Department of Chemical Engineering, College of Engineering, Al-Hussain Bin Talal University, Maan, Jordan
Department of Chemistry, College of Sciences, Al-Hussain Bin Talal University, Maan, Jordan
a r t i c l e
i n f o
Article history:
Received 6 June 2015
Received in revised form 3 August 2015
Accepted 12 August 2015
Keywords:
DAF
Waste water treatment
Heavy metals removal,polymers
Chitosan
a b s t r a c t
Dissolved air otation (DAF) process has been widely used for many applications including waste water
treatment. For the purpose of heavy-metal removal, this study will implement several commercial polymers as collectors in DAF process. The investigated polymers are polyvinyl alcohol, polyethylene glycol,
and chitosan which will be used as separation-enhancing agents in the air otation process. On the other
hand, the studied heavy metals are zinc chloride, lead(II) nitrate, manganese(II) chloride, nickel chloride,
and cadmium chloride. Different parameters have been studied in this work such as the concentration
and types of collectors, modication of polyvinyl alcohol, and the type and concentration of the heavy
metals.
The results showed that chitosan was generally better than the other investigated polymers in affecting
the removal of Cd (29%), Ni (27%), Mn (31%), and Pb (29%). The removal of Zn was not consistently high for
any type of polymers, although it was less with chitosan. Polyvinyl alcohol was modied by carboxylation
and the modied polymers were found to be more effective at removing the smaller metals such as Ni
(30%), and Zn (28%), and less effective at removing the larger metals Cd (24%) and Pb (29%) at heavy
concentration of 250 ppm.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Wastewater treatment represents one of the main processes for
recycling water that compensates the shortage of water in many
areas in the world. The facilities that treat wastewater are not
enough at the present, only about 10% of the wastewater generated
is treated and the remaining is disposed into our water bodies [1].
As such, pollutants enter groundwater, rivers, seas and other water
sources. Such water, which ultimately ends up in our households,
is often highly contaminated and carries disease-causing microbes.
All of these reasons motivate the researchers to investigate different ways to treat wastewater. Heavy metals, at high concentration
levels, are the most important contaminants in wastewater, as
their presence leads to serious environmental and human problems
[2]. For example, Manganese is associated with some neurological
disorders such as anger, aggression, inability to inhibit inappropriate responding, and criminality. Nickel was named allergen of the
year in 2008 by the American Contact Dermatitis Society (ACDS)
[3]. It was also suggested to play a role in breast cancer [4]. Zinc
used in antidandruff shampoo was shown to cause allergic contact
dermatitis, and high levels of exposure over time can cause brittle hair and nails, as well as neurological abnormalities. Zinc also
could cause gastrointestinal disorders and convulsions [56]. Cadmium and lead cause damage to the kidneys and severely affect the
neurological system [7]. Table 1 shows some types of wastewater
produced from some industries and their main heavy metal concentration compared to their standard concentration limits according
to the World Health Organization (WHO) [812]. As an example,
the table shows that lead concentration varies between 2.99 and
7083 mg/l while the standard limit for lead is 5 mg/l.
Several methods were implemented for the removal of heavy
metals from wastewater such as ltration, membranes, disinfection, settling, coagulation, occulation and otation [1112,13].
The later method is the most effective method which has been used
widely in mineral processing, paper, pulp, food, and wastewater
treatment [1,1419].
The otation method relies on differences in the surface properties of different particles, specically wetting characteristics, to
separate one particle type from another. The hydrophobic particles
escape from water by attaching to air bubbles, which rise to the
20
Table 1
Pb, Mn, Zn, Ag levels reported in industrial waste water [811].
Source
Pb
Mining
Lead diazide
production
Steel production
Mn
Titanium dioxide
production
Mining
Zn
Paint manufacturing
Zinc plating
Pigment
manufacturing
Metal processing
Textile dying
Steel works
Ni
Coating industry
Cd
Cadmiumnickel
batteries
Cadmium plating
Mining
Heavy metals
concentrations in
wastewater (mg/l)
Maximum allowable
limit (mg/l) [12]
10
2.997083
1500
20500
0.05
46
4106700
5
0.377.4
21050
01702
0.21.0
26
2.11210
0.01
0.06930.11
0.005
100200
100200
01
surface, and are captured in the froth phase. The froth is removed
and the concentrate of separated hydrophobic particles is used as
is or is sent off for further processing [1].
