Professional Documents
Culture Documents
951-955, 1997
© 1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
ELSEVIER
PIh S0016-2361(97)00082-3 0016-2361/97 $17.00+0.00
Correlations of properties of
Spanish coals with their natural
radionuclides contents
Proximate analyses, heating values and natural radionuclide contents (238U,23ZTh,40K)of 36 samples of bituminous
coals and 4 samples of anthracite were determined. The proximate analysis data and higher heating value were
correlated by multiple linear re~ression analysis with the radionuclide contents. For each coal rank, the correlations
obtained (giving in most cases r > 0.9) are comparable with previous correlations based on measurements of natural
gamma-ray activity of coal. Some improved correlations were obtained by considering separately the coals from each
washing plant, with a degree of accuracy in accordance with the reproducibility tolerances of the Spanish and
international standards UNE 32 004, 32 019 and ISO 1928-76. © 1997 Elsevier Science Ltd.
(Keywords: coal properties; prediction; natural radionuclides)
Coals have a very important function in the energy- characteristics of the selected coals. Sampling was carried
producing sector, so their good characterization is essential out at the power plant, the samples being separated by the
for the rational and efficient use of this energy resource. The station's own laboratory facilities. Most of the samples are
characterization of coal by determining technological classified as bituminous coal (samples 1-36); four are
parameters such as ash yield, volatile matter and heating anthracites (samples 37-40).
value is necessary since these parameters are required in
many engineering calculations to evaluate the performance Proximate analysis and higher heating value
of existing combustion systems and/or to design new com- Routine proximate analyses (moisture, volatile matter,
bustion systems. These parameters are generally determined ash) together with heating value determinations were
by slow standardized analysis tests; but due to the fact that carried out at the Lada power plant laboratories. The
the level of natural gamma radiation emitted by coal determinations were performed for each coal as described
increases linearly with ash yield, the use of the radiometric below.
technique of measuring natural gamma radiation yields a A LECO MAC-400 thermogravimetric coal analyser was
rapid and accurate method for determining the ash yield of used for ash, volatile matter and moisture determinations
coals 1-3. Based on both the content of natural radionuclides according to ASTM standard D5142-90. These analyses
238U, 232Th and 4°K analysed by gamma-ray spectrometry were repeated at least three times for good accuracy.
and the existence of proved relations between ash yield and A LECO AC-300 adiabatic calorimeter was used to
the above additional parameters 5, the development of determine higher heating values of air-dried coal samples
correlations to predict the coal properties from composition according to ASTM standard D2015-91. Calorific value
of the natural radionuclides can be of great interest. determinations were also repeated at least three times for
The aim of this work was to study the relations between each coal, the results differing by < 50 kJ kg-l. The data
the properties of Spanish coals and the contents of their are shown in Table 1.
natural radionuclides 238U, 232Th and 4°K, as well as to
develop correlations for estimating such properties in good Natural radionuclide analysis
agreement with the measured values, establishing both the The analysis of natural radionuclides in the coal, namely
scope and the accuracy of the correlations found. To this 238U, Z32Thand 4°K, w a s performed by both scintillation and
end, an experimental survey was carried out on a number of semiconductor gamma-ray spectrometry. The results of the
coals from several coal washing plants situated in the north two analysis techniques agreed (see Table 1).
of Spain (Asturias), used for electric power generation. The scintillation gamma-ray analyses were carried out in
the Nuclear Energy Laboratories at the University of Oviedo
EXPERIMENTAL by using a gamma-ray spectrometer equipped with an
NaI(T1) gamma-ray detector and a multichannel analyser
Sampling (Camberra Series 35 with 1024 channels) 2. The semicon-
Samples of coal used were supplied by Lada power plant ductor gamma-ray analyses were carried out at Barcelona
(Asturias), being representative of the whole range of University by using a high-resolution semiconductor
grade of correlation between variables, IVF -> 10. The inde- contents of the mineral matter may be expressed by the
pendent variables showing multicollinearity (IVF > 10) following general linear correlations:
were excluded 6.
