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Journal of Water Process Engineering 8 (2015) 1927

Contents lists available at ScienceDirect

Journal of Water Process Engineering


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

Removal of heavy metals from wastewater by economical polymeric


collectors using dissolved air otation process
Habis Al-Zoubi a, , Khalid A. Ibrahim a , Khaleel A. Abu-Sbeih b
a
b

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)

Corresponding author. Fax: +962 32179050.


E-mail addresses: habisa@yahoo.com, HabisAl-Zoubi@ahu.edu.jo (H. Al-Zoubi).
http://dx.doi.org/10.1016/j.jwpe.2015.08.002
2214-7144/ 2015 Elsevier Ltd. All rights reserved.

[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

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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

spiral-wound module nanoltration (SWNF) to treat the Tagus


River surface water in Valadas, Portugal using aluminum sulphate,
ferric chloride, and chitosan as coagulants [29]. With this hybrid
system, the silt density index (SDI) value was accepted for the
treated surface water. In another work, DAF with ultraltration was
used as pretreatment for reverse osmosis (RO) performed on open
seawater intake at a pilot plant located in the Persian Gulf [30]. In
this study, the studied parameters for the water quality characterization were suspended solids, turbidity, fouling tendency, organic
matters, and algae content. The ltered water obtained by the pilot
plant was very steady, and SDI was below the required value. Based
on these promising results, a full industrial plant, a 37.5 MGD open
seawater intake desalination plant located in Fujairah, was constructed. However, the previous study did not consider the removal
of heavy metals form seawater.
Ferric chloride is the most used coagulant. However, Bunker
et al. [31] indicated that the selection of the coagulant should be
based on water temperature and raw water characteristics such as
particle concentration as well as the type and the concentration and
nature of natural organic matter. Klute et al. [32] demonstrated the
importance of the optimization of the coagulation process prior to
DAF with an extensive investigation of pH effects, coagulant concentration, and mixing and occulation intensity in a pilot plant.
In another study, aluminum and ferric sulphates have been used to
remove oil from emulsion solution [33]. However, there are some
drawbacks in the application of inorganic coagulation/occulation
to treat wastewater:
(1) It increases the production of inorganic sludge which results
in increasing sludge handling costs and a signicant amount of
remaining ashes after sludge incineration. (2) It causes an increase
in the salinity of the efuent due to the release of counter ions by the
occulants. Polymers are effective over a wider pH range than inorganic coagulants. They can be applied at lower doses, and produce
smaller volumes of more concentrated, rapidly settling occulants.
The occulants formed from the use of a properly selected polymer
will be more resistant to shear, resulting in less carryover and a
cleaner efuent.
Polymers have been utilized in coagulation/occulation processes for water purication for almost four decades [34]. In
comparison with alum, some of the advantages from the use of
polymers in water treatment are [3536]:
1.
2.
3.
4.
5.

Lower coagulant dose requirements,


A smaller volume of sludge,
A smaller increase in the ionic load of the treated water,
A reduced level of aluminum in treated water,
Cost savings of up to 2530%.

Synthetic organic polymers used in water treatment are most


commonly sold in the form of dry powders or inverse emulsion
and are categorized into two major types [37].
(1) Low to mid molecular weight cationic coagulants based on
nonquaternised dimethylamine (polyamines) and diallyldimethyl
ammonium chlorides (DADMACs); (2) Very high molecular weight
polyacrylamides (PAMs) occulants, which may be anionic, cationic
or nonionic.
In this research, different polymers will be investigated as
collectors to remove heavy metals from wastewater using DAF process. These polymers are polyvinyl alcohol (PVA), modied PVA,
polyethylene glycol (PEG), and chitosan. The heavy metal salts that
were used in this work are CdCl2 , ZnCl2 , MnCl2 , Pb(NO3 )2 , and NiCl2 .
Different parameters will also be studied in this work such as the
concentration and types of collectors, modication of collectors,
and the type and concentration of the investigated heavy metals.
Finally, DAF process will be implemented to treat sea water as a
real practical application to the otation process since sea water

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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

Fig. 1. Batch dissolved air otation.

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

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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

Collector concentraon (ppm)

3.2. Removal of heavy metals using DAF

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)

where, Ci and Cf denote the initial and nal concentrations of the


heavy metal based on TDS values. A Sea water sample was collected
from the Gulf of Aqaba (Red Sea) in Jordan to be used in DAF cell as
an application case using the investigated collectors. Table 3 shows
some properties of this sample including pH, conductivity, and TDS.
The removal of dissolved solids was calculated based on total TDS.

3. Results and discussion


This section will present the results and discussions of the
treatment of ve different heavy metal salt solutions using seven
polymeric collectors in a DAF process. The last section will present
results of the application of DAF process to treat Red Sea water as
an alternative process for pretreatment processes.

3.1. Effect of collector concentrations


In order to choose the suitable concentration of the collectors
through DAF process, different experiments were carried out for
PbCl2 at 100 ppm using PVA 9000 collector and the results are
shown in Fig. 2. The results show that the percentage removal
increased by increasing the concentration of PbCl2 till an optimum
value was obtained at 80100 ppm. Therefore, the concentration
of 80 ppm of the polymeric collector was chosen in this research
for all investigated heavy metals due to its high removal and low
concentration compared to other high concentrations such as 100
and 150 ppm.

