Chemical Engineering Journal 171 (2011) 350–356

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Preparation of a new inorganic–organic composite flocculant used

in solid–liquid separation for waste drilling fluid
Jing Zou, Hong Zhu ∗ , Fanghui Wang, Haiyun Sui, Jiantao Fan
Department of organic chemistry, Institute of Modern Catalyst, State Key Laboratory of Chemical Resource Engineering, School of Science,
Beijing University of Chemical Technology, 15 Beisanhuan East Road, Beijing 100029, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, a new inorganic–organic composite flocculant CSSAD was prepared by the reaction of corn
Received 23 February 2011 starch (st), acrylamide (AM), and (2-methacryloyloxyethyl) trimethyl ammonium chloride (DMC) with
Received in revised form 29 March 2011 a previously prepared SiO2 sol by using the aqueous solution polymerization process. The different fac-
Accepted 30 March 2011
tors affecting the preparation were investigated and the optimal synthesis conditions were established:
polymerization temperature was 70 ◦ C, reaction time was 4 h, w(DMC):w(st) was 1.5, w(AM):w(st) was
Keywords:
3, and the ratio of initiator to acrylamide was 0.5 wt.%. CSSAD was characterized by FTIR spectroscopy,
Flocculant
scanning electron microscopy, and gel permeation chromatography. The different factors affecting the
Waste drilling fluid
Starch
flocculating ability of CSSAD for waste drilling fluid were studied. These factors included the dose, stirring
Acrylamide rate, and time. When the dosage of CSSAD was 0.3 g (per 100 g waste drilling fluid) with a stirring rate of
Water content 60 r/min and a stirring time of 2 min, the water content of the flocculated precipitate was the lowest at
Weight removal 21.34%. And CSSAD showed better flocculating ability than other flocculants in the same dose (0.3 wt.%).
Crown Copyright © 2011 Published by Elsevier B.V. All rights reserved.

1. Introduction
It is well know that solid–liquid separation by flocculation is an
important process for waste water treatment, sludge dewatering,
and pulp and paper production, as well as in the pharmaceutical,
cosmetics, and metal working industries [1]. In this process, floc-
culants are used to aggregate colloidal particles and regulate the
stability and flocculation properties of the disperse system [2].
Generally, the flocculants used in water treatment can be clas-
sified into three groups: inorganic flocculants, such as alum, ferrite
flocculants, or polyaluminium chloride; synthetic organic floccu-
lants, such as polyacrylamide derivatives; and naturally occurring
flocculants, such as sodium alginate or microbial flocculants [3].
In addition, natural polymer derivatives, such as starch deriva-
tives [4–9]; starch and chitosan crosslinking copolymer [10]; humic
acid [11]; and inorganic–organic complexes, such as Al(OH)3 -
polyacrylamide [12], can be used as flocculants to good effect. The
flocculation of suspensions depends critically on some physico-
chemical factors including particle size and distribution, particle
concentration, pH and ionic strength of the suspending medium,
molecular weight and charge density of the flocculants [4]. But
some researches indicated that the most important factors affect-
ing the flocculation are the nature of adsorption of the polymer on
∗ Corresponding author. Tel.: +86 1064444919; fax: +86 1064444919.
E-mail address: zhuho128@126.com (H. Zhu).
the particles surface and the conformation of the adsorbed polymer
[13–15].
Starch is one of the most abundant and cheapest natural materi-
als used widely in the world. In its crude form, starch is a mixture of
two polymers of anhydroglucose units: amylase and amylopectin.
Starch can be chemically modified and converted into flocculants
by substituting some of the OH− groups in the anhydroglucose
monomer units with ionic functional groups. In particular, cationic
starch derivatives have wide applications in the fields of paper
making, petroleum well drilling, medicine, daily chemicals, and
flotation [16–18]. In this study, corn starch was used to synthe-
size one new flocculant and to reduce the cost of the treatment of
waste drilling fluid.
A special problem in the oil drilling field is the disposal of large
quantities of waste drilling fluids. This disposal has proven to be one
of the most difficult environmental problems in the world because
waste drilling fluids are made up of minerals, clay, organic materi-
als, etc., and the chroma is deep. There has not been any effective
method to treat these fluids. Many inorganic and organic polymer
flocculants have been used to flocculate the suspended solids in
the waste drilling fluids, but the effect is poor. The objective of
this work was to prepare a flocculant of a combination of SiO2
with starch grafted acrylamide and DMC (named CSSAD) and to
examine the flocculation performance in the waste drilling fluids.
This flocculant was first prepared by in situ polymerization in our
laboratory. Different factors affecting the preparation were investi-
gated, i.e. mass ratio of DMC to corn starch, mass ratio of acrylamide

