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Redemption of acid fuchsin dye from wastewater using de-oiled biomass: Kinetics and isotherm analysis
Journal Pre-proof Redemption of acid fuchsin dye from wastewater using de-oiled biomass: Kinetics and isotherm analysis
A. Annam Renita, P. Senthil Kumar, S. Anuradha Jabasingh PII:
S2589-014X(19)30190-2
DOI:
https://doi.org/10.1016/j.biteb.2019.100300
Reference:
BITEB 100300
To appear in:
Bioresource Technology Reports
Received date:
15 July 2019
Revised date:
2 August 2019
Accepted date:
2 August 2019
Please cite this article as: A.A. Renita, P.S. Kumar and S.A. Jabasingh, Redemption of acid fuchsin dye from wastewater using de-oiled biomass: Kinetics and isotherm analysis, Bioresource Technology Reports(2019), https://doi.org/10.1016/j.biteb.2019.100300
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Journal Pre-proof
Redemption of Acid Fuchsin Dye from Wastewater using De-oiled Biomass : Kinetics and Isotherm Analysis Annam Renita A1, P. Senthil Kumar2* and Anuradha Jabasingh S3 1
Department of Chemical Engineering, Sathyabama Institute of Science and Technology, Chennai, India Email:[email protected] 2*
Department of Chemical Engineering, SSN College of Engineering, Chennai, India Email: [email protected]
3
Process Engineering Division, School of Chemical and Bio Engineering, Addis Ababa Institute of Technology,
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Addis Ababa University, Addis Ababa, Ethiopia. Email:[email protected]
*Corresponding author details
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Abstract
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In this research, de-oiled biomass (Sargassum myriocystum) was utilized as biosorbent for the
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redemption of dye from wastewater. Response surface methodology was adopted to optimize the biosorption influencing parameters. The de-oiled biomass of 3 g had the potential to
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remove the maximum amount of the dye from wastewater for a contact time of 50 min and at
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35 °C in the predicted optimized conditions. The linear regression analysis was done for equilibrium data and the Langmuir model showed good fit. Langmuir monolayer capacity of
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biosorbent for acid Fuchsin dye was 9.9 mg/g. The dye removal kinetic data informs that the
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dye removal followed the pseudo-second order rate kinetics. This inferred that the removal rate is controlled by chemisorption principle. The spent biosorbent can be recycled thrice without appreciable loss in its adsorption capacity. The newly prepared biosorbent showed excellent adsorption ability for dye wastewater.
Keywords: Sargassum myriocystum; Biosorbent; Isotherm; Kinetics; Equilibrium; Process Optimization
Journal Pre-proof 1. Introduction India with more than 2200 dyeing industries produces approximately 30,000 tons of dyestuff annually (Keharia et al., 2004). Most of these untreated colored water being dumped into the nearby water bodies which leads to detrimental effects on human and aquatic life (SenthilKumar et al., 2010; Kumar et al., 2011; Ponnusamy and Surbamaniam, 2013; Senthamarai et al., 2013; Kumar et al., 2014; Sharma et al., 2017; Jeevanantham et al., 2019; Joshiba et al., 2019; Pavithra et al., 2019; Saravanan et al., 2019). Acid Fuchsin is one of the
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toxic and carcinogenic dye which is widely used in dyeing textile fabrics, silk, nylon, wool
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and leather (Gong et al., 2018) apart from its usage as a laboratory reagent and corrosion
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inhibitor. Adsorption process is a more efficient, cost effective, versatile and best suited
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operation for Acid fuschin dye removal (Yunchuan et al., 2017) because these dyes are very slow degradation nature, mutagenic and carcinogenic characteristics. Very few literatures
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have been found on adsorption studies of acid Fuchsin dye till date in spite of its toxic and
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persistent nature due to nitrogen bonds in the back bone structure. Maximum adsorption capacity of 22 mg/g for acid Fuchsin dye was obtained by nickel oxide nanosheet NiO(111)
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nanosheets and 12 mg/g by commercial nickel oxide (Song et al., 2009). Ultrathin SnO2
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single-crystalline nanorods was used for the removal of acid Fuchsin and it was reported that 146.38 mg/g was the maximum sorption capacity (Xi and Ye, 2010). Zeolite obtained from fly ash was used to study the adsorption capability of acid Fuchsin dye and it was reported that a maximum adsorption of 40.64 mg/g was attained (Xu et al., 2014). Carbon-alumina composite pellet was used for the removal of acid Fuchsin dye in a batch adsorption studies and the maximum adsorption capacity was found to be 181.82 mg/g (Dutta and Basu, 2014 ). Acid Fuchsin dye removal was also investigated by adsorption onto chitosan/magnetic cellulose/sugarcane bagasse beads on a lab scale and received the maximum adsorption capacity of 208.33 mg/g (Gomathi and Vijayalakshmi, 2018). Graphene oxide/chitosan 2
Journal Pre-proof composite fibers which were prepared by wet spinning method was investigated for the removal of acid Fuchsin dye and the maximum adsorption capacity attained was 197.6 mg/g (Li et al., 2014). Dye adsorption of acid Fuchsin with nano sheets of zinc oxide (size 1.5 nm) synthesized from Zn(Ac)2·2H2ONa2SeO3-KBH4-pyridine solvothermal system for 24 h at 100 °C was reported with an adsorption capacity of 7154.9 mg/g (Cuijin et al., 2016). The above utilized adsorbents for dye removal was found to be the costly processing methods besides catering to their associated leaching problems in the dye effluent. Hence, this
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cost comparative and environmental friendly process.
