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Front. Mater. Sci.

China 2008, 2(1): 105112


DOI 10.1007/s11706-008-0019-3

RESEARCH ARTICLE

Preparation of H-oleoyl-carboxymethyl-chitosan and the


function as a coagulation agent for residual oil
in aqueous system
Gang-zheng SUN1, Xi-guang CHEN (*)1, Yan-yan LI1, Bo ZHENG2, Zheng-hui GONG3, Jian-jun SUN3,
Heng CHEN3, Jie LI3, Wen-xing LIN3
1 College of Marine Life Science, Ocean University of China, Qingdao 266003, China
2 Materials and Equipments Supplying Department, GuDao Oil Plant, Shengli Oil Field of China, Dongying 257231, China
3 Technology, Quality and Safety Supervision Center, GuDao Oil Plant, Shengli Oil Field of China, Dongying 257231, China

E Higher Education Press and Springer-Verlag 2008

Abstract In this study, H-form oleoyl-carboxymethyl- waste-water treatments. There are a number of different
chitosan (H-O-CMCS) was prepared as a coagulation mechanisms involved in the coagulation process, includ-
agent to clean up the residual oil from the waste-water ing ionic layer compression, adsorption and charge
of oil extraction (WWOE). The Fourier transform infra- neutralization, inter-particle bridging, and sweep coagu-
red (FTIR) spectra confirmed the formation of an amide lation [4].
linkage between amino groups of carboxymethyl chitosan In conventional waste-water treatment systems, com-
(CMCS) and carboxyl groups of oleic acid. The adsorp- mon industrial coagulants, e.g. polyacrylamide (PAM),
tion capacities of four absorbents (H-O-CMCS, chitosan, polyaluminium chloride (PAC) and aluminum sulphate,
activated carbon and polyaluminium chloride (PAC)) for are widely used because they are effective, cheap and
the residual oil were investigated. Compared with chit- easy to handle [5]. PAC is the most extensively used
osan, activated carbon and PAC, H-O-CMCS was more coagulant for flocculating the residual oil from the oily
effective in removing the residual oil from WWOE, waste-water [6,7]. However, its non-biodegradability is a
which could successfully wash up almost 99% of residual major disadvantage. These industrial coagulants create
oil from WWOE at the dosage of 0.2 g/L, the mixing hazardous activated sludge which may cause side effects
time of 3 min, 500 rpm, and a broader range of pH (the when discharged into the open water course [8]. It has
system temperature (45uC). In similar conditions, com- been pointed out that intake of large amount of alumi-
paratively, chitosan, activated carbon and PAC could num salt will cause Alzheimers disease [8]. Therefore,
wash 90%, 82% and 92% of residual oil from WWOE, biodegradable materials, with the excellent flocculating
respectively. ability for the residual oil, will be advantageous in this
respect.
Keywords H-oleoyl-carboxymethyl-chitosan (H-O- A number of natural sorbents have been studied for
CMCS), residual oil, adsorption cleaning up the residual oil, e.g. activated carbon, ben-
tonite and chitosan. Activated carbon has been one of
the most popular and widely used adsorbent in waste-
1 Introduction water treatment applications. Despite of its prolific use,
activated carbon is still considered as an expensive
Treatment and disposal of oily waste-water, such as the material, so not much work has been done in flocculat-
waste-water of oil extraction (WWOE), is presently one ing the residual oil [9]. Chitosan has the high affinity
of the serious environmental problems contributors [1]. with the residual oil and the excellent properties such
The major difficulty in disposing the residual oil is clean- as biodegradability, hydrophilicity, biocompability,
ing up the emulsified oil droplets [2]. Numerous methods adsorption property, flocculating ability, polyelectroli-
have been used to remove residual oil from waste-water sity, antibacterial property and its capacity of regenera-
[3]. Coagulation method is widely used in water and tion in many applications [10]. It has been used as
non-toxic floccules in the treatment of organically pol-
Received December 9, 2007; accepted December 30, 2007 luted waste-water [11]. However, the excellent flocculat-
E-mail: xgchen@ouc.edu.cn ing ability for the residual oil of chitosan has only been
106 Gang-zheng SUN, et al.

