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Comparison of classic Fenton with ultrasound Fenton processes on industrial textile wastewater
Accepted Manuscript Comparison of classic Fenton with ultrasound Fenton processes on industrial textile wastewater Semanur Giray, Mehmet Hakan Morcali, Sümeyye Akarsu, Cengiz Ayhan Ziba, Mustafa Dolaz PII:
S2468-2039(17)30313-8
DOI:
10.1016/j.serj.2018.02.001
Reference:
SERJ 119
To appear in:
Sustainable Environment Research
Received Date: 3 October 2017 Revised Date:
14 December 2017
Accepted Date: 7 February 2018
Please cite this article as: Giray S, Morcali MH, Akarsu S, Ziba CA, Dolaz M, Comparison of classic Fenton with ultrasound Fenton processes on industrial textile wastewater, Sustainable Environment Research (2018), doi: 10.1016/j.serj.2018.02.001. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT Received 5 October 2017 Received in revised form 14 December 2017 Accepted 7 February 2018
Comparison of classic Fenton with ultrasound Fenton processes on industrial textile
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wastewater
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Mustafa Dolaz*
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Semanur Giray, Mehmet Hakan Morcali, Sümeyye Akarsu, Cengiz Ayhan Ziba,
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Department of Environmental Engineering, Kahramanmaras Sutcu Imam University,
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Kahramanmaras 46100, Turkey
* Corresponding author. E-mail address: [email protected]
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ACCEPTED MANUSCRIPT ABSTRACT This study provides a comparison between classic and modified (i.e., ultrasound) Fenton process on the industrial textile wastewater. For this purpose, the classic, and ultrasound Fenton process were investigated and compared using the following parameters:
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pH of solution, amount of ferrous ion (Fe(II)), and hydrogen peroxide as well as reaction time. With these parameters, degrading organic compounds (i.e., decolorization percentage) was calculated. The best decolorization percentage (95% for Pt-Co) was found using 0.10 g
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L-1 of Fe(II), and 2.20 g L-1 of H2O2 for 90 min at pH 3 for classic Fenton process. Similar experiments were carried out using 35 kHz ultrasonic irradiation, and the best decolorization
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percentage (99% for Pt-Co) was obtained via 0.05 g L-1 of Fe (II) and 1.65 g L-1 H2O2 for 60 min at pH 3 for ultrasound Fenton process. The results showed that decolorization increased with decreasing amount of chemical for the ultrasound Fenton process. Additionally, the contact time was decreased by comparing performance with classic Fenton process. In light
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of these results, the ultrasound Fenton process can be used for decolorization of textile wastewater to save reaction time and chemical costs. Also, the decolorized water (e.g., treated
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exchange process.
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water) may be reused in the plant for washing the textile materials after applying ion
Keywords: Textile wastewater; Fenton process; Ultrasound fenton process; Removal; Color. 1. Introduction
Textile industries, which are known as the largest company group on the earth, use fresh water in all production steps (i.e., bleaching, washing, and dyeing etc.). They produce more wastewater which usually contains organic matter, detergents and soaps, oil-grease, sulfide and sodas. To eliminate these pollutants in the wastewater, some chemical/physical/biological treatment methods have been applied [1-4]. However, these processes have some
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ACCEPTED MANUSCRIPT disadvantages, such as a low decolorization percentage, and high maintenance-intensive processes and especially, health and safety issues for biological treatment [4-5]. Advanced Oxidation Technologies (AOTs) are used for treatment of contaminating municipal or industrial wastewaters [6-10]. To remove color from industrial effluent, AOTs
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are generally preferred by industries [11,12]. The application of AOTs for the treatment of a wastewater from a textile industry using Fenton process was conducted by some companies such as Ecole Politechnique de Lausanne in Switzerland. The AOTs use additional energy
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and/or chemicals to generate highly reactive oxidizing species, most commonly the hydroxyl radical (•OH) which is responsible for oxidative destruction of a wide variety of organic
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compounds [10,13]. The efficiency of hydroxyl radical production is important with respect to its application as AOTs [8,10,14,15]. Owing to the increase in environmental problems and restrictions in industrial effluents, the development of AOTs is still kept importance. The related studies with the AOTs are presently a hot topic for researchers who aim to decrease
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the amount of chemical with increasing color removal percentage. Nowadays, there is a growing interest in the cleaning of textile wastewater for environmental protection in the world. Due to the government restriction and the water pollution control regulation, the
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wastewater should not contain azo dyes which cause an adverse effect on people health who
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live in these regions [16]. For this reason, several color removal methods have been studied by several researchers [17,18]. To eliminate the color originating dying stuff, Fenton process is generally preferred. The scientists presented a possible mechanism for the decomposition of hydrogen peroxide (i.e., Fenton process), which was included the formation of radicals, most notably the hydroxyl radical (see Eq. (1)). Fe2+ + H2O2 → Fe3+ + •OH + OH-
(1)
The Fe(II) oxidized to Fe(III), and the hydroxyl radical was produced. This species (i.e., (•OH)) is a powerful oxidizer and tends to react by addition to double bonds or by
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ACCEPTED MANUSCRIPT extraction of hydrogen atoms. In the literature, the process is called Fenton process which involves homogenous reaction. It is environmentally acceptable, and a system based on the generation of very reactive oxidizing free radicals, namely, hydroxyl radicals [19]. In addition to this reaction in photo-Fenton process, the following reaction occurs (Eq. (2) and