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research paper proposes the utilization of spent biomass for acid Fuchsin dye removal for a
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Commercialization of algal biodiesel is hindered by its processing costs. Biodiesel
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from algae can become economical only when the biomass after the lipid extraction is utilized for other applications like manure, feedstock, adsorbent or as a biocrude for the
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extraction of amino acids, pigments and Poly Unsaturated Fatty Acids (PUFA) (Liu et al.,
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2018). Algal morphology is the best suited for both absorption and adsorption with an advantage that many species can be grown in the industrial effluents. Few literature can be
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found on adsorption of dye by algae: Astrazon Blue FGRL, Astrazon Red GTLN and
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methylene blue were treated with Caulerpa species (Marungrueng and Pavasant, 2007; Cengiz and Cavas, 2008), Malachite green, Acid Red 324, Acid Blue 337 by Enteromorpha carbon (Jayaraj et al., 2011; Ozer et al., 2005).. Safranine O and malachite green by activated Ulva lactuca (ULV-AC) and Systoceira stricta (SYS-AC) (Salima et al., 2013), crystal violet dye by kappa-Carrageenan beads (Mahdavinia et al., 2014; Mahdavinia et al., 2015) and reactive blue dye by Gracilaria edulis (Devi et al., 2015). In this research work, the removal of acid Fuchsin dye was obtained by using de-oiled biomass (Sargassum myriocystum). The optimization of adsorption parameters by response surface methodology iss carried out and it was found that the adsorption process was highly 3
Journal Pre-proof influenced by operating parameters such as adsorbent amount, time, initial concentration of dye wastewater and temperature. The equilibrium and kinetic studies have been tested with different isotherm and kinetic models. The desorption ability of the spent adsorbent was also studied. 2. Experimental 2.1 Materials Sargassum myriocystum was collected from Kovalam, Tamilnadu, India. The biomass after
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the lipid extraction was used for the present research (Annam Renita et al., 2014). Acid
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fuschin dye (Fischer Scientific Ltd., India) used for the study was of analytical grade.
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2.2 Adsorbent Preparation
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Sargassum myriocystum was lipid extracted and it was discussed in our previous research (Annam Renita et al., 2014). The de-oiled biomass was washed with distilled water to
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remove the solvent used in the lipid extraction and sun-dried until the moisture content of the
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biomass was <5%, followed by mild heating at 60 °C in hot air oven for further removal of moisture (Jothirani et al., 2016; Suganya et al., 2017). The dried biomass was ground with a
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mortar and pestle to a fine powder. The biosorbent before and after the adsorption was
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characterized using Scanning Electron Microscope (FlexSEM 1000, Hitachi, Japan). BET surface analyzer was utilized for the estimation of surface properties of the adsorbent ((Micromeritics ASAP 2020 Surface Area and Porosity Analyzer V3.00H, USA)). 2.3 Process optimization Central composite design was implemented for the study using Design Expert Software version 11. Response surface methodology was used to study the influence of adsorption parameters (Subramaniam and Ponnusamy 2015) which includes adsorbent dosage (1 - 5 g), temperature (25 - 45 oC), initial dye concentration (200 - 1000 mg/L) and time (10 - 90 min) on dye removal percentage. 4
Journal Pre-proof 2.4 Adsorption studies Acid Fuchsin stock solution was diluted to various concentrations (200-1000 mg/L) with double distilled water for this study. Experiments were conducted in batch mode with deoiled biomass (3 g) in series of conical flasks with 100 mL of dye solution with vigorous shaking in an orbital shaker at various temperatures to study the effect of temperature on adsorption. Once the equilibrium was attained, the adsorption mixtures was filtered using Whattman filter paper and 5 mL of sample was pipetted out to study the residual dye
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concentration after adsorption. UV-vis spectrophotometer (Hitachi, Japan) was used to
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determine the concentration of dye adsorbed before and after the adsorption at 544 nm which
Co Ce V m
(1)
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Quantity of dye adsorbed at equilibrium =
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is represented by Eq. (1)
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Where Co is initial dye concentration (mg/L), Ce is dye concentration at equilibrium (mg/L),
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V is volume of sample (L) and m is the amount of adsorbent (g). Batch studies were carried out with varying initial dye concentration of acid fuschin dye. Adsorbent dosage, temperature
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and time were varied to find their effect on percentage dye removal. Adsorption isotherms are
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useful to study the binding characteristics of adsorbate onto the adsorbent at equilibrium conditions. The influence of dye concentration on the dye removal by the biosorbent was useful to analyze the isotherm models which include Langmuir, Freundlich and Temkin models. The influence of contact time data has been analyzed by using pseudo-first order and pseudo-second order kinetic models. 2.5 Desorption studies The batch desorption experiments have been carried out for the spent adsorbent to check its regeneration ability. After the dye adsorption, the spent adsorbent was washed with distilled water to remove the unadsorbed dyes on the deoiled biomass surface. The desorption studies have been conducted at 35 oC by using 100 mL of 0.1 M nitric acid in an incubation shaker 5
Journal Pre-proof for about 60 min. After this particular time, the desorption mixtures have been separated as filtrate and adsorbent using Whatman filter paper. The desorbed dye concentration in the filtrate was analysed using UV-vis spectrophotometer. 3. Results and discussion 3.1 Characterization studies The scanning electron microscopic (SEM) analysis of the adsorbent was analyzed to verify the surface morphology of the adsorbent (Magnification: X5000 and EHT: 20 kV). The
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surface of the adsorbent exhibits the unstructured nature with distinct macropores. These
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pores were facilitate the removal of dye from wastewater (Premkumar et al., 2013; Anitha et
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al., 2016; Devi et al., 2016; Tharaneedhar et al., 2017; Manikandan et al., 2018; Suganya and
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Kumar, 2018). After the dye adsorption, the dye loaded adsorbent was also analyzed for its surface morphology. The SEM results for dye loaded adsorbent showed that the pores are not
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able to visible due to the adsorption of dye molecules over the adsorbent surface. The SEM
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results before and after adsoption infers that the dye molecules gets attached to surface of the adsorbent and this was clearly identified by the SEM results. BET surface area, pore volume,
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correlation coefficient and molecular cross-sectional area of deoiled biomass was found to be
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2.1197 + 0.0043 m2/g, 0.1318 cm3/g, 0.999478 and 0.1750 nm2, respectively. 3.2 Process optimization
The quadratic equation suggested by the model is represented by Eq. (2) Dye Removal (%) = 88.80 +14.67A +2.92B+ 2.42C -1.33D -2.50AB -2.00AC -3.50AD 0.25BC -4.00BD +2.5CD -13.69A2 -5.32B2 -3.07C2-3.94D2
(2)
Where A, B , C and D are the coded values for the adsorbent dosage (g), initial concentration of dye (mg/L) ,time (min) and temperature (°C) respectively. AB, BC, AC and AD are the interaction terms of adsorbent dosage, initial concentration and time on dye removal capacity and A2, B2 , C2 and D2 are the independent variables square terms. In this adsorption study, A, 6
Journal Pre-proof A² and B² are the significant model terms. Analysis of Variance (ANOVA) for the quadratic model is shown in Table 1. It can be inferred that regression coefficient of 0.9036 is in reasonable agreement with the Adjusted R² of 0.8071. Adeq Precision measures the signal to noise ratio and the ratio 10.033 indicates an adequate signal. The Model F-value of 9.37 implies the model is significant. There is only a 0.01% chance that an F-value this large could occur due to noise. P-values less than 0.0500 indicate model terms are significant. The Lack of Fit F-value of 0.37 implies it is not significant relative to the pure error.
