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CHAPTER 5

Mahogany Fruit Shell: A new low-cost adsorbent for removal of basic dye from aqueous solutions

Swietenia mahogani (Mahogany)

Mahogany Fruit

Mahogany Shells

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5.1 INTRODUCTION The first synthetic dye, Mauveine, was discovered by Perkin long time back in 1856 and hence the dyestuff industry can rightly be described as mature. However, it remains a vibrant, challenging industry, requiring a continuous stream of new products because of the quickly changing world in which we live. Apart from one or two notable exceptions, all the dye types used today were discovered in the 1800s. The most important basic dye is Methylene Blue (MB), discovered by Caro in 1878. Methylene Blue is a dark green powder or crystalline solid [1]. Highly colored substances, widely known as colorants, can be used to impart color to an infinite variety of materials described technically as (1) dyes and (2) pigments. Colorants can be subdivided into dyes, which are soluble in the medium in which they are applied and pigments, which are insoluble in the application medium. Dyes are defined as coloured substances that when applied to fibers impart them a permanent color which are resistant to action of light, water, and soap. Practically every dyestuff is made from one or more of the compounds obtained by the distillation of coal tar [2]. Among all industrial sectors, textile industries are rated as high polluters, taking into consideration the volume of discharge and effluent composition. Colour is a visible pollutant. Textiles, dye manufacturing industries, paper and pulp mills, tanneries, electroplating industries, distilleries, food industries and a host of other industries discharge coloured waste water. It is resented by the public on the ground that colour is an indicator of pollution [3]. Dye wastewater arises as a direct result of the production of the dye and also as a consequence of its use in the textile and other industries. There are more than 1,00,000 commercially available dyes and nearly 7x105 tones of dyes produced annually. It is estimated that 2% of dyes produced annually are discharged in effluent from manufacturing operations while 10% is discharged from textile and associated industries [4]. The release of colored waste water from
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these industries may present an eco-toxic hazard and introduce the potential danger of bioaccumulation, which may eventually affect man through the food chain [5]. Methylene Blue can cause eye burns which may be responsible for permanent injury to the eyes of human and animals. On inhalation, it can give rise to short periods of rapid or difficult breathing while ingestion through mouth produces a burning sensation and may cause nausea, vomiting, profuse sweating, mental confusion and methemoglobinemia [6]. Methylene Blue exhibits several synergistic modes of actions which enable the dose-limiting neurotoxicity of alkylating chemotherapy with ifosfamide in cancer patients to be overcome [7]. The dyes absorb and reflect sunlight entering water and so can interfere with growth of bacteria and hinder photosynthesis in aquatic plants [4].Therefore, the treatment of effluent containing such dye is of interest due to its harmful impacts on receiving waters. In general, several difficulties are encountered in removal of dyes from waste waters. By design, dyes are highly stable molecules, made to resist degradation by light, chemical, biological and other exposures. Commercial dyes are usually a mixture of large number complexes and have often unreported molecular structure and properties. Dyes also vary widely in chemical composition. Furthermore, dyeing waste water compositions are not simple solutions of dye in water, but include many other materials such as particulates, processing assistants, salts, surfactants, acids and alkalis. Basic dyes are considered as one of the more problematic classes of dye which are consider as toxic colorants. As a result, improved or cost effective technologies are required to remove them from textile effluents [8]. During the past three decades, several physical, chemical and biological decolorization methods have been reported. Amongst the numerous techniques of dye removal, adsorption is the procedure of choice and gives the best results as it can be used to remove different types of coloring materials. Recently, numerous
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approaches have been studied for the development of cheaper and effective adsorbents. Many non-conventional low cost adsorbents, including natural materials, biosorbents, and waste materials from agriculture and industry, have been proposed by several workers. These materials could be used as adsorbents for the removal of dyes from aqueous solution [6]. Many treatment processes have been applied for the removal of dyes from waste water such as: photocatalytic degradation [9], sonochemical degradation [10], ultrafiltration [11], membrane technology [12], and adsorption [13]. The synthetic dyes in waste water cannot be efficiently decolorized by traditional methods, such as coagulation, flocculation, oxidation, precipitation, filtration, electrochemical processes, etc. Chemical methods of dye removal accumulate sludge that can create disposal problems. These methods require chemicals and large amount of electrical energy which further poses problems for environment as well as economically they are not feasible. Amongst the techniques, adsorption seems to be one of the most effective methods because of simple operation and easy handling [13]. The adsorption of synthetic dyes on inexpensive and efficient solid supports was considered as a simple and economical method for their removal from water and waste water. In present study, we are introducing the novel adsorbent Mahogany fruit shell. As the medicinal uses of Mahogany concerned, the bark extracts are used as an astringent for wounds. It is used to cure malaria, anemia, diarrhea, fever, dysentery and depurative. Its wood is used in making furniture, fixtures, musical instruments, inlay, boat, caskets and many more. Its wood is a very popular material for drum making. Meanwhile, saponins have efficacy as a pest deterrent, could also be used to reduce the fat in the body, to boost the immune system, to prevent blood clotting, to strengthen heart function and to lower the blood clotting process. Mahogany could also heal, high blood pressure (hypertension), lack of appetite, fever; diabetes (Diabetes Mellitus), cold, ekzema,

