Basic Civil Engineering first year Notes- Chapter 4 Building.pptx
Defence PPT.pptx
1. Removal Of Indigo Carmine Dye
Using Natural Bio sorbent
Prepared From Press Mud
3/6/2023
1
MAARIJ MEMON
MS Research Scholar
19F-MS-ENVE-13
Supervisor: Prof. Dr. Zubair Ahmed
Co-Supervisor: Dr. Naveed Ahmed
2. Table Of Contents
Introduction
1
Problem Statement
2
Literature Review
3
3/6/2023
Hypothesis
4
Novelty statement
5
Objectives
6
2
Materials and Methods
7
Expected Outcomes
8
Results and Discussion
9
Conclusion
10
References
11
4. Introduction
Industry majorly contribute to the disposal of sewage waste (Anjum, Gill and Tuteja, 2017)
for about 51%
the dyeing process solely releases for about 70 billion tons of wastewater yearly
Indigo Carmine dye Textile is (Alkhatib, 2018)
One of the most widely used dye which is water soluble in nature
possessing acid blue or food blue color
(persistent color)
(low biodegradability, high temperature and pH )
Methods to remove these dyes
physical, biological and chemical purification processes.
Adsorption is one of the most promising and well-known process. (Kaykhaii, Sasani and
Marghzari, 2018)
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4
5. Chemical Structure Of Indigo Carmine
3/6/2023 5
Characteristics
IUPAC name
3,3′-dioxo-2,2′-bis-
indolyden-5,5_-
disulfonic acid
disodium salt
Chemical formula C16H8N2Na2O8S2
Molecular structure
Molecular weight 466.36 g/mol
Absorption
maximum (water)
608–612 nm
Composition Dye content, ∼85%
Charge Negative(anonic)
Table:1
Figure:1 (FATOMBI ET AL., 2019).
6. Adsorbent Material
The press mud (dark to brownish, spongy amorphous and soft material having sugar,
fiber, coagulated colloids, inorganic salts, wax, allunnoids and soil particles) (Satish and
Devarajan, 2007).
There is an utmost need to consume these wastes and by products using a sensible
technology as there disposing off in large scale can cause environmental problems
(Satisha and Devarajan, 2007).
To reduce these various waste related problems currently a higher attention is being
paid on using naturally available, abundant and ecofriendly sorbents instead of
conventional and expensive sorbents (Sulyman, Namiesnik and Gierak, 2017).
Using press mud as a low cost selected adsorbent due to its porous structure after
being modified and various functional groups, higher carbon content and an increased
specific surface area that helps in the reactions occurring in the adsorption(Rondina et
al., 2019).
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6
6
7. Adsorbent Material
Production
• The estimated generation for press mud is approximately 30 kg per 1 ton of cane processed.
Managing and transportation issues
• Smell
• High water content
• Tendency to attract insects and other pests
• High (biochemical oxygen demand)
Utilization
• Fertilizer
• Fuel
• Biogas
• Wax production (Raimondi et al., 2020
3/6/2023
7
7
8. Adsorbent Material
Press mud as an adsorbent
• High specific surface area ( compared to other bio sorbents such as wheat straw, sugarcane
baggase,olive stone and coffee grounds)
• Presence of oxygen surface functional groups
• A promising material for adsorption of contaminants from wastewater (Raimondi et al., 2020
Characterization of press mud(FTIR)
• The absorption bands and peaks provides evidence for the present of some surface functional
groups such as carbonyl, hydroxyl and silica that are capable of adsorbing (Mohd Azme and
Murshed, 2018)
• Recently, the literature reveals that, so far, no considerable effort has been made to utilize press
mud as a precursor for activated carbon (Rondina et al., 2019).
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8
8
9. Problem Statement
Textile industries are discarding indigo carmine dye into a huge amount
without any treatment. About 22,000 tons was estimated to be
disacrded of synthetic indigo dye in 2001 (Tian et al., 2013).
3/6/2023
Utilizing the press mud due to its surface properties and carbonaceous
content as an adsorbent for removal of indigo carmine dye.
9
10. Literature Review
Main Findings References
One of the oldest and most toxic dyes belonging from
indigoid class is Indigo carmine dye.
this dye possesses the property of restricting the growth
of aquatic flora by photosynthesis obstruction.
