Kinetic Study of Adsorption of Oil from Oilfield Produced Water Using
Modified Porous Ceramics Filtration Media in Column Mode
Fangwen Lia , Xiaoai Wua ,Jianfeng Wub , Xiaohong Xub , Songjiang Maa
a
School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201,
P.R. China
b
School of Materials Science and Technology, Wuhan University of Technology, Wuhan 430074, P.R. China
E-mail: lifangweng1@126.com
Abstract
Adsorption kinetic for oil in the oilfield produced water
(OPW) onto modified porous ceramics filtration media
(MPCFM) in fixed bed column was studied. Porous filtration
media was modified with containing hydrogen silicone oil
(CHSO). The effects of important parameters, such as filtering
velocity, initial oil content and filtering layer thickness, on oil
removal were discussed. The experimental column data were
fitted to Yoon and Nelson model equations using linear
regressive analysis, next, kinetic parameters were figured out
and oil removal mechanism was analyzed. All the results
suggested that reducing filtering velocity, increasing oil
content and filtering layer thickness make for oil removal, and
mechanism of oil adsorption removal be wetting adsorption
coalescence. Farther, adsorption of oil onto filtration media
followed Yoon and Nelson kinetic model well by entirely
fitting (at low and middle oil content) or stepwise fitting (at
high oil content).
Keywords: Modified porous ceramics filter media, oilfield
produced water, adsorption kinetic, breakthrough curve
1. Introduction
Oilfield produced water is dehydrated water which
originates from dewatering process of output fluid in various
oil beds. At present, many oilfields adopt to water reinjection
process to drive oil from strata in China. In order to prevent
formation plugging and pipeline jam, content of oil and
suspended solids in OPW must be reduced and meet with
definite standards before reinjection. Although various
treatment techniques have been employed to treat OPW,
including membrane separation process, hydrocyclone
technology, adsorption process, air floatation process,
biological process, etc., most of these methods suffer from
some drawbacks such as ineffective, expensive, difficult to be
regenerated and ineffectiveness for emulsified oil. In recent
years, coalescence filtration composite process based on low-
cost lipophilic adsorption materials such as fiber ball and
walnut shell has been widely used owing to better efficiency
than foregoing process. However, fiber ball and walnut shell
978-1-4244-1748-3/08/$25.00 © 2008 IEEE
possess themselves deficiency, for example, lower mechanical
strength, shorter run life and difficulty in surface adsorptive
oil removal by backwashing. Hence, there is a crucial need for
new lipophilic adsorption coalescence materials.
For this reason, porous ceramic filtration media on the
basis of red mud were modified and treatment efficiency for
oil removal in OPW was investigated in fixed-bed column.
The present study aims at kinetics of oil removal in column
and the Yoon and Nelson model is used to describe it with
linear regressive analysis. Furthermore, kinetic parameters
were figured out and oil removal mechanism was analyzed.
2. Materials and methods
2.1. Materials
Porous ceramics filtration media were prepared whose
major raw materials were mud, fly ash, coal gangue and poor
clay which came from a certain large-sized mining industry
[1]. At the same time, appropriate amount pore forming agent,
forming accessory ingredient and sintering accessory
ingredient were added to regulate porosity, plasticity and
strength, respectively. Compared with common quartz sand
filter, porous ceramics filtration media have excellent
performances which include higher mechanical strength,
longer filtration cycle and better effluent quality. These
properties make up drawbacks of fiber ball and walnut shell
just. CHSO was chose as lipophilic modifier and oilfield
produced water came from Jianhan Oilfield of China.
2.2. Methods
2.2.1. Modification of porous ceramics filtration media. As
demonstrated [2], porous ceramics filtration media were
modified in that its surface is hydrophilic and not strong
enough for oil to be adsorbed. According to the same
preparation process as filtration media, patch matrixes for
contact angle test with droplet camera shooting were made.
2.2.2. Removal and determination of oil. MPCFM were
packed into an acid type burette (1.068cm inner diameter and
75cm in height). At the bottom of burette, quartz sands were
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laid as supporting layer whose thickness was 2cm, and on the
top, a separating funnel whose volume was 125ml was put. So,
filtering velocity of the fixed column may be controlled by
piston of separating funnel and burette. The temperatures of
all experiments were 298K. Samples were collected at regular
intervals in all the adsorptive process. The content of oil in the
effluent was analyzed using an infrared spectrophotometry oil
meter (JDS-109U, China).
2.2.3. Adsorption kinetic models. In adsorption process,
batch study has been widely researched whose kinetics is
described with pseudo first order kinetic model and pseudo
second kinetic model. But most of actual applications are
column adsorption whose kinetic models include Thomas
model[3] 、 Yoon and Nelson model[4] 、 Adams—
Bohartmodel[5]、Clark model[6]. Of which, the Yoon and
Nelson model not only is less complicated than other models,
but also requires no detailed data concerning the
characteristics of adsorbate, the type of adsorbent, and the
physical properties of adsorption column. Therefore, it is
widely used. The Yoon and Nelson model has the following
form:
Ct exp(τ KYN − KYN t )
= (1)
C0 1 + exp(τ KYN − KYN t )
Where KYN is the rate constant(min -1
); τ
,the time required for
50% adsorbate breakthrough(min) and t is the
breakthrough(sampling)time(min);C0 is the influent oil
content(mgl-1);Ct is the effluent oil content(mgl-1).
The linear form of the Yoon and Nelson model is as
follows:
Ct
ln = KYN t − τ KYN (2)
C0 − Ct
The values of KYN and τ can be determined from lnCt/
(C0-Ct) against t using linear least-square regressive analysis.
In order to confirm the fit model for the adsorption system,
it is necessary to analyze the data using error analysis,
combining the values of determined correlation coefficient (R2)
from regressive analysis. The Chi-square statistic test which
expresses the differences between the experimental data and
data obtained by calculating from model is used. The relative
mathematical formula is
(τ exp − τ theo )2
x2 = ∑ (3)
τ theo
Where τ exp is the time for Ct/C0 equal to 0.5 from
experiment (min); τ theo is the time for Ct/C0 equal to 0.5 from
model (min). If data from the model are similar to the
experimental data, x2 will be a small number; if they are
different, x2 will be a large number.
3. Results and discussion
The performance of packed column is described through
the concept of the breakthrough curve that is plotted-giving
ratio of effluent and influent concentrations (Ct/C0) and time
(min) for varying operating conditions. The time for
breakthrough appearance and the shape of the breakthrough
curve are very important characteristics for determining the
operation and the dynamic response of a column.
3.1. Effect of modification on wettability of filtration
media
Wetting is a phenomenon occurring on the interface
