626

Ind. Eng. Chem. Res. 2000, 39, 626-634

Release of Fuel-Bound Nitrogen during Biomass Gasification

Jiachun Zhou, Stephen M. Masutani,*, Darren M. Ishimura, Scott Q. Turn,, and
Charles M. Kinoshita,
Hawaii Natural Energy Institute, and Biosystems Engineering Department, University of Hawaii at Manoa,
Honolulu, Hawaii 96822

Gasification of four biomass feedstocks (leucaena, sawdust, bagasse, and banagrass) with
significantly different fuel-bound nitrogen (FBN) content was investigated to determine the effects
of operational parameters and nitrogen content of biomass on the partitioning of FBN among
nitrogenous gas species. Experiments were performed using a bench-scale, indirectly heated,
fluidized-bed gasifier. Data were obtained over a range of temperatures and equivalence ratios
representative of commercial biomass gasification processes. An assay of all major nitrogenous
components in the gasification products was performed for the first time, providing a clear
accounting of the evolution of FBN. Important findings of this research include the following:
(1) NH3 and N2 are the dominant species evolved from fuel nitrogen during biomass gasification;
>90% of FBN in feedstock is converted to NH3 and N2; (2) relative levels of NH3 and N2 are
determined by thermochemical reactions in the gasifier; these reactions are affected strongly
by temperature; (3) N2 appears to be primarily produced through the conversion of NH3 in the
gas phase; (4) the structural formula and content of fuel nitrogen in biomass feedstock
significantly affect the formation and evolution of nitrogen species during biomass gasification.
Introduction
Biomass gasification is an attractive technology to
convert biomass fuels to gaseous products which can be
used in power generation and alternative transportation
fuel production. During gasification of biomass fuels,
nitrogenous compounds, such as ammonia (NH3), hydrogen cyanide (HCN), and oxides of nitrogen (NO +
NO2 or NOx; N2O), may be produced from fuel-bound
nitrogen (FBN) in biomass feedstock. These gas-phase
species pass through end-use systems of the product gas,
where they can poison catalysts or may undergo further
oxidization and be emitted as NOx, which is the primary
contributor to photochemical smog. Although research
on biomass gasification has been pursued for many
years, to date only a few studies have been conducted
on the associated formation, deposition, and abatement
of nitrogenous pollutants. Additional effort in this area
is warranted given the current interest in utilizing
biomass gas for IGCC (integrated gasification combined
cycle) power systems and liquid fuel synthesis.
It is well recognized that a major source of NOx from
coal combustion and gasification is the conversion of fuel
nitrogen in the coal. Conversion of volatile nitrogenous
species is the primary contributor to fuel NOx emissions.1 These volatile NOx precursors include HCN and
NH3.2,3 Other nitrogenous species, such as NOx and N2,
are also produced during pyrolysis and combustion of
coal.4 Although coal nitrogen emission studies have
provided insight into FBN evolution, it is unclear
whether those results can directly be applied to biomass,
because nitrogen is bound in different forms in the
two solid fuels; earlier work suggests that the fuel
structure significantly influences FBN evolution.3-5
Nitrogen evolution during thermochemical conversion
* To whom correspondence should be addressed. E-mail:
masutan@wiliki.eng.hawaii.edu.
Biosystems Engineering Department.
Hawaii Natural Energy Institute.

of biomass fuels has not been investigated extensively.