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rheumatism [14]. The fruit shell is unemployed, so we have decided to apply it as adsorbent. The adsorption study of MG has been carried out with inexpensive Mahogany fruit shell adsorbent, to determine the parameters like, pH, agitation period, speed, initial concentration of MB etc. as well as the isotherm models were applied. The kinetic study was done with pseudo-first and pseudo-second order model. The result of this study reveals that, the present adsorbent is effective and economical for removal of MB dye from aqueous solution. 5.2 LITERATURE SURVEY OF ADSORPTION OF METHYLENE BLUE Adsorption techniques for waste water treatment have become more popular in recent years owing to their efficiency in the removal of pollutants. Adsorption can produce high quality water, while also being a process that is economically feasible [4]. The vital role in this process is selection of adsorbent. There are number of adsorbents developed as the advantages of this technique come in front of the world in both sense to control the pollution as well as economical. The adsorbents such as sand, fly ash, clay, zeolite, polymer, carbon nanotubes, activated carbon, biomass etc. are now in very much focus. Removal of MB dye from aqueous solution on sand surface, carried out at room temperature was reported by S B. Bukallah (2007). The conditions of maximum adsorption of the dye were optimized. It was observed that under optimized conditions, up to 92% dye can be removed from solution on the sand surface [15]. Fly ash is a waste material originating in great amounts in combustion processes. At present, a number of thermal power plants fuelled with coal are in operation in many countries. When the fly ash was used as adsorbent, maximum removal of 58.24% of MB was observed at adsorbent dosage of 900 mg/dm3 at pH 6.75 for an initial MB concentration 65 mg/dm3 [16]. The zeolites synthesized from coal fly ash were investigated as adsorbent to remove MB, from
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aqueous solution. The maximum adsorption capacity of MB by fly ash, calculated using the Langmuir equation, ranged from 23.70 to 50.51 mg/g [17]. The naturally available things were used for removal of MB; natural zeolite is one of them. Natural zeolite, which exists and is easily obtained in many places, is vast and cheap and could be used effectively for removal of MB from aqueous solution [18]. R. Han et al. (2009) were studied adsorption equilibrium and kinetic of MB on natural zeolite in a batch system. Langmuir isotherm nonlinear method and linear method has shown 19.94 and 16.37 mg/g adsorption capacity respectively both at 298 K for same adsorbent [19]. Adsorption isotherms and kinetics of MB onto mesoporous carbons prepared by using acid and alkaline treated zeolite X as the template and furfuryl alcohol as carbon source through vapor deposition polymerization method were determined. The maximum adsorption capacities of MB at 293 K on the carbons prepared using acid and alkaline treated zeolite X as the template were found to be 262.87 and 436.55 mg/g respectively [20]. The ability of clay to remove MB from aqueous solution has already been shown with high adsorption capacity, which is exceeding that of activated carbon under the same conditions of temperature and pH in various reports. One of the case with higher adsorption capacity, montmorillonite clay has been utilized as the adsorbent with 348.87 mg/g capacity [21]. The enhancement of adsorption capacity had been reported with various treatments; in case of the Moroccan clay capacity has increased up to 500 mg/g by thermal activation [22], while purified Moroccan clay mineral known as a ghassoulite or rhassoulite has been reported 135 mg/g as the adsorption capacity [23]. As kaolin itself was a relatively good adsorbent, the adsorption capacity was improved by purification and by treatment with NaOH solution. The adsorption capacities where reported for raw kaolin 27.49 mg/g, pure kaolin 91.87 mg/g, calcined raw kaolin 13.44 mg/g, calcined

