Strategically dewaxed honeycomb powder is a promising and eco-friendly alternative for the removal of malachite green through fixed bed column

Strategically dewaxed honeycomb powder is a promising and eco-friendly alternative for the removal of malachite green through fixed bed column | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Strategically dewaxed honeycomb powder is a promising and eco-friendly alternative for the removal of malachite green through fixed bed column Roshni Kumari, Md. Adnan Khan, Mithilesh Mahto, Md. Atif Qaiyum, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3766609/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract A fixed-bed column study for the removal of malachite green (MG) from the aqueous phase was demonstrated using strategically dewaxed honeycomb powder (HCP). The removal efficiency was tested at several working column parameters such as column bed height, initial dye concentration, working pH, and flow rate. Breakthrough curves have been plotted using throughput volume versus concentration ratio for different parameters to identify the pathway of uptake. Thomas and BDST kinetic models have been exercised to obtain rate constants and uptake capacity. BDST model suggests an adsorption capacity of 196.28 mg/L. The column performance was seen to vary with solution pH and was found favorable at higher pH.The adsorption rate decreases with increasing flow rate but increases with increasing concentration of the dye. Easy regeneration ensures multi-cycle operations. The mechanism of dye adsorption by HCP has been proposed to be a blend of electrostatic attraction and weak forces. Henceforth the use of HCP for removal of MG in column mode may be extrapolated to serve as a promisingagent in the treatment of dye-containing water and wastewater. Honeycomb column biosorption malachite green Thomas BDST Figures Figure 1 Novelty statement Present column investigation offers dual advantagein dye removal from water. A new plant-bee symbiotic material provides a new effective alternative treatment material as well as extends the possibility of direct implementationof the pilot scale deployment in the relevant commercial sector. The method of investigation demonstrated several optimized parameters like different pH, concentration, bed depth in order to estimate and predict the direct pilot deployment of the material on real ground basis in industries. In addition to this, the techno-economic perspective of the material could be justified since the material generates significant quantity of wax as a by-product during its preparation which can be commercialized. The material and the method invariably emerges as a cost effective and eco friendly route in the field of separation treatment technologies. Introduction Freshwater comprises just 3% of the total water present on the planet, but industrialization and escalated demand for clothes, plastic, paints, and body care products have necessitated the maximized use of various dyes. Thus industrial effluents have started polluting the water bodies slowly but steadily. Synthetic dyes are persistent contaminants because of their complex chemical structure [1–2] . Dyes hinder sunlight penetration thereby causing a drastic effect on aquatic flora and fauna [3] . The mixing of dyes into water bodies not only causes harm to aquatic animals but humans too as many dyes have been already recognized as carcinogenic and mutagenic in nature causing cancer, skin allergies, gastrointestinal diseases such as nausea, and hepatic disorders. Ingestion of MG can affect the central nervous system, kidney, liver, pituitary gland, and brain cells. In catfish, it causes serum calcium depletion and decrement in protein levels. It is highly poisonous in mammalian as incidents of tumors in the lungs, breast, and ovary have been reported. Hence, the treatment of wastewater by different technologies came into play. Conventional physical methods for wastewater treatment include ion exchange, membrane separation, electrolysis, coagulation/flocculation, membrane filtration, photo-degradation, etc. Barring a few, most of these methods have limited utility due to lack of economic feasibility, availability, toxic waste production, complicated design, and lack of sustainability. Thus a need aroused for the search for innovative, low cost, and environmentally sound ways of treating wastewater [4–6] . Among the various physical methods, adsorption is one of the most promising for dye removal from industrial effluent as it involves simple operation, low maintenance cost, and the versatile availability of adsorbentsincluding bio-sorbents and chemi-sorbents. Biosorbents such as phytosorbents are eco-friendly in nature and their abundant availability makes them an ideal choice for dye detoxification. Natural biomass or agricultural waste materials comprise an important class of adsorbents containing cellulose, lignin, and various polyphenolic matrixes.Fruit peels, seeds, rice husk, Korean cabbage, sugarcane bagasse, sawdust, nutshell, etchave been well demonstrated in the last decade. [7–11] Moreover, end products of such treatments are biodegradable which is an additional advantage from an environmental perspective. Previously we have successfully demonstrated the use of eucalyptus leaves, mahua seeds, coconut peat and fiber, and water chestnut for the removal of cationic and anionic dyes. Besides, we have shown the excellent removal capacity of dewaxed honeycomb for dye removal from water by batch techniques. [10–14,25] The batch efficiency of dewaxed honeycomb powder for the removal of malachite green dye was investigated and optimized at various experimental conditions [12] . A detailed cost-benefit analysis has also been presented. The carcinogenic nature of malachite green (MG) and extensive usage in industries was the reason for its selection as the model contaminant [13, 14] .However batch experiments are constricted to limited use for large-scale detoxification,thus there is an emerging need for a column-based pilot-scale study for the possible application of the material in industries and long-term foothold in commercial sectors. With this aim, extensive breakthrough column experiments have been conducted for the removal of MG by HCP with varying parameters. To demonstrate the column adsorption capacity of dewaxed HCP for MG removal; the following parameters such as the effect of pH, concentration, flow rate, and bed height have been optimized. By applying Thomas and BDST kinetic models through the breakthrough curve, the rate of dye adsorption was evaluated. Regeneration and multi-cycle reuse were attempted. Materials and methods Preparation of HCP Honeycomb, after extraction of honey usually left out as waste material. Such waste honeycomb was collected from our institute itself. Following our earlier reported procedure, dewaxing of honeycomb (HC) was done. Finally, HC was ground in the electric grinder for making a fine fibrous adsorbent which is denoted as dewaxed honeycomb powder (HCP). Preparation of dye solution Preparations of stock solution of malachite green were carried out by dissolving 1 g of malachite green (MG) in 1000 mL of distilled water to get 1000 mg/L concentration, while the working concentrations were prepared by using the Eq. ( 1 ). All the experiments were carried out using double distilled water and performed in duplicate sets for better accuracy of results. $${N}_{1}\times {V}_{1}={N}_{2}\times {V}_{2}$$ 1 Thomas model The determination of the maximum adsorption capacity of an adsorbent in column mode is essential to evaluate the efficiency of the material on large scale [15] . Thomas model is employed for estimation of column effectiveness of material under optimized conditions. This model is based upon Langmuir assumptionsthat correlatepseudo-second-order kinetics. The experimental data were used to calculate the maximum solid-phase concentration of MG on the adsorbent and the adsorption rate constant using the kinetic model developed byThomas [16] . This model is one of the most general and widely used methods in column performancetheory [17] , which is expressed as Eq. ( 2 ). $$\text{ln}\left(\frac{{C}_{0}}{C-1}\right)={K}_{T}{q}_{0}\raisebox{1ex}{$m$}\!