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Eq. (3)) [19,20]: H2O2 + UV → •OH + •OH Fe3+ + H2O + UV → •OH + Fe2+ + H+
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(3)
(2)
Photo-Fenton (e.g., photo assisted Fenton) has been addressed in the literature over the
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last decade [14,21-23]. Ultra violet light can provide energy to facilitate hydroxyl radical generation by the photo-Fenton reaction (Eq. 2) and hydrogen peroxide degradation. In recent years, attention has turned to the possible application of the Fenton reaction as an oxidative treatment for contaminated water. Many researchers have reported that optimal
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oxidation of target chemicals has occurred using Fenton-based systems (both dark and photo) at a pH of 2-3, which also corresponds to the optimal pH conditions for the Fenton reaction. They have also found that oxidation of target compounds usually occurs very quickly,
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relative to other AOTs such as UV/H2O2 or UV/TiO2/H2O2 [23-27]. However, results vary
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with respect to treatment of the target compound's oxidation products, namely complete mineralization of all of the organic carbon is not always achieved. The following examples help to illustrate the interest in classic Fenton and photo-Fenton reactions as methods of water remediation and the wide range of organic compounds that have been studied. The hydroxyl radical decompose the color where comes from organic dyes. It also triggers chemical oxygen demand (COD) since ferrous ions need more oxygen to convert ferric state. Besides more ferrous ion dosage is needed in attempt to produce moderate hydroxyl radical. Therefore, the use of ultrasonic irradiation has more and more attention in the treatment of dye wastewater
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ACCEPTED MANUSCRIPT [11,15,18,28]. Ultrasonic irradiation process has improved the generation of hydroxyl radical by ultrasonic sound and minimizes the amount of chemical on Fenton process. To obtain the highest decolorization, an ideal ultrasound Fenton process on textile effluent solution should satisfy a number of requirements such as initial solution pH, dosage of hydrogen peroxide,
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reaction time etc. Some of them have been studied on the removal of textile wastewater [15]. However, the process needs some improvements based on experimental parameters [16,17]. The current study using modified Fenton process in the presence of ultrasound is an easy and
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alternative method for the removal of color by breaking the azo bonds. Another advantage of the proposed process is that less chemical quantity is needed as compared to the classic
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Fenton process.
The main purpose of this work was to compare two Fenton processes to address some critical issues for the industrial textile wastewater, especially decolorization of water by these methods. The effects of experimental conditions on decolorization and COD were
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investigated. As a result, the best color removal (%) and the highest COD removal (%) were obtained with ultrasound Fenton process. 2. Materials and methods
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All experiments were carried out with the effluent solution which was provided from a
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textile company in Kahramanmaras, Turkey. Hydrogen peroxide (H2O2), sodium hydroxide (NaOH), and sulphuric acid (H2SO4) were used in analytical grade. Classic Fenton process was conducted in 600 mL capacity borosilicate glass beaker with a programmable jar tester (Lovibond, Germany). The method simulates a full-scale water treatment process. Adjusting the amount of treatment chemicals and the sequence was entailed via jar tester. The sonication (i.e., ultrasound) was generated by an ultrasonic cleaner (Kudos, China) in order to perform ultrasound Fenton process. The COD was determined by standard test method [29]. The color of the samples was measured using UV-visible spectrophotometer
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ACCEPTED MANUSCRIPT (Hach Lange DR 5000, USA). The solution of pH was measured by portable pH meter (Hanna, USA). Unless otherwise specified, all experiments (i.e., classic Fenton and ultrasound Fenton process) were independently performed in order to ascertain the consistency of the results. Ten milliliters solution was passed through a whatman paper
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(grade 1). Before measurements, a decomposition procedure with 40 mg manganese dioxide (MnO2) as a reductive was performed for removing excess hydrogen peroxide. Afterward the solution was filtered by using a 45 µm syringe filter prior to analysis. The decolorization
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measurements were carried out at 465 (for Pt-Co), 436, 525 and 620 nm. The COD analysis was performed with ISO 6060:1989 standard method [29].
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Classic Fenton and ultrasound Fenton experiments were employed to achieve the highest decolorization percentage and COD removal (%) using different parameters such as: pH, H2O2 concentrations, ferrous (Fe2+) concentrations and reaction time. All classic Fenton experiments were conducted in jar tester. Ultrasound Fenton process was performed by
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ultrasonic bath in which ultrasonic irradiation was adjusted to 35 kHz. All reactants were added into wastewater before starting reaction. 3. Result and discussion
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In the literature, several methods (e.g., precipitation, coagulation, ion exchange etc.) have
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been applied so as to remove organic pollutions from textile wastewater. However, some of them usually generate new problems or wastes after decomposition organic compounds or other processes. Fenton process is one of the most effective processes which are occurred in hydroxyl radical pathway. This process applies for decolorization (i.e., decomposition of organic compounds) and also reducing Fenton reagents quantity, reaction time. 3.1.