Several researchers have studied the formation of
nitrogen-containing species during biomass gasification.5-8 These studies identified NH3, HCN, and N2
as the major nitrogenous components of the product
gas and documented effects of varying gasification
conditions on their concentrations. In these earlier
studies, however, N2 concentrations were inferred from
a nitrogen balance, rather than being measured directly.
A level of uncertainty therefore remains concerning the
partitioning of FBN.
While previous investigations have provided important information on FBN emission during biomass
gasification, results from different studies vary considerably, and the mechanisms for the formation and
evolution of nitrogenous species are still unclear. The
observed differences may reflect differences in test
conditions and feedstocks. The present study attempts
to clarify the effects of gasification conditions and fuel
on the release and evolution of biomass FBN through
parallel experiments utilizing four different biomass
feedstocks having significantly different FBN contents.
Facility
All tests in the present study were performed by
employing a bench-scale fluidized-bed gasification system (Figure 1), which includes an indirectly heated
fluidized-bed gasifier, a screw biomass feeder, and a hot
gas char filter. The reactor consists of an 89 mm i.d.
stainless steel pipe enclosed within a stack of electric
heaters that allow uniform temperatures to be maintained in the fluidized bed. Alumina beads (0.21-0.42
mm diameter) comprise the bed which has a static
height of about 700 mm. Biomass is fed into the reactor
from a sealed hopper with an auger-type screw feeder.
Oxygen and argon are injected into the gasifier to serve
as an oxidizer and a tracer gas, respectively. Product
gases exiting the gasifier pass through a high-temperature char filter before entering the sampling system.

10.1021/ie980318o CCC: $19.00 2000 American Chemical Society

Published on Web 01/29/2000

Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000 627

Figure 1. Gasification system and sampling train.

The major nitrogenous species, NH3, N2, HCN, and

NOx, were quantified either on-line or by off-line analysis of extracted gas samples. A gas chromatograph (GC),
ion-specific electrodes (ISE), and a chemiluminescence
analyzer (CLA) were the principal instruments employed in this study.

A nitrogen species gas sampling system, shown in

Figure 1, was installed downstream of the sinteredmetal char filter. NH3 and HCN were collected by
absorption into liquid solutions and measured with
ISEs. The NH3/HCN sampling train consisted of four
bubblers arranged in series. The first two bubblers were

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Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000

Table 1. Feedstock Properties (Dry Basis)

process method

leucaena

sawdust

moisture
volatile matter
fixed carbon
ash

10.40
74.28
18.54
7.18

7.68
84.16
15.47
0.37

[C]:
[H]:
[O]:
[S]:
[N]:
ash

48.43
5.64
36.02
0.22
2.51
7.18

48.45
5.11
46.01
0.03
0.03
0.37

carbon
hydrogen
oxygenb
sulfur
nitrogen

Banagrass1
JC-PRPa

Banagrass2
FC-PRPa

Banagrass3
FC-Pa

Proximate Analysis, %
6.40
79.25
14.92
5.83

11.36
80.55
15.7
3.75

7.07
81.52
15.48
3.00

7.07
79.45
16.48
4.07

Ultimate Analysis, %
46.27
5.27
42.41
0.05
0.12
5.83

47.04
5.11
43.81
0.04
0.22
3.75

47.39
5.24
43.76
0.14
0.36
3.00

46.93
5.09
43.01
0.14
0.44
4.07

bagasse

These designators refer to the different feedstock treatments.11

filled with 150 mL of 0.1 M sulfuric acid (H2SO4) used

to trap NH3. The remaining bubblers were filled with a
mixture of 145 mL of 0.1 M sodium hydroxide (NaOH)
and 5 mL of 0.117 M lead acetate trihydrate (PbAce
3H2O), which reacts with and absorbs HCN.
Downstream of the bubblers, a small slipstream of the
biomass product gas was directed into a CLA to detect
and quantify NOx. The CLA was calibrated before each
experiment with two certified EPA Protocol gas mixtures containing 9 and 90 ppm NO in N2. The CLA was
recalibrated after each test run to assess instrument
drift. Because the accuracy of CLA measurements of NO
may be affected by other species present in the product
gas mixture (e.g., H2 and CO), a correction recommended by Matthews et al.9 was applied to the raw data.
A second sampling train in parallel with the NH3/
HCN bubblers was used to collect product gas samples.
Gases were analyzed with a Perkin-Elmer Auto System
GC equipped with a thermal conductivity detector
(TCD). A stainless steel packed column (12.2 m 3.2
mm) from Alltech Associates, Inc., was employed to
separate the adjacent Ar, O2, and N2 chromatogram
peaks. Analyses were conducted at low chamber temperatures and carrier gas flow rates. A PE Nelson model
1020 personal integrator interfaced with the GC was
used to determine gas concentrations from the chromatograms (manual integration was sometimes used to
infer O2 concentrations). The GC was calibrated with
two gas mixture standards that had compositions
similar to the biomass gas.
Although the GC was capable of measuring N2 in the
collected gas samples to within 2%, contamination of
the samples by ambient air posed a problem (note that
the present tests used an O2/Ar mixture, rather than
air, to gasify the biomass). Because the gasifier was
operated at positive internal pressures and the fuel
hopper was sealed, the possibility of tramp air leaking
into the gasifier is negligible. Any contamination therefore arose from air leaks into the collection bulbs and
vials or into the GC during sampling and analysis.
Fortunately, air contamination of this type can be
identified via its O2 content.
Because gasification occurs with a deficiency of oxidizer, both experiments and simulations indicate that
residual O2 levels in the products are negligibly low. Any
O2 detected by the GC may then be attributed to air
contamination. The known N2/O2 ratio in the air can
be applied to quantify the contaminant N2 from the
O2 measurements. This amount may then be subtracted
from the total N2 detected with the GC to estimate N2
formed from FBN.