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pure kaolin 56.31 mg/g, NaOH treated raw kaolin 204.00 mg/g, and NaOH treated pure kaolin 122.01 mg/g [24]. Removal of MB from aqueous solution by adsorbing it on gypsum was investigated by batch method and the maximum monolayer adsorption capacity was reported to be 36 mg/g [25]. The removal of MB from aqueous solution by peat was analyzed. An adsorption time of around 4.5 h was sufficient to reach the equilibrium for all temperatures, in the concentration range studied. Peat was found to be highly effective in the removal of MB from aqueous solution with removals exceeding 90 % [26]. In a slightly basic medium synthetic magnesium silicate (Florisil), Amberlite XAD-2 and activated carbon showed 149.3 mg/g, 16.8 mg/g and 212.8 mg/g adsorption capacity respectively [27]. In case of industrial waste like Fe(III)/Cr(III) hydroxide, adsorption capacity was reported to be 22.8 mg/g [28]. Carbon nanotubes (CNTs), with nano-sized diameter and tubular microstructure, have been the world wide hotspots of study since their discovery because of their unique morphologies and various potential applications. Because of their relatively large specific surface areas and easily modified surfaces, much attention has been paid to the adsorption of various contaminants as well as dyes by CNTs. The batch adsorption experiments were carried out for the removal of MB as a basic dye from aqueous solutions using CNTs which has shown 64.7 mg/g adsorption capacity [29] and in another report it was 132.6 mg/g [30]. The adsorption of MB from an aqueous solution by polyacrylic acid-bound iron oxide magnetic nanoparticles was prepared which had maximum adsorption amount of 0.199 mg/g [31]. A series of porous carbon xerogels were synthesized from resorcinol-formaldehyde resin and one of the series had maximum adsorption capacity of 222 mg/g, which is comparable to good adsorbing activated carbons [32]. Calcined titanate nanotubes were synthesized with hydrothermal treatment of the commercial TiO2 (Degussa P25) followed by calcination. The samples
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exhibited a tubular structure and a high surface area of 157.9 m2/g with maximum adsorption capacity of 133.33 mg/g [33]. The halloysite nanotubes (HNTs) were used as nano-adsorbents for the removal of the MB, from aqueous solutions and a maximum adsorption capacity of 84.32 mg/g of MB was achieved. It was noted that the dye adsorbed halloysite nanotubes had poor stability in aqueous suspension and deposited completely within 30 minutes while the original aqueous suspension of halloysite nanotubes remained stable for months [34]. Depending on the layers involved the carbon nanotubes have been referred to single walled or multiwalled carbon nanotubes. The kinetics, isotherms and thermodynamic of atrazine adsorption on multiwalled carbon nanotubes (MWCNTs) containing 0.85%, 2.16%, and 7.07% oxygen was studied. The adsorption capacities of three MWCNTs followed a descending order: MWCNTsO (0.85%) > MWCNTs-O (2.16%) > MWCNTs-O (7.07%) and having 61.10, 36.62 and 25.62 mg/g adsorption capacities respectively. This suggests that the adsorption capacity decreased when the surface oxygen contents of the MWCNTs increased [35]. The adsorption kinetics of MB, on the silica nano-sheets derived from vermiculite via acid leaching was investigated in aqueous solution in a batch system and maximum adsorption capacity was found to be 11.77 mg/g for MB [36]. A novel nano adsorbent was fabricated by the surface modification of Fe3O4 nanoparticles (MNP) with carboxymethyl--cyclodextrin (CM- -CD) and the feasibility of employing these nano-adsorbents for removal of MB from aqueous solutions was investigated. The adsorption capacities of MB on CMCDMNP (P) and CMCDMNP (C) are found to be 277.8 and 140.8 mg/g respectively [37]. The introduced montmorillonite could generate a loose and porous surface that is of benefit to adsorption ability of the nanocomposite. Batch adsorption experiments were carried out for the removal of MB cationic dye from its aqueous solution using chitosan-g-poly(acrylic acid)/montmorillonite nanocomposites as adsorbent having maximum adsorption capacity 1859 mg/g [38].
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The activated carbon has proved the ability to remove the coluring matter effectively at application level. The commercial sample of activated carbon has great adsorption capacity as compared to the other adsorbents. Activated carbon F-400 was reported to remove the MB, with increasing the adsorption capacity from 469.6 to 708.8 mg/g with increasing temperature from 303 to 338 K [39]. Various activated carbons have been used for MB removal from aqueous solution. It has been found that the adsorption capacity is influenced by the physical and surface chemical properties of carbon and the pH of the solution. S. Wang et al. (2005) used three types activated carbons, the order of the adsorption capacity of them was as, BPL = BDH > F100 [40]. In another case, three commercial granular activated carbons, 12x40 mesh size, namely Filtrasorb 400, Norit and Picacarb have been used as adsorbents. The adsorptive capacities of these were 319 14, 280 7 and 260 6 mg/g for Filtrasorb 400, Norit and Picacarb, respectively [41]. The powdered activated carbon (Norit SA3) and granular activated carbon (Nuchar WWH) showed the adsorption capacity 91 mg/g and 21.5 mg/g respectively [42]. As it is well known that, the adsorption with commercial activated carbon has great efficiency to remove the contaminant, but it is not economical, so there is need to develop the alternative to it. Many researchers have tried to develop the low cost activated carbon; some reports have shown the great adsorption capacity which is comparable to commercial samples. The removal of basic dye MB from aqueous solution using bituminous coal-based activated carbon has been investigated and maximum adsorption capacity of 580 mg/g at equilibrium was achieved [43]. Activated carbons were prepared from walnut shells by vacuum chemical activation with zinc chloride as the activation agent have surface area of 1800 m2/g and 315 mg/g maximum adsorption capacity [44]. Adsorption of MB from aqueous solutions on activated carbon prepared from Egyptian rice hulls has studied experimentally and results indicate the
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removal efficiency of MB at 298 K exceeds 99% and the adsorption process is highly pH-dependent which has 60.1 mg/g adsorption capacity [45]. The activated carbon prepared from cotton stalk with ZnCl2 activation was investigated under microwave radiation with optimum conditions such as microwave power of 560 W, microwave radiation time of 9 min and the impregnation ratio of ZnCl2 was of 1.6 g/g which had the maximum 315.04 mg/g adsorption capacity [46]. Activated carbons were prepared from the biomass of oil palm wood via two stages, pyrolysis and physical activation. By using an environmentally friendly pyrolysis pilot plant and an activation pilot plant were studied. The latter uses the outlet flue gases from limestone calcination process as activating agents and the maximum adsorption capacity 90.9 mg/g was reported [47]. Preparation of the activated carbon from sunflower oil cake by sulphuric acid activation with different impregnation ratios was carried out. The developed activated carbons were denoted as AC1 without impregnation, AC2 with the impregnation ratio of 0.85, and AC3 with the impregnation ratio of 1.90. The maximum adsorption capacity for MB was found to be 10.21, 16.43 and 15.798 mg/g for AC1, AC2 and AC3 respectively [48]. Commercial activated carbon (CAC) and indigenously prepared activated carbons (IPACs) such as bamboo dust carbon (BDC), coconut shell carbon (CSC), groundnut shell carbon (GNSC), rice husk carbon (RHC) and straw carbon (SC) were studied to find out the possibility of using these carbonaceous materials as low cost adsorbents for the removal of MB. Relative adsorption capacity values of these carbons for adsorption of MB are, CAC=100 mg/g, BDC=7.20 mg/g, GNSC=7.50 mg/g, CSC=8.16 mg/g, RHC=37.57 mg/g, and SC=42.60 mg/g. Cost wise the IPACs are nearly five times cheaper than the CAC. Hence, the IPACs are cost effective adsorbent materials for the removal of dyes/colour [49]. Microwave radiation has been proved to be an efficient and rapid method for the modification of activated carbons. Modification of bamboo based activated carbon was carried
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out in a microwave oven under N2 atmosphere which has 286.1 mg/g maximum adsorption capacity [50]. Activated carbon prepared from non-wood forest product waste (rattan sawdust) has been utilized as the adsorbent for the removal of MB dye from an aqueous solution with maximum monolayer adsorption capacity of 294.14 mg/g [51]. Activated carbons were obtained by activation with H3PO4 at 773 K, under increasing acid concentrations of 30-70%. Products were characterized by N2 at 77 K and proved to be highly microporous with high surface area and pore volume that increased with impregnation ratio. Two modified carbons were prepared by concurrently passing N2 during pyrolysis of impregnated precursor with 50% and 70% H3PO4 at 773 K and post-heat treatment at 1073 K. The adsorption capacity was from 198 to 412 mg/g as per treatment which is associated with the texture properties [52]. For the dehydrated wheat bran carbon, the optimum adsorption conditions were found to be pH 2.5 and temperature 318 K and it shows 222.20 mg/g adsorption capacity [53]. Thermally activated coir pith carbon prepared from coconut husk was used for removal of MB and the adsorption capacity was found to be 5.87 mg/g [54]. The vetiver roots have been utilized for the preparation of activated carbon by chemical activation with different impregnation ratios of phosphoric acid, (g H3PO4/g precursor): 0.5:1; 1:1 and 1.5:1. Textural characterization, determined by nitrogen adsorption at 77 K shows that mixed microporous and mesoporous activated carbons with high surface area (>1000m2/g) and high pore volume (up to 1.19 cm3/g) can be obtained and having 375 to 423 mg/g adsorption capacity [55]. High surface area activated carbons were prepared by simple thermo-chemical activation of Jatrophacurcas fruit shell with NaOH as a chemical activating agent. The results present that the activated carbon possesses a large apparent surface area (SBET = 1873 m2/g) and high total pore volume (1.312 cm3/g) with average pore size diameter of 28.0 [56]. Jute fiber obtained from the stem of a plant was used to prepare activated carbon using
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phosphoric acid. Feasibility of employing this jute fiber activated carbon for the removal of MB from aqueous solution was investigated whose adsorption capacity was found to be 225.64 mg/g [57]. From the list of adsorbent, one of the very important is biosorbent which may be used as it is or by activation and having good capacity. The Brazilian pinefruit shell (Araucaria angustifolia) is a food residue, which was used in natural and carbonized forms, as low cost adsorbent for the removal of MB from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with sulfuric acid produced a non-activated carbonaceous material (C-PW). Both PW and C-PW were tested as low-cost adsorbents for the removal of MB from aqueous effluents and showed 185 and 413 mg/g adsorption capacity respectively [58]. Batch and column kinetics of MB adsorption on calcium chloride, zinc chloride, magnesium chloride and sodium chloride treated beech sawdust were simulated, using untreated beech sawdust as control, in order to explore its potential use as a lowcost adsorbent for dye removal. The results showed that salt treated beech sawdust enhances its adsorption properties considerably. The maximum adsorption capacity for MB by beech sawdust treated with calcium chloride, zinc chloride, magnesium chloride and sodium chloride found to be 12.2 1.8, 13.2 2.0, 15.6 2 and 9.7 0.6 mg/g respectively [59]. It was seen that cotton stalk (CS), cotton dust (CD) and cotton waste (CW) could be used successfully as adsorbent for the removal of MB from aqueous solution by sorption technique. The maximum dye removals for CS, CW and CD were between 26.0% and 48.36 %, between 50.0% and 85.41%, between 62.0% and 97.50% as well as 4.52, 8.33, 9.75 mg/g adsorption capacity respectively [60]. Recently the use of low cost materials to remove colour has been reported by several workers. The ability of coconut husk to remove MB from solution was investigated with 99 mg/g as Langmuir isotherm maximum adsorption capacity [61]. Batch experiments were carried out for the adsorption of MB on mango seed
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kernel particles, which had reported 142.857 mg/g adsorption capacity at 303 K [62]. A natural wheat straw was used adsorbent for removal of copper and MB from aqueous solution. A batch system was applied to study the behavior of Cu(II) and MB adsorption in single and binary systems on wheat straw. The adsorption capacities of Cu(II) and MB at 273 K and pH 5 were 7.05 and 60.66 mg/g respectively [63]. Rice straw was esterified thermochemically with citric acid to produce potentially biodegradable cationic adsorbent. The modified rice straw (MRS) and crude rice straw (CRS) were evaluated for their MB removal capacity from aqueous solution. Langmuir model was used to determine adsorption capacities which were found to be 80.0 and 270.3 mg MB per gram of CRS and MRS, respectively [64]. The study indicates the potential use of pretreated rice husk (RH) and rice husk ash (RHA) for the removal of MB from waste water. Maximum monolayer adsorption capacity has a value of 1347.7 mg/g for adsorption on RH and 1455.6 mg/g for adsorption on RHA at a temperature of 323 K [65]. In another report maximum percentage removal of MB was 99.939 %, with 18.149 mg/g adsorption capacity for same adsorbent [66]. Tea waste has been used as adsorbent for the removal of MB from its aqueous solution. It is a household waste available in huge amount which is an oxygen demanding pollutant and also it takes a long time for biodegradation. The tea waste was incinerated and used as a cost effective adsorbent having 85.16 mg/g adsorption capacity [67]. Langmuir isotherm model with maximum monolayer adsorption capacities of rejected tea were found to be 147, 154 and 156 mg/g at 303, 313 and 323 K respectively [68]. The removal of a MB from aqueous solution using NaOH-modified rejected tea was investigated, the adsorption isotherm data fitted well to Langmuir isotherm with monolayer adsorption capacity of 242.11 mg/g [69]. Spent tea leaves were used as a new non conventional and low cost adsorbent for the MB adsorption in a batch process, at 303 K and the Langmuir isotherm monolayer adsorption capacity was found to be
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300.052 mg/g [70]. Spent coffee powdered residue from the soluble coffee industry was evaluated as an adsorbent for the removal of MB from aqueous solution with 18.7 mg/g adsorption capacity [71]. An algal industrial waste from agar extraction process, algae Gelidium and a composite material obtained by immobilization of the algal waste with polyacrylonitrile were used as biosorbents for dyes removal using MB as model. Equilibrium isotherms are described by the Langmuir equation, giving maximum uptake capacities of 171, 104 and 74 mg/g, respectively for algae, algal waste and composite material [72]. The biomass of bakers yeast was modified with poly (methacrylic acid) through a graft copolymerization reaction which was prepared to improve the adsorption capacities for three dyes: MB, Rhodamine B (RB) and basic magenta (BM). The maximum uptake capacities for MB, RB and BM were 869.6, 267.4 and 719.4 mg/g respectively [73]. Adsorbents prepared from Parthenium hysterophorus, weed, was successfully used to remove MB from an aqueous solution in a batch reactor. The adsorbents included sulphuric acid treated parthenium and phosphoric acid treated parthenium have 39.68 and 88.49 mg/g adsorption capacities respectively [74]. Cost effective cedar sawdust and crushed brick were selected as adsorbents for the investigation of adsorption of MB from aqueous solution with maximum adsorption capacities of 142.36 and 96.61 mg/g respectively [75]. Meranti (Philippine mahogany) sawdust, an inexpensive material, showed strong scavenging behaviour through adsorption for the removal of MB from aqueous solution. The monolayer adsorption capacity of meranti sawdust for MB was found to be 120.48, 117.64, 149.25 and 158.73 mg/g at 303, 313, 323 and 333 K respectively [76]. The potential use of Indian Rosewood (Dalbergia sissoo) sawdust, pretreated with formaldehyde (SD) and sulphuric acid (SDC), for the removal of MB dye from simulated waste water was reported. Maximum dye was removed within 30 min from start of every experiment. The adsorption for SDC
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was increased from 12.49 mg/g to 51.4 mg/g as the MB concentration in the test solution was increased from 50 mg/dm3 to 250 mg/dm3. Similarly, unit adsorption for SD was increased from 11.8 mg/g to 46.1 mg/g as the dye concentration in the test solution was increased from 50 mg/dm3 to 250 mg/dm3 [77]. The ability of coconut bunch waste, an agricultural waste available in large quantity to remove MB from aqueous solution by adsorption was studied and capacity was found to be 70.92 mg/g at 303 K [78]. The feasibility of using papaya seeds, abundantly available waste, for the MB adsorption has been investigated; a maximum adsorption capacity of 555.56 mg/g was found [79]. E. I. Unuabonah et al. (2009) were defatted Carica papaya seeds and used for the adsorption of MB dye. The specific surface area of the defatted undefatted Carica papaya seeds was found to be 143.27 m2/g respectively as well as defatting Carica papaya seed adsorbent increased its adsorption capacity for MB dye from 769.23 to 1250 mg/g [80]. Modified wheat straw with citric acid was employed to enhance the adsorption capacity of the by-product for selected copper ions and MB. Langmuir model capacity for Cu(II) and MB was found to be 39.17 and 396.9 mg/g at 293 K, respectively [81]. Broad bean peels, an agricultural waste, was evaluated for its ability to remove MB from aqueous solutions and adsorption capacity was found to be 192.7 mg/g [82]. The potential of garlic peel, agricultural waste, to remove MB from aqueous solution was evaluated in a batch process. The maximum monolayer adsorption capacities were found to be 82.64, 123.45, and 142.86 mg/g at 303, 313, and 323 K temperatures, respectively [83]. To obtain the potential feasibility of removing colour by peanut hull, it was dehydrated with sulphuric acid and used for adsorption of MB from aqueous solution and adsorption capacity was found to be 161.3 mg/g [84]. Ethylenediaminetetraacetic dianhydride (EDTAD) modified sugarcane bagasse (SB) was prepared. The adsorption capacity of the EDTAD-modified SB 115.3 mg/g for MB showed a significant increase compared with SB [85]. The adsorption kinetics of MB on the hazelnut
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shell was tested and activation energy was reported to be 45.6 kJ/mol. The pseudosecond order equilibrium adsorption capacity of hazenut shell was reported as 20.6 mg/g [86]. Caulerpa racemosa var. cylindracea is one of the well known invasive species in the Mediterranean Sea. Dried biomass of C. racemosa var. cylindracea was shown 5.23 mg/g adsorption capacity for MB at 291 K [87]. Kinetics adsorption experiments were conducted to evaluate the adsorption characteristics of a MB on nitric acid treated water-hyacinth. This study showed 333 mg/g adsorption capacity [88]. Yellow passion fruit peel (Passiflora edullis, F. flavicarpa) and mandarin peel (Citrus reticulata) as biosorbents were used and they got the equilibrium in 48 h [89] and in another case it was 56 h with yellow passion fruit (Passiflora edulis Sims. f. flavicarpa Degener) peel a powdered solid waste, which has the maximum adsorption capacity of 2.06 mg/g after 50 h of contact time at pH 9.0 and temperature 298 K [90]. The study described adsorption of MB by peanut husk in batch and fixed-bed column modes at 293 K and observed the 72.133.03 mg/g adsorption capacity [91]. Many solid wastes, that are available in large quantities, have the potential to adsorb pollutants from aqueous effluents. The gulmohar plant leaf powder was investigated for its potential adsorption capacity of 186.22 mg/g [92]. Batch sorption experiments were carried out using guava leaf powder, for the removal of MB from aqueous solutions, maximum dye uptake was observed to be 295 mg/g [93]. Kinetics of MB adsorption on three low cost adsorbents namely guava leaf powder teak leaf powder and gulmohar leaf powder was predicted using film pore diffusion model. Based on the values of Biot number it was concluded that MB adsorption on guava, teak and gulmohar leaf powders were controlled by internal pore resistance. It was also noticed that external-film coefficient increased with increase in temperature [94]. Continuous fixed-bed studies were undertaken to evaluate the efficiency of jackfruit leaf powder as an adsorbent for the removal of
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MB from aqueous solution and under the effect of various parameters, it showed 252.83 mg/g as adsorption capacity [95]. The MB dye was adsorbed on an adsorbent prepared from mature leaves of the neem tree (Azadirachta indica). The Langmuir monolayer capacity had a mean value of 8.76 mg/g [96]. The ability of an unconventional bio-adsorbent, pineapple leaf powder for the adsorption of MB from aqueous solution was studied. The adsorption was favorable at higher pH and lower temperature, and the equilibrium data were well fitted by the Langmuir isotherm. The maximum adsorption capacity varied from 141.81 to 281.18 mg/g when pH increases from 3.5 to 9.5 [97]. The adsorption of two basic dyes, MB and crystal violet on wood apple shell was investigated using a batch adsorption technique. It was observed that the wood apple shell adsorbent showed higher adsorption capacity for crystal violet (130 mg/g) than MB (95.2 mg/g) and followed the pseudo-second order kinetics [98]. The literature survey shows that the various adsorbents were used for removal of MB from aqueous solution, the fruit shell also used for the same but they are very few in number. As per all remarks about adsorption capacity there is still need of inexpensive adsorbent. We are introducing the fruit shell of Swietenia mahagoni, known as West Indian or Indian mahogany as adsorbent, the names are as per the region. After complete development the fruit gets burst self. The seed for next germination is medicinally useful and shells are unemployed, so we have tried to use this shell as adsorbent. The adsorbent characterization has been done with FTIR, SEM, C, H, N, S analyzer as well as the properties were determined. In the study various parameters were investigated as well as the isotherm study has been done with Langmuir and Fruedlich isotherm models. The pseudo-first and pseudo-second order models were used for the kinetic study. The results indicated that, the Swietenia mahagoni fruit shell is good adsorbent to remove the MB from aqueous solution effectively and economically.
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5.3 EXPERIMENTAL 5.3.1 Preparation of materials and dye solution The Swietenia mahagoni, fruit shell is used as adsorbent for the adsorption of MB. The general botanical classification of mahogony as; Kingdom-plantae, Division- Magnoliophyta, Class- Magnoliopsida Order Sapindales, FamilyMeliaceae, Genus- Swietenia, Species- S. mahagoni, Scientific Name- Swietenia mahagoni [99]. The Mahogany Fruit Shell (MSF) has been employed successfully as adsorbent in this study without any chemical or physical treatment. The MSF material was collected from the Shivaji University, Campus. Fruit has the bursting characteristic to spread the seeds, and the shells remains as worthless. These shells were collected and developed as adsorbent. The shells were dried naturally and then washed thoroughly under tap water to remove dirt and again dried in oven at 383 K and then cut into small pieces and again washed. The dried sample was crushed and at this stage the material was washed till all colouring contents are removed out which may interfere into further process. The material was dried at 383 K for 24 h and sieved through BSS 25. The Methylene Blue dye structure is shown in Fig. 5.1. It has molecular formula C16H18N3SCl, (max=670 nm). Stock solution of 1g/dm3 was prepared with deionized water. All working solutions used in tests were prepared by appropriate dilutions of the stock solution to a pre-determined concentration. All chemicals used in this study were of analytical reagent grade and purchased from S. D. Fine Chem. Ltd. India. 5.3.2 Characterization of adsorbent The characterization of adsorbent has been done with Fourier Transform Infra Red Spectroscopy (FTIR) to analyze the functional groups present, Scanning Electron Microscopy (SEM) has employed to know the surface morphology of the
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adsorbent and C, H, N, S analyzer was used for quantitative elemental analysis. The elemental analysis and various properties such as ash content, moisture content and bulk density are given in Table 5.1. The FTIR (Perkin Elmer Spectrum 100) spectrum of MFS is given in Fig. 5.2 for before adsorption and Fig. 5.3 for after adsorption. From the Fig. 5.2, the value at 3400 cm-1 has denoted the presence of OH group, while 2923 cm-1 corresponds to C-H stretching. The values at 1733, 1626, 1434, 1372, 1250 and 1049, 896 cm-1 gives the information about the presence of C=O, N-H bending, CH2 from cellulose, N=O symmetric stretching, C-O stretch and C-H bending and =C-H bending respectively. The SEM (JEOL, JSM-6360) images are shown in Fig. 5.4(a) before adsorption and Fig. 5.4(b) after adsorption, which indicates the difference in the external appearance of the MFS. Before adsorption the surface was very rough and after adsorption it appears getting just like formation of a layer on surface. The C, H, N, S elemental analyzer (Quanta 3D FEI) confirms the presence of carbon is maximum percentage amongst all. 5.3.3 Batch adsorption experiment The experiments were carried out by batch adsorption method. The isotherm study has been done by varying the initial concentration of the MB from 100 to 700 mg/dm3 at constant MFS of 450 mg/dm3 as adsorbent. The batch was agitated for 420 min on orbital shaker at constant temperature 299 2 K and at pH of 9 in the Erlenmeyer flasks with 180 rpm as agitation speed. For the thermodynamic study, temperature was varied from 303 K to 323 K. The equilibrium adsorption capacity of MSF was evaluated.

