Dye removal from waste water by using low cost adsorbent: A review

Submitted to
National Conference
on
Emerging Research Trends in Engineering-2016
Paper ID - 125

Chemical Engineering Department

Vishwakarma Government Engineering College
Chandkheda-382424
Year: – 2016
 Contents

1. Introduction
2. Adsorption
3. Adsorbent
4. Literature review
5. Future scope
6. References
 1. Introduction
•The quality of our water resources is getting worse and use of dyes
generates colored wastewaters, which give cause of environmental concern.

•Textile wastewater includes a large variety of dyes and chemical additions

that make the environmental challenge for textile industry not only as liquid
waste but also in its chemical composition.

•Main pollution in textile wastewater come from dyeing and finishing

processes.

•These processes require the input of a wide range of chemicals and

dyestuffs, which generally are organic compounds of complex structure.
•Water is used as the principal medium to apply dyes and various
chemicals for finishes.

•Because all of them are not contained in the final product, became waste
and caused disposal problems.

•Major pollutants in textile wastewaters are high suspended solids,

chemical oxygen demand, heat, colour, acidity, and other soluble
substances.

•Substances which need to be removed from textile wastewater are mainly

colour, COD, BOD, pH, TDS.
 Harmful Effects

• Toxic
• Carcinogenic
• Mutagenic
• Teratogenic
• Retards photosynthetic activity
• Inhibits growth of aquatic biota
 Permissible Limits

• pH is 6.5-8.5
• The maximum permissible COD limit is < 150 mg/L
• The maximum permitted BOD content of < 100 mg/L.
• TDS limit is 2100 mg/L
• Color limit 100 hazen
 The Technologies

Treatment methods for effluents

Chemical methods Physical methods Biological methods

Oxidation Ozonation Filtration Adsorption Enzymes

Coagulation/ Microbes
Flocculation
 2. Adsorption

• A process wherein a material is concentrated at a solid surface from

its liquid or gaseous surroundings.

• Adsorption is considered as the best wastewater treatment technique

because of its all-inclusive nature, modesty and simplicity of
operation.

• Basically, adsorption is the accumulation of a substance at a surface

or interface.
 Why Adsorption ??

• Simplest

• Low capital and operating costs

• Can have good physical properties

• Adsorbents are easily available

 Adsorption processes: Applications
Purifications: Separations:

- Removal of organics from - N2/O2

vent gases
- Acetone from vent stream
gas phase

- SO2 from vent gases

- C2H4 from vent
- H2O from air, methane, N2
- Normal paraffins/ Iso praffins
- Removal of solvent, odours
from air - CO, CH4, CO2, N2, Ar from
hydrogen
- NOx from N2

- Organics from water solution - Normal paraffins from Iso paraffins

liquid phase

- Water from organic solution - Normal paraffins from olefins

- Decolourization
 3. Adsorbent

• Adsorption processes is the interaction of adsorbate molecules

with the surface of adsorbent

• Therefore adsorbent materials are usually materials with

extensive porous structure

Criteria for adsorbent selection:

* Selectivity
* Capacity
* Chemical and thermal stability
* Cost
 Classification of adsorbents

(I) On basis of their availability

(a) Natural materials
(b) Industrial/Agricultural/ Domestic wastes or by-products
(c) Synthesized products

(II) Depending on their nature

(a) Inorganic
(b) Organic

An application of bio-sorption using fungi, yeasts and bacteria for the

removal of organic pollutants
 Adsorbents: Characterization
1) Crystalline/amorphous
2) Hydrophobic/Hydrophilic
3) Surface area (100-1000 m2/gm)
4) Pore size
r < 2 nm Microporous
2 nm < r < 50 nm Mesoporous
r > 50 nm Macroporous

5) Pore shape: slits, channels, cavities, cages, shapeless

- often modelled as cylindrical channels
 Factors Affecting Adsorbents Properties

