AIC 2004 Color and Paints, Interim Meeting of the International Color Association, Proceedings

Influence of chemical structure of dyes on decolouration effects

Djurdjica PARAC-OSTERMAN, Ana Marija GRANCARI, and Ana SUTLOVIC University of Zagreb, Faculty of Textile Technology, Zagreb, Croatia

ABSTRACT From the ecological and physiological point of view the effluents from textile industries are the most expressive polluted. For achieving the water of high quality for recycling use the most important thing in decolouration of effluent is removal of dyes and others compounds. On the base of the fact that decolouration of textile dye effluent with azo dyes gives the best results the most methods are based on the removal of these dyes. The aim of this paper is achieving the complete decolouration of wastewater with different chromogen dye systems. For such purpose the effluent with next two reactive and two acid dyes are chosen: C.I. Acid Blue 158 (azo), C.I.Reactive Blue 19 (anthraquinon), C.I. Acid Red 52 (xanthen) and C.I. Reactive Blue116 (phtalocyanin). The decolouration of dyed water was carried out by the next methods: using Fentons reagent (with and without ultrasound) and coagulation/flocculation method. The degree of decolouration was determined spectrophotometrically. Additionally it was determined the biodegradable of dye as BOD5/COD value. It was concluded that total water decolouration is achieved only in the case of water coloured with azo dye.

1. INTRODUCTION Textile industries consume the large volumes of water and chemicals for wet processing of textiles. The chemical reagents used are very diverse in chemical composition, ranging from inorganic compounds to polymers and organic products (Mishra and Tripathy 1993). The presence of very low concentrations of dyes in effluent is highly visible and undesirable (Nigam et al. 2000). Many dyes are difficult to decolourise due to their complex structure and synthetic origin. There are many structural varieties of dyes that fall into either the cationic, nonionic or anionic type. The effluents thus generated contain a wide range of contaminants, such as salts, dyes, enzymes, surfactans, scouring agents, oil, oxidizing and reducing agents. Different methods are used for the purification and decolouration of textile coloured wastewater: mechanical, chemical, physical-chemical and biological or their combination (Schulze-Rettmer 1998, Ferrero 2000, Parac-Osterman et al. 2002). 2. MATERIAL AND METHODS 2.1 Dyestuff Investigations were performed on coloured wastewater containing 1 g/l dyestuff of different chemical constitution:

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AIC 2004 Color and Paints, Interim Meeting of the International Color Association, Proceedings

OH NaO3S -N=N-

OH

SO3Na

(H5C2)2N -

N(C2H5)2

SO3

C.I.Acid Blue 158

SO3Na

C.I.Acid Red 52

NH2 SO3Na
N

N N Cu N N N N SO2HNHO3S - NH N Cl N N NH2

NH O SO2CH2CH2OSO3Na

C.I.Reactive Blue 19

C.I. Reactive Blue 116

2.1 Methods The decolouration of dyed water was carried out by the next methods: using Fentons reagent (with and without ultrasound) and coagulation/flocculation method. Fenton treatment (H2O2 FeSO4) Process was carried out with and without ultrasound at 25 0C and 60 0C: In 1 g/l dye solution were added: 0.5 ml/l H2SO4 p.a.(pH3), 50 ml/l H2O2 36% and 5 g/l FeSO4. Coloured wastewater was mixed 15 minutes with magnetic mixer (700 rpm). pH 8 was set with NaOH 32%. Changing of concentration of dyes in wastewater was measured spectrophotometricly on Carry 50. Degree of decolouration is shown on Figure 1. Coagulation/flocculation method: The wastewater was treated with the coagulant 0.1% Beifloc ACI (CHT) (modified polyacrylamide, anionactive,) and in jar testes were carried out at a particular coagulant dosage, pH 7, was mixed 30 minutes (100 rpm). After the addition of the coagulant was added 7.5 ml/l flocculant Beifloc CV (CHT) (condensation nitrogen compounds, cationactive) was mixed 10 minutes (50 rpm). After 24 h samples were filtered through cotton fabric. Concentration of dyes in effluent was measured spectrophotometricaly on Carry 50 (Varian). Degree of removed dyes is shown on Figure 2. Wastewater biological control: Before and after decolouration treatments the COD and BOD5 were measured (according ISO 5000) and determined the biodegradability of dye as BOD5/COD value (Figure 3.)

