International Journal of Scientific Research in Environmental Sciences (IJSRES), 1 (12), pp. 357-364, 2013 Available online at http://www.ijsrpub.

com/ijsres ISSN: 2322-4983; 2013 IJSRPUB http://dx.doi.org/10.12983/ijsres-2013-p357-364

Full Length Research Paper Methyl Violet Removal from Synthetic Wastewater by Liquid-Liquid Extraction using Vegetable Oils as Solvent
Amir Talebi, Tjoon Tow Teng*, Abbas F.M. Alkarkhi, Yong Su
Division of Environmental Technology, School of Industrial Technology, Universiti Sains Malaysia (USM), 11800 Penang, Malaysia *Corresponding Author: E-mail: ttteng@usm.my; Tel.: +604 6532215; Fax: +604 6573678 Received 5 September 2013; Accepted 14 November 2013 Abstract. A laboratory study on methyl violet removal from aqueous solutions by liquidliquid extraction system has been carried out, using crude palm oil and soy bean oil as solvent. The concentration of methyl violet has been studied in the range of 100 mg/L to 200 mg/L. The efficiency of dye extraction increased when two extractant di-2-ethylhexyl phosphoric acid and tributhyl phosphate were used as carrier. Under optimized conditions, 82% to 89% dye removal in 5 minutes rapid mix followed by 60 minutes slow mixing was achieved. The aqueous to organic phase volume ratio (A/O) was fixed at 1, pH varied from 1-6 and extraction study was carried out at [TBP]: 200mM and [D2EHPA]: 75mM. Key words: Liquid-Liquid extraction, Methyl violet, D2EHPA, TBP

1. INTRODUCTION Synthetic dyes are essential refractory organic compounds and are often found in the environment as a result of their wide industrial usage (Das and Hamdaoui, 2010). Dyes are broadly used in numerous industries such as textile, paper, artificial manufacturing, cosmetics and leather, for tinting and colouring the products. The discharge of dye wastewater from these industries contains harmful and toxic materials and is considered as a potential source of pollutants in environment which may accumulate to a toxic concentration and cause serious problems (Muthuraman and Teng, 2009). Based on above mentioned facts, the dye removal from water and as the main source, industrial wastewater is very important and essential treatment is somehow required before contaminated industrial waste discharge. Typical and popular wastewater treatment methods are not very effective for dye removal, particularly because the dye stability against light oxidation and also being resistant to aerobic bio-oxidation (Poots et al., 1976). Liquidliquid extraction (LLE) is considered as a treatment method for purification of various compounds in mixtures (Garg et al., 2008; Njau et al., 2000; Cheng 2000; Thornton 1992). Extraction is a diffusion separation process of moving analyses from the matrix to a physically separate location where further processing and analysis occur. LLE is based on the distribution of a solute in a specific ratio between two immiscible solvents (Robbins and Cusack, 1997; Lee et al., 2009). 357

However, typical and popular organic solvents used in LLE as a diluent is considered hazardous, recalcitrant and toxic to environment and researchers are trying to find better and non-toxic diluent which are environmentally friendly and less harmful, such as vegetable oils. In this research, the LLE efficiency of a cationic dye namely methyl violet (MV) using di-2-ethylhexyl phosphoric acid (D2EHPA) and tributhyl phosphate (TBP) prepared in crude palm and soy bean oil as organic phase was studied. The effect of pH, extractant type and different vegetable oils were investigated and the process was optimized by factorial design. 2. EXPERIMENTAL DESIGN AND METHOD 2.1. Reagents The required stock solutions of MV was prepared by dissolving the certain amount of the dye in distilled water and made up to 1000 mL. MV was purchased from Merck. Other chemicals such as NaOH, H2SO4 were obtained from R&M. 2.2. Apparatus and Measurements For pH measurement of aqueous phase, pH meter (HACH, Germany) was used. Dye concentration was measured and analysed by Spekol 1200, Germany Spectrophotometer. An overhead stirrer (IKDK, Germany) was used for solutions mixing and agitation.