\left/ \!\raisebox{-1ex}{$Q$}\right.-{K}_{T}{C}_{0}\frac{V}{Q}$$ 2 where C 0 and C are dye concentration at initial and equilibrium stage in mg/L respectively, K T is Thomas rate constant(L/mg.min), m is mass of HCP (g), V is throughput volume(mL) and Q is flow rate(mL/min). The kinetic coefficient and the adsorption capacity of the column q 0 can be determined from a plot of C / C 0 against t for a given flow rate using nonlinear regression analysis. BDST model BDST model is used for predicting the relationship between bed depth( Z ) and service time ( t) in terms of process concentrations and adsorption parameters. Such model is based on the assumption that the rate of adsorption is controlled by time of surface interaction between adsorbate molecules and the unused (unloaded) capacity of the adsorbent i.e., it correlates bed depth with service time to evaluate column efficiency of the material [18] . The breakthrough time obtained for various bed heights has been judiciously optimized using this model. BDST model describes a linear relationship between bed depth and service time [19] which is given by Eq. ( 3 ). $$t=\frac{{N}_{0}Z}{{C}_{0}F}-1/{K}_{a}{C}_{0}\text{ln}\left(\frac{{C}_{0}}{C-1}\right)$$ 3 A plot of t vs. Z yields a straight line where N 0 and K a , represent the adsorption capacity and rate constant, respectively and can be determined from the slope and intercept respectively. Here, C 0 is the initial concentration (mg/L) of dye solution, C is the concentration of the dye at time t(min), F is the flow rate of effluent(mL/min). Instrumentation Analytical balance (Denver instruments corp.) was used for weighing the desired samples. pH measurements have been done bySystronic digital pH meter-802. UV-visible spectrophotometer (Hitachi Double beam; model U-2900), equipped with UV-solutions program NSJ was used for absorbance measurements. A drying oven (Binder) was used to dry the samples. Remi benchtop centrifuge (R-8 M) was used for centrifugation. Column experiment Several governing parameters such as the effect of solution pH, initial dye concentration, flow rate, and column bed height have been investigated to optimize column adsorption efficiency [15–17] . The experimental setup for a column run consists of a stoppered fixed glass column (height 30cm, diameter 2.1cm) packed with the measured amount (except for bed height experiment) of HCP (1g) and the effluent dye solution of known strength of 5mg/L (except for concentration study) was passed through it at a particular flow rate of 3mL/min (except for flow rate study). The continuous flow was maintained using an overhead dropping funnel. The initial and final pH was measured to analyze the experimental resultsin a better way. The detoxified volume which is also called throughput volume was collected, centrifuged and absorbance was measured at regular intervals. The resultant data have been used for the analysis and prediction of throughput volume, breakthrough curves, and the C/C 0 ratio.For the study of the effect of pH on column biosorption of dye, effluent solution of MG (strength 5 mg/L) was passed through a packed column bed of height 8 cm(at a flow rate of 3 mL/min, a dose of 1 g at room temperature [20] . The initial pH of the dye solution was varied (6,7 and 8) using dilute hydrochloric acid and sodium hydroxide. The final solution pH and concentration were measured using a pH meter and absorbance was measured by UV-Vis spectrophotometer at regular intervals. A plot of C/C 0 vs. throughput volume at different pH was made. For bed height variation, column bed height has been set to 4, 8, and 12cmwhile the dose of HCPwas varied (0.5, 1, 1.5g) for each height keeping other parameters constant. The resultant absorbance and thereby concentrations were used for plotting different C/C 0 versus throughput volume plots for different bed heights. Similarly, to check the effect of initial dye concentration, all others parameters were kept constant except the effluent dye concentration(3, 5, 7 mg/L). [21] A plot of C/C 0 vs. throughput volume was made. Flow rate (1.2, 2.1, 3 mL/min) variation has also been carried out keeping other parameters fixed. The adsorption coefficients were estimated using Thomas and BDST models at a similar experimental setup for various column parameters. For the desorption test, a measured amount of dye saturated HCP (0.5g) was stirred in three different media namely hydrochloric acid, sodium hydroxide, and sodium chloride(100 mL, 0.01 M) on a magnetic stirrer at 300rpm overnight. The resultant dye solution was separated from the material followed by centrifugation and absorbance measurement. The concentration of the desorbed dye in the solution was estimated [22–24] . All experiments were carried out at 300 ± 5 K (room temperature). Results and discussions Effect of pH The effect of pH on column performance of HCP for removal of MG was estimated with the help of a plot of C/C 0 versus throughput volume (T). The plot shows better column performance with increasing pH (6 < 7 < 8) which could be depicted through the increasing throughput volume and the shifting of the curve from left to right (Fig. 1a). This is attributed to the fact that the increasing pH favors the adsorption of a cationic dye on the surface of HCP due to electrostatic attraction. In addition to that,such observation can be correlated with the ZPC value of HCP (pH ZPC 5.5) which suggests the surface to be positive below this value and negative above this value, predicting better adsorption of cationic dye at higher pH on the negative surface of HCP with electrostatic attraction as the major driving force. Effect of concentration The effect of concentration variation on throughput volume and the C/C 0 ratio was investigated (Fig. 1b). The breakthrough curves show increasing throughput volume with increasing concentration, suggesting an increased driving force by the adsorbed dye molecules at the solid-solution interface. This force provides the inertia to overcome the resistance offered by the mass flow to the approaching molecules to favorably accumulate at the sorbent surface. Effect of flow rate The effect of flow rate on throughput volume was estimated with the help of a plot between C/C 0 against throughput volume (Fig. 1c). The plotshows a decrease in the volume with an increase in flow rate. The plot depicts that as the flow rate increases from 1.2mL/min to 3mL/min, the C/C o value showed an upward shift from 0.005 to 0.03. This could be attributed