exhibited in the acid condition [12]. Thus, it is necessary 2.2.2 H-O-CMCS preparation
to develop an efficient, environmental friendly chitosan
derivative for removing the residual oil in a broader pH Oleoyl-carboxymethyl chitosan (O-CMCS) was synthe-
range. sized by the reaction of CMCS with oleoyl chloride. Na-
The objective of this research work was to synthesize an form CMCS (23 g), acetones (50 mL) were added into a
amphiphilic chitosan derivative, H-oleoyl-carboxy- flask (500 mL) to swell at 0uC5uC for 1 h [16]. The oleoyl
methyl-chitosan (H-O-CMCS), and investigate the effec- chloride (26 mL) was dissolved in acetone (26 mL), and
tiveness of H-O-CMCS as a coagulation agent to added into the reaction mixture drop-wise for 30 min and
flocculate the residual oil from the WWOE. Chitosan, sodium hydroxide solution (4 mol/L) added into the reac-
activated carbon and PAC were chosen to compare with tion mixture drop-wise at the same time and reacted for
H-O-CMCS in removing the residual oil from WWOE. 5 h at the same temperature, then stopped by adding 70%
The influences of coagulants dosages, mixing time, pH ethyl alcohol (200 mL). The solid was filtered and rinsed
and temperature on flocculating the residual oil of in 70%90% ethyl alcohol to desalt and dewater, and
WWOE were also observed. vacuum dried at room temperature. The products were
Na salt O-CMCS (Na-O-CMCS). Na-O-CMCS (1 g)
was suspended in 80% ethyl alcohol aqueous solution
(100 mL); hydrochloric acid (10 mL, 37%) was added
2 Experimental and stirred for 30 min. The solid was filtered and rinsed
in 70%90% ethyl alcohol to neutral, vacuum dried. And
2.1 Materials the process of preparing H-O-CMCS was similar as in
above section [13,15].
Chitosan was made from crab shell and obtained from
Biochemical Medicine Plant of Qingdao (Qingdao, 2.3 Fourier transform infrared (FTIR) spectroscopy
China), degree of deacetylation 83.7%, molecular weight
66 kDa, white powder, less than 120 mesh in size. The FTIR spectra of H-O-CMCS, H-CMCS and chitosan
Chloroactic acid, oleoyl chloride, chloroform, tetrachlor- were recorded on a FTIR spectrometer (FT/IR-430, Jasco
omethane, activated carbon and PAC, etc., were pur- Co., Tokyo, Japan) at room temperature based on the
chased from Kermel Chemicals Co., China. method of Shigemasa [17]. A pellet was formed from
Samples of WWOE were collected from Shengli Oil Field 2 mg H-O-CMCS and 100 mg KBr. Data analysis was
of China, at the temperature ranging from 40uC to 50uC. carried out using Jwstda-32 (Windows xp).
The samples were cooled to 18uC before experiments.
2.4 Flocculating experiment
2.2 Synthesis of H-O-CMCS
The WWOE is colloidal suspension, which contains 100
2.2.1 Carboxymethyl chitosan (CMCS) preparation 200 mg/L of oil and 8001000 mg/L of suspended solids.
It is light brown liquid and discharge at temperature
CMCS was prepared by the method of Chen [13]. between 40uC and 50uC. It is fairly alkalescent with pH
Chitosan (10 g), sodium hydroxide (10 g), isopropanol ranging from 7.5 to 8.5. Table 1 shows the characteristics
(40 mL) and water (50 mL) were added into a flask of raw WWOE. The oil droplets of WWOE can be found
(500 mL) to swell and alkalize at a given temperature in two phases. One is suspended in the supernatant as the
for 1 h. The temperature was maintained in a water bath emulsion, and the other is floating as oil droplets on the
(Thermo-controller, Comabiotech. Co., Korea). The upper layer of the suspension [18]. The residual oil drop-
monochloroacetic acid (15 g) was dissolved in isopropa- lets in WWOE are solvent extractable [19].
nol (20 mL), added into the reaction mixture drop-wise
Table 1 Characteristics of WWOE
for 30 min and reacted for 3 h at the same temperature,
then stopped by adding 70% ethyl alcohol (200 mL). The Parameter WWOE
solid was filtered and rinsed in 70%90% ethyl alcohol to Oil and grease 100200 mg?L21
desalt and dewater, and vacuum dried at room temper- Chemical oxygen demand 524 mg?L21
ature. The products were Na salt CMCS (Na-CMCS). Suspended solids 890 mg?L21
pH 7.58.5
Na-CMCS (1 g) was suspended in 80% ethyl alcohol
aqueous solution (100 mL), hydrochloric acid (10 mL,
37%) was added and stirred for 30 min [14]. The solid At first, WWOE was sedimentated for 2 h and sepa-
was filtered and rinsed in 70%90% ethyl alcohol to neut- rated. After sedimentation and separation, the supernat-
ral, vacuum dried. The products were the H-form CMCS ant and floated oil was taken out. And the residual oil
(H-CMCS) [13,15]. content was analyzed for the following experiment [20].
Preparation of H-O-CMCS and the function as a coagulation agent for residual oil in aqueous system 107