1385-8947/$ – see front matter. Crown Copyright © 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.03.100
 J. Zou et al. / Chemical Engineering Journal 171 (2011) 350–356 351

Table 1 flask with the solution being cooled to room temperature, 0.1 g/mL
Basic characteristics of waste drilling fluid.
hydrochloric acid was added to the solution to adjust the pH to 7.
Item Numerical value

Density (g/mL) 1.62 2.2.1.3. Preparation of CSSAD. The preprepared SiO2 sol and starch
Apparent viscosity (mPa s) 36.50 solution were added to a 250-mL flask under stirring, and nitro-
Plastic viscosity (mPa s) 26.70 gen was purged into the solution to remove the dissolved oxygen.
Dynamical cutting force (Pa) 9.80 Different doses of acrylamide and DMC were used. Then, the flask
Solid content (%) 54.40
Oil content (%) 5.00
was placed in a thermostatted water bath, and different doses of
pH 11.64 potassium persulfate as the initiator after dissolved in 10 mL water
were titrated into the flask. Then, the flask was kept in the ther-
mostatted water bath at some temperatures from 50 ◦ C to 80 ◦ C for
and corn starch, mass ratio of initiator to acrylamide, polymerize 2–7 h. Then, the solution in the flask was transferred to a 250 mL
reaction temperature and time, and moreover, some factors affect- beaker and precipitated and washed with ethanol and acetone. The
ing the flocculation properties were studied, such as the dosage of precipitate was extracted for 12 h by using an ethanol:acetic acid
CSSAD, stirring rate and time. mixture (40:60 V/V), and finally dried in a vacuum drying oven at
40 ◦ C for 24 h.
2. Materials and methods
2.2.2. Flocculation experiments
2.1. Materials The flocculation experiments were conducted at room tempera-
ture. Waste drilling fluid (100 g) was added to a 250 mL beaker, the
Sodium hydroxide, hydrochloric acid, acrylamide (AM), potas- pH of the fluid was adjusted to 7.0–8.0 with dilute HCl, and differ-
sium persulfate, acetone, ethanol, magnesium chloride, and ent amount (0–8 mL) of 20 wt.% MgCl2 or 5 wt.% AlCl3 solution as
aluminium chloride were of analytic grade and supplied by Bei- gel breakers were then added under vigorous stirring for 10 min.
jing Chemistry Reagent Co. Ltd. Corn starch was supplied by Rapid mixing provides a good dispersal of the gel breaker and
Shandong Jincheng Co., Ltd., China. Water glass (modulus 3.3) is commonly associated with particulate destabilization, whereas
was supplied by Beijing Dahongmen Chemical Materials Co. (2- slow mixing is believed to optimize floc growth by limiting the
methacryloyloxyethyl) trimethyl ammonium chloride (DMC) (the breakdown of aggregates [19]. A solution of the above prepared
concentration is 78 wt.% in water) as the cationic reagent was CSSAD was added in different doses. Immediately after the addi-
bought from Le Tai Chemical Supermarket, Beijing, China. The tion of the flocculant, the fluid was stirred at different speeds
structural formula of DMC was as follows: (20–120 r/min) for different times (0.5–4.5 min). The flocs were
CH2 = C(CH3 )COOCH2 CH2 N+ (CH3 )3 Cl− then allowed to settle down for 10 min. The flocs and liquid in the
beaker were transferred to a centrifuge cup and centrifuged at a
Several flocculants, such as polyferric sulfate, polyaluminium speed of 3500 rpm for 10 min. After that, the liquid in the upper
sulfate and polyacrylamide are supplied by Shandong Taihe Water part of the centrifuge cup was poured out, and the precipitate at
Treatment Co. Ltd. The waste drilling fluid was supplied by the bottom of the cup was weighed before and after drying.
Shandong Shengli Oil Field, China. The physical and chemical char-
acteristics of the waste drilling fluid are shown in Tables 1–3. 3. Results and discussion

2.2. Methods 3.1. Effect of synthesis conditions on flocculating activity of CSSAD

2.2.1. Preparation of CSSAD We used the water content of precipitate and weight removal
2.2.1.1. Preparation of SiO2 sol. First, 1.5 mL water glass was added to describe the flocculating ability of CSSAD. The water content of
to the reaction vessel containing 30 mL deionized water under stir- precipitate and weight removal are defined as follows:
ring at room temperature. Then 0.1 g/mL hydrochloric acid solution  m1

was added dropwise to provide a pH of 7. Stirring was continued water content % = 1− × 100
m2
until a smooth colloid was formed.
 m1