Fatombi, J. K. et al. (2019)
‘Adsorption of Indigo Carmine
from Aqueous Solution by
Chitosan and Chitosan/Activated
Carbon Composite: Kinetics,
Isotherms and Thermodynamics
Studies’, Fibers and Polymers,
20(9), pp. 1820–1832. doi:
10.1007/s12221-019-1107-y.
Press mud a byproduct from sugar industry was used as
low-cost adsorbent for removing methylene blue from
aqueous solutions.
Marwati, S. et al. (2010)
‘NoR.Praveen kumar,
swambabu
Varanasi,V.purushothaman
Title’, Turkish Journal of
Chemistry, 53(2), pp. 391–
401.
3/6/2023 10
11. Literature Review
Main Findings References
Dyes are considered as serious water pollutants.
There are a wide variety of methods to remove pollutants from
environmental waters(biological, chemical, physical)
All of them adsorption is one of the most promising and well-
known process.
Kaykhaii, M., Sasani, M. and
Marghzari, S. (2018)
‘Removal of Dyes from the
Environment by Adsorption
Process’, Chemical and
Materials Engineering, 6(2),
pp. 31–35. doi:
10.13189/cme.2018.060201.
press mud was used to remove the methyl orange dye by
producing activate carbon through it.
Press mud was chosen because the adsorbent showed the
characteristics of clear fibrous appearance and the structure with
micropores that could easily trap the dyes
To remove the Methyl orange dye that is anionic dye the press mud
due to its profuse layering structure of the pores could be utilized.
Rondina, D. J. G. et al. (2019)
‘Utilization of a novel
activated carbon adsorbent
from press mud of sugarcane
industry for the optimized
removal of methyl orange dye
in aqueous solution’, Applied
Water Science. Springer
International Publishing, 9(8),
pp. 1–12. doi: 10.1007/s13201-
019-1063-0.1
3/6/2023 11
12. Literature Review
Main Findings References
Sugar press-mud was modified and utilized to make an advanced
carbon.
In the current work, a simple activation and purification method
where a silica-rich biomass
waste (sugar press-mud, SPM) is sono-impregnated and
fractionated with an alkaline solution.
A specific fraction of sugar-press mud has resulted in a highly
porous carbon with high surface area and large pore size
distribution. This porous carbon has a relatively low diffusion-
induced ohmic losses.
Mayyas, M. and Sahajwalla, V.
(2019) ‘Carbon nano-sponge with
enhanced electrochemical
properties: A new understanding
of carbon activation’, Chemical
Engineering Journal, 358(June
2018), pp. 980–991. doi:
3/6/2023 12
13. Hypothesis
Adsorption technique is one of the most reliable methodology to remove the indigo
carmine dye from wastewater.
Press mud could be utilized as an adsorbent in a better way and can provide the
solution for the removal of indigo carmine
3/6/2023
13
PRESS
MUD
14. 3/6/2023
Novelty
Statement
Using a waste by product of sugar
industry namely press mud as an
adsorbent for the removal of
indigo carmine dye that has not
been previously utilized and
analyzing it through
characterization.
14
15. Objectives
3/6/2023
15
To prepare an adsorbent from Press mud (a by-product of sugar
industry)
To characterize surface and chemical structure of the prepared
adsorbent.
To investigate equilibrium, kinetic, and adsorption properties of
prepared adsorbent for removal of Indigo Carmine dye from water
S
16. Methodology
3/6/2023
16
Experimental study
(Batch and fixed bed
column studies)
Drying,crushing,seivin
g,washed with nitric
acid,fitering,drying in
furnace,washing and
again drying
Collection of samples
(press mud and indigo
carmine)
Preparation of
Adsorbent
Characterization of the
Adsorbent FTIR,XRD,SEM, UV
ANALYSIS
17. Batch Study Experimental Setup
3/6/2023
Dye
Adsorption
Filtration
Filtrate
for analysis
Adsorbent
addition
Adsorbent
Experiment
Press mud
adsorbent
Indigocarmine
dye solution
17
(REZA ET AL., 2016)
18. Fixed Bed Column Experimental Setup
3/6/2023
adsorbent
Column
Peristalic
Pump
Outlet
Inlet
Pressure
Gauge
18
(AHMED ET AL., 2019)
19. Analysis
3/6/2023
• Initial concentration
• Removal rate
UV
Spectrophotometer
• Crystallographic structure
XRD(X-RAY
diffraction)
• Functional group analysis
FTIR( Fourier transform
infrared spectroscopy)
• Surface area analysis
SEM (Scanning
Electron Microscopy )
• Pseudo-First-order kinetics
• Pseudo-second-order kinetics
Kinetic study and
Isotherm Parameters
19
21. 3/6/2023
Adsorption Isotherms
The experimental data fitted two isotherm models namely Langmuir and freundlich
expressing the type of adsorption.
