Removal of Anionic Dye from Textile Industries' Effluents by using Tunisian clay as adsorbent. Electrophoretic and Streaming potential investigations

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1 Removal of Anionic Dye from Textile Industries' Effluents by using Tunisian clay as adsorbent. Electrophoretic and Streaming potential investigations Dr Nejib ABIDI (LHYGES-CNRS-Strasbourg-France) Dr Joëlle DUPLAY (LHYGES-CNRS-Strasbourg-France) Dr Amane Jada (IS2M-CNRS-Mulhouse-FRANCE) Dr Emna Errais (LPMNMH-Faculté des Science de Bizerte, Bizerte-Tunisia) Dr Malika Ghazi (TERIVA Environment, Schiltigheim-France) Dr Khadija Semhi (Sultan Qabos University, Muscat- Sultanate of Oman) Prof Malika Trabelsi-Ayadi (LACREsNE-Faculté des Sciences de Bizerte, Bizerte-Tunisia)

Textile industry Effluents Textile effluents are very

manufacture or processing of fibers to those from

Waste products from textile processing contain many

inorganic substances, which are toxic to fish,

2 Textile industry Effluents Textile effluents are very diverse, ranging from those resulting from the manufacture or processing of fibers to those from dyeing and finishing operations. Waste products from textile processing contain many substances such as dyes, surfactants, by-products, inorganic substances, which are toxic to fish, vegetation or other biological organisms and affect the oxygen consumption of the discharge.

3 Importance of the study Globally, it is estimated that over 0,7 million ton and approximately 10,000 different dyes (carbon based organic compounds) and pigments (inorganic compounds) are produced annually world-wide, it is estimated that 2-50% of them are lost into wastewaters, causing environmental contaminations. Up to 90% of reactive textile dyes still persist even after the treatment by conventional wastewater treatment plants. The dyes are of various compositions, among them reactive dyes are widely used in the textile industry and are particularly difficult to degrade. It is difficult to totally remove the color, and the treatment is expansive.

4 Methods generally used to remove dye from textile effluents Biological treatment Coagulation/flocculation Ozone treatment Chemical oxidation and photocatalytic processes Membrane processes Adsorption

5 Summary Importance of the study Objectives Materials & Method Results Concluding remarks

Investigating alternative, inexpensive, available and effective adsorbents such as natural clays.

6 Objectives INDUSTRIAL EFFLUENT CLEAN WATER FOR AGRICULTURE Exploring sustainable treatment methods of dyers effluents in order to achieve the standards of irrigation water. Investigating alternative, inexpensive, available and effective adsorbents such as natural clays. Comparing the decolorizing potential of clays of different species by focusing on an anionic dye used in the textile industry.

7 Materials Anionic dye Reactive Red 120 (RR 120) This dye is commonly used in the textile industry and it is chosen as adsorbate in this study. It is a bifunctional azo-based chromogens dye incorporating bis (monochloro-s-triazine) its molecular weight is M =1338 g mol -1. The absorption maximum wavelength of RR 120 in the visible range is λ=535 nm, which was used to analyse the supernatant of the anionic dye aqueous dispersions.

Materials (continued) Two Natural Clays from Tunisia

standards from USA Tabarka: Kaolinite 62% Illite 38%

Smectite 60% Kaolinite: 30% Illite: 10% CEC(meq/100

Kaolinite CEC(meq/100 g)=3,3 S sp (m 2 /g)= 23,5

8 Materials (continued) Two Natural Clays from Tunisia were used as adsorbents and were compared to two standards from USA Tabarka: Kaolinite 62% Illite 38% CEC(meq/100 g)=15 S sp (m 2 /g)= 47 Fouchana: Smectite 60% Kaolinite: 30% Illite: 10% CEC(meq/100 g)=34,3 S sp (m 2 /g)= 80 Kga-2 (CMS, USA) Pure Kaolinite CEC(meq/100 g)=3,3 S sp (m 2 /g)= 23,5 Palygorskite (CMS, USA) Pure fibrous clay CEC(meq/100 g)=19,5 S sp (m 2 /g)= 136,4

Smectite structure Kaolinite structure Interlayer spacing Substitution by Al 3+ or Fe 3+ Si 4+ Al 3+ or Mg 2+ Si 4+ Te Oc Te Substitution by Mg 2+,Fe 2+ or Li + Interlayer spacing Negative permanent

9 Smectite structure Kaolinite structure Interlayer spacing Substitution by Al 3+ or Fe 3+ Si 4+ Al 3+ or Mg 2+ Si 4+ Te Oc Te Substitution by Mg 2+,Fe 2+ or Li + Interlayer spacing Negative permanent structural charge ph-independent Retention of cations at clay surface Charge resulting from protonation/deprotonation reactions of oxide-like sites ph - dependent (Hydroxyles on the edges of the sheets)

10 Methods Adsorption of the dye from water onto various clays Batch experiments, T=20-50 C Effects of various parameters on the adsorption: - Contact time adsorbent-adsorbate - Ionic strength - ph of the aqueous phase - Initial dye concentration - Temperature. Electrokinetic measurements to elucidate dye-clay interactions Electrophoretic Mobility and Streaming Induced Potential (SIP)

11 Adsorption isotherms of RR 120 dye from water onto various clays Effect of the initial dye concentration As the specific surface area of the clay increases, the adsorbed amount of the dye decreases. Others considerations should be taken into account in the explanation of the variation of the adsorbed amount of the dye on the clay surface.

