Effects of chemicals and blending petroleum coke on the

properties of low-rank Indonesian coal water mixtures

Renfu Xu
a
, Qihui He
a
, Jun Cai
a
, Yi Pan
b
, Jian Shen
b,c
, Baixing Hu
a,

a
School of Chemistry and Chemical Engineering, Nanjing University, Hankou Road No. 22, 210093 Nanjing, Jiangsu, China
b
Research Center of Surface and Interface Chemistry and Engineering Technology, Nanjing University, Hankou Road No. 22,
210093 Nanjing, Jiangsu, China
c
College of Chemistry and Environment Science, Nanjing Normal University, Ninghai Road No. 122, 210097 Nanjing, Jiangsu, China
A R T I C L E I N F O A B S T R A C T
Article history:
Received 11 April 2007
Received in revised form
7 November 2007
Accepted 13 November 2007
In this study, the effects of different chemical additives including dispersant and stabilizer
on the solid loading, viscosity, rheological behaviour and static stability of coal water
mixtures have been investigated. In the experiments, naphthalene sulfonate formaldehyde
condensate (NSF) was selected as dispersant and carboxymethyl cellulose sodium salt
(CMC-Na) and nano-stabilizer were employed as stabilizers. An Indonesian low-rank coal,
taken from Berau, East Kalimantan, was used for the study. To obtain high-loaded slurry,
Liaohe petroleum coke was used to blend with Indonesian coal sample. The results of the
experiments showed that adding chemical additives and blending Liaohe petroleum coke
can effectively improve the slurryability of Indonesian low-rank coal.
2007 Elsevier B.V. All rights reserved.
Keywords:
Petroleum coke
Low-rank coal
Coal water mixture
Dispersant
Stabilizer
1. Introduction
Low-rank coals, such as sub-bituminous coal and lignite,
cannot be conveniently used like anthracite and bituminous
coal due to low caloric value and high moisture content, being
rich in oxygen and high tendency to spontaneous combustion.
As a result, low-rank coals are mainly used for power
generation by firepower plant around the colliery. Therefore,
the utilization of low-rank coals is far from satisfying in the
world.
It is necessary to solve above problems in order to use low-
rank coals as efficiently as possible. One of the efficient
methods is to upgrade low-rank coals. Various dewatering and
upgrading processes have been developed since the 1920s.
Among them are the superheated and pressurized steam
drying, hot and supercritical water drying, hydrothermal
mechanical compression drying and upgraded brown coal
processes [19].
Coal blending is becoming a normal practice in large
combustion and gasification plants, which utilize low-cost
imported coals for blending with local coals, as operators
attempt to increase the flexibility of fuel types. By blending
with high-rank coals, such as anthracite and bituminous coal,
low-grade factors in low-rank coals will be weakened.
An efficient technology is to use low-rank coals in the
preparation of a coal water mixture (CWM). CWM with
advantages such as the production of high solids concentra-
tion, saving from transport, storage and dewatering costs are
regarded as an alternative to fuel oil [10]. CWM can be stored
without the danger of coal-dust explosion, pumped, trans-
ported in pipelines and combusted like fuel oil in an
environmentally benign manner [11,12]. CWMs prepared
F U E L P R O C E S S I N G T E C H N O L O G Y 8 9 ( 2 0 0 8 ) 2 4 9 2 5 3
Corresponding author.
E-mail address: baixinghu1010@yahoo.com (B. Hu).
0378-3820/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.11.026
www. el sevi er. com/ l ocat e/ f upr oc
from low-rank coals have shown excellent combustion
characteristics in the gas turbine [13].
In CWMtechnology, one major problemis howto maintain
the highest possible coal concentration and stability simulta-
neously, at a given optimum viscosity. To resolve this
problem, it is necessary to manipulate two major factors:
the addition of suitable dispersants and stabilizers and the
size distribution of the coal particles. The chemical additives
must be chosen such that they should provide sufficient
viscosity, electrokinetic potential and the desired stability.
Numerous studies have been made of CWM rheological
properties in an effort to obtain acceptable fluidity and
maintain sufficient stability against sedimentation of the
coal particles [1420].
This study focused on the effects of different chemicals
used as dispersing agent and stabilizer on the solid loading,
viscosity and stability of CWM prepared from Indonesian low-
rank coal. At a given optimum viscosity (about 1000 mPa s at a
shear rate of 28.38 s
1
), to obtain high loading slurry, Liaohe
petroleum coke sample was used to blend with Indonesian
coal sample. Based on the results, the factors governing the
solid loading, viscosity and stability of slurries have been
discussed.