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5.4 RESULT AND DISCUSSION 5.4.1 Analysis of adsorbent The adsorption of MB on MFS was clearly identified from Fig. 5.3, FTIR spectrum of MFS (Fig.5.3 (A)), MB (Fig.5.3 (B)) and MB adsorbed on MFS (Fig.5.3(C)). The major peaks are present from 2000 to 400 cm-1. The several peaks from MFS and MB are merged or they are slightly shifted. The peak at 1736 cm-1 in Fig.5.3(C) is due to C=O which is only present in MFS (Fig. 5.3(A)) at 1733 cm-1. The peak at 1626 cm-1 is due to presence of N-H bending present in MFS (Fig. 5.3(A)) and 1601 cm-1 peak from (Fig. 5.3(B)) MB is due to C=C group. Both these are merged and show weak peak at the 1620 and 1602 cm-1 and form broad peak together. The peak at 1508 cm-1 is due to C=N stretching from MB in Fig.5.3(C) as it shows peak originally at 1488 cm-1 in MB (Fig. 5.3(A)). Peak at 1383 cm-1 in Fig.5.3(C) is due to merging of peak from both MSF and MB peak at 1372 and 1396 cm-1 respectively but peak at 1330 cm-1 (Fig. 5.3(C)) is shifted from 1356 cm-1 which indicates C-H bending in MB (Fig.5.3(B)). In case of MSF, peak at 1250 cm-1 (Fig. 5.3(A)) is due to C-O stretching which is shifted to 1248 cm-1 in Fig. 5.3(C) MB adsorbed on MFS. The peaks from MB (Fig. 5.3(B)) at 1142 and 1182 cm-1 are due to merging of C=S stretching with strong peak at 1048 cm-1 from MFS (Fig. 5.3(A)) and show broad peak at 1051 cm-1 in MB adsorbed on MFS (Fig. 5.3(C)). Peak at 886 cm-1 in MB (Fig. 5.3(B)) is due to C=C aromatic bending, it slightly shifted at 889 cm-1 in Fig.5.3(C). The FTIR results reveal the adsorption of MB on MFS. The merging and shifting was already observed in some reports [72, 74, 81]. In case of SEM study, the change in surface morphology was observed. In Fig. 5.4 (A) before adsorption and Fig. 5.4(B) after adsorption it is clearly observed that, the layer was formed on initial rough surface. Similar observations in case of SEM are also reported [69, 70, 76, 78, 82, 83].

