Microsoft Word - 43-50 ??? ????? ????? ????? ?????   Al-Khwarizmi Engineering Journal Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, March, (2021) P. P. 43- 50   Adsorption of Indigo Carmen Dye by Using Corn Leaves as Natural Adsorbent Material Omar H. Fadhil* Mohammed Y. Eisa** Dina Abdalrahman Salih*** Ziad R. Nafeaa **** *Department of Medical Laboratory Technology/ College of Medical Science/ Al-Mashreq University **,***,**** Department of Biochemical Engineering/ Al-Khwarizmi College of Engineering/ University of Baghdad *Email: omarhisham.94@yahoo.com **Email: mohammedyeisa@yahoo.com ***Email: dina_ar6@yahoo.com ****Emial: inspiron514@googlemail.com (Received 26 September 2020; accepted 16 November 2020) https://doi.org/10.22153/kej.2021.11.002 Abstract In this paper, the ability of using corn leaves as low-cost natural biowaste adsorbent material for the removal of Indigo Carmen (IC) dye was studied. Batch mode system was used to study several parameters such as, contact time (4 days), concentration of dye (10-50) ppm, adsorbent dosage (0.05-0.25) gram, pH (2-12) and temperature (30-60) oC. The corn leaf was characterized by Fourier-transform infrared spectroscopy device before and after the adsorption process of the IC dye and scanning electron microscope device was used to find the morphology of the adsorbent material. The experimental data was imputing with several isotherms where it fits with Freundlich (R2 = 0.9937) and followed pseudo second order kinetic. The highest removal percent was equal to 91% of the dye which makes the corn leaves a suitable efficient material for the removal of IC dye from aqueous solutions. Keywords: Adsorption, batch, Corn leaf, Indigo Carmen dye, Isotherm, Kinetics. 1. Introduction The wastewater that produced from textiles, papers, food, and pharmaceutical industries contains complex organic and aromatic compounds due to the types of dyes used that may be harmful and toxic to humankind and other living creatures. The major problem of the contaminated wastewater is that it contains very low concentrations of the dyes that minimizes the quality of water resource and increase environmental concern, that is why it must be treated before disposal to the assigned places [1]. Many methods are used these days for the treatment of polluted and colored wastewater. One of the common methods that widely used is adsorption due to its ease of operation, high recovery and efficiency [2]. Agriculture bio-waste is used as alternative adsorbent materials for the adsorption of dyes because of its cheapness, high surface area, high removal efficiency, availability, and eco-friendly to the environment which are used for fixing environmental pollution problems. The adsorption of dyes by using biowaste adsorbents had been studied by many researchers such as the adsorption of Methyl orange by corn leaves [3], Aniline blue by rice husk [4] and methyl red by tree park powder [5]. Omar H. Fadhil Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, P.P. 43- 50(2021)   44 Indigo carmine is a synthetic dye which is used as dermatological agent, biological stain and antibacterial agent. Also it is a carcinogen material, recalcitrant, and very toxic to mammalian cells [6]. Indigo carmen dye structure is shown in Figure 1. Fig. 1. Structure of Indigo carmen dye. The aim of this paper is to study the adsorption of Indigo carmen dye by using corn leaves from aqueous solution. 