MATERIALSAND METHODS - Shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/72660/3/...23 Blue -...
Transcript of MATERIALSAND METHODS - Shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/72660/3/...23 Blue -...
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MMAATTEERRIIAALLSS AANNDD MMEETTHHOODDSS
MATERIALS
3.1 Collection of the Adsorbent
The adsorbent used in this work, Blue-Green Algae, was collected from the nearby
ponds of agricultural land area situated in Coimbatore district, Tamilnadu, India. The
impurities and contaminants are removed by washing with water. It is dried in sunlight for
fifteen days, then it is grinded to powder using laboratory pulveriser. The powdered
biomass is sieved using 250 - mesh wire sieve and stored in airtight container.
3.1.1 Characteristics of the Adsorbent
Scientific Classification of Blue-Green Algae (Appendix I)
KINGDOM : Plant
PHYLUM : Cyanobacteria
CLASS : Cyanophyceae
ORDER : Oscillatoriales
FAMILY : Pseudanabaenaceae
GENUS : Geitlerinema
SPECIES : Geitlerinema Splendidum
Algae are simple aquatic plants that occur naturally in habitats such as rivers, lakes,
dump soil, tree trunks, hot springs and snow. Blue-Green Algae are small organism and
can be seen under the microscope as a strings of cells (trichomes). Some accumulations
may be so large that they are easily seen with the naked eye.
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Blue - Green Algae
3.2 Preparation of the Adsorbate
The dyes Methylene Blue, Methyl Violet, Acid Violet and Acid Blue used in the
present study are procured commercially from the dyeing powder agents, Coimbatore. All
the chemicals used in this study are of analytical-grade. The stock solution of the dyes
used in this study is prepared by accurately weighing 5g of the dye and dissolving it in
1000ml of distilled water.
The dyes Methylene Blue, Methyl Violet, Acid Violet and Acid Blue used as adsorbate
in this study are denoted as MB, MV, AB and AV respectively throughout this thesis.
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Blue - Green Algae
3.2 Preparation of the Adsorbate
The dyes Methylene Blue, Methyl Violet, Acid Violet and Acid Blue used in the
present study are procured commercially from the dyeing powder agents, Coimbatore. All
the chemicals used in this study are of analytical-grade. The stock solution of the dyes
used in this study is prepared by accurately weighing 5g of the dye and dissolving it in
1000ml of distilled water.
The dyes Methylene Blue, Methyl Violet, Acid Violet and Acid Blue used as adsorbate
in this study are denoted as MB, MV, AB and AV respectively throughout this thesis.
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Blue - Green Algae
3.2 Preparation of the Adsorbate
The dyes Methylene Blue, Methyl Violet, Acid Violet and Acid Blue used in the
present study are procured commercially from the dyeing powder agents, Coimbatore. All
the chemicals used in this study are of analytical-grade. The stock solution of the dyes
used in this study is prepared by accurately weighing 5g of the dye and dissolving it in
1000ml of distilled water.
The dyes Methylene Blue, Methyl Violet, Acid Violet and Acid Blue used as adsorbate
in this study are denoted as MB, MV, AB and AV respectively throughout this thesis.
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Methylene Blue Dye
Methyl Violet Dye
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Methylene Blue Dye
Methyl Violet Dye
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Methylene Blue Dye
Methyl Violet Dye
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Acid Blue Dye
Acid Violet Dye
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Acid Blue Dye
Acid Violet Dye
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Acid Blue Dye
Acid Violet Dye
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Table 1
Dyes used in this Study
Name of the Dye Structure of the Dye
Methylene Blue
C14H18N3SCl
C.I No : 52015
CAS No : 61-73-4
λmax : 665nm
S
N
NNCH3
CH3CH3
CH3+
Methyl Violet 7
C25H30N3Cl
C.I No : 42555
CAS No: 548-62-9
λmax : 590nm
Acid Violet 17
C41H44N3NaO6S2
C.I No : 42640
CAS No: 4321 -69-1
λmax : 548nm
Acid Blue 9
C37H34N2Na2O9S3
C.I No : 42755
CAS No : 28631-66-5
λmax : 602nm
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Table 1
Dyes used in this Study
Name of the Dye Structure of the Dye
Methylene Blue
C14H18N3SCl
C.I No : 52015
CAS No : 61-73-4
λmax : 665nm
S
N
NNCH3
CH3CH3
CH3+
Methyl Violet 7
C25H30N3Cl
C.I No : 42555
CAS No: 548-62-9
λmax : 590nm
Acid Violet 17
C41H44N3NaO6S2
C.I No : 42640
CAS No: 4321 -69-1
λmax : 548nm
Acid Blue 9
C37H34N2Na2O9S3
C.I No : 42755
CAS No : 28631-66-5
λmax : 602nm
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Table 1
Dyes used in this Study
Name of the Dye Structure of the Dye
Methylene Blue
C14H18N3SCl
C.I No : 52015
CAS No : 61-73-4
λmax : 665nm
S
N
NNCH3
CH3CH3
CH3+
Methyl Violet 7
C25H30N3Cl
C.I No : 42555
CAS No: 548-62-9
λmax : 590nm
Acid Violet 17
C41H44N3NaO6S2
C.I No : 42640
CAS No: 4321 -69-1
λmax : 548nm
Acid Blue 9
C37H34N2Na2O9S3
C.I No : 42755
CAS No : 28631-66-5
λmax : 602nm
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3.3 Equipments
Elico - 110 pH meter is used to measure pH. The pH meter is standardised using
buffer potassium hydrogen phosphate (pH 4).