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5.4.2 Effect of pH The pH study is important for development of every successful method, because pH can alter the results. In present study pH was varied from 1 to 11 (Table 5.2) with concentration of MB of 100 mg/dm3, 450 mg amount of MFS, 299 2 K temperature and agitation at 180 rpm for 420 min. The result in Fig. 5.5 shows that, the maximum adsorption was observed at pH above 6. At pH 6 the MB removal percentage was 98.24% and amount adsorbed was 10.91 mg/g which was risen up to 99.05 % and 11.01 mg/g when pH rises up to 9.0. We have chosen pH 9.0 as constant pH throughout the study. The Methylene Blue adsorption usually increases as the pH is increased. Lower adsorption of MB at acidic pH is probably due to the presence of excess H+ ions competing with the cation groups on the dye for adsorption sites. At higher pH, the surface of MFS particles may get negatively charged, which enhances the adsorption of positively charged dye cations through electrostatic forces of attraction [78]. Such observations were also reported by B.H. Hameed [82] and S. Cengiz [87]. 5.4.3 Effect of time The effect of agitation period on the removal of MB by MFS at initial concentrations of MB 100 mg/dm3, pH 9, 450 mg adsorbent and agitation speed at 180 rpm is shown in Fig. 5.6. The agitation period was varied from 0 to 600 min (Table 5.3) at constant temperature. The time plot shows that, the removal of adsorbate is rapid in early stages but it gradually slows down until it reaches the equilibrium. This is due to the fact that a large number of vacant surface sites are available for adsorption during the initial stage, and after a lapse of time the remaining vacant surface sites are difficult to be occupied due to repulsive forces between the solute molecules on the solid surface and in bulk phase [76]. The equilibrium was attained after shaking for 420 min. Once equilibrium was
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attained, the percentage sorption of MB did not change with further increases of time. So, it was assumed that longer treatment might not have further effect to change the properties of the adsorbent therefore time 420 min was fixed for further study. A similar trend was also observed for MB adsorption on hazelnut shells [86]. 5.4.4 Effect of initial concentration of MB The amount of MB adsorbed per unit mass of adsorbent increased with the increase in initial concentration and percentage removal of MB from aqueous solution decreased with the increase in initial concentration (Fig.5.7). The amount of MB adsorbed at equilibrium (qe) increased from 11.01 to 50.73 mg/g as the initial concentration was increased from 100 to 700 mg/dm3 (Table 5.4). The initial concentration provides an important driving force to overcome all mass transfer resistances of the MB between the aqueous and solid phases. Hence, a higher initial concentration of dye will enhance the adsorption process [70]. However, the MB percentage removal decreased from 99.05% to 65.23% as the MB concentration was increased from 100 to 700 mg/dm3. For this study the pH, temperature, agitation speed, time etc. were kept constant. The same observation was also reported for other adsorbents like meranti sawdust [76]. 5.4.5 Effect of adsorbent dosage The effect of adsorbent dosage on the removal of MB was studied for an initial dye concentration of 100 mg/dm3, by varying the adsorbent from 50 to 450 mg/dm3 at temperature 299 2 K and by keeping all other parameters constant (Fig. 5.8, Table 5.5). The Percentage dye removal increased with increase in adsorbent dosage. Only 4.33% removal of MB was observed when 50 mg adsorbent was used, but it increases up to 99.05% removal when 450 mg adsorbent was employed. This may be due to the fact that the active sites could be
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effectively utilized when the dosage was low (i.e. low ratio of adsorbent / adsorbate). When the adsorbent dosage is higher (high ratio of adsorbent / adsorbate) it is more likely that a significant portion of the available active sites remains uncovered, leading to lower specific uptake [92]. The amount of dye adsorbed per unit mass of adsorbent decreased with increasing adsorbent mass, due to the reduction in effective surface area [71]. The present observations are in good agreement with the previous findings by Bhattacharrya and Sharma [96], D. Ozer [84] and S.Cengiz [87]. 5.4.6 Effect of agitation speed In the batch adsorption systems, agitation speed plays a significant role in affecting the external boundary film and the distribution of the solute in the bulk solution. The experiments were carried out by varying agitation speed from 50 rpm to 240 rpm by keeping all other conditions constant. When the speed was increased from 50 to 240 rpm (Fig. 5.9, Table 5.6) the amount adsorbed and percentage removal of MB, both were increased simultaneously. At the 50 rpm, 50.75 % removal of MB was observed, which was increased up to 99.05% with increasing speed of agitation up to 180 rpm. The influence of agitation speed was negligible after 180 rpm; both amount and percentage remains steady. Thus we selected 180 rpm agitation speed for further study. The simialr observations were also reported in the literature [59, 97]. 5.4.7 Adsorption isotherm Equilibrium studies that give the capacity of the adsorbent and adsorbate are described by adsorption isotherms, which is usually the ratio between the quantity adsorbed and remained in solution at equilibrium at constant temperature [45]. The amount of MB dye adsorbed (qe) has been plotted against the equilibrium concentration (Ce) and plot is shown in Fig. 5.10 (Table 5.7). The
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equilibrium adsorption density, qe increased with the increase in dye concentration. Several models have been reported in the literature to describe the experimental data of adsorption isotherms. The Langmuir and Freundlich are the most frequently employed models. In this work, both models were used to describe the relationship between the amount of dye adsorbed and its equilibrium concentration. 5.4.8 Langmuir isotherm The Langmuir adsorption isotherm has been successfully applied to many adsorption processes and has been the most widely used. The Langmuir adsorption isotherm study has been done by varying the initial concentration of MB from 100 to 700 mg/dm3, keeping all other conditions constant. A plot of Ce/qe versus Ce (Fig. 5.11, Table 5.8) indicates a straight line of slope 1/qm and an intercept of 1/KLqm, where, Ce is the equilibrium concentration (mg/dm3), qe is the amount of metal ion adsorbed (mg/g), qm is qe for a complete monolayer (mg/g); KL is sorption equilibrium constant (dm3/mg). The essential characteristic of a Langmuir isotherm, related to the isotherm shape, can be expressed in terms of a dimensionless constant separation factor, also called the equilibrium parameter RL. The adsorption of MB on MFS follows the Langmuir isotherm model for metal adsorption. The value of qm and KL were evaluated and given in Table 5.9. The dimensionless parameter RL between 0.039 to 0.913 is consistent with favorable adsorption. The high value of correlation coefficient R2 indicates a good agreement between the parameters and confirms the monolayer adsorption of MB on the adsorbent surface. 5.4.9 Freundlich isotherm The Freundlich isotherm assumes that the adsorption occurs on heterogeneous surface at sites with different energy of adsorption and with nonREMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

