S. Choudhury* et al.

/ (IJITR) INTERNATIONAL JOURNAL OF INNOVATIVE TECHNOLOGY AND RESEARCH

Volume No. 1, Issue No. 1, December-January 2013, 013 - 018

Studies on Demineralization of Coal:

Fractional Factorial Design
S. Choudhury
Department of Chemical Engineering
National Institute of Technology
Rourkela-769008, Odisha, India.

Abstract-Demineralization of coal from Chitra mines of Jharkhand was investigated by using alkalies and acid of different
concentration. Measurements of demineralization using Parr formula have been studied by changing particle size (d),
time (t), temperature (T), conc. of alkalies and acids to determined the optimal operating parameters for the reactor, i.e.
the experimental condition for which maximum removal of mineral matter occurred. The largest mineral matter (MM)
removal was attained when the reactor was controlled at temperature about 90 0C, at time of 2h, with particle size of
0.22mm and alkali-acid combination (i.e. NaOH+ HCl). It was observed that below particle size 0.22 mm demineralization
decreased for which the range of particle size was maintained within range 0.22- 0.51mm. To validate the experimental
findings dimensional and statistical analysis were carried out. Mean deviation and standard deviations indicated that the
developed correlations can be used suitably over a wide range of parameters. Combination of NaOH and HCl was found
to be most dominant parameter for dematerializing coal samples.

Key words: Demineralization, Mineral matter, Leaching, Fractional Factorial Design.

by both physical and chemical methods. The physical

I. INTRODUCTION
The mineral matters in coal have detrimental
effects on utilization of the coal for combustion,
gasification, carbonization, liquefaction etc.
purposes. Combustion of high sulphur and high ash
coal leads to environmental pollution and other
deleterious effects. Therefore, removal of the mineral
matter from a coal prior to its utilization has attracted
interest of all concerned. Demineralization of coal
may be achieved by both physical and chemical
methods. The physical methods are based on the
differences in the physical properties of the minerals
and the carbonaceous part of the coal.
Demineralization by chemical means involves
solubilization of the inorganic constituents or their
converted forms in various solvents. The physical
methods are not effective in separation of the finely
dispersed minerals and those bound to the coal
structure. Coal treated by this method can used to
manufacture of graphite electrode, because the
mineral matter can be removed up to < 0.05% by
using alkali and acid process. Risk of pollution by
this coal is also very less so it can be used for both
purpose domestic as well as industrial use. These
coals are used mainly in aluminum, iron and steel
industries. In some country (U.S.A, China, Malaysia,
Russia etc) coals are used for production of
electricity. But Successful commercialization of this
chemical process would largely depend on the
economization of alkali and acid requirements [1-3].
The minerals commonly found in coals are various
form of silica, Clay, Carbonates, Sulphide and
Sulphate. Demineralization of coal may be achieved
methods are based on the differences in the physical
properties of the minerals and the carbonaceous part
of the coal. Demineralization by chemical means
involves solubilization of the inorganic
constituents or their converted forms in various
solvents. The physical methods are not effective in
separation of the finely dispersed minerals and those
bound to the coal structure [3-6].
II. LITERATURE
The major minerals in coal are alumina, quartz,
pyrites, and carbonates. Among these, the alumina
and silica generally constitute 85-90% of the total
mineral matter [5,6]. The alkali used in leaching
process may attack these minerals through a number
of consecutive reactions. The alkali used in this
leaching process is expected to attack the mineral
constituents of the coal as follows [3-5].
2NaOH + SiO2 → Na2SiO3 + H2O (1)
2NaOH + Al2O3→ 2NaAlO2 + H2O (2)
30NaOH+8FeS2→4Fe2O3+14Na1S
+Na2SO3+15H2O (3)
Then acid treatment (HCl, H2SO4, HF etc.) is also
carried out to remove residual caustic from the alkali
treated coal, and this might have contributed to the
demineralization by removing some minerals, such as
carbonates, Fe2O3 and sulfides, which had survived
after the alkali treatment [2,4,7].