There are several types of otation methods such as ion otation, electrolytic otation, precipitate otation, and dissolved air
otation (DAF) [1,2021]. The latter method is the most effective
one as it has an ability to separate light and small suspended solids
[22].
Collectors are reagents that are used in the DAF process to selectively adsorb onto the surfaces of particles. Collectors can be either
chemisorbed or physically adsorbed [23]. They form a monolayer
on the particle surface that essentially makes a thin lm of nonpolar hydrophobic hydrocarbons. The collectors greatly increase
the contact angle so that bubbles adhere to the surface. Selection
of the correct collector is critical for an effective separation by
froth otation. Organic polymer collectors are used in metallurgical waste [20]. They can be characterized by two properties, the
molecular weight and the length of polymer chain. These polymers
can be classied into low molecular weight (LMW), mid molecular
weight (MMW), and high molecular weight (HMW) [24].
Many workers [2530] used DAF as a treatment process for
waste water. Offringa reported that suspended solids of 200 to
300 mg/l in sewage water were successfully reduced to 10 mg/l
using DAF [25]. In another study, DAF was investigated to treat
wastewater produced in pulp and paper mills [26]. Under proper
occulation conditions, solids removal between 80 and 98% was
successfully achieved from feed concentrations of 600 to 6000 mg/l.
On the other hand, DAF process was found to be preferred over
the sedimentation process in many waste water treatment applications. Tassel et al. [27] studied the removal of mercury from
mercury diethyl dithicarbonate using DAF and the settling process.
The results showed that DAF was a very good technique in which
98% of solids were removed. In comparison to the settling technique, DAF was more efcient as higher purity and lower turbidity
of the product was obtained.
DAF was implemented by other workers to treat surface and
seawater [28]. DAF was used as a pretreatment process for
21
Table 2
Physical state and chemical structure for the polymeric collectors under study.
Polymer property
PVA
PEG
Chitosan
Physical state
Crystal
Granules
Powder
1.26
85
1.13
60
0.6
350
Chemical structure
Density (g/cm3 )
Glass transition
temperature, C
contains trace heavy metals in addition to dissolved salts and suspended solids.
2. Experimental
2.1. Materials
Seven different polymers have been used as collectors in DAF
process. These polymers are:
1. Polyvinyl Alcohol (PVA) with two molar masses of 9000 and
13,000 g/mol.
2. Modied PVA derived through carboxylation of PVA 9000 and
PVA 13,000 g/mol.
3. Polyethylene glycol (PEG) with two molar masses of 10,000 and
35,000 g/mole.
4. Chitosan.
The reason for using these polymers is that they have oxygen
hetero-atoms capable of binding to different metal ions effectively. Furthermore, these polymers are cheap and available. Table 2
shows the physical properties of the investigated polymers used in
this study. These polymers (ACS grade) were supplied by Merck,
U.S.A. The modied polymers were prepared as described below.
The sources of the chemicals used in the modication are (all are
of analytical grade except were indicated): chloroacetic acid from
Lancaster, England, potassium carbonate from Riedel-de Han,
Germany, potassium iodide from Medex, U.K., dimethyl formamide
and diethyl ether (ACS grade) from Tedia, U.S.A., and ethanol from
Avonchem, U.K. The heavy metal salts that were used in this work
are CdCl2 (ACS grade) which was supplied by Fischer, U.S.A., ZnCl2
(analytical grade) supplied by Riedel-de Han, MnCl2 (analytical
grade) supplied by Rasayan Laboratory, India, Pb(NO3 )2 (analytical
grade) supplied by Scharlau, Spain, and NiCl2 (ACS grade) supplied
by SigmaAldrich, U.S.A.
Each heavy metal salt was prepared at the following concentrations: 20, 50, 100, 150, 200 and 250 ppm. For each experiment,
total dissolved solid (TDS) and conductivity are measured before
and after each experiment.
