Effect of the physical-chemistry property of minerals on coal water slurry

Hongying Liu, Shuquan Zhu & Qi Wang

Sch. of Chemical and Environmental Engineering, CUMTB, Beijing, China

Jie Cheng
Library of CUMT, Xuzhou, China

ABSTRACT: Surfactants are used to make the Coal Water Slurry (CWS), a coarse sized dispersed system,to
be stable. Coal is a complicated matter which consists of high molecular compound and different minerals so the
effect of minerals on CWS can not be neglected. In order to analyze the effect of the physical-chemistry property
of minerals on CWS the adsorption of additives such as condensed naphthalene sulphonic acid (add-1), multi-
acid copolymer (add-2), PCA (add-3), sulfonated humic acid (add-4), and sulfonated xylem element (add-5) on
the surface of minerals and the change rule of -potential of the surface of minerals and coal were researched.
At the same time the microcalorimeter was used to analyze the mechanism of adsorption of additives.

1 INTRODUCTION 2.2 Method

The control of particle size: Six minerals were broken
Coal Water Slurry (CWS) is a coal based fluid fuel.
into pieces <75 micron. Malven Laser Particles Ana-
The CWS technology is a branch of China Clean Coal
lyzer were utilized to control particle size distribution
Program. Recently, several big CWS plants have been
of the minerals and to make the average diameter of
set up in the provinces of Shandong, Shanxi, and
particles to be similar to that of coal.
Guangdong. The rapid commercialization process has
The determination of -potential: The particle of
attracted more fundamental studies (Zhu, 2003).
coal and minerals was laid up for 24 hours in solution
Coal is a complicated matter that consists of high
then was measured by Zetamaster potentiometer.
molecular compound and different minerals (Liu,
The determination of heat value: The heat value that
2002). So the effect of mineral on the slurry-forming
minerals and coal release in water and the solution
ability of CWS cant be neglected. This paper intro-
were determined by microcalorimeter.
duces the adsorption of five additives on the surface
of minerals and the change rule of -potential of the
surface of minerals and coal. The result is helpful to 3 RESULT AND DISCUSSION
understand the role of mineral in CWS.
3.1 Content and particle size of minerals
The content of minerals were shown in Table 1.
2 EXPERIMENTAL Illite was treated with hydrochloric acid and more
than 90% illite can be achieved.
2.1 Materials
Table 1. Mineral content determined by X-ray
The coal sample: Datong low ash coal was selected. diffractometer.
The sample was well cleaned to about 1% of ash by
friction-electrostatic separator. Minerals Content (%)
The Minerals: Na-montmorillonite, kaolinite, illite
quartz, pyrite, and calcite were collected and their Quartz 96.5
Calcite 99.8
component was determined by X-ray diffractometer.
Pyrite 99.0
The Additives: Five kinds of dispersants were used Na-montmorillonite 83.0
in CWS preparation.They are add-1 (Condensed naph- Kaolinite 84
thalene sulphonic acid), add-2 (Multi-acid copoly- Illite* 65.5
mer), add-3 (PCA), add-4 (Sulfonated humic acid) and
add-5 (Sulfonated xylem element). * Sample was treated with hydrochloric acid.

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chap-106 10/8/2004 15: 3 page 548

The average diameter of particles was shown in -70

Table 2.
Except for Na-montmorillonite that easily adsorbed -60
water into layer and cause expansion, the particle size

Zeta potential(mv)
of other five minerals is close to that of coal. -50

-40
3.2 The results of -potential determination
Figures 17 are the results of -potential of five -30
minerals and coals with five additives respectively. -20 add-1 add-3
Table 2. The average diameter of particles. add-2 add-4
-10
add-5
Minerals Average diameter (micron) 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Coal 19.14 The content of additives (g/l)
Quartz 26.78
Calcite 20.87 Figure 3. -potential of the surface of pyrite with five
Pyrite 17.98 additives.
Kaolinite 14.42
Illite 18.12
-90

-90 -80

-80 -70
Zeta potential(mv)
Zeta potential(mv)

-70 -60

-60 -50

-50 -40 add-1 add-3

-30 add-2 add-4
-40 add-1 add-3 add-5
add-2 add-4 -20
-30 add-5 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.0 0.2 0.4 0.6 0.8 1.0 1.2 The content of additives (g/l)
The content of additives (g/l)
Figure 4. -potential of the surface of kaolinite with five
Figure 1. -potential of the surface of quartz with five additives.
additives.