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identical adsorption sites that are not always available. The KF value is related to the adsorption capacity; while 1/n value is related to the adsorption intensity. A plot of log qe versus log Ce (Fig. 5.12) from the values in Table 5.10 gives a straight line. KF and 1/n were determined from the intercept and the slope, respectively and the results are given in table 5.11. The value of the correlation coefficient, R , obtained in this case indicates that the Langmuir isotherm model fits better than the Freundlich isotherm model. 5.4.10 Adsorption kinetics The experiments were carried out at constant temperature as well as speed and pH. Amount of adsorption of MB on MSF was studied at various time intervals from 0 to 420 min. In order to investigate the mechanism of adsorption on MSF, kinetic model has been used to identify the possible mechanisms of such adsorption process. In this study, pseudo-first and pseudo-second order kinetic models have been proposed to elucidate the mechanism of adsorption depending on the characteristics of the adsorbent. Plot of log (qeqt) vs. t (Fig. 5.13, Table 5.12) gives a straight line for first order adsorption kinetics, which allow computation of the adsorption rate constant, k1. The k1 and qe value for the initial concentration of 100 mg/dm3 are given in Table 5.14 which are not correlated much accurately. The value R2 was 0.932 for pseudo-first order which is not so promising. The pseudo-second-order rate equation is used to study the adsorption of MB on MSF. The rate parameters k2 and qe can be directly obtained from the intercept and slope of the plot of t/qt vs. t (Fig. 5.14, Table 5.13). The values obtained graphically for pseudo-first and pseudo-second order models are listed in Table 5.14. The results show that the pseudo-second order model provided a better approximation to the experimental kinetic data than the pseudo-first order model.
2

