Received 07 December 2009; accepted 08 March 2010

*Corresponding author. Tel: 86 516 83885878

E-mail address: cumtlxb@126.com.
doi: 10.1016/S1674-5264(09)60280-5
Adsorption of oil from waste water by coal:
characteristics and mechanism
LI Xiaobing
*
, ZHANG Chunjuan, LIU Jiongtian
School of Chemical Engineering and Technology, China University of Mining & Technology, Xuzhou 221116, China
Abstract: The work described here was focused on exploring the potential application of coal to purification of oily waste water.
Coal was added to oily waste water as an adsorbent and then removed through a flotation process. This allowed economical and
highly efficient separation of oil from the waste water. The absorption time, coal type, coal particle size distribution, pH value and
oil concentration were investigated. The results indicate that oil absorption by a coal increases for a period of 1.5 h and then gradu-
ally tends toward an equilibrium value. It appears that the absorption capacity of anthracite is more than that of lean coal or lignite,
given the same coal particle size distribution. The absorption capacity of a coarse coal fraction is less than that of finer coal, given
the same of coal type. The absorption capacity of anthracite decreases slightly as the pH increases from 4 to 9. The adsorption of oil
on anthracite follows the Freundlich isothermal adsorption law: given initial oil concentrations of 160.5 or 1023.6 mg/L the absorp-
tion capacity was 23.8 or 840.0 mg/g. The absorption mechanism consists of two kinds of absorption, a physical process assisted by
a chemical one.
Keywords: oily wastewater; waste water; separation; coal; oil; adsorption; mechanism
1 Introduction
Oily waste water is one of the most serious envi-
ronmental issues created by production in oil fields.
The treatment of oily waste water is important not
only from an economic view point but also in terms
of ending the pollution of water resources. Com-
monly used technologies for treating oily waste water
include physical treatment, physical chemistry,
chemical de-emulsifying, biochemistry and electro-
chemistry
[1-4]
. However, application of these tech-
niques has been limited for both technical and eco-
nomic reasons. A flotation process has been attracting
much recent attention from scholars because of its
high separation efficiency, low capital investment and
operational costs. Some new types of flotation de-
vices and some new methods for quick and highly
efficient separation of oily waste water have been
developed
[5-9]
.
Currently, many oil fields in China have entered a
medium-high water-cut stage during their mid to late
phase of oil extraction. The development and applica-
tion of the polymer-flooding technology in oil fields
has resulted in the production of water containing a
large amount of high molecular weigh polymer that is
highly emulsified and has a high water-phase viscos-
ity. This makes treatment of the polymer-flooding
waste water considerably more difficult.
Hao Z T et al. used fly ash as an adsorbent to ad-
sorb oil from oily waste water
[10]
. Oil removal effi-
ciencies reached 70%~80% in that scheme and the
adsorption process fit an S-shaped isothermal adsorp-
tion law. Yan L H et al. reported that the adsorption
process follows the Freundlich isothermal adsorption
law when fly ash was used as an adsorbent for sepa-
ration of oil from oily waste water at room tempera-
ture
[11]
. The results showed that the residual oil con-
centration in the waste water would not be too high
when the adsorption process was helped by stirring.
However, the recovered oil can not be recycled effec-
tively when fly ash is used as the adsorbent.
The objective of this study was to explore the po-
tential application of using coal to treat oily waste
water. The oil can first be separated from the waste
water with a novel method where the coal is used as
an oil adsorbent and then the coal-oil mixture is
separated from the waste water by flotation eco-
nomically and with high efficiently. As a result, oil
removal from waste water was successfully per-
formed and the recycled oil could then be used as fuel,
namely a coal-oil-water multiphase fuel. The adsorp-
tion of oil droplets onto a coal particle surface from
oily waste water was also studied.
Mining Science and Technology 20 (2010) 07780781
MINI NG
SCIENCE AND
TECHNOLOGY
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LI Xiaobing et al Adsorption of oil from waste water by coal 779
2 Experimental
2.1 Materials
The oily waste water was polymer-flooding water.
Samples were obtained from the Shengli Gudao Oil
Field, China. The initial oil mean concentration in the
water was 246.40 mg/L. The oil droplet size distribu-
tion was analyzed with a laser particle size analyzer
(LS-100Q). About 13.4% of the oil droplets were 1
m in diameter or smaller and about 99.1% were 10
m or smaller. The oily waste water is very difficult
to separate because of the small mean size of the
droplets that consist of emulsified oil and polymer.
The coals used as sorbent in the experiments were
Yongcheng anthracite from Henan province, China,
Anyang lean coal from Henan province, China and
Wuhai lignite from Inner Mongolia province, China.
These coal samples were ground into fine particles
for 8 minutes using a XMB-67 ball mill. Then they
were screened with a bushing screen into fractions of
particle size +0.51.0, +0.1250.5, +0.0740.125,
+0.0460.074 and 0.046 mm.