between solid and liquid, namely, gas of solid or liquid
surface is replaced by liquid. Because porous ceramics
filtration media own higher surface energy, they are modified
by CHSO in order that oil may be wetting and spreading on
the surface of MPCFM. After modification , the contact angle
of patch matrixes to water augmented from 25° to 138° and
lipophilicity of MPCFM surface was improved obviously,
which induced that dispersed oil in OPW was able to wet and
spread surface of MPCFM. MPCFM were encircled by oil in
this way, which provided convenience to wetting and
adsorption of subsequent oil. Consequently, coalescence of
oil on MPCFM brought to success.
3.2. Effect of filtering velocity on breakthrough
curve
1.0
10mh
-1
15mh
-1
0.8
-1
20mh
0.6
C t\C0
0.4
0.2
0.0
0 10 20 30 40 50 60
Ti me /min
Figure 1. Breakthrough curves for oil
adsorption at different filtering velocity
Fig.1 showed breakthrough curves when filtering velocity
was 10mh-1, 15mh-1 or 20mh-1, at pH value of 6.8, at initial
oil content of 18.9243mgl-1 and at filtering layer thickness of
450mm, respectively. It was seen from Fig.1 that filtering
column was apt to breakthrough with increase of filtering
velocity. When at a low filtering velocity, oil had more time
to contact with MPCFM and it resulted in higher removal of
oil from OPW in column. Other than breakthrough curves
(which exhibit a characteristic “S” shape.) of conventional
sorbents such as activated carbon and zeolite, the slope of
breakthrough curves in Fig.1 at initial time was very steep,
which revealed that surface wetting adsorption was major
adsorption mechanism and there was not adsorption zone
moving down by layer. Thus, all MPCFM in column were
wetted by oil and oil not being wetted, adsorbed and
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intercepted by MPCFM was discharged. On the other side,
when wetting adsorption oil of MPCFM surface coalesced to
some size and thickness, it would fall off at water flow
impact and were intercepted between filtration media. The
size of oil drop fallen off was bigger in low filtering velocity
than in high filtering velocity because effect of water flow
impact was different. Fatherly, bigger oil drop was more
prone to be intercepted. It was one of reasons that filtering
column was apt to breakthrough at high filtering velocity.
3.3. Effect of initial oil content on breakthrough
curve
The effect of influent oil content on the shape of the
breakthrough curves at pH value of 6.8, at filtering velocity
of 15mh-1 and at filtering layer thickness of 450mm was
shown in Fig.2. As shown in Fig.2, in interval of 30min, the
value of Ct/C0 reached 0.7462, 0.6593 and 0.3684 when
initial oil content was 8.5621, 18.9243 and 53.6989mgl-1,
respectively.
1.0
-1
8.5621mgl
-1
18.9243mgl
0.8 -1
53.6989mg
0.6
Ct/C0
0.4
0.2
0.0
0 10 20 30 40 50 60
Ti me /min
Figure 2. Breakthrough curves for oil
adsorption at different initial oil content
It was clear that effect of concentration gradient on
breakthrough curve was opposite to effect on conventional
breakthrough curve. The breakthrough time increased with
increasing initial oil content, and the fact that oil removal rate
increased at initial and metaphase run and it deduced at
telophase run further revealed that adsorption mechanism of
oil onto MPCFM was wetting adsorption coalescence. The
reasons were that oil drops were more apt to wetting
adsorption coalescence at high oil content and coalescence
speed was faster also. The explanation was approved by data
from Table 1 as well. At initial oil content of 53.6989mgl-1,
the Yoon-Nelson rate constants are 0.04887min-1(Entirely
linear fitting), 0.01029 min-1(Stepwise linear fitting) and
0.12446 min-1(Stepwise linear fitting), which are above rate
constants at initial oil content of 8.5621mgl-1 and
18.9243mgl-1. At the same time, rapid detachment of bigger
oil drops from MPCFM surface at telophase run brought out
more oil intercepted between MPCFM, which accelerated
breakthrough of filter column.
3.4. Effect of filtering layer thickness on
breakthrough curve
To investigate the effect of layer thickness on oil
adsorption, filtering velocity, initial oil content and pH were
held constant at 15mh-1, 18.9243mgl-1 and 6.8, respectively.
The breakthrough curves were shown in Fig.3. It was found
from Fig.3, in the interval of 30min, that the value of Ct/C0
reached 0.6757, 0.6593 and 0.2353 when filtering layer
thickness was 350mm, 450mm and 550mm, respectively.
1.0
350mm
450mm
0.8
550mm
0.6
Ct/C0
0.4
0.2
0.0
0 10 20 30 40 50 60
Ti me /min
Figure 3. Breakthrough curves for oil
adsorption at different filtering layer thickness
It was shown that breakthrough generally occurred more
slowly with higher filtering layer thickness. The reason was
that it had more MPCFM surface to contact with oil. At
550mm, breakthrough curve rose gently in whole run and oil
content of effluent was significantly lower than that of
effluent at other filtering thickness height, which disclosed a
critical height being at current operation parameters.
3.5. Kinetics parameters of the Yoon and Nelson
model
Data in Fig.1, Fig.2 and Fig.3 were fitted to the Yoon and
Nelson model by Origin7.0 using linear regressive analysis.
Table 1 listed the model parameters of the Y-N model and
values of R2, x2 and τ exp. The value of τ exp was determined
from Fig.1, Fig.2 and Fig.3.
As shown in Table 1, except for the experiment at initial
oil content of 53.6989mgl-1, the correlation coefficients of all
other experiments were larger than 0.90, showing that
adsorption of oil onto MPCFM followed Y-Nelson model
well.
The values of τ theo could also explain effect of operation
parameters on breakthrough curves. In Table 1, when
filtering velocity increased from 10mh-1 to 20mh-1, the value
of τ theo deduced from 27min to 0.9min. The same
conclusion as 3.1 was drawn that filtering bed was apt to
breakthrough with filtering velocity increasing. When initial
oil content rose from 8.5621mgl-1 to 53.6989mgl-1, the value
of τ theo rose from -9.6min (Negative value showed that the
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values of τ theo exceeded 0.5 once run) to 33.9min also.
When filtering lay thickness increased from 350mm to
550mm, the values of τ theo increased from 5.6min to 58min.
The conclusion that oil content and filtering lay thickness
increase were beneficial to oil removal could be achieved,
which was also in accordance with foregoing research.
Fig.4 showed linear fit to high oil content with the Yoon
and Nelson model. The solid black line expressed linear
fitting to the Y-N model at whole run, and actually measured
data were deviation from fitting line, which revealed that
fitting effect was not good at whole run. The value of R2 and
x2 in Table 1 expressed the same idea. Fortunately, date may
be fitted with grading, including anterior forty minutes and
posterior twenty minutes, whose correlation coefficient were
0.91145 and 0.9398. So, the fitting effect with grading was
good, and reasons were that oil onto MPCFM had completed
the processes of wetting, adsorption, coalescence and release
in forty minutes at high oil content. Then, next process
began. Because surface properties of MPCFM during the two
processes, such as wettability and isoelectric point, were
different, difference of kinetic parameters with grading fitting
was resulted in.