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5.4.11 Intraparticle diffusion study The adsorbate species are most probably transported from the bulk of the solution in to the solid phase through intraparticle diffusion process, which is often the rate limiting step in many adsorption processes. The possibility of intraparticle diffusion was explored by using the intraparticle diffusion model [100]. The intraparticle diffusion rate constant (kid) was determined from the slope of the linear gradients of the plot qt versus t1/2 as shown in Fig. 5.15 (Table 5.15). The rate constant of intraparticle diffusion at different temperatures is shown in Table 5.16. The adsorption of MB on MSF adsorbent was a multi-step process, involving adsorption on the external surface and diffusion into the interior. All the steps slow down as the system approaches equilibrium. If the steps are independent of one another, the plot of qt vs. t1/2 usually shows two or more intersecting lines depending on the exact mechanism, the first one of these lines representing surface adsorption and the second line shows intraparticle diffusion. The absence of such features in the plots of the present work indicated that the steps were indistinguishable from one another and that the intraparticle diffusion was a prominent process right from the beginning of dye-solid interaction. If the uptake of the adsorbate varies with the square root of time, intraparticle diffusion can be taken as the rate limiting step. If the qt vs. t1/2 plots pass through the origin then intraparticle diffusion is the sole rate limiting step [96]. Since this was also not the case in the present work it may be concluded that, surface adsorption and intraparticle diffusion were concurrently operating during the MB-MSF interactions. 5.4.12 Adsorption thermodynamics The temperature plays a vital role in the adsorption capacity of adsorbent and it is clear from Fig. 5.16 (Table 5.17), that increase in temperature increases
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the amount of adsorption. The temperature was increased from 303 to 323 K with 5 K interval and the results were showing very much difference in the adsorption; it was increased from 53.05 to 61.85 mg/g. This indicates that the adsorption reaction was endothermic in nature. The enhancement in the adsorption capacity may be due to the chemical interaction between adsorbate and adsorbent, creation of some new adsorption sites and the increased rate of intraparticle diffusion of MB into the pores of the adsorbent at higher temperatures. The thermodynamic parameters such as standard Gibbs energy (G), standard enthalpy (H) and standard entropy (S) were determined at MB concentration of 700 mg/dm3 by keeping all other parameters constant. The plot of lnKc vs 1/T gives straight line as shown in Fig. 5.17 (Table 5.18). H and S values were obtained from the slope and intercept of this plot. The standard free energy change (G), standard enthalpy change (H) and standard entropy change (S) were obtained from the Gibbs free energy equation. Thermodynamic parameters for the adsorption of MB on MSF are listed in Table 5.19. Negative values of G indicate the feasibility of the process and spontaneous nature of the adsorption with a high performance of MB for MSF. Positive value of H indicates the endothermic nature of the process, while positive value of S reflects the affinity of the adsorbents for the MB and suggests some structural changes in adsorbate and adsorbent. 5.5 Comparison of adsorption capacity of MFS with other adsorbents In Table 5.20, the adsorption capacity of MFS is compared with other reported adsorbents. From the economical and adsorption capacity point of view, MFS is good adsorbent.

