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FACILEECO-FRIENDLYTREATMENTOFADYEWASTEWATERMIXTUREBYINSITUHYBRIDIZATIONWITHGROWINGCALCIUMCARBONATE
BY-MONIKA JAINPOONAM BARGERAVI MALVIYASHAGUN MISHRABE FINAL YEAR
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INTRODUCTION
Almost every industrial dye process involves a solution of a dye in water,in which the fabrics are dipped or washed. After dying a batch of fabric,its cheaper to dispose the used water dye effluent than to clean andre-use the water in the factory.So dye factories across the world aredisposing millions of tons of dye effluent into rivers.
ABOUT DYES-
Dyes can be said to be colored, ionizing and aromatic organic compoundswhich shows an affinity towards the substrate to which it is being applied.It is generally applied in a solution that is aqueous. Dyes may also require
a mordant to better the fastness of the dye on the material on which it isapplied.
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BUT WHY DO WE NEED TOAPPLY THIS HYBRIDPROCESS???
The majority of color removal techniques are based oncoagulation/adsorption of dyes by physical methods or the completedestruction of dye molecules by chemical methods such as electrolysis,ozonation, etc.
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The objective of this work is to establish a new type of wastewatertreatment method by immobilizing waste
anionic (e.g. Congo red, CR)cationic (e.g. Methylene blue, MB)dyes by conjugation onto a harmless inorganic skeleton (e.g. CaCO3).Also, based on the dye wastewater characteristics, the feasibility of reuse
of the dye-immobilized CaCO3 sludge was investigated (e.g. as filler inpolymer products) in order to avoid secondary pollution. Illustration ofthe two-dye (CR/MB) mixture treatment process is given. A: CR mixedwith MB; B: Na2CO3 and then CaCl2 were added. The treated water wasdischarged after settling the suspending substance (C) and the
dye-contaminated sludge separated (D). The colored sludge was reused
as the color filler of a polymer product (E).
OBJECTIVE
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Common effects of dye effluents:-
Impart colour to water bodies even if present in small quantity.
Reduces light penetration and photosynthesis.Carcinogenic or mutagenic.Azo dyes are more toxic as they affect microbes thereby affecting biologicaldegradation treatment.Dyes increases BOD of effluent thereby affecting aquatic life
Toxic to fish & microbial organismsThe discharge of heavy metals into aquatic ecosystems increase the alkalinityof waterThe turbidity and colour along with oil and scum create an unsightlyappearance.The mineral materials, mostly sodium salts increase salinity of the water
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Classification of waste water treatmentprocess
Treatment Primary Secondary Tertiary
Operations ScreeningSedimentation,Equalization,Neutralization,Mechanicalflocculation,
Chemicalcoagulation
Aerated lagoon,Tricklingfiltration,Activated sludgeprocess,Oxidation ditch &
pond,Anaerobicdigestion
Oxidationtechnique,Electrolyticprecipitation &Foamfractionation,
Membranetechnologies,Electrochemicalprocesses,Ion exchangemethod,
Photo catalyticdegradation,Adsorption(ActivatedCarbon etc.),Thermal
evaporation
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HYBRIDIZATION OF TREATMENT PROCESSES
Hybridizationmeans the use of different separation process
simultaneously, or the collection of contacting stages. Hybridization isused in industrial processes to:
Accomplish separations that cannot be achieved in a single stage, and/orReduce the required amount of the mass- or energy- separating agent.
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PROPERTIES OF CHEMICALS USED
METHYLENE BLUE
Methylene blue is a heterocyclicaromaticchemical compound withmolecular formula: C16H18N3SCl and molecular weight 319.85 gm/mole.It has many uses in a range of different fields, such as biology andchemistry. At room temperature it appears as a solid, odorous, darkgreen powder, which yields a blue solution when dissolved in water.Its IUPAC name is 3,7- bis (Dimethylamino) phenothiazin-5- ium
chloride.
CONGO REDCongo red is the sodium salt of benzidinediazo-bis-1-naphthylamine-4-sulfonic acid (formula: C32H22N6Na2O6S2; molecular weight: 696.66 g/mol). Itis a secondary diazo dye. Congo red is water soluble, yielding a red colloidal
solution; its solubility is better in organic solvents such as ethanol. Its IUPACname is sodium 3,3-(1E, 1E)-biphenyl-4,4-diybis(diazene-2,1-diyl) bis (4-amoniaphthalene-1-sulfonate).