Effect of initial pH Acidic regime is the most important parameter in order to remove color as well as COD
for both Fenton processes, since the Fe (II) ions are not stable around pH 5. For this reason,
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ACCEPTED MANUSCRIPT different pH values versus decolorization percentage were studied to understand the effect of pH. In this experimental series, the effect of pH on the removal of color and removal of COD was investigated. 200 mL of the wastewater, 0.10 g L-1 Fe2+ ion, 1.40 g L-1 H2O2 and 45 min reaction time were applied as reaction parameters. The comparison of classic Fenton and
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ultrasound Fenton process was presented at different pH in Figs. 1a and 1b, respectively. As seen from these figures, pH was changed up to 4.5 removing percentage of color was increased. The maximum percentage was obtained at pH 3 for both processes. At this point, it
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is understood that the removal percentage was varied increasing pH value. For ultrasound Fenton process, the pH altered from 2 to 3, the color removal was enhanced from 87 to 96%
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for Pt-Co. Similar trend was observed for classic Fenton process, the color removal was changed from 75 to 88% for Pt-Co. The solution pH has a significant impact on the oxidation potential of ferrous ions in Fenton process. The concentration of Fe2+ ions and (•OH) radicals can be easily effected changing hydronium ion concentration [11]. The solution pH was
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raised around 6 or high, divalent iron ions can be easily precipitated as iron (II) hydroxide since it is well known that the precipitation of divalent iron depends on pH. A similar trend for the effect of pH was observed in a study by Özdemir et al. [11].
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The influence of pH versus COD removal was presented in Fig. 1c. Similar experimental
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conditions were used. It was apparent that COD removal efficiency positively altered up to 70% at pH 3 for classic Fenton process. At the same condition for ultrasound Fenton process, COD percentage was measured around 77% at pH 3. This result shows that COD value was mutated around 10% with ultrasound process. After increasing pH value from 3 to 4.5, the COD percentage value decreased, and the final value was determined 67% for classic Fenton process. After that point, COD value was found as 70% at pH 4.5 for ultrasound process. As a result of this study, the maximum COD removal was measured 77% at pH 3 for ultrasound Fenton process.
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3.2.
Effect of ferrous ion concentration In this experimental series, the influence of ferrous ions (Fe2+) concentration on removal
of color, and COD was studied in the range of 0.05 to 0.20 g L-1. 200 mL of the wastewater
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and 1.40 g L-1 H2O2, pH 3 and 45 min reaction time were preferred as reaction parameters. The removal of color and COD removal percentage as a function of ferrous ion concentration is presented in Figs. 2 and 3, respectively. As is evident from Figs. 2a and 2b, when
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escalating ferrous concentration from 0.05 to 0.20 g per 1000 mL solution, the removal of color with classic and ultrasound Fenton process increasing from 75 to 98% and from 90 to
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99% for Pt-Co, respectively. Additionally, similar trends were observed at different wavelengths (at 436, 525, 620 nm). Interestingly, it was examined that around 90% (Pt-Co) removal of color was obtained with 0.05 g L-1 Fe2+ ion were employed in ultrasound Fenton process. This result shows that ultrasound Fenton can successfully be achieved decreasing
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amount of ferrous ions as an alternate to application for environmentally friendly process for the treatment of dye containing waste solutions [30]. Ultrasound Fenton process requires relatively lower concentration of Fe2+ ion than classic Fenton process while comparing color
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removal (%) result. However it is noted that the color removal was perceptibly affected by
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ferrous concentration when investigating classic Fenton process. The ultrasound Fenton process is more effective than ferrous ion concentration. As shown in Fig. 3 increasing concentration of Fe2+ ions enhanced the COD removal. The reaction parameters were kept constant for within the same experimental series. While the COD removal by classic Fenton process increased from 62 to 73% by varying the concentration of Fe2+ ions from 0.05 to 0.20 g L-1. Interestingly, removal efficiencies of COD were decreased by increasing the dosage of Fe2+ ions to 0.22 g L-1. Thus, the optimum Fe2+ concentration for classic Fenton process was determined as 0.20 g L-1. This finding was also
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ACCEPTED MANUSCRIPT in accordance with studies undertaken by Sahinkaya [17]. Similar trend was observed with ultrasound Fenton process. When Fe2+ ion concentration was increased from 0.05 to 0.20 g L, the removal of COD efficiency was increased from 59 to 87%.
3.3.
Effect of H2O2 concentration
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The dosages of the hydrogen peroxide (H2O2) were varied, ranging from 1.1 to 2.8 g L-1 in the experimental series. 200 mL of the wastewater, 0.10 g L-1 Fe2+, (0.05 g L-1 Fe2+ for
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ultrasound) pH 3 and 45 min reaction time were preferred for both Fenton process as reaction parameters. The removal of color and COD with increasing peroxide dosages was presented
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in Figs. 4 and 5, respectively. The removal percentages were enhanced with increasing dosage of peroxide until reaching at the optimum concentration for both parameters. Since it is the main sources of (•OH) radicals yielded in Fenton process. The effect of H2O2 plays an important role on the efficiency of both the classic Fenton and ultrasound Fenton process.
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The color removal percentage was obtained 97% for Pt-Co; 97% at 436 nm, 98% at 525 nm and 97% at 620 nm, respectively when using 2.20 g L-1 H2O2 for classic Fenton process (see Fig. 4a). While H2O2 concentration was increased at 2.80 g L-1, removal of color was
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negatively fluctuated around 5%.