2.2. Preparation of poly (vinyl acetate)
PVA 9000 or PVA13000 with a mass of 1.0 g was dissolved in
50 ml of dimethyl formamide (DMF) at 50 C in a 250 ml roundbottomed ask. Then 1.38 g of potassium carbonate was added to
this solution and the mixture stirred at the same temperature for
1 h. 0.94 g of chloroacetic acid and catalytic amounts of potassium
iodide (0.2 g) were then added to the stirring mixture. Stirring was
continued at 50 C for 4 more hours. The solution was stored in
the fridge at 4 C for three days then ltered and the white solid
washed with three consecutive 5-ml fragments of ethanol followed
by three consecutive 5-ml fragments of diethyl ether. The product
was nally dried under vacuum for 4 h. The product was found to
be soluble in dimethyl sulfoxide (DMSO) and water.
The 1 H NMR spectra of the modied poly(vinyl alcohol) samples
were recorded on a Varian Gemini 2000, 300 MHz spectrometer.
The samples were dissolved in DMSO.
2.3. Apparatus and experimental procedure
The batch DAF cell that was used in this study is shown in Fig. 1.
The apparatus is available in our laboratory at Al-Hussein Bin Talal
University. The main target of DAF is to oat the particles and to
remove suspended solids and partially dissolved ions found in the
wastewater using investigated polymeric collectors.
The DAF cell consists of six 1-l beakers equipped with a plastic
drainage valve at the bottom of each one. A movable mixer module
paddle drive system and an injection system were mounted on top
of the Plexiglas beakers. An 8-l stainless steel pressure vessel was
used for water saturation. Recycled water was injected into the jars
and was controlled by a solenoid valve connected to injection tubes
tted with a 1.2 mm injection nozzle. 700 ml of the investigated
heavy metal solution was poured into the DAF beaker and stirred
for 1 min; After that 50 ml of the investigated polymer (collector)
was added; then a frother (0.5 ml) called methyl isobutyl carbinol
(MIBC) at a concentration of 25 ppm was added and mixed for an
extra minute at 300 rpm. Five liters of deionized water were added
to the saturation vessel, and then air was pumped to this vessel by
a compressor until the pressure reached 550 kPa.
After setting the mixing speed, saturated air was injected for10 s
into the DAF cell. After 1 min of mixing, 100 ml-sample was then
drawn from the bottom of DAF beakers, by opening its drainage
valve, representing the otation sink (tailing water) while oat
(concentrate water) remained in the DAF cell. Three experiments
with the same operating parameters were conducted simultaneously in three beakers, and the average results were reported.
For each experiment, the conductivity and the pH values were
measured using a SensionTM 5 conductivity meter (Hach Company,
22
Table 3
Some properties of Red Sea used in DAF process.
35
Parameters
pH
TDS (ppm)
Conductivity(mS/cm)
Values
7.97
40400
61.6
30
Removal%
25
30
% Removal
25
20
15
10
PEG10000
PEG35000
Chitosan
50
100
150
200
Concentraon (ppm)
250
Fig. 3. The percentage removal for CdCl2 using the investigated collectors.
50
20
80
100
150
Fig. 2. The percentage removal of PbCl2 at 100 ppm using PVA 9000 collector at
different concentrations.
USA). More details about the DAF cell have been reported by AlThyabat and Al-Zoubi [14]. All experiments were carried out at
a recycle ratio of 10%. The recycle ratio percentage is dened as
the volumetric percentage of saturated air introduced into the DAF
cell compared to it is initial value in the saturated tank. All experiments were carried out at the laboratory temperature (20 1 C).
The removal percentage (R%) of the heavy metal was determined
using the following equation:
R% = (1 (
PVA13000
15
10
PVA9000
20
Cf
Ci
)) 100
(1)
The results of the experimental work conducted on the treatment of waste water containing different heavy metals using DAF
will be covered in this section at a recycle ratio of 10% and a speed
of stirring of 300 rpm using seven different polymeric collectors.
The investigated heavy metal salts are CdCl2, ZnCl2 , NiCl2, MnCl2 ,
and Pb(NO3 )2 . Each heavy metal was used at the following concentrations: 50, 100, 150, 200 and 250 ppm.
Fig. 3 shows the percentage removal of CdCl2 at the investigated
concentration based on the conductivity measurements. It is clear
that the highest removal (29%) was obtained using chitosan over
the studied concentration ranges. This could be attributed to the
stronger afnity of chitosans amide nitrogen for the soft Cd. The
cyclic nature of chitosans monomeric units also helps to strengthen
their chelation to metal ions. Moreover, chitosan is considered the
only polymer in this study that contains the nitrogen-containing
functional groups suitable for removing heavy metals. PVA 13,000,
at high concentrations, has relatively high removal (25%). At low
concentrations, PVA 13,000 has a lower percentage removal values
compared to PVA 9000. Similar to PVA, PEG 35,000 has a higher
removal (23%) at higher concentrations compared to PEG 10,000.
