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Dye removal from wastewater using efficient
and magnetically separable graphene oxide
composite: Modeling and optimization
through response surface methodology
Dr. Muhammad Zahid
University of Agriculture, Faisalabad.
Water Pollution: The Cost of Industrial Growth
TEXTILE MEDIATED WATER POLLUTION:
Textile industry of Faisalabad constitutes more than 65% of the textile export
market of Pakistan. But this increasing commercialization has taken a toll on
its environment. Over a million tons of industrial effluent is generated
annually.
50
20
5
20
10
0 10 20 30 40 50 60
REACTIVE
ACID
BASIC
VAT
DISPERSE
% Loss of dyes in effluent
 The discharge of wastewater from textile industry contains high concentrations dyes
characterized by high BOD, COD suspended solids etc.
“Causeasevereshortageofpotablewaterandinfrastructure”
water
Dyes have striking visibility
in recipients; hence
influence photosynthetic
activity of aquatic lives…
They are persistent to
microbial degradation and
their accumulation in certain
forms of aquatic life may lead
to toxic products.
Textile industries generate
100-170 lit dye effluent per
kg of cloth processed which
could be characterized by
strong odour and colour
due to presence of dye.
Solution: Wastewater treatment
Photocatalysis
Photocatalysis, as an environmental application is a relatively novel subject with tremendous potential in
the near future but efficiency issues relating to the use of photocatalyst has yet to be main objective to be
address like in semiconducting TiO2
Toxicity which nanoparticle cause when their sizes reduces to enhance their surface area.
Less photocatalytic activity due to recombination of light generated electron hole and narrow band gap.
Narrow light absorbance range.
Poor adsorptive power.
Difficulty in the separation of photocatalyst from water after wastewater treatment.
Adsorption-enhanced-Photocatalysis:
The adsorption of pollutant molecules onto the photocatalyst surface, which increases the use of the
photoinduced electron–hole pairs.
MODIFICATION OF TiO2
For that purpose we need following,
• Support for adsorption
• Introduction magnetic separation property
A miracle material of 21st century act as adsorbent,
because of its tremendous properties from high surface
area to having semiconducting properties, high
dispersibility and irreversible aggregation.
Graphene oxide:
Synthesis of Graphene Oxide and Magnetic Graphene Oxide
Graphene oxide:
Synthesis:
Synthesis of graphene oxide by top down approach,
using graphite as a precursor,
Hummer’s Method((Hummer et al., 1958).
 Modified Hummer’s Method
 Pressurized oxidation Method (Chenlu et al., 2012).
Pressurized Oxidation Method
Lab testing:
 Yellow coloration after addition of hydrogen peroxide is the first indication of graphene
oxide.
 High quality graphene oxide disperse in water and a suspension still stable overnight.
 A high quality graphene oxide give a more stable graphene hydrogel.
Synthesis of magnetic graphene oxide by co-precipitation
Method(Guangyu et al., 2013)
SYNTHESIS OF MAGNETIC GRAPHENE OXIDE
Magnetic nanoparticles
CHARACTERIZATION:FTIR
Epoxy (C-O-C)
(C-OH)
C=O
O-H O-H
C=O
(C-OH)
Epoxy (C-O-C)
O-H C-O C=C
SEM of graphene oxide
EDS of graphene oxide
Fe3O4
Graphene oxide
Fe3O4
Graphene oxide
EDS of magnetic graphene oxide
SEM of magnetic graphene oxide
XRD of graphene oxide
ADSORPTION ANALYSIS ON STANDARD DYE BY GRAPHENE OXIDE AND MAGNETIC
GRAPHENE OXIDE
0
10
20
30
40
50
60
70
80
90
100
0 2 4 6 8 10
%
removal
pH
Magnetic graphene oxide graphene oxide
0
20
40
60
80
100
120
0 100 200 300
%
removal
Concentration of adsorbent
Magnetic graphene oxide graphene oxide
10
30
50
70
90
110
0 20 40 60 80
%
removal
dye concentration
Magnetic graphene oxide
Graphene oxide
y = 0.0093x + 0.3962
R² = 0.6569
y = 0.0068x + 0.3472
R² = 0.5818
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 20 40 60 80 100 120 140
log(qe
-
qt)
time(min)
GO GO@Fe3O4
y = 0.05x + 0.572
R² = 0.9558
y = 0.1021x + 0.4444
R² = 0.9942
0
2
4
6
8
10
12
14
0 20 40 60 80 100 120 140
t/qt
time (min)
GO GO@Fe3O4
Pseudo First order kinetics of removal of dye Pseudo second order kinetics of removal of dye.