-80 -90

-70 -80

-60
Zeta potential(mv)

-70
Zeta potential(mv)

-50
-60
-40
-50
-30
-40
add-1 add-3 add-1 add-3
-20
add-2 add-4 -30 add-2 add-4
-10 add-5 add-5
-20
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
The content of additives (g/l) The content of additives (g/l)

Figure 2. -potential of the surface of calcite with five Figure 5. -potential of the surface of illite with five
additives. additives.

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chap-106 10/8/2004 15: 3 page 549

Curves of all minerals but montmorillonite go up
quickly at the beginning till the turning points appear
and then lines go up slowly (Czapla, 2000). It suggests
that additives were adsorbed on the surface of particles
of minerals and coal till the saturation point reached
when all adsorption sites were taken and adsorption
-90
capacity was saturated.These additives are anionic sur-
factants so the -potential of minerals and coal was cut
down (the absolute value of surface potential adds)
evidently at first and then changed slowly with the
increase of additives. According to the DLVO theory,
the increase of the absolute value of static electrical
potential is favorable for particlesdispersing (Gaudin,
1955).

-80
Zeta potential(mv)

-70

-60

-50
add-1 add-2
-40 add-3 add-4
add-5
-30
0.0 0.2 0.4 0.6 0.8 1.0 1.2 where R1 , R2 = radius of particles; 0 = dielectric coef-
The content of additives (g/l) ficient of dispersion medium; 01 , 02 = surface
potential of particles; 1 = Debye constant; and
Figure 6. -potential of the surface of montmorillonite with VE = electrostatic energy.
five additives. From the above equation, the higher surface poten-
tial is, the more electrostatic energy is, so the particles
-90 are dispersed and CWS is stable.
It is also shown that although the value of the -
-80 potential for five additives is different, the -potential
of minerals is similar to that of coal. That is to say,
-70 the surface charge of particles chiefly depends on the
Zata potential(mv)

charge of functional groups of additives. The action

-60 between particles of coal and the action between coal
and minerals are the same.
-50 The negative value of -potential of montmoril-
lonite is too large to adsorb anionic surfactant on its
-40 add-1 add-2 surface.
add-3 add-4
-30 add-5 3.3 The results of -potential determination
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 The quantity of heat that coal and six minerals release
The content of additives (g/l) in water and solution including five additives was
determined by microcalorimeter and the result was
Figure 7. -potential of the surface of coal with five shown in Table 3.
additives.

Table 3. Reaction heat between minerals and additives (J/g).

Water Add-1 Add-2 Add-3 Add-4 Add-5

Coal 12.831 14.546 14.135 15.042 13.824 15.473

Quartz 0.383 0.474 0.666 0.910 0.599 0.305
Calcite 0.248 0.343 0.817 0.938 0.450 0.326
Pyrite 36.769 43.126 49.942 43.181 40.524 44.032
Kaolinite 3.572 3.149 3.129 3.950 3.284 3.513
Illite 1.513 0.330 0.879 0.861 0.541 0.440
Na-montmorillonite 29.619 29.139 31.217 28.748 29.941 30.238

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chap-106 10/8/2004 15: 3 page 550
When minerals and coal dissolve in water can
produce the wetting heat, the dissolution heat, the
dissociation heat, etc (Fu, 1997). While when they dis-
solve in solution including five additives of adsorption
heat and the reaction heat can also be produced. So the
quantity of heat is total calorific value.
According to adsorption theory the quantity of
adsorption heat that is directly related to how strong
and how weak of bond energy is. So it is one of the
important value which can show the physico-chemical
property of the surface of solid. The quantity of phys-
ical adsorption heat is small (<40 kJ/mol) than that of
chemistry adsorption heat (80400 kJ/mol).
The value of the heat in water subtracting the heat
in solution is not big. It suggests that the heat of
adsorption of five additives on the surface of coal and
minerals is small. Therefore physical adsorption is pri-
mary and five surfactants dont adsorb specially on the
surface of minerals in CWS.
4 CONCLUSIONS
Except of montmorillonite , Condensed naphthalene
sulphonic acid, Multi-acid copolymer, PCA, Sul-
fonated humic acid and Sulfonated xylem element can
be adsorbed on the surface of kaolinite, illite quarts,
pyrite and calcite and coal. The value of the -potential
of minerals is similar to that of coal.
The quantity of adsorption heat of five additives
on the surface of coal and minerals is small. So five
surfactants dont adsorb specially on the surface of
minerals in CWS.
550
Copyright 2004 Taylor & Francis Group plc, London, UK
The physicochemical property of minerals will not
bring notable effect on the property of CWS.
ACKNOWLEDGEMENT
The project was supported by the Natural Science
Foundation of China (50074033).
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