http://en.wikipedia.org/wiki/Heterocyclic_ringhttp://en.wikipedia.org/wiki/Aromaticityhttp://en.wikipedia.org/wiki/Chemical_compoundhttp://en.wikipedia.org/wiki/Molecular_formulahttp://en.wikipedia.org/wiki/Carbonhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Nitrogenhttp://en.wikipedia.org/wiki/Sulfurhttp://en.wikipedia.org/wiki/Chlorinehttp://en.wikipedia.org/wiki/Biologyhttp://en.wikipedia.org/wiki/Chemistryhttp://en.wikipedia.org/wiki/Water_(molecule)http://en.wikipedia.org/wiki/Diazo_dyehttp://en.wikipedia.org/wiki/Colloidhttp://en.wikipedia.org/wiki/Colloidhttp://en.wikipedia.org/wiki/Diazo_dyehttp://en.wikipedia.org/wiki/Water_(molecule)http://en.wikipedia.org/wiki/Chemistryhttp://en.wikipedia.org/wiki/Biologyhttp://en.wikipedia.org/wiki/Chlorinehttp://en.wikipedia.org/wiki/Sulfurhttp://en.wikipedia.org/wiki/Nitrogenhttp://en.wikipedia.org/wiki/Hydrogenhttp://en.wikipedia.org/wiki/Carbonhttp://en.wikipedia.org/wiki/Molecular_formulahttp://en.wikipedia.org/wiki/Molecular_formulahttp://en.wikipedia.org/wiki/Chemical_compoundhttp://en.wikipedia.org/wiki/Aromaticityhttp://en.wikipedia.org/wiki/Heterocyclic_ring -
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WASTE WATER TREATMENT PROCESS
Treatment process followed is described as below:
Dissolved 0.007gm of CR in 100ml of tap water to prepare 100M solution ofCR. Similarly, 0.0032gm of MB in 100ml of tap water for 100M solution of MBand 0.106gm of Na2CO3 and 0.222gm of CaCl2 in 100ml of distilled water toprepare 10mM of Na2CO3 and 20M of CaCl2 respectively.Mixed the prepared solutions of CR and MB.Added sodium carbonate into the CR-MB mixture, and stirred thoroughly.
Added calcium carbonate slowly with continuous mixing.Left the solution for settling of conjugated dye and noted down thesedimentation height at definite time interval.Most of the conjugated dye was settled in first 30min, and then the settlingrate was very slow. The solution was kept overnight for complete settlingand obtaining the clear solution.
After the complete settling of conjugated dye, the solution was filtered toremove the sludge (conjugated-dye-CaCO3 hybrid) and for obtaining clearsolution.Clear solution was used to determine various parameters like COD,color, etc. and the dye contaminant sludge was used to manufacture paint.
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D
A
B C
E
Waste water 2 (cationic e.g. MB)
Waste water 1 (anionic e.g. CR)
Na2CO3
CaCl2
MIXING DISCHARGE
SLUDGE
PAINT
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+
Figure3.4- Ion-pair interaction between CR and MB.
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Solution 1 Solution 2 Solution 3 Solution 4 Solution 5
Weight of CR 0.007 gm 0.007gm 0.007gm 0.009gm 0.007gm
Weight of MB 0.0032gm 0.0032gm 0.0032gm 0.0032gm 0.0032gm
Weight of Na2CO3 0.107gm 0.800gm 0.53gm 0.303gm 0.303gm
Weight of CaCl2 0.222gm 0.701gm 0.111gm 0.461gm 0.461gm
Initial colour of
solution
Dark blue Bluish black Dark blue Mud red Bluish black
Final colour of
solution after 24 hrBlue colour clear water Dark blue clear water Blue colour clear water Clear water Blue colour clear
water
Sludge settled after 30
minutes0.3cm 0.27cm 0.29cm 0.31cm 0.25cm
SOLUTION MAKING-
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0.08
0.2
0.3
0.05
0.18
0.27
0.07
0.19
0.29
0.09
0.24
0.31
0.04
0.16
0.25
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
10 minute 20 minute 30 minute
solution 1
solution 2solution 3
solution 4
solution 5
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Experiment of Absorbance measurement by spectrophotometerWavelength of CR-MB solution taken as 490nm.Absorbance of fresh CR-MB solution= 1380Absorbance of CR-MB solution after keeping it still for 15 minutes= 759Absorbance of CR-MB solution after keeping it still for 24 hr= 14
% removal of colour= (c/d) 100Where, c = weight of dye effluent removed
= (final weight of filter paper) (initial weight of filter paper)=1.127- 0.816
c = 0.311 gmd = total of initial weight of the CR, MB and Na2CO3
=0.009 + 0.003 +0.303=0.315gm
% removal of colour = (c/d) 100= (0.311/0.315) 100=98.7%
EXPERIMENTAL WORK DONE SO FAR-
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COD calculation-After open reflux method,we titrated the solutions.
Molarity of FAS solution,Volume 0.04167M K2Cr2O7
Solution titrated, ml
Sample Initialburettereadin
g
Finalburettereadin
g
Totalreading
1 0 15 15
2 0 14 14
3 0 11.3 11.3
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= X 0.25Volume FAS used in titration, ml
= (20ml/100ml)* 0.25
= 0.05(A B) M 8000COD as mg O2/L = ml sample
COD for solution 1 = (15-11.3)*0.05*8000/100= 14.8 mg/l
COD for solution 2 = (14-11.3)*0.05*8000/100=10.8 mg/l
Where:A = ml FAS used for sample,B = ml FAS used for blank,
M = molarity of FAS, and= mili equivalent weight of oxygen X 1000 ml/L.
pH measurement-When universal indicator was added to sample, the colour changed to green-blue.This shows that pH lies between 7 to 7.5 .
When pH was obtained from pH meter ,the pH obtained was 7.23.
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THANK YOU.