Energy & Fuels 2002, 16, 915-919 915

Repressing NOx and N2O Emissions in a Fluidized Bed

Biomass Combustor
Göran Olofsson,* Wuyin Wang, Zhicheng Ye, Ingemar Bjerle, and
Arne Andersson

Department of Chemical Engineering II, Lund University, SE-221 00 Lund, Sweden

Received November 20, 2001. Revised Manuscript Received April 12, 2002

The emission of NOx and N2O were studied experimentally in a fluidized bed biomass combustor.
To investigate effectively the influence of different parameters on the NOx formation with a limited
number of experiments, an orthogonal experimental design was adapted. Four biomass fuels,
three NOx-repressing additives, four bed materials, and four alkali-capturing additives were tested
in a temperature range of 670-900 °C and at two pressure levels, 1.0 and 1.5 MPa. The NOx-
repressing additive was added to repress the formation of NOx and N2O and the alkali-capturing
additive was added to prevent the bed from agglomeration. In the present study it was found
that it was not possible to minimize both NO (NOx) and N2O with the same combination of
parameters. Instead, either NO formation or N2O formation has to be minimized. The results
also showed that the NOx-repressing additives were active in repressing NOx and N2O, except
for NH4HCO3. The optimal combination of the parameters investigated in the present study for
minimizing the emissions were: sawdust, bone ash, mullite, and urea for NO minimizations,
and straw, bone ash, clay, and Na2CO3 for N2O minimizations.

Introduction earth metals, causing it to melt at relatively low

The increased awareness of the need to reduce NOx/
SOx emissions from combustion systems has led to an
interest in biomass as a fuel source. Biomass has been
considered a good alternative to coal. Biomass is espe-
cially important for the reduction of CO2 emissions. The
interest in biomass as fuel is continuously increasing
and in combination with fluidized bed combustion
technology NOx emissions to the atmosphere can be
lowered. However, the nitrogen content in biomass fuel
is too high to be neglected when the NOx and N2O
emissions are of concern.
Considerable research has been directed at techniques
for the thermochemical conversion of biomass and at
their application and commercialization. One of these
techniques, fluidized bed combustion, has the advantage
of more effective heat transfer, greater fuel flexibility,
lower operational temperatures, and lower emissions of
SO2/NOx as compared with other technologies. The low
emission of NOx is partly due to the low combustion
temperature. However, the relatively low combustion
temperature also increases the emission of N2O relative
to other combustion systems.1,2
Although fluidized bed combustion is a mature tech-
nique for use with coal, frequent operational problems
have been encountered in its application to biomass.
One of these is agglomeration of the bed material.
Biomass ash is relatively rich in alkali and alkaline
* Author to whom correspondence should be addressed. E-mail:
goran.olofsson@chemeng.lth.se.
(1) Johnsson, J. E. Fuel 1994, 73, 1398.
(2) de Diego, L. F.; Londono, C. A.; Wang, X. S.; Gibbs, B. M. Fuel
1996, 75, 971.
temperatures. Fouling of the heat exchangers is an
additional problem.
While NOx limit values have existed for a long time,
N2O has received more attention only recently, as its
effect on greenhouse gas has become clearer.3 In fluid-
ized bed combustion of biomass, the NOx and N2O
emissions originate mainly from the fuel-bound nitro-
gen. Thermal NOx are of minor importance since 1300
°C is usually quoted as the beginning temperature of
thermal NOx formation. Most of the reactions proceeding
in which nitrogen oxides are formed or reduced are
catalytic ones. NOx formation due to oxidation of N-
containing components is favored by CaO, which acts
as a catalyst under the oxidation conditions. On the
other hand, NO reductions are catalytically accelerated
as well by CO, with char and ash as a catalyst. N2O
decomposition is enhanced over CaO, MgO, and iron
oxide.3
Air staging is a technique being successfully used to
reduce NOx emission, but its effect on N2O emission is
unclear.4,5 Limestone addition to a fluidized bed com-
bustor (FBC) has been shown to reduce the N2O emis-
sion and to increase the NOx emission.2 Staged com-
bustion combined with NH3 injection has been shown
to have potential for reducing NOx formation.6 A way
to lower NOx and N2O emission is to add specific
chemicals to the fuel. Those chemicals then react with
(3) Köpsel, R. F. W.; Halang, S. Fuel 1997, 76, 345.
(4) Lyngfelt A.; Leckner, B. Fuel 1993, 72, 1553.
(5) Hosada, H.; Hirama, T. A Novel Technique for Simultaneous
Reduction of Nitrous and Nitrogen Oxides Emissions from a Bubbling
Fluidized-Bed Combustor. Proceedings of the International Conference
on Fluidized Bed Combustion; 1995, 2, 1469-1475.