2. Materiais and Methods A group of runs were conducted at Al- Khwarizmi college of engineering / Baghdad University to study the effect of several parameters on the adsorption process. A sets of design of experiments were used for batch adsorption studies in which different concentrations of the dye from 10 to 50 ppm were put in 100 ml containers and mixed with various amounts of the adsorbent from 0.05 to 0.25 g/L with constant temperature (30℃) and initial pH (6.2). In the first set of experiments, containers were shaken at 150 rpm with contact time in the range (1-4) days with a step of one day. The effect of both pH and temperature was investigated using another set experiment. The ranges were (2-12) for pH and (30-60)℃ for temperature respectively. Factors studied in the first set were fixed at the optimum values. The equilibrium concentrations of IC dye were determined by measuring the absorbance using UV-visible spectrophotometer (Shimadzu 1800) device at a wavelength of 610 nm. The plot of absorbance vs. concentrations was observed as linear as shown in Figure 2. This curve will be the standard expression of the dye concentration with respect to the absorbance recorded at 610 nm using UV-Vis spectrophotometer all over the experimental work. The equilibrium concentrations and dye removal efficiency were calculated using the following equations [7]: Qe = (Co – Ce) … (1) % removal = 100 … (2) where Ce and Co are the equilibrium and initial concentrations of the dye (mg/L), respectively, Qe is the equilibrium dye concentration per adsorbent amount (mg/g) V is the volume of dye solution (L) M is the dosage of adsorbent (g). Fig. 2. Calibration curve of IC concentration vs. absorbance. The corn leaves were collected from College of Agriculture Engineering Sciences, University of Baghdad during the summer season. Washed few times to get rid of dust and other impurities, then, dried in the oven at 50 oC overnight. After that, they crushed and sieved to get a particle size of 125 ϻm, then, saved in a dried containers for further use. The dye was prepared by dissolving 1 g in 1 L of distilled water to get the stock solution with concentration of (1000 ppm), then diluted to obtain several concentrations of (10-50) ppm. 3. Resuits and Discussion Characterization of Corn leaves Fourier Transform Infrared spectroscopy (FTIR) was used to characterize the corn leaves powder. The spectrum is shown in Figures 3 and 4. By observing Figure 3, it can be seen that the functional OH group absorption at the region of (3200-3500) cm-1 stretching vibration in phenolic and aliphatic structures. The band at (2910-2920) cm-1 is assigned to C–H stretching vibration in aromatic methoxyl groups. A peak of C=C stretch was observed at (1650-1660) cm-1 which refers to alkenyl group, also, C-O single bonds appear at around 1180 cm-1 [8][3]. Omar H. Fadhil Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, P.P. 43- 50(2021)   45 The change in the surface of adsorbent shows that there was an adsorption process happened during the sorption and strong interaction between IC dye and the corn leaves was predominant. The Scanning Electron Microscopic (SEM) showed the morphological picture of the corn leaves particles which is bright on the surface as shown in Figure 5. Fig. 3. FTIR spectrum of corn leaves adsorbent before adsorption. Fig. 4. FTIR spectrum of IC dye with corn leaves after adsorption. Fig. 5. SEM of corn leaves adsorbent. Effect of Concentration The effect of the removal efficiency on the concentration is shown in Figure 6. As the concentration increased from 10 to 50 ppm, the removal efficiency increased at the beginning, then, decreased until it reached the equilibrium point. The adsorption capacity also decreased with increasing the concentration. This can be explained to the lack of the free active sites on the adsorbent surface which is fastly reached to the saturation state. This results is matched with the results of [9] where the removal efficiency also increased