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 S. Choudhury* et al. / (IJITR) INTERNATIONAL JOURNAL OF INNOVATIVE TECHNOLOGY AND RESEARCH
Volume No. 1, Issue No. 1, December-January 2013, 013 - 018
The ash content in the coal sample can be
converted into the mineral matter by several
formulas. As per the Parr formula [2], the mineral
matter of coal is derived from the following
expression.
MM= (1.08×A) + (0.55×S) (4)
Where, MM - % mineral matter, S -% total sulphur,
A - % ash present in coal respectively.
Since Indian coals are in general low in sulphur and
carbonate. Hence, a simplified version of Parr
formula [2] as following expression can be used for
these coals.
MM = 1.1A (5)
A. Fractional Factorial design
In statistics, fractional factorial designs are
experimental designs consisting of a carefully chosen
subset (fraction) of the experimental runs of a full
factorial design. The subset is chosen so as to exploit
the sparsity-of-effects principle to expose information
about the most important features of the problem
studied, while using a fraction of the effort of a full
factorial design in terms of experimental runs and
resources. Fractional designs are expressed using the
notation lk − p, where l is the number of levels of each
factor investigated, k is the number of factors
investigated, and p describes the size of the fraction
of the full factorial used. Formally, p is the number of
generators, assignments as to which effects or
interactions are confounded, i.e., cannot be estimated
independently of each other (see below). A design
with p such generators is a 1/( l p ) fraction of the full
factorial design. For example, a 25 − 2 design is 1/4 of
a two level, five factor factorial design. Rather than
the 32 runs that would be required for the full 25
factorial experiment, this experiment requires only
eight runs.
A fractional factorial experiment is generated
from a full factorial experiment by choosing an alias
structure. The alias structure determines which
effects are confounded with each other. For example,
the five factor 25 − 2 can be generated by using a full
three factor factorial experiment involving three
factors (say A, B, and C) and then choosing to
confound the two remaining factors D and E with
interactions generated by D = A*B and E = A*C.
These two expressions are called the generators of
the design. So for example, when the experiment is
run and the experimenter estimates the effects for
factor D, what is really being estimated is a
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combination of the main effect of D and the two-
factor interaction involving A and B. An important
characteristic of a fractional design is the defining
relation, which gives the set of interaction columns
equal in the design matrix to a column of plus signs,
denoted by I. For the above example, since D = AB
and E = AC, then ABD and ACE are both columns of
plus signs, and consequently so is BDCE. In this case
the defining relation of the fractional design is I =
ABD = ACE = BCDE. The defining relation allows
the alias pattern of the design to be determined [8].
III. EXPERIMENTATION
A. Materials
Different coal samples having particle size in the
range of 0.51-0.19 mm from Chitra- mines of
Jharkhand were studied. Proximate analysis of these
sample measures ash content, moisture content,
volatile matter and fixed carbon in the range of 7.35
- 9.54%, 3.95 - 7.39%, 39.66 - 48.31% and 48.33 -
33.98% respectively. The concentration of selected
alkali (NaOH/Na2CO3) varies from 10-50% (w/v).
The concentration of selected acid (HCl/H2SO4)
varies from 0.1-0.5(N).
B. Methods
Experimental setup as shown in Fig. 1(a & b)
consists of reactor which is nothing but a 250ml
conical flask fitted with rubber cork and insulated
with both asbestos rope and plaster of Paris.
Fig. 1 (a)
One connector and one thermocouple are connected
to the reactor. Connector is used to remove gases
formed during reaction and thermocouple is
connected to control temperature of various ranges
(70-90 0C). Heater cum magnetic stirrer is used to
heat the reactor and also to control the speed of the
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 S. Choudhury* et al. / (IJITR) INTERNATIONAL JOURNAL OF INNOVATIVE TECHNOLOGY AND RESEARCH
Volume No. 1, Issue No. 1, December-January 2013, 013 - 018
stirrer present inside the reactor by controlling the parameters were varied for three other combinations
knob. Speed of the stirrer is maintained at around of alkali and acid (such as NaOH &H2SO4, Na2CO3
1500-1800 rpm. & HCl and NaOH & HCl) to study their effects on
the demineralization of coal.

IV. Results and discussion

A. Development of correlation

The effects of different parameters (viz. time (t),

temperature (T), conc. of alkalies (C”), conc. of acid
(C’), size of particles (d) ) on removal of mineral
matters i.e. percentage demineralization was finally
studied by developing correlations on the basis of the
dimensional analysis. The dematerialized coal
samples were correlated against different system
parameters as follows. Four different combinations of
alkali and acid were selected for experimentation.
Thus four different correlations for both the
dimensional and statistical analysis are designed as
per the following.