10.1021/ef0102768 CCC: $22.00 © 2002 American Chemical Society

Published on Web 05/29/2002
916 Energy & Fuels, Vol. 16, No. 4, 2002
Figure 1. A picture of the combustion test rig at LU.
NOx and produce N2 and water. The added chemicals
will in most cases first be converted to NH3. NH3 is
known to react selectively with NO in the gas phase to
produce N2 and water through reactions 1 and 2. This
technique is an example of a selective noncatalytic
reduction (SNCR)7
4NH3 + 6NO f 5N2 + 6H2O (Reaction 1)
4NH3 + 4NO + O2 f 4N2 + 6H2O (Reaction 2)
Ammonia species are both initiators of NO formation
and able to reduce the NO already formed. NO can also
be transferred into molecular nitrogen by reaction with
carbon monoxide. The reaction is catalyst by CaO, char,
and ash.3 NO can react to molecular nitrogen with the
nitrogen retained in char. The relative importance of
oxidation and reduction reactions consequently deter-
mines the resultant nitrogen oxide emissions. Most of
these reactions are catalytic.8
Some chemicals (CaO, MgO, and Na2CO3) added to
the fuel will act as catalysts and enhance the degrada-
tion of NO by reaction with CO. Sodium carbonate will
decompose to sodium oxide (Na2O) and CO2. It is
believed that Na2O can act as a catalyst in the same
way as CaO. In addition to coal, soot, and coke particles,
the coal ash has catalytic effects.
(6) Gibbs, B. M.; Salam, T. F.; Sibtain, S. F.; Pragnell, R. J.; Gauld,
D. W. In Twenty-Second Symp. (Internation) on Combustion; The
Combustion Institute: Pittsburgh, 1988; pp 1147-1154.
(7) Wuyin, W. Study and Modeling of the Reduction of Sulfur
Dioxide, Nitrogen Oxides and Hydrogen Chloride by Dry Injection
Technologies. Ph.D. Thesis, Lund University, 1997.
(8) Furusawa, T.; Koyama, M.; Tsujimura, M. Fuel 1985, 64, 413.
Olofsson et al.
In a biomass fired fluidized bed combustor several
operational problems relating to the fuel and bed
material can occur. The bed material can agglomerate,
leading to less fluidization. In the worst case it can
result in total defluidization. An important parameter
for the agglomeration tendency is the alkali content of
the bed material.
Relative little information on NOx emissions from
biomass combustion can be found in the literature. Most
of the work reported concerns fossil fuel; especially coal.
This paper present a study of the influence of three fuel
additives (NH4HCO3, (NH2)2CO, and Na2CO3) for re-
pressing the formation of NOx and N2O during combus-
tion of biomass in a pressurized fluidized bed combustor.
The influence of bed materials, fuel, and alkali-captur-
ing additive in combination with NOx-repressing addi-
tives on the NOx and N2O emission has also been
studied.
Experimental Section
The experiments were carried out in pressurized fluidized
bed combustor with a fuel feeding capacity of 90 kWth, shown
in Figure 1. It consists of three main parts: a combustion
reactor, a SiC-candle filter, and a catalytic reactor. Each of
these three parts is placed in a separate cylindrical pressure
vessel with an inner diameter of 0.5 m. The catalytic reactor
was not in operation in the present study. The combustor can
perform at a fuel-feeding rate of 10-20 kg/h. A detailed
description of the facility and of the operating procedures was
provided in an earlier publication.9
Four biomass or biomass-derived fuels and four types of bed
materials were tested. The four types of fuel were sawdust,
straw, willow, and meat and bone meal (MBM). The compo-
Repressing NOx and N2O Emissions in a Biomass Combustor Energy & Fuels, Vol. 16, No. 4, 2002 917