Talebi et al. Methyl Violet Removal from Synthetic Wastewater by Liquid-Liquid Extraction using Vegetable Oils as Solvent

2.3. Procedure Solvent extraction experiments were undertaken at room temperature. H2SO4 and NaOH were used for pH adjustment. Aqueous phase containing dye (100 mg/L, 25 mL) and the organic phase containing vegetable oil and carrier (25 mL) were mixed for 5 minutes at 120 rpm (rapid mixing) followed by one hour slow mixing at 50 rpm. Aqueous and organic phases were introduced in a separating funnel to separate. After certain time of settlement, the samples were taken from the lower phase of the separated funnel (aqueous phase), filtered through filter paper and the dye concentration was measured by UVSpectrophotometer. Dye removal percentage (extraction percentage) was calculated based on equation below:

3. RESULTS AND DISCUSSIONS 3.1. VARIABLES, RESPONSES, DESIGN of EXPERIMENTS and DATA ANALYSIS Two major variables were chosen based on the literature review most effective parameters. Among various effective variables such as stirring time, solvent type, different organic carriers, temperature etc. solvent, carriers and initial pH were chosen as main and most effective variables. Then a factorial design was applied for optimization process, including more than 100 different and various runs (by 5 different designs) in order to get the best applicable design of experiments. Then after, analysis of variance was applied for data analysis and results were examined to find the optimum condition for dye removal. 3.1. Statistical Analysis and Optimization

Where [dye]aq0: initial dye concentration in the aqueous phase (mg/L); [dye]aq: dye concentration of aqueous phase after extraction (mg/ L). For preliminary studies, in each experiment, 25ml of aqueous solution with 100 mg/L dye concentration was poured into a 250 ml beaker. A ratio of 1 was selected for aqueous to organic phase ratio. According to the literature, if the aqueous to organic phase ratio is beyond 1/1, then further increase in the volume of internal aqueous solution will have a negative effect on both the rate and efficiency of extraction process (Das and Hamdaoui, 2010). Based on previous studies, this is due to the fact that in case higher aqueous to organic phase ration beyond 1, increase of the emulsion viscosity and also an increase of the diameter of internal droplets will occur (Djenouhat et al., 2008; Chiha et al., 2006). On the other hand, the bigger droplets diameter will have a direct negative effect on interfacial contact area between the two phases and as a consequence, this will drop the extraction efficiency. In addition to, the other difficulty for higher volume ratios is due to the volume of membrane solution which is not enough for infolding the stripping solution (Juang and Lin, 2004). All the experiments were run base on statistical design of experiments in duplicate and analytical parameters were performed in triplicate for each run. The pH was adjusted to desired value (1-6). The organic phase was prepared for three types of carrier (TBP and D2EHPA and a mixture of carriers) and introduced into two different vegetable oils (crude palm oil and crude soy bean oil) as solvent.

Factorial designs are the way to investigate the relationships among several factors, each at more than one level. Factorial designs produce efficient experiments. Each observation provides information about all of the factors and enables the researcher to look at responses to one factor at different levels of another factor in the same experiment. Furthermore, factorial designs provide information whether the factors act on the experimental units independently of one another or they dont act independently indicating to the presence of interaction between the factors. Factorial designs allow the researcher to study: 1- The response variation created by a verify in the level of the factor which is called the main effect. 2- The alteration in response between the levels of one factor and all levels of another factor which is called the interaction (Myer and Montgomery, 2004; Tabachnick and Fidell, 2007). General case of factorial design where there are a levels of factor A, b levels of factor B, c levels of factor C, and so on, in this case there will be a, b, c n total number of observations (n represents the number of replication). In applying factorial design it is compulsory to use at least two replicates in order to determine a sum of squares due to error if all interactions are included in the model. Special cases of factorial designs are the threelevel factorial designs, where each factor at three levels, and two-level factorial designs, where each factor at two levels. Three major factors were selected for the factorial design and process optimization. pH (4-6), carrier ([TBP]: 200 mM : , [D2EHPA]: 75 mM and mixture of both carriers) and vegetable oil (crude palm oil and soy bean oil). 358

International Journal of Scientific Research in Environmental Sciences (IJSRES), 1 (12), pp. 357-364, 2013