2. Experimental
2.1. Materials
Indonesian low-rank coal taken from Berau, East Kalimantan,
and Chinese Liaohe petroleumcoke samples were used for the
study. The chemical analyses of experimental samples are
given in Table 1.
The raw coal and petroleum coke were crushed in jaw and
roll type crushers to obtain particles of sizes less than 3 mm,
respectively. Then the crushed particles were comminuted in
a bill mill to obtain samples. The particle size distributions of
the samples were determined by LS-CWM (2) type particle
sizer produced by Omec Science and Technology Ltd., Zhuhai
of China. The particle size distributions and some size
parameters of two samples are shown in Fig. 1 and Table 2,
respectively.
The particle size is corresponding to the accumulative
weight percentage of particles that pass the size on the
distribution curve. D
25
, D
50
, D
75
and D
90
in Table 2 refer to the
particle sizes that 25%, 50%, 75%, 90% of coal particles by
weight can exactly pass, respectively. As seen from both Fig. 1
and Table 2, Liaohe petroleum coke sample contains signifi-
cant amount of finer particles than Indonesian coal sample.
The CWM preparation procedure was identical for all
tested samples. The weighed coal sample was slowly poured
into a beaker containing predetermined quantity of additive,
stabilizer and distilled water. The contents were continuously
stirred by a propeller-type agitator during addition of coal, and
then the stirring of the slurry was continued for further
20 min. Before testing, the slurry samples were always
thoroughly mixed by stirring to ensure homogeneity. The
solids loading of the CWM was determined from the weight
difference upon drying in an oven at 105 C for 2 h.
An anionic surfactant, naphthalene sulfonate formalde-
hyde condensate (NSF), was selected as a dispersant. Carbox-
ymethyl cellulose sodium salt (CMC-Na, weight average
molecular weight: 7.610
4
) and inorganic nano-stabilizer
were used as stabilizers. The nano-stabilizer was the com-
pound of spherical nanoparticles and fibrous nanoparticles,
and their weight proportion was 1:1 [16]. Two kinds of
nanoparticles were based on different manufacturing pro-
cesses and sourced from attapulgite clay, which was very rich
and cheap in China. The dosage of dispersant and stabilizer
was based on dry coal, unless otherwise stated.
Table 1 Chemical analyses of coal and petroleum coke
samples on dry basis
Parameter Indonesian
coal
Liaohe petroleum
coke
Inherent moisture (wt.%)
a
12.15 1.22
Ash (wt.%) 2.29 0.34
Volatile matter (wt.%) 44.34 10.90
C (wt.%) 68.51 85.48
H (wt.%) 4.71 3.82
N (wt.%) 1.72 1.71
S (wt.%) 1.51 1.52
O (wt.%, by difference) 23.55 7.47
Hardgrove grindability
index
50.5 74.2
Calorific value (MJ/kg) 29.34 35.60
a
Air dried basis.
Fig. 1 Particle size distributions of Indonesian coal and
Liaohe petroleum coke samples.
Table 2 Particle size parameters of coal and petroleum
coke samples
Sample D
25
(m) D
50
(m) D
75
(m) D
90
(m)
Indonesian coal 17.23 40.92 80.92 133.31
Liaohe petroleum
coke
6.32 18.17 47.26 99.78
250 F U E L P R O C E S S I N G T E C H N O L O G Y 8 9 ( 2 0 0 8 ) 2 4 9 2 5 3
2.2. Viscosity and static stability measurements
The apparent viscosity of CWM was measured using NXS-11A
rotary viscometer made in Chengdu of China, which was
equipped with a circulating water bath. The geometry of NXS-
11A viscometer was a rotational concentric cylinder (rotor-
cylinder) system. There were five sets of rotor-cylinder
measure systems (A, B, C, D and E) for different viscosity
ranges. At a constant temperature of 25 C, measures were
performed using B system and required sample volume was
60 ml. For B system, cylinder inner diameter and rotor outer
diameter were 4 and 3.177 cm, respectively, and the gap size
between rotor and cylinder was about 0.41 cm. A whole
viscosity measurement was spent about 150 s. Based on the
computer program, when the recorded numerical values
under different shear rates were input the computer, the
apparent viscosity at 28.38 s
1
shear rate would be obtained.
The measured apparent viscosity in the paper was corre-
sponding to this shear rate, unless otherwise stated.
The evaluation of static stability was based on the CWM
Quality Testing Methods (CCUJ Unified Methods, Center for
Coal Utilization, Japan, 1994). The static stability of slurry
could be estimated according to the particles sedimentation
rate. The average static sedimentation rate could be deter-
mined after the slurry sample statically held for 7 days [14].