A conventional beaker (100 mL) was used to coagulate soluble in aqueous solution and the change of pH could
WWOE with the four adsorbents for quantitative ana- not influence its solubility.
lysis. The beakers were filled with 50 mL of WWOE for
each test run and stirred simultaneously at a defined speed 3.2 The spectra of chitosan and the derivatives
(500 rpm) with six-spindle of steel paddles. After adding
the adsorbents into the suspension, the beakers were The infrared spectra of chitosan, H-CMCS and H-O-
rapidly mixed at various mixing time for different doses CMCS were shown in Fig. 2. The basic characteristics of
of adsorbents [21]. The clarified and sedimentated super- chitosan (Fig. 2(a)) were reflected at the peaks of
natant was then analyzed for its residual oil content. The 3455 cm21 (OH stretch), 2900 cm21 (CH stretch),
samples were analyzed with different dosages of H-O- 1596 cm21 (NH bend), 1154 cm21 (bridge-O- stretch),
CMCS. Functions such as the effect of contact time, the and 1094 cm21 (CO stretch). The characteristic adsorp-
effect of pH, the effect of temperature and the effect of tions of H-CMCS (Fig. 2(b)) were at the peaks of
initial concentration of oil were also analyzed. 1740 cm21 (COOH), 10701136 cm21 (CO) and
1596 cm21 (NH3+). The peaks at 2924 cm21 (d 5 CH2),
2.5 Residual-oil analysis 2854 cm21 (d 5 CH2), 1464 cm21 (d 5 CH2) and
1182 cm21 (twisting vibration of CH2) were stronger and
The residual-oil content was measured using the oil and shaper in the latter [23]. Meanwhile, the band of 3200
grease method recommended by American Public Health 3500 cm21 (OH, NH2) became weaker, and the vibra-
Association, American Water Works Association and tional band corresponding to primary amino groups at
Water Pollution Control Federation, with tetrachloro- 1570 cm21 decreased. These results confirmed that the
methane being used as the oil-extraction solvent [22]. H-O-CMCS (Fig. 2(c)) was successfully prepared.
The oil and grease content in the suspension was deter-
mined for each sample of WWOE both before and after
experiment. Three replicates of each test run were under-
taken with the mean value obtained for residual-oil con-
tent being calculated from the replicates. All tests were
carried out at an ambient temperature of 26uC30uC.

3 Results and discussion

3.1 The structure of chitosan derivatives

The structure of H-O-CMCS was represented in Fig. 1.


H-O-CMCS was the light yellow powder which was not

Fig. 2 The spectra of chitosan and the derivatives: (a) chit-


osan; (b) H-CMCS; (c) H-O-CMCS

3.3 Effect of adsorbent dosage

The effects of the adsorbent dosage of H-O-CMCS and


other adsorbents (chitosan, activated carbon and PAC)
for removing the residual oil were shown in Figs. 3 and
4 with the mixing time of 30 min, the mixing rate of
500 rpm, the sedimentation time of 60 min, the original
pH 8.05 and the residual oil concentration of 106.1 mg/L.
H-O-CMCS, chitosan, activated carbon and PAC could
respectively wash up about 99%, 90%, 82% and 92% of
residual oil from WWOE when the adsorbents dosages
were 10 mg/50 mL (0.2 g/L).
It was observed that H-O-CMCS had the best adsorp-
tion capacity for removing the residual oil from WWOE
Fig. 1 The structure of H-O-CMCS (pH 8.05), i.e., 99%, among such four adsorbents when
108 Gang-zheng SUN, et al.