then decreased until it reached the equilibrium point (91.2%) for Basic violet dye. The best selected IC dye concentration was equal to 10 ppm. 5007501000125015001750200022502500275030003250350037504000 1/cm 30 35 40 45 50 55 60 65 70 %T 0 0 6 4 .9 3 0 .3 5 1 6 3 5 .6 4 1 2 7 1 .0 9 1 0 2 8 .0 6 5007501000125015001750200022502500275030003250350037504000 1/cm 10 15 20 25 30 35 40 45 50 55 60 %T 3 4 4 6 .7 9 3 4 1 4 .0 0 3 3 4 2 .6 4 3 2 9 4 .4 2 3 1 5 5 .5 4 2 8 7 7 .7 9 2 8 5 0 .7 9 2 8 3 9 .2 2 2 8 0 2 .5 7 2 7 7 7 .5 0 2 7 0 8 .0 6 2 6 9 0 .7 0 2 6 6 1 .7 7 2 6 4 6 .3 4 2 6 3 4 .7 6 1 6 5 8 .7 8 1 6 5 1 .0 7 1 3 9 0 .6 8 1 2 6 3 .3 7 3 5 7 2 .8 6 5 5 7 .4 3 5 4 3 .9 3 5 2 8 .5 0 4 9 9 5 6 Omar H. Fadhil Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, P.P. 43- 50(2021)   46 Fig. 6 The effect of initial dye concentration on the removal efficiency of IC dye at 30 oC and contact time of 4 days. Effect of Adsorbent Dosage The effect of the adsorbent dosage on the dye removal percent is shown in Figure 7. As the dosage of corn increased, the removal efficiency increased due to the increase of the surface area of the adsorbent material. The adsorption capacity decreased as the dosage increased as the particles of the adsorbent overlapping, as demonstrated by [10] where the sorption rate of aniline and methyl orange dyes decreases in the higher dosages of aloe vera leaves waste. The best amount of adsorbent dosage was 0.25 gm for achieving the higher removal percentages of dye. Fig. 7. The effects of dosage on the removal efficiency at 30 oC , 4 days contact time. Effect of Contact Time The removal percentage of the dye was increased as the contact time increased, also the amount of dye adsorbed per unit weight of adsorbent increased. This can be explained by the formation of the driving force between dye solution and the corn leaf adsorbent that leads to high amounts of IC molecules being transferred to the surface of the adsorbent. A similar result was described by [11] where the adsorption increased with the increase of contact time for Congo red dye using Brewers’ Spent Grain. The effect of contact time is shown in Figure 8. Fig. 8. Contact time effect on the removal of IC dye at 30 oC, 10 ppm dye concentration and 0.25 gm adsorbent dosage. Effect of pH The effect of the pH on the removal efficiency is shown in Figure 9. It is noticed that as the pH increase from 2 to 12, both the removal efficiency and adsorption capacity increased, this may be attributed to the surface functional groups and nature of the dye as evidenced by [12] where the amount of adsorbed crystal violet dye was found to increase with an increase in pH using walnut shell powder. Fig. 9. Effect of pH on the removal of IC dye at 30 oC, 4 days contact time, 10 ppm dye concentration and 0.25 gm adsorbent dosage. Omar H. Fadhil Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, P.P. 43- 50(2021)   47 Effect of Temperature Figure 10 shows that as the temperature increases from 30 to 60, the removal efficiency and the adsorption capacity both decreased. This can be explained by weak bonds between the IC dye molecules and the active sites of the corn leaves adsorbent at high temperatures. The results are in agreement with [3] where both the removal efficiency and the adsorption capacity of methyl orange dye decreased using corn leaves adsorbent material. Fig. 10 Effect of temperature on the removal efficiency of IC dye at 30 oC, 4 days contact time, 10 ppm dye concentration and 0.25 gm adsorbent dosage. Adsorption Isotherm The equilibrium relationship between the adsorbent dose and the dye concentration with respect to time was depicted using Langmuir and Freundlich isotherms. The linear form of Langmuir