For ultrasound Fenton process, 200 mL of the wastewater, 0.05 g L-1 Fe2+, pH 3 and 45
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min reaction time were chosen. It was observed that the H2O2 dosages increase to 1.65 g L-1 the percentages of color removal 97% for Pt-Co. As seen at Fig. 4b, while the concentration of H2O2 increased more 1.65 g L-1 the removal of color efficiency decrease at 95% for Pt-Co. In the light of this information, the consumption of peroxide was reduced around 30% with ultrasound Fenton process. Fig. 5 presents the COD removal percentage and such results indicate the ultrasound fenton process was effective for COD removal percentage. The maximum COD removal was
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ACCEPTED MANUSCRIPT 88% at a concentration of H2O2 1.65 g L-1. Around 73% of the COD value was found using 2.20 g L-1 of H2O2. While concentration of H2O2 rose to 2.80 g L-1, the removal percentage of COD decreased around 70% for both of the processes.
Effect of reaction time
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3.4.
In the last experimental series, the effect of reaction time was investigated for Fenton and ultrasound Fenton process. 200 mL of the wastewater, 2.20 g L-1 H2O2, 0.10 g L-1 Fe2+ and
reaction is important between ferrous ions and H2O2.
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pH 3 were favored for classic fenton reaction parameters. It is well known that the stability of
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200 mL of the wastewater, 1.65 g L-1 H2O2, 0.05 g L-1 Fe2+ and pH 3 were preferred for ultrasound Fenton reaction parameters. Figs. 6a and 6b present the effect of contact time on the removal of color for classic Fenton and ultrasound Fenton process in the range of 15 to 180 min, respectively. For classic Fenton process, the best color removal was found at 90 min
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for 95% with Pt-Co. However, the removal of color was decreased when increasing reaction time. This situation is unexpected result because the reaction should be improved with reaction time. Nevertheless, almost 95% color removal was achieved with classic Fenton
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process for 90 min. The color removal percentage was obtained 99% Pt-Co for 60 min. In
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other words, reaction time was elevated around 33% with ultrasound Fenton process comparing classic Fenton process. As seen from Fig. 6c, increasing the reaction time from 10 to 180 min exhibited some increase in the COD removal percentage for ultrasound Fenton process. However, there was significant increase for classic Fenton process up to 60 min. This result implies that effect of time after 60 min did not change the COD removal for classic Fenton process but reaction time increased the removal of COD when using ultrasound process under same conditions. In
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ACCEPTED MANUSCRIPT the literature, similar studies reported that much longer reaction times needed COD removal percentage. 4.
Conclusions This study involves the decolorization of industrial wastewater using the classic Fenton
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and ultrasound Fenton process. In the applied decomposition of dye in the solution, aromatic organic compounds are oxidized through both Fenton processes and the aromatic compounds can be converted into aliphatic organic compounds. For this purpose, the experiments were
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performed to investigate the effects of H2O2, Fe2+ dosage, pH, and reaction time on decolorization and removal of COD. Based on the above results, the best conditions were
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found at pH 3, 0.10 g L-1 Fe2+, 2.20 g L-1 H2O2 for 90 min (for decolorization), for 60 min (COD removal) with classic Fenton process. Furthermore, the best conditions were achieved at pH 3, 0.05 g L-1 Fe2+, 1.65 g L-1 H2O2 for 60 min for decolorization and 90 min for COD with ultrasound Fenton process. This result should be directly related with amount of
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hydrogen peroxide and ferrous concentration. When compared both of the processes, ultrasound Fenton process is more economical because the use of hydrogen peroxide and ferrous ions are much less from classic Fenton process. Thus, using fewer chemicals higher
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treatment efficiency was reached. It is well known that use of less hydrogen peroxide and
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ferrous ensures clean solution and less environmental concern. The result of this study indicates that ultrasound Fenton oxidation process is more sufficient than classic Fenton process. In the light of these results, the ultrasound Fenton process can be used for the decolorization of textile wastewater to save reaction time and chemical costs. Also, the decolorized water (e.g., decomposed water) may be reused in the plant for washing the textile materials after applying ion exchange process. Acknowledgements
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Fig. 1. The effect of different pH values on (a) the classic Fenton process (b) the ultrasound Fenton process (c) COD removal for the Fenton processes (0.1 g L-1 Fe+2, 1.4 g L-1 H2O2, 45 min).
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Fig. 2. Effect of Fe2+ ion concentration on (a) the classic Fenton process (b) the ultrasound
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Fenton process (pH: 3, 1.4 g L-1 H2O2, 45 min).
Fig. 3. Effect of Fe2+ ion concentration on COD removal for Fenton processes (pH: 3, 1.4 g L1
H2O2, 45 min).
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Fig. 4. The effect of H2O2 concentration on (a) the classic Fenton process (pH: 3, 0.1 g L-1
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Fe+2, 45 min) (b) the ultrasound Fenton process (pH: 3, 0.05 g L-1 Fe+2, 45 min).
Fig. 5. The effect of H2O2 concentration on COD removal for classic Fenton process (pH: 3, 0.1 g L-1 Fe+2, 45 min) and ultrasound Fenton process (pH: 3, 0.05 g L-1 Fe+2, 45 min).
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Fig. 6. The variation of reaction time on (a) the classic Fenton process (pH: 3, 0.1 g L-1 Fe+2, 2.2 g L-1 H2O2) (b) the ultrasound Fenton process (pH: 3, 0.05 g L-1 Fe+2, 1.65 g L-1 H2O2) (c) COD removal for the Fenton processes.