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Fig.1a represents the percentage removal of dye for varying time period and for
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varying adsorbent dosage. It can be inferred from the surface and contour plot that the
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percentage decolorization potential increases up to 3g, attains equilibrium and drops
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thereafter. This is attributed to the approach of equilibrium due to the non availability of vacant sites for adsorption. Fig.1b shows the effect of time and for different initial
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concentration (200, 400, 600, 800, 1000 mg/L) on dye removal capacity and it can be noted
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that percentage removal increases from 0 min to 50 min and shows a declining nature beyond 50 min. This is in confirmation with earlier studies that active sites get overlapped providing
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less surface for more dye adsorption (Senthil Kumar et al. 2018). Fig.1c represents the effect
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of temperature and dosage of adsorbent on the dye removal capacity. It can be noted that adsorption carried out at 35 °C gives a higher percentage of dye removal and this is in confirmation with earlier studies that acid Fuchsin adsorption is an exothermic process and depends on temperature (Elsherbiny, 2013; Dutta and Basu, 2012). Fig.1d explains the influence of temperature and time on decolorization of dye with constant adsorbent dosage at 3 g. A maximum dye removal of 88% is achieved at 35 °C for 3 g and 50 min. The model was validated by carrying out experiments based on the parameters suggested by the software and the percentage of dye removal was found to be 89.5% which was consistent with the value of the model. 7
Journal Pre-proof 3.3 Adsorption Isotherms Langmuir (1918) isotherm represents monolayer adsorption. As per the model, all adsorption sites have equal energy and are homogeneous. The adsorbate reaches an equilibrium after which the adsorption of dye on adsorbent is not much effective. The Langmuir isotherm is represented as follows in Eq. (3):
1 1 1 q e q m K L Ce q m
(3)
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Where qe is the equilibrium adsorption capacity of adsorbent, KL is the Langmuir constant
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and qm is the Langmuir maximum monolayer capacity of the adsorbent. It can be understood
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from Fig.2(a) that this model fits well with high coefficient of regression R2=0.919 with
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experimental data. The value of Langmuir constants, qm and KL are 9.9 mg/g and 0.0092 L/mg, respectively.
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Freundlich (1906) isotherm equation is represented by Eq. (4), which applies mainly to dilute
1 ln Ce n
(4)
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ln q e ln K F
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aqueous solutions and for heterogeneous surfaces which is given by earlier research.
Where, n and KF are Freundlich constants. To study the isotherm, Eq. (4) was used and ln qe
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was plotted against ln Ce. From Fig.2(b), it can inferred that Freundlich isotherm fits the experimental data with R2 = 0.811, KF = 0.821 and n = 2.739. Temkin isotherm (Temkin and Pyzhev 1940) is illustrated by Eq. (5). It is obtained by plotting qe and ln Ce.
q e K m lnhCe
(5)
Where Km and h are Temkin constants. From a plot of qe and Ce, it can be inferred that from Fig.2(c), that it fits with experiment, with regression coefficient R2=0.87 and Temkin constants, h =1.742 and Km to be 0.5. From the adsorption isotherm results, it was confirmed that the adsorption isotherm data was best obeyed with Langmuir isotherm model as 8
Journal Pre-proof compared with other adsorption isotherm models. This indicates that the de-oiled biomass had homogeneous surface and it can able to occupy equal dye molecules over its active surface. 3.4 Adsorption Kinetics The equation corresponding to the pseudo-first-order kinetic model (Lagergren, 1898) is expressed as follows by Eq. (6).
k1 t 2.303
(6)
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lnq e q t ln q e
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Where qt (mg/g) is the amount of dye adsorbed at any time, t (min), respectively, and k1 is the
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rate constant of the pseudo-first order adsorption (min-1). k1 was found to be 0.113 min-1. The kinetic data were further analyzed using pseudo-second order kinetics, represented by Eq. (7),
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(Ho and McKay,1999) .