Oxygen: determined by the difference method.

Overview of Experiments
Four types of biomass feedstocks were used in the
experimentssleucaena, sawdust, bagasse, and banagrass. Leucaena (Leucaena leucocephala), a fast-growing
plant and a potential biomass energy resource,10 has a
high nitrogen concentration compared to the other
feedstocks. The leucaena feedstock, consisting primarily
of leaves and small branches, was harvested from
leucaena trees and exposed to air for several days to
reduce the moisture content in the raw material. The
low-FBN sawdust consisted of a mixture of several
hardwood and softwood species (e.g., fir, poplar, oak,
ash). Banagrass (Pennisetum Purpureum), a fast-growing tropical grass, is being considered as a possible
short-rotation, intensive-culture energy crop.10 In some
of the tests reported herein, freshly harvested banagrass
was treated using different processing steps to remove
or to reduce various inorganic components. These treatments attempt to minimize negative impacts of inorganics on the gasification process and some end-use
technologies (e.g., combustion in gas turbines). The FBN
content was determined also to depend on the treatment. Details of the treatments and their effects have
been documented by Turn et al.11 All feedstocks were
milled using the same machine to yield particle sizes
generally (>95%) less than 3 mm. Proximate and ultimate analyses of the feedstocks are given in Table 1.
A screw feeder was employed to transport the feedstock from a small hopper into the gasifier. The housing
of the feeder screw between the feeder and gasifier was
water-cooled to minimize thermochemical decomposition
of biomass in the screw prior to entering the gasifier.
The feeding rate was determined via calibration.
Parametric tests were performed to investigate the
effects of operating parameters on fuel-bound nitrogen
evolution during gasification. The parameters that were
varied were bed temperature and equivalence ratio
(ER). ER is defined as the actual oxidizer-to-fuel ratio
(mass basis) divided by the stoichiometric oxidizer-tofuel ratio. ER ranged from 0.18 to 0.40 in the tests. Bed
temperatures between 700 and 950 C, which are
representative of commercial gasifiers,12 were investigated.
Each test was conducted at a fixed equivalence ratio
with pure oxygen as the oxidizer. Argon was employed
as a tracer gas, and no steam was injected although the
biomass feedstocks contained small amounts of moisture. All data were obtained after steady-state operation
had been attained. The criterion for steady-state operation in this study was stabilization of the temperatures

Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000 629

Figure 3. NH3 and N2 concentrations vs temperature (ER ) 0.25,

leucaena).
Figure 2. Major gas species composition vs temperature (ER )
0.25, leucaena).