Table 1. Kinetics parameters by linear regression analysis with the Yoon and Nelson model
Initial oil content（ Filtering velocity（ Filtering lay KYN τ theo τ exp R2 x2
mgl-1） mh-1） thickness（mm） (min-1) (min) (min)
18.9243 10 450 0.04896 27.0 30.5 0.94637 0.4537
18.9243 15 450 0.02384 3.2 2.7 0.96401 0.07813
18.9243 20 450 0.03591 0.9 0.6 0.90765 0.10
8.5621 15 450 0.02673 -9.6 -- 0.9997 --
18.9243 15 450 0.02384 3.2 2.7 0.9640 0.07813
53.6989 15 450 0.04887 33.9 45 0.7070 3.6345
18.9243 15 350 0.03375 5.6 0.9 0.9243 4.11
18.9243 15 450 0.02384 3.2 2.7 0.9640 0.07813
18.9243 15 550 0.05302 58.0 57.4 0.9597 0.0062
3.0 protection from solid wastes”, Journal of Ceramics, China,
♦ Actually measured data
2.5 Solid line Linear fitting to the Y-N model at whole run
Aug. 2003, vol.24, no.4, PP.197-200.
Dash line Linear fitting to the Y-N model at anterior forty minutes
2
2.0 Dot line Linear fitting to the Y-N model at posterior twenty minutes
[2] LI Fangwen, WU Jianfeng, XU Xiaohong, et al, “Impact of
1.5
Heat Treatment in Shuttle Kiln on Solidification of Oleophilic
Modification of Porous Ceramics Filter Ball”, Materials
ln(Ct/C0-Ct)