Table 1. Fuel Characterizationa

fuel sawdust MBM straw willow
HHV, MJ/kg 19.31 n.a. 16.9 18.3
LHV, MJ/kg 17.90 n.a. n.a.
volatile, % 76.03 n.a. 73.4 76
fixed carbon, % 14.87 n.a. n.a. n.a.
water, % 8.36 2 6.9 10.1
wt % dry
ash 0.76 43 8.2 3.25
C 51.27 n.a. 45 48.6
H 6.21 n.a. 6.1 6
N 0.25 1.26 0.54 0.6
O 41.56 n.a. n.a. 41.5
S 0.01 0.2 n.a. 0.04
Cl 0.01 0.12 0.365 0.005 Figure 2. Suggested7 reaction scheme for nitrogen reactions.
Na 0.01 0.59 0.025 0.028
K 0.76 0.19 0.65 0.34
Results
a n.a. - not analyzed.
NOx is the sum of NO and NO2. The emission of NO2
Table 2. Compositions (in %) of Bed Materials and
in the present study was very low (a few ppm) so all
Additives
the calculations for NOx were made on NO only. The
Fyle sand magnesite mullite bone ash calcite clay results from the evaluation of the experiments are listed
Na2O 0.03 0.0035 0.2 3 0.006 0.07 in matrix form in Tables 4 and 5. The impact of each
MgO 0.01 84.4 0.03 1.7 0.21 0.82 parameter (j) at each level (i) was calculated as the
Al2O3 0.45 0.34 75.2 0.7 0.05 18.2
SiO2 98.2 3.93 24.5 8 0.25 38.45
average emission of NOx and N2O (in ppm), (ki,j) (i ) 1,
P2O3 0.0015 0.05 0.0003 28.8 0.005 0.005 2, 3, 4, and j ) A, B, C, D, E), for all experiments in
SO2 0 0.16 0 0.6 0.012 0.014 which the parameter level of concern was employed. The
K2O 0.06 0.007 0.01 1.67 0.014 1.28 impact of urea on the emission of NO, for example, is
CaO 0.04 7.55 0.02 44.82 53.8 0.29
the average emission of NO for all the experiments in
TiO2 0.49 0.013 0.01 0.03 0.003 0.40
Fe2O3 0.21 3.07 0.03 4.8 0.035 7.56 which urea was employed as an NOx-repressing addi-
tive. The importance of each parameter (fuel, NOx
sitional analyses are shown in Tables 1 and 2. The tempera- additive, bed material, or alkali additive) on emissions
tures were measured at 5 positions in the reactor, at the were indicated by the maximum difference in the ki,j
bottom, below and above the feeding point for the fuel, the value for it in column Rj. The relative importance of
upper part of the reactor, and at the free board, T1-T5 in different parameters can be quantified then by compar-
Figure 1. The temperatures tested were in the range of 670- ing their Rj value.
900 °C. Two pressure levels were selected: 1.0 and 1.5 MPa. As can be seen from Table 4, the most significant
Both the flow rate of the carrier gas and the fuel-feeding rate factor for NO emissions was the type of fuel, followed
were adjusted so that an oxygen concentration of approxi-
by the bed material and NOx-repressing additive. From
mately 6 vol % in the product gas could be maintained. The
gas velocity in the reactor was 0.25 m/s for 1.5 MPa and 0.30 Table 5 it can be seen that for the N2O emissions the
m/s for 1.0 MPa and the residence times for the gas were 13.2 fuel was the most significant factor, followed by the bed
and 11 s, respectively. Particles of the bed materials were material and the NOx-repressing additive.
nominally 200 µm in size. Na2CO3, urea, and NH4HCO3 were
added to the fuel input as pure chemicals in a ratio of 5 wt % Discussion
for suppressing NOx emissions The additives used for captur-
ing the alkali were mullite, calcite, clay, and a mixture of clay At high temperatures, the ammonium bicarbonate
and calcite. They were added in a ratio of 10 wt % and the (NH4HCO3) decomposes to ammonia, CO2, and water,
compositional analyses are shown in Table 2. A test takes while urea ((NH2)2CO) at 300 °C is converted mainly to
about 1 day (20 h) to perform, including the time for heating ammonia and isocyanic acid (HNCO). Above 500 °C urea
the reactor to the operational temperature. The reactor is then decomposes completely to volatile products.10 During the
running at steady state for about 5 h.
heating of the fuel, the fuel-bound nitrogen is partly
An orthogonal experimental design was adopted so as to be
released. A part of the nitrogen escapes as cyanic (CN)
able to investigate the influence of different parameters on
emission of NOx and N2O in an effective way with use of only and amino (NH) compounds. These compounds can be
a limited number of experiments. The fuel, the NOx additive, transformed into nitrogen oxides by several complex
the bed material, and the alkali additive selected served as reaction steps during the combustion. A suggested
experimental parameters, each parameter having four levels. reaction scheme is given in Figure 2.7
The emissions of NOx and N2O occurring were evaluated and The most significant factor for NO and N2O emissions
were related to the parameters selected. The combustion gas was the type of fuel. From Tables 4 and 5 it can be seen
was analyzed on-line by means of mass spectrometry (Balzers that the R-factor is 312 and 246 for NO and N2O,
QMG 420 MS) and Fourier transform infrared spectrometry respectively, which are the highest of the R-values.
(Gasmet FT-IR gas analyzer). The used bed material from the
Since all biomass contains nitrogen compounds, see
bottom of the reactor and the fly ash from the filter were also
sampled and analyzed by means of atomic absorption spec-
Table 1, the combustion of biomass always leads to
troscopy (GBC 908AA) and scanning electron microscopy emissions of NOx. However, MBM has a high content
(JEOL JSM-840A SEM). of proteins, and as a consequence a high nitrogen
content (1.26%) compared to the other fuels (0.25-0.6%);
(9) Padban N.; Wang W.; Ye, Z.; Bjerle, I.; Odenbrand, I. Energy
Fuels 2000, 14, 603-611. (10) Wynne, A. M. J. Chem. Educ. 1987, 64, 180.
918 Energy & Fuels, Vol. 16, No. 4, 2002 Olofsson et al.