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S2468-2039(17)30313-8
DOI:
10.1016/j.serj.2018.02.001
Reference:
SERJ 119
To appear in:
Sustainable Environment Research
Received Date: 3 October 2017 Revised Date:
14 December 2017
Accepted Date: 7 February 2018
Please cite this article as: Giray S, Morcali MH, Akarsu S, Ziba CA, Dolaz M, Comparison of classic Fenton with ultrasound Fenton processes on industrial textile wastewater, Sustainable Environment Research (2018), doi: 10.1016/j.serj.2018.02.001. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT Received 5 October 2017 Received in revised form 14 December 2017 Accepted 7 February 2018
Comparison of classic Fenton with ultrasound Fenton processes on industrial textile
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wastewater
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Mustafa Dolaz*
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Semanur Giray, Mehmet Hakan Morcali, Sümeyye Akarsu, Cengiz Ayhan Ziba,
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Department of Environmental Engineering, Kahramanmaras Sutcu Imam University,
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Kahramanmaras 46100, Turkey
* Corresponding author. E-mail address: [email protected]
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ACCEPTED MANUSCRIPT ABSTRACT This study provides a comparison between classic and modified (i.e., ultrasound) Fenton process on the industrial textile wastewater. For this purpose, the classic, and ultrasound Fenton process were investigated and compared using the following parameters:
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pH of solution, amount of ferrous ion (Fe(II)), and hydrogen peroxide as well as reaction time. With these parameters, degrading organic compounds (i.e., decolorization percentage) was calculated. The best decolorization percentage (95% for Pt-Co) was found using 0.10 g
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L-1 of Fe(II), and 2.20 g L-1 of H2O2 for 90 min at pH 3 for classic Fenton process. Similar experiments were carried out using 35 kHz ultrasonic irradiation, and the best decolorization
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percentage (99% for Pt-Co) was obtained via 0.05 g L-1 of Fe (II) and 1.65 g L-1 H2O2 for 60 min at pH 3 for ultrasound Fenton process. The results showed that decolorization increased with decreasing amount of chemical for the ultrasound Fenton process. Additionally, the contact time was decreased by comparing performance with classic Fenton process. In light
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of these results, the ultrasound Fenton process can be used for decolorization of textile wastewater to save reaction time and chemical costs. Also, the decolorized water (e.g., treated
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exchange process.
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water) may be reused in the plant for washing the textile materials after applying ion
Keywords: Textile wastewater; Fenton process; Ultrasound fenton process; Removal; Color. 1. Introduction
Textile industries, which are known as the largest company group on the earth, use fresh water in all production steps (i.e., bleaching, washing, and dyeing etc.). They produce more wastewater which usually contains organic matter, detergents and soaps, oil-grease, sulfide and sodas. To eliminate these pollutants in the wastewater, some chemical/physical/biological treatment methods have been applied [1-4]. However, these processes have some
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ACCEPTED MANUSCRIPT disadvantages, such as a low decolorization percentage, and high maintenance-intensive processes and especially, health and safety issues for biological treatment [4-5]. Advanced Oxidation Technologies (AOTs) are used for treatment of contaminating municipal or industrial wastewaters [6-10]. To remove color from industrial effluent, AOTs
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are generally preferred by industries [11,12]. The application of AOTs for the treatment of a wastewater from a textile industry using Fenton process was conducted by some companies such as Ecole Politechnique de Lausanne in Switzerland. The AOTs use additional energy
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and/or chemicals to generate highly reactive oxidizing species, most commonly the hydroxyl radical (•OH) which is responsible for oxidative destruction of a wide variety of organic
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compounds [10,13]. The efficiency of hydroxyl radical production is important with respect to its application as AOTs [8,10,14,15]. Owing to the increase in environmental problems and restrictions in industrial effluents, the development of AOTs is still kept importance. The related studies with the AOTs are presently a hot topic for researchers who aim to decrease
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the amount of chemical with increasing color removal percentage. Nowadays, there is a growing interest in the cleaning of textile wastewater for environmental protection in the world. Due to the government restriction and the water pollution control regulation, the
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wastewater should not contain azo dyes which cause an adverse effect on people health who
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live in these regions [16]. For this reason, several color removal methods have been studied by several researchers [17,18]. To eliminate the color originating dying stuff, Fenton process is generally preferred. The scientists presented a possible mechanism for the decomposition of hydrogen peroxide (i.e., Fenton process), which was included the formation of radicals, most notably the hydroxyl radical (see Eq. (1)). Fe2+ + H2O2 → Fe3+ + •OH + OH-
(1)
The Fe(II) oxidized to Fe(III), and the hydroxyl radical was produced. This species (i.e., (•OH)) is a powerful oxidizer and tends to react by addition to double bonds or by
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ACCEPTED MANUSCRIPT extraction of hydrogen atoms. In the literature, the process is called Fenton process which involves homogenous reaction. It is environmentally acceptable, and a system based on the generation of very reactive oxidizing free radicals, namely, hydroxyl radicals [19]. In addition to this reaction in photo-Fenton process, the following reaction occurs (Eq. (2) and