%removal =
+93.21
-0.59 * A
+5.05 * B
+7.93 * C
+2.97 * D
+8.20 * AB
-0.083 * AC
+4.53 * AD
+3.05 * BC
+9.84 * BD
+3.80 * CD
-7.40 * A^2
-8.29 * B^2
-14.12 * C^2
-9.52 * D^2
STATISTICAL ANALYSIS: RESPONSE SURFACE METHODOLOGY
In this case conc of photocatalyst, pH* Conc of dye, Conc of dye* Time of
irradiation, (pH)2, Conc of dye^2, Conc of photocatalyst^2, Time of
irradiation^2 are significant model terms.
% removal = +90.83 +10.11* A (pH) +4.59* B(dye concentration) -
0.42* C(catalyst dose) -1.49*D(time of irradiation) -
4.29* AB (pH x dye concentration) +2.91* AC ( pH x
catalyst dose)+1.48* AD(pH x time of irradiation) +2.91
*BC(dye concentration x catalyst dose) +6.60* BD(dye
concentration x time of irradiation) +2.44* CD(catalyst
dose x time of irradiation) -6.66* A^2( pH)2-9.74 *
B^2(dye concentration)2 -9.24 C^2( catalyst dose)2 -7.19
*D^2(time of irradiation)2-13.42 * ABD (pH x catalyst
concentration x time).
Interactive effect of different parameters in removal of Reactive Voilet 5R
dye by GO@Fe3O4 nanocomposite.
OPTIMIZATION OF INFLUENCING FACTORS FOR MAXIMUM
PHOTOCATALYTIC DEGRADATION OF DYE:
A:pH = 2.80177
2.00675 3.49325
B:Conc of photocatalyst = 260.582
180.405 269.595
C:Conc of dye = 20.9134
16.0809 33.9191
D:Time of irradiation = 36.1508
18.1079 41.8921
% removal = 99.3503
30 94.7368
Desirability = 1.000
It is expected that the proposed ternay nanocomposite, photocatalyst would pave the
way for the development of more efficient and easily separable agent to deal with
pollutants and toxins in contaminated water.
We are working on
• Optimization of yield of ternary nanocomposite of Graphene oxide- Fe3 O 4 - TiO2 .
• Optimization of recyclability of ternary nanocomposite.
• Toxicity of treated water to use for different purposes like crop irrigation and
industrial use.
CONCLUSION AND FUTURE OUTLOOKS:
ACKNOWLEDGEMENT:
Dr. Muhammad Zahid
Department of Chemistry, University of Agriculture, Faisalabad.
Dr. Asma Rehman
Nanobiotech, National Institute for Biotechnology & Genetic Engineering (NIBGE)
Dr. Rune Wendelbo,
CEO, Abalonyx, Norway.
Save Planet
Conserve water
Thanks for
your attention

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Dr-Zahid-Presentation.pptx

  • 1. Dye removal from wastewater using efficient and magnetically separable graphene oxide composite: Modeling and optimization through response surface methodology Dr. Muhammad Zahid University of Agriculture, Faisalabad.
  • 2. Water Pollution: The Cost of Industrial Growth
  • 3. TEXTILE MEDIATED WATER POLLUTION: Textile industry of Faisalabad constitutes more than 65% of the textile export market of Pakistan. But this increasing commercialization has taken a toll on its environment. Over a million tons of industrial effluent is generated annually. 50 20 5 20 10 0 10 20 30 40 50 60 REACTIVE ACID BASIC VAT DISPERSE % Loss of dyes in effluent  The discharge of wastewater from textile industry contains high concentrations dyes characterized by high BOD, COD suspended solids etc. “Causeasevereshortageofpotablewaterandinfrastructure”
  • 4. water Dyes have striking visibility in recipients; hence influence photosynthetic activity of aquatic lives… They are persistent to microbial degradation and their accumulation in certain forms of aquatic life may lead to toxic products. Textile industries generate 100-170 lit dye effluent per kg of cloth processed which could be characterized by strong odour and colour due to presence of dye.
  • 5. Solution: Wastewater treatment Photocatalysis Photocatalysis, as an environmental application is a relatively novel subject with tremendous potential in the near future but efficiency issues relating to the use of photocatalyst has yet to be main objective to be address like in semiconducting TiO2 Toxicity which nanoparticle cause when their sizes reduces to enhance their surface area. Less photocatalytic activity due to recombination of light generated electron hole and narrow band gap. Narrow light absorbance range. Poor adsorptive power. Difficulty in the separation of photocatalyst from water after wastewater treatment. Adsorption-enhanced-Photocatalysis: The adsorption of pollutant molecules onto the photocatalyst surface, which increases the use of the photoinduced electron–hole pairs.