Digital Systronics Colorimeter-112 is used for spectrophotometric work.
Horizontal electrical bench shaker with temperature control and 120-200 rpm speed
(sub zero make) is used for agitation of the solution containing the adsorbate and
adsorbent BGA.
pH meter Colorimeter
Electrical shaker with Horizontal electrical bench shakertemperature control
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METHODS
3.4 Analytical Procedures – Characterisation of the Adsorbent
3.4.1 Determination of pH
About 15g of the dried Algae is weighed and transferred to 500ml beaker, then 300ml
of freshly boiled and cooled water (adjusted to pH 7.0) is added and heated to boiling. After
digesting for 10minutes, the solution is filtered and the first 50ml of the hot filtrate is
decanted. The remaining filtrate solution is cooled to room temperature and is analysed for
pH using Elico pH meter (Shanmugavalli, 2003).
3.4.2 Determination of Moisture Content
About 5g of the dried Algae is weighed in a Petridish, the dish is placed in an electric
oven maintained at 110 ± 5°C for about 5 hours. The dish is covered and cooled in a
desiccator. Heating, cooling and weighing are repeated at 30 minutes interval until the
difference between the two consecutive weights are less than 5mg. The loss in weight
gives the moisture content (Shashi Chawla, 2009).M - X
Moisture Content (%) = x 100M
where,M = Weight of the adsorbent (g)
X = Weight of the adsorbent taken after drying (g)
3.4.3 Determination of Surface Area (BET method)
Surface area of the adsorbents used in this study namely, Blue-Green Algae and
Commercial Activated Carbon are determined using surface area analyser (TriStar 3000V
6.07A) by BET (Brunauer, Emmett and Teller) method at Sud-Chemie India Private (Ltd),
Research and Development Division, Cochin, Kerala, India and the results obtained are
shown in Appendix II & III.
The Commercial Activated Carbon used in this study is denoted as CAC and the
selected low cost adsorbent Blue-Green Algae is denoted as BGA throughout this thesis.
3.5 Adsorption Experiments
Batch mode experiments are carried out to study the adsorption capacity of the
adsorbent BGA. Batch experiments are simpler and effective for evaluating the basic
parameters affecting the adsorption.
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3.5.1 Effect of variation of initial concentration of the dye on the adsorption
Batch mode experiments are performed with 500mg of adsorbent BGA by varying
the initial concentration of dye solutions used in this study at pH 7.0 ± 0.2 and at 32 ± 2˚C.
100ml of dye solutions containing 60, 80, 100 and 120mg dye (Methylene Blue, Methyl
Violet, Acid Blue and Acid Violet) are prepared from the stock solution. The dye solutions
are taken into Pyrex bottles containing 500mg of the adsorbent (BGA) each, and are
agitated at 150 rpm speed thoroughly on a horizontal electrical bench shaker at 32 ± 2˚C
for various time intervals (10, 20, 30, 40, 50, 60, 90, 120, 150 and 180minutes). The
solutions are filtered and the dye concentrations are estimated colorimetrically at 480nm for
Methylene Blue & Acid Blue dyes and at 420nm for Methyl Violet & Acid Violet dyes.
3.5.2 Effect of variation of pH on the adsorption of dye
The effect of pH on dye removal is studied by varying the pH from 5 to 9 (5, 6, 7, 8
and 9). 100ml of the dye solution containing 100mg of the dye (Methylene Blue, Methyl
Violet, Acid Blue and Acid Violet) are prepared from the stock solution. The pH of the dye
solutions are adjusted to a desired pH using 0.1N H2SO4 or 0.1N NaOH and the solutions
are taken in Pyrex bottles containing 500mg of the adsorbent. These solutions are shaken
using horizontal electrical bench shaker by varying the contact time from 10 to 180minutes.