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t 1 t q t k 2 q e2 q t
(7)
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Pseudo-second order plot can be obtained by plotting t/qt vs t. From the plot, the rate constant
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k2 was determined to be 0.1311 mg g-1min-1 and qe was 7.143 mg/g. From Fig.3, it can be
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inferred that the kinetic data fitted well with the pseudo-second order kinetic expression as compared with the pseudo-first order kinetic expression based on the correlation coefficient values. The adsorption capacity at equilibrium for experimental and theoretical was similar for pseudo-second order kinetic model as compared with the pseudo-first order model. The kinetic results indicate that the adsorption was controlled by chemical adsorption. 3.5 Desorption Process Studies on desorption is valuable as the data on number of recycle times can be useful from an economic point of view for practical applications. Sargassum myriocystum was desorbed with water medium and 0.1M nitric acid. Desorption in water medium gave negligible results and hence nitric acid medium was selected since the same medium gave better results for 9
Journal Pre-proof algae belonging to same phylum (Jalali et al., 2002). This is in confirmation that acid medium clears the active pores facilitating binding of dye molecules onto the biomass (Jerold and Sivasubramanian, 2016). The desorption results showed that the dye removal capacity started decreasing appreciably after the third run and can be suggested that effective reuse of deoiled biomass which has no end value can be reused up to three times. 4. Conclusion This research work proposes the utilization of waste de-oiled biomass as an adsorbent for
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acid fuchsin dye removal. A maximum of 89.5 % dye removal was obtained for a contact
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time of 50 min and for an adsorbent dosage of 3 g. Used de-oiled biomass could be recycled
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up to three times without any major loss in adsorption potential. From the present research
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work, it can be concluded that the de-oiled biomass have the ability to remove from the
wastewater treatment.
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Supplementary Files Details
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wastewater and this material can be used as an effective biosorbent for an industrial
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Conflicts of Interest
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Fig.S1. SEM images (a) before and (b) after dye adsorption Table S1. Coded levels for variables used in adsorption study Table S2. Design matrix for Sargassum myriocystum biosorption studies
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SenthilKumar, P., Umaiyambika, N., Gayathri, R. 2010. Dye removal from aqueous solution by electrocoagulation process using stainless steel electrodes. Environ. Eng. Manage. J. 9(8), 1031-1037. Senthil Kumar, P., Fernando, P.S.A., Ahmed, R.T., Srinath, R., Priyadharshini, M., Vignesh, A. M., Thanjiappan, A. 2014. Effect of temperature on the adsorption of methylene blue dye onto sulfuric acid–treated orange peel. Chem. Eng. Commun. 201(11), 15261547. Senthil Kumar, P., Varjani, S.J., Suganya, S. 2018. Treatment of dye wastewater using an ultrasonic aided nanoparticle stacked activated carbon: kinetic and isotherm modeling. Bioresour. Technol. 250, 716-722. Sharma, G., ALOthman, Z.A., Kumar, A., Sharma, S., Ponnusamy, S.K., Naushad, M. 2017. Fabrication and characterization of a nanocomposite hydrogel for combined photocatalytic degradation of a mixture of malachite green and fast green dye. Nanotechnol. Environ. Eng. 2: 4.
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Journal Pre-proof Song, Z., Chen, L.F., Hu, J.C. ,and Richards, R.(2009). NiO (111) nanosheets as efficient andrecyclable adsorbents for dye pollutant removal from wastewater. Nanotechnol., 20(27),1-9. Subramaniam, R., Ponnusamy, S.K., 2015. Novel adsorbent from agricultural waste (cashew NUT shell) for methylene blue dye removal: Optimization by response surface methodology. Water Res. Ind., 11, 64-70. Suganya, S., Kumar, P.S. 2018. Kinetic and thermodynamic analysis for the redemption of effluents containing Solochrome Black T onto powdered activated carbon: A validation of new solid-liquid phase equilibrium model. J. Mol. Liquids 259, 88-101.
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Suganya, S., Kumar, P.S., Saravanan, A., Rajan, P.S., Ravikumar, C. 2017. Computation of adsorption parameters for the removal of dye from wastewater by microwave assisted sawdust: Theoretical and experimental analysis. Env. Toxicol. Pharmocol. 50, 45-57.
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Temkin, M.J., Pyzhev, V. 1940. Recent modifications to Langmuir isotherms. Acta Physicochim. URSS 12, 217-225.
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Tharaneedhar, V., Kumar, PS., Saravanan, A., Ravikumar, C., Jaikumar, V. 2017. Prediction and interpretation of adsorption parameters for the sequestration of methylene blue dye from aqueous solution using microwave assisted corncob activated carbon. Sustain. Mater. Technol. 11, 1-11.
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Xi, G., Ye, J. 2010. Ultrathin SnO2 nanorods: template and surfactant free solution phase synthesis, growth mechanism, optical, gas-sensing, and surface adsorption properties. Inorg. Chem. 49(5), 2302–2309.
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Xu, H.Y., Wu, L.C. , Shi, T.N., Liu, W.C., Qi, S.Y. 2014. Adsorption of acid fuchsin onto LTA-type zeolite derived from fly ash. Sci. China Tech. Sci. 57(6), 1127–1134.
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Yunchuan, Qi., Yang, M., Xu, W., He, S., Men, Y. 2017. Natural polysaccharides-modified graphene oxide for adsorption of organic dyes from aqueous solutions. J. Colloid Interface Sci. 486, 84-96.
