FACILE ECO-FRIENDLY TREATMENT OF

A DYE WASTEWATER MIXTURE BY IN

SITU HYBRIDIZATION WITH GROWING CALCIUM CARBONATE

BYMONIKA JAIN POONAM BARGE RAVI MALVIYA SHAGUN MISHRA BE FINAL YEAR

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 and re-use the water in the factory.So dye factories across the world are disposing millions of tons of dye effluent into rivers.
ABOUT DYESDyes can be said to be colored, ionizing and aromatic organic compounds which 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 is applied.

BUT WHY DO WE NEED TO APPLY THIS HYBRID PROCESS???

The majority of color removal techniques are based on coagulation/adsorption of dyes by physical methods or the complete destruction of dye molecules by chemical methods such as electrolysis, ozonation, etc.

OBJECTIVE The objective of this work is to establish a new type of wastewater treatment 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 in polymer products) in order to avoid secondary pollution. Illustration of the two-dye (CR/MB) mixture treatment process is given. A: CR mixed with MB; B: Na2CO3 and then CaCl2 were added. The treated water was discharged 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).

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 biological degradation treatment. Dyes increases BOD of effluent thereby affecting aquatic life Toxic to fish & microbial organisms The discharge of heavy metals into aquatic ecosystems increase the alkalinity of water The turbidity and colour along with oil and scum create an unsightly appearance. The mineral materials, mostly sodium salts increase salinity of the water

Classification of waste water treatment process Treatment Primary Secondary

Operations Screening Sedimentation, Equalization, Neutralization, Mechanical flocculation, Chemical coagulation Aerated lagoon, Trickling filtration, Activated sludge process, Oxidation ditch & pond, Anaerobic digestion

Tertiary Oxidation technique, Electrolytic precipitation & Foam fractionation, Membrane technologies, Electrochemical processes, Ion exchange method, Photo catalytic degradation, Adsorption (Activated Carbon etc.), Thermal evaporation

HYBRIDIZATION OF TREATMENT PROCESSES Hybridization means the use of different separation process simultaneously, or the collection of contacting stages. Hybridization is used in industrial processes to:

Accomplish separations that cannot be achieved in a single stage, and/or Reduce the required amount of the mass- or energy- separating agent.

PROPERTIES OF CHEMICALS USED

METHYLENE BLUE Methylene blue is a heterocyclic aromatic chemical compound with molecular formula: C16H18N3SCl and molecular weight 319.85 gm/mole. It has many uses in a range of different fields, such as biology and chemistry. At room temperature it appears as a solid, odorous, dark green powder, which yields a blue solution when dissolved in water. Its IUPAC name is 3,7- bis (Dimethylamino) phenothiazin-5- ium chloride. CONGO RED Congo red is the sodium salt of benzidinediazo-bis-1-naphthylamine-4sulfonic acid (formula: C32H22N6Na2O6S2; molecular weight: 696.66 g/mol). It is 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 IUPAC name is sodium 3,3-(1E, 1E)-biphenyl-4,4-diybis(diazene-2,1-diyl) bis (4amoniaphthalene-1-sulfonate).

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 of CR. Similarly, 0.0032gm of MB in 100ml of tap water for 100M solution of MB and 0.106gm of Na2CO3 and 0.222gm of CaCl2 in 100ml of distilled water to prepare 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 the sedimentation height at definite time interval. Most of the conjugated dye was settled in first 30min, and then the settling rate was very slow. The solution was kept overnight for complete settling and obtaining the clear solution. After the complete settling of conjugated dye, the solution was filtered to remove the sludge (conjugated-dye-CaCO3 hybrid) and for obtaining clear solution. Clear solution was used to determine various parameters like COD, color, etc. and the dye contaminant sludge was used to manufacture paint.

CaCl2

Waste water 2 (cationic e.g. MB)

Na2CO3

A MIXING DISCHARGE

Waste water 1 (anionic e.g. CR)

PAINT D SLUDGE E

Figure3.4- Ion-pair interaction between CR and MB.

SOLUTION MAKINGSolution 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 solution Final

colour

of Dark blue

Bluish black

Dark blue

Mud red

Bluish black

colour

of Blue colour clear water

Dark blue clear water

Blue colour clear water

Clear water

Blue

colour

clear

solution after 24 hr

water

Sludge settled after 30 0.3cm minutes

0.27cm

0.29cm

0.31cm

0.25cm

0.35

0.3

0.31 0.3 0.29 0.27

0.25 0.24

0.25

0.2

0.2 0.19 0.18 0.16

solution 1 solution 2 solution 3

0.15

solution 4
solution 5

0.1 0.09 0.08 0.07 0.05 0.05 0.04

0 10 minute 20 minute 30 minute

EXPERIMENTAL WORK DONE SO FAR-

Experiment of Absorbance measurement by spectrophotometer Wavelength of CR-MB solution taken as 490nm. Absorbance of fresh CR-MB solution= 1380 Absorbance of CR-MB solution after keeping it still for 15 minutes= 759 Absorbance of CR-MB solution after keeping it still for 24 hr= 14
% removal of colour= (c/d) 100 Where, c = weight of dye effluent removed = (final weight of filter paper) (initial weight of filter paper) =1.127- 0.816 c = 0.311 gm d = 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%

COD calculationAfter open reflux method,we titrated the solutions.

Sample Initial burette readin g 1 2 3 0 0 0

Final Total burette readin readin g g 15 14 11.3 15 14 11.3

Molarity of FAS solution, Volume 0.04167M K2Cr2O7 Solution titrated, ml

X 0.25 Volume FAS used in titration, ml = (20ml/100ml)* 0.25 = 0.05 ml sample

(A B) M 8000 COD as mg O2/L = 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 measurementWhen 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.

THANK YOU.