The solutions are filtered and analysed colorimetrically at 480nm for Methylene Blue & Acid
Blue dyes and at 420nm for Methyl Violet & Acid Violet dyes to find the amount of dye
adsorbed.
3.5.3 Effect of variation of adsorbent dosage on the adsorption of dye
The effect of adsorbent dosage on the adsorption of dyes (Methylene Blue, Methyl
Violet, Acid Blue and Acid Violet) is studied at pH 7.0 ± 0.2 and 32 ± 2˚C. 100ml of dye
solutions containing 100mg of dye are prepared from stock solution. The solutions are
taken in Pyrex bottles containing 200, 300, 400 and 500mg of the adsorbent BGA. The
Pyrex bottles containing adsorbent and adsorbate are shaken using horizontal electrical
bench shaker at room temperature by varying the contact time from 10 to 180 minutes.
Then the solutions are filtered and analysed colorimetrically at 480nm for Methylene Blue &
Acid Blue dyes and at 420nm for Methyl Violet & Acid Violet dyes to find the amount of dye
removed by the adsorbent BGA.
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3.5.4 Effect of variation of temperature on the adsorption of dye
To study the effect of temperature, 100ml of dye solutions containing 100mg of the
dyes (Methylene Blue, Methyl Violet, Acid Blue and Acid Violet) are prepared from the
stock solution and taken in Pyrex bottles containing 500mg of BGA. The pH of the dye
solution is maintained as 7.0 ± 0.2 for this study. These solutions are taken in a
temperature controlled horizontal electrical bench shaker and agitated by varying the
contact time from 10 to 180minutes at 22˚C, 32˚C and 42˚C. Then the solutions are filtered
and analysed colorimetrically at 480nm for Methylene Blue & Acid Blue dyes and at 420nm
for Methyl Violet & Acid Violet dyes to find the amount of dye adsorbed by the adsorbent
BGA.
3.5.5 Removal of Methylene Blue, Methyl Violet, Acid Blue and Acid Violet dyes byAdsorption from Dyeing Industrial Effluent using the adsorbent BGA
The textile dye effluent containing Methylene Blue and Acid Violet are collected from
Sri Ram Dyeing, Angeripalayam, Tiruppur, Tamilnadu, India. Dye effluent containing Acid
Blue and Methyl Violet are collected from Dhanalakshmi Dyeing Company, Tiruppur,
Tamilnadu, India. Batch mode experiments are conducted using the adsorbent BGA and
the dyeing industrial effluent containing Methylene Blue, Methyl Violet, Acid Blue and Acid
Violet dyes. The pH of the dyeing industrial effluent collected varied from 8.76 to 10.57.
Therefore, the pH of the dyeing industrial effluent is adjusted to pH 7.0 ± 0.2 using 0.1N
H2SO4. 100ml of the effluent containing 100mg of the dyes (Methylene Blue, Methyl Violet,
Acid Blue and Acid Violet) are prepared from the industrial effluent and taken in the Pyrex
bottles containing 500mg of the adsorbent BGA and agitated using horizontal electrical
bench shaker at 32 ± 2˚C for predetermined time intervals of 10 to 180minutes. The
solutions are filtered and analysed colorimetrically at 480nm for Methylene Blue & Acid
Blue dyes and at 420nm for Methyl Violet & Acid Violet dyes to find the amount of dye
adsorbed.
Batch mode experiments are also conducted using Commercial Activated Carbon
(CAC) as an adsorbent. The pH of the dyeing industrial effluent is adjusted to pH 7.0 ± 0.2
using 0.1N H2SO4. 100ml of the effluent containing 100mg of the dyes (Methylene Blue,
Methyl Violet, Acid Blue and Acid Violet) are prepared from the dyeing industrial effluent
and taken in the Pyrex bottles containing 500mg of the adsorbent CAC and agitated using
horizontal electrical bench shaker at 32 ± 2˚C for predetermined time intervals of 10 to
180minutes. The solutions are filtered and analysed colorimetrically at 480nm for
Methylene Blue & Acid Blue dyes and at 420nm for Methyl Violet & Acid Violet dyes to find
the amount of dye adsorbed.