isotherm can be represented by the following equation [13]: ... (3) where: qe (mg/g) the amount of dye adsorbed at equilibrium qm (mg/g) the amount of dye adsorbed at saturation Ce the equilibrium dye concentration (mg/l) and Kl is Langmuir constant. The linear form of Freundlich equation is expressed as: ln 𝑞 ln 𝑘 ln 𝐶 … (4) Where: Kf\ and n are Freundlich constants which give a measure of the adsorption capacity and adsorption intensity, respectively. (Ce/Qe) vs (Ce) was plotted to find values of the constants (K and 𝑞 ) and the correlation coefficient (R2) as shown in Table 1 for Langmuir Isotherm. The results indicate that the adsorption of IC by corn leaves did not match with Langmuir isotherm. The data in Table 1 indicates that the adsorption of IC by Corn leaf as adsorbent follows Freundlich isotherm. Table 1, Adsorption isotherm parameters for IC adsorption on corn leaves at 30oC. Langmuir Ce/qe = 1/kLqm + Ce/qm qm -5.8377 KL -7.3578 R2 0.7524 Freundlich ln qe = ln KF + 1/n ln Ce n -1.7117 Kf 2.2109 R2 0.9264 Adsorption Kinetics Pseudo first and second order were used to study the kinetics of IC dye on Corn leaf. The pseudo first order model is expressed by the equation: ln(qe – qt) = ln qe – (k1) t ... (5) Where: qe and qt are the amounts of the adsorbent (mg/g) at equilibrium and at time t (min), respectively. k1 is the rate constant of adsorption (min −1). Pseudo second order equation can be expressed as [14]: t ... (6) Where k2 (g/mg.min) is the adsorption rate constant of pseudo second order adsorption rate. Fitting the experimental data into different kinetic models such as Pseudo first and second order was performed to investigate the adsorption rate, model the process and foretell the information of adsorbent/adsorbate interaction [15]. The accordance between the model values and the experimental data was expressed by correlation coefficient (R2). Adsorption kinetics was shown in Figure 8 as the change in percentage of dye removal with time. Value of the first order rate constant could be calculated by plotting Lagergren plot of log (qe-qt) with the adsorption time (t) in a linear representation as shown in Figure 11. Similarly, the pseudo second order constants are calculated by plotting each of (t/qt) versus Omar H. Fadhil Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, P.P. 43- 50(2021)   48 adsorption time (t) as shown in Figure 12 with the values of correlation coefficients (R2). Fig. 11 Pseudo first order plot of IC Adsorption by corn leaves. Fig. 12 Pseudo Second order plot of IC Adsorption by corn leaves Table 2 shows the kinetic models, their constants and the correlation coefficients. Table 2, Kinetic parameters values with R2 for IC adsorption. Pseudo first order ln(qe-qt) = ln(qe) – K1 t qe 52.5623 k1 -1.7438 R2 0.8194 Pseudo second order: t/qt = (1/k.qe)+(1/qe)t qe 16.92 k2 0.1759 R2 0.9937 Based on the results, the sorption of IC dye using Corn leaves adsorbent is conformed well by pseudo second order kinetic model. 4. Conclusions In this study, the feasibility of using corn leaves as efficient, low cost natural adsorbent material for the adsorption of indigo Carmen dye for batch study was investigated. The best conditions were 10 ppm concentration, 0.25 gm adsorbent dosage, pH of 12, temperature of 30oC and contact time of 4 days for 91% removal efficiency. It was found that as the concentration and temperature increased the removal efficiency decreased and as the dosage, contact time and pH increased, the removal efficiency increased. The equilibrium data fits with Freundlich isotherm and the rate of sorption followed Pseudo second order kinetics with a correlation factor of 0.9937. The results proved that the corn leaves as bio waste