A formula for the mineral matter to ash ratio

for low rank coals

Vincent R. Gray
Coal Research Association of New Zealand (Inc.), PO Box 3041, Wellington, New
Zealand
(Received 1 June 1982)

Existing formulae relating mineral matter to ash yield of coal, which assume that all the mineral matter is
separate from the coal, do not apply to low rank coal because part of the mineral matter is bound in the
coal substance. A mineral matter/ash formula is derived for low rank coal that allows the calculation of
the ratio of mineral matter to ash for a sample of any coal the basic properties of which have been
determined. The formula requires a modification to the procedures previously developed for calculating
basic properties of low rank coals. Basic properties and the parameters determining the mineral matter
to ash ratio are presented for New Zealand sub-bituminous Waikato coals.

(Keywords: coal; low rank; mineral matter; ash)

Conventional coal analyses give the properties of a raphically distinct, minerals. The ash is considered to
mixture of water, coal substance and mineral matter. To consist entirely of the solid resulting from the effects of
determine the properties of the coal substance it is heat treatment on the mineral fraction during combustion
necessary to isolate its properties from those of the water of the coal.
and mineral matter that accompany it. Instead of mineral This assumption is not true for low rank coals and it is
matter, the ash yield is measured. The latter may be only an approximation even for high rank coals. A
defined as the fraction of solid material remaining when proportion of the inorganic elements present in a sample
the sample is oxidized in air under standard conditions. of low rank coal is vound in the coal substance itself, as
The mineral matter may be defined as that part of the coal exchangeable ions or chelate compounds. If ‘mineral
that does not burn (but including burnable minerals such matter’ is defined as that part of the coal that does not
as pyrite). The mineral matter fraction of any coal sample burn, then for low rank coal it consists of a mixture of two
may be calculated if the ratio between its mineral matter components, the one derived from the coal (‘pure-coal
content and its ash yield is known. mineral matter) and the other derived from the minerals
Many formulae have been proposed for this ratio, (‘minerals’ mineral matter). The terms used are illustrated
beginning with that of Parr,’ recently summarized by diagrammatically in Figure 1.
Given and Yarzab. 2*3 The formulae are based on an The pure-coal mineral matter is released from the coal
assumed, calculated or measured loss in weight during on combustion in the form of inorganic oxides, both
ashing of the minerals associated with a range of coal
samples, their relative proportions being assumed to be
approximately constant. The more elaborate formulae,
such as that proposed by King et aL4 require a number of
separate determinations (in their case pyritic, sulphate
and ash sulphur, carbonate and chloride). Other ap- Coal Mineral Mwwral
proaches include a formula based on direct determination sample matter free
of mineral matter (Brown, et d5), and a direct measure- dry free coal
ment of the mineral matter to ash ratio from low tem- basis coal (pure
coal)
perature and high temperature ash (Savage,6 Gaigher’).
Recently’- lo attention has been drawn to the empirical
method for deriving mineral matter to ash ratio, orig- b
Combustion
inally developed by Brinsmaid,” and others’ ‘*I3 includ-
ing Radmacher, l4 Himus and Bazak,’ 5 and Ingles16 when
a dry property (specific energy, volatile matter or carbon
content) is plotted against ash yield (dry basis), the
mineral matter to ash ratio being derived from the slope
of the regression line. Mlneml M~nemls

All these methods assume that dry coal consists of matter

solely organic coal substance composed only of carbon,

hydrogen, nitrogen, oxygen and sulphur (and possibly
halogens), mixed with discrete, chemically and crystallog- Figure 1 Illustration of terms used