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Journal Pre-proof Tables Table 1. ANOVA and regression coefficient estimate Sum of df Mean F P value Squares Square Value Pro>F Model 4225.92 14 301.85 9.37 < 0.0001 significant A 2581.33 1 2581.33 80.12 < 0.0001 B 102.08 1 102.08 3.17 0.0968 C 70.08 1 70.08 2.18 0.1624 D 21.33 1 21.33 0.6622 0.4294 AB 25.00 1 25.00 0.7760 0.3932 AC 16.00 1 16.00 0.4966 0.4925 AD 49.00 1 49.00 1.52 0.2378 BC 0.2500 1 0.2500 0.0078 0.9311 BD 64.00 1 64.00 1.99 0.1805 CD 25.00 1 25.00 0.7760 0.3932 A2 1215.97 1 1215.97 37.74 < 0.0001 B2 183.35 1 183.35 5.69 0.0317 2 C 61.00 1 61.00 1.89 0.1904 D2 100.78 1 100.78 3.13 0.0987 Residual 451.05 14 32.22 Lack of Fit 216.25 10 21.62 0.3684 0.9087 not significant Pure Error 234.80 4 58.70 9.37 Cor Total 4676.97 28 R2-0.9036 Adj R2-0.8071 Pre R2-0.7952
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Fig. 1. 3D plot of effect of (a) adsorbent dosage and time on dye removal (b) time and initial concentration on dye removal (c) temperature and adsorbent dosage on dye removal (d) temperature and time on dye removal Fig. 2. Isotherm model fits for the dye removal Fig. 3. Kinetic model fits for the dye removal
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Journal Pre-proof Graphical abstract Research Highlights The deoiled algae was used as biosorbent for dye removal.
The process parameters of biosorption have been optimized using RSM.
Langmuir and Pseudo-second order model best obeyed the data.
The deoiled biomass showed excellent adsorption properties.
Study proposes the application of waste biomass as an integrated biorefinery
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Figure 1
Figure 2
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A. Annam Renita, P. Senthil Kumar, S. Anuradha Jabasingh PII:
S2589-014X(19)30190-2
DOI:
https://doi.org/10.1016/j.biteb.2019.100300
Reference:
BITEB 100300
To appear in:
Bioresource Technology Reports
Received date:
15 July 2019
Revised date:
2 August 2019
Accepted date:
2 August 2019
Please cite this article as: A.A. Renita, P.S. Kumar and S.A. Jabasingh, Redemption of acid fuchsin dye from wastewater using de-oiled biomass: Kinetics and isotherm analysis, Bioresource Technology Reports(2019), https://doi.org/10.1016/j.biteb.2019.100300
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. 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.
© 2019 Published by Elsevier.
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Redemption of Acid Fuchsin Dye from Wastewater using De-oiled Biomass : Kinetics and Isotherm Analysis Annam Renita A1, P. Senthil Kumar2* and Anuradha Jabasingh S3 1
Department of Chemical Engineering, Sathyabama Institute of Science and Technology, Chennai, India Email:[email protected] 2*
Department of Chemical Engineering, SSN College of Engineering, Chennai, India Email: [email protected]
3
Process Engineering Division, School of Chemical and Bio Engineering, Addis Ababa Institute of Technology,
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Addis Ababa University, Addis Ababa, Ethiopia. Email:[email protected]
*Corresponding author details
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Abstract
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In this research, de-oiled biomass (Sargassum myriocystum) was utilized as biosorbent for the
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redemption of dye from wastewater. Response surface methodology was adopted to optimize the biosorption influencing parameters. The de-oiled biomass of 3 g had the potential to
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remove the maximum amount of the dye from wastewater for a contact time of 50 min and at
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35 °C in the predicted optimized conditions. The linear regression analysis was done for equilibrium data and the Langmuir model showed good fit. Langmuir monolayer capacity of
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biosorbent for acid Fuchsin dye was 9.9 mg/g. The dye removal kinetic data informs that the
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dye removal followed the pseudo-second order rate kinetics. This inferred that the removal rate is controlled by chemisorption principle. The spent biosorbent can be recycled thrice without appreciable loss in its adsorption capacity. The newly prepared biosorbent showed excellent adsorption ability for dye wastewater.
Keywords: Sargassum myriocystum; Biosorbent; Isotherm; Kinetics; Equilibrium; Process Optimization
Journal Pre-proof 1. Introduction India with more than 2200 dyeing industries produces approximately 30,000 tons of dyestuff annually (Keharia et al., 2004). Most of these untreated colored water being dumped into the nearby water bodies which leads to detrimental effects on human and aquatic life (SenthilKumar et al., 2010; Kumar et al., 2011; Ponnusamy and Surbamaniam, 2013; Senthamarai et al., 2013; Kumar et al., 2014; Sharma et al., 2017; Jeevanantham et al., 2019; Joshiba et al., 2019; Pavithra et al., 2019; Saravanan et al., 2019). Acid Fuchsin is one of the
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toxic and carcinogenic dye which is widely used in dyeing textile fabrics, silk, nylon, wool
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and leather (Gong et al., 2018) apart from its usage as a laboratory reagent and corrosion
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inhibitor. Adsorption process is a more efficient, cost effective, versatile and best suited
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operation for Acid fuschin dye removal (Yunchuan et al., 2017) because these dyes are very slow degradation nature, mutagenic and carcinogenic characteristics. Very few literatures
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have been found on adsorption studies of acid Fuchsin dye till date in spite of its toxic and
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persistent nature due to nitrogen bonds in the back bone structure. Maximum adsorption capacity of 22 mg/g for acid Fuchsin dye was obtained by nickel oxide nanosheet NiO(111)
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nanosheets and 12 mg/g by commercial nickel oxide (Song et al., 2009). Ultrathin SnO2
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single-crystalline nanorods was used for the removal of acid Fuchsin and it was reported that 146.38 mg/g was the maximum sorption capacity (Xi and Ye, 2010). Zeolite obtained from fly ash was used to study the adsorption capability of acid Fuchsin dye and it was reported that a maximum adsorption of 40.64 mg/g was attained (Xu et al., 2014). Carbon-alumina composite pellet was used for the removal of acid Fuchsin dye in a batch adsorption studies and the maximum adsorption capacity was found to be 181.82 mg/g (Dutta and Basu, 2014 ). Acid Fuchsin dye removal was also investigated by adsorption onto chitosan/magnetic cellulose/sugarcane bagasse beads on a lab scale and received the maximum adsorption capacity of 208.33 mg/g (Gomathi and Vijayalakshmi, 2018). Graphene oxide/chitosan 2
Journal Pre-proof composite fibers which were prepared by wet spinning method was investigated for the removal of acid Fuchsin dye and the maximum adsorption capacity attained was 197.6 mg/g (Li et al., 2014). Dye adsorption of acid Fuchsin with nano sheets of zinc oxide (size 1.5 nm) synthesized from Zn(Ac)2·2H2ONa2SeO3-KBH4-pyridine solvothermal system for 24 h at 100 °C was reported with an adsorption capacity of 7154.9 mg/g (Cuijin et al., 2016). The above utilized adsorbents for dye removal was found to be the costly processing methods besides catering to their associated leaching problems in the dye effluent. Hence, this
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cost comparative and environmental friendly process.
