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Fuel
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h i g h l i g h t s g r a p h i c a l a b s t r a c t
a r t i c l e i n f o a b s t r a c t
Article history: In the present work an attempt have been made to upgrade the low grade Indian coal to high grade coal
Received 15 January 2016 by using caustic (NaOH) leaching followed by acid (H2SO4) treatment. The experimental works aimed at a
Received in revised form 25 February 2016 selective attack on in situ MCL (Mahanadi Coal Limited) coal, Odisha, India with some fluxing agents like
Accepted 27 January 2017
NaOH and H2SO4. The leaching experiments were carried out in a stainless steel batch reactor of 2.5 L
Available online 4 February 2017
capacity with controlled heating facility. Initially, the coal sample with 16+100 mesh particle size
was leached with 50–150 g/L of NaOH solution at 100 °C for one hour and then subjected to leach further
Keywords:
with 20% sulfuric acid. The maximum demineralization from the level of 26% ash with NaOH (100 g/L)
Coal
Leaching
leaching 27.5% is achieved and with combined chemical treatment method (100 g/L NaOH followed by
Demineralization 20% H2SO4) was obtained 48% effectively. In addition, the results showed that the percent of demineral-
Particle size ization improved adequately by decreasing the particle size also with rise of the leaching time and tem-
SEM perature. Coal characterization of raw and treated coal was done by Scanning Electron Microscopy (SEM)/
EDS Energy Dispersive Spectroscopy (EDS) analysis and also showed that the calorific value of coal was
increased with increase the percent of demineralization of coal.
Ó 2017 Elsevier Ltd. All rights reserved.
1. Introduction
The low cost and availability of low grade coal are best feed
⇑ Corresponding author at: Department of Chemical Engineering, Indian Institute
materials for fuel and energy production. The high ash coals are
of Technology (IIT) Kharagpur, Kharagpur Technology, Paschim Medinipur, West
Bengal 721 302, India.
unsuitable for use in combustion, gasification, carbonization or liq-
E-mail address: bcmeikap@che.iitkgp.ernet.in (B.C. Meikap). uefaction process. However theses coals have several drawbacks
http://dx.doi.org/10.1016/j.fuel.2017.01.088
0016-2361/Ó 2017 Elsevier Ltd. All rights reserved.
S.K. Behera et al. / Fuel 196 (2017) 102–109 103
like lower specific energy due to low carbon content, highly min- seam) and Investigated the effect of concentration, contact time
eral and moisture contents and also low calorific value [1–6]. Coal and temperature on the removal of ash and sulfur. They reported
contains variable amounts of largely incombustible mineral matter maximum demineralization was achieved from 30 to 70% from lig-
co-existing with the organic matrix called as impurity. Mineral nite coal type [22]. Onal et al. studied six Turkish lignite coal were
matter is consist of all the inorganic minerals (discrete phases), treated with HCl or CH3CH2ONa solution at 150 °C. They concluded
as well as all elements (apart from C, H, O, N and S) that are in, from the investigation, HCl treatment was effective demineraliza-
or associated with, coal. The mineral matter in coal exists in differ- tion but not CH3CH2ONa while effective desulfurization by CH3-
ent forms such as the coal discrete crystalline particles, amorphous CH2ONa treatment but not HCl [7]. Adeleke et al. reported the
mineral phases, inorganic elements chemically bound to the effect of multistage caustic leaching of Nigerian Lafia-Obi coal.
organic material and compounds dissolved in the pore or surface The average ash reduction was achieved 38.66% at low molar con-
water of the coal [7]. Clay minerals are the most abundant mineral centration 1:20 mass reagent (H2O-Na2CO3-H2O) to coal in the
species and quartz is the second most abundant mineral phase in absence of stirring [23].
the coal [8,9]. Except this, other mineral matters are also found A literature review revealed that the demineralization of coal
in the original coal that includes silicas or shales (kaolinite type), can be improved by chemical leaching process. Several authors’
calcite, gypsum, siderite, carbonates, pyrites, disulfides, sulfides, has been studied the demineralization with low ash coals to gener-
sulfates, feldspars and trace elements [5,10]. ate ultra clean coal while, in the present investigation we select
The presence of mineral matter in the coal has adverse affects high ash Indian coal. Since the Indian coals are high ash content
on coal utilization and processing. Mineral matter is the inert solid and the nature of low ash coal is completely different from Indian
material in the coal which form ash during combustion [11]. The coal. In the present communication, an effort has been made to
effects of treatments on different forms of the mineral matters investigate the effect of alkali concentration and followed by acid
may be different from coal to coal. It is difficult to reduce ash con- treated on the demineralization of high ash coal by varying leach-
tent to a minimum limit by physical method because the ash form- ing temperature and contact time and also particle size. The char-
ing mineral are intermixed to the organic part of coal. In the acterization of raw and leached coal was analyzed by SEM-EDS and
physical method the coal is crushed into fine particles and the XRF analysis.