to the fact that as the flow rate increases, the contact time or the interaction between the sorbent surface and the dye molecules decreases resulting in less adsorption and thereby low adsorption rate. Effect of bed height The effect of bed height on the corresponding throughput volume and C/C 0 ratio was presented which suggeststhat an increase in bed height or the dose of HCP in column bed slows the adsorption rate (Fig. 1d). It was seen that 4 cm of column bed height with 3 mL/min of flow rate is much more efficient than 8 cm and 12 cm of bed height at 3mL/min flow rate. This could be attributed to the fact that an increase in dose or bed height increases the overall resistive force offered by theadsorbent surface to the incoming molecules. In addition to this, the larger availability of the adsorbent sites increases the competitive mobility of the adsorbate molecules which in turn increases the frictional resistance thereby decreasing the column adsorption rate with bed height. Thomas model The column data were fitted to the Thomas model to determine the rate constant (K T ) and column uptake capacity at different parameters. The linear regression method was employed for determining relative constants.R 2 values ranged from 0.924 to 0.973 showing the correlation of C/C 0 and T(throughput volume)is significant enough to explain and justify the column efficiency. Thomas's model supports the breakthrough curve with an inference that an increase in flow rate decreases the adsorption of MG on the adsorbent surface. Thus the q 0 value decreases from 72.28 mg/g to 63.43 mg/g as the flow rate increases from 1.2 mL/min to 3 mL/min. Similarly, for bed height calculation R 2 ranges between 0.877–0.980 and q 0 decreasesfrom 72.27 to 57.74 as bed height increases from 4 cm to 12 cm height respectively. The results of this kinetic model at different parameters were given in Table 1 – 4 . Figure 1. Effect of (a) pH (b) initial concentration (c) flow rate (d) bed height on column biosorption of MG Table 1 Calculated Thomas model constants at a different flow rate Flow rate (mL/min) Z (cm) C 0 (mg/L) K T (mL min − 1 mg − 1 ) q o (mg g − 1 ) R 2 1.2 8 5 0.0820 72.28 0.973 2 8 5 0.0896 71.50 0.936 3 8 5 0.1920 63.43 0.924 Table 2 Calculated Thomas model constants at different bed heights of HCP Z (cm) Bed height Flow rate ml/min C 0 K T (ml min − 1 mg − 1 ) q o (mg g − 1 ) R 2 4 3 5 0.390 72.27 0.980 8 3 5 0.144 66.79 0.893 12 3 5 0.108 57.74 0.877 Table 3 Calculated Thomas model constants at different initial pH pH Z (cm) Bed height Flow rate ml/min C 0 K T (mL min − 1 mg − 1 ) q o (mg g − 1 ) R 2 6 8 3 5 0.290 79.34 0.880 7 8 3 5 0.101 68.50 0.921 8 8 3 5 0.068 59.21 0.899 Table 4 Calculated Thomas model constants at different concentrations Z (cm) Bed height Flow rate ml/min C 0 C K T (ml min − 1 mg − 1 ) q o (mg g − 1 ) R 2 8 3 5 3 0.068 78.21 0.961 8 3 5 5 0.046 69.66 0.883 8 3 5 7 0.012 64.34 0.842 BDST model The bed depth versus time plot provides a linear graph showing that the output volume is correlated with the time and bed depth of the material packed in the column. The column adsorption capacity N 0 and the adsorption rate constants were calculated from the slope and the intercept respectively. Table 5 summarizes important values. The adsorption capacity was found to increase with an increasing C/C 0 ratio. Table 5 Calculated BDST model constants C/C 0 a (min/cm) b (min) K a (l-mg − 1 min − 1 ) N 0 (mg/L) R 2 0.05 5.13 0.52 0.490 76.95 0.95 0.10 8.63 4.1 0.0970 129.45 0.93 0.15 12.13 7.4 0.052 196.28 0.93 The results obtained demonstrates an increased adsorption capacity (N 0 ) with increasing C/C 0 values. The uptake capacity of 196.28 mg/L suggests high efficiency and validity of the material in-field application. This was seen due to the greater difference in concentration gradient developed between the solute and the solution phase. The use of these calculated BDST model constants can be designed for the prediction of this model constant for new flow rate values or new bed depth values. Mechanism The kinetic data suggested strong adsorptive forces were responsible for adsorbate-adsorbent interaction. The chief driving force for adsorption includes vander waals forces, electrostatic attraction and hydrogen bonding forces which holded the dye molecules on the solid surface of the material. In addition to this since the dye and the adsorbent both have several aromatic organic moieties, pi-pi stacking also supports the adherence of the dye on the surface of the adsorbent [12] . Regeneration and reuse Successful regeneration and possible reuse of material make it advantageous. Regeneration was achieved up to 78%with 1 M NaCl solution which marked its efficiency for reusability as a potent biosorbent. It is proposed that there may be some ion-exchange interactions between the cationic dye molecule and sodium ion.Such regenerated molecule when adjusted to the working pH, it showed valuable removal capability up to three cycles. This underlines the ground for a viable biosorbent model that can withstand commercial sectors for treatment purposes. However, a significant loss in activity was noticed thereafter, consistent with any biodegradable material. Conclusion The scavenging ability of dewaxed honeycomb powder for the optimum removal of malachite green dye in column mode was presented. The column parameters were better explained by the two statistical models BDST and Thomas models. The breakthrough curves have been utilized to estimate the adsorption efficiency in terms of throughput volume under various adsorption parameters such as bed height, flow rate, pH, and concentration. The adsorption efficiency increases with increasing pH as the electrostatic attraction exerts the major driving force responsible for the dye-binding at higher pH. The effect of concentration variation on throughput volume showed an increasing pattern suggesting increased driving force by the dye molecule that overcomes the mass flow resistance of the approaching molecules towards the vacant sites. The high efficiency of 196.28 mg/L has been obtained from the BDST model which suggests a field application potential and long-termviabilityat an industrial scale. Thomas constants described the interaction of the dye at different parameters evaluating rate constant and uptake capacity. The investigation of column biosorption of MG onto HCP was thus justified as a newly developed material for use in commercial sectors in the long run. Declarations Acknowledgments M.A.Q., J.M., P.P.S. thank Central University of Jharkhand for fellowships. Declaration of interest statement The authors declare that they have no conflict of interest. 