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AIC 2004 Color and Paints, Interim Meeting of the International Color Association, Proceedings

3. RESULTS Figure 1 and 2 show the results of water decolouration after Fentons and coagulation / flocculation treatment, respectively.

100 80

decoloration (%)

250 C 600 C
0 C+ ultr.sound 25 0

60 40 20 0

600 C + ultr.sound

C.I.Ac. Blue 158 C.I.Ac.Red 52 C.I.Reac. Blue 19 C.I.Reac. Blue 116 azo xanthren anthraquinone phthalocyanine

Figure 1. Degree of decolouration after Fenton treatment.

100 95 90 85 80 75 70 65 60 55 50 C.I.Ac.Blue 158 azo C.I.Ac.Red 52 xanthren C.I.Reac.Blue 19 C.I.Reac. Blue 116 anthraquinone phthalocyanine

decolouration (%)

coagul./flocc. after filt. effluents

Figure 2. Degree of water decolouration after coagulation / flocculation treatment. Biodegradability of dyed water before and after treatment can be seen on Figure 3.
0,9 0,8 0,7
s olution of dye s

biodegradable

BOD /COD

0,6 0,5 0,4 0,3 0,2 0,1 0 1 2 3 4 1 2 3 4

tr e ate d w ith Fe nton

1- C.I.Ac.Blue 158 2-C.I.Ac.Red 52 3-C.I.Reac.Blue 19 4-C.I.Reac.Blue 116 0-bath w ith coagl./flocc.

tr e ate d w ith coagl./flocc.

unbiodegradable
0 1 2 3 4

Figure 3. Biodegradability of dyes: BOD5/COD values of water before and after the treatments.

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AIC 2004 Color and Paints, Interim Meeting of the International Color Association, Proceedings

4. CONCLUSION The coloured wastewaters with four dyes with different chromogen system were decolourated with the next methods: chemical oxidative method using Fanton reagent and physicochemical, coagulation/flocculation method. Fanton reagent has multifunctional activity having the oxidative and flocculation action. The lack of this method is the low oxidative degradability of some dyes, as the consequences of molecule stability. The lowest decolouration degree are shown in the case of acid dye C.I. Acid Red 52 with xanthen chromophore (80%) and for C. I. Reactive Blue 116 with phtalocyanine copper complexon. It is expected, as in the literature accepted, the highest decolouration degree given for azo dye, C.I. Acid Blue 158. The dyeing temperature above 25oC decreases the activity of Fantons reagent because the catalytic degradation of H2O2 is happened. With exception of azo dyes, by using the combination of Fantons reagent/ultrasound, there is no considerable decolouration effect of other dyes. It is confirmed, that chemical effect of water decolouration depends on molecular stability and for such reason the priority is given to physico-chemical methods. Applied coagulation/ flocculation methods are shown very high decolouration degree of more than 95%. After the decolouration of effluents, according ISO standard, the water has to be biologically controlled. It is very often given by BOD5/COD values. Coloured waters, with exception of phtalocyanine dye, treated with Fantons reagent are more biologically accepted, having the BOD5/COD values less than 0.2. Coloured water treated by coagulation/flocculation method, without any father filtering procedure, biologically loads the water. It is confirmed by given very low degradability biological values that is lower than 0.2. REFERENCES
Ferrero, F. 2000. Oxidative degradation of dyes and surfactant in the Fenton and photo-Fenton treatment of dyehouse effluents. Journal of the Society of Dyers and Colourists 116: 148-153. Mishra, G., and M. Tripathy. 1993. A critical review of the treatments for decolourization of textile effluent. Colourage 40: 35-38. Nigam, P., G. Armour, I. M. Banat, and D. Singh. 2000. Physical removal of textile dyes and solid state fermentation of dyes-adsorbed agricultural residues. Bioresour. Technol. 72: 219-226. Parac-Osterman, D., A. Sutlovi, and B. Karaman. 2002. Natural recourses as wastewater purifying adsorbents. In 1th Internat. Textile Clothing & Design Conference-Magic World of Textile, Book of Papers, pp. 719-725. Schulze-Rettmer, R. 1998. Treatment of textile dyeing wastewater by adsorption/bio-oxidation process. Textile Chemist and Colourist 30: 19-23. Address: Djurdjica Parac-Osterman, University of Zagreb Faculty of Textile Technology, Pierottijeva 6, 10000 Zagreb, Croatia E-mails:

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