2.2.1.2. Gelatinization of corn starch. To a 250-mL flask 1.5 g insol- weight removal % = 1− × 100
m2
uble corn starch and 20 mL deionized water were added under
stirring. Then 0.15 g sodium hydroxide was added in. The flask was here m1 and m2 are the weights of the flocculated precipitate after
placed in a 70 ◦ C thermostatted water bath for 30 min. After the and before drying, respectively, and m is the weight of suspended

Table 2
Pollutants of waste drilling fluid.

Number Pollutant Concentration (mg L−1 ) Number Pollutant Concentration (mg L−1 )

1 Overall Cr 1.55 6 Pb 1.2

2 Hexad Cr <0.004 7 Zn 0.12
3 Hg 0.0004 8 Cu <0.1
4 Cd 0.22 9 Content of solid 344
5 As 0.024 10 Fluoride 5.27

Table 3
Primary composition and content of solid particles in waste drilling fluid.

Mineral substance Quartz Potassium feldspar Plagioclase Calcite Dolomite Barite Clay minerals

Content (%) 10.5 – 1.6 9.3 7.3 68.8 2.5

352 J. Zou et al. / Chemical Engineering Journal 171 (2011) 350–356

a 30
34
29 98

28 32

water content / %

weight removal / %
27
water content / %

30 96
26
28
25

94
24 26
a
23 b
c 24
22 92
0 2 4 6
21 w (AM): w (st) / (g:g)
0.0 0.5 1.0 1.5 2.0 2.5

w(DMC):w(st)/(g:g) Fig. 2. Effect of ratio of AM to st on flocculating ability.

b 100
Fig. 1(a) and (b), the conditions that can meet our objective are
w(DMC):w(st) = 1.5, 5 wt.% AlCl3 as the gel breaker, and the water
96
content and weight removal were 28.77% and 95.78%, respectively.

92
3.1.2. Effect of mass ratio of acrylamide to corn starch
weight removal / %

(w(AM):w(st)) on flocculating ability of CSSAD

88 a The effect of the ratio of AM to st on water content and weight
b
c
removal is shown in Fig. 2. When the mass ratio of AM to st rose
84 from 1 to 3, the water content decreased from 33.51 to 24.10, and
the weight removal increased from 92.56 to 97.56. As the ratio of
80 AM to st rose, the degree of crosslinking and molecular weight of
CSSAD increased, the absorbing and bridging capability improved,
76 and thus the flocculating ability was enhanced. However, at dose
ratios higher than 3, the molecular weight of CSSAD became too
72 large and the solubility of CSSAD in water decreased, making the
0.0 0.5 1.0 1.5 2.0 2.5 movement of flocculant molecules difficult. The wrapping of func-
w(DMC):w(st)/(g:g) tion groups led to a decrease in flocculating ability.

Fig. 1. Effect of mass ratio of st to DMC on flocculating ability: (a) without gel
breaker; (b) 4 mL 5% AlCl3 as gel breaker; (c) 8 mL 20% MgCl2 as gel breaker.
solid in 100 g waste drilling fluid and the value is 54.4 g. The dosage
of CSSAD was 0.3% for flocculation in this study.
The effects of synthesis conditions on the water content of pre-
cipitate and weight removal of CSSAD were investigated.
3.1.1. Effect of mass ratio of DMC to st and gel breaker on
flocculating ability of CSSAD
The effect of the mass ratio of DMC to corn starch
(w(DMC):w(st)) on the water content of the precipitate was stud-
ied. Fig. 1(a) and (b) illustrate the effect of w(DMC):w(st) on the
water content of the precipitate and weight removal of the sus-
pended solid flocculated by CSSAD. Curves a, b, and c represent
the cases with no gel breaker, 4 mL of 5 wt.% AlCl3 , and 8 mL of
3.1.3. Effect of mass ratio of initiator to acrylamide
(w(K2 S2 O8 ):w(AM)) on flocculating ability of CSSAD
We used K2 S2 O8 as an initiator for the reaction system. The
effect of mass ratio of initiator to AM on water content and weight
removal is shown in Fig. 3. When the mass ratio of initiator to AM
rose from 0.1% to 0.5%, the water content decreased quickly from
35.72% to 23.67%, and the weight removal increased from 89.15%
to 98.35%. As the mass ratio of initiator to AM increased, the con-
centration of free radicals increased, thus increasing the ratio of
100
36
98
34
32 96
weight removal /%
water content / %