00162361/83/010094-04f13.00
01983 Butterworth & Co. (Publishers) Ltd
94 FUEL, 1983, Vol 62, January
 Mineral matter to ash ratio for low rank coals: V. R. Gray

metallic (calcium, sodium, iron, etc.) and non-metallic From (5)

phosphorus, boron). If this mixture of oxides remained x = (&a, - 1)/&a, - 1) (7)
e nchanged the mineral matter-to-ash ratio for pure-coal
Ssh would equal unity:In practice the alkaline oxides Substituting in (6) leads to
absorb sulphur oxides so that the total mass of pure-coal
ash is greater than that of the oxides released. The mineral f, =Sm(l -f,a,)/(l -_&,a,) - (l/a,)a,(f, -f,)/(l -_&,a,) (8)
matter to ash ratio of the pure-coal mineral matter is
therefore obtained by dividing the weight of the original =A-B/a, (9)
oxides (total ash minus the sulphate) by the weight of the where
total ash
A =f,( 1 -fca,)/( 1 -_&a,) (10)
and
fc =(l -(SO,))/1 (1) B = ac(fm-fc)/(l -&a,) (11)
where (SO,), fraction of sulphur trioxide in the pure-coal The relationship between the dry specific energy (Ed)
ash; fc, mineral matter to ash ratio of pure coal. A and the ash yield, dry basis (a,) is given by the equation
previous paper lo has shown how (SO,) can be obtained.
When all the coal is burned most of the mineral & = Edm(l-0,) (12)
substances mixed with the coal are changed by the heat
treatment. Quartz is one substance that is unchanged. where E,, is the dry, mineral-matter-free specific energy
Clays lose water of constitution. Carbonates are con- (in MJ/kg).
verted to oxides and these oxides may react to form Substitute f, from (9)
sulphates with sulphur oxides released in combustion of
the coal or of the minerals. Pyrite will burn to give sulphur E,=E,,(l+B-Au,)
oxides and iron oxide. The net result of all these changes is
to give an ash resulting from the mineral fraction that has =E&n(l -f,a,)(l -fca,)/(l -ha,) (13)
a lower mass than that of the minerals from which it is
formed, so that the mineral matter to ash ratio of pure which is of the form
Ed=a-_a, (14)
minerals is greater than unity, and may be as high as 1.24.
where
This means that for coal samples that differ only in the
proportion of pure coal to minerals in the sample (evident a = -&( 1 -fca,)/( 1 -&a,) (15)
from the differences in ash yield) the mineral matter to ash
ratio can vary from a low figure (perhaps as low as 0.8) for B =fmEdm(1 -fca,)/( 1 -&a,) (16)
so
a low ash sample, in which the mineral matter comes
predominantly from the coal substance, to a high figure fm = PIa (17)
and
(perhaps as high as 1.2) for a high ash sample that has a
high proportion of minerals. J%, = a( 1 -f&)/(1 -La,) (18)

So the belief expressed previously*- lo that a = E,, and

THEORETICAL that /?/a =f, is incorrect for low rank coals, but correct for
Let x parts of pure coal with ash yield a, be mixed with l-x high rank coals, when a, can be considered equal to zero.
parts of pure minerals with ash yield a, to give a coal The true situation for low rank coals is illustrated in
sample with ash yield a, (ash yield in fractions, not Figure 2, which is a plot of specific energy (dry basis)
percentages).
Let fm be the mineral matter to ash ratio of pure
minerals

= l/a, (2)

fc be the mineral matter to ash ratio of pure coal

= m,la, (3)

where m,, the mineral matter content (sum of inorganic

oxides) as a fraction of the pure coal; a,, the ash yield of
pure coal.
Then j;, the mineral matter to ash ratio of the coal
sample is given by .
0 002 0.06 0.10 0.14 0.20
f, = (xm, + 1 -x)/a, (4) fJC
Ash yield (wt%)