Details on the operation for static sedimentation rate mea-
surements could be found in reference [16].
3. Results and discussion
3.1. Effect of coal loading on apparent viscosity for
dispersant
In order to evaluate the performance of dispersant towards
the coal loading of CWM prepared from Indonesian coal
sample and its effect on the viscosity, the studies were carried
out with dispersant dosages of 0.6, 0.8 and 1.0% based on dry
coal, respectively. The coal loading was varied and the
viscosity data was recorded. The results are presented in Fig. 2.
It is seen in Fig. 2 that the solid loadings of slurries with
viscosity values about 1000 mPa s were 52.2, 52.8 and 53.6%
when the dispersant concentrations are 0.6, 0.8 and 1.0%,
respectively. The solid contents were so low that the slurries
were not practical.
The rank of the coal, hence its porosity, volatile matter, C
and O contents are the factors causing different slurry
viscosities. Usually, the higher the rank of the coal, the more
solids the slurry can be fed. When mixed with water to prepare
CWM, low-rank coals in a way dilute the suspension with the
inherent moisture presenting on the coal surfaces. Therefore,
CWMs prepared from low-rank coals exhibit much lower solid
contents at the same viscosity as those obtained from high-
rank coals, naturally hydrophobic coals [9,10]. Depending onthe
properties of low-rank Indonesian coal, the limitations on the
viscosity values forced it to be worked with lower solid loading.
3.2. Blending process
Slurries were preparedby blending Indonesiancoal sample with
Liaohe petroleum coke in different weight proportions on dry
basis. Considering the high heating value and the good
compatibility between low-rank coal and petroleum coke, it is
interesting to prepare coalpetroleum cokewater slurry. The
characteristics of slurries with dispersant concentration of 0.8%
are given in Table 3. As is observed in Table 3, when blending
processes were adopted, solid loadings of slurries with viscosity
value about 1000 mPa s were effectively increased.
The improvement in the slurryability when partial Indone-
sian coal particles is replaced by ground Liaohe petroleumcoke
may be attributed to the lower water absorption capacity of the
latter. Since it is generally accepted that the absorption of water
involves the interaction of water molecules with the functional
oxygenated surface sites on the particles, the low oxygen
content of petroleum coke is correlation to low hydrophilicity.
The hydrophilic behaviour of low-rank Indonesian coal has a
negative effect on the viscosity of the suspension by increasing
the absorption of water withinthe coal particles. Due to the lack
of oxygenated functional groups, a low absorption of water by
the particles of petroleumcoke can be assumed, which allows a
larger amount of water to fluidize the suspension [21].
In addition, because of the differences in the surface
properties of the low-rank coal and petroleum coke, the
dispersant NSF employed in this study can be expected to
differently react with them. Anionic dispersant NSF should not
adsorb well onthe surface of low-rankcoals since suchcoals are
highly negatively charged due to, mostly, the high content of
oxygen groups [22,23]. As is observed in Fig. 2, low-rank coal
Fig. 2 Effect of coal concentration on apparent viscosity at
different dispersant dosages.
Table 3 The characteristics of slurries prepared from
blending of Indonesian coal with Liaohe petroleum coke
Sample Blend
ratio
(wt/wt)
Solid
loading
(wt.%)
Apparent
viscosity
(mPa s)
Indonesian coal 52.75 1000
Coal/coke blending 2:1 59.61 1050
1:1 62.02 960
1:2 65.74 1030
Liaohe petroleum coke 69.11 1020
251 F U E L P R O C E S S I N G T E C H N O L O G Y 8 9 ( 2 0 0 8 ) 2 4 9 2 5 3
slurries donot respondwell to increasing dosages of NSF. It may
turn out that high solid loading of the slurry prepared from
blending of low-rank coal withpetroleumcoke is a result of very
selective adsorption of NSF on the coke component of the blend
and not on the low-rank coal component.
As is seen from both Fig. 1 and Table 2, Liaohe petroleum
coke contains significant amount of finer particles than
Indonesian coal sample. The small coke particles may enter
the voids between the larger coal particles, and less water is
required to fill the inter-particle voids. Furthermore, the
smaller particles filling the gaps between larger particles can
even act as a lubricant, in turn leading to higher relative
mobility of the coal particles in the suspension and conse-
quently to lower the viscosity.
Some disadvantageous factors on slurryability in Indone-
sian low-rank coal are weakened by blending with Liaohe
petroleum coke. Additional, the difference in particle sizes of
two samples are useful for obtaining high loading slurries with
low viscosity.