20 wt.% MgCl2 , respectively, per 100 g waste drilling fluid. The reac-
tion temperature, dose ratio of initiator to AM, mass ratio of st 30
94
to AM, and reaction time were 70 ◦ C, 1%, 1:2, and 3.0 h, respec-
28
tively. As w(DMC):w(st) increased from 0 to 2.5, the water content
92
increased first and then leveled off, and the weight removal also
26
increased. The lowest water content and highest weight removal
were obtained without DMC and gel breaker. Increasing the mass 90
24
of DMC can improve the weight content, but excessive DMC, which
is water soluble and hydrophilic, can largely reduce the viscosity of 22 88
the CSSAD solution and lead to a decrease of the molecular weight 0.1 0.2 0.3 0.4 0.5 0.6 0.7
of CSSAD and increase the water content of the precipitate of floc- w (K2S2O8) : w (AM)/(g:g)
culation. Our objective was to obtain a low water content (<30%)
and a high weight removal (>90%) at the same time. As shown in Fig. 3. Effect of mass ratio of initiator to AM on flocculating ability.
 J. Zou et al. / Chemical Engineering Journal 171 (2011) 350–356 353

45
32
98

30 40
96

weight removal / %
28
water content / %

35

water content / %
94
26

30
24 92

25
22
90

20
20
0 2 4 6
reaction time / h
0.1 0.2 0.3 0.4 0.5 0.6
Fig. 4. Effect of reaction time on flocculating ability. dosage of CSSAD / g

Fig. 6. Water content as a function of usage of CSSAD on flocculation of waste drilling

grafting and the molecular weight of CSSAD. However, when the fluid.
mass ratio of initiator to AM was higher than 0.5%, the flocculat-
ing ability of CSSAD decreased. One possible explanation is that
and 4 h, respectively. The flocculating ability increased as the reac-
the excessive initiator first enhanced monomer homopolymeriza-
tion temperature increased from 50 ◦ C to 70 ◦ C, reached a peak
tion, but then the probability of the termination of free radicals
value at the temperature of 70 ◦ C, and decreased thereafter. As the
increased, thus reducing the molecular weight of the flocculant.
reaction temperature increased, the reaction efficiency as well as
the degree of substitution of starch and the molecule weight of
3.1.4. Effect of polymerization reaction time on flocculating
the reaction product increased. Hence, the flocculating ability of
ability
CSSAD improved. The decrease in flocculating ability at tempera-
Six different reaction times from 1 h to 6 h were evaluated to
tures higher than 70 ◦ C can be explained as follows: the molecular
study the effect of reaction time on flocculating ability of CSSAD,
chains of CSSAD may break at high temperatures, leading to a
and the results are shown in Fig. 4. The mass ratio of starch to AM,
macromolecular configuration that cannot provide valid bridges
mass ratio of DMC to st, dose ratio of initiator to AM, and reaction
between suspended particles.
temperature were 1:3, 1.5:1, 0.5%, and 65 ◦ C, respectively. The floc-
culating ability increased with increasing reaction time between
3.2. Evaluation of CSSAD
1 h and 4 h and decreased with increasing reaction time thereafter.
With the extension of reaction time, the reaction efficiency and the
3.2.1. Effect of the dosage of CSSAD and contact time on
molecular weight of the product increased until the reaction was
flocculating ability of CSSAD
terminated by the hydrolysis of reaction monomers, such as starch
The addition of CSSAD to the waste drilling fluid leads to attrac-
and DMC.
tion between the flocculant molecules and the suspended particles.
The flocculant molecules attached to the suspended particles still
3.1.5. Effect of polymerization reaction temperature on
have free active centers that could be adsorbed on the remaining
flocculating ability
free surface of other solid particles. This process results in bridging
The reaction temperature was varied from 50 ◦ C to 80 ◦ C to eval-
between solid particles and in the consequent formation of large
uate the flocculating ability of CSSAD, and the results are shown in
flocs having a three-dimensional network structure [7]. The floc-
Fig. 5. The mass ratio of st to AM, mass ratio of DMC to starch,
culation depends on several factors, such as the rate of transport
dose ratio of initiator to AM, and reaction time was 1:3, 1.5:1, 0.5%,
of polymer molecules to the suspended particles in the fluid, the
rate of adsorption of macromolecules on the surface, the time scale
100 necessary for the polymer layer to reach equilibrium, the rate of
34 aggregation of particles having adsorbed polymers, and the fre-
98 quency of collisions of particles with adsorbed polymer to form
32 flocs.
96 Fig. 6 shows the water content of precipitate as a function of the
water content / %