The selected range for each variable is chosen based on literature review and also considering that the novelty and new contribution be satisfied. Based in literature, the highest dye removal by LLE is achieved in acidic range of pH, however, in preliminary study both acidic and alkaline regions were gone under examination (Muthuraman and Teng, 2009; Madaeni et al. 2011). The results of analysis of variance ANOVA for color removal showed that the main effect of selected factors on dye removal was significant individually; meaning that each selected factor, pH, carrier and vegetable oil shows a direct and significant effect can remove the dye. However, the interaction between selected pH values and each carrier or mixture of carriers and the interaction between pH and vegetable oils did not show any significant affect. But results of

NOVA reveals that interaction between the carriers and vegetable oil shows a significant impact on the dye removal. 3.2. Results The results of analysis of variance (ANOVA) for dye removal are given in Table 1. The analysis of variance revealed that a first-order model adequately fitted the experimental data. The linear effect of pH (A), carriers (B) and vegetable oils (C) were significant (p-values 0.05). The interaction between selected pH value (4-6) and two other factors were not significant, while the interaction between carriers and vegetable oils was significant, with R-Square: 0.9858, Adj R-Squared: 0.9766.

Table 1: ANOVA for Selected Factorial Model Analysis of variance table

Regression model was fitted to the data and a model was built, the model shows only significant terms in coded form includes the main effect for all factors and the interaction between carrier and vegetable oil is given in Eq.2 Dye removal (%) = +70.00-1.03 * A-19.00 * B[1]+7.67 * B[2]+3.32 * C+0.42-4.08 *B[1]C +1.88* B[2]C Where A, B and C represent the pH, carrier and the vegetable oil, respectively. A positive sign for the regression coefficient in the fitted model indicates the ability of the factor to increase the response, while the negative sign

indicated the ability of a factor to decrease the response. The results of various combinations of different factors are shown in Table 2. The highest dye removal (89.1%) was achieved at pH 4, when a mixture of 200mM TBP and 75mM D2EHPA were used as the carrier and crude palm oil was used as the solvent. The regression model obtained for dye removal is satisfactory since the value of the coefficient of determination R2 is high and close to 1. The value of R2 for dye removal model is 0.9858 and the value for adjusted R2 is 0.9766. Interaction plot for significant interaction between carriers and vegetable oil is given in Fig. below showing the behaviour of these factors.

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Talebi et al. Methyl Violet Removal from Synthetic Wastewater by Liquid-Liquid Extraction using Vegetable Oils as Solvent Table 2: Results of factorial design of experiments
Run 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Carrier TBP TBP TBP TBP D2 D2 D2 D2 Mix Mix Mix Mix TBP TBP TBP TBP D2 D2 D2 D2 Mix Mix Mix Mix Solvent (crude oil) Soya Soya Soya Soya Soya Soya Soya Soya Soya Soya Soya Soya Palm Palm Palm Palm Palm Palm Palm Palm Palm Palm Palm Palm Initial pH 4 4 6 6 4 4 6 6 4 4 6 6 4 4 6 6 4 4 6 6 4 4 6 6 Final pH 3.89 3.77 5.47 5.5 3.87 3.77 5.39 5.47 3.91 3.9 5.42 5.51 3,92 3.94 5.42 5.6 3.87 3,96 5.49 5.6 3.91 3.87 5.63 5.63 Initial color 328 192 328 192 328 192 328 192 328 192 328 192 92 324 92 324 92 324 92 324 92 324 92 324 Final color 162 92 151 95 84 51 97 54 69 44 82 53 41 167 46 171 14 57 16 59 10 45 11 51 Predicted Value (%) 52.35 52.35 51.15 51.15 73.50 73.50 71.45 71.45 77.25 77.25 74.35 74.35 50.85 50.85 49.65 49.65 83.90 83.90 81.85 81.85 88.30 88.30 85.40 85.40 Actual Value (%) 50.6 52 53.9 50.5 74.3 73.4 70.4 71.8 78.9 77 75 72.3 55.4 48.4 50 47.2 84.7 82.4 82.6 81.8 89.1 86.1 88 84.2

