Contents

 Introduction
 Literature Review
 Research Gaps
 Research Objectives
 Research Methodology
 Synthesis of Magnetic Anionic Hydrogel (MAH)
 Results and Discussion
 Conclusion
 Future Plan

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Introduction

 Common threats of heavy metals

• Most of the heavy metal ions are toxic and carcinogenic even
at very low concentrations (Mahmoud, 2013 & Ozay et al.,
2010)
 Common sources of heavy metals
• Electroplating, mining activities, battery manufacture, etc.
 Common treatment technologies of heavy metals
• Chemical precipitation, ion exchange, resins, electrolysis, hyper-
filtration, oxidation, biosorption and adsorption, etc.
 Discharge standard of the heavy metals (i.e. Cu and Ni)
• Maximum allowable discharge limit in China is <1.0 mg/L

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Research Gaps

• Long equilibrium time (slow kinetics)

• Recovery of fine particles from treated water
• Limited reusability in multiple cycles

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Research Objectives

(i) To develop a novel magnetic anionic hydrogel (MAH) and

characterize its physicochemical properties
(ii) To conduct pH study, sorption isotherms study, and sorption
kinetics using the developed MAH
(iii) To investigate reusability (adsorption-desorption-resorption) of
the developed MAH over multiple cycles
(iv) To investigate the underlying sorption-desorption mechanisms
(v) To evaluate the practical applicability of MAH by studying the
effects of copresence of typical electroplating effluent’s
constituents, and finally applying the developed MAH in the
treatment of real electroplating effluent

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Synthesizing Magnetic Nanoparticles (MNP) using
Coprecipitation Method (Tang et al., 2010)
6.1 g FeCl3·6H2O + 3.1 g FeSO4·7H2O

25 mL 6.5 M NaOH

Wash 3 times in UPW

1 time in Ethanol

Black precipitates of magnetite

• 100 mL UPW Dry @ 150°C for 2 h in
• 1 h Mixing oven to obtain 10 nm
• T = 22±2 oC maghemite (γ-Fe2O3)

Brown colored MNP

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 Synthesizing MAH using Radical Polymerization
Method (Tang et al., 2010)
AMPS-Na+ = 4.0 g MBA (3.6 mol%) = 0.05 g After cooling,
TEMED (1.6 mol%) = 20 µL wash 6 times @4 h
MNP (15 wt%) = 0.3 g
5 min N2 gas interval in 24 h
APS (1.6 mol%) = 40.0 µL
purging

N2

5 min mixing in each stage Heat released ~55oC

T = 22±2 oC

Dry 12 h in vacuum
oven @40oC

After grinding 8 µm MAH

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Results and Discussion

Relation between turbidity and MAH concentration

300

250
In itia l T u rb id ity (N T U )

200
• Linear relation between
150 turbidity and MAH
concentration observed.
100
y = 289.99x+4.0455
50
R2 = 0.9992

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

M agnetic H ydrogel C oncen (g/L)

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Fine-tuning X-linkers Content in MAH
M a g n e tic S e p e a rtio n E ffic ie n c y (% )

100
98
96
94
92
90
88
86
84 • At 3.6 mol% to monomer, the
82
80
maximum magnetic separation
78 was achieved (99%)
76
74
72
70
0 1 2 3 4 5 6 7 8 9 10 11
M B A C o nte nt (m o l% )

MAH = 0.5 g/L and 5 min magnetic separation

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pH Study
140
130 160
Adsorption Amount (mg/g)

A dsorption A m ount (m g/g)

120 150
140
110 Cu 130 Ni
100 120
90 110
80 100
90
70
80
60 70
50 60
50
40
40
30 30
3 4 5 6 3 4 5 6 7 8

pH Co= 50 mg/L, MAH = 0.3 g /L, @26 rpm, 60 min pH

• The removal of Cu and Ni increases with the increase of solution pH

• Max. adsorption: Cu (134 mg/g) & Ni (158 mg/g) at pH 6.0 & 8.0
• But, high pH causes metal hydroxide precipitation that may lead to
inaccurate interpretation of adsorption (Mahmoud, 2013)
• Strong competition between H+ & Mn+ for binding sites causes poor
adsorption at low pH (Mahmoud, 2013)
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pH Study (Cont’d)

Fig. a) Cu2+; and b) Ni2+ speciation as a function pH (Kleinübing et al., 2010).