Fig. 3 Percentage of residual oil adsorption vs. dosage of H- Fig. 4 Percentage of residual oil adsorption vs. dosage of
O-CMCS chitosan, activated carbon and PAC

the dosages of adsorbents were 0.2 g/L. The adsorption had little change with its weight of the dosage increasing.
capacity of H-O-CMCS for the residual oil had a great So activated carbon is not an ideal adsorbent to remove
increase between 5 and 10 mg (per 50 mL WWOE), and the residual oil from WWOE. Normally, activated carbon
when the weight dosage was 25 or 1020 mg (per 50 mL is used for the separation technology, i.e., color and
WWOE), the trend of the H-O-CMCS adsorption capa- organic compounds removal in waste and water treat-
city for residual oil tended to balance. As H-O-CMCS had ments [27].
a high charge density, it required only a little quantity of When the dosage of adsorbents was 10 mg (per 50 mL
H-O-CMCS to destabilize the residue oil droplets. As a WWOE), all the four adsorbents achieved preferable per-
coagulation agent, there was an optimum dosage of H-O- centages of removing residual oil from WWOE. Thus we
CMCS for removing the residual oil from WWOE. Due to took 10 mg (per 50 mL WWOE) as the experimental dos-
the oleoyl groups, H-O-CMCS tended to be dissolved in age in the following experiments.
the oil system at the low dosage. However, it would also
produce the bubbles at the high dosage, which could influ- 3.4 Effect of mixing time
ence the adsorption capability of H-O-CMCS for residual
oil from WWOE. The effects of mixing time (0180 min) for the residual oil
Chitosan is a well-known coagulation agent, with adsorption were shown in Fig. 5 using the fixed adsorbent
amine functional groups, which are very attracted to dosage (10 mg/50 mL). The other experimental condi-
anionic ions, therefore, it could easily bind and bridge into tions were similar to those in the above section. It was
flocs [24,25]. At pH 7.58.5 (the initial pH of WWOE), all observed that H-O-CMCS only needed 3 min to achieve
the free ions were neutralized, which could not further the maximum amount (99%). For chitosan, 30 min was
adsorb the carbonyl ions of residual oil [26]. Thus, neu- needed to achieve the maximum percentage (87%) of
tralization could influence the ability of chitosan in residual oil, while for activated carbon and PAC, 30 and
adsorbing the residual oil strongly [12], and H-O-CMCS
had the better capability than chitosan in removing the
residual oil from WWOE at the initial pH (pH 8.05), as
shown in Figs. 3 and 4.
As another well-known coagulation agent, PAC had
good flocculating capability in forming flocs of residue
oil from WWOE. However, when PAC dosage exceeded
10 mg (0.2 g/L), the percentage of residual oil adsorption
had a little decrease. When the superfluous dosage of PAC
was used for removing the residual oil, the surface of res-
idue oil droplets would be covered by the inorganic PAC
polymers, and this would lead the repulse of the two res-
idue oil droplets, thus the percentage of the residual oil
adsorption would decrease.
For activated carbon, it is a poor choice of adsorbent to
remove residual oil from WWOE compared with other Fig. 5 Percentage of residual oil adsorption vs. mixing time
adsorbents. The percentage of residual oil adsorption for H-O-CMCS, chitosan, activated carbon and PAC
Preparation of H-O-CMCS and the function as a coagulation agent for residual oil in aqueous system 109