B. By dimensional analysis
Fig. 1 (b)
For combination of Na2CO3 and H2SO4
10 grams of coal (0.19-0.51 mm in size) sample and
 
0 . 913
alkali (NaOH/ Na2CO3) solution of known  d  0 .284 C " 0.306 
% Dem  0 . 1387   
concentration are taken in the reactor. Concentration
of the alkali solution is varied from 10-50 (w/v) %.
 t 0 .420 T 1 .094 C '   0 . 414

Thermocouple is insulated with glass wool and (6)
dipped in the solution to measure the temperature.
The temperature of the solution is also controlled by For combination of NaOH and H2SO4
adjusting the controller switch. The pulp in the
 
0 . 925
 d  0 .253 C " 0 .288 
reactor is then slowly heated (on a hot plate) from % Dem  0 . 7   
room temperature to the required leaching
temperatures in 5-20 minute. The leaching
 t 0 .409 T 0 .671 C '  0 . 33

(7)
temperature is varied (70-90 0C) for the required time
(30-120 min), after which the reactor is cooled
For combination of Na2CO3 and HCl
quickly in air. The reaction temperature was
 
0.858
controlled within ±1°C.The decrease in volume of the d 0.282 C " 0.288 
solution due to evaporation is made up by adding % Dem  0.1135   
distilled water. The magnetic stirrer is placed at the  
t 0.40 T 1.261 C ' 0.331 
bottom of the reactor and is driven at stirring speeds (8)
of around 1500-1800 rpm to avoid solution in For combination of NaOH and HCl
homogeneities during the leaching operation. After
 
0 .818
 d  0 .265 C " 0 .194 
cooling, the pulp is filtered and then washed with % Dem  2 . 36   
both dilute acid (HCl/H2SO4) and hot distilled water  
 t 0 .252 T 0 .766 C ' 0 . 315

to remove the residual caustic. Concentration of acid
(9)
is varied from 0.1(N) to 0.5(N). The acid treatment is
performed at temperatures of about 70°C. The sample
is then dried at 105-110°C in a heater and weighed. C. By statistical analysis (25-2 Fractional
Its ash content is determined using proximate FactorialDesign)
analysis. Different system parameters are varied as
Treatment combination for a 25-2 design is shown in
per the scope of the experiment. Scope of the
Table I.
experiment for combination of Na2CO3 and H2SO4 is
given in TableI as an example. Similarly the

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 S. Choudhury* et al. / (IJITR) INTERNATIONAL JOURNAL OF INNOVATIVE TECHNOLOGY AND RESEARCH
Volume No. 1, Issue No. 1, December-January 2013, 013 - 018
TABLEI. EFFECTS PARAMETECOMBINATION
FOR 25-2 DESIGN

Treatment
combination A B C D E AC BC
a0 -1 -1 -1 -1 1 1 1
a1 1 -1 -1 1 -1 -1 1
a2 -1 1 -1 1 -1 1 -1
a3 1 1 -1 -1 1 -1 -1
a12 -1 -1 1 1 1 -1 -1
a13 1 -1 1 -1 -1 1 -1
Fig. 2(a): Na2CO3 and H2SO4 combination
a23 -1 1 1 -1 -1 -1 1
a123 1 1 1 1 1 1 1

Where, D= ABC & E= AB.

The above developed correlations were validated

further with the correlations developed by the
fractional factorial design. With 25-2 fractional
factorial design the following correlations were
developed for four different combinations of alkali
and acid.
For combination of Na2CO3 and H2SO4

1.36    A  2.67   B   5.63  C  Fig. 2(b): NaOH and H2SO4 combination.

% Dem  43.24   0.668  D   0.841  E  

 0.58   AC   0.886  BC  
(10)

For combination of NaOH and H2SO4

1.4    A  2.96   B   5.52   C 

% Dem  46.35    0.337   D   0.857   E  

  0.405    AC   1.06   BC  
(11)
Fig. 2(c): Na2CO3 and HCl combination.
For combination of Na2CO3 and HCl

0.862   A  3.3  B   5.45  C 

% Dem  49.38   0.855  D   0.577  E  

 0.12   AC   0.735  BC  
(12)
For combination of NaOH and HCl

1.64   A  2.97  B   6.01  C 

%Dem  60.46   0.521  D   0.138  E  

 0.176   AC   0.143  BC  
(13)
Fig. 2(d): NaOH and HCl combination.
The correlation plots against system parameters on
the basis of dimensional analysis for four different The calculated values for demineralization of coal
combinations of alkali and acid are shown in Fig. 2 obtained through above correlations (developed by
(a, b, c and d). both methods) have also been compared with

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 S. Choudhury* et al. / (IJITR) INTERNATIONAL JOURNAL OF INNOVATIVE TECHNOLOGY AND RESEARCH
Volume No. 1, Issue No. 1, December-January 2013, 013 - 018
experimental values. A sample plot of comparison for Where, DA-dimensional analysis & SA-statistical analysis.
combination of Na2CO3/H2O4 has been shown in
Fig.3. From plots (Fig.6) it is observed that individual effect
of alkali Na2CO3 and acid H2SO4 on demineralization
It is observed that by increasing alkalis concentration is more as compare to other alkali and acid but
mineral matter removal rate increased up to some treatment of coal with sodium hydroxide solution and
extent and then it is more or less constant. Decrease hydrochloric acid is more effective than any other
in particle size of coal increases the extent of alkali-acid combinations i.e. NaOH+H2SO4 or
demineralization up to range 0.51-0.22 mm further Na2CO3+H2SO4 or Na2CO3+HCl, whereas
reduction in size i.e. below 0.22 mm results decrease Na2CO3+H2SO4 combination has least effect on
indemineralization. Effect of different concentrations removal of mineral matter from coal.
of alkali and acid on demineralization process has
been shown in Fig. 4 and Fig. 5 respectively.