A = a + b[238U] ÷ c[232Th] ÷ d[a°K] (1)
Multiple linear regression. The independent variables VM = e +f[238U] + g[232Th] ÷ h[4°K] (2)
(radionuclide contents) were selected by the stepwise
regression method, and the coefficients for multiple linear HHV = m + n[238U] +p[232Th] + q[4°K] (3)
correlation were calculated for the equation Y = a + bXj +
cX2 ÷ dX3, where Xi represent the independent variables where A, VM and HHV are the ash yield (wt%), volatile
(radionuclide contents) and Y the dependent variable (the matter (wt%) and higher heatinAg value (kJ kg -1) respec-
measured values of a property). tively, and [238U], [23~Th] and [4~K] are the concentrations
of the natural radionuclides in the coal (ppmw). All data are
Residuals analysis. The autocorrelation errors in the expressed on a dried-coal basis.
model obtained were determined by analysis of residuals The relations between the coal properties studied and the
both by a graphic method consisting in plotting the meas- concentrations of natural radionuclides were determined for
ured values versus residuals and by the Durbin Watson all the coals as one group, for each rank of coal, and for the
method 7. coal from each coal washing plant. Tables 2 - 4 show the
experimental ranges of values, the linear correlations
obtained for each property studied, the squared linear
RESULTS AND DISCUSSION
correlation coefficients ( r 2) , the standard deviation and the
Proximate analyses, higher heating values and concentra- maximum errors of prediction for the derived equations.
tions of trace components of the coals studied are given in To indicate the accuracy of the above equations, the terms
Table 1. Analysis of Table 1 shows that: 'satisfactory' and 'indicative' are used. The term 'satis-
factory' is used to denote that the results obtained with a
(1) Ash yield varies from 5.2 to 40.4 wt% for the bituminous
given correlation have the same degree of accuracy as
coals and from 30.6 to 38.2 wt% for the anthracites.
the results obtained, taking account of the requirements of
(2) Volatile matter varies from 14.2 to 37 wt% for the
the experimental methods, and therefore the errors in the
bituminous coals and from 5.5 to 8.4 wt% for the
predicted values are in accordance with the reproducibility
anthracites.
tolerances of the corresponding UNE and ISO reference
(3) Higher heating value varies from 20.39 to
methods. The term 'indicative' shows that the results are
33.22MJkg -1 for the bituminous coals and from
less accurate than those obtained with the above reference
18.80 to 23.04 MJ kg -~ for the anthracites.
methods, although the correlations found are valid for
(4) The variables investigated as alternative correlating
design and other industrial purposes. According to UNE
parameters for the above coal properties were the natu-
ral radionuclides 238U, 232Th and 4°K. For bituminous 32004 and 32019, for ash yields < 10 and > 10 wt%, the
reproducibility tolerances are -< 0.3% and --- 3% for ash,
coals, the 238Ucontents are in the range 0.3-2.9 ppmw,
and -< 0.5% and -< 5% for volatile matter, respectively.
with 232Th0.1-8.2 ppmw and 4°K 0.01-1.7 ppmw. For
According to ISO 1928-76, the maximum admissible
anthracites, the ranges of values are 1.7-3.3, 3.3-5.5
deviation is 300 kJ kg -~ for higher heating value.
and 0.8-1.2ppmw respectively. These values are
,)
within the ranges for Spanish coals , except for the Ash correlations
low 4°K contents of samples 35 and 36, whose measured
The linear correlations found are shown in Table 2.
values are 0.1 and 0.01 ppmw respectively. This may be
The experimental parameters fitted the above linear equa-
due to the low ash yield of these samples, since 4°K is
tions reasonably, yielding correlation coefficients > 0.9,
associated with inorganic matter of coal .
except for the set of bituminous coal samples with ash yield
The dependence of the coal properties (ash yield, volatile > 30 wt%.
matter and higher heating value) on the natural radionuclide For anthracites, the correlation obtained is 'satisfactory',
a E x c l u d i n g coals f r o m T u r 6 n
Table 4 Natural radionuclide correlations for coal higher heating value (HHV)
Samples Higher heating Correlation Equation Correlation Standard Max.