12 Adsorption isotherms of RR 120 dye from water onto various clays Effect of the contact time and the ionic strength The effect of the Ionic strength was expected.

13 Adsorption isotherms of RR 120 dye from water onto various clays Effect of the aqueous phase ph As the ph increases, the clay becomes highly negatively charged repelling hence the negatively charged dye molecules.

process of the dye onto various clays is spontaneous, feasible and

14 Adsorption isotherms of RR 120 dye from water onto various clays Effect of the temperature Thermodynamic parameters The adsorption process of the dye onto various clays is spontaneous, feasible and exothermic according to G and H values, although not favoured at high temperature.

15 The measured interfacial parameter such as the electrophoretic mobility, the zeta potential, the surface potential, will depend on the interfacial structure.

16 Charged surface Electrokinetic measurements i - d d distance 0 x i Electrical Double Layer Ions concentrations - + = potential at shear plane ; Smoluchowski equation : Ue = ( ) Ue = electrophoretic mobility d solution Electrostatic potential 0 d d i 0 x i distance

17 Effect of the ph and adsorbed amount of dye on the electrophoretic mobility of the clay Tabarka Fouchana Electrophoretic mobility (cm 2 sec -1 V -1 ) -8,0x ,0x ,2x ,4x ,6x ,8x ,0x ,2x ,4x ,6x ph Tabarka Tabarka-RR120 Electrophoretic mobilty (cm 2 sec -1 v -1 ) 2,0x10-4 1,0x10-4 0,0-1,0x ,0x ,0x ,0x ph Fouchana-RR120 Fouchana Zeta potential measurements Surface charge determination: Microelectrophoresis Measurement of electrophoretic mobility Ue, which is converted into zeta potential, according to the Smoluchowski s equation: Electrophoretic mobility (cm 2 sec -1 V -1 ) 1,5x10-4 1,0x10-4 5,0x10-5 0,0-5,0x ,0x ,5x ,0x ,5x10-4 KGa ph KGa-2 KGa-2-RR120 Palygorskite Electrophoretic mobility (cm 2 sec -1 v -1 ) 5,0x10-5 Palygorskite clay Palygorskite clay RR-120 0,0-5,0x ,0x ,5x ,0x ,5x ph Ue where and are, respectively, the viscosity and the permittivity of the aqueous medium. View of the electrophoretic cell (depth H = 0.2 cm) (Electro-osmotic and counter flows for positive charges ) Upon adsorption of the anionic dye, the magnitude of the electrophoretic mobility decreases Stationary levels + Field direction - H ernational Conference on Sustainable Solid Waste Management June 2017, Athens, Greece

18 Effect of the added amount of dye on the electrophoretic mobility of the clay Correlation between SIP and adsorbed amount of dye. The magnitude of SIP increases when the adsorbed amount increases significantly

19 Adsorption isotherms of RR 120 dye from water onto various clays Langmuir Data modeling Freundlich Dubinin-Radushkevich Harkins-Jura Halsey

20 RR 120 anionic dye- clay particle interaction Scheme of adsorption of the dye RR 120 on a smectite sheet Scheme of adsorption of the dye RR 120 on a Kaolinite sheet

21 Concluding remarks Palygorskite even though it has the highest surface area, it has the lowest capacity for adsorption of RR 120 anionic dye. Kaolinite, Kga-2, which has the lowest surface area, shows the highest adsorption capacity for the anionic dye. Tabarka shows also a better adsorption capacity than Fouchana and palygorskite. Electrokinetic measurements indicate that adsorption occurs on the clay surfaces, which process should be difficult owing to the negative surface charge of the clays and the anionic character of the dye. The process is spontaneous, feasible and exothermic according to G and H values, although not favoured at high temperature. In case of palygorskite the positive values of G confirm that the adsorption process is difficult, which indicates again that porosity and specific surface are not relevant parameters in the adsorption of anionic dye

Acknowledgments This work was done in the frame of two projects: the ERANETMET SETPROpER project (2016-2019) with the support of the funding agencies of France (National Research Agency, ANR) and

22 Acknowledgments This work was done in the frame of two projects: the ERANETMET SETPROpER project ( ) with the support of the funding agencies of France (National Research Agency, ANR) and Tunisia (Ministry of Higher Education Scientific Research, and TIC TUNISIA); the French-Tunisian PHC UTIQUE project (12G21002), with the support from the French Ministries of Foreign Affairs (MAE) and Education and Research (MESR), and the Tunisian Minister of Higher Education and Scientific Research. THANK YOU FOR YOUR ATTENTION

HPAN TEXTILE FIBER WASTES FOR REMOVAL OF DYES FROM INDUSTRIAL TEXTILE EFFLUENTS

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