adsorbent are efficient and economical material for the removal of IC dye from aqueous solutions. Notation Ce Equilibrium concentration of adsorbate, mg/L Co Influent concentration, mg/L FTIR Fourier Transform Infrared spectroscopy k1 Rate constant of adsorption of pseudo first order, min−1 k2 Rate constant of adsorption of pseudo second order, g/mgꞏmin kf , n Freundlich constants, dimensionless kl Langmuir constant, L/mg M mass of adsorbent, (gm) PFO Pseudo First order PSO Pseudo second order qe The uptake of adsorbate at equilibrium, mg/g qm Amount of adsorbate required to form a monolayer, mg/g qt Amounts of the adsorbent at time t, mg/g SEM Scanning Electron Microscopy V Volume of solution, (L) Acknowledgments The authors are grateful for the Department of Biochemical Engineering, Al-Khwarizmi College of Engineering, University of Baghdad for the permission to use all the laboratory facilities and the support materials needed in this study. Omar H. Fadhil Al-Khwarizmi Engineering Journal, Vol. 17, No. 1, P.P. 43- 50(2021)   49 5. References [1] A. P. 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Alkaim, “Kinetics and Equilibrium Study for The Adsorption of Textile Dyes on Coconut Shell Activated Carbon,” Arab. J. Chem., 2017. [8] O. M. Paşka, C. Pәcurariu, and S. G. Muntean, “Kinetic and Thermodynamic Studies on Methylene Blue Biosorption Using Corn- Husk,” Rsc Adv., 2014. [9] A. Ibrahim, M.B and Umar, “Adsorption Thermodynamics of Some Basic Dyes Uptake from Aqueous Solution Using Albizia Lebbeck Shells,” Chemsearch J., Vol. 7, No. 1, Pp. 43–51, 2016. [10] Y. O. Khaniabadi, R. Heydari, H. Nourmoradi, H. Basiri, and H. Basiri, “Low- Cost Sorbent for The Removal of Aniline and Methyl Orange from Liquid-Phase: Aloe Vera Leaves Wastes,” J. Taiwan Inst. Chem. Eng., Vol. 68, Pp. 90–98, 2016. [11] A. Kezerle, N. Velic, D. Hasenay, and D. Kovačevic, “Lignocellulosic Materials as Dye Adsorbents: Adsorption of Methylene Blue And Congo Red on Brewers’ Spent Grain,” Croat. Chem. Acta, 2018, Doi: 10.5562/Cca3289. [12] B. K. Aziz and K. Faraidoon, “Adsorption Of Crystal Violet on Walnut Shell from Aqueous Solution,” No. 04, Pp. 4–8, 2015. [13] Y. S. Ho and G. Mckay, “A Comparison of Chemisorption Kinetic Models Applied to Pollutant Removal on Various Sorbents,” Process Safety and Environmental Protection. 1998. [14] A. E. Martins Et Al., “The Reactive Surface of Castor Leaf [Ricinus Communis L.] Powder as A Green Adsorbent for The Removal of Heavy Metals From Natural River Water,” Appl. Surf. Sci., 2013. ) 2021( 43- 50، صفحة 1، العدد17دي الهندسية المجلجلة الخوارزمم عمر هشام فاضل 50 امتزاز صبغة كارمن النيلية بأستخدام اوراق الذرة كمادة مازة طبيعية ** محمد يعقوب عيسى *عمر هشام فاضل ***زياد رافع نافع ***عبد الرحمن صالح يناد *قسم المختبرات الطبية/ كلية تقنيات العلوم الطبية/ جامعة المشرق جامعة بغداد **قسم الهندسة الكيميائية االحيائية/ كلية الهندسة الخوارزمي/ * **،** *، * omarhisham.94@yahoo.com :البريد االلكتروني* mohammedyeisa@yahoo.com :البريد االلكتروني** dina_ar6@yahoo.com***البريد االلكتروني: inspiron514@googlemail.com :البريد االلكتروني*** الخالصة دد تم دراسة قابلية استخدام اوراق الذرة كمادة مازة طبيعيه رخيصه الثمن ألزاله صبغه كارمن النيليه. تم استخدام نظام الدفعات لدراسة ع ،في هذا البحث ) درجة ٦٠-٣٠) والحرارة (١٢-٢الحامضية ( ،) غرام٠٫٢٥- ٠٫٠٥الكمية ( ،) جزء من المليون٥٠-١٠تركيز الصبغه ( ،ايام) ٤من المتغيرات مثل الزمن ( لمعرفه الشكل السطحي للمادة SEMقبل وبعد امتزاز الصبغه وكذلك تم استخدام جهاز ال FTIRسيليزية. ورق الذرة تم تشخيص خصائصه بأتسخدام جهاز ال ٪ ٩١ويتبع المعادلة الحركية الكاذبة من الدرجة الثانية اعلى نسبة ازالة كانت Freundlichوانطبقت مع isothermالمازة. النتائج التجريبية انسبت لعدة للصبغه مما يجعل اوراق الذرة مادة مناسبة وكفوءة ألزالة صبغه كارمن النيلية من المحاليل المائية.