2.2 Methods
2.2.1 Oil concentration measurement and the
absorption capacity calculation
The oil concentration of the waste water was de-
termined by UV spectrophotometry (UV2602).
The adsorption capacity for crude oil was calcu-
lated using Eq.(1)
0
( ) /
e
C C v m = (1)
where is the superficial adsorption capacity; C
0
the
initial concentration of crude oil in the oily waste wa-
ter; C
e
the equilibrium concentration of crude oil in the
waste water; and m the quantity of coal added to the
sample.
2.2.2 Equilibrium absorption time
In a typical experiment 0.25 g of anthracite, the
lean coal or the lignite was used for each trial. The
coal was first added to a 250 mL conical flask along
with 50 mL of oily waste water. The mixture was then
mixed with a thermostatically controlled oscillator at
(251) C. The mixing time was programmed from 0
to 3.0 h. Finally, the oil concentration of these sam-
ples was measured after absorption by the coal. The
results are presented in Fig. 1.
Fig. 1 Absorption as a function of time
Fig. 1 shows that absorption equilibrium occurs
later than 1.5 hours after initial contact. Thus, a 3.0 h
contact time was chosen as being most suitable by
experiment. The absorption process of each of the
three coals may be divided into two stages, a quick
and a slow absorption stage. The absorption capacity
during the quick absorption stage is more than 90%
of the total absorption capacity. The absorption
gradually comes to equilibrium during the slow, final
absorption stage.
2.2.3 Selection of coal type and particles size
0.25 g samples of anthracite, the lean coal or the
lignite were used. The particle sizes of the samples
were 0.046, 0.074 +0.046, 0.125+0.074, 0.5+
0.125 or 1.0+0.5 mm. The coal sample was put into
a 250 mL conical flask along with 50 mL of oily
waste water. Then the mixture was mixed in a ther-
mostatically controlled oscillating bath at (251) C
for 3.0 h. The results are shown in Fig. 2.
2.2.4 pH value
0.25 g anthracite samples with a particles size of
0.074+0.046 mm were used for this part of the work.
The coal sample was added to a 250 mL conical flask
along with 50 mL of oily waste water. Then the pH of
the mixture was adjusted by adding either NH
3
H
2
O
or HCl to it. The flask was mixed in a thermostati-
cally controlled oscillating mixer at (251) C for 3.0
h. The results are shown in Fig. 3.
2.2.5 Oil concentrations
Samples with different oil concentrations in the
water were prepared at a pH value of 7.0. Again, 0.25
g of anthracite, particle size +0.0460.074 mm, were
placed in a 250 mL conical flask along with 50 mL of
oily waste water. This mixture was mixed in the
thermostatically controlled oscillating mixer at (251)
C for 3.0 h. The results from this trial are shown in
Fig. 4.
3 Results and discussion
3.1 Effect of coal type and particles size on the
absorption capacity
Fig. 2 shows that the absorption capacity of an-
thracite exceeds that of the lean coal and the lignite
for each particle size. The equilibrium adsorption
capacities of anthracite, lean coal and lignite were
24.4, 18.6 and 20.7 mg/g, respectively, when the par-
ticle size was 0.046 mm.
The coarser lean coal had greater absorption capac-
ity than the coarser lignite. For example, the equilib-
rium adsorption capacities of lean coal and lignite
were 11.3 and 9.3 mg/g respectively when the particle
size was 1.0+0.5 mm. However, the absorption ca-
pacity of the lean coal is less than the lignite when the
particle size was smaller. For example, the adsorption
capacities of the lean coal and the lignite were 14.1
and 17.8 mg/g respectively when the particle size was
Mining Science and Technology Vol.20 No.5 780
0.125+0.074 mm.
1.0
0.5
0.5
0.125
0.125
0.074
0.074
0.046
0.046
0
4
8
12
16
20
24
Particle size (mm)
Anthracite
Lean coal
Lignite
Fig. 2 Effect of coal type and particles size on the
absorption capacity
The quantity of oil absorbed increased as the parti-
cle size decreased. This was true for all coals and oc-
curs because the specific surface area of coal particles
increases as their size decreases. It is difficult for the
suspended solids to be removed completely, however,
if the particle size is too fine. Under these conditions
the amount of suspended solids in the waste water
might increase. This experiment shows that the parti-
cle size of anthracite should be kept within the range
of 0.074+0.046 mm.
3.2 Effect of pH on absorption by anthracite
Fig. 3 shows that the absorption capacity of an-
thracite decreases as the pH value increases. The ad-
sorption capacity under acidic condition is clearly
greater than for alkaline condition. However, on the
whole, the effect pH is rather small and the adsorp-
tion capacity of the anthracite ranges from 22.0 to
25.0 mg/g over the pH range examined. Therefore,
the pH of the oily waste water need not be adjusted
when anthracite is used as the sorbent.