Now Figure 2 Dry specific energy DSpE (MJ/kg) against ash yield a,
a,=xa,+(l-x)a,=xa,+(l-x)/f, (5) (as fraction), dry basis, for Huntly West coal, Kupakupa seam.
Regression line is DSpE=30.47-33.3a, (171 observations);
correlation coefficient ~-0.94; ~,,,=1.09+0.06. Point K is 30.47.
snbstituting in (4)
Point L is true mineral-matter-free dry specific energy=30.33
MJ/kg. Point N is the ash yield of pure coal=0.0175. Point M is
f, =_&&&a,+ 1 -x)/G&la, + 1 - x) (6) the dry mineral-free specific energy of pure coal=29.90 MJ/kg

FUEL, 1983, Vol 62, January 95

Mineral matter to ash ratio for low rank coals: V. R. Gray

Table 1 Mean basic properties of Waikato sub-bituminous coals

Coalfield Sector % fc f,(E) Edm fmW “dm A 6 f,kalc)

Renown Seam
Wai kare Wai kare (0.0241a (0.85) 1.20 r 0.41 20.33 0.97 k 0.94 0.4464 1.21 0.0086
Wai kare Ohinewai 0.0249 0.87 1.01 + 0.07 29.17 1.37 f 0.10 0.4376 1.01 0.00368 1.15
Huntly Rangiriri W 0.0321 (0.85) 1.07 f 0.14 30.12 1.00* 0.13 0.4491 1.08 0.0073 1.09
Huntly Huntly W O-02 14 (0.85) 1.08 + 0.06 30.16 1.23 ? 0.09 0.4424 1.09 0.00504 1.15
Huntly Okowhao 0.0255 (0.85) 1.02 ? 0.10 30.30 1.18~ 0.14 0.4421 1.03 0.00445 1.11
Huntly Huntly E IO.0241 (0.85) 1.08 f 0.07 30.36 1.17 * 0.09 0.4519 1.09 0.00567 -
Huntly Weavers (0.024) (0.85) 1 .Ol f 0.08 30.06 1.11 f 0.25 0.4515 1.01 0.00394 -
Rotowaro Callaghans
(Waipuna) 0.0494 0.75 1.04 + 0.09 30.12 1.13? 0.16 0.4707 1.06 0.0149 1 .lO
Kupakupa Seam
Maramarua Maramarua 0.0328 0.88 0.99 t 0.10 28.70 1.47 ? 0.16 0.4432 0.99 0.00370 1.13
Waikare Wai kare 0.0295 0.85 0.87 f 0.14 29.22 1.73 f 0.26 0.4237 0.87 0.0048 1.09
Wai kare Ohinewai 0.0228 0.82 0.97 + 0.06 29.31 1.21 * 0.10 0.4500 0.97 0.00357 1.17
Huntly Rangiriri W 0.0162 0.82 1.09 -f 0.05 30.33 1.22 * 0.08 0.4368 1.10 0.00440 1.11
Huntly Huntly W 0.0175 0.83 1.09 * 0.06 30.33 1.25 + 0.06 0.4451 1.12 0.00493 1.15
Huntly Okowhao 0.0195 0.86 1.01 ? 0.09 30.63 1.12 * 0.14 0.4531 1.01 0.00298 1.14
Huntly Huntly E 0.0210 (0.85) 1.09 f 0.04 30.56 1.14 f 0.06 0.4506 1.10 0.00516 1.14
Huntly Weavers 0.0 0.90 1.10 i 0.10 30.28 1.18 f 0.15 0.4447 1.11 0.00465 1.22
Rotowaro Callaghans
(Maori
Farm) 0.0208 0.81 1.06 + 0.05 29.99 1.41 r 0.07 0.4375 1.07 0.00527 1.18
Rotowaro (Waipuna) 0.0207 0.93 1 .lO 2 0.08 30.03 1.34 f 0.28 0.4411 1.10 0.00364 1.10
Taupiri Seam
Rotowaro Callaghans
(Maori
Farm) 0.0327 0.88 1.03 * 0.05 30.01 1.33 * 0.10 0.4435 1.04 0.00514 1.15
Rotowaro (Waipuna) 0.0301 0.87 1.07 f 0.01 30.05 1.51 f 0.18 0.4317 1.08 0.00616 1.11

a Values in parentheses have been estimated

,,I...