a) Langmuir Isotherm
This model assumes that adsorption occurs at specific equal sites within the adsorbent
means no other molecule can occupy that particular space once the dye molecule occupies
it. This monolayer adsorption is represented by
Ce/qe = 1/Qmax*KL + Ce/Qmax (Mahmoud et al..,2016)
b) Freundlich Isotherm
The model predicts heterogeneous or multilayer adsorption and the linearized form of the
freundlich equation is as follows
log qe = log KF + 1/n *log Ce (Mahmoud et al..,2016)
As shown in fig 5a and 5b respectively
21
22. Expected Outcome
1 • Utilizing the press mud as an adsorbent and achieving a better removal rate.
2
• Removal of dangerous textile dye from water to prevent human health
3
• Treating the wastewater to make it feasible for reuse and reducing pollution to
enhance its quality (SDG-6.3)
3/6/2023
22
23. 3/6/2023 2323
Fig 1: Effect of adsorbent dose
volume of the solution
(25ml)
Room temperature
operating the shaker
(150rpm)
Sampling time (15 mints)
PH (6.5)
concentration (50ppm)
0
5
10
15
0 20 40 60 80 100 120
QE
(MG/G)
TIME (MINTS)
100mg 200mg 300mg 400mg 500mg
Results
24. 3/6/2023 2424
As the graph shows it was observed that the adsorbent capacity which was calculated
using the formula qt=(Co-Ct)*V/m eventually decreases by increasing the dosage of
adsorbent as 100mg dosage gave the best results
principally the number of active sites should have increased with increasing the
amount of dose but on contrary it showed that increasing amount of adsorbent caused
a greater inter-particle interactions similar pattern was also witnessed in the study of
(Bhowmik ,S., 2022) when indigo carmine was treated by sawdust that resulted in
reducing the surface area of the adsorbent.
While a small amount of adsorbent provided a good contact between the surface of
dye and adsorbent
25. 3/6/2023
0
5
10
15
20
25
30
35
40
45
50
55
60
65
0 20 40 60 80 100 120
QE
MG/G
TIME (MINTS)
50ppm 100ppm 150ppm 200ppm 250ppm
25
Fig 2: Effect of dye concentration
volume of the solution
(25ml)
Room temperature
operating the shaker
(150rpm)
Sampling time (15 mints)
PH (6.5)
concentration (50-250ppm)
Dose 100mg
26. 3/6/2023
The graph shows that with the increase in concentration there is also an increase
in the amount of dye adsorbed per unit mass of adsorbent.
This is due to increase in the driving force similarly followed the pattern in the
study of (Lakshmi, Uma R 2009) due to an increase in the driving force and
concentration gradient that leads to a higher rate at which a molecule of dye is
passed from solution to the surface of particle
26
27. 3/6/2023
• Effect of PH
• As the pH of the solution was varied in the range of (2-10) following the similar
conditions as above.
• Minimum adsorption capacity is observed at pH 2 this illustrates that dye solution
repels the adsorbent molecules as it becomes H+ charged however an increase is
obtained in the adsorption capacity as pH increases which indicates that dye
molecules are being attached to the adsorbent surface as H+ions are replaced
with OH− ions.
• It followed the similar trend when indigo carmine was treated with Brazil nut
shells observed by (H. Andrade, Suzana Brito)
• As the graph in fig 3 shows a slight change or the adsorption process not so
affected by the change of pH due to a slight or no ion exchange occurring
between the surface and aqueous solution (H. Andrade, Suzana Brito).
27
28. 3/6/2023 28
Fig 3: Effect of PH
53
54
55
56
57
58
59
60
61
2 4 6 8 10
Qe
(mg/g)
pH
volume of the solution
(25ml)
Room temperature
operating the shaker
(150rpm)
Sampling time (15 mints)
PH (6.5)
concentration (250ppm)
Dose 100mg
29. 3/6/2023
Effect of Temperature
The adsorbent was also utilized on various temperatures and
the amount of sorption at time t was achieved highest at 35
and 45 degree centigrade as the process was known to be
endothermic in nature as shown in fig 4.