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Eq. (3)) [19,20]: H2O2 + UV → •OH + •OH Fe3+ + H2O + UV → •OH + Fe2+ + H+
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(3)
(2)
Photo-Fenton (e.g., photo assisted Fenton) has been addressed in the literature over the
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last decade [14,21-23]. Ultra violet light can provide energy to facilitate hydroxyl radical generation by the photo-Fenton reaction (Eq. 2) and hydrogen peroxide degradation. In recent years, attention has turned to the possible application of the Fenton reaction as an oxidative treatment for contaminated water. Many researchers have reported that optimal
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oxidation of target chemicals has occurred using Fenton-based systems (both dark and photo) at a pH of 2-3, which also corresponds to the optimal pH conditions for the Fenton reaction. They have also found that oxidation of target compounds usually occurs very quickly,
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relative to other AOTs such as UV/H2O2 or UV/TiO2/H2O2 [23-27]. However, results vary
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with respect to treatment of the target compound's oxidation products, namely complete mineralization of all of the organic carbon is not always achieved. The following examples help to illustrate the interest in classic Fenton and photo-Fenton reactions as methods of water remediation and the wide range of organic compounds that have been studied. The hydroxyl radical decompose the color where comes from organic dyes. It also triggers chemical oxygen demand (COD) since ferrous ions need more oxygen to convert ferric state. Besides more ferrous ion dosage is needed in attempt to produce moderate hydroxyl radical. Therefore, the use of ultrasonic irradiation has more and more attention in the treatment of dye wastewater
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ACCEPTED MANUSCRIPT [11,15,18,28]. Ultrasonic irradiation process has improved the generation of hydroxyl radical by ultrasonic sound and minimizes the amount of chemical on Fenton process. To obtain the highest decolorization, an ideal ultrasound Fenton process on textile effluent solution should satisfy a number of requirements such as initial solution pH, dosage of hydrogen peroxide,
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reaction time etc. Some of them have been studied on the removal of textile wastewater [15]. However, the process needs some improvements based on experimental parameters [16,17]. The current study using modified Fenton process in the presence of ultrasound is an easy and
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alternative method for the removal of color by breaking the azo bonds. Another advantage of the proposed process is that less chemical quantity is needed as compared to the classic
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Fenton process.
The main purpose of this work was to compare two Fenton processes to address some critical issues for the industrial textile wastewater, especially decolorization of water by these methods. The effects of experimental conditions on decolorization and COD were
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investigated. As a result, the best color removal (%) and the highest COD removal (%) were obtained with ultrasound Fenton process. 2. Materials and methods
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All experiments were carried out with the effluent solution which was provided from a
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textile company in Kahramanmaras, Turkey. Hydrogen peroxide (H2O2), sodium hydroxide (NaOH), and sulphuric acid (H2SO4) were used in analytical grade. Classic Fenton process was conducted in 600 mL capacity borosilicate glass beaker with a programmable jar tester (Lovibond, Germany). The method simulates a full-scale water treatment process. Adjusting the amount of treatment chemicals and the sequence was entailed via jar tester. The sonication (i.e., ultrasound) was generated by an ultrasonic cleaner (Kudos, China) in order to perform ultrasound Fenton process. The COD was determined by standard test method [29]. The color of the samples was measured using UV-visible spectrophotometer
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ACCEPTED MANUSCRIPT (Hach Lange DR 5000, USA). The solution of pH was measured by portable pH meter (Hanna, USA). Unless otherwise specified, all experiments (i.e., classic Fenton and ultrasound Fenton process) were independently performed in order to ascertain the consistency of the results. Ten milliliters solution was passed through a whatman paper
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(grade 1). Before measurements, a decomposition procedure with 40 mg manganese dioxide (MnO2) as a reductive was performed for removing excess hydrogen peroxide. Afterward the solution was filtered by using a 45 µm syringe filter prior to analysis. The decolorization
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measurements were carried out at 465 (for Pt-Co), 436, 525 and 620 nm. The COD analysis was performed with ISO 6060:1989 standard method [29].
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Classic Fenton and ultrasound Fenton experiments were employed to achieve the highest decolorization percentage and COD removal (%) using different parameters such as: pH, H2O2 concentrations, ferrous (Fe2+) concentrations and reaction time. All classic Fenton experiments were conducted in jar tester. Ultrasound Fenton process was performed by
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ultrasonic bath in which ultrasonic irradiation was adjusted to 35 kHz. All reactants were added into wastewater before starting reaction. 3. Result and discussion
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In the literature, several methods (e.g., precipitation, coagulation, ion exchange etc.) have
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been applied so as to remove organic pollutions from textile wastewater. However, some of them usually generate new problems or wastes after decomposition organic compounds or other processes. Fenton process is one of the most effective processes which are occurred in hydroxyl radical pathway. This process applies for decolorization (i.e., decomposition of organic compounds) and also reducing Fenton reagents quantity, reaction time. 3.1.
