azo dyes removal by freezing coupled with solar ...

Fourth International Conference on Energy, Materials, Applied Energetics and Pollution. ICEMAEP2018, April29-30, 2018, Constantine, Algeria. M.KADJA,A.ZAATRI, H.CHEMANI, R.BESSAIH, S.BENISSAAD and K. TALBI (Editeurs.).

AZO DYES REMOVAL BY FREEZING COUPLED WITH SOLAR PHOTOCATALYSIS FOR ZERO LIQUID DISCHARGE S. Igoud1, D. Tassalit1, K. Douadi2, L. Fellah2 1

Unité de Développement des Equipements Solaires, UDES, Centre de Développement des Energies Renouvelables, CDER, 42415, Tipaza, Algérie. 2b Faculté de Génie des procédés, Université des Sciences et de la Technologie Houari-Boumédiène USTHB, 16200, Bab-ezzouar, Algérie.

ABSTRACT Dyes still widely applied especially in textile industries. Their use is problematic because, after textiles treatment, rejected water stills polluted even if treated by conventional wastewater treatment. The azo dyes are the most used representing around 65% of the dye market sales. In other hand, they are recognized to have the highest degradation resistance. Untreated, they threaten human health and environmental balance. Facing this situation, several studies experimented their removal by unique and coupled processes. This paper suggests the azo dyes removal by freezing coupled with photocatalysis as a zero liquid discharge (ZLD) system. This new research approach aims the reuse both of dyes and wastewater. Two dyes models 1) Tartrazine (E 104) and 2) Ponceau 4R (E 124) are completely recovered from wastewater by freezing at low concentration. For high concentrations: 10mg to 40mg, the removal efficiency ranged respectively from 55% to 82% and from 66% to 87%. The residual dyes were eliminated from wastewater by photocatalysisi which recorded between 95% and 100% removal.

Keys Words: Wastewater treatment, Azo dyes, freezing, photocatalysis, sustainability.

1. INTRODUCTION Industrial effluents remained difficult to eliminate during conventional wastewater treatment especially those recalcitrant. The azo dyes are among those pollutants due to their high degradation resistance caused by their complex aromatic structures [1, 2]. This is problematic because, they are widely used representing around 65% of the dye market sales [3]. Also, they are suspected to have negative effects on the human health [4-6] because among others carcinogen [7]. They also cause the environmental imbalance especially in the aquatic biota [8, 9]. To eliminate these threats, the azo dyes used in food products are controlled and banned in many countries [10]. Nevertheless, because of their low-cost, they still used in other activities. They are highly used in textile industries, especially in tanneries [11, 12]. Facing this, several specific treatments have been experimented to increase azo dyes removal as biological process using bacteria and algae [1, 13-15], biotechnology by fungi enzymes [16-18] and the advanced oxidation techniques especially photocatalysis [19-21]. This last process seems to be the most promising one but applied for low concentrations. So, in order to lift this barrier, the coupling of others treatment processes has been successfully experimented such as adsorption [22, 23], biosorption [24] and biodegradation [25]. Another promising treatment consists on the dyes extraction from aqueous solution using liquid emulsion membrane [26, 27]. The dyes extraction recorded elimination rates ranging from 70% for Red 3BS Dye [27] to 99% for methylene blue [26]. Freezing also allows dyes separation and it is considered as an environmental friendly treatment. The process principle is based on the phase change to separate

ICEMAEP2018, April29-30, 2018, Constantine, Algeria.