• Starting materials (e.g., coal vs. wood based) and activation

• Pores and pore size distributions
• Internal surface area
• Surface chemistry (esp. polarity)
• Apparent density
• Particle Size: Granular vs. Powdered (GAC vs. PAC)
 Surface area and cost [23]

Adsorbents Surface area ( m2/gm ) Cost (RS/kg)

Commercial activated carbon 500 - 2000 500

Bentonite clay 47 - 73 150

Silica gel 250 - 900 120

Alumina 200 - 300 110

Bauxite 25 - 250 90

Banana peel 20.6 - 23.5 60

Kaolinite clay - 40

Fuller’s earth - 15

Wood 3.8 - 6.4 10

Bagasse 607 -
 4. Literature review
Author Adsorbent Dye Parameter Isotherms and
model
Nevine Kamal Amin Sugarcane reactive orange (RO) contact time, Langmuir and
(2008) bagasse pith dye adsorbent dose Freundlich
[15] and pH adsorption
isotherms
V.K. Garg , Renuka Sawdust malachite green contact time, first order rate
Gupta, Anu Bala Yadav, adsorbent dose expression and
Rakesh Kumar (2003) and pH Lagergren
[22] equation
K. Santhy, P. Selvapathy Coir pith reactive contact time, Freundlich model
(2006) dyes(orange12, red 2, adsorbent dose
[12] blue 4) and pH
V.K. Garg, Moirangthem Indian methylene blue adsorbent dosage, first order rate
Amita, Rakesh Kumar, Rosewood initial dye equation and fit
Renuka Gupta (2004) Sawdust concentration, pH the Lagergren
[21] and contact time equation
 F. Ferrero Ground Methylene Blue, - Lagergren’s model, but the best fit
(2007) hazelnut and Acid Blue 25 was achieved by a second order
[7] shells and Equation
sawdust
Freundlich and Langmuir
isotherms

P.K. Malik Mahogany Direct Blue 2B and - Langmuir equation as well as the
(2004) sawdust: Direct Green B dyes pseudo-second-order
[16] rate equation
C. Namasivayam, Coir pith Congo Red agitation time, Langmuir and
D. Kavitha dye concentration, Freundlich isotherms
(2002) adsorbent dose, pH
[4] and temperature
Dipa Ghosh, Kaolinite clay methylene blue pH Freundlich and Langmuir
Krishna G. equations
Bhattacharyya
(2002) [5]
B.H. Hameed, A.L. rattan methylene blue Effect of initial dye
Ahmad, K.N.A. sawdust concentration on Langmuir and Freundlich models
Latiff adsorption
(2007) [3]
G. Atun, G. Hisarli, W.S. Fuller’s earth methylene blue dependence on -
Sheldrick, and initial
M. Muhler concentration
(2003) Effect of
[8] temperature on
MB adsorption
V. J. P. Poots, G. McKay, wood Atrazone Contact time,
J. J. Healy (1978) Blue initial conc of dye Langmuir and
[20] Freundlich
models
Hung-Yee Shu, Ming- advanced phthalocyanine dye initial hydrogen -
Chin Chang oxidation peroxide
(2005) process concentration,
[10] Effect of UV light
power, , initial dye
concentration, pH

Li-yan Fu, Xiang-hua acclimated copper- Influence of CPC -

Wen, Li-jie Xu, Yi Qian sludge, phthalocyanine dye concentration on
(2002) microbial
[13] activity
Factors affecting dye adsorption onto adsorbent
 pH

• High pH solution results in an increase in the percentage of cationic dye

removal because the positive charge on the solution interface will decrease
and the adsorbent surface appears negatively charged.

• Low pH solution results in an increase in the percentage of anionic dye

removal because of the electrostatic attraction between anionic dye and the
positive surface charge of the adsorbent.
 Adsorbent Dosage

• In general, the dye removal percentage is increasing with the increase

of the adsorbent dosage.