I quantity has been tabulated for Waikato sub-bituminous

coals.’ O
The ash yield of pure coal may also be found as a sum of
oxides that derive from ion-exchangeable and other
bound elements, determined by methods described by
Kiss and King, I7 Miller and Given I8 or Morgan et af.,‘9
or by an extrapolation technique abplied to float-or-sink
analysis.
Table I gives the corrected figures for the dry, mineral
matter free specific energy, together with fo a,, f, and the
constants A and B for the sets of analytical data from the
Waikato coalfield studied previously.8-‘0
Examples of the values obtainable for fX, the mineral
matter to ash ratio, as a function of ash yield, are given in
Ash yield (wt%) Figure 3.
Figure 3 Mineral matter-to-ash ratio f, against ash yield, dry
basis a, (reciprocal scale) for some Waikato coals, all Kupakupa
seam. MA, Maramarua; OH, Ohinewai; HW, Huntly West; OK,
VOLATILE MATTER
Okowhao; MF, Maori Farm; WA, Waipuna
The equation for volatile matter’ may be treated in the
same way.
against ash yield (dry basis) for Huntly West coal,
Kupakupa seam. The slope of the graph gives the mineral v,= v,fn-(f,v,,-f,+ Ua, (19)
matter to ash ratio for the pure mineral component .f,,
but in order to derive the true dry mineral-matter-free substituting for f, from (8), and obtaining the regression
specific energy E,, (point L) it is necessary to know the ash equation
yield of pure coal, a, (point N), and the mineral matter to
ash ratio of pure coal, fC. Point M is the dry mineral-free (20)
specific energy, or the specific energy of pure coal. one obtains
Previous papers’,’ O have indicated one method of
measuring a, andf,. The ash yield of pure coal is assumed v,, =p(l -f*4)/(I -_&a,) +a,(f, -f,MI -f,a,) (21)
to be the ash yield at which the silica content of the ash is
zero. The mineral matter-to-ash ratio of the pure coal is and
given by equation (1) above, the sulphate content of pure- _&=(I --4)/(l -P) (22)
coal ash being obtained by extrapolating the sulphate
content of the ash to the ash yield of pure coal. This where V,, the volatile matter, dry basis (expressed as a