Based on preliminary results, a minor fluctuation in pH was observed after the extraction process was completed. This further increasing or decreasing pH in the feed phase which led to lower extraction efficiency could be due to the reducing fraction of MV molecules in the cationic form which exists in the aqueous solution. The observed low extraction efficiency of MV at pH <4 is caused by declining the driving force of the extraction process. Similar behaviour was observed for peptide extraction as reported by Drapala, 2004. Figure1. shows the interaction effect between the pH and the carriers. Based on this and ANOVA analysis, if the pH value varies from 4-6, the carrier selection (D2EHPA, TBP or a mixture of both carriers) does not show any significant effect. The results reveal that at 100 mg/L of MV and 200mM TBP, 55.4% removal was achieved at pH 4 and 50% removal was achieved at pH 6, using palm oil as diluent. For the same reason, when the pH was fixed at 4, 100mg/L of initial MV at 200mM TBP, showed 50.6% dye removal, and at pH 6, 50.5% dye removal was achieved. Figure 2. shows the interaction effect between the carriers and diluents. The interaction was significant and the highest removal occurred when the palm oil 360

used as the diluent and a mixture of TBP and D2EHPA used as carrier. The highest removal in this combination (89.1%) dye removal was for pH 4.0, 100 mg/L initial concentration of MV, 75 mM of D2EHPA and 200mM of TBP, using palm oil as diluent. For soy bean oil, the highest dye removal (78.9%) achieved for pH 4.0, 75 mM of D2EHPA and 200mM of TBP. These results show that significant interaction is due to the presence of TBP and D2EHPA together as carrier. Transport of MV using D2EHPA and TBP carrier, follows the same method in which metallic cations (Cote and Bauer, 1998) in a facilitated countercoupled transport obeys, according to the equation represented in the equilibrium below: MV+(aq) + HA MVA(org) + H+(aq) (2) where MV+ is methyl violet (cationic dye) and A is ligand. It should be mentioned that in reality, the complexes do not encompass the molecular form (HA) of the monomeric carrier in solution, which is totally in contrast to their analog structure containing one or more oxygen atoms (Sole and Hiskey, 1995). Figure 3 shows the extraction process in organic and aqueous interface. HA represents the D2EHPA or

International Journal of Scientific Research in Environmental Sciences (IJSRES), 1 (12), pp. 357-364, 2013

TBP as the carrier that subsists in the organic phase. Based on the results obtained, the MV+ is carried across the interface containing D2EHPA and TBP which can be explained as follows. 1. The MV+ diffuses from aqueous phase to the surface of two phases interface through aqueous boundary layer. 2. At the aqueous phase interface, the MV+ forms a neutral ion pair complex with TBP or D2EHPA.

3. The formed complex of MV+ and TBP or D2EHPA then diffuses through the organic phase due to the potential gradient between aqueous and organic phases. 4. Then on the organic phase, the MV+ is exchanged with a proton and is released. 5. Finally, the free D2EHPA or TBP acid is diffused back to the aqueous phase and the cycle is repeated (Drapala, 2004).

DESIGN-EXPERT Plo t Resp o n se 1 X = A: p H Y = B: Co n cen tratio n B1 TBP B2 D2 B3 Mix Actu al Facto r C: Oil = So y a

Interaction Grap h
B: Co n cen t rat i o n
89.1

78.625

Response 1

68.15

57.675

47.2

A: pH

Fig. 1: Interaction plot for pH and Carriers

DESIGN-EXPERT Plo t Resp o n se 1 X = B: Co n cen tratio n Y = C: Oil C1 So y a C2 Palm Actu al Facto r A: p H = 4

Interaction Grap h
C: O i l
90.4956

79.6717

Response 1

68.8478

58.0239

47.2

TBP

D2

Mix

B: Co n cen t rat i o n

Fig. 2: Interaction plot for Vegetable oils and Carriers

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Talebi et al. Methyl Violet Removal from Synthetic Wastewater by Liquid-Liquid Extraction using Vegetable Oils as Solvent

