amount of fuel-bound nitrogen converted to NO(g) during
combustion of the blends was consistent with expectations based on the amount of
NO(g) released during combustion of the pure fuels. Once again, the blending ratio may
affect the relative amount of NO(g) released but there were no synergistic effects during
Bench-Scale Biomass/Coal Cofiring Studies 575

combustion of the blends to suggest that any more or less NO(g) was released than
expected based on the combustion results for the pure fuels. The wheat straws have less
fuel-bound nitrogen, on a dry basis, (1.08 wt%—Imperial Wheat Straw and 1.04 wt%—
Danish Wheat Straw) than the Eastern Kentucky coal (1.49 wt%). The Red Oak contains
very little fuel-bound nitrogen on a dry basis (0.20 wt%). In reality, higher blending ratios
of biomass with coal may have a more substantial effect on production because
more biomass in the fuel blend may decrease flame temperatures, catalyze reactions,
or have other effects on the combustion process that can affect thermal production
in utility boilers.
Figure 5 shows the measured and calculated amount of HCl(g) released during
combustion of the Eastern Kentucky coal/biomass blends. The amount of HCl(g)
detected during the combustion of the Eastern Kentucky coal/Red Oak blends should be
minimal because neither the Red Oak nor the coal contain very much chlorine. There-
fore, the amount of HCl(g) detected during the combustion of the Eastern Kentucky
coal/Red Oak blends was consistent with the expected values based on the combustion
results for the pure fuels. For the Eastern Kentucky coal/wheat straw blends, however,
more HCl(g) was released during combustion of the blends compared to the expected
amounts of HCl(g) determined from the combustion results for the pure fuels. The
amount of Imperial Wheat Straw in the blend does not appear to affect this result.
Figure 6 summarizes the amount of KCl(g) detected during combustion of the
Eastern Kentucky coal/biomass blends compared to the amount of KCl(g) expected to
be released based on the combustion results for the pure fuels. Converse to the HCl(g)
results, the amount of KC1 vapor detected during combustion of the 85% Eastern Ken-
tucky coal/15% Imperial Wheat Straw blend was less than expected. For the 95% Eastern
Kentucky coal/Imperial Wheat Straw blend this conclusion is not as evident given the
large error bar on the measured value. The results for the 85% Eastern Kentucky
576 D. Belle-Oudry and D. C. Dayton

coal/Danish Wheat Straw blend were also not as conclusive because of the large error
bar on the measured value. The Red Oak has very low potassium and chlorine contents,
which suggests that the measured values for KC1 vapor detected during combustion of
the Eastern Kentucky coal/Red Oak blends may be near or below the detection limits for
KCl(g).
Similar data for the relative amounts of NaCl(g) detected during the combustion
of the Eastern Kentucky coal/biomass blends were also obtained. These data suggest that
less NaCl(g) was detected during the combustion of the Eastern Kentucky coal/wheat
straw blends than expected based on the combustion results for the pure fuels. The
amount of NaCl(g) released during combustion of the Eastern Kentucky coal/Red Oak
blends was negligible and insensitive to the blending ratio.

3.2. Thermochemical Equilibrium Calculations

An equilibrium analysis of the biomass/coal blend combustion was undertaken in
an attempt to explain some of the observations made during the batch combustion exper-
iments. These calculations were not an attempt to model the batch experiments preformed
in this study. The calculations were performed using a modified version of STANJAN
[Reynolds, 1986], a thermodynamic equilibrium computer code that minimizes the Gibbs
free energy of the system by the method of element potentials with atom population con-
straints. The theory relates the mole fraction of each species to element potentials for
each independent atom in the system. This method is particularly suited to large systems
because the element potentials and the total number of moles in each phase are the only
variables.
Gas-phase species were treated as ideal gases in the calculations, and the condensed
phase was assumed to be an ideal solution. This simplified treatment of the condensed
phase may not accurately represent reality, and caution should be exercised in over-
interpreting the calculated condensed-phase species mole fractions [Blander, et al., 1997].
Bench-Scale Biomass/Coal Cofiring Studies 577