The larger size of PVA 13,000 and PEG 35,000 compared to their
smaller counterparts makes them more efcient at the entrapment
of Cd at higher concentrations of the metal since the higher molecular weight means higher concentration of OH groups in the repeated
units of the polymer.
The pretreatment of waste water containing ZnCl2 using DAF
was investigated at different concentration levels using different
collectors (Fig. 4). As shown in Fig. 4, the highest removal percentage was obtained with PVA 9000 and PVA 13000. The removal of
ZnCl2 with chitosan is almost concentration-independent and is
lower than with PVA. PEG was less effective than PVA as well. The
hydroxyl-chelating PVA appears to be more suitable for the binding
of the small Zn ion. The same trends were obtained for NiCl2 except
for the removal using chitosan which has the highest removal (26%)
for Ni, apparently due to the stronger binding to Ni just as in the
case of Cd (Fig. 5).
The removal of MnCl2 using the investigated collectors is shown
in Fig. 6. It is clear that chitosan has the highest removal among
the used polymers, where the removal is fairly independent of the
metal concentration. Similar to Ni and Cd, the relatively soft Mn(II)
has a high afnity for chitosan. For the other polymers, the removal
has an inverse relation to the molar mass of the polymer.
The situation is different for the removal of Pb(NO3 )2 , as the
removal slightly increases with Pb concentration using chitosan as
35
35
30
30
25
25
20
PVA9000
15
PVA13000
Removal%
Removal%
PEG10000
10
PVA9000
20
PVA13000
15
PEG10000
PEG35000
10
PEG35000
Chitosan
23
Chitosan
5
0
0
50
100
150
200
Concentraon (ppm)
50
250
100
150
200
Concentraon (ppm)
250
Fig. 7. The percentage removal for Pb(NO3 )2 using the investigated collectors.
Fig. 4. The percentage removal for ZnCl2 using the investigated collectors.
35
30
30
25
Removal %
PVA13000
15
PEG10000
Removal%
25
PVA9000
20
PEG35000
10
20
15
10
Chitosan
0
0
50
100
150
200
Concentraon (ppm)
CdCl2
250
Pb(NO3)2
ZnCl2
NiCl2
MnCl2
Heavy metal
Fig. 5. The percentage removal for NiCl2 using the investigated collectors.
Fig. 8. The percentage removal for each heavy metal using PVA 9000 as a collector.
35
35
30
30
PVA9000
20
PVA13000
PEG 10000
15
PEG 35000
10
Chitosan
20
15
10
5
5
0
Removal%
Removal%
25
25
0
CdCl2
50
100
150
200
250
Pb(NO3)2
ZnCl2
NiCl2
MnCl2
Heavy metal
Concentraon (ppm)
Fig. 9. The percentage removal for each heavy metal using PVA 13,000 as a collector.
Fig. 6. The percentage removal for MnCl2 using the investigated collectors.
a collector (Fig. 7). For PVA 9000, again the removal has an inverse
relation to the molar mass of the polymer, while the removal has a
direct relation to the molar mass of PEG.
3.3. Effect of collector types
In this section, the percentage removal results for all single
heavy metals at a specic concentration of 150 ppm and a specic collector concentration of 80 ppm of all studied collectors will
be discussed. Fig. 8 shows the percentage removal for all heavy
metals under study using PVA9000 as a collector. As shown in the
Fig., PVA9000 was the most effective in removing MnCl2 with the
24
25
35
30
20
Removal%
Removal%
25
20
15
15
10
10
5
5
0
CdCl2
Pb(NO3)2
ZnCl2
heavy metal
NiCl2
MnCl2
PVA9000
PVA13000
PEG10000
PEG35000
Chitosan
Heavy metal
Fig. 10. The percentage removal for each heavy metal using PEG 10,000 as a collector.
Fig. 13. The percentage removal for sea water using different collectors.
35
30
25
Removal%
20
15
25
20
5
0
CdCl2
Pb(NO3)2
ZnCl2
Heavy metals
NiCl2
MnCl2
Fig. 11. The percentage removal for each heavy metal using PEG 35,000 as a collector.