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Adnan Khan","email":"","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Md.","middleName":"Adnan","lastName":"Khan","suffix":""},{"id":261706503,"identity":"491435a9-3e92-4d47-a554-e70cb4f197a9","order_by":2,"name":"Mithilesh Mahto","email":"","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Mithilesh","middleName":"","lastName":"Mahto","suffix":""},{"id":261706504,"identity":"d9ed27f5-d025-4325-a5f8-7f911b0694f5","order_by":3,"name":"Md. Atif Qaiyum","email":"","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Md.","middleName":"Atif","lastName":"Qaiyum","suffix":""},{"id":261706505,"identity":"bce1cfde-74cc-44f5-9c21-40fda0644f38","order_by":4,"name":"Jhilirani Mohanta","email":"","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Jhilirani","middleName":"","lastName":"Mohanta","suffix":""},{"id":261706506,"identity":"f754e256-c1be-4fe1-a60a-b2ca6ef6413a","order_by":5,"name":"Banashree Dey","email":"","orcid":"","institution":"The Graduate School College for Women","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Banashree","middleName":"","lastName":"Dey","suffix":""},{"id":261706507,"identity":"aef9511e-6cab-41bc-92c6-c6d71668510f","order_by":6,"name":"Priyanka Priyadarsini Samal","email":"","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Priyanka","middleName":"Priyadarsini","lastName":"Samal","suffix":""},{"id":261706508,"identity":"f699fd67-e3d1-4344-a5f9-2c71cfb3b9a1","order_by":7,"name":"B. Sambasivaiah","email":"","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"B.","middleName":"","lastName":"Sambasivaiah","suffix":""},{"id":261706509,"identity":"4a1e6221-1df9-4caf-8819-a74e3b92efc4","order_by":8,"name":"Soumen Dey","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA4ElEQVRIiWNgGAWjYBADxgYG5gMMDDxQNpFa2BJI1sJjQJyD5Nt7TDd83MEg2y+R8/EzjwyDPH8Dc9sDfFoMzpwxuznzDIPxzBm5m6V5eBgMZxxgbMdrn4FEjtlt3jaGxA03crcxA7UwbmBgbJPA67AZQC1/gVr238h5BtJiT1ALww2gFkaQLRI5bCAtiQS1GJw5Vnazt03CeMaZZ8aSc3gkkmccJuSw9uZtN3622cj2tyc//PC2x8a2v739GX6HQQBQjUACMHZ6gAxmItRDAP8BIPGDaOWjYBSMglEwggAAXEBFhH6PKE8AAAAASUVORK5CYII=","orcid":"","institution":"Central University of Jharkhand","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Soumen","middleName":"","lastName":"Dey","suffix":""}],"badges":[],"createdAt":"2023-12-17 09:29:10","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3766609/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3766609/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":48824385,"identity":"11272b31-b354-4160-827a-c5c21b46963d","added_by":"auto","created_at":"2023-12-26 23:28:59","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":205934,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of (a) pH (b) initial concentration (c) flow rate (d) bed height on column biosorption of MG\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-3766609/v1/edbf264f5fb24402b359ab08.png"},{"id":49501505,"identity":"6cc1b6f2-6eb9-4062-afe0-afc8f17d081b","added_by":"auto","created_at":"2024-01-12 01:37:24","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":560935,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3766609/v1/a23f4c1c-38c8-41fe-95aa-d0feb8857793.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Strategically dewaxed honeycomb powder is a promising and eco-friendly alternative for the removal of malachite green through fixed bed column","fulltext":[{"header":"Novelty statement","content":"\u003cp\u003ePresent column investigation offers dual advantagein dye removal from water. A new plant-bee symbiotic material provides a new effective alternative treatment material as well as extends the possibility of direct implementationof the pilot scale deployment in the relevant commercial sector. The method of investigation demonstrated several optimized parameters like different pH, concentration, bed depth in order to estimate and predict the direct pilot deployment of the material on real ground basis in industries. In addition to this, the techno-economic perspective of the material could be justified since the material generates significant quantity of wax as a by-product during its preparation which can be commercialized. The material and the method invariably emerges as a cost effective and eco friendly route in the field of separation treatment technologies.\u003c/p\u003e\n"},{"header":"Introduction","content":"\u003cp\u003eFreshwater comprises just 3% of the total water present on the planet, but industrialization and escalated demand for clothes, plastic, paints, and body care products have necessitated the maximized use of various dyes. Thus industrial effluents have started polluting the water bodies slowly but steadily. Synthetic dyes are persistent contaminants because of their complex chemical structure \u003csup\u003e[1\u0026ndash;2]\u003c/sup\u003e. Dyes hinder sunlight penetration thereby causing a drastic effect on aquatic flora and fauna \u003csup\u003e[3]\u003c/sup\u003e. The mixing of dyes into water bodies not only causes harm to aquatic animals but humans too as many dyes have been already recognized as carcinogenic and mutagenic in nature causing cancer, skin allergies, gastrointestinal diseases such as nausea, and hepatic disorders. Ingestion of MG can affect the central nervous system, kidney, liver, pituitary gland, and brain cells. In catfish, it causes serum calcium depletion and decrement in protein levels. It is highly poisonous in mammalian as incidents of tumors in the lungs, breast, and ovary have been reported. Hence, the treatment of wastewater by different technologies came into play. Conventional physical methods for wastewater treatment include ion exchange, membrane separation, electrolysis, coagulation/flocculation, membrane filtration, photo-degradation, etc. Barring a few, most of these methods have limited utility due to lack of economic feasibility, availability, toxic waste production, complicated design, and lack of sustainability. Thus a need aroused for the search for innovative, low cost, and environmentally sound ways of treating wastewater \u003csup\u003e[4\u0026ndash;6]\u003c/sup\u003e. Among the various physical methods, adsorption is one of the most promising for dye removal from industrial effluent as it involves simple operation, low maintenance cost, and the versatile availability of adsorbentsincluding bio-sorbents and chemi-sorbents. Biosorbents such as phytosorbents are eco-friendly in nature and their abundant availability makes them an ideal choice for dye detoxification. Natural biomass or agricultural waste materials comprise an important class of adsorbents containing cellulose, lignin, and various polyphenolic matrixes.Fruit peels, seeds, rice husk, Korean cabbage, sugarcane bagasse, sawdust, nutshell, etchave been well demonstrated in the last decade. \u003csup\u003e[7\u0026ndash;11]\u003c/sup\u003e Moreover, end products of such treatments are biodegradable which is an additional advantage from an environmental perspective. Previously we have successfully demonstrated the use of eucalyptus leaves, mahua seeds, coconut peat and fiber, and water chestnut for the removal of cationic and anionic dyes. Besides, we have shown the excellent removal capacity of dewaxed honeycomb for dye removal from water by batch techniques.\u003csup\u003e[10\u0026ndash;14,25]\u003c/sup\u003e The batch efficiency of dewaxed honeycomb powder for the removal of malachite green dye was investigated and optimized at various experimental conditions \u003csup\u003e[12]\u003c/sup\u003e. A detailed cost-benefit analysis has also been presented. The carcinogenic nature of malachite green (MG) and extensive usage in industries was the reason for its selection as the model contaminant \u003csup\u003e[13, 14]\u003c/sup\u003e.However batch experiments are constricted to limited use for large-scale detoxification,thus there is an emerging need for a column-based pilot-scale study for the possible application of the material in industries and long-term foothold in commercial sectors. With this aim, extensive breakthrough column experiments have been conducted for the removal of MG by HCP with varying parameters.