in the gasifier. Because pressure in the gasifier typically

exceeds atmospheric pressure and varies slightly over
time as the outlet filter resistance increases, parameters
such as the residence time were adjusted to account for
pressure variations. Mass balance calculations for major
elements, O, H, C, and N, were performed for all
parametric tests.
Temperature strongly affects chemical reactions in
the gasifier. Because a uniform temperature distribution
greatly facilitates interpretation of the data, the heaters
and the heater control were configured to obtain a
uniform temperature distribution within the fluidizedbed section. Within the bed, temperature varied by less
than 15 C during steady-state operation.13 Maximum
departures from the set-point temperature were less
than 4%; the largest departures occur at a location near
the biomass inlet. At the inlet, rapid pyrolysis and
exothermic oxidation reactions which occur when the
fresh biomass contacts oxygen-rich gas entering from
the distributor elevate temperature about the set point.
Results and Discussion
Effect of Temperature. Tests were conducted employing leucaena and sawdust feedstocks. Gasifier temperature was varied between 750 and 950 C (leucaena)
or between 700 and 900 C (sawdust) at a constant
equivalence ratio. Because trends were similar for all
ERs, a single case at ER ) 0.25 will be discussed.
Gas composition results for major species from leucaena, shown in Figure 2, indicate that both H2 and CO
increase with increasing temperature. Between 750 and
950 C, hydrogen increases from 26% to 33% (dry, inert
free; DIF) and CO increases from 29% to 41% (DIF); CO2
decreases from 34% to 18% (DIF), and C2H2 decreases
from 2% to 0.6% (DIF). The temperature does not
significantly influence the concentration of CH4. The gas
yield increases from about 1 to 1.37 m3/kg between 750
and 950 C. Carbon and hydrogen balances performed
for this test range from 94% to 98% and from 88% to
99%, respectively. The observed trends in gas composition and gas yield as functions of temperature agree

with the results of previous experimental studies14 and

the theoretical analysis conducted by Wang.12
Measured NH3 and N2 concentrations in the leucaena
product gas are plotted as functions of temperature in
Figure 3. NH3 decreases sharply from 31 240 ppmV at
750 C to 6060 ppmV at 900 C. A slight increase in
the NH3 concentration was observed at 950 C. Over
the same temperature range, molecular nitrogen (N2)
generally increased with increasing temperature (from
9480 to 16 750 ppmV); however, a slight decrease in the
N2 concentration was detected at 950 C.
The high levels of NH3 in the product gas suggest that
it may be the major nitrogenous species formed when
biomass is rapidly pyrolyzed after entering the gasifier.
Because NH3 and N2 exhibit opposite trends as the
temperature varies, there is a basis to propose that the
conversion of NH3 to N2 is the dominant thermochemical
process which determines the final fate of FBN in the
gas phase under gasification conditions examined in the
present study.
To assess the relevance of equilibrium on the evolution of FBN, an equilibrium analysis of the biomass
gasification process was performed in an earlier study
using the STANJAN program.14 The results of the
analysis indicated that the majority of FBN is converted
to N2 at equilibrium under typical biomass gasification
conditions (700-900 C; ER 0.2-0.4). The absolute
concentrations of nitrogenous species (including N2) that
were predicted at equilibrium were observed to differ
greatly from experimental data. For example, at 800 C,
the predicted and measured NH3 concentrations are
about 10 and 18 000 ppmV, respectively. Equilibrium
HCN levels are less than 4 ppmV versus measurement
data indicating about 40 ppmV. These differences
emphasize the importance of kinetics in the distribution
of FBN among nitrogenous components of the gasified
biomass.
The present measurements of N2 support the contention by Ishimura14 and others that biomass FBN not
detected as amines, cyanogens, NOx, or tars exists as
N2. Although several sources of measurement uncertainty discussed above affect the nitrogen balance,
relatively good closure of the N-atom inventory was
attained in the present investigation, ranging from
105% to 116% after correcting for air leakage.

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Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000

Figure 4. NO and HCN concentrations vs temperature (ER )

0.25, leucaena).

Figure 5. Nitrogen species concentration vs temperature (ER )

0.25, sawdust).