29
Fig 4: Effect of temperature
59
59.5
60
60.5
61
61.5
62
62.5
15 24 35 45
Qe
(mg/g)
Temperature (Degree)
volume of the solution
(25ml)
Room temperature
operating the shaker
(150rpm)
Sampling time (15 mints)
PH (6.5)
concentration (250ppm)
Dose 100mg
Temperature (15-45)
∆H ° ∆S°
(J mol-1) (JKmol-1k-1)
9.07606124 0.02976412
∆G °
(Jmol-1K-1)
-8168.651059
31. Functional Groups Interpretation
3/6/2023
Wavelength Peak Cm−1
Functional Group Range Actual Bond
Silanol (alcohol) 3700-3200 3750.53 O-H Stretch
Aromatic amino acids (amide) 1600-1555 1507.25 N-H Bend
Aliphatic anhydride
(alkane/alkyl)
1470-1425 1418.13 C-H Bend
Alkyl Halides 1090-1020 1000.00 C-F Stretch
Unsaturated hydrocarbon
(alkane/alkyl)
855-785 872.98 C-H Bend
Tertiary amine hydrochloride
(alkane/alkyl)
850-680 777.477 C-H Bend
Similar functional groups were also found in the study of [Rondina, D. J. G. et al. (2019)] when similarly press mud was
utilized as an adsorbent for the removal of methyl orange dye that particular and the high content of carbon derived from
press mud also helps in adsorption process
31
35. 3/6/2023 35
Pseudo First and Second Order Kinetics
The obtained data best fits into pseudo first as well as second order
reaction following physio sorption and chemisorption respectively.
Similarly when indigo carmine was treated with composite activated
carbon prepared from banana waste and banana pseudo stem and both
the process agree with adsorption while the one that best fits at the
surface of sample was pseudo second order pattern of chemisorption (B
Debina ,2020).
36. 3/6/2023
-1
-0.5
0
0.5
1
1.5
2
2.5
3
3.5
4
0 20 40 60 80 100
ln(qe-qt)
Time (Mints)
0
0.5
1
1.5
2
2.5
0 20 40 60 80 100
t/qt
Time (Mints)
36
Fig 6a: Pseudo First Order Fig 6b: Pseudo Second Order
Pseudo First order
In(qe–qt) = In (qe ) – K1
qe(mg/g)
40.8074
K1 -
0.00044
R2
0.91336
Pseudo second order
t/qt = (1/k.qe ) + (1/qe )
qe(mg/g)
47.61905
K2
18022.27
R2
0.98682
37. 3/6/2023 37
Fixed bed column study
The experiments were performed using a laboratory column setup and the
specifications of the column were as follows
Constant flow rate 5ml/min
Column height 15cm
Diameter 2.5cm
PH 6.5-7
Bed height 8cm
Concentration 50mg/l
Dose of the adsorbent (bed depth) 10 gram
The readings were taken with a specific gap of 20 minutes in order to achieve
a break through curve from the concentration time profile.
Fixed bed column study
The experiments were performed using a laboratory column setup and the specifications of
the column were as follows
Constant flow rate 5ml/min
Column height 15cm
Diameter 2.5cm
PH 6.5-7
Bed height 8cm
Concentration 50mg/l
Dose of the adsorbent (bed depth) 10 gram
The readings were taken with a specific gap of 20 minutes in order to achieve a break
through curve from the concentration time profile.
38. 3/6/2023
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
20 40 60 80 100 120 140 160 180 200 220 240
Ct/Co
Time (Mints) 38
As (N khadri , 2019) also performed a column study of indigo carmine onto activated
carbon derived from date palm petiole in order to understand the dynamic response
of the adsorbent system and various models namely Thomas model. Yoon Nelson
model and Adam Bohart model were utilized to predict the maximum adsorption
capacity as also shown respectively in fig 8a, 8b and 8c
As predicted in graph the breakthrough curve was achieved at 0.5 (Ct/Co) where a rise
in concentration is observed and the amount adsorbed is propotional on both sides of
the graph. Fig 7
Fig 7: Column Adsorption
41. 3/6/2023
CONCLUSION
• This study proposes that press mud a by of sugar industry which was earlier being utilized as a
fertilizer and is being naturally produced in a bulk amount is also proved to be a good adsorbent as
well especially for the removal of indigo carmine dye.