(
m
g
/
g
)
Fig. 3 Effect of pH value on absorption capacity
3.3 Effect of oil concentration on the absorption
capacity of anthracite
Fig. 4 shows the absorption as a function of oil
concentration with anthracite as the absorbent. Oil
concentrations of 42.2, 160.5, 523.6 or 1023.6 mg/L
resulted in adsorption capacities of 9.5, 23.8, 499.9 or
840.0 mg/g, respectively. The results shown in Fig. 4
indicate that the adsorption capacity of anthracite fits
the Freundlich isothermal adsorption law. Initially the
adsorption capacity is small, which indicates that the
absorption of oil is affected by other substances in the
waste water. A single terminal group of the crude oil
molecules is targeted for adsorption on the coal sur-
face. Increasing the oil concentration results in im-
proved adsorption capacity, especially at high con-
centrations, which may result from oil molecules
saturating the coal surface and then providing a ther-
modynamically more stable site for further adsorp-
tion.
(
m
g
/
g
)
Fig. 4 Effect of oil concentration on the absorption
capacity of anthracite
4 Mechanism of oil absorption onto coal
particles
Coal is a solid material consisting of crevices and
growth holes. It has a double porosity and contains
both micro- and macro-pores: it has a large surface
area and included volume
[12-14]
. Coal particles ab-
sorbed oil droplets from the waste water, especially
the smaller sized droplets and the emulsified oil. Oil
is absorbed to the coal particles and then separated
from the water through flotation.
The adsorption of oil depends on three processes:
diffusion of oil molecules into the substrate; capillary
action of the oil at the fiber structure/substrate inter-
face; and, aggregation of oil in cavities such as pores,
microcracks and uncovered interfaces. The pores and
surface microcracks are the main locations for ab-
sorption of oil by coal (Fig. 5).
Fig. 5 Adsorption of oil on coal particles
FTIR spectra can demonstrate the adsorption
mechanism. The FTIR spectra of anthracite and an-
thracite with oil adsorbed on it are shown in Fig. 6.
LI Xiaobing et al Adsorption of oil from waste water by coal 781
4000 3500 3000 2500 2000 1500 1000 500
10
20
30
40
50
1100~1200
C-H
730~770
690~710
Wavenumber (cm
1
)
OH3300~3450
Anthracite
Anthracite adsorbed oil

C-O
CO, CC 1600~1650

C-H
Fig. 6 FTIR spectra of anthracite and anthracite plus oil
Referring to Fig. 6, the peak at 3450~3300 cm
1
is
attributed to the absorption of hydroxyl. Hydroxyls in
coal-based compounds are generally hydrogen
bonded, therefore the peak moves from 3300 to 3450
cm
1
becomes broad and strong along with the shift to
shorter wavelengths. Most of the oil in the waste wa-
ter consists of hydrocarbons, which contribute to the
methyl and methylene absorptions. The vibrations at
1650 to 1600 cm
1
arise from three types of covalent
bonds including stretching vibrations of >C=O and
the stretching vibrations of C=C in alkenes or arenes.
This absorption in the untreated anthracite may be
attributed to C=C stretching in alkenes or arenes. As
to another aspect, compared to another weak peak at
2750 cm
1
, it may be inferred that >C=O is contained
in the molecular structure of the coal as arene is one
of the main components in crude oil. So the absorp-
tion here is slightly stronger after oil treatment than
before.
The absorption at 1200~1100 cm
1
results from the
bending vibrations of C-O in alcohols and may con-
firm the presence of hydrogen bonded hydroxyl along
with the absorption peak at 3450~3300 cm
1
. The
other peak at 900~700 cm
1
reflects the bending vi-
bration of aromatic and alkene moieties and grows
with increased of coalification.
The FTIR spectra reveal small differences in ab-
sorption frequency and intensity before and after
treatment. While there was no new characteristic ab-
sorption detected we can infer that the oil absorption
mechanism consists of two kinds: a physical process
assisted by chemical one.
5 Conclusions
1) The results of this work show that coal type and
particles size are important factors that significantly
affect the absorption of oil from waste water. The
absorption capacity of anthracite is larger than that of
the lean coal or the lignite for all particle sizes tested.
For each kind of coal, the absorption capacity of the
fine fractions is larger than that of the coarse frac-
tions.
2) The time to reach equilibrium absorption is
longer for lean coal and lignite than for anthracite.
The absorption capacity of anthracite decreases gra-
dually as the pH value of the mixture increases. In
practical terms the effect of pH is negligible. Oil ad-
sorption on anthracite follows the Freundlich iso-
thermal adsorption law.
Acknowledgements
The authors are grateful to the Science and Tech-
nology Fund of China University of Mining & Tech-
nology (No.2006A019) and the National Natural
Science Foundation of China (No.50974119) for their
support of this project.
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