\u003c/p\u003e \u003cp\u003eTo demonstrate the column adsorption capacity of dewaxed HCP for MG removal; the following parameters such as the effect of pH, concentration, flow rate, and bed height have been optimized. By applying Thomas and BDST kinetic models through the breakthrough curve, the rate of dye adsorption was evaluated. Regeneration and multi-cycle reuse were attempted.\u003c/p\u003e"},{"header":"Materials and methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003ePreparation of HCP\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eHoneycomb, after extraction of honey usually left out as waste material. Such waste honeycomb was collected from our institute itself. Following our earlier reported procedure, dewaxing of honeycomb (HC) was done. Finally, HC was ground in the electric grinder for making a fine fibrous adsorbent which is denoted as dewaxed honeycomb powder (HCP).\u003c/p\u003e \u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003ePreparation of dye solution\u003c/h2\u003e \u003cp\u003ePreparations of stock solution of malachite green were carried out by dissolving 1 g of malachite green (MG) in 1000 mL of distilled water to get 1000 mg/L concentration, while the working concentrations were prepared by using the Eq.\u0026nbsp;(\u003cspan refid=\"Equ1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). All the experiments were carried out using double distilled water and performed in duplicate sets for better accuracy of results.\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$${N}_{1}\\times {V}_{1}={N}_{2}\\times {V}_{2}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eThomas model\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eThe determination of the maximum adsorption capacity of an adsorbent in column mode is essential to evaluate the efficiency of the material on large scale\u003csup\u003e[15]\u003c/sup\u003e. Thomas model is employed for estimation of column effectiveness of material under optimized conditions. This model is based upon Langmuir assumptionsthat correlatepseudo-second-order kinetics. The experimental data were used to calculate the maximum solid-phase concentration of MG on the adsorbent and the adsorption rate constant using the kinetic model developed byThomas\u003csup\u003e[16]\u003c/sup\u003e. This model is one of the most general and widely used methods in column performancetheory\u003csup\u003e[17]\u003c/sup\u003e, which is expressed as Eq.\u0026nbsp;(\u003cspan refid=\"Equ2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Equ2\" class=\"Equation\"\u003e \u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$\\text{ln}\\left(\\frac{{C}_{0}}{C-1}\\right)={K}_{T}{q}_{0}\\raisebox{1ex}{$m$}\\!\\left/ \\!\\raisebox{-1ex}{$Q$}\\right.-{K}_{T}{C}_{0}\\frac{V}{Q}$$\u003c/div\u003e \u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003ewhere C\u003csub\u003e0\u003c/sub\u003e and C are dye concentration at initial and equilibrium stage in mg/L respectively, K\u003csub\u003eT\u003c/sub\u003e is Thomas rate constant(L/mg.min), m is mass of HCP (g), V is throughput volume(mL) and Q is flow rate(mL/min).\u003c/p\u003e \u003cp\u003eThe kinetic coefficient and the adsorption capacity of the column q\u003csub\u003e0\u003c/sub\u003ecan be determined from a plot of \u003cem\u003eC\u003c/em\u003e/\u003cem\u003eC\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e against \u003cem\u003et\u003c/em\u003e for a given flow rate using nonlinear regression analysis.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eBDST model\u003c/h2\u003e \u003cp\u003eBDST model is used for predicting the relationship between bed depth(\u003cem\u003eZ\u003c/em\u003e) and service time (\u003cem\u003et)\u003c/em\u003e in terms of process concentrations and adsorption parameters. Such model is based on the assumption that the rate of adsorption is controlled by time of surface interaction between adsorbate molecules and the unused (unloaded) capacity of the adsorbent i.e., it correlates bed depth with service time to evaluate column efficiency of the material\u003csup\u003e[18]\u003c/sup\u003e. The breakthrough time obtained for various bed heights has been judiciously optimized using this model. BDST model describes a linear relationship between bed depth and service time\u003csup\u003e[19]\u003c/sup\u003e which is given by Eq.\u0026nbsp;(\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e\n$$t=\\frac{{N}_{0}Z}{{C}_{0}F}-1/{K}_{a}{C}_{0}\\text{ln}\\left(\\frac{{C}_{0}}{C-1}\\right)$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eA plot of \u003cem\u003et\u003c/em\u003e vs. \u003cem\u003eZ\u003c/em\u003e yields a straight line where \u003cem\u003eN\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e and \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e, represent the adsorption capacity and rate constant, respectively and can be determined from the slope and intercept respectively. Here, C\u003csub\u003e0\u003c/sub\u003e is the initial concentration (mg/L) of dye solution, C is the concentration of the dye at time t(min), F is the flow rate of effluent(mL/min).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003eInstrumentation\u003c/h2\u003e \u003cp\u003eAnalytical balance (Denver instruments corp.) was used for weighing the desired samples. pH measurements have been done bySystronic digital pH meter-802. UV-visible spectrophotometer (Hitachi Double beam; model U-2900), equipped with UV-solutions program NSJ was used for absorbance measurements. A drying oven (Binder) was used to dry the samples. Remi benchtop centrifuge (R-8 M) was used for centrifugation.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eColumn experiment\u003c/h2\u003e \u003cp\u003eSeveral governing parameters such as the effect of solution pH, initial dye concentration, flow rate, and column bed height have been investigated to optimize column adsorption efficiency\u003csup\u003e[15\u0026ndash;17]\u003c/sup\u003e. The experimental setup for a column run consists of a stoppered fixed glass column (height 30cm, diameter 2.1cm) packed with the measured amount (except for bed height experiment) of HCP (1g) and the effluent dye solution of known strength of 5mg/L (except for concentration study) was passed through it at a particular flow rate of 3mL/min (except for flow rate study). The continuous flow was maintained using an overhead dropping funnel. The initial and final pH was measured to analyze the experimental resultsin a better way. The detoxified volume which is also called throughput volume was collected, centrifuged and absorbance was measured at regular intervals. The resultant data have been used for the analysis and prediction of throughput volume, breakthrough curves, and the C/C\u003csub\u003e0\u003c/sub\u003e ratio.For the study of the effect of pH on column biosorption of dye, effluent solution of MG (strength 5 mg/L) was passed through a packed column bed of height 8 cm(at a flow rate of 3 mL/min, a dose of 1 g at room temperature \u003csup\u003e[20]\u003c/sup\u003e. The initial pH of the dye solution was varied (6,7 and 8) using dilute hydrochloric acid and sodium hydroxide. The final solution pH and concentration were measured using a pH meter and absorbance was measured by UV-Vis spectrophotometer at regular intervals. A plot of C/C\u003csub\u003e0\u003c/sub\u003e vs. throughput volume at different pH was made.