Effect of initial pH Acidic regime is the most important parameter in order to remove color as well as COD
for both Fenton processes, since the Fe (II) ions are not stable around pH 5. For this reason,
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ACCEPTED MANUSCRIPT different pH values versus decolorization percentage were studied to understand the effect of pH. In this experimental series, the effect of pH on the removal of color and removal of COD was investigated. 200 mL of the wastewater, 0.10 g L-1 Fe2+ ion, 1.40 g L-1 H2O2 and 45 min reaction time were applied as reaction parameters. The comparison of classic Fenton and
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ultrasound Fenton process was presented at different pH in Figs. 1a and 1b, respectively. As seen from these figures, pH was changed up to 4.5 removing percentage of color was increased. The maximum percentage was obtained at pH 3 for both processes. At this point, it
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is understood that the removal percentage was varied increasing pH value. For ultrasound Fenton process, the pH altered from 2 to 3, the color removal was enhanced from 87 to 96%
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for Pt-Co. Similar trend was observed for classic Fenton process, the color removal was changed from 75 to 88% for Pt-Co. The solution pH has a significant impact on the oxidation potential of ferrous ions in Fenton process. The concentration of Fe2+ ions and (•OH) radicals can be easily effected changing hydronium ion concentration [11]. The solution pH was
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raised around 6 or high, divalent iron ions can be easily precipitated as iron (II) hydroxide since it is well known that the precipitation of divalent iron depends on pH. A similar trend for the effect of pH was observed in a study by Özdemir et al. [11].
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The influence of pH versus COD removal was presented in Fig. 1c. Similar experimental
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conditions were used. It was apparent that COD removal efficiency positively altered up to 70% at pH 3 for classic Fenton process. At the same condition for ultrasound Fenton process, COD percentage was measured around 77% at pH 3. This result shows that COD value was mutated around 10% with ultrasound process. After increasing pH value from 3 to 4.5, the COD percentage value decreased, and the final value was determined 67% for classic Fenton process. After that point, COD value was found as 70% at pH 4.5 for ultrasound process. As a result of this study, the maximum COD removal was measured 77% at pH 3 for ultrasound Fenton process.
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3.2.
Effect of ferrous ion concentration In this experimental series, the influence of ferrous ions (Fe2+) concentration on removal
of color, and COD was studied in the range of 0.05 to 0.20 g L-1. 200 mL of the wastewater
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and 1.40 g L-1 H2O2, pH 3 and 45 min reaction time were preferred as reaction parameters. The removal of color and COD removal percentage as a function of ferrous ion concentration is presented in Figs. 2 and 3, respectively. As is evident from Figs. 2a and 2b, when
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escalating ferrous concentration from 0.05 to 0.20 g per 1000 mL solution, the removal of color with classic and ultrasound Fenton process increasing from 75 to 98% and from 90 to
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99% for Pt-Co, respectively. Additionally, similar trends were observed at different wavelengths (at 436, 525, 620 nm). Interestingly, it was examined that around 90% (Pt-Co) removal of color was obtained with 0.05 g L-1 Fe2+ ion were employed in ultrasound Fenton process. This result shows that ultrasound Fenton can successfully be achieved decreasing
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amount of ferrous ions as an alternate to application for environmentally friendly process for the treatment of dye containing waste solutions [30]. Ultrasound Fenton process requires relatively lower concentration of Fe2+ ion than classic Fenton process while comparing color
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removal (%) result. However it is noted that the color removal was perceptibly affected by
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ferrous concentration when investigating classic Fenton process. The ultrasound Fenton process is more effective than ferrous ion concentration. As shown in Fig. 3 increasing concentration of Fe2+ ions enhanced the COD removal. The reaction parameters were kept constant for within the same experimental series. While the COD removal by classic Fenton process increased from 62 to 73% by varying the concentration of Fe2+ ions from 0.05 to 0.20 g L-1. Interestingly, removal efficiencies of COD were decreased by increasing the dosage of Fe2+ ions to 0.22 g L-1. Thus, the optimum Fe2+ concentration for classic Fenton process was determined as 0.20 g L-1. This finding was also
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ACCEPTED MANUSCRIPT in accordance with studies undertaken by Sahinkaya [17]. Similar trend was observed with ultrasound Fenton process. When Fe2+ ion concentration was increased from 0.05 to 0.20 g L, the removal of COD efficiency was increased from 59 to 87%.
3.3.
Effect of H2O2 concentration
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The dosages of the hydrogen peroxide (H2O2) were varied, ranging from 1.1 to 2.8 g L-1 in the experimental series. 200 mL of the wastewater, 0.10 g L-1 Fe2+, (0.05 g L-1 Fe2+ for
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ultrasound) pH 3 and 45 min reaction time were preferred for both Fenton process as reaction parameters. The removal of color and COD with increasing peroxide dosages was presented
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in Figs. 4 and 5, respectively. The removal percentages were enhanced with increasing dosage of peroxide until reaching at the optimum concentration for both parameters. Since it is the main sources of (•OH) radicals yielded in Fenton process. The effect of H2O2 plays an important role on the efficiency of both the classic Fenton and ultrasound Fenton process.
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The color removal percentage was obtained 97% for Pt-Co; 97% at 436 nm, 98% at 525 nm and 97% at 620 nm, respectively when using 2.20 g L-1 H2O2 for classic Fenton process (see Fig. 4a). While H2O2 concentration was increased at 2.80 g L-1, removal of color was
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negatively fluctuated around 5%.
For ultrasound Fenton process, 200 mL of the wastewater, 0.05 g L-1 Fe2+, pH 3 and 45
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min reaction time were chosen. It was observed that the H2O2 dosages increase to 1.65 g L-1 the percentages of color removal 97% for Pt-Co. As seen at Fig. 4b, while the concentration of H2O2 increased more 1.65 g L-1 the removal of color efficiency decrease at 95% for Pt-Co. In the light of this information, the consumption of peroxide was reduced around 30% with ultrasound Fenton process. Fig. 5 presents the COD removal percentage and such results indicate the ultrasound fenton process was effective for COD removal percentage. The maximum COD removal was
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ACCEPTED MANUSCRIPT 88% at a concentration of H2O2 1.65 g L-1. Around 73% of the COD value was found using 2.20 g L-1 of H2O2. While concentration of H2O2 rose to 2.80 g L-1, the removal percentage of COD decreased around 70% for both of the processes.