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research paper proposes the utilization of spent biomass for acid Fuchsin dye removal for a
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Commercialization of algal biodiesel is hindered by its processing costs. Biodiesel
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from algae can become economical only when the biomass after the lipid extraction is utilized for other applications like manure, feedstock, adsorbent or as a biocrude for the
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extraction of amino acids, pigments and Poly Unsaturated Fatty Acids (PUFA) (Liu et al.,
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2018). Algal morphology is the best suited for both absorption and adsorption with an advantage that many species can be grown in the industrial effluents. Few literature can be
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found on adsorption of dye by algae: Astrazon Blue FGRL, Astrazon Red GTLN and
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methylene blue were treated with Caulerpa species (Marungrueng and Pavasant, 2007; Cengiz and Cavas, 2008), Malachite green, Acid Red 324, Acid Blue 337 by Enteromorpha carbon (Jayaraj et al., 2011; Ozer et al., 2005).. Safranine O and malachite green by activated Ulva lactuca (ULV-AC) and Systoceira stricta (SYS-AC) (Salima et al., 2013), crystal violet dye by kappa-Carrageenan beads (Mahdavinia et al., 2014; Mahdavinia et al., 2015) and reactive blue dye by Gracilaria edulis (Devi et al., 2015). In this research work, the removal of acid Fuchsin dye was obtained by using de-oiled biomass (Sargassum myriocystum). The optimization of adsorption parameters by response surface methodology iss carried out and it was found that the adsorption process was highly 3
Journal Pre-proof influenced by operating parameters such as adsorbent amount, time, initial concentration of dye wastewater and temperature. The equilibrium and kinetic studies have been tested with different isotherm and kinetic models. The desorption ability of the spent adsorbent was also studied. 2. Experimental 2.1 Materials Sargassum myriocystum was collected from Kovalam, Tamilnadu, India. The biomass after
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the lipid extraction was used for the present research (Annam Renita et al., 2014). Acid
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fuschin dye (Fischer Scientific Ltd., India) used for the study was of analytical grade.
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2.2 Adsorbent Preparation
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Sargassum myriocystum was lipid extracted and it was discussed in our previous research (Annam Renita et al., 2014). The de-oiled biomass was washed with distilled water to
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remove the solvent used in the lipid extraction and sun-dried until the moisture content of the
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biomass was <5%, followed by mild heating at 60 °C in hot air oven for further removal of moisture (Jothirani et al., 2016; Suganya et al., 2017). The dried biomass was ground with a
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mortar and pestle to a fine powder. The biosorbent before and after the adsorption was
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characterized using Scanning Electron Microscope (FlexSEM 1000, Hitachi, Japan). BET surface analyzer was utilized for the estimation of surface properties of the adsorbent ((Micromeritics ASAP 2020 Surface Area and Porosity Analyzer V3.00H, USA)). 2.3 Process optimization Central composite design was implemented for the study using Design Expert Software version 11. Response surface methodology was used to study the influence of adsorption parameters (Subramaniam and Ponnusamy 2015) which includes adsorbent dosage (1 - 5 g), temperature (25 - 45 oC), initial dye concentration (200 - 1000 mg/L) and time (10 - 90 min) on dye removal percentage. 4
Journal Pre-proof 2.4 Adsorption studies Acid Fuchsin stock solution was diluted to various concentrations (200-1000 mg/L) with double distilled water for this study. Experiments were conducted in batch mode with deoiled biomass (3 g) in series of conical flasks with 100 mL of dye solution with vigorous shaking in an orbital shaker at various temperatures to study the effect of temperature on adsorption. Once the equilibrium was attained, the adsorption mixtures was filtered using Whattman filter paper and 5 mL of sample was pipetted out to study the residual dye
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concentration after adsorption. UV-vis spectrophotometer (Hitachi, Japan) was used to
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determine the concentration of dye adsorbed before and after the adsorption at 544 nm which
Co Ce V m
(1)
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Quantity of dye adsorbed at equilibrium =
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is represented by Eq. (1)
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Where Co is initial dye concentration (mg/L), Ce is dye concentration at equilibrium (mg/L),
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V is volume of sample (L) and m is the amount of adsorbent (g). Batch studies were carried out with varying initial dye concentration of acid fuschin dye. Adsorbent dosage, temperature
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and time were varied to find their effect on percentage dye removal. Adsorption isotherms are
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useful to study the binding characteristics of adsorbate onto the adsorbent at equilibrium conditions. The influence of dye concentration on the dye removal by the biosorbent was useful to analyze the isotherm models which include Langmuir, Freundlich and Temkin models. The influence of contact time data has been analyzed by using pseudo-first order and pseudo-second order kinetic models. 2.5 Desorption studies The batch desorption experiments have been carried out for the spent adsorbent to check its regeneration ability. After the dye adsorption, the spent adsorbent was washed with distilled water to remove the unadsorbed dyes on the deoiled biomass surface. The desorption studies have been conducted at 35 oC by using 100 mL of 0.1 M nitric acid in an incubation shaker 5
