VOLUME 13, NUMBER 6 NOVEMBER/DECEMBER 1999

© Copyright 1999 American Chemical Society

Articles
Influence of Coal Properties on Emissions of Nitrous
Oxides and Nitric Oxides

De-Chang Liu,* Bo-Xiong Shen, Bo Feng, Zhi-Jie Lin, and Ji-Dong Lu

National Laboratory of Coal Combustion, Huazhong University of Science and Technology,

Wuhan 430074, China

Received February 8, 1999

Grey System Theory is applied to study the influence of the coal properties on the emissions
of nitric oxides from fluidized bed coal combustion. Grey correlation coefficients for the emissions
of nitrous oxides and nitric oxides in relation to the contents of nitrogen and carbon, fixed carbon,
volatile matter, nitrogen fractions in char, and volatile, and the O/N ratio, fuel ratio, etc., are
calculated. A large correlation coefficient of coal property means that the emission of nitrous
oxides and nitric oxides is in close relation with the relevant property, in other words, the relevant
coal property is the main affecting factor for nitrous oxides and nitric oxides formations. The
calculation results show that the N2O emission is determined mainly by the nitrogen carbon
content, fixed carbon, and the nitrogen fraction in char. While the carbon content, fixed carbon,
nitrogen fraction in char mainly influence the NOx emission and nitrogen and hydrogen contents,
it suggests that combustion of high rank coal with high nitrogen content in fluidized bed emits
more nitrous oxides and nitric oxides. The O/N and fuel ratios are not important for emissions
of nitrous oxides and nitric oxides compared with other factors. And the results are in agreement
with experimental data.

Introduction Leckner,2 Moritomi et al.,3 and Brown and Thomas,4

Fluidized bed combustion technology has gained
extensive application, due to its excellent fuel flexibility,
high combustion efficiency, and good environmental
performance. However, it has been discovered that the
nitrous oxides emission from fluidized bed coal combus-
tion is much higher than that from pulverized coal
combustion.
Many researchers, such as Collings,1 Amand and
have studied the effects of coal properties on N2O
emission in fluidized bed combustion. The research
findings reveal that the coal rank is the most important
factor in influencing nitrous oxides emissions. But there
are so many properties of coal, such as nitrogen, carbon
contents, fixed carbon, volatile matter, nitrogen frac-
tions in char and volatile, hydrogen content, O/N ratio,
and fuel ratio, etc., that influence the NOx and N2O
emissions. Unfortunately, until now we can not know

* Corresponding author. E-mail: dcliu@public.wh.hb.cn.
(1) Collings, M. E.; Mann, M. D.; Yong, B. C.; Btros, P. E. The effect
of coal-fuel properties on N2O emission in fluidized bed combustion.
12th International Conference on FBC, ASME, 1993, pp 619-627.
(2) Amand, L. E.; Leckner, B. Formation of N2O in CFB boilers.
Energy and Fuel 1991, 50, 813-823.
(3) Moritoni, H.; Susuki, Y.; Kido, N.; Ogisu, Y. NOx Formation
mechanism on CFB combustion. 11th International Conference on
Fluidized Bed Combustion, ASME, 1991, pp 1005-1012.
(4) Brown, S. D.; Thomas, K. M. A comparison of NO release from
coals and entrained flow reactor chars during temperature-pro-
grammed combustion. Fuel 1993, 72, 259-365.

10.1021/ef990016e CCC: $18.00 © 1999 American Chemical Society

Published on Web 09/24/1999
1112 Energy & Fuels, Vol. 13, No. 6, 1999 Liu et al.