Table 2. Distribution of Fuel Nitrogen as a Function of

Temperature (Leucaena, ER ) 0.25)
T, C
N(NOx)/Nfuel, %
N(NH3)/Nfuel, %
N(HCN)/Nfuel, %
N(char)/Nfuel, %
N(N2)/Nfuel, %

750

800

850

900

950

0.06
63.5
0.11
7.7
38.6

0.04
48.74
0.09
5.2
69.9

0.02
25.81
0.08
2.0
80.3

0.02
13.49
0.07
2.0
88.7

0.01
10.48
0.07
1.2
85.7

NO concentrations measured with the CLA and HCN

concentrations determined by the ISE method are
plotted versus the nominal gasification temperature in
Figure 4. The nitric oxide concentration decreases from
30 ppmV at 750 C to 5 ppmV at 950 C, and HCN
concentrations fall from 55 ppmV at 750 C to 30 ppmV
at 950 C. The NO and HCN concentrations are 2-3
orders of magnitude lower than those of NH3 and N2.
The distribution of FBN among the nitrogenous
species NH3, N2, NO, and HCN for gasification of
leucaena at ER ) 0.25 (750-950 C) is given in Table
2. Most of the fuel nitrogen resides in NH3 and N2; less
than 1% of the FBN is detected as HCN and NO. The
strong influence of temperature is apparent from the
datasbetween 750 and 950 C, the fraction of FBN as
NH3 in the product gas decreases from approximately
64% to 18%. Over this same temperature range, fuel
nitrogen bound in N2 increases from 40% to about 85%.
Nitrogen species concentrations for sawdust gasification are plotted in Figure 5. NH3 in the synthesis gas
was observed to decrease from 950 ppmV at 700 C to
about 400 ppmV at 900 C. NO and HCN are once again
detected at much lower levels than NH3. The general
trends in nitrogen species concentrations exhibited in
the sawdust tests are similar to those recorded in
leucaena tests; however, concentrations are lower because of the reduced FBN (2 orders of magnitude) in
sawdust. The exception is NO, which was detected in
greater amounts in the gasified sawdust. A possible
explanation for this will be proposed when the effects
of feedstock are discussed.
Effect of Equivalence Ratio. Theoretical computations have determined that the optimum range of
equivalence ratios for gasification of biomass is 0.20.4.12 Tests were performed at three values of equiva-

Figure 6. Major gas species composition vs ER (800 C, leucaena).

lence ratio within this range to determine how ER

impacts FBN chemistry. Inert-free product gas composition at 800 C for leucaena gasification is plotted in
Figure 6 as a function of the equivalence ratio. The data
indicate that CO and H2 decrease, and CO2 increases,
as the equivalence ratio increases. Concentrations of
higher hydrocarbon compounds, which include methane,
remain virtually constant. These trends are consistent
with earlier predictions and experimental results.12,14
Unlike temperature, the equivalence ratio does not
significantly impact the concentrations of nitrogenous
species in gasified biomass. Figures 7 and 8 summarize
the influences of both the equivalence ratio and temperature on the amounts of NH3 and N2 produced when
leucaena is gasified. At temperatures in excess of
800 C, NH3 concentrations measured for the three
values of ER are comparable and do not show significant
variation for values of ER between 0.18 and 0.32. The
N2 concentration (Figure 8) appears to be more sensitive
to ER. This may, however, simply reflect the greater
uncertainty in the N2 data. The mass balance calculation results, presented in Table 3, indicate that the
percentages of FBN existing as NH3 or N2 do not vary
significantly with ER.

Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000 631

Figure 9. NO and HCN concentrations vs ER (800 C, leucaena).

Figure 7. Influences of temperature and ER on the NH3
concentration (leucaena).

Figure 10. Nitrogenous species concentrations vs ER (800 C,

sawdust).
Figure 8. Influences of temperature and ER on N2 concentration
(leucaena).
Table 3. Fuel Nitrogen Distribution in NH3 and N2 as
Functions of ER and T (C) (Leucaena)
T, C
750