(a) Effects of conc. of acid on

(b) Effects of conc. of acid on
demineralization with
demineralization with NaOH.
Fig. 3. Na2CO3.
It is found that the calculated values match with the
experimental values in most of the cases indicating
that the developed correlations can be used over a
wide range of parameters. Standard deviation and
mean deviation for both the methods have been listed
in TableII.

TABLE II. DEVIATION OF CALCULATED VALUES BY

BOTH THE METHODS FROM EXPERIMENTAL VALUES.
(c) Effects of conc. of acid on
System Analysis Standard Mean (d)Effects of conc. of acid on
demineralization with
demineralization with NaOH.
type deviation deviation Na2CO3.
DA 6.1150 -0.1976 Fig. 4
Na2CO3+H2O4 SA 3.3934 -0.00561
DA 0.0860 -0.0045
NaOH+H2SO4 SA 0.01753 -0.00101
DA 6.9456 -0.3225
Na2CO3+HCl SA 11.4965 -0.7683
DA 3.176 -0.0412
NaOH+HCl SA 0.0130 0.01381

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 S. Choudhury* et al. / (IJITR) INTERNATIONAL JOURNAL OF INNOVATIVE TECHNOLOGY AND RESEARCH
Volume No. 1, Issue No. 1, December-January 2013, 013 - 018
industrial applications. Again properties of coal can
thus be modified as per the requirement of the
industries.

(a) Effects of conc. of alkali on
demineralization with sulphuric
acid.
(b) Effects of conc. of alkali
on demineralization with
hydrochloric acid.
NOMENCLATURE
a0, a1, a2, a3, a12, a13, a23, a123 - mean effects different
factor
A, B, C, D, E, AC, BC - factor for factorial design
D - particle size in mm
t - time in minutes
T- temperature in 0C
C”- concentration of alkalies in W/V%
C’- concentration of acids in normality

(c) Effects of conc. of alkali on (d) Effects of conc. of alkali
demineralization with sulphuric on demineralization with
acid. hydrochloric acid.
Fig. 5
REFERENCES
[1] O. P. Mahajan and Jr. P. L.Walker “Effect ct of inorganic
matter removal from coals and chars,” Fuel, 58 (1979) 333-
337.
[2] R. T. Wang,S. K. Das and B. M. C.Tsai, “Coal
demineralization using sodium hydroxide and acid
solutions,” Fuel, 64 (1985) 735-742.
[3] M. Kumar and R.C. Gupta, “Graphitization study of Indian
Assam coking coal,” Fuel Processing Technology, 43 (1995)
169- 176.
[4] M. Kumar and R.C. Gupta, “Demineralization Study of
Indian Assam Coking Coal by Sodium Hydroxide Leaching,”
Energy Sources, Part A: Recovery, Utilization, and
Environmental Effects, 19(1997) 723 -730.
[5] M. Kumar and R. S Hari., “Removal of Ash from Indian
Assam Coking Coal Using Sodium Hydroxide and Acid
Solutions,” Energy Sources, 22( 2000) 187- 196.
[6] S.Mukherjee and P.C. Borthakur, “Chemical
demineralization / desulphurization of high sulphur coal
using sodium hydroxide and acid solutions,” Fuel, 80 (2001)
2037-2040.
[7] S.Mukherjee and P.C. Borthakur, “Effect of leaching high
sulphur sub-bituminous coal by potassium hydroxide and
acid on removal of mineral matter and sulphur,” Fuel, 82
(2003) 783–788 .
[8] http://en.wikipedia.org/wiki/Fractional_factorial_design

Fig. 6

Maximum demineralization is observed to be

achieved by NaOH and HCl combination.

V. CONCLUSION

Treatment of coal with sodium hydroxide

solution and hydrochloric acid is found to be more
effective than any other alkali-acid combination.
Such combination will provide a great scope to find
out the optimum conditions for demineralization of
coal. Thus applying this method coal can be
converted to the higher grade type containing low
mineral matter which will be applicable for industrial
uses. It is also environmental friendly. Thus the
developed correlations can be scaled up suitably for

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