• The results also showed that a small amount of dosage was effective for the removal of indigo
carmine at higher concentrations as well.
• Equilibrium isotherm reveals that the adsorption process follows pseudo first order as well as second
order kinetics following physio sorption and chemisorption both while the data also fitted both the
monolayer and multilayer adsorption of dye molecules onto the surface of adsorbent.
• On the other hand a laboratory column was also utilized for real scale application achieving a break
through curve while the experimental data fitted all three models namely Thomas model, Adam
boharts model and Yoon Nelson model and the Thomas model was very well fitted with a R2 value of
0.97 obeying the extended mathematical calculation of langmuir kinetics that goes with 2nd order
kinetics reaction of adsorption desorption- study.
• This concludes that this by product of sugar industry produced in bulk can easily be utilized as a good
adsorbent for indigo carmine dye removal
41
42. References
3/6/2023
1.Anjum, N. A., Gill, S. S. and Tuteja, N. (2017) ‘Enhancing cleanup of environmental pollutants’, Enhancing Cleanup of
Environmental Pollutants, 2, pp. 1–374. doi: 10.1007/978-3-319-55423-5
2. Alkhatib, A. J. (2018) ‘Photocatalytic Degradation of Indigo Carmine in Aqueous Solutions by the Antibacterial Agent
Pefloxacin and UVA’, Biomedical Journal of Scientific & Technical Research, 5(5). doi: 10.26717/bjstr.2018.05.001275
3. Kaykhaii, M., Sasani, M. and Marghzari, S. (2018) ‘Removal of Dyes from the Environment by Adsorption Process’,
Chemical and Materials Engineering, 6(2), pp. 31–35. doi: 10.13189/cme.2018.060201.
4. Satisha, G. C. and Devarajan, L. (2007) ‘Effect of amendments on windrow composting of sugar industry pressmud’,
Waste Management, 27(9), pp. 1083–1091. doi: 10.1016/j.wasman.2006.04.020.
5. Sulyman, M., Namiesnik, J. and Gierak, A. (2017) ‘Low-cost adsorbents derived from agricultural by-products/wastes
for enhancing contaminant uptakes from wastewater: A review’, Polish Journal of Environmental Studies, 26(2), pp.
479–510. doi: 10.15244/pjoes/66769.
6. Tian, C. et al. (2013) ‘Decolorization of indigo dye and indigo dye-containing textile effluent by Ganoderma
weberianum’, Decolorization of indigo dye and indigo dye-containing textile effluent by Ganoderma weberianum, 7(11),
pp. 941–947. doi: 10.5897/AJMR12.904.
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Carbon Composite: Kinetics, Isotherms and Thermodynamics Studies’, Fibers and Polymers, 20(9), pp. 1820–1832. doi:
10.1007/s12221-019-1107-y
8. Marwati, S. et al. (2010) ‘NoR.Praveen kumar, swambabu Varanasi,V.purushothaman
Title’, Turkish Journal of Chemistry, 53(2), pp. 391–401.
9. Kaykhaii, M., Sasani, M. and Marghzari, S. (2018) ‘Removal of Dyes from the Environment by Adsorption Process’,
Chemical and Materials Engineering, 6(2), pp. 31–35. doi: 10.13189/cme.2018.060201
42
43. 10. Rondina, D. J. G. et al. (2019) ‘Utilization of a novel activated carbon adsorbent from press mud of sugarcane industry for
the optimized removal of methyl orange dye in aqueous solution’, Applied Water Science. Springer International Publishing,
9(8), pp. 1–12. doi: 10.1007/s13201-019-1063-0.1
11. Mayyas, M. and Sahajwalla, V. (2019) ‘Carbon nano-sponge with enhanced electrochemical properties: A new
understanding of carbon activation’, Chemical Engineering Journal. Elsevier, 358(June 2018), pp. 980–991. doi:
10.1016/j.cej.2018.10.094.
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arightarrow-b-is/
15.’figure:3 . http://www.chemistrylearning.com/adsorption-isotherm/
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process.
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Kinetics, Desorption, and Bioaccessibility’, Water, Air, and Soil Pollution, 231(7). doi: 10.1007/s11270-020-04746-0.
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44. 19. Lakshmi, Uma R., Vimal Chandra Srivastava, Indra Deo Mall, and Dilip H. Lataye. "Rice husk ash as an effective
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Materials Science and Chemical Engineering, 8(12), 39-55.
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3/6/2023 44