0.5 min were needed, respectively, to achieve the max- WWOE had the stronger decrease compared with that
imum percentages (82% and 92%). The results demon- of H-O-CMCS. Among four adsorbents, the flocculating
strated that using H-O-CMCS and PAC could achieve capacity of activated carbon for removing residual oil had
the maximum percentage of residual oil adsorption within better stability by the pH change.
5 min.
Compared with H-O-CMCS and chitosan, PAC (0.2 g/
L) could wash up 92% of residual oil from WWOE only in
1 min, but when the mixing time was prolonged to 30 min,
the residue oil would introduce again in the suspension
resulting in the percentage of residual oil adsorption was
90%. For PAC, it could just agglomerate and bridge the
residue oil, which could not adsorb the residue oil. Hence,
when the mixing time was prolonged, the flocs tended to
break and release again the residue oil into the supernatant
of WWOE [28]. And H-O-CMCS and chitosan had the
similar trend and there was no noticeable change in residue
oil adsorption when the mixing time was prolonged from 3
to 180 min. This was because that they not only agglomer-
ated, but also adsorbed the suspended residue oil in
WWOE. So the flocs formed by H-O-CMCS and chitosan Fig. 6 Percentage of residual oil adsorption using H-O-
were more stable compared with those by PAC. CMCS, chitosan, activated carbon and PAC vs. pH of WWOE
For activated carbon, it was very obvious that residual oil
was introduced again into the suspension for activated car- Chitosan could clean up about 97% of residual oil from
bon mixing time of 30180 min. This phenomenon is due to WWOE at lower pH (pH , 4.5), however, at pH 57, there
the high and intense agitation, which may cause the adsor- was a strong decrease for the flocculating capacity of chit-
bents to break-up and introduce the residual oil again into osan. At lower pH (,4.5) the adsorption percentage was
the system [29]. The adsorption of residual oil by activated almost the same for chitosan which is around 97%. This is
carbon is merely favorable on the surface of the adsorbent because chitosan has reached its saturation point at pH 4.5
and the interaction force between the residual oil and [12]. Strong acidic conditions can help aggravate WWOE to
adsorbent was very weak. Therefore, the residual oil tends break oil droplets and destabilize suspended solids in the
to break easily and introduced again into the suspension suspension, resulting in the enhancement of the coagulation
[18]. For other adsorbents, it was suggested that not just an of residue oil in WWOE. In the acidic condition, chitosan
adsorption on the surface but strong bonding of residual oil provokes physicochemical effect, apparently serving to
onto their surface as well diffusion of residual oil into their demulsify and increase the droplet size and enhance the
particles. So activated carbon was still a poor choice of adsorption of oil and grease. More protons will be available
adsorbent to remove residual oil from WWOE. to protonate amine groups of chitosan molecules to form
Furthermore, for such four adsorbents, the percentage NH3+ groups [12]. This diminished the ability of the amine
of residual oil adsorption had been increasing from 0 to group of chitosan to attack the carbonyl group of residual
30 min. This was because that the breakage of the oil oil and led to a reduction in the electrostatic attractions
droplets were enhanced, resulting in the reduction of the between the residual oil molecules and the adsorption sites
diameter of oil droplets (emulsification) which caused of chitosan. Therefore, the electrostatic attractions between
more interfacial areas for the adsorption to happen and residue oil molecules and adsorption sites will increase and
encouraged the adsorption of residue oil by adsorbents. indirectly enhance the adsorption of residue oil onto chit-
Therefore, the time of the mixing between oil molecules osan. At pH 4.57.0, as shown in Fig. 6, the percentage of
and adsorbent particles was important in adsorbing the adsorption of chitosan was decreased, compared with that
residue oil from WWOE. at pH 4.5. This may be due to the destabilization of chit-
osan under the condition of a weaker acid [30].
3.5 Effect of pH H-O-CMCS could clean up 99% of residual oil at a
broader pH range. The percentage of residual oil adsorp-
The effects of pH (0.58.5) of four adsorbents for remov- tion also had a slight decrease at pH 57. This might be due
ing the residual oil from WWOE were shown in Fig. 6. to not all amine groups of CMCS had been modified by
The other experimental conditions were similar to the oleoyl chloride in the procedure of synthesis H-O-CMCS.
above section. It was noticed that the pH value could So H-O-CMCS also had some amine groups (NH2) which
influence the percentage of residual oil adsorption for all would affect the adsorption capacity of H-O-CMCS for the
the four adsorbents. At pH 57, the adsorption capacity residual oil by the pH change. Oleoyl groups and carbox-
of chitosan and PAC for removing residual oil from ymethyl groups of H-O-CMCS offered it the amphiphilic
110 Gang-zheng SUN, et al.