• When excess adsorbent dosage is used, a significant portion of the

adsorption sites remain unsaturated. This obviously leads to low
specific adsorption capacity.

• When the adsorbent dosage was lowered, the number of active sites
saturated with dyes increased; therefore, specific uptake also
increased.
 Time

• At higher contact time, the rate of adsorption decreases, gradually

leading to equilibrium due to decrease in total adsorbent surface area
and less available binding sites.

• The decrease in dye removal with time may be due to aggregation of

the dye molecules around the adsorbent particles.
 Freundlich adsorption isotherm
• Is an empirical relation between the concentration of a solute on the surface of an adsorbent to
the concentration of the solute in the liquid with which it is in contact.
• The Freundlich Adsorption Isotherm is mathematically expressed as

1
𝑞 = 𝐾𝑝 𝑛
It can be written as,

1
log 𝑞 = log 𝐾 + log 𝑝
𝑛
Or

𝑥 1
= 𝐾𝐶 𝑛
𝑚 Where, q = amount of solute adsorbed
C= eq. concentration
1
log 𝑞 = log 𝐾 + log 𝐶 K= adsorption coefficient
𝑛
n= slope
• Freundlich adsorption isotherm failed at higher pressure.
 Simple isotherm equations: Langmuir

ni
Assumptions:   m ax
ni
- Single layer
nim ax
- Interaction between
molecules in the layer are
negligible

Kpi ni Kn pmax
   max ni  i i

1  Kpi ni 1  Kpi
Simple isotherm equations: Langmuir

Knimax pi
ni  pi
1  Kpi ni
1
pi 1 pi nim ax
 m ax  m ax 1
ni ni K ni nim axK

pi

More convenient units

q [kg of adsorbate]/
[kg of pure adsorbent]
HY
q
1  bY Y [kg of adsorbate/kg carrier gas]
 Lagergren equation

• Lagergren first order model which is generally expressed as

𝑑𝑞
= 𝑘1 (𝑞𝑒 − 𝑞)
𝑑𝑡
Where, k1 is the first-order-rate constant.

• The kinetic rate expression can be written as

𝑘1
log(𝑞𝑒 − 𝑞)= log 𝑞𝑒 − 𝑡
2.303
 5. Future scope

• Low cost adsorbents can be used for water treatment and waste management.

• There is a need to develop more efficient selective, inexpensive and eco-friendly

low cost adsorbents for water treatment.

• Continuous process can be used for adsorption process.

• Many work is to be carried out in the area of desorption process.

 6. References
[1] A.L. Ahmad, S.W. Puasa, Reactive dyes decolourization from an aqueous solution by combined
coagulation/micellar-enhanced ultrafiltration process, Chemical Engineering Journal 132 (2007) 257–265.

[2] Aysegul Pala, Enis Tokat, Color removal from cotton textile industry wastewater in an activated sludge system
with various additives, Water Research 36 (2002) 2920–2925.

[3] B.H. Hameed, A.L. Ahmad, K.N.A. Latiff, Adsorption of basic dye (methylene blue) onto activated carbon
prepared from rattan sawdust, Dyes and Pigments 75 (2007) 143-149.

[4] C. Namasivayam, D. Kavitha, Removal of Congo Red from water by adsorption onto activated carbon
prepared from coir pith, an agricultural solid waste, Dyes and Pigments 54 (2002) 47–58.

[5] Dipa Ghosh, Krishna G. Bhattacharyya, Adsorption of methylene blue on kaolinite, Applied Clay Science 20
(2002) 295– 300.

[6] Esther Forgacs, Tibor Cserhati, Gyula Oros, Removal of synthetic dyes from wastewaters: a review,
Environment International 30 (2004) 953– 971.

[7] F. Ferrero, Dye removal by low cost adsorbents: Hazelnut shells in comparison with wood sawdust, Journal of
Hazardous Materials 142 (2007) 144–152.
[8] G. Atun, G. Hisarli, W.S. Sheldrick, and M. Muhler, Adsorptive removal of methylene blue from colored
effluents on fuller’s earth, Journal of Colloid and Interface Science 261 (2003) 32–39.