96 FUEL, 1983, Vol62, January

 Mineral matter to ash ratio for low rank coals: V. R. Gray

fraction); V,,, dry, mineral-matter-free volatile matter Although the calculated values are consistently higher
(expressed as a fraction). than the derived values one-third of them fall within the
So the belief expressed previously’ - lo that V,, = p and 95% scatter limits of the derived value.
f, =(l - q)/(l -p) is incorrect for low rank coals, but
correct for high rank coals.
The corrected values for the dry, mineral-matter-free
volatile matter for Waikato coals are given in Table 1. REFERENCES
It may be noted once more thatf, is usually higher from 1 Parr, S. W. and Wheeler, W. F., Bulletin No. 37, University of
a volatile matter plot (f,(V)) than from a specific energy Illinois Engineering Experimental Station, 1909
plot (fm(E)). There are two possible additional reasons for 2 Given, P. H. and Yarzab, R. F., ‘Problems and Solutions in the
those advanced previously.8 First, carbonates present in Use of Coal Analyses’, Coal Research Section, Pennsylvania
State University Report PSU-TR-1, 1976
the minerals have been shown by Choudhury and Ga- Given, P. H. and Yarzab, R. F. in ‘Analytical Methods for Coal
nguly” to have a significant effect on volatile matter, as and Coal Products’, (Ed. C. Karr Jr.), Vol. 2, p. 3, 1978
the carbon dioxide reacts with part of the remaining King, J. G., Maries, M. B. and Crossley, H. E., J. Sot. Chem. Ind.
carbon. Secondly, inert matter may affect volatile matter 1936, 55, 277
by a nucleation effect. Sinnatt and Grounds21 showed Brown, N. A., Belcher, C. B. and Callcott, T. G., J. Inst. Fuel,
1965, 38, 198
that added inert matter can increase volatile matter, Savage, W. H. D., South African Chemical Processing 1967-8, CP
particularly when finely divided. However, at least equal 171
amounts to the coal ( > 50 %) were needed for significant Gaigher, J. L., ‘The Mineral Matter in some South African Coal
effects. It may be that minerals already present in the coal Products’, Report 45, 1980 Fuel Research Institute of South
Africa (restricted circulation)
are more finely divided and more intimately mixed with 8 Gray, V. R., Fuel, 1980, 59, 551
the coal than added inert matter, and may thus be more 9 Gray. V. R., Fuel, 1981, 60, 362
effective in increasing the volatile matter. 10 Gray, V. R. NZ J. Sci. 1981, 24,
11 Brinsmaid, W., Ind. Eng. Chem. 1909, 1, 65
12 Stansfield. E. and Sutherland. J. W. in ‘Classification of Coal’.
NORMATIVE ANALYSIS Amer. Inst. Min. Engrs. 1931: p. 66
13 SchoIz, A., Circulaire d’informations techniques, Centre de
Independent calculations of&, the mineral matter to ash documentation sidtrurgique, 1977,ll. 2357,2367; Fuel 1980.59,
ratio for the mineral component, were carried out from 197
the extrapolated values of the mineral composition ob- 14 Radmacher, W., Gluckauf, 1951,87, 1093
15 Himus, G. W. and Basak, G. C., Fuel, 1949. 28, 57
tained previously from high temperature ash analyses.9s1o 16 Ingles, 0. G., Austr. J. Appl. Sci. 1957, 8, 62
The method of ‘normative analysis’ was used.22-24 The 17 Kiss, T. L. and King, T. N., Fuel, 1977, 56, 340; 1979, 58, 547
following assumptions were made: (1) All alumina is 18 Miller, R. N. and Given, P. H., ‘A Geochemical Study of the
present as kaolinite (1.22 % water of constitution); (2) all Inorganic Constituents in some Low Rank Coals’. FE 2494-TRl.
Coa<Research Station, Pennsylvania State University PSU TR
sulphur is in the form of pyrite (loss of 0.625 of %S); (3) an
lL, 1978
excess of iron oxide (as FeO) and CaO + MgO are in the 19 Morgan, M. E., Jenkins, R. G. and Walker, P. L. Jr. ‘Inorganic
form of carbonates; (4) sulphate (SO,) is deducted. Constituents of American Lignite’, FE 2030-TR 21, Pennsylvania
The results are given as the final column in Table 1. The State University Technical Report 21, April 1980
calculated figures are, on average, 0.09 greater than the 20 Choudhury, S. S. and Ganguly, P. C., Fuel, 1978, 57, 175
21 Sinnatt, F. S. and Grounds, A. ‘The Influence of Addition of Inert
derived figures from specific energy. Possible reasons for Matter upon the Volatile Matter evolved when Coal is Heated,
this must await further work on the mineral composition Lancashire and Cheshire Coal Research Association, Bulletin 3,
of these coals, but they might include the presence of other 1919
clays, such as illite, that have a lower water of constitution 22 Gauger, A. W., Barret, E. P. and Williams, F. J., Trans. Am. Inst.
Mining Met. Engs. 1934, 180, 226
than kaolinite, and the fact that the basic oxides are not all
23 Thiessen, G., Ball, C. G. and Gratts, P. E., Ind. Eng. Chem. 1936,
present as carbonates (e.g. iron is probably present as zs, 355
oxide or hydroxide). 24 Pollack, S. S. Fuel 1979, 58, 76

FUEL, 1983, Vol 62, January 97