Journal Pre-proof for about 60 min. After this particular time, the desorption mixtures have been separated as filtrate and adsorbent using Whatman filter paper. The desorbed dye concentration in the filtrate was analysed using UV-vis spectrophotometer. 3. Results and discussion 3.1 Characterization studies The scanning electron microscopic (SEM) analysis of the adsorbent was analyzed to verify the surface morphology of the adsorbent (Magnification: X5000 and EHT: 20 kV). The
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surface of the adsorbent exhibits the unstructured nature with distinct macropores. These
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pores were facilitate the removal of dye from wastewater (Premkumar et al., 2013; Anitha et
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al., 2016; Devi et al., 2016; Tharaneedhar et al., 2017; Manikandan et al., 2018; Suganya and
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Kumar, 2018). After the dye adsorption, the dye loaded adsorbent was also analyzed for its surface morphology. The SEM results for dye loaded adsorbent showed that the pores are not
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able to visible due to the adsorption of dye molecules over the adsorbent surface. The SEM
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results before and after adsoption infers that the dye molecules gets attached to surface of the adsorbent and this was clearly identified by the SEM results. BET surface area, pore volume,
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correlation coefficient and molecular cross-sectional area of deoiled biomass was found to be
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2.1197 + 0.0043 m2/g, 0.1318 cm3/g, 0.999478 and 0.1750 nm2, respectively. 3.2 Process optimization
The quadratic equation suggested by the model is represented by Eq. (2) Dye Removal (%) = 88.80 +14.67A +2.92B+ 2.42C -1.33D -2.50AB -2.00AC -3.50AD 0.25BC -4.00BD +2.5CD -13.69A2 -5.32B2 -3.07C2-3.94D2
(2)
Where A, B , C and D are the coded values for the adsorbent dosage (g), initial concentration of dye (mg/L) ,time (min) and temperature (°C) respectively. AB, BC, AC and AD are the interaction terms of adsorbent dosage, initial concentration and time on dye removal capacity and A2, B2 , C2 and D2 are the independent variables square terms. In this adsorption study, A, 6
Journal Pre-proof A² and B² are the significant model terms. Analysis of Variance (ANOVA) for the quadratic model is shown in Table 1. It can be inferred that regression coefficient of 0.9036 is in reasonable agreement with the Adjusted R² of 0.8071. Adeq Precision measures the signal to noise ratio and the ratio 10.033 indicates an adequate signal. The Model F-value of 9.37 implies the model is significant. There is only a 0.01% chance that an F-value this large could occur due to noise. P-values less than 0.0500 indicate model terms are significant. The Lack of Fit F-value of 0.37 implies it is not significant relative to the pure error.
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Fig.1a represents the percentage removal of dye for varying time period and for
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varying adsorbent dosage. It can be inferred from the surface and contour plot that the
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percentage decolorization potential increases up to 3g, attains equilibrium and drops
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thereafter. This is attributed to the approach of equilibrium due to the non availability of vacant sites for adsorption. Fig.1b shows the effect of time and for different initial
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concentration (200, 400, 600, 800, 1000 mg/L) on dye removal capacity and it can be noted
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that percentage removal increases from 0 min to 50 min and shows a declining nature beyond 50 min. This is in confirmation with earlier studies that active sites get overlapped providing
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less surface for more dye adsorption (Senthil Kumar et al. 2018). Fig.1c represents the effect
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of temperature and dosage of adsorbent on the dye removal capacity. It can be noted that adsorption carried out at 35 °C gives a higher percentage of dye removal and this is in confirmation with earlier studies that acid Fuchsin adsorption is an exothermic process and depends on temperature (Elsherbiny, 2013; Dutta and Basu, 2012). Fig.1d explains the influence of temperature and time on decolorization of dye with constant adsorbent dosage at 3 g. A maximum dye removal of 88% is achieved at 35 °C for 3 g and 50 min. The model was validated by carrying out experiments based on the parameters suggested by the software and the percentage of dye removal was found to be 89.5% which was consistent with the value of the model. 7
Journal Pre-proof 3.3 Adsorption Isotherms Langmuir (1918) isotherm represents monolayer adsorption. As per the model, all adsorption sites have equal energy and are homogeneous. The adsorbate reaches an equilibrium after which the adsorption of dye on adsorbent is not much effective. The Langmuir isotherm is represented as follows in Eq. (3):
1 1 1 q e q m K L Ce q m
(3)
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Where qe is the equilibrium adsorption capacity of adsorbent, KL is the Langmuir constant
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and qm is the Langmuir maximum monolayer capacity of the adsorbent. It can be understood
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from Fig.2(a) that this model fits well with high coefficient of regression R2=0.919 with
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experimental data. The value of Langmuir constants, qm and KL are 9.9 mg/g and 0.0092 L/mg, respectively.
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Freundlich (1906) isotherm equation is represented by Eq. (4), which applies mainly to dilute
1 ln Ce n
(4)
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ln q e ln K F
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aqueous solutions and for heterogeneous surfaces which is given by earlier research.