1.0
Review, China, May.2007, Vol.21,Special, PP.230-233.
0.5

0
0.0
[3] H.C.Thomas, “Heterogeneous ion exchange in a flowing
system”, J.Am.Chem.Soc, 1944, Vol.66, PP.1664-1666.
-0.5

-1.0 [4] Yoon YH, Nelson JH, “Application of gas adsorption

10 20 30 40 50 60
kinetics.1.A theoretical model for respirator cartridge service
Ti me/ mi n
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Figure 4. Linear fitting of Yoon and Nelson
kinetic model at high oil content [5] Texier AC, Andres Y, Faur-Brasquet C, et al., “Fixed-bed study
for lanthanide(La, Eu, YB) ions removal from aqueous
4. Conclusion solutions by immobilized Pseudomonas aeruginosa:
experimental data and modelization”, Process Biochem, 2002,
(a) MPCFM was found to be an effective adsorbent for Vol.47, PP.333-342.
removal of oil from OPW.
(b) The removal efficiency of oil was increased when [6] Tran HH, Roddick FA, “Comparison of chromatography and
desiccant silica gels for the adsorption of metal ions”, Water
reducing filtering velocity, increasing oil content and
Res, 1999, Vol.33, PP.3001-3011.
filtering layer thickness.
(c) The Yoon and Nelson mathematical model adequately
described the adsorption of oil onto MPCFM. Shape and
property of breakthrough curves showed that mechanism of
oil removal was wetting adsorption coalescence, including
wetting adsorption, coalescence, release and interception.

5. References
[1] Xu Xiaohong, Di Yongjiang, Wu Jianfeng, et al, “Study on
porous ceramic filtration materials for environmental

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