Table 3. Values of Some Interesting Parameters in the Present Study

fuel amount (g/min) airflow (sl/min) ERa temperature range (°C)
fuel 1.0 MPa 1.5 MPa 1.0 MPa 1.5 MPa 1.0 MPa 1.5 MPa below fuel inlet above fuel inlet
sawdust 51 63 350 450 1.54 1.72 810-850 840-900
straw 56 58 350 450 1.59 1.78 740-770
willow 50 74 350 450 1.62 1.45 780-820 840-880
MBM 66 n.a. 350 450 1.34 700-750
a ER ) equivalence ratio (QO2 in/QO2 stoichiometric).

Table 4. Parameter Significance on NO Emission (ppm) a low N content could be an effective way to decrease
j the emissions, but often the fuel is given and hence to
bed alkali NOx
choose fuel is not an alternative.
fuel material additive additive pressure A method to decrease the NOx and N2O emissions is
i A B C D E to choose a proper bed material. The bed material was
1 straw MgO clay Na2CO3 10 the second most important parameter for decreasing NO
2 MBM sand calcite NH4HCO3 15 and N2O emissions. Bone ash was the best bed material
3 willow bone Ash mullite none for both NO and N2O minimization. The reason for that
4 sawdust mullite C1 + C2 OdC(NH2)2
could be the high content of CaO in the bone ash (44.8%)
k1 200 271 198 154 185.5 and its catalytic action. CaO is also active as a catalyst
k2 396 161 227 250 197.6
k3 160 55 135 220 for formation of NO, but if the right condition for the
k4 84 251 214 121 degradation reaction exists (for examples CO and some
R 312 216 92 129 12.1 char) the net result could be a decrease in NO and N2O
emissions. In the cases where mullite was used as bed
Table 5. Parameter Significance on N2O Emission (ppm)
material, the N2O emissions were comparatively high.
j Mixing NOx-repressing additive into the fuel was the
bed alkali NOx third most important parameter for decreasing the NO
fuel material additive additive pressure and the N2O emissions (R-value ) 129 and 104, respec-
i A B C D E
tively). Of the three NOx-repressing additives studied,
1 straw MgO clay Na2CO3 10 two were nitrogen-containing compounds (urea and
2 MBM sand calcite NH4HCO3 15
3 willow bone Ash mullite none ammonia bicarbonate) and one was an alkali-containing
4 sawdust mullite C1 + C2 OdC(NH2)2 compound (sodium carbonate). It was found that urea
k1 26 89 22 37 97.9 was the best additive for repressing NO; Na2CO3 was
k2 271 53 89 141 69.7 the best one for repressing N2O. The worst additive was
k3 84 21 115 96 NH4HCO3. In both cases the emissions were greater
k4 34 167 73 41 with NH4HCO3 as an additive than it was without any
R 246 146 93 104 28.2
additives at all. If the amount of NH4HCO3 was too
Table 6. Conversion of Fuel-N to NO and N2Oa high, the excess of the released ammonia could be
oxidized to NO.
N-conversion to NO (%) N-conversion to N2O (%)
Pressure was one of the parameters studied. The
fuel 1.0 Mpa 1.5 MPa 1.0 MPa 1.5 MPa
effect of pressure and that of temperature were found
sawdust 15 3 21 2 in the present study, however, to be related. To retain
straw 13 19 n.a. 8
willow 16 8 15 10
a similar gas velocity in the bed, the air input needs to
MBM 9 n.a. 18 n.a. be increased at elevated pressure. Since the extra inert
nitrogen increases the cooling effect of the gas on the
a n.a. - not analyzed.
fluid bed, the tests were performed in such way that
therefore, as can be seen from Tables 4 and 5, MBM an increase in the operating pressure in the reactor also
greatly contributes to the emissions. As a consequence, resulted in a reduction in the bed temperature. Theo-
if MBM is excluded as a fuel, the parameter fuel should retical calculations of the equilibrium composition at 10
not be so noticeable. The conversion of fuel-nitrogen to and 15 bar and 1100 K were performed and showed the
NOx and N2O are different for different fuels. In the increase in pressure to have no effect on NOx and N2O
present study the conversion to NO was found to be emissions. The impact of the fuel-N is more difficult to
between 9 and 16% for the pressure level of 1.0 MPa. calculate. It is presumably not affected by the equilib-