Effect of reaction time
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3.4.
In the last experimental series, the effect of reaction time was investigated for Fenton and ultrasound Fenton process. 200 mL of the wastewater, 2.20 g L-1 H2O2, 0.10 g L-1 Fe2+ and
reaction is important between ferrous ions and H2O2.
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pH 3 were favored for classic fenton reaction parameters. It is well known that the stability of
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200 mL of the wastewater, 1.65 g L-1 H2O2, 0.05 g L-1 Fe2+ and pH 3 were preferred for ultrasound Fenton reaction parameters. Figs. 6a and 6b present the effect of contact time on the removal of color for classic Fenton and ultrasound Fenton process in the range of 15 to 180 min, respectively. For classic Fenton process, the best color removal was found at 90 min
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for 95% with Pt-Co. However, the removal of color was decreased when increasing reaction time. This situation is unexpected result because the reaction should be improved with reaction time. Nevertheless, almost 95% color removal was achieved with classic Fenton
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process for 90 min. The color removal percentage was obtained 99% Pt-Co for 60 min. In
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other words, reaction time was elevated around 33% with ultrasound Fenton process comparing classic Fenton process. As seen from Fig. 6c, increasing the reaction time from 10 to 180 min exhibited some increase in the COD removal percentage for ultrasound Fenton process. However, there was significant increase for classic Fenton process up to 60 min. This result implies that effect of time after 60 min did not change the COD removal for classic Fenton process but reaction time increased the removal of COD when using ultrasound process under same conditions. In
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ACCEPTED MANUSCRIPT the literature, similar studies reported that much longer reaction times needed COD removal percentage. 4.
Conclusions This study involves the decolorization of industrial wastewater using the classic Fenton
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and ultrasound Fenton process. In the applied decomposition of dye in the solution, aromatic organic compounds are oxidized through both Fenton processes and the aromatic compounds can be converted into aliphatic organic compounds. For this purpose, the experiments were
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performed to investigate the effects of H2O2, Fe2+ dosage, pH, and reaction time on decolorization and removal of COD. Based on the above results, the best conditions were
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found at pH 3, 0.10 g L-1 Fe2+, 2.20 g L-1 H2O2 for 90 min (for decolorization), for 60 min (COD removal) with classic Fenton process. Furthermore, the best conditions were achieved at pH 3, 0.05 g L-1 Fe2+, 1.65 g L-1 H2O2 for 60 min for decolorization and 90 min for COD with ultrasound Fenton process. This result should be directly related with amount of
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hydrogen peroxide and ferrous concentration. When compared both of the processes, ultrasound Fenton process is more economical because the use of hydrogen peroxide and ferrous ions are much less from classic Fenton process. Thus, using fewer chemicals higher
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treatment efficiency was reached. It is well known that use of less hydrogen peroxide and
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ferrous ensures clean solution and less environmental concern. The result of this study indicates that ultrasound Fenton oxidation process is more sufficient than classic Fenton process. In the light of these results, the ultrasound Fenton process can be used for the decolorization of textile wastewater to save reaction time and chemical costs. Also, the decolorized water (e.g., decomposed water) may be reused in the plant for washing the textile materials after applying ion exchange process. Acknowledgements
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ACCEPTED MANUSCRIPT This study was supported by Kahramanmaras Sutcu Imam University, (Project Number: 2013/4-7 YLS). We thank the Editor and two anonymous reviewers for their comments that help improve the manuscript. References Weber WJ, Smith EH. Removing dissolved organic contaminants from water.
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Fig. 1. The effect of different pH values on (a) the classic Fenton process (b) the ultrasound Fenton process (c) COD removal for the Fenton processes (0.1 g L-1 Fe+2, 1.4 g L-1 H2O2, 45 min).
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Fig. 2. Effect of Fe2+ ion concentration on (a) the classic Fenton process (b) the ultrasound
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Fenton process (pH: 3, 1.4 g L-1 H2O2, 45 min).
Fig. 3. Effect of Fe2+ ion concentration on COD removal for Fenton processes (pH: 3, 1.4 g L1
H2O2, 45 min).
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Fig. 4. The effect of H2O2 concentration on (a) the classic Fenton process (pH: 3, 0.1 g L-1
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Fe+2, 45 min) (b) the ultrasound Fenton process (pH: 3, 0.05 g L-1 Fe+2, 45 min).
Fig. 5. The effect of H2O2 concentration on COD removal for classic Fenton process (pH: 3, 0.1 g L-1 Fe+2, 45 min) and ultrasound Fenton process (pH: 3, 0.05 g L-1 Fe+2, 45 min).
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Fig. 6. The variation of reaction time on (a) the classic Fenton process (pH: 3, 0.1 g L-1 Fe+2, 2.2 g L-1 H2O2) (b) the ultrasound Fenton process (pH: 3, 0.05 g L-1 Fe+2, 1.65 g L-1 H2O2) (c) COD removal for the Fenton processes.
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