Magnetic Alginate Bead Methylene Blue Removal.pdf

It is generally known that Fe3O4 nanoparticles are magnetically separable and thus, have been widely used in water treatment. However, magnetophoresis of the singly dispersed Fe3O4 nanoparticles has been proven to be slow. Realizing this limitation, the present work aims to immobilise various quantities of nano-Fe3O4 onto the surface of an alginate bead to promote cooperative magnetophoresis. The formed nano-Fe3O4 deposited alginate beads were characterized for their surface morphology and magnetic properties using scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM), respectively. SEM analysis showed that the external surface of the alginate bead turns porous upon subjecting to sonication process. The pores serve as the template to hold the Fe3O4 nanoparticles in place. Upon the deposition of Fe3O4 nanoparticles, the external surface of alginate bead turned rougher. Besides changes in surface morphology, the saturation magnetization value of the beads recorded a substantial increment along with the loading amount of Fe3O4. Such observation proved that it is feasible to induce a cooperative magnetic effect by immobilise various quantities of Fe3O4 onto the surface of alginate bead.

1. SYNTHESIS OF MAGNETITE
MACRO-BEAD FOR WATER
REMEDIATION: PROCESS
OPTIMIZATION VIA
MANIPULATION OF BEAD SIZE
AND SURFACE MORPHOLOGY
Link to Full Text:

https://www.researchgate.net/publication/342123086_Characterization_of_Surface
_Morphology_and_Magnetic_Properties_of_Fe_3_O_4_-
Deposited_Alginate_Bead

2. (a)
(b)

3. INTRODUCTION

•Dye is one of the sources for water pollution – dyeing industry.

•Methods to treat – adsorption, biological treatment, membrane filtration.

•Adsorption technology with no chemical degradation is attractive – effectiveness, efficiency and economy.

•Alginate (biosorbent material) – adsorbent for dye removal.

•Alginate bead been modified with nanoparticles by increasing the total surface area.

•Magnetic nanoparticles ( Iron oxide nanoparticles) – magnetophoresis properties.

•Iron oxide (Fe
3O
4) nanoparticles usually produced by co-precipitation method.

•Magnetite-decorated alginate bead – loading of Fe
3O
4 on the surface of alginate bead.

4. PROBLEM STATEMENT

•Water contamination
•Textile industry one of
the major contribution
•Low biodegradation of
dyes – conventional
biological treatment is
not effective

Discharged up to 200
000 tons of dyes
annually – inefficiency
of dyeing processes
(Farah et al., 2015;
Ogugbue et al., 2011)
•Very effective for removal
of dye.
•Only can remove cationic
pollutants
•Centrifugation process is
very expensive to remove
dyes.

•Fe
3O
4 –doped
alginate beads can
solve the problem
Anionic & cationic
pollutants can be
removed –
manipulating pH
value

5. OBJECTIVES

•To synthesis alginate beads surface coated with iron oxide nanoparticles.


•To correlate the medium pH and different iron oxide loadings to dye
removal efficiency.


•To determine the mechanisms of the adsorption process via isotherms
and kinetic study.

6. LITERATURE REVIEW
•Magnetic iron oxide nanoparticles (MIONPs)
•Classification of dyes based on particle charge

7. MIONPs
MAGNETIC IRON OXIDE NANOPARTICLES (MIONP s)
•Magnetic and catalytic
bifunctionalities (Yeap
et al., 2017)
•Inexpensive to
produce
•Biocompitable
•Physically and
chemically stable
•Environment safe (Lu
et al., 2007)

Structure of MIONPs
•Hematite (α-
Fe
2O
3), magnetite
(Fe
3O
4) and
maghemite (γ-
Fe
2O
3)

Crystal structure
of magnetite cubic
Magnetophoresis of MIONPs

8. Dyes
Anionic Dyes
Acid Dyes
Direct Dyes
Reactive Dyes
Cationic Dyes
Basic Dyes
Nonionic Dyes
Disperse
Dyes
CLASSIFICATION OF DYES BASED ON PARTICLE CHARGE
•Classified based on the molecular charge upon dissolved in the aqueous
(i)Brilliant Blue RAW
(anionic)
(ii)Methylene Blue
(cationic)
(iii)Disperse Yellow

9. METHODOLOGY
•Preparation of alginate beads
•Loading of Fe
3O
4 nanoparticles on alginate beads
•Preparation of dyes solution with constant concentration
•Adsorption process
•Magnetic separation of adsorbed Fe
3O
4 – doped alginate bead

10. RESEARCH FLOW DIAGRAM

START
Preparation of Alginate beads
Loading of Fe
3O
4 nanoparticles on Alginate beads
Preparation of dye solution of methylene blue and methyl orange
Removal of anionic
dyes at pH below
6.3
Removal of cationic
dyes at pH above
6.3
Magnetic Separation of Fe
3O
4 – with different Fe
3O
4 loading
Mechanism of the adsorption process via isotherms and kinetic
study
END

11. STEP 1: PREPARATION OF ALGINATE BEADS
•Reaction of sodium alginate and calcium chloride.

•The sodium alginate powder weighted 2g was dispersed in 100 mL of deionized water to give an
alginate solution of 2% concentration (Anastasios and Ioannis, 2002).

•The sodium alginate aqueous solution is added by dropping the solution into a continuously
stirred calcium chloride solution.

•The formation of spherical particles when the formation of spherical droplets of sodium alginate
solution being dispersed in calcium chloride solution.