3.3. Rheological behaviour
The apparent viscosities of slurries prepared from the blend-
ing of Indonesian coal with Liaohe petroleum coke were
measured under different shear rates, and the weight propor-
tionof two samples was 1:1. For eachslurry sample, a constant
concentration of 0.8% dispersing agent and a solid loading of
62.0% were used. The results for addition of different
stabilizers are given in Fig. 3.
As it is seen in Fig. 3, the slurries exhibited shear-thinning
or pseudo-plastic behaviour with an apparent viscosity
decreasing with increasing shear rate. The use of CMC-Na
resulted an increase in the viscosity of slurries, and there was
no remarkable effect on the viscosity when nano-stabilizer
was used. When 0.3% nano-stabilizer and 0.02% CMC-Na were
used, the viscosity was varied from 750 to 790 and 1150 mPa s
at 128 s
1
shear rate, respectively. Consequently, at a given
viscosity, use of nano-stabilizer would result in a higher solid
loading than use of CMC-Na under the same condition.
3.4. Static stability
Slurries were prepared from different blend compositions of
Indonesian coal and Liaohe petroleum coke, and a constant
concentration of 0.8% dispersant was used. Static sedimenta-
tion results of the slurries with and without stabilizer are
given in Table 4. When the static sedimentation rate was
Fig. 3 Effect of shear rate on the apparent viscosity of slurry.
Fig. 4 Effect of nano-stabilizer concentration on
sedimentation rate.
Table 4 Effects of stabilizer on static sedimentation rates of Indonesian coal-Liaohe petroleum cokewater slurries
Coal/petroleum coke
(wt/wt)
Solid loading
(wt.%)
Stabilizer Stabilizer concentration
(wt.%)
Apparent viscosity
(mPa s)
Sedimentation rate
for 7d (wt%/day)
2:1 59.6 0 1050 2.52
CMC-Na 0.02 1460 0.32
Nano-
stabilizer
0.3 1090 0.27
1:1 62.0 0 960 2.35
CMC-Na 0.02 1390 0.21
Nano-
stabilizer
0.3 1030 0.18
1:2 65.7 0 1030 1.86
CMC-Na 0.02 1560 0.16
Nano-
stabilizer
0.3 1080 0.12
252 F U E L P R O C E S S I N G T E C H N O L O G Y 8 9 ( 2 0 0 8 ) 2 4 9 2 5 3
measured, a slurry sample would statically hold for 7 days.
The sedimentation rate was an average value corresponding
to per day, and the resulting unit was wt.%/day. As is observed
in Table 4, while the sedimentation rates of CWMs in the
absence of the stabilizer are 2.52%, 2.35% and 1.86%/day,
respectively, these rates evidently decrease with addition of
0.3% nano-stabilizer or 0.02% CMC-Na.
The static sedimentation rate of slurries with respect to
nano-stabilizer concentration is given in Fig. 4. As it is seen in
the figure, static sedimentation rates rapidly decrease when
nano-stabilizer is added, and sedimentation rates decrease
with increasing amounts of nano-stabilizer. Also, there is no
significant effect on the sedimentation rate when nano-
stabilizer concentration exceeds 0.25%. Thus, it is established
that the optimum concentration of nano-stabilizer should be
0.250.35%.
4. Conclusions
In the investigation of the slurryability of Indonesian low-rank
coal sample in the presence of naphthalene sulfonate
formaldehyde condensate (NSF) as a dispersant and Carbox-
ymethyl cellulose sodium salt (CMC-Na) and inorganic nano-
stabilizer as stabilizers, the following results are obtained:
Slurries with acceptable viscosities (about 1000 mPa s)
made by Indonesian low-rank coal are not practical because of
low solid loadings.
Blending petroleum coke is an effective approach to
improve the solid loadings of Indonesian low-rank coal
water mixtures. Furthermore, it can increase calorific values
of coal slurries.
Indonesian coal-Liaohe petroleum cokewater slurries
exhibit shear-thinning or pseudo-plastic behaviour. At a
given viscosity, use of nano-stabilizer would result in a higher
solid loading than use of CMC-Na due to the viscosity increase
effect of the latter.
The experimental results of static stability show the
sedimentation rate decreases with increasing amount of
nano-stabilizer and the optimum concentration of nano-
stabilizer is 0.250.35%.
In sum, the slurryability of Indonesian low-rank coal can be
effectively improved by adding chemical additives and blend-
ing petroleum coke.
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253 F U E L P R O C E S S I N G T E C H N O L O G Y 8 9 ( 2 0 0 8 ) 2 4 9 2 5 3