characters. H-O-CMCS could attract the residual oil easily section. The adsorption capacity of H-O-CMCS for
for its oleoyl groups, and its carboxymethyl groups would removing residual oil from WWOE is instable with tem-
improve the polar of H-O-CMCS which prevented it from perature rising. The adsorption capacity of chitosan had a
solving the oil system. This may be the mechanism that H- little increase when the temperature was less than 50uC.
O-CMCS could flocculate the residual oil from WWOE. The adsorption capacity of activated carbon and PAC for
Therefore, H-O-CMCS has the advantage in removing removing residual oil from WWOE had the good stability
the residual oil from WWOE compared with chitosan. with the temperature rising.
PAC had the similar trend as H-O-CMCS and chitosan
in removing the residual oil from WWOE, which also had
a slight decrease at pH 57. PAC was more effective at a
broader pH range and forms positive charged Al species
that adsorb negatively charged natural particles, resulting
in the charge neutralization [31]. By destabilizing oil
droplets and destroying emulsions via addition of PAC,
polyelectrolytes have been shown to be effective as a
pretreatment coagulant to separate oil and grease [32].
So the change of pH might influence the process of form-
ing hydrolysates and polyelectrolytes of PAC, and the
percentage of the residual oil adsorption would alter along
with the change of pH.
The results also verified that the adsorption of residual oil
on activated carbon was significant at strong acid regent.
The pH of the solutions affects the surface charge of these Fig. 7 Percentage of residual oil adsorption using H-O-
adsorbents and the degree of ionization making it a better CMCS, chitosan, activated carbon and PAC vs. temperature
residual-oil adsorbent under this condition. Babel and of WWOE
Kurniawan explained that the electrostatic interactions of
activated carbon in the acidic regent favor the adsorption H-O-CMCS could clean up almost 99% of residual oil
capacity of any positively charged adsorbate [9]. It was from WWOE, when the temperature was lower than 45uC.
observed that at pH 57, the removal of residual oil was However, the percentage of residual oil adsorption had a
also poor for activated carbon. This is because activated large decrease if the temperature exceeded 45uC. When the
carbon became unstable in this pH condition [33]. temperature achieved 84uC, the percentage of residual oil
Furthermore, for four adsorbents, when pH . 7, the adsorption was only about 33%. This was might because
percentage of residual oil adsorption had increased, com- the configuration of H-O-CMCS was broken and the
pared with that at pH 57. Saponification process would oleoyl groups would probably deviate from the H-O-
occur in a suspension with residue oil at the alkaline con- CMCS while the temperature was rising. So the amine
dition. Whereby, the residue oil will go through hydrolysis groups emerged at the surface of H-O-CMCS again. At
process with sodium hydroxide to produce glycerol and the pH 8.05, the amine groups did not have the excellent
fatty acid salt called soap. For this reason, at alkaline pH, adsorption capacity for removing the residual oil. This
the percentage of residue oil adsorption increased, com- was also might because the interaction force between the
pared with that at pH 57. At strong alkaline pH, residue oil molecules and the adsorbents particles had been
oil was hydrolyzed in WWOE and was not extracted by destroyed with temperature rising. Furthermore, with
the solvent, thus indirectly yielding a higher percentage of the rising of temperature, the emulsification would go
residue oil adsorption. Moreover, when the pH value stronger and H-O-CMCS was easier to dissolve the oil
shifted from the light acidic agent to neutral, the adsorp- system. Thus the temperature was an important factor
tion process itself was unstable due to that the character- in removing the residual oil for H-O-CMCS. This phe-
istics of WWOE had changed. nomenon provided the recycling possibility of H-O-
Therefore, the pH value affected not only the degree of CMCS for removing the residual oil from WWOE. The
ionization and adsorption of residual oil for the absor- further research would be carried out to investigate it.
bents, but also the emulsion of WWOE [34]. Chitosan achieved the maximum percentage of residual
oil adsorption at the temperature rage from 40uC to 50uC.
3.6 Effect of temperature With the temperature rising (,50uC), the percentage of
residual oil adsorption also increased. This was because
The effect of temperature for the residual oil adsorption that the chitosan particles and the emulsified oil droplets
was conducted by the weight dosage 0.2 g/L, the mixing would be more active in higher temperature compared
time 30 min, at 500 rpm of rotation speed (Fig. 7). The with in lower temperature, so the flocs could be formed
other experimental conditions were similar to the above easily. But when the temperature exceeded 50uC, the
Preparation of H-O-CMCS and the function as a coagulation agent for residual oil in aqueous system 111

Table 2 Characteristics of disposal water by H-O-CMCS, chitosan, activated carbon, PAC

Parameter WWOE/mg?L21 H-O-CMCS/mg?L21 Chitosan/mg?L21 Activated carbon/mg? PAC/mg?L21


L21
Oil and grease 106.1 010 1020 1830 515
Chemical oxygen demand 524 39 54 59 41
Suspended solids 890 40 56 71 66
pH 7.58.5 7.32 7.04 7.79 4.73

construction of chitosan might be destroyed. So the per- suspended solid from the WWOE. The pH of the disposal
centage of removed residual oil by chitosan from WWOE water holds the line with the initial pH of WWOE. It was
would decrease if the temperature exceeded 50uC. proved that H-O-CMCS was a potential biomaterial as a
Activated carbon and PAC had less temperature influ- coagulation agent for removal the residual oil in this
ence compared with H-O-CMCS and chitosan. Activated paper.
carbon had a little decrease in the residual oil adsorption
capability with the temperature rising. This phenomenon Acknowledgements The authors are indebted to the financial support
from the National Natural Science Foundation of China (Grant No.
is due to that the adsorption of residual oil by activated 30670566) and the ISTCP (No. 2006DFA33150).
carbon was a physical adsorption reaction, which was an
exothermic reaction. PAC was an artificial synthesized
polymer, which was very stable in high temperature. References
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