the binary solution: water and pollutant. For the treatment of polluted aqueous solutions, freezing is applied to purified water from soluble and non-soluble pollutants. During the process, showed in the eutectic diagram, ice is crystallized from pure water in first which separates it from the pollutants. These last are concentrated in the liquid phase [27, 28]. This facilitates their recovery for recycling. However, this process is less efficient especially when applied in progressive freezing conditions. The pollutants are trapped in the ice front due to the small dimensions of the ice crystal lattice [28 -31]. In these conditions, the removal rates ranged from 84.6% to 86.4% [31]. For low dyes concentration, photocatalysis treatment has also proven its efficiency. This especially for recalcitrant dyes which are not suitable for biological processing due to their inherent toxicity [32]. However, the high dyes concentration constitute a barrier for an alone treatment. This paper suggests the freezing coupled with photocatalysis as a zero liquid discharge (ZLD) system [33]. This combination allowed firstly the dyes separation for reuse using freezing. Secondary, as a finishing treatment, photocatalysis is applied for the degradation of the residual dyes trapped in the ice front. It is to note that the photocatalytic water treatment using nanocrystalline titanium dioxide (TiO 2 ) is a well-known advanced oxidation process for environmental remediation. However, its use in this combination as a finishing treatment is suggested for the first time in this study for the treatment of water polluted with industrial dyes. The study also investigated a sustainability approach by the integration of solar energy for the freezing energy supply and solar photocatalytic degradation. The main advantages of this coupling are the easy system mounting, the non use of adsorbent, microorganisms, enzymes…, also the conventional energy saving and significant improvement in water purification and dyes recycling. 2. MATERIALS AND METHODS The study was conducted in the Development Unit of Solar Equipments (UDES) (latitude 36.633 and longitude 2.700) located at 30 km west of Algiers. The azo dyes removal study was conducted by three successive experimentation steps using two steps of freezing and the photocatalysis processes. For this, two azo dyes: 1) Tartrazine (E 104) and 2) Ponceau 4R (E 124) were used. The freezing test bench (figure 1) was carried using a commercial freezer powered by a solar photovoltaic energy system [34] which temperature is fixed at -7C°±2C°. For the three experimentation steps, each dye was prepared to constitute a concentration of 5 mg/l, 10 mg/l, 20 mg/l, 30 and 40 mg/l. Then each stock solution was distributed in 8 of 100 ml-beakers and placed in the freezer. After 1 hour, required for the starting of pure water crystal growth, the first sample was recovered and analyzed. After this, the seven remaining samples were analyzed with a time set of 15 minutes. The last (i.e. 8th sample) dye concentration was reported to start the second experimentation step of freezing. For this, the same sampling protocol described before was adopted again. By the same manner, the last (i.e. 8th sample) dye concentration obtained by bi-freezing was reported to continue the dye remowal by solar photocatalysis. The experiment essay used 500 ml Erlenmeyer flasks placed on a plate of 6 multi-position magnetic stirrers (figure 1). Preliminary photocatalysis essay was conducted to optimize the catalyst, used at a concentration of 0.3 g/l of TiO 2 , and the stirring speed fixed at 300 rpm. During the three experiment steps, the kinetics of the azo dyes removal was followed using a Shimadzu UV1800 spectrophotometer.

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FIGURE 1. Freezing test bench.

FIGURE 2. Solar photocatalysis test bench

3. RESULTATS As showed in figure 3, after the solution freezing, the studied dyes were separated from pure water. The removal rates of tartrazine ranged from 37% to 55% and they are inversely proportional to the concentration (figure 4). The same result is observed for ponceau 4R; the removal rates evolved from 34 to 50% (figure 5). The obtained results recorded less efficiency comparatively to similar studies. Removal rates comprised between 84.6% and 86.4% were recorded [31]. However, it is to note that the mentioned study applied the progressive freezing for an urban wastewater treatment. Also, during the experiments, the samples were recovered after a low freezing rate.

FIGURE 3. Azo dyes concentration by freezing treatment

To increase the rate of the azo dyes removal obtained during this first experimentation step, a second freezing step was conducted. For 5% concentration of tartrazine, the removal rate achieved 99%. But this result remained inversely proportional for the highest concentrations. Removing rates decreased from 82% to 55% when the concentrations of tartrazine increased from 10 mg/l to 40 ml/l (figure 4). The same evolution of the ponceau 4R kinetics removal has been observed. The highest removal estimated at 99% was recorded for the lowest concentration: 5mg/l. Then the efficiency decreased for high concentrations. It passed from 87% to 63% (figure 5) for concentrations fixed respectively at 10 mg/l and 40 mg/l. The obtained results were predictable. As mentioned in the introduction, during the progressive freezing treatment, total dyes removal could not be reached. During the ice growth step, the pollutants concentration of the liquid phase increases continuously while reducing its volume. Also the pollutants diffusion is described slower than the advancing solid interface speed [29]. Consequently, the pollutants are trapped in the ice front due to the small dimensions of the ice crystal lattice [28-31]. As a solution, radial freezing was applied. It consists on the use of a rotational movement to repel the pollutants out of the ice during its growth [28, 29, 31]. This solution was applied during the essays (cf. figure 3) but the experimentation conditions were difficult to reproduce. 3


40,00

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FIGURE 4. Tartrazine removal kinetic by freezing 35

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FIGURE 5. Ponceau removal kinetic by freezing

To improve the alone freezing process as a wastewater treatment, its coupling with solar photocatalysis was studied. The two treatments combination allowed firstly the decrease of the high dyes concentrations until 55% for tartrazine and 66% for ponceau 4R. This allows the dyes recovery for reuse according to the ZLD concept. Secondary, the continuous treatment of the residual dyes were removed from treated water by solar photocatalysis. The obtained results, shown in figures 6 and 7, present the ponceau 4R and tartrazine temporal removal by freezing coupled with photocatalysis for different initial concentrations of these pollutants. The integration of photocatalysis increased the efficiency treatment both of tartrazine and ponceau 4R. A total dyes removal has been reached for the concentrations inferior to 30 mg/l. Beyond this concentration, the dyes removal reached more than 95% yield. It is to note that the photocatalytic water treatment using nanocrystalline titanium dioxide (TiO 2 ) is a well-known advanced oxidation process for environmental remediation. However, its use in this combination as a finishing treatment is suggested for the first time in this study for the treatment of water polluted with industrial dyes.