removal of mineral matter based on their physical properties like
surface phenomena (wettability) and specific gravity [12–14]. It
is only possible in the chemical method for removal of associated 2. Material and methods
mineral and bound to coal matrix or structure. The mineral species
is dissolute in water acid or alkali solution in the chemical method. 2.1. Materials
The method used in the chemical cleaning of coal include acid
leaching or alkali leaching and or followed both acid and alkali at In the present investigation, the coal sample were collected
varying physical parameters. It is more expensive than physical from Bhubaneswari OCP (Open Cast Project) of Mahanadi Coal
methods concerning of total cost (fixed and operating cost). Chem- Field (MCL), Orissa. The coals were crushed in a ball mill and sieved
ical cleaning of coal is using simple equipment and an aqueous to 16+100 British standard sieves (BSS) mesh size particle, was
solution of common industrial chemicals and operation is easier used for conducting the experiments. Before the actual start of
when it operate under mild condition but the cost of chemicals the experiment, the coal sample was characterized by using stan-
needed [15]. dard proximate (ASTM D3172 – 13) and ultimate (ASTM D3176 –
A review of the literature on the chemical leaching of coal 15) analysis method. The results are summarized in Table 1. The
reveals that the methods of acid and aqueous alkali or combined chemical reagent used in the present work is the commercially
leaching under moderate temperature and pressure conditions to available sulfuric acid (98% concentration by wt.%) and sodium
demineralize and desulfurize from various coals is suitable tech- hydroxide pellets.
nique. Sharma et al. reported the method of chemical leaching of
low grade coals through alkali-acid leaching under mild condition 2.2. Experimental set up and procedure
at atmospheric pressure resulting 75% demineralization [4]. Araya
et al. observed demineralization of sub bituminous coal from the La The leaching experiments were conducted in a bench scale unit
Union are treated with aqueous alkali, and the elimination of ash consist of a batch reactor of capacity 2.5 L with heating facilities,
increases with reaction time, temperature and concentration of condenser provision for reflux and temperature measured by a
solution [16]. Various organic acids and aqueous alkali used in thermometer. The batch reactor made up stainless steel reactor
the demineralization studies for production of ultra clean from dif- (SS-316) which consist of 0.11 m diameter and 0.22 m height with
ferent types of coal reported by (Steel and Patrick, steel et al., Teflon coating inside. The reactor is heated with four heating coils
Nabeel et al.) and also the removal of mineral matter during chem-
ical leaching depend on the coal characteristics, types and quantity Table 1
Chemical analysis of coal sample.
of mineral matter, size of coal particle, and solvent concentration
and contact time of leaching [17–20]. Culfaz et al., observed from Bhubaneswari coal seams
investigation the effect of temperature, caustic concentration and Proximate analysis (wt%, dry basis)
time on the degree of demineralization of Turkish low and high Ash 26.3
grade lignite coal (Beypazari 35.6% ash, and Soma 7% ash) are trea- Volatile matter 38.7
Fixed carbon 35.0
ted with Caustic and after washed with HCl solution. In the effect
of caustic treatment, most of silica (SiO2) and calcium oxide Ultimate analysis (wt%, daf)
Carbon 52.9
(CaO) in the ash were removed. However, most of iron oxide
Hydrogen 4.5
(Fe2O3) and Sodium oxide (Na2O) remained in the coal matrix. Nitrogen 1.5
The degree of demineralization was obtained 90% for both coal Sulfur 1.3
seams [21]. Karaca et al. studied the leaching effect of hydrogen Oxygen (by difference) 39.8
peroxide (H2O2) on Turkish two lignites (Beypazari and Tuncbilek Calorific value (kcal/kg) 4632
104 S.K. Behera et al. / Fuel 196 (2017) 102–109
of 1KW capacity each, which fitted outside of the circumference of 3. Results and discussion
the reactor. A stainless steel stirrer is firmed in motor and whose
propeller placed at 0.06 m above from the bottom of the reactor. 3.1. Effect of concentration on demineralization of coal
A motor moves the stirrer and its speed measured by the sensor
that mounted in front of the motor. The stirrer usually operate at The caustic concentration has the direct effect on the deminer-
600–900 rpm. The layout of bench scale experimental setup is alization of coal and the result depicted in Fig. 2. Up to 100 g/L
shown in Fig. 1. NaOH, as the concentration of NaOH increases the percent dem-
For each test, 50 gm of coal (16+100 mesh size) sample was ineralisation of the coal increases. Above 100 g/L NaOH increased
added to 500 ml NaOH solution of known concentration (50– concentration of NaOH decreases the percent demineralisation. In
150 g/L) in stainless steel reactor at temperature 100 °C for one the alkali leaching, the coal containing silica and alumina and other
hour. The coal slurry was heated from a room temperature to silica alumina clay bearing minerals may dissolve and formed
leaching temperature and maintained constant time. In the second sodium silicate and sodium aluminate, which is leached out to
set of experiments, 50 gm of coal (-16+100 mesh size) was treated the solution. The following reaction as shown in (1), (2) and (3).