\u003c/p\u003e \u003cp\u003eFor bed height variation, column bed height has been set to 4, 8, and 12cmwhile the dose of HCPwas varied (0.5, 1, 1.5g) for each height keeping other parameters constant. The resultant absorbance and thereby concentrations were used for plotting different C/C\u003csub\u003e0\u003c/sub\u003e versus throughput volume plots for different bed heights. Similarly, to check the effect of initial dye concentration, all others parameters were kept constant except the effluent dye concentration(3, 5, 7 mg/L).\u003csup\u003e[21]\u003c/sup\u003eA plot of C/C\u003csub\u003e0\u003c/sub\u003e vs. throughput volume was made. Flow rate (1.2, 2.1, 3 mL/min) variation has also been carried out keeping other parameters fixed. The adsorption coefficients were estimated using Thomas and BDST models at a similar experimental setup for various column parameters.\u003c/p\u003e \u003cp\u003eFor the desorption test, a measured amount of dye saturated HCP (0.5g) was stirred in three different media namely hydrochloric acid, sodium hydroxide, and sodium chloride(100 mL, 0.01 M) on a magnetic stirrer at 300rpm overnight. The resultant dye solution was separated from the material followed by centrifugation and absorbance measurement. The concentration of the desorbed dye in the solution was estimated \u003csup\u003e[22\u0026ndash;24]\u003c/sup\u003e. All experiments were carried out at 300\u0026thinsp;\u0026plusmn;\u0026thinsp;5 K (room temperature).\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and discussions","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eEffect of pH\u003c/h2\u003e \u003cp\u003eThe effect of pH on column performance of HCP for removal of MG was estimated with the help of a plot of C/C\u003csub\u003e0\u003c/sub\u003e versus throughput volume (T). The plot shows better column performance with increasing pH (6\u0026thinsp;\u0026lt;\u0026thinsp;7\u0026thinsp;\u0026lt;\u0026thinsp;8) which could be depicted through the increasing throughput volume and the shifting of the curve from left to right (Fig.\u0026nbsp;1a). This is attributed to the fact that the increasing pH favors the adsorption of a cationic dye on the surface of HCP due to electrostatic attraction. In addition to that,such observation can be correlated with the ZPC value of HCP (pH\u003csub\u003eZPC\u003c/sub\u003e5.5) which suggests the surface to be positive below this value and negative above this value, predicting better adsorption of cationic dye at higher pH on the negative surface of HCP with electrostatic attraction as the major driving force.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eEffect of concentration\u003c/h2\u003e \u003cp\u003eThe effect of concentration variation on throughput volume and the C/C\u003csub\u003e0\u003c/sub\u003e ratio was investigated (Fig.\u0026nbsp;1b). The breakthrough curves show increasing throughput volume with increasing concentration, suggesting an increased driving force by the adsorbed dye molecules at the solid-solution interface. This force provides the inertia to overcome the resistance offered by the mass flow to the approaching molecules to favorably accumulate at the sorbent surface.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eEffect of flow rate\u003c/h2\u003e \u003cp\u003eThe effect of flow rate on throughput volume was estimated with the help of a plot between C/C\u003csub\u003e0\u003c/sub\u003e against throughput volume (Fig.\u0026nbsp;1c). The plotshows a decrease in the volume with an increase in flow rate. The plot depicts that as the flow rate increases from 1.2mL/min to 3mL/min, the C/C\u003csub\u003eo\u003c/sub\u003e value showed an upward shift from 0.005 to 0.03. This could be attributed to the fact that as the flow rate increases, the contact time or the interaction between the sorbent surface and the dye molecules decreases resulting in less adsorption and thereby low adsorption rate.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003eEffect of bed height\u003c/h2\u003e \u003cp\u003eThe effect of bed height on the corresponding throughput volume and C/C\u003csub\u003e0\u003c/sub\u003e ratio was presented which suggeststhat an increase in bed height or the dose of HCP in column bed slows the adsorption rate (Fig.\u0026nbsp;1d). It was seen that 4 cm of column bed height with 3 mL/min of flow rate is much more efficient than 8 cm and 12 cm of bed height at 3mL/min flow rate. This could be attributed to the fact that an increase in dose or bed height increases the overall resistive force offered by theadsorbent surface to the incoming molecules. In addition to this, the larger availability of the adsorbent sites increases the competitive mobility of the adsorbate molecules which in turn increases the frictional resistance thereby decreasing the column adsorption rate with bed height.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003eThomas model\u003c/h2\u003e \u003cp\u003eThe column data were fitted to the Thomas model to determine the rate constant (K\u003csub\u003eT\u003c/sub\u003e) and column uptake capacity at different parameters. The linear regression method was employed for determining relative constants.R\u003csup\u003e2\u003c/sup\u003evalues ranged from 0.924 to 0.973 showing the correlation of C/C\u003csub\u003e0\u003c/sub\u003e and T(throughput volume)is significant enough to explain and justify the column efficiency. Thomas's model supports the breakthrough curve with an inference that an increase in flow rate decreases the adsorption of MG on the adsorbent surface. Thus the q\u003csub\u003e0\u003c/sub\u003e value decreases from 72.28 mg/g to 63.43 mg/g as the flow rate increases from 1.2 mL/min to 3 mL/min. Similarly, for bed height calculation R\u003csup\u003e2\u003c/sup\u003e ranges between 0.877\u0026ndash;0.980 and q\u003csub\u003e0\u003c/sub\u003edecreasesfrom 72.27 to 57.74 as bed height increases from 4 cm to 12 cm height respectively. The results of this kinetic model at different parameters were given in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cb\u003eFigure\u0026nbsp;1.\u003c/b\u003e Effect of (a) pH (b) initial concentration (c) flow rate (d) bed height on column biosorption of MG\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCalculated Thomas model constants at a different flow rate\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFlow rate (mL/min)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZ (cm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eC\u003csub\u003e0\u003c/sub\u003e (mg/L)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eK\u003csub\u003eT\u003c/sub\u003e\u003c/p\u003e \u003cp\u003e(mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eq\u003csub\u003eo\u003c/sub\u003e(mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.0820\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e72.