what ones are the most important factors in sequence. Table 1. Proximate and Ultimate Analyses of Coal (%)
It is also impossible to know by experiment due to the coal type A B C D E F G H
experimental complexity. For the purpose of modeling M 1.9 1.2 1.5 2.7 8.7 12.8 5.0 1.08
and understanding the mechanism of NOx and N2O VM 4.5 11.6 31.9 40.4 53.3 53.9 0.01 10.86
formations, it is very necessary to know the most FC 95.5 88.4 68.1 59.6 46.1 46.4 100 71.17
important coal properties to influence the formation of Ash 2.1 8.3 2.3 12.0 11.6 4.1 3.1 16.90
FC/VM 21.22 7.62 2.13 1.48 0.86 0.86 10.00 6.55
nitrous oxides and nitric oxides. Collings et al.1 had tried C 94.1 92.4 88.2 81.2 75.0 65.9 98.2 72.9
to find the relationship between the emission of nitrous H 2.7 3.5 4.9 4.8 5.1 4.5 0.3 3.46
oxides and nitric oxides and the coal properties using N 0.9 1.4 1.7 1.7 0.9 0.6 0.3 1.18
S 0.6 0.5 0.9 1.1 0.3 0.3 0.0 1.06
the REQUARE model-selection method of the REG O 1.7 2.2 4.3 11.2 18.7 28.6 1.2 21.3
procedure of the SAS/STAT statistical software. This O/N 1.89 1.57 2.53 6.59 20.78 47.67 4.0 18.05
procedure fits the linear regression model by least
squares. But the model does not point out the relative Table 2. Correlation Coefficients for N2O at Various
Temperatures
importance of each coal property.
Correlation Analysis of Grey System Theory. temperature, K
This paper uses a new mathematical methodsthe Grey coal type 973 1073 1173 1273
correlation analysis method to study the relative im- M 0.77878 0.77508 0.77508 0.77391
portance of the coal property. This method is based on VM 0.81801 0.81903 0.80776 0.75242
Fuzzy Mathematics and is called Grey System Theory, FC 0.92070 0.91610 0.92930 0.92467
Deng.5 An indicator is defined to express the relative Ash 0.84278 0.84275 0.83958 0.78916
FC/VM 0.72789 0.72862 0.72845 0.73676
distance of a parent parameter to all descendent pa- C 0.91525 0.91104 0.91892 0.90359
rameters. The larger the indicator is, the nearer the H 0.88692 0.88846 0.88185 0.82193
descendent parameter and the parent parameter are. N 0.92732 0.92168 0.91354 0.85147
In this study, N2O and NOx emissions are the parent S 0.89770 0.89219 0.88301 0.82495
O 0.78125 0.77589 0.78657 0.74682
parameters, and the coal properties are the descendent O/N 0.76690 0.76213 0.77231 0.74286
parameters. If the indicator of some property of coal is Nv 0.82232 0.82446 0.81882 0.76396
the largest, then this property is considered to be the Nc 0.91769 0.91290 0.92567 0.92169
most important factor to influence the N2O and NOx
Table 3. Correlation Coefficients for NOx at Various
emissions. On the basis of the Grey System Theory, the Temperatures
indicator is defined for the ith descendent parameter
and the kth coal as: temperature, K
coal type 973 1073 1173 1273
ξi(k) ) M 0.86152 0.84132 0.82487 0.81316
min min|x0(k) - xi(k)| + ζ min min|x0(k) - xi(k)| VM 0.84651 0.81202 0.78742 0.77933
i k i k FC 0.91190 0.93656 0.95517 0.97316
(1) Ash 0.82136 0.82669 0.83412 0.83645
|x0(k) - xi(k)| + ζ min min|x0(k) - xk(k)| FC/VM 0.72499 0.72340 0.72327 0.72384
i k
C 0.93559 0.94252 0.95855 0.95600
where σ is a coefficient between 0 and 1, commonly set H 0.89883 0.88980 0.87621 0.86415
N 0.84730 0.85499 0.87378 0.89759
at 0.5, and xi and x0 are the values of the descendent S 0.82657 0.83417 0.83307 0.84793
parameter and the parent parameter, respectively. In O 0.83061 0.81012 0.79907 0.78860
this research xi represents the coal property, and x0 O/N 0.81438 0.80328 0.78890 0.78542
represents the emission of N2O or NOx. The correlation Nv 0.85046 0.82293 0.79919 0.78988
Nc 0.91229 0.93697 0.95377 0.98159
coefficient of xi and x0 is the average of the indicator
values for all coals, i.e.
(FC/VM) proposed by some researchers are included in
N the descendent parameters.
1
ri ) ∑ ξi(k)
N i)1
(2) Table 2 shows the relative importance of the effect of
coal property on N2O formation. At temperatures 973
and 1073 K, the importance sequence is nitrogen > FC
where N is the number of coal type. > N in char > carbon > sulfur > hydrogen > ash > N
in volatile > VM > oxygen > moisture > O/N ratio >
Results and Discussion fuel ratio.
At 1173 K, the importance sequence has a little
The proximate and ultimate analyses and O/N ratios change. The FC instead of nitrogen becomes the first
of eight types of coals used in the research are listed in most important factor to influence the N2O emission,
Table 1. According to the data in Table 1, using eqs 1 the nitrogen content effect on N2O emission becomes the
and 2, the correlation coefficients for N2O and NOx at fourth one. At 1273 K, only the sequence of moisture
various temperatures are calculated, and the results are effect on N2O emission changes from 11th to eighth. The
listed in Tables 2 and 3. To make clear, the effects of sequence of balance properties has no change. From the
the O/N ratio proposed by Aho et al.6 and the fuel ratio importance sequence, it is found that the most impor-
(5) Deng, J. L. Basic methods of Grey system theory; Press of
tant four key properties to influence N2O emission are
Huazhong University of Science and Technology: Wuhan, China, 1998; nitrogen, carbon contents, fixed carbon and nitrogen
pp 1-100 (in Chinese). fraction in char. At lower temperature (973-1073 K),
(6) Aho, M. J.; Rantanen, J. T.; Linna, V. L. NO and NO2 emissions
from peat and coal in pulverized fuel combustion between 730 and 950. nitrogen in coal is the most important factor, showing
Fuel 1990, 15, 1-6. that N2O comes mainly from fuel nitrogen. As temper-
Coal Properties and Emissions of Nitrogen Oxides Energy & Fuels, Vol. 13, No. 6, 1999 1113