weight removal / %

30
usage of CSSAD at room temperature. The dosage of the flocculant is
94 mainly related to the content of suspended solids in the fluid, and
28
the flocculating effect generally tends to be better with increas-
92 ing usage of flocculant. However, the flocculating effect reaches a
26
maximum and then decreases with further increases in the usage
90
of the flocculant. As shown in Fig. 6, the water content of precipitate
24
first decreased and then increased with increasing dosage of CSSAD.
When the dosage of CSSAD was 0.3 g (per 100 g waste drilling fluid),
22 88
the water content was the lowest at 21.34%. If the dosage of CSSAD
45 50 55 60 65 70 75 80 85 was excessive, the waste drilling fluid would regenerate a stable
reaction temperature / °C system that cannot reach the purpose of solid–liquid separation.
Fig. 7 shows the variation of flocculation efficiency with time for
Fig. 5. Effect of reaction temperature on flocculating ability. different initial flocculant concentrations at the room temperature.
354 J. Zou et al. / Chemical Engineering Journal 171 (2011) 350–356

Table 4
Comparison of flocculation performance between polyferric sulfate, polyaluminium sulfate, polyacrylamide, and CSSAD.

Performance Flocculant

Polyferric sulfate Polyaluminium sulfate Polyacrylamide CSSAD

Water content (%) 35.36 34.67 32.16 21.30

Weight removal (%) 96.48 98.53 89.72 98.15

Table 5
Analytical results of GPC.

Max. RT Start RT End RT Flow rate correction Mp Mn Mw

10.91 8.73 15.80 1.00 1,103,130 598,212 1,010,008

Height (mV) Height (%) Area (mV s) Area (%) Mz Mv Mw/Mn Mz/Mn

8.81 100.00 1160.41 100.00 1,365,776 955,307 1.69 2.28

The flocculation rate of CSSAD was found to be very high during 32

the initial 1 min and thereafter the flocculation of the copoly-
mer slowed down. No distinct change in the flocculation rate of
30
the copolymer was observed after 3 min. In other words, a quasi-
equilibrium state was reached after 3 min contact time. Since the
time of flocculation in our experiments was 3 min, the adsorption 28

water content / %
of CSSAD on suspensions in waste drilling fluid can be assumed to
be close to the equilibrium adsorption condition. As a result, 3 min
26
can be considered the equilibrium time for maximum adsorption
of flocculant.
As shown in Fig. 7, the weight removal increased with increasing 24
initial CSSAD concentration. The weight removal increased from
80.47% to 97.43% by increasing the initial CSSAD concentration
22
from 0.1 wt.% to 0.4 wt.%. The result indicates that the adsorption of
CSSAD is fast at the initial stages of the treatment time and becomes
slower near the equilibrium state. 20
20 40 60 80 100 120
-1
stirring rate / (r·min )
3.2.2. Effect of stirring rate and time on flocculating ability of
CSSAD Fig. 8. Water content of precipitate as a function of stirring rate.
Figs. 8 and 9 show the variations of water content of precipitates
with stirring rate and time, respectively, at the room temperature.
An appropriate stirring rate and time can be propitious to exe- stirring rate is too slow and the stirring time too short, the floc-
cute the flocculant function, accelerate the flocculating process, and culant cannot be dispersed well in the waste drilling fluid and in
enhance the flocculating effect. When the stirring rate is too rapid adequate contact with the colloid particles, resulting in failure of
and the stirring time too long, large precipitated colloid particles the particles in the waste drilling fluid to join with each other and
can be broken down into small particles that cannot be precipitated, the flocculant to catch more particles. As shown in Figs. 8 and 9,
and as a result the flocculating effect was decreased. But when the the water content first decreases and then increases with the