12. STEP 2: LOADING OF FE
3O
4 NANOPARTICLES ON
ALGINATE BEADS

Yeap at el., 2018

13. EXPECTED RESULT OF FE
3O
4 DOPED – ALGINATE BEAD

14. PARAMETER AFFECTING DYES REMOVAL
pH

Amount of adsorbent loading

Concentration of dyes

Temperature

Contact time

Types of adsorbent

Manipulated variables
Controlled variables

15. STEP 3: PREPARATION OF DYES SOLUTION WITH
CONSTANT CONCENTRATION
Dyes used:
1.Methylene blue (MB) – cationic dyes
2.Methyl orange (MO) – anionic dyes
•Concentration of
dyes measured by
UV-visible
spectrometry

•100 ml of 100 ppm
will be poured into
250 ml beaker and
been used for each of
experiment.

16. STEP 4: ADSORPTION PROCESS
pH of cationic dyes (MB) solution will be measured initially using pH
meter with constant of 50mg/L concentration.
Five sets of cationic dye solutions will be adjusted to pH 2, pH 4, pH
6, pH 8 and pH 10
Five samples of Fe
3O
4 -Alginate beads with 1 g/L Fe
3O
4 loadings will
be added into the each sets of anionic dye solutions.
Same procedure will be carried out with anionic dye (MO) solution
with constant of 50mg/L concentration
a) Effect of pH

17. b) Effect of dyes concentration
The dyes solution is prepared for concentration 20 mg/L, 40 mg/L, 50 mg/L, 60 mg/L, 80 mg/L and 100
mg/L by diluting 100 mg/L of the dyes solution to the desired concentration
The pH of MB concentration were measured to pH 8 and 1 g/L of Fe
3O
4 loadings were fixed in this
experiment
15 mL of 20 mg/L concentration were poured into sample bottles with 0.3g of Fe
3O
4 -Alginate beads
The steps are repeated for different concentration in the range of 20 mg/L until 100 mg/L using the
stock solution of MB and MO
The pH of the solution is adjusted by dropping 0.01M of HCl and NaOH by using micropipette until it
reached pH 8

18. c) Effect of Fe
3O
4 loading at constant pH
Adsorption of anionic and cationic dyes by using different loadings
of Fe
3O
4 will be studied at constant neutral pH.
The cationic dyes solution will be adjusted to pH 8 with either 0.1
M HCl or 0.1 M NaOH solution.
1 g/L of the Fe
3O
4-doped alginate beads will be added into the
cationic dye solution for adsorption process.
The same procedure will be repeated by using different loadings of
Fe
3O
4 which are 0.0 g/L (pure), 0.25 g/L, 0.5 g/L, 2.0 g/L and 3.0 g/L
in cationic dyes and anionic dyes solution with constant pH 8 and
pH 2.

19. STEP 5: MAGNETIC SEPARATION OF ADSORBED FE
3O
4-
DOPED ALGINATE BEAD
•Observation
of
experiment
after
adsorption
process
occurred.

20. RESULTS AND DISCUSSION
•Characterization of sample
•Affecting factors on adsorption
•Adsorption isotherm
•Adsorption kinetic

21. CHARACTERIZATION OF SAMPLE
a b
c d
TEM (a) and
SEM (b,c,d)
FTIR spectra

22. AFFECTING FACTORS ON ADSORPTION
a) Effect of pH
Percentage removal of methylene blue against pH
[Fixed condition: 50 mg/L dye concentration]
Percentage removal of methyl orange against pH
[Fixed condition: 50 mg/L dye concentration]

23. b) Effect of dye concentration
Percentage removal of methylene blue against
concentration [Fixed condition: pH 8]
Percentage removal of methyl orange against
concentration [Fixed condition: pH 2]

24. c) Effect of Fe
3O
4 loading at constant pH
Percentage removal of methylene blue against Fe
3O
4
loadings [Fixed condition: 100 mg/L of dye
concentration, pH 8]
Percentage removal of methyl orange against Fe
3O
4
loadings [Fixed condition: 100 mg/L of dye
concentration, pH 2]

25. ADSORPTION ISOTHERM
Langmuir - MB
Langmuir - MO
Freundlich - MB
Freundlich - MO

26. KINETIC STUDY
Pseudo first
order - MB
Pseudo first
order - MO
Pseudo second
order - MB
Pseudo second
order - MO

27. Pseudo First Order
Form
Mean Correlation
Coefficient, R
2

Linear 0.9396
Pseudo Second
Order Form
Mean Correlation
Coefficient, R
2

Type 1 0.9990
Pseudo First Order
Form
Mean Correlation
Coefficient, R
2

Linear 0.9795
Pseudo Second
Order Form
Mean Correlation
Coefficient, R
2

Type 1 0.9953
Mean correlation coefficient comparison for
methyl orange
Mean correlation coefficient comparison for
methylene blue

28. CONCLUSION
Objectives Conclusion
•To synthesis alginate beads surface coated with iron
oxide nanoparticles.

The iron oxide nanoparticles successfully attached to
the surface of alginate beads with different loadings of
iron oxide.
•To correlate the medium pH and different iron
oxide loadings to dye removal efficiency.

The adsorption is affected by three main factors which
are effect of pH, effect of dye concentration and effect
of Fe
3O
4 loadings. The best condition for methylene
blue and methyl orange are successfully achieved.
•To determine the mechanisms of the adsorption
process via isotherms and kinetic study.

Langmuir and Freundlich are used to determine the
mechanisms of adsorption isotherm. Meanwhile,
pseudo first order and pseudo second order are used
to determine the mechanisms of adsorption kinetic.
Freundlich and pseudo second order model are
selected for isotherm and kinetic study.

29. END

Link to Full Text:

https://www.researchgate.net/publication/342123086_Characterization_of_Surface
_Morphology_and_Magnetic_Properties_of_Fe_3_O_4_-
Deposited_Alginate_Bead