800

850

ER ) 0.18
ER ) 0.25
ER ) 0.32

63.1
63.5
47.2

N(NH3)/Nfuel, %
50.5
27.6
40.5
24.0
44.7
27.6

ER ) 0.18
ER ) 0.25
ER ) 0.32

37.8
38.6
42.3

N(N2)/Nfuel, %
67.8
97.6
69.9
80.3
51.0
67.8

900

950

12.8
16.0
11.0

10.6
18.2
17.4

108.2
88.7
81.0

114.9
85.7
90.6

The dependence of NO and HCN concentrations on

ER at 800 C is shown in Figure 9. Higher ER promotes
lower concentrations of these species in the product gas.
This effect, however, does not significantly impact the
partitioning of FBN because NO and HCN amount to
only a very small fraction of the fuel nitrogen (<1%).
The modest influence of ER on concentrations of
nitrogenous species in gasification product gases can
also be observed in the results of the sawdust gasification experiments. As seen in Figure 10, a change in ER
from 0.25 to 0.37 at 800 C only induces NH3 concentra-

tions to increase slightly from 310 to 350 ppmV. The

single data point of NH3 concentration at ER ) 0.18
suggests that NH3 may be affected strongly by this
parameter below ER ) 0.25. No experiments were
performed at ER less than 0.18, because this falls
outside the normal range of commercial gasifier operating conditions.
Effect of Feedstock. Biomass is generally defined
as any material derived directly from living organisms.
The structure and composition of a biomass feedstock
are affected by several factors, such as the types of
plants, processing methods after harvest, etc. Biomass
fuels therefore are likely to have more complex physical
characteristics and properties than coal or petroleum,
which may significantly impact fuel nitrogen chemistry
during high-temperature gasification. Biomass feedstocks with substantially different fuel nitrogen contents, as listed in Table 1, were gasified in this study
to determine the effect of feedstock on the formation of
nitrogen species in the gasifier.
Feedstocks used in the experiments contained between 0.08% and 2.51% (by weight, dry basis) FBN.
Leucaena, consisting primarily of leaves and small
stems, has the highest nitrogen content. Sawdust, a
mixture of several hardwood species, has the lowest
nitrogen content. Bagasse, the residue of cane sugar

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Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000

Figure 11. NH3 concentration for six feedstocks (800 C, ER ) 0.25).

Figure 12. NO concentration for six feedstocks (800 C, ER ) 0.25).

production, has a nitrogen content of 0.12% and was

milled to yield particle sizes comparable to those of the
other feedstocks. Banagrass was hand harvested from
local plots and processed with various methods to obtain
feedstocks with different nitrogen contents ranging from
0.22% to 0.44%. In the feedstock tests, the gasifier
temperature was set at 800 C and ER ) 0.25.
Measured NH3 concentrations in the product gas are
plotted for each feedstock in Figure 11 (NH3 concentration data for bagasse and banagrass are from Turn et
al.15). The amount of NH3 is clearly impacted by the
nitrogen content of the feedstock. The NH3 concentration for gasified sawdust is only about 400 ppmV, in
comparison with the approximately 18 000 ppmV detected for leucaena. Experimental data for the three
banagrass feedstocks suggest that NH3 increases approximately linearly with the FBN content.
Test results indicate that NO levels are inversely
affected by the fuel nitrogen content (Figure 12). Sawdust, which has the lowest nitrogen content, produces
a product gas with the highest NO concentration. The
amount of NO in gasified leucaena is very low even

though its nitrogen content is much higher than that

of the other feedstocks.
The tested feedstocks not only differ with respect to
nitrogen content but also have unique physical characteristics and chemical structure. Nitrogen exists in
plants in several forms.16 Nitrogen is absorbed by the
roots of plants as NO3- and NH4+. NO3- and NH4+ must
move from the roots to leaves and young stems. Portions
of NO3- and NH4+ are absorbed when these species are
transported through the xylem. The bulk of NO3- and
NH4+ is deposited in leaves. NO3- is converted to amino
acids or proteins in the leaves and stems. Thus, most
of the fuel nitrogen in a plant is stored in the leaves
and shoots in the form of amino acids while a small
portion of fuel nitrogen exists in the xylem, predominantly as NO3- and, to a lesser extent, as NH4+.
Table 4 lists the amounts of nitrogen present as NH4+
and NO3- in the tested feedstocks. The leucaena feedstock contains mostly leaves and green stems while
sawdust comprises hardwood which primarily consists
of xylem. Leaves contain more NH4+, and xylem contains more NO3-. Hence, the NO3-/NH4+ ratio is higher