100 34
95
32
90

85 30
weight removal / %

water content / %

80
28
75

70 0.1%
26
0.2%
65 0.3%
60
0.4% 24

55
22
50
20
0 50 100 150 200 250 300
0 1 2 3 4 5
time / s
stirring time / min
Fig. 7. Weight removal of CSSAD on flocculation of waste drilling fluid as a function
of time. Fig. 9. Water content of precipitate as a function of stirring time.
 J. Zou et al. / Chemical Engineering Journal 171 (2011) 350–356
12
10
y=-0.28047x + 9.10207
8
Voltage / mV
4
0 b
0 5 10 15
t / min
Fig. 10. GPC of CSSAD.
increase of stirring rate and time, and the water content reached
a minimum at a stirring rate of 60 r/min and a stirring time of
2 min.
3.3. Comparison of flocculation performance between polyferric
sulfate, polyaluminium sulfate, polyacrylamide, and CSSAD
A comparison of the flocculation performance between poly-
ferric sulfate, polyvaluminium sulfate, polyacrylamide, and CSSAD
for waste drilling fluid was made. The dose of the four floc-
culants was 0.3 wt.% each. The results are shown in Table 4. It
can be seen that CSSAD has the best performance of weight
removal, and its performance of water content is just sec-
ond to that of polyaluminium sulfate. CSSAD is considered to
be a strong and effective flocculant for waste drilling fluid
because it has the integrated properties of inorganic and organic
flocculants.
3.4. GPC, FTIR and SEM analyses
We used gel permeation chromatography (GPC) to analyze the
molecular structure of CSSAD. The results obtained are shown in
Fig. 10 and Table 5.
The CSSAD and starch samples were dried and pressed into pel-
lets together with potassium bromide (KBr) to be used for FTIR
studies. The FTIR spectra of starch and CSSAD are shown in Fig. 11.
Fig. 11a shows the FTIR spectrum of corn starch. The broad band
at 3406 cm−1 was due to the stretching mode of the O–H groups
in the backbone of corn starch. The intense band at 1657 cm−1
Fig. 12. SEM micrographs of (a) corn starch and (b) CSSAD.
355
10
8
log M
6
4 a
20
4500 4000 3500 3000 2500 2000 1500 1000 500
-1
μ / cm
Fig. 11. FTIR spectra of corn starch and CSSAD: (a) corn starch; (b) CSSAD.
was assigned to the first overtone of O–H bending vibration. The
bands at 1157 cm−1 and 2932 cm−1 were assigned to C–O stretch-
ing and C–H stretching, respectively. The bands at 1010 cm−1 and
1084 cm−1 were attributed to CH2 –O–CH2 stretching vibrations.
Fig. 11b shows the FTIR spectrum of CSSAD. The broad peak at
3423 cm−1 was due to O–H stretching vibration. The two strong
bands at 2930 cm−1 and 1157 cm−1 were due to C–H stretching and
C–O stretching vibration, respectively. The bands at 1670 cm−1 and
1615 cm−1 were attributed to C O stretching vibration and –NH2
blending vibration, respectively. The two bands at 1010 cm−1 and
1084 cm−1 were attributed to CH2 –O–CH2 stretching vibrations.
The bands at 850 cm−1 and 1080 cm−1 were assigned to Si–O
stretching vibrations. The band at 1411 cm−1 was assigned to C–N
stretching vibration. These results confirm the incorporation of
SiO2 , AM, and DMC groups onto the backbone of the starch.
The FTIR results were verified by SEM observations. Scanning
electron microscopy (SEM) was used to investigate the surface mor-
phology of starch and CSSAD. The SEM photographs of corn starch
and CSSAD are shown in Fig. 12. It is obvious that the surface of
CSSAD was ragged and larger than that of the corn starch, which
had a smooth surface. The molecular chains of the components in
CSSAD were connected to form a network structure, promoting the
adsorption and bridging performance of CSSAD as a flocculant for
waste drilling fluid.
356 J. Zou et al. / Chemical Engineering Journal 171 (2011) 350–356
4. Conclusion
A novel flocculant CSSAD with high flocculation performance
on waste drilling fluid based on corn starch and water glass
was prepared for the first time in our laboratory. The follow-
ing optimal synthesis conditions were confirmed: polymerization
temperature was 70 ◦ C, reaction time was 4 h, w(DMC):w(st)
was 1.5, w(AM):w(st) was 3, and the ratio of initiator to acry-
lamide was 0.5 wt.%. CSSAD had better flocculating ability at
room temperature than other inorganic and organic floccu-
lants in the same dose (0.3 wt.%) for the waste drilling fluid.
When the dosage of CSSAD was 0.3 g (per 100 g waste drilling
fluid) with a stirring rate of 60 r/min and a stirring time of
2 min, the water content of the flocculated precipitate was the
lowest at 21.34%.
Acknowledgment
The authors gratefully acknowledge the financial supports from
National Hi-Tech Research and Development Program of China
(863program) (2008BAC43B02).
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