[9] Gregorio Crini, Recent developments in polysaccharide-based materials used as adsorbents in wastewater
treatment, Prog. Polym. Sci. 30 (2005) 38–70.

[10] Hung-Yee Shu, Ming-Chin Chang, Decolorization and mineralization of a phthalocyanine dye C.I. Direct
Blue 199 using UV/H2O2 process, Journal of Hazardous Materials B125 (2005) 96–101.

[11] Imran Ali, Mohd. Asim, Tabrez A. Khan, Low cost adsorbents for the removal of organic pollutants from
wastewater, Journal of Environmental Management 113 (2012) 170-183.

[12] K. Santhy, P. Selvapathy, Removal of reactive dyes from wastewater by adsorption on coir pith activated
carbon, Bioresource Technology 97 (2006) 1329–1336.Klaus Hunger (Editor), Industrial Dyes Chemistry,
Properties, Applications, 2003.

[13] Li-yan Fu, Xiang-hua Wen, Li-jie Xu, Yi Qian, Removal of a copper-phthalocyanine dye from wastewater by
acclimated sludge under anaerobic or aerobic conditions, Process Biochemistry 37 (2002) 1151–1156.

[14] Maria Cristina Silva, Angelita Duarte Correa Decolorization of the phthalocyanine dye reactive blue 21 by
turnip peroxidase and assessment of its oxidation products, Journal of Molecular Catalysis B: Enzymatic 77
(2012) 9– 14.
[15] Nevine Kamal Amin, Removal of reactive dye from aqueous solutions by adsorption onto activated
carbons prepared from sugarcane bagasse pith, Desalination 223 (2008) 152–161.

[16] P.K. Malik, Dye removal from wastewater using activated carbon developed from sawdust: adsorption
equilibrium and kinetics, Journal of Hazardous Materials B113 (2004) 81–88.

[17] Sanna Hokkanen, Amit Bhatnagar, Mika Sillanpaa, A review on modification methods to cellulose-based
adsorbents to improve adsorption capacity, Water Research 91 (2016) 156-173.

[18] Sarika Diwaniyan, Deepti Kharb, Chandralata Raghukumar, Ramesh Chander Kuhad, Decolorization of
Synthetic Dyes and Textile Effluents by Basidiomycetous Fungi, Water Air Soil Pollut (2010) 210:409–419.

[19] Shaobin Wang, Yuelian Peng, Natural zeolites as effective adsorbents in water and wastewater treatment,
Chemical Engineering Journal 156 (2010) 11–24.

[20] V. J. P. Poots, G. McKay and J. J. Healy, Removal of Basic Dye from Effluent Using Wood as an
Adsorbent, Journal (Water Pollution Control Federation), Vol. 50, No. 5 (May, 1978), pp. 926-935.

[21] V.K. Garg, Moirangthem Amita, Rakesh Kumar, Renuka Gupta, Basic dye (methylene blue) removal
from simulated wastewater by adsorption using Indian Rosewood sawdust: a timber industry waste, Dyes and
Pigments 63 (2004) 243-250.
[22] V.K. Garg, Renuka Gupta, Anu Bala Yadav, Rakesh Kumar, Dye removal from aqueous
solution by adsorption on treated sawdust, Bioresource Technology 89 (2003) 121–124.

[23] V.K. Gupta, Suhas, Application of low-cost adsorbents for dye removal – A review, Journal
of Environmental Management 90 (2009) 2313–2342.

[24] W.T. Tsai, K.J. Hsien and J.M. Yang, Silica adsorbent prepared from spent diatomaceous
earth and its application to removal of dye from aqueous solution, Journal of Colloid and
Interface Science 275 (2004) 428–433.
Questions ??
Thank you