  • 6. MODIFICATION OF TiO2 For that purpose we need following, • Support for adsorption • Introduction magnetic separation property A miracle material of 21st century act as adsorbent, because of its tremendous properties from high surface area to having semiconducting properties, high dispersibility and irreversible aggregation. Graphene oxide:
  • 7. Synthesis of Graphene Oxide and Magnetic Graphene Oxide Graphene oxide: Synthesis: Synthesis of graphene oxide by top down approach, using graphite as a precursor, Hummer’s Method((Hummer et al., 1958).  Modified Hummer’s Method  Pressurized oxidation Method (Chenlu et al., 2012). Pressurized Oxidation Method
  • 8. Lab testing:  Yellow coloration after addition of hydrogen peroxide is the first indication of graphene oxide.  High quality graphene oxide disperse in water and a suspension still stable overnight.  A high quality graphene oxide give a more stable graphene hydrogel. Synthesis of magnetic graphene oxide by co-precipitation Method(Guangyu et al., 2013) SYNTHESIS OF MAGNETIC GRAPHENE OXIDE Magnetic nanoparticles
  • 10. SEM of graphene oxide EDS of graphene oxide Fe3O4 Graphene oxide Fe3O4 Graphene oxide EDS of magnetic graphene oxide SEM of magnetic graphene oxide
  • 12. ADSORPTION ANALYSIS ON STANDARD DYE BY GRAPHENE OXIDE AND MAGNETIC GRAPHENE OXIDE 0 10 20 30 40 50 60 70 80 90 100 0 2 4 6 8 10 % removal pH Magnetic graphene oxide graphene oxide 0 20 40 60 80 100 120 0 100 200 300 % removal Concentration of adsorbent Magnetic graphene oxide graphene oxide 10 30 50 70 90 110 0 20 40 60 80 % removal dye concentration Magnetic graphene oxide Graphene oxide y = 0.0093x + 0.3962 R² = 0.6569 y = 0.0068x + 0.3472 R² = 0.5818 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 0 20 40 60 80 100 120 140 log(qe - qt) time(min) GO GO@Fe3O4 y = 0.05x + 0.572 R² = 0.9558 y = 0.1021x + 0.4444 R² = 0.9942 0 2 4 6 8 10 12 14 0 20 40 60 80 100 120 140 t/qt time (min) GO GO@Fe3O4 Pseudo First order kinetics of removal of dye Pseudo second order kinetics of removal of dye.
  • 13.
  • 14. %removal = +93.21 -0.59 * A +5.05 * B +7.93 * C +2.97 * D +8.20 * AB -0.083 * AC +4.53 * AD +3.05 * BC +9.84 * BD +3.80 * CD -7.40 * A^2 -8.29 * B^2 -14.12 * C^2 -9.52 * D^2 STATISTICAL ANALYSIS: RESPONSE SURFACE METHODOLOGY In this case conc of photocatalyst, pH* Conc of dye, Conc of dye* Time of irradiation, (pH)2, Conc of dye^2, Conc of photocatalyst^2, Time of irradiation^2 are significant model terms. % removal = +90.83 +10.11* A (pH) +4.59* B(dye concentration) - 0.42* C(catalyst dose) -1.49*D(time of irradiation) - 4.29* AB (pH x dye concentration) +2.91* AC ( pH x catalyst dose)+1.48* AD(pH x time of irradiation) +2.91 *BC(dye concentration x catalyst dose) +6.60* BD(dye concentration x time of irradiation) +2.44* CD(catalyst dose x time of irradiation) -6.66* A^2( pH)2-9.74 * B^2(dye concentration)2 -9.24 C^2( catalyst dose)2 -7.19 *D^2(time of irradiation)2-13.42 * ABD (pH x catalyst concentration x time).
  • 15. Interactive effect of different parameters in removal of Reactive Voilet 5R dye by GO@Fe3O4 nanocomposite.
  • 16. OPTIMIZATION OF INFLUENCING FACTORS FOR MAXIMUM PHOTOCATALYTIC DEGRADATION OF DYE: A:pH = 2.80177 2.00675 3.49325 B:Conc of photocatalyst = 260.582 180.405 269.595 C:Conc of dye = 20.9134 16.0809 33.9191 D:Time of irradiation = 36.1508 18.1079 41.8921 % removal = 99.3503 30 94.7368 Desirability = 1.000
  • 17. It is expected that the proposed ternay nanocomposite, photocatalyst would pave the way for the development of more efficient and easily separable agent to deal with pollutants and toxins in contaminated water. We are working on • Optimization of yield of ternary nanocomposite of Graphene oxide- Fe3 O 4 - TiO2 . • Optimization of recyclability of ternary nanocomposite. • Toxicity of treated water to use for different purposes like crop irrigation and industrial use. CONCLUSION AND FUTURE OUTLOOKS:
  • 18. ACKNOWLEDGEMENT: Dr. Muhammad Zahid Department of Chemistry, University of Agriculture, Faisalabad. Dr. Asma Rehman Nanobiotech, National Institute for Biotechnology & Genetic Engineering (NIBGE) Dr. Rune Wendelbo, CEO, Abalonyx, Norway.
  • 19. Save Planet Conserve water Thanks for your attention