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%

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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

highest percentage removal of 27.4%. The other heavy metals have


similar removal percentage values except for NiCl2 with a percentage removal of 23.5%. On the other hand, the efciency of another
polymer PVA 13000 in removing the heavy metal is shown in Fig. 9.
It is clear that the increase in the size of the polymer only affected
the removal of Pb, which decreased signicantly because of the
larger size of Pb compared to the other metals.
For the second type of polymers, PEG, the results are shown in
the Figs. 10 and 11. The highest removal (27%) was obtained for
MnCl2 using PEG 10000 while the lowest one was obtained for Pb
removal (20%). For the higher molecular mass of PEG, the removal
of all investigated heavy metals was almost constant except the
removal of Pb and Mn. The removal of the rst heavy metal was

24

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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.

ied polymers in removing CdCl2 . For the removal of both Pb(NO3 )2


and ZnCl2 , PVA has an inverse relation to the molar mass while PEG
has a direct relation to it. NiCl2 has almost constant removal for all
investigated collectors, while MnCl2 has an inverse removal relation to the molar mass of both PVA and PEG. Finally, the removal of
MnCl2 using chitosan is clearly higher than with the other studied
collectors.

35
30
25
Removal%

20
15

3.4. Pretreatment of seawater using DAF process


10

25

DAF was implemented in this research to treat Red Sea water


in order to test its validity as a pretreatment method in desalination process. Fig. 13 shows the removal of dissolved salts in sea
water using all investigated polymers. The process is usually used
as pretreatment process for desalination processes. It is clear that
the best collector in the treatment of sea water is the high molecular weight PEG35000 with its ability to trap many ions present
in sea water including those present in high concentration such as
Na, Ca, and Cl. PVA13000 is slightly better than PVA 9000 and chitosan. Finally, the lowest removal was obtained for PEG 10000 as
shown in Fig. 13. Again, it appears that larger polymers give better
results than smaller ones because of their ability to physically trap
different metal ions.

20

3.5. Heavy metals removal by modied PVA

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

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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.

their results with previous non-modied polymers (PVA 9000 and


PVA 13000). Fig. 15 shows the removal of CdCl2 using the investigated modied and non-modied collectors. Different results were
obtained for Cd removal especially for the MPVA 13000 collector, where the removal is less than that of PVA 13000 over the
studied concentration range of CdCl2 . MPVA 9000, however, has
less removal than PVA 9000 only at 100 and 150 ppm. The differ-

ent trends observed with Cd can be explained by remembering


that the large soft Cd ion does not have a great afnity for the
newly introduced hard carboxylate groups on PVA. On the other
hand, The MPVA 9000 improved the removal of Zn at concentrations above 130 ppm as shown in Fig. 16. Below this concentration,
the removal decreased upon using the modied polymer. Similarly, MPVA 13000 gave better results than the non-modied PVA

26

H. Al-Zoubi et al. / Journal of Water Process Engineering 8 (2015) 1927

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

Treatment of waste water containing different heavy metals


was investigated in this study using DAF process. Seven different
polymeric collectors were used in DAF process including polyvinyl
alcohol (PVA) with two molar mass of 9000 and 13000, polyethylene glycol (PEG) with two molar mass of 10000 and 35000,
modied MPVA 9000 and MPVA 13000, and chitosan.
The results showed that the separation of various heavy metals using the DAF technique was affected by the type of polymer
chosen as a carrier. The removal of Zn was not consistently higher
for any type of polymers, although it was less with chitosan than
with other polymers. On the other hand, chitosan was found to
be generally better than the other investigated polymers in affecting the removal of the heavy metals Cd, Pb, Ni, Fe, and Mn at
the studied concentrations (50250 ppm). On the other hnad, both
polyvinyl alcohol 9000 and 13000 were modied via carboxylation of some of their hydroxyl groups and the modied polymers
were found to be more effective at removing the smaller metals
(Ni, Mn, and Zn), and less effective at removing the larger metals
(Cd and Pb).
All used polymers are commercially available at relatively low
prices, making them attractive choices for their implementation
as carriers in the air otation process. In particular, chitosan can
be used for the removal of Cd and Pb, which cause serious environmental problems. Finally, the DAF process was implemented to
treat Red Sea water as a practical applications using the investigated polymeric collectors and the results showed that PEG 35000
gave the highest removal among the studied collectors.
Acknowledgements

30
25
Removal%

removal of Mn after its concentration reached 130 ppm as shown


in Fig. 18.
Finally, the removal of Pb using both MPVA 9000 and MPVA
13000 as collectors is shown in Fig. 19. MPVA 9000 improved the
removal of Pb at the concentrations 50 and 150 ppm only, while
MPVA 13000 produced less removal in comparison to the nonmodied polymer. These results are similar to those of Cd and can
be as well explained by the low afnity of the large soft Pb to the
hard carboxylate groups.

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.
References

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.

13000 at higher concentrations of Zn. Again, MPVA 9000 and MPVA


130000 are better than non-modied PVA in removing Ni except
at the lowest concentration used as shown in Fig. 17. Similar to
both Ni and Zn, both MPVA 9000 and MPVA 13000 improved the

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