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3.6 Kinetics, Adsorption Isotherm and Thermodynamic Studies for the Removal ofDyes
The results of the above mentioned studies are used to determine the rate constants
for the adsorption of the dyes from aqueous solution and also from dyeing industrial effluent
using Lagergren rate equation, Intraparticle diffusion rate equation and Elovich rate
equation. Langmuir & Freundlich adsorption isotherms and Thermodynamic parameters
(∆S, ∆G and ∆H) are evaluated for the adsorption of Methylene Blue, Methyl Violet,
Acid Blue and Acid Violet dyes.
3.7 Scanning Electron Microscope and FTIR Spectral Analysis
The Scanning Electron Microscope is a microscope that uses electrons, instead of
light to form an image. Since their development in the early 1950’s has developed new
areas of study. The SEM has allowed researchers to examine a much bigger variety of
specimens.
The Scanning Electron Microscope has many advantages over traditional
microscopes. The SEM has a large depth of field, which allows more of a specimen to be in
focus at one time. The SEM also has much higher resolution, so closely spaced specimens
can be magnified at much higher levels, because the SEM uses electromagnets rather than
lenses and the researcher has much more control in the degree of magnification. All of
these advantages, as well as the actual strikingly clear images, make the Scanning
Electron Microscope is one of the most useful instruments in research today. The surface
morphology of the adsorbent BGA before and after adsorption of the dyes used in this
study is observed using Scanning Electron Microscope (FEI Quanta 200 SEM).
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The SEM photographs of the following are obtained:
The adsorbent Blue-Green Algae (BGA)
Adsorbent BGA with the adsorbed Methylene Blue dye from aqueous solution
Adsorbent BGA with the adsorbed Methyl Violet dye from aqueous solution
Adsorbent BGA with the adsorbed Acid Blue dye from aqueous solution
Adsorbent BGA with the adsorbed Acid Violet dye from aqueous solution
Adsorbent BGA with the adsorbed Methylene Blue dye from Industrial Effluent
Adsorbent BGA with the adsorbed Methyl Violet dye from Industrial Effluent
Adsorbent BGA with the adsorbed Acid Blue dye from Industrial Effluent
Adsorbent BGA with the adsorbed Acid Violet dye from Industrial Effluent
FTIR Spectral Analysis of the Adsorbent Blue-Green Algae
Infrared spectrum of the adsorbent, Blue-Green Algae is obtained using a Fourier
Transform Infrared spectrometer (Perkin Elmer Model Spectrum RX1 in the wavenumber
range 4000 – 400cm-1, using KBr pellet technique).
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The SEM photographs of the following are obtained:
The adsorbent Blue-Green Algae (BGA)
Adsorbent BGA with the adsorbed Methylene Blue dye from aqueous solution
Adsorbent BGA with the adsorbed Methyl Violet dye from aqueous solution
Adsorbent BGA with the adsorbed Acid Blue dye from aqueous solution
Adsorbent BGA with the adsorbed Acid Violet dye from aqueous solution
Adsorbent BGA with the adsorbed Methylene Blue dye from Industrial Effluent
Adsorbent BGA with the adsorbed Methyl Violet dye from Industrial Effluent
Adsorbent BGA with the adsorbed Acid Blue dye from Industrial Effluent
Adsorbent BGA with the adsorbed Acid Violet dye from Industrial Effluent
FTIR Spectral Analysis of the Adsorbent Blue-Green Algae
Infrared spectrum of the adsorbent, Blue-Green Algae is obtained using a Fourier
Transform Infrared spectrometer (Perkin Elmer Model Spectrum RX1 in the wavenumber
range 4000 – 400cm-1, using KBr pellet technique).
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The SEM photographs of the following are obtained:
The adsorbent Blue-Green Algae (BGA)
Adsorbent BGA with the adsorbed Methylene Blue dye from aqueous solution
Adsorbent BGA with the adsorbed Methyl Violet dye from aqueous solution
Adsorbent BGA with the adsorbed Acid Blue dye from aqueous solution
Adsorbent BGA with the adsorbed Acid Violet dye from aqueous solution
Adsorbent BGA with the adsorbed Methylene Blue dye from Industrial Effluent
Adsorbent BGA with the adsorbed Methyl Violet dye from Industrial Effluent
Adsorbent BGA with the adsorbed Acid Blue dye from Industrial Effluent
Adsorbent BGA with the adsorbed Acid Violet dye from Industrial Effluent
FTIR Spectral Analysis of the Adsorbent Blue-Green Algae
Infrared spectrum of the adsorbent, Blue-Green Algae is obtained using a Fourier
Transform Infrared spectrometer (Perkin Elmer Model Spectrum RX1 in the wavenumber
range 4000 – 400cm-1, using KBr pellet technique).