Ind. Eng. Chem. Res., Vol. 39, No. 3, 2000 633

Table 4. NH4+-Nitrogen and NO3--Nitrogen in
Feedstocks
feedstock
sawdust
leucaena
bagasse
Banagrass1
Banagrass2
Banagrass3

N(NH4+),
ppmw

N(NO3-),
ppmw

N(NO3-)/N(NH4+)

27.68
214.89

29.18
41.04

1.05
0.19

5.44
12.16
20.44
46.81

9.86
17.99
43.02
52.68

1.82
1.45
2.10
1.13

Figure 13. Overall reactions in the thermal de-NOx process.

in sawdust than in leucaena. It is observed in Figure

12 that more NO is produced during gasification of
sawdust than leucaena. As indicated in Table 4, Banagrass2 has a higher NO3-/NH4+ ratio than the other
banagrass and bagasse feedstocks. Banagrass2 was
observed to generate higher levels of NO in the product
gas than those other banagrass and bagasse feedstocks
(Figure 12). These results and comparisons may add
some credence to the conjecture that, at given gasification conditions, the amount of nitrate nitrogen (NO3-)
in the feedstock will impact NO yield. Additional
research is required to test this hypothesis.
The thermal de-NOx reaction mechanism17 also may
impact NO evolution in a biomass gasifier. Figure 13
presents the overall reaction steps of the de-NOx process. NH3 decomposes by reactions with radicals to form
NH2, which may undergo oxidation to produce NO or
may react with NO, leading to N2 formation. Two
operational characteristics of biomass gasification promote the formation reaction of N2. The low level of O2
in the gasifier restricts the oxidation of NH2 and limits
the formation of NO. However, the NO produced initially from pyrolysis and other reactions can react with
NH2 to form N2 and H2O.
Thermal de-NOx occurs within a narrow temperature
window ranging from about 1500 K (815 C) to 900 K
(482 C). Biomass gasification usually is conducted
within this range. Reduction of NO by NH2 to form N2
may therefore play a role in the evolution of nitrogenous
species during biomass gasification.
Summary and Conclusions
Parametric tests were performed using a bench-scale
fluidized, bed reactor to investigate the influence of
operating conditions and fuel nitrogen content on FBN
evolution during high-temperature gasification of biomass. Salient findings of this investigation include the
following:
1. A method accurately to quantify N2 in the gasification products was developed. Applying this method, a
complete inventory of fuel nitrogen was obtained for the
first time for biomass gasification.
2. The major gas-phase nitrogenous species generated
by biomass gasification include NH3, N2, NOx, and HCN.
Most of the FBN in feedstock is converted to NH3 and
N2 during gasification. HCN and NOx are present at

very low concentrations in the product gas. N2 appears

to be produced primarily by thermochemical conversion
of NH3.
3. Concentrations of the nitrogen species generally
depend strongly on the temperature and weakly on the
equivalence ratio over the range of conditions examined.
As the temperature increases, the amount of NH3
decreases sharply while the amount of N2 rises.
4. A preliminary investigation of the influence of solid
biomass fuel properties on nitrogen evolution in the
gasifier has been performed by comparing product gas
from different feedstocks. NH3 is detected in amounts
proportional to the FBN content. Although NO levels
are always much lower than those of NH3, it is conjectured that the NO3- content of the feedstock and the
NH3 level in the gasifier can impact the NO concentration of the product gas.
Acknowledgment
This work was supported by the U.S. Department of
Energy through the Hawaii Integrated Biofuels Research Program (Subcontract No. XZ-2-12025-1) of the
Hawaii Natural Energy Institute, administered by the
National Renewable Energy Laboratory (Dr. Ralph
Overend, Technical Monitor).
Literature Cited
(1) Kambara, S.; Takarada, T.; Yamamoto, Y.; Kato, K. Relation
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Received for review May 26, 1998

Revised manuscript received December 3, 1998
Accepted November 2, 1999
IE980318O