For the pressure level 1.5 MPa the conversion was rium and higher concentrations of NO and N2O are
between 3 and 19%. The conversion to N2O was found therefore possible to obtain.
to be between 15 and 21% for the lower pressure and The best combination of the parameters investigated
between 2 and 10% for the higher pressure. The conver- in the present study for minimizing the NO emission
sion to N2O is rather high, which can be explained by would be sawdust as fuel, urea as a NOx-repressing
the relatively low combustion temperatures (<900 °C). additive, bone ash as bed material, and mullite as alkali-
In the present study, the tendency was that a higher capturing additive. For repressing N2O emissions, the
pressure level gave a lower N-conversion to NO and N2O best combination would be straw, Na2CO3, bone ash,
if the temperature was at the higher end of the range and clay.
(850-900 °C), see Tables 3 and 6. In the case of straw, It was difficult to minimize both NO and N2O at the
the conversion increased with the pressure, but here the same time. As mentioned earlier the NOx emissions
temperature was lower (<800 °C). To choose fuel with would increase and the N2O emission would decrease
Repressing NOx and N2O Emissions in a Biomass Combustor
when the temperature is increased. From the results it
can be seen that the best combination for minimizing
NO (sawdust, bone ash, mullite, and urea) was not the
best for minimizing N2O (straw, bone ash, clay, and Na2-
CO3). It can also be seen that the best alkali-capturing
additive for minimizing emissions of NO, mullite, was
on the other hand the worst alkali-capturing additive
for the N2O emission.
Even though Na2CO3 seems to be a good NOx-
repressing additive, care must be taken if Na2CO3 is
used as an additive. A fluidized bed is sensitive to the
alkali metal (Na and K) content in the bed, especially
if silicon is present.11 Alkali metals and Si can react and
form alkali silicates that have melting points below the
operational temperature in the fluidized bed.12,13 The
fluidized bed will then agglomerate and might even
cease to fluidize with a shut-down of the plant as a
result. The sodium content in Na2CO3 can contribute
to the agglomeration phenomena. Na2CO3 should be
avoided as a NOx-repressing additive if the bed material
(11) Moilanen, A.; Kurkela, E.; Laatikainen-Luntama, J. In Impact
of Mineral Impurities on Solid Fuel Combustion; Gupta, R. P., Wall,
T. F., Baxter, L., Eds.; Kluwer Academic/Plenum Publishers: New
York, 1999; pp 555-567.
(12) Grubor, B. D.; Oka, S. N.; Ilic, M. S.; Dakic, D. V.; Arsic, B. T.
Biomass FBC combustion-bed agglomeration problems. Proc. Int.
Conf. Fluid. Bed Combust. 1995, 13 (1), 515-522.
(13) Lin, W.; Dam-Johansen, K. Agglomeration in fluidized bed
combustion of biomass-Mechanisms and co-firing with coal. Proc. Int.
Conf. Fluid. Bed Combust. 1999, 15, 1188-1191.
Energy & Fuels, Vol. 16, No. 4, 2002 919
and/or the used fuel have a high Si content. For
example, the combination of Fyle sand and straw is not
a good combination as bed material and fuel, respec-
tively, if Na2CO3 is used as a NOx-repressing additive.
Urea and ammonia bicarbonates are unlikely to con-
tribute to the agglomeration process.
Conclusions
It is not possible to minimize both NO (NOx) and N2O
in the same experiment. Instead two alternatives exist
either to minimize NO or N2O. On the basis of the
experimental results and considerations discussed above,
the following conclusions concerning biomass combus-
tion in a fluidized bed can be drawn:
1. The best combination of parameters for minimizing
the formation of NO is to:
a. choose sawdust as fuel,
b. use urea as NOx-repressing additive,
c. use mullite as alkali-capturing additive,
d. use bone ash as bed material.
2. The best combination of parameters for minimizing
the formation of N2O is to:
a. choose straw as fuel,
b. use Na2CO3 as NOx-repressing additive,
c. use clay as alkali-capturing additive,
d. use bone ash as bed material.
EF0102768