value range no. coefficient deviation error(%)
(kJ kg - i) (r E)
Anthracites
All 18799-23040 HHV = 27429.5 - 3490.21232Th]+ 8815.114°K] 23 0.994 -< -+120 2.3
Bituminous
coals
All 2O 3 9 0 - 3 3 218 HHV = 34220.1 - 1513.5123SU] - 6689.014°K] 24 0.964 -< __.800 4.4
A < 25 wt% 2 6 7 0 3 - 3 3 218 HHV = 33 694.2 - 8861.414°K] 25 0.908 -< 4-1720 6.2
A > 30wt% 20 3 9 0 - 2 3 801 HHV = 28 366.4 - 414.31232Th] - 2915.514°K] 26 0.672 -< _+1000 9.8
Candin 26 7 0 3 - 3 3 2 1 8 HHV = 35 152.0 - 4348.2123SU] - 4362.714°K] 27 0.962 _< _+600 7.1
Carrocera 21 1 5 2 - 2 7 118 HHV = 35 588.1 - 3108.9123SU] + 308.81232Th] - 6841.414°K] 28 0.999 ------+90 1.2
Modesta 21 3 1 5 - 2 9 2 9 1 HHV = 34856.7 - 11 197.714°K] 29 0.961 -- -+1200 4.6
Modesta" 29 6 9 7 - 3 0 819 HHV = 34988.1 - 3713.1123SU] - 323.71232Th] 30 0.792 -< -+175 2.2
Tur6n 20 6 2 0 - 2 9 215 HHV = 34669.7 - 1057.91238U] - 1559.91232Th] 31 0.996 -- -+250 2.9
Asturleonesa 20 3 9 0 - 2 3 212 HHV = 37 788.5 - 1595.4123SU] + 235.21232Th] - 9693.014°K] 32 0.995 -< _+90 1.3
Special coal
50.00 50.00
' I ' I ' I ' I '/// ' I ' I ' I ' I ', /
X Candin (Eq, 8) J
-I- Anthracites (Eq. 4) / - / .
Zl Carrocera (Eq. 9) / "
0 Bituminous Coals (Eq. 5) Oj ~" -- /
40.00 40.00 0 Modesta (Eq. 10) J
Diagonal line ~r
Jr- Special Modesta (Eq. 11)
- -
._¢
>-
J:
30.00
#.. A
._Q 30.00
>-
J:
[] Turon (Eq, 12)
Asturleonesa (Eq. 13) ,~
f.~ -
m m
<
"O "O
20.00 20.00
_o
ca ca
O
10.00 10.00
0.00 i I , I = I , I , 0.00 , I , I , I J I = I
0.00 10.00 20.00 30.00 40.00 50.00 0.00 10.00 20.00 30.00 40.00 50.00
Measured Ash Yield (%) Measured Ash Yield (%)
Figure 1 Ash yield of coals using the linear correlations from Figure 2 Ash yield of coals using the linear correlations from
coal rank coal washing plant
shown in Table 4. For anthracites, the results obtained acceptable correlations than those developed for blends of
are 'satisfactory'. The corresponding equation in Table 4 coals. Some of the equations obtained can be used in process
(23) reproduces the experimental higher heating value research and design, having a similar accuracy to that
with a maximum error of 2.3%, the standard deviation being obtained by the corresponding UNE and ISO test methods,
-< +120. and are valid for application in industrial practice.
For the whole set of bituminous coals, the correlation
obtained is not acceptable. For the two sets of samples with
ash yields < 25 and > 30 wt%, the correlations found did REFERENCES
not improve the results (see Table 4).
The correlations obtained for the higher heating value for 1 Alvarez, M. C. and Dopico, M. T., Nuclear Geophysics,
each coal washing plant are quite satisfactory. The best 1991, 5, 507.
correlations are found for Carrocera, Asturleonesa and the 2 Alvarez, M. C. and Dopico, M. T., International Journal of
special coal from Modesta, while the correlation obtained Environmental Issues in Minerals and Energy Industry,
for Tur6n can be classified as 'indicative'. On the other 1993, 63.
3 Alvarez, M. C., Dopico, M. T. and Gonz~ilez, J., Inter-
hand, the correlation obtained for Modesta is not acceptable.
national Journal of Environmental Issues in Minerals and
Energy Industry 1993, 95.
CONCLUSIONS 4 Alvarez, M. C., Garz6n, L. and P6rez, J. M., Industria
Minera, 1988, (280), 35.
Linear correlations were found between technological 5 Urkan,M. K. and Arikol, M., Fuel, 1989, 68, 527.
parameters of coal (ash yield, volatile matter and 6 Berenson, M. I. and Levine, D. D., Basic Business Statistics
higher heating value) and natural radionuclide contents Concepts and Applications. Prentice-Hall, Mexico, 1989.
(2~U, 232Th and 4°K). Coals from a single washing plant 7 Canavos,G. C., Probability and Statistics. Applications and
have low variation in properties and produce generally more Methods. McGraw-Hill, Mexico, 1989.