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.973\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.0896\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e71.50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.936\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.1920\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e63.43\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.924\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCalculated Thomas model constants at different bed heights of HCP\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ (cm)\u003c/p\u003e \u003cp\u003eBed height\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eFlow rate ml/min\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eC\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eK\u003csub\u003eT\u003c/sub\u003e\u003c/p\u003e \u003cp\u003e(ml min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eq\u003csub\u003eo\u003c/sub\u003e(mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.390\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e72.27\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.980\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.144\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e66.79\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.893\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.108\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e57.74\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.877\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCalculated Thomas model constants at different initial pH\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003epH\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZ (cm)\u003c/p\u003e \u003cp\u003eBed height\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eFlow rate ml/min\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eC\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eK\u003csub\u003eT\u003c/sub\u003e\u003c/p\u003e \u003cp\u003e(mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eq\u003csub\u003eo\u003c/sub\u003e(mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.290\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e79.34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.880\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.101\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e68.50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.921\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.068\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e59.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.899\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCalculated Thomas model constants at different concentrations\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ (cm)\u003c/p\u003e \u003cp\u003eBed height\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eFlow rate ml/min\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eC\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eC\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eK\u003csub\u003eT\u003c/sub\u003e\u003c/p\u003e \u003cp\u003e(ml min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eq\u003csub\u003eo\u003c/sub\u003e(mg g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.068\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e78.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.961\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.046\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e69.66\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.883\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.012\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e64.34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e0.842\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003eBDST model\u003c/h2\u003e \u003cp\u003eThe bed depth versus time plot provides a linear graph showing that the output volume is correlated with the time and bed depth of the material packed in the column. The column adsorption capacity N\u003csub\u003e0\u003c/sub\u003e and the adsorption rate constants were calculated from the slope and the intercept respectively. Table\u0026nbsp;\u003cspan refid=\"Tab5\" class=\"InternalRef\"\u003e5\u003c/span\u003e summarizes important values. The adsorption capacity was found to increase with an increasing C/C\u003csub\u003e0\u003c/sub\u003e ratio.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab5\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCalculated BDST model constants\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC/C\u003csub\u003e0\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003ea (min/cm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eb (min)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eK\u003csub\u003ea\u003c/sub\u003e(l-mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eN\u003csub\u003e0\u003c/sub\u003e (mg/L)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.52\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.490\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e76.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.95\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e0.10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.0970\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e129.45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.93\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e0.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e12.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e7.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.052\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e196.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.93\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe results obtained demonstrates an increased adsorption capacity (N\u003csub\u003e0\u003c/sub\u003e) with increasing C/C\u003csub\u003e0\u003c/sub\u003e values. The uptake capacity of 196.28 mg/L suggests high efficiency and validity of the material in-field application. This was seen due to the greater difference in concentration gradient developed between the solute and the solution phase. The use of these calculated BDST model constants can be designed for the prediction of this model constant for new flow rate values or new bed depth values.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003eMechanism\u003c/h2\u003e \u003cp\u003eThe kinetic data suggested strong adsorptive forces were responsible for adsorbate-adsorbent interaction. The chief driving force for adsorption includes vander waals forces, electrostatic attraction and hydrogen bonding forces which holded the dye molecules on the solid surface of the material. In addition to this since the dye and the adsorbent both have several aromatic organic moieties, pi-pi stacking also supports the adherence of the dye on the surface of the adsorbent\u003csup\u003e[12]\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003eRegeneration and reuse\u003c/h2\u003e \u003cp\u003eSuccessful regeneration and possible reuse of material make it advantageous. Regeneration was achieved up to 78%with 1 M NaCl solution which marked its efficiency for reusability as a potent biosorbent. It is proposed that there may be some ion-exchange interactions between the cationic dye molecule and sodium ion.Such regenerated molecule when adjusted to the working pH, it showed valuable removal capability up to three cycles. This underlines the ground for a viable biosorbent model that can withstand commercial sectors for treatment purposes. However, a significant loss in activity was noticed thereafter, consistent with any biodegradable material.