35
Removal%
30
15
10
5
0
CdCl2
Pb(NO3)2
ZnCl2
Heavy metal
NiCl2
MnCl2
Fig. 12. The percentage removal for each heavy metal using Chitosan as a collector.
relatively high while the removal of the latter one was relatively
low. The results of the last polymer, chitosan, are shown in Fig. 12.
The results show that chitosan is better than the other investigated
polymers in removing the soft heavy metals such as Cd, Pb, and
Mn. However, the removal of the relatively hard Zn using chitosan
is less than with the other polymers.
By summarizing the previous removal results for each collector,
it is apparent that there are variable removal values for each heavy
metal. For the PVA collector, the removal of CdCl2 has an inverse
relation to its molar mass while the removal is not effected by the
molar mass of PEG. Chitosan was the best collector among the stud-
Modied PVA (MPVA) was conducted via a carboxylation reaction of a fraction of the hydroxyl groups of PVA with chloroacetic
acid in DMF in the presence of a catalytic amount of KI. The base
K2 CO3 was also added to facilitate the substitution reaction with
chloroacetic acid through the abstraction of a proton from the OH
groups of PVA. Moreover, the reaction was also done with heating
(50 C) in order to accelerate the reaction. The success of the carboxylation reaction was veried by comparing the 1 H NMR spectra
of the modied polymers, Fig. 14b and c to that of PVA itself, Fig. 14a.
The 1 H NMR spectrum of the modied polymer MPVA 9000 shows
the appearance of an intense peak at 3.9 ppm and a smaller peak
at 4.1 ppm that can be assigned to the CH2 protons of the newly
introduced CH2 COO group. The 1 H NMR spectrum of MPVA 13000
shows an intense peak at 3.9 as well as two small peaks at 4.01 and
4.16 ppm proving the presence of CH2 COO groups in the modied
polymer. This procedure cannot be applied to PEG. This polyether
lacks the hydroxyl groups present in PVA with the exception of
the terminus, which is insufcient to introduce any measurable
differences to the properties of PEG.
MPVA 9000 and MPVA 13000 were implemented in the DAF process to treat waste water containing heavy metals and to compare
Fig. 14.
H NMR spectra of (a) poly vinyl alcohol (PVA 9000), and (b) modied poly vinyl alcohol (MPVA 9000).
30
35
25
30
25
PVA9000
MPVA9000
15
PVA13000
10
MPVA13000
Removal%
20
Removal%
25
PVA9000
20
MPVA9000
15
PVA13000
10
MPVA13000
5
0
0
50
100
150
200
Concentraon (ppm)
250
50
100
150
200
250
Concentraon (ppm)
Fig. 15. The percentage removal of CdCl2 using modied and non-modied PVA
9000 and PVA 13000.
Fig. 16. The percentage removal of ZnCl2 using modied and non-modied PVA
9000 and PVA 13000.
26
35
30
Removal%
25
PVA9000
20
MPVA9000
15
PVA13000
MPVA13000
10
4. Conclusion
5
0
50
100
150
200
250
Concentraon (ppm)
Fig. 17. The percentage removal of NiCl2 using modied and non-modied PVA
9000 and PVA 13000.
35
30
Removal%
25
PVA9000
20
MPVA9000
15
PVA13000
10
MPVA13000
5
0
50
100
150
200
Concentraon (ppm)
250
Fig. 18. The percentage removal of MnCl2 using modied and non-modied PVA
9000 and PVA 13000.
35
30
25
Removal%
PVA9000
20
MPVA9000
15
PVA13000
MPVA13000
10
5
This project is funded by the, Abdul Hameed Shoman Foundation, Fund for Scientic Research Support, Jordan. Moreover, all
experiments were carried out in the laboratories of the colleges
of Engineering and Sciences at Al-Hussein Bin Talal University. The
authors would like to thank the mentioned institutions for their
encouragement and support. Finally, the authors would also like
to thank the engineers Niveen Assaf and Rawan Shakour and the
chemists Yousef Shanan and Marwan Al-Azzeh for their help in the
experimental part.
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0
50
100
150
200
250
Concentraon (ppm)
Fig. 19. The percentage removal of Pb(NO3 )2 using modied and non-modied PVA
9000 and PVA 13000.
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