Table 4. Conversions to N2O and NOx of Nitrogen ratio. At temperature 1273 K, the relative importance
in Coals sequence is N in char > FC > carbon > nitrogen >
coal type A B C D E F G H hydrogen > sulfur > ash > moisture > N in volatile >
N in volatile, Nv (%) 4.5 5.3 37.9 40.4 53.5 48.8 0 21.6 oxygen > O/N ratio > fuel ratio.
N in char, Nc (%) 95.5 94.7 62.1 59.6 46.5 51.2 100 78.4 Comparing the importance sequences at four temper-
Conv. of N to N2O (%) atures it can be found that the most important three
973 K 41 37 39 30 12 15 15 19 parameters to influence the NOx emission are carbon
1073 K 32 34 30 27 8 12 13 16 content, fixed carbon, and nitrogen fraction in char.
1173 K 22 24 18 15 5 8 9 14 With temperature increase the effect of nitrogen content
1273 K 10 12 6 5 1 1 7 6
on NOx emission becomes more important. At temper-
Conv. of N to NOx (%) ature 973 K, the nitrogen sequence is seventh, while it
973 K 22.5 10 18 18 26 26 25 15 becomes fourth at temperature 1273 K. The importance
1073 K 37 23 24 24 36 32 42 27
1173 K 45 42 27 27 36 34 53 34
of carbon content and fixed carbon means that the high
1273 K 55 55 34 34 35 33 58 47 rank coal will emit more NOx. The importance of
nitrogen in char suggests that the NOx comes mainly
ature increases the fixed carbon instead of nitrogen from char combustion as N2O does. This finding is
content becomes the most important factor. This means inagreement with experimental results as shown in
that the N2O emission is in agreement with the experi- Table 4.
mental results that are listed in Table 4 for N2O The importance of hydrogen content that is the fourth
emission of eight types of coals at different tempera- position in sequence at temperatures 973-1173 K may
tures. The data of coal A to coal G are the experimental be due to facilitating the formation of HCN and NHi
results of Wojtomicz et al.7 and Pels et al.8 The data of by H. As the temperature increases, the effects of
coal H are from our experimental results.9 At higher nitrogen in char and nitrogen content on NOx emissions
temperature the amount of N2O decreases sharply, and become more important.
that is in agreement with much experimental findings. At four temperatures, the effects of both the O/N ratio
The effects of volatile matter and nitrogen fraction in and the fuel ratio on N2O and NOx emissions are not
volatile are not important for N2O formation. important, and the fuel ratio is always the last param-
From Table 3, according to the correlation coefficient eter in the importance sequence, this is in conflict with
value, the relative importance of effect of coal property findings of Aho et al.6
on NOx emission can be seen. At temperature 973 K,
the relative importance is as follows: carbon > N in char Conclusions
> FC > hydrogen > moisture > N in volatile > nitrogen • The nitrogen, carbon content, fixed carbon, and
> VM > oxygen > sulfur > ash > O/N ratio > fuel ratio. nitrogen fraction in char are the most important four
At temperature 1073 K, the relative importance se- properties to influence N2O emission.
quence is carbon > N in char > FC > hydrgen > • The carbon content, fixed carbon, nitrogen content
nitrogen > moisture > sulfur > ash > N in volatile > in char, nitrogen, and hydrogen contents are the most
VM > oxygen > O/N ratio > fuel ratio. At temperature important five properties to influence NOx emission.
1173 K, the relative importance sequence is carbon > • The effects of the O/N ratio and fuel ratio on N2O
FC > N in char > hydrogen > nitrogen > ash > sulfur and NOx emissions are the least important.
> moisture > N in volatile > oxygen > O/N ratio > fuel • The findings obtained by Grey System Theory are
in agreement with the results obtained from experi-
(7) Wojtowicz, M. A.; Lohuis, T. A.; Tromp, P. T. J.; Moulijn, T. A. ments.
N2O formation in FBC of coal. 11th International Conference on
Fluidized Bed Combustion, ASME, 1991, pp 1013-1020.
(8) Pels, J. R.; Wojtowicz, M. A.; Moulijn, J. A. Rank dependence of Acknowledgment. The authors thank the National
N2O emission in FBC of coal. Fuel 72, 299-301.
(9) Eng, Bo; Yuan, J. W.; Lin, Z. J.; Liu, D. C. The Relative Natural Science Foundation of China for financial
Importance of Char Nitrogen on the Formation of Nitric Oxides. J. support of this work.
HuaZhong University of Science and Technology 1997, 25 (Sup(II),
109-112 (in Chinese). EF990016E