Fig. 3: Extraction direction between aqueous and organic phase

5. CONCLUSION Methyl violet was extracted from synthetic aqueous solution by liquid-liquid extraction. Crude palm and soy bean oil were used as solvent and D2EHPA and TBP were used as carriers. Based on factorial design of experiments the optimum conditions for dye removal varied from 89% to 82% in 5 rapid mix followed by 60 minutes slow mixing. The aqueous to organic phase volume ratio (A/O) was fixed. pH varied from 1-6 and extraction study was carried out at [TBP]: 200mM and [D2EHPA]: 75mM. Acknowledgment The authors acknowledge the USM for providing all facilities. The study was funded through USM research university grant (grant number 1001/PTEKIND/814045. The authors are greatly indebted to Soon Soon Oil Mill Sdn. Bhd., Malaysia, for their supply the vegetable oils used in this work. REFERENCES Chiha M, Samar MH, Hamdaoui O (2006). Extraction of chromium(VI) from sulphuric acid aqueous solutions by a liquid surfactant membrane (LSM). Desalination, 194: 6980. Cheng CY (2000) Purification of synthetic laterite leach solution by solvent extraction using D2EHPA. Hydrometallurgy, 56: 369386 Cote G, Bauer D (1989). Metal complexes with organothiophosphorus ligands and extraction phenomena. Reviews in Inorg.Chem., 10: 121 126. Das A, Hamdaoui O (2010). Extraction of anionic dye from aqueous solutions by emulsion liquid membrane. J.Hazard.Mater., 178: 973981. Djenouhat M, Hamdaoui O, Chiha M, Samar MH (2008). Ultrasonication-assisted preparation of water-in-oil emulsions and application to the removal of cationic dyes from water by emulsion liquid membrane. Sep. Purif. Technol., 62: 636641. 362

Drapala A, Wieczorek P(2004). Facilitated SLM extraction of peptides with D2EHPA as a carrier, Desalination, 163: 47-53. Garg UK, Kaur MP, Garg VK, Sud D (2008) Removal of Nickel(II) from aqueous solution by adsorption on agricultural waste biomass using a response surface methodological approach. Bioresource Technology, 99: 13251331 Juang RS, Lin KH (2004). Ultrasound-assisted production of W/O emulsions in liquid surfactant membrane processes, Colloids Surf. A: Physicochem. Eng. Aspects., 238: 4349. Lee JY, Rajesh Kumar J, Kim JS, Kim DJ, Yoon HS (2009). Extraction and separation of Pt(IV)/Rh(III) from acidic chloride solutions using Aliquat 336, J. Ind. Eng. Chem., 15: 359364. Madaeni SS, Jamali Z, Islami N (2011). Highly efficient and selective transport of methylene blue through a bulk liquid membrane containing Cyanex 301 as carrier. Sep Purif Technol, 81: 116123. Muthuraman G, Teng TT (2009). Extraction and recovery of rhodamine B, methyl violet and methylene blue from industrial wastewater using D2EHPA as an extractant. J.Ind.Eng.Chem., 15: 841846. Myer RH, Montgomery DC (2004). Response Surface Methodology, Process and Product Optimization Using Design Experiments, 2nd ed. John Wiley & Sons, New York, USA. Naju KN, Woude M, Visse GJ, Janssen LJJ (2000). Electrochemical removal of nickel ions from industrial wastewater. Chemical Engineering Journal 79: Chem. Eng. J., 187195 Poots VJP, McKay G, Healy JJ (1976).The removal of acid dye from effluent using natural adsorbentsII wood. Water. Res., 10: 1061. Robbins LA, Cusack RW (1997). Liquid-liquid Extraction Operations and Equipment, in: R.H. Perry, D.W. Green (Eds.), Perrys Chemical Engineers Handbook (1997), 7th ed., McGrawHill, New York 15: 220.

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Sole KC, Hiskey JB (1995). Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301, Hydrometallurgy, 37: 129133. Tabachnick BG, Fidell LS (2007). Experimental Design using ANOVA, Duxbury, USA.

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Talebi et al. Methyl Violet Removal from Synthetic Wastewater by Liquid-Liquid Extraction using Vegetable Oils as Solvent

Amir Talebi, He is a PhD Candidate in Environmental Technology, School of Industrial Technology, Universiti Sains Malaysia.

Tjoon Tow Teng, He is a Professor in Environmental Sciences at the School of Industrial Technology, Universiti Sains Malaysia

Abbas F.M. Alkarkhi, is an Associate Professor in Environmental Sciences at the School of Industrial Technology, Universiti Sains Malaysia

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