Information about the mechanics and mathematics of the program is available in the lit-
erature [Van Zeggemon and Storey, 1970]. The main program has been modified to accept
as many as 600 species and 50 phases [Hildenbrand and Lau, 1993]. A comprehensive
database of species and related thermodynamic data was used to predict the equilibrium
gas- and condensed-phase compositions given an initial temperature and pressure as well
as the mole fractions of the following atoms in the fuel or blend: Al, Ba, C, Ca, Cl, Fe,
H, He, K, Mg, Mn, N, Na, O, P, S, and Si.
Equilibrium product compositions were calculated for the Eastern Kentucky coal,
the three biomass fuels, and the three 85% coal/15% biomass blends. The equilibrium cal-
culations suggest that the mole fractions of NO(g) and for the blends are consis-
tent with the linear combination of NO(g) and calculated for the pure fuels. This
signifies that any difference in the amounts of and NO(g) measured during com-
bustion of 85% Eastern Kentucky coal/15% biomass blends was caused by dilution. This
is consistent with the experimental observations.
The equilibrium results for HC1 and KC1 vapors showed similar trends as the exper-
imental results. Less gas-phase KC1 was predicted from the compositions of the blends
versus the amount of KC1 calculated from the ratios of the equilibrium results for the
pure fuels. Conversely, more gas phase HC1 was predicted from the equilibrium calcula-
tions on the compositions of the blends compared to the amount of HC1 calculated from
the combinations of HC1 predicted from the pure fuels.
Within the limitations of how realistically the equilibrium calculations treat the con-
densed phase, the effect of blending coal and biomass on the composition of the ash can
be interpolated from the equilibrium calculations. For instance, the amount of
condensed-phase KC1 calculated from the composition of the blends was lower than
the amount of condensed-phase KC1 predicted from the linear combinations of the
equilibrium results for the pure fuels. The results of the calculations suggest that the
concentrations of the alkali aluminosilicates were enhanced when coal and wheat straw
578 D. Belle-Oudry and D. C. Dayton

were blended compared to a simple ratio based on the equilibrium results for the pure
fuels. Therefore, it can be inferred from the equilibrium results that the reduction in
KCl(g) and subsequent increase in HCl(g) that was observed during the combustion of
wheat straw/coal blends results because potassium is being sequestered by the coal
mineral matter. Less potassium is available for volatilization, therefore, the volatile Cl is
released as HCl(g).

4. CONCLUSIONS

The MBMS results for the relative amount of detected during combustion
of the coal/biomass blends suggested that any decrease in the amount of observed
because of blending coal and biomass was the result of diluting the sulfur in the fuel
blend. The conversion of fuel-bound nitrogen to NO(g) during combustion of
coal/biomass blends met expectations based on the combustion results for the pure fuels.
This may not be the case, however, in full-scale biomass/coal cofiring applications. The
MBMS experiments were isothermal and the NO(g) detected was the result of fuel bound
nitrogen conversion to NO(g) because He was used as the diluent in the reactor atmos-
phere instead of N 2 eliminating the formation of thermal NOx. Of course, in a full-scale
cofiring situation there are many other engineering factors that contribute to for-
mation. Utility boilers are far from isothermal and addition of biomass in a pulverized
coal-fired boiler can significantly change the flame structure and characteristics. The addi-
tion of biomass can potentially have positive effects for reduction in commercial
facilities because of the high oxygen and volatiles content of biomass. Adding biomass
can also reduce flame temperatures leading to lower levels of thermal and the high
moisture content of some biomass may also be effective for reduction at full-scale.
Therefore, the bench-scale experiments described herein suggest that there are no syner-
gistic interactions between the pure fuels in a given biomass/coal blend all else being
equal. In full-scale cofiring applications, where all else is not equal, this conclusion may
be quite different
The chlorine released during the combustion of the coal/biomass blends did appear
to be affected by blending the two fuels beyond just a dilution effect. The amount
of KCl(g) and NaCl(g) detected during the combustion of the coal/wheat straw blends
was lower than expected. The results of the equilibrium calculations suggest that
potassium from the biomass was sequestered in the ash by the coal mineral matter
as alkali aluminosilicates. The high concentrations of alumina and silica in the coal
tend to interact with the large amount of potassium in the wheat straws. With less
potassium available for volitilization, the amount of HCl(g) released during the
combustion of the coal/wheat straw blends was higher than expected based on the
combustion results for the pure fuels. Blending coal and high chlorine- and alkali-
containing fuels apparently affects the chlorine equilibrium in such a way that cannot
be explained based on just mixing the pure fuels. Some other chemical interactions
between alkali metals in biomass and mineral matter in coal affects the partitioning
of chlorine in the gas phase between alkali and hydrogen chlorides. A reduction in
gas-phase alkali chlorides could potentially lead to lower than expected fouling and slag-
ging in commercial-scale systems when cofiring a high alkali containing biomass fuel with
coal. In fact, these effects with alkali metals may be enhanced in continuous feeding
systems where the gas/solid contact time would be longer compared to the batch exper-
iments discussed above.
Bench-Scale Biomass/Coal Cofiring Studies 579

5. ACKNOWLEDGMENTS

The authors acknowledge support from the Solar Thermal and Biomass Power
Division of the U.S. Department of Energy, Office of Energy Efficiency and Renewable
Energy. Special thanks go to Richard L. Bain and Thomas A. Milne for both program-
matic and technical support and guidance. Dr. Larry Baxter and Dr. Alien Robinson,
Sandia National Laboratories, supplied the biomass and coal samples.

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