\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe scavenging ability of dewaxed honeycomb powder for the optimum removal of malachite green dye in column mode was presented. The column parameters were better explained by the two statistical models BDST and Thomas models. The breakthrough curves have been utilized to estimate the adsorption efficiency in terms of throughput volume under various adsorption parameters such as bed height, flow rate, pH, and concentration. The adsorption efficiency increases with increasing pH as the electrostatic attraction exerts the major driving force responsible for the dye-binding at higher pH. The effect of concentration variation on throughput volume showed an increasing pattern suggesting increased driving force by the dye molecule that overcomes the mass flow resistance of the approaching molecules towards the vacant sites. The high efficiency of 196.28 mg/L has been obtained from the BDST model which suggests a field application potential and long-termviabilityat an industrial scale. Thomas constants described the interaction of the dye at different parameters evaluating rate constant and uptake capacity. The investigation of column biosorption of MG onto HCP was thus justified as a newly developed material for use in commercial sectors in the long run.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eM.A.Q., J.M., P.P.S. thank Central University of Jharkhand for fellowships.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of interest statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no conflict of interest.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eA.S.Sartape, A.M.Mandhare, V.V.Jadhav,P.D.Raut, M.A.Anuse,S.S.Kolekar; Removal of malachite green dye from aqueous solution with adsorption technique using Limoniaacidissima (wood apple) shell as low cost adsorbent. \u003cem\u003eArab J Chem.\u003c/em\u003e;10(2) (2017) 3229-3238.\u003c/li\u003e\n\u003cli\u003eB. Dey, L. Dipty, S. Dey; Efficient Removal of Malachite Green using Saal (\u003cem\u003eShorearobusta\u003c/em\u003e) Flower from Contaminated Water; \u003cem\u003eI J Green and Herbal Che.;\u003c/em\u003eSec. A; 7 (2) (2018) 392-405.\u003c/li\u003e\n\u003cli\u003eD.P.Tiwari, S.K.Singh, N.Sharma ;Sorption of Methylene Blue on Treated Agricultural Adsorbents: Equilibrium and Kinetic Studies;\u003cem\u003eJ App waterSci;, \u003c/em\u003e4 (1) (2014) 81-88.\u003c/li\u003e\n\u003cli\u003eD.Wang, L.Liu ,X. Jiang , J.Yu , X.Chen; Adsorption and removal of malachite green from aqueous solution using magnetic \u0026beta;-cyclodextrin-graphene oxide nanocomposites as adsorbents. \u003cem\u003eColloids Surf APhysicochemEng Asp.\u003c/em\u003e ;466 (2015) 166-173.\u003c/li\u003e\n\u003cli\u003eD.Wang, L.Liu ,X. 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P., Dey, B., Dey, S* (2021) Alkali treated water chestnut (\u003cem\u003eTrapanatans L\u003c/em\u003e.) shells as a promising phytosorbent for malachite green removal from water. http://dx.doi.org/10.1080/15226514.2021.1977912\u003c/li\u003e\n\u003cli\u003eR. Kumari, S. Dey; A breakthrough column study for removal of malachite green using coco-peat; \u003cem\u003e I. J. Phytoremediation;\u003c/em\u003e 21(12) (2019) 1263-1271.\u003c/li\u003e\n\u003cli\u003eR. Rajeshkannan, M. Rajasimman and N. R. Mohan ;Packed Bed column studies for the removal of dye using novel sorbent. \u003cem\u003eChem. Ind. and Chem. Engi. Quartel;\u003c/em\u003e19(4) (2013) 461-470\u003c/li\u003e\n\u003cli\u003eR.Kumari, M. A. Khan, M.Mahto,M.A.Qaiyum, J.Mohanta,B.Dey, S.Dey; Dewaxed Honeycomb as an Economic and sustainable scavenger for Malachite Green fromWater.;\u003cem\u003eACS Omega\u003c/em\u003e ,5,(2020) 19548\u0026minus;19556\u003c/li\u003e\n\u003cli\u003eS. Nawaz, H.N. Bhatti, TH. Bokhari, S..Sadaf ;Removal of Novacron Golden Yellow dye from aqueous solutions by low-cost agricultural waste: Batch and fixed bed study. \u003cem\u003eChemistry and Ecology\u003c/em\u003e.; 30(1) (2014) 52-65.\u003c/li\u003e\n\u003cli\u003eS.Noreen, N. H. Bhatti; Continuous fixed bed removal of Novacron Orange P-2R using sugarcane bagasse: prediction of breakthrough curves. \u003cem\u003eDesalin Water Treat\u003c/em\u003e.; 57 (2016) 12814\u0026ndash;12821.\u003c/li\u003e\n\u003cli\u003eSaechiam, G. SripongpunSongklanakarin; Adsorption of malachite green from synthetic wastewaterusing banana peel adsorbent; \u003cem\u003eJ. Sci. Technol\u003c/em\u003e.;41 (1) (2019)21-29,\u003c/li\u003e\n\u003cli\u003eT.Ahmad , M.Danish ,M. Rafatullah , A.Ghazali , O.Sulaiman ,R. Hashim, M.N.M.Ibrahim; The use of date palm as a potential adsorbent for wastewater treatment; a review.\u003cem\u003eEnvironSciPollut.;\u003c/em\u003e19(5) (2012) 1464\u0026ndash;1484.\u003c/li\u003e\n\u003cli\u003eU. Maheshwari ,S.Gupta ;Removal of Cr(VI) from wastewater using activated neem bark in a fixed-bed column: interference of other ions and kinetic modelling studies. \u003cem\u003eDesalin. Water Treat\u003c/em\u003e ;57(18) (2016) 8514\u0026ndash;8525\u003c/li\u003e\n\u003cli\u003eU.Sami, R.Altaf, U.Fida, R.Abdur, A.Tausif, V.Eva, G.Michal, M.M.Niyar, U.Haseeb; Adsorption of Malachite Green Dye onto Mesoporous Natural Inorganic Clays: Their Equilibrium Isotherm and Kinetics Studies; \u003cem\u003eWater 13\u003c/em\u003e\u003cem\u003e(7),\u003c/em\u003e(2021), 965\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Honeycomb, column biosorption, malachite green, Thomas, BDST","lastPublishedDoi":"10.21203/rs.3.rs-3766609/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3766609/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA fixed-bed column study for the removal of malachite green (MG) from the aqueous phase was demonstrated using strategically dewaxed honeycomb powder (HCP). The removal efficiency was tested at several working column parameters such as column bed height, initial dye concentration, working pH, and flow rate. Breakthrough curves have been plotted using throughput volume versus concentration ratio for different parameters to identify the pathway of uptake. Thomas and BDST kinetic models have been exercised to obtain rate constants and uptake capacity. BDST model suggests an adsorption capacity of 196.28 mg/L. The column performance was seen to vary with solution pH and was found favorable at higher pH.The adsorption rate decreases with increasing flow rate but increases with increasing concentration of the dye. Easy regeneration ensures multi-cycle operations. The mechanism of dye adsorption by HCP has been proposed to be a blend of electrostatic attraction and weak forces. Henceforth the use of HCP for removal of MG in column mode may be extrapolated to serve as a promisingagent in the treatment of dye-containing water and wastewater.\u003c/p\u003e","manuscriptTitle":"Strategically dewaxed honeycomb powder is a promising and eco-friendly alternative for the removal of malachite green through fixed bed column","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-12-26 23:28:54","doi":"10.21203/rs.3.rs-3766609/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"9e2d1278-1fce-47a8-967b-2d9eb5fc4335","owner":[],"postedDate":"December 26th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-02-06T15:16:35+00:00","versionOfRecord":[],"versionCreatedAt":"2023-12-26 23:28:54","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3766609","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3766609","identity":"rs-3766609","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}