with 50 g/L NaOH concentration of 500 ml solution for 60–120 min While at higher concentration of alkali solution, the dissolution
at reaction temperature 65–150 °C. In both stages, the caustic lea- of silica and alumina decreases because formation complex sodium
ched coal is followed by 20% sulfuric acid similar reaction time and compound called sodium-aluminosilicate. The decrease in percent
respective leaching temperature. After leaching the hot coal slurry demineralization with the increase in alkali concentration is
is cooled, filtered and washed with distilled water for diluting the because the concentration of silicate and aluminate ions exceeds
concentration of alkali and acid treated coal. The sample is then the solubility product of sodium-aluminosilicate. Several author
dried at 75–85 °C for 3–4 h and weighed. Finally, the ash content also observed similar case as decrease demineralization with
of treated coal was determined by using standard methods (ASTM increases alkali concentration [4,15]. In the investigation maxi-
D3174 - 12). mum percent demineralization was obtained 27% at 100 g/L NaOH
1 Legends
5
1. Fixing Stand
3
2. Batch Reactor
3. Motor and stirrer assembly
6 7 4. Heating Coil
5. Temperature Controller
2
6. Feed Inlet
4 7. Condenser Line
8. Outlet Valve of Reactor
9. Filtration Equipment
8 10. Filtering Plate(Mesh)
11. Filtrate Outlet Valve
10
11
and 54% for acid followed alkali treated coal while in the case of
the alkali treated coal only 72 mesh particle size was maximum
demineralized. Throughout the investigation, 60 and 72 mesh
particle size is the best demineralization of coal. However, very
fine ground particle (over 100 mesh particle size) were inhibited
to extent of the demineralization. The reason might be the very
finer particles were stick to each other due to greater cohesive
force between the particles (above 100 mesh) and it is difficult to
handling. It also reduces the rate of diffusion of the leaching agent
to the reactive part of the coal and very less yield and also more
time to take for filtration.
Fig. 6. SEM analysis of (1) Raw coal (2) 50 g/L NaOH (3) 100 g/L NaOH (4) 150 g/L NaOH treated coal and 20% sulfuric acid followed by (5) 50 g/L NaOH (6)100 g/L NaOH (7)
150 g/L NaOH treated coal.
3.6. Calorific value treated coal. The increase these value found to be 13% and 45%
of the alkali and followed acid treated coal respectively. The
The calorific value of coal (moisture free basis) was deter- maximum calorific value was found in the acid followed by
mined by high pressure oxygen Bomb calorimeter (LECO AC alkali treated coal as compared to alkali treated and raw coal.
500). The calorific value (C.V) of coal is one of the most impor- The reason might be soluble of non-carbonaceous mineral mat-
tant indexes in assessing the quality of coal. The calorific value ters by the chemical treatment, which have no heating value.
of coal increased ranging from 4631.5 kcal/kg to 5241.7 kcal/kg The composition of calcite (Carbonaceous group) is the main fac-
for alkali leached coal which increases to 6733.3 kcal/kg for acid tor for affect the calorific value of coal [24].
108 S.K. Behera et al. / Fuel 196 (2017) 102–109
Table 2
EDS analysis of coal samples.
Element (wt.%) Raw coal NaOH concentration (g/L) NaOH (g/L) followed by 20% H2SO4
50 100 150 50 100 150
C 48.95 65.23 68.38 65.85 67.24 71.13 70.1
O 36.48 24.24 22.69 16.51 18.72 20.24 19.0
Mg 0.13 0.38 0.42 0.51 0.7 0.01 0.05
Al 4.29 1.88 1.22 3.15 3.21 1.63 3.44
Si 9.16 5.78 3.35 8.51 7.73 4.23 5.7
S 0.22 0.27 0.62 0.4 1.35 1.46 1.05
K 0.2 0.12 0.2 0.96 0.02 0.41 0.12
Ca 0.08 0.32 0.08 0.69 0.23 0.12 0.01
Ti 0.3 0.37 0.12 0.99 0.16 0.16 0.24
Mn 0.04 0.06 0.09 0.03 0.06 0.07 0.06
Fe 0.15 1.25 2.65 2.4 0.08 0.54 0.21
Table 3
Ash analysis of coals.
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