Where, n and KF are Freundlich constants. To study the isotherm, Eq. (4) was used and ln qe
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was plotted against ln Ce. From Fig.2(b), it can inferred that Freundlich isotherm fits the experimental data with R2 = 0.811, KF = 0.821 and n = 2.739. Temkin isotherm (Temkin and Pyzhev 1940) is illustrated by Eq. (5). It is obtained by plotting qe and ln Ce.
q e K m lnhCe
(5)
Where Km and h are Temkin constants. From a plot of qe and Ce, it can be inferred that from Fig.2(c), that it fits with experiment, with regression coefficient R2=0.87 and Temkin constants, h =1.742 and Km to be 0.5. From the adsorption isotherm results, it was confirmed that the adsorption isotherm data was best obeyed with Langmuir isotherm model as 8
Journal Pre-proof compared with other adsorption isotherm models. This indicates that the de-oiled biomass had homogeneous surface and it can able to occupy equal dye molecules over its active surface. 3.4 Adsorption Kinetics The equation corresponding to the pseudo-first-order kinetic model (Lagergren, 1898) is expressed as follows by Eq. (6).
k1 t 2.303
(6)
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lnq e q t ln q e
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Where qt (mg/g) is the amount of dye adsorbed at any time, t (min), respectively, and k1 is the
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rate constant of the pseudo-first order adsorption (min-1). k1 was found to be 0.113 min-1. The kinetic data were further analyzed using pseudo-second order kinetics, represented by Eq. (7),
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(Ho and McKay,1999) .
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t 1 t q t k 2 q e2 q t
(7)
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Pseudo-second order plot can be obtained by plotting t/qt vs t. From the plot, the rate constant
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k2 was determined to be 0.1311 mg g-1min-1 and qe was 7.143 mg/g. From Fig.3, it can be
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inferred that the kinetic data fitted well with the pseudo-second order kinetic expression as compared with the pseudo-first order kinetic expression based on the correlation coefficient values. The adsorption capacity at equilibrium for experimental and theoretical was similar for pseudo-second order kinetic model as compared with the pseudo-first order model. The kinetic results indicate that the adsorption was controlled by chemical adsorption. 3.5 Desorption Process Studies on desorption is valuable as the data on number of recycle times can be useful from an economic point of view for practical applications. Sargassum myriocystum was desorbed with water medium and 0.1M nitric acid. Desorption in water medium gave negligible results and hence nitric acid medium was selected since the same medium gave better results for 9
Journal Pre-proof algae belonging to same phylum (Jalali et al., 2002). This is in confirmation that acid medium clears the active pores facilitating binding of dye molecules onto the biomass (Jerold and Sivasubramanian, 2016). The desorption results showed that the dye removal capacity started decreasing appreciably after the third run and can be suggested that effective reuse of deoiled biomass which has no end value can be reused up to three times. 4. Conclusion This research work proposes the utilization of waste de-oiled biomass as an adsorbent for
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acid fuchsin dye removal. A maximum of 89.5 % dye removal was obtained for a contact
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time of 50 min and for an adsorbent dosage of 3 g. Used de-oiled biomass could be recycled
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up to three times without any major loss in adsorption potential. From the present research
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work, it can be concluded that the de-oiled biomass have the ability to remove from the
wastewater treatment.
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Supplementary Files Details
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wastewater and this material can be used as an effective biosorbent for an industrial
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Conflicts of Interest
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Fig.S1. SEM images (a) before and (b) after dye adsorption Table S1. Coded levels for variables used in adsorption study Table S2. Design matrix for Sargassum myriocystum biosorption studies
Authors declares that there is no any conflicts of interest for this research article. Authors also confirms that this research work is not funded by any research funding agencies. References Abkenar, S.D., Khoobi, M., Tarasi, R., Hosseini, M., Shafiee, A., Ganjali, M.R. 2019. Fast removal of methylene blue from aqueous solution using magnetic modified Fe3O4 nanoparticles. J. Environ. Eng. 141(1), 04019025. Anitha, T., Kumar, P.S., Kumar, K.S. 2016. Synthesis of nano-sized chitosan blended polyvinyl alcohol for the removal of Eosin Yellow dye from aqueous solution. J. Water Proc. Eng. 13, 127-136.
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Journal Pre-proof Tables Table 1. ANOVA and regression coefficient estimate Sum of df Mean F P value Squares Square Value Pro>F Model 4225.92 14 301.85 9.37 < 0.0001 significant A 2581.33 1 2581.33 80.12 < 0.0001 B 102.08 1 102.08 3.17 0.0968 C 70.08 1 70.08 2.18 0.1624 D 21.33 1 21.33 0.6622 0.4294 AB 25.00 1 25.00 0.7760 0.3932 AC 16.00 1 16.00 0.4966 0.4925 AD 49.00 1 49.00 1.52 0.2378 BC 0.2500 1 0.2500 0.0078 0.9311 BD 64.00 1 64.00 1.99 0.1805 CD 25.00 1 25.00 0.7760 0.3932 A2 1215.97 1 1215.97 37.74 < 0.0001 B2 183.35 1 183.35 5.69 0.0317 2 C 61.00 1 61.00 1.89 0.1904 D2 100.78 1 100.78 3.13 0.0987 Residual 451.05 14 32.22 Lack of Fit 216.25 10 21.62 0.3684 0.9087 not significant Pure Error 234.80 4 58.70 9.37 Cor Total 4676.97 28 R2-0.9036 Adj R2-0.8071 Pre R2-0.7952
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Fig. 1. 3D plot of effect of (a) adsorbent dosage and time on dye removal (b) time and initial concentration on dye removal (c) temperature and adsorbent dosage on dye removal (d) temperature and time on dye removal Fig. 2. Isotherm model fits for the dye removal Fig. 3. Kinetic model fits for the dye removal
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Journal Pre-proof Graphical abstract Research Highlights The deoiled algae was used as biosorbent for dye removal.
The process parameters of biosorption have been optimized using RSM.
Langmuir and Pseudo-second order model best obeyed the data.
The deoiled biomass showed excellent adsorption properties.
Study proposes the application of waste biomass as an integrated biorefinery
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Figure 1
Figure 2
Figure 3