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45,00

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FIGURE 6. Tartrazine removal kinetic by freezing coupled with photocatalysis 45 40

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FIGURE 7. Ponceau removal kinetic by freezing coupled with photocatalysis

These results are very significant when taking in account the water depollution efficiency and treatment cost. This additionally to the possibility to reuse both of treated water and dyes recovered at the end of the coupled treatment which presents economic and environmental benefits comparing with others destructive treatments. This approach is not concretizes when applying the combination of photocatalytic and biological processes because both are destructives. This case has been studied by the coupling of photocatalysis and membrane bioreactor where a high efficiency dyes removal from industrial effluent was achieved [35]. The results recorded 91% of chemical oxygen demand (COD) reduction and the dye elimination has been proved by a decrease in absorbance at 591 nm during the first feeding days. Another study suggested the biological depollution coupled with Fenton’s oxidation to treat dyes and organic substances contained in textile wastewater [36]. COD removal efficiency reached the maximum value 97.6%. In a other laboratory-scale study [37], a closer approach to our study coupled the adsorption to the heterogeneous photocatalysis for the treatment of the 2-chlorophenol (2-CP). The removal of 2-CP through this combination was achieved in a reasonable acceptable time interval. However, the adsorption requires its regeneration which is more complicated and expensive to implement compared to freezing process.

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4. CONCLUSIONS Azo dyes removal has been suggested according to zero liquid discharge system which allows the reuse both of water and dyes. Water dyed by tartrazine (E 104) and ponceau 4R (E 124) at 5, 10, 30 and 40 mg/l was treated by freezing coupled with photocatalysis. For the both dyes concentrations which increased from 5 mg/l to 40 mg/l, the first treatment by freezing recorded an efficiency which decreased from 55% and 37% for tartrazine and from 50% to 34% for ponceau 4R. The second treatment using bi-freezing allowed the increase of efficiency until 99% for low concentration: 5mg/l. But for the superior concentrations; between 10 mg/l and 40 mg/l, the efficiency was lower. It ranged from 82% to 55% for tartrazine and from 87% to 63% for poceau 4R. These dyes removed from water could be reused after their dewatering. During the tertiary treatment, the residual dyes contained in the ice thawed were removed by photocatalysis. This finishing treatment recorded a partial removal of tarazine, evaluated at 95% because voluntarily stopped, and a total elimination of ponceau 4R for all the studied concentrations. These last results allowed water reuse as the case for dyes. Considering the continuous treatment: freezing-photocatalysis, finally the obtained results have recorded the total removal of ponceau 4R and 95% of tartrazine from water polluted by 5 mg/l, 10 mg/l, 30 mg/l and 40 mg/l. REFERENCES [1] Forgacs, E., Cserháti, T., Oros, G., “Removal of synthetic dyes from wastewaters: a review”, Environ. Int., 30, 953-971 (2004). [2] Shaul, G.M., Holdsworth, T.J., Demmpsey, C.R., Dostal, K.A., “Fate of water soluble azo dyes in the activated sludge process”, Chemosphere, 22, 107-119 (1991). [3] Ahlström, L. H., Eskilsson, C. S., & Björklund, E. (2005). Determination of banned azo dyes in consumer goods. Trends in Analytical Chemistry, 24, 49–56. [4] Kadirvelu, K., Kavipriya, M., Karthika, C., Radhika, M., Vennilamani, N., Pattabhi, S., “Utilization of various agricultural wastes for activated carbon preparation and application for the removal of dyes and metal ions from aqueous solutions”, Bioresource Technol., 87, 129-132 (2003). [5] Nagaraja, T. N., & Desiraju, T. (1993). Effects of chronic consumption of metanil yellow by developing and adult rats on brain regional levels of noradrenaline, dopamine and serotonin, on acetylcholine esterase activity and on operant conditioning. Food and Chemical Toxicology, 31, 41–44. [6] Novotny, C., Dias, N., Kapanen, A., Malachova, K., Vandrovcova, M., Itavaara, M., “Comparative use of bacterial, algal and protozoan tests to study toxicity of azo and anthraquinone dyes”, Chemosphere, 63, 1436-1442 (2006). [7] Khehra, M. S., Saini, H. S., Sharma, D. K., Chadha, B. S., & Chimni, S. S. (2006). Biodegradation of azo dye CI Acid Red 88 by an anoxic–aerobic sequential bioreactor. Dyes and Pigments, 70, 1– 7. [8]

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