“It is necessary to keep the pH below 5.0 for copper ions and about 6.0
for nickel ions for adsorption study” (Kleinübing et al., 2010).
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pH Study (control test without using MAH)
100
P E S -S F
90 Cu C N -D T F P

80
In te rfe re n c e (% )

70
60
50
40
30
20
10
• Physical observation on metal
0
5.0 5.5 6.0 hydroxide formation at high pH
100
pH
P E S -SF
using 0.45 μm cellulose nitrate disk
Ni
90 C N -D T FP
type filter paper (CN-DTF) and
In te rfe re n c e (% )

80
70 polyethersulfone syringe filter (PES-
60
50 SF).
40
30
20
10
• No interreference for Cu at pH 5.5
0
6.0 6.5 7.0
• No interreference for Ni at pH 6.0
pH
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Particle Size Distribution of MAH

14

12

10
N um ber (% )

6 • Mean particle size is ~8μm

4

1 10 100

Particle D iam eter (µm )

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Fitting Curve with Pseudo-second-order Model

2.5 Cu
• The sorption process of
2.0
Cu2+ions onto MAH can be
1.5 well described by a pseudo-
second-order model, thus,
t/qt

1.0
the sorption rates of metal
0.5 ions onto the adsorbents
were probably controlled
0.0
by a chemical process
0 50 100 150 200 250
t (m in)
T = 22±2 oC, pH = 5.5, Co= 50 mg/L, MAH dosage = 0.48g /L

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Adsorption Kinetic Study of Ni using MAH

100
R em oval Efficiency (% )

80 Ni

60
• 97% removal achieved at
40 equilibrium after 120 min.
• Why Co = 50 mg/L?
20

0
0 50 100 150 200 250

Tim e (m in)
T = 22±2 oC, pH = 6.0, Co= 50 mg/L, MAH dosage = 0.49 g /L
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Fitting Curve with Pseudo-second-order Model

Ni
2.5
• The sorption process of
2.0 Ni2+ ions onto MAH can
be well described by a
1.5
pseudo-second-order
t/qt

1.0 model, thus, the sorption

rates of metal ions onto
0.5
the adsorbents were
0.0
probably controlled by a
chemical process
0 50 100 150 200 250
t (m in)
T = 22±2 oC, pH = 6.0, Co= 50 mg/L, MAH dosage = 0.49 g /L

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Fitting Experimental Data with Langmuir Model

140 Cu
120
A dsorbed am ount (m g/g)

100
• Best fit with Langmuir
80
model which implies a
60 E xperim ental data monolayer sorption of Cu
Langm uir m odel
40
ions onto the homogeneous
surface of MAH
20

0
0 10 20 30 40 50 60 70 80
A queous equilibrium concntration (m g/L)

T = 22±2 oC, pH = 5.5, MAH dosage = 0.3g/L, at 26 rpm and 70 min contact time
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Fitting Curve for Langmuir Isotherm Model

Cu

• qm = 114 mg Cu/g MAH

• KL = 1.06 (L/mg)

T = 22±2 oC, pH = 5.5, MAH dosage = 0.3g/L, at 26 rpm and 70 min contact time
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Fitting Curve for Langmuir Isotherm Model

Ni

• qm = 103 mg Ni/g MAH

• KL = 0.76 (L/mg)

T = 22±2 oC, pH = 6.0, MAH dosage = 0.3g/L, at 26 rpm and 130 min contact time
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Conclusion

• Magnetic separation efficiency of MAH is very high (99%)

• Surface of MAH is permanently negative which is able to remove

heavy metal cations irrespective of the solution pH.

• Adsorption capacity of MAH is 114 mg/g and 103 mg/g for Cu and
Ni, respectively.

• Equilibrium time for adsorption has been significantly reduced from

800 min to 60 and 120 min for Cu and Ni, respectively.

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Future Work

• Batch Study:
• Competitive adsorption study (to determine the specie with which
MAH has the highest affinity)
• Regeneration study (to understand the reusability of MAH)
• Coexisting study (to understand the effect of copresence of
typical electroplating effluent’s constituents)
• Material Characterization
• XRD (to identify the crystalline structure of MNP)
• XPS (to understand the chemical composition)
• SEM (to understand the surface morphology of MAH)
• TGA (to quantify the exact amount of MNP)
• Performance evaluation of MAH with real electroplating effluent

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 Hong Kong University of
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