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5.6 CONCLUSION 1) The results of the adsorption of MB on MFS are very satisfactory and the preparation cost of adsorbent is nearly zero. 2) The removal of MB was possible by MFS up to 99.05 % when concentration of the dye was 100 mg/dm3. 3) The study was evaluated with isotherm models amongst them, Langmuir adsorption was fitted better than Freundlich isotherm. The maximum adsorption capacity was 51.81 mg/dm3 as well as regression factor was 0.997. 4) The kinetic study has shown that, the pseudo-second order is more suitable than pseudo-first order. 5) The process is endothermic and spontaneous, and evaluated thermodynamic parameters such as standard free energy change (G), standard enthalpy change (H), and standard entropy change (S) which supports the favorable adsorption. 6) The MSF is effective, inexpensive adsorbent to remove MB from aqueous solution as well as it may be useful for waste water treatment.

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Table 5.1 Elemental Analysis and properties of MSF

Property Ash content Bulk density Moisture content Carbon Hydrogen Nitrogen

Result 2.53% 0.237gm/cm3 9.92% 60.77 1.76 0.57

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Table 5.2 Effect of pH on removal, % and amount adsorbed, mg/g of MB MB =100 mg/dm3, Time = 420 min, T= 299 2 K, MFS=405 mg, agitation speed= 180 rpm pH 1 2 3 4 5 6 7 8 9 10 11 Amount adsorbed, q mg/g 3.42 5.38 7.86 9.76 10.53 10.91 10.97 10.99 11.01 10.99 10.94 Removal of MB, % 30.77 48.43 70.70 87.80 94.73 98.24 98.69 98.95 99.05 98.90 98.44

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Table 5.3 Effect of shaking period on removal, % and amount adsorbed, mg/g of MB MB=100 mg/dm3, pH=9, T= 299 2 K, MFS=450 mg, agitation speed= 180 rpm Time, min 30 60 120 180 240 300 360 420 480 540 600 Amount adsorbed, qt mg/g 3.41 5.66 7.53 9.18 10.1 10.74 10.97 11.01 11.01 11.01 11.01 Removal of MB, % 30.73 50.02 67.73 82.58 90.88 96.65 98.75 99.05 99.05 99.05 99.05

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Table 5.4 Effect of initial concentration of MB on amount adsorbed, mg/g, and removal, % of MB Time=420min, pH=9, T= 299 2 K, MFS= 450 mg, agitation speed= 180 rpm Initial Conc MB mg/dm3 100 150 200 250 300 350 400 500 600 700 Amount adsorbed, q mg/g 11.01 16.33 21.59 26.98 31.62 34.87 38.98 45.76 48.03 50.73 99.05 98.02 97.19 96.04 94.85 90.04 87.70 81.50 72.05 65.23 Removal of MB, %

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Table 5.5 Effect of adsorbent dosage on removal, % and amount adsorbed, mg/g, of MB pH=9, MB = 100mg/dm3, Time= 420min, T= 299 2 K, mg/dm3, agitation speed= 180 rpm MSF, mg 50 100 150 200 250 300 350 400 450 Amount adsorbed, q mg/g 4.33 5.48 6.72 8.54 9.66 10.12 10.79 11.00 11.01 Removal of MB, % 4.33 10.95 20.17 34.14 48.30 60.75 75.58 88.05 99.05

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Table 5.6 Effect on agitating speed on removal, % and amount adsorbed, mg/g of MB MB=100 mg/dm3, Time= 420 min, T= 299 2 K, MFS=450 mg, pH=9 Agitation speed, rpm 50 70 100 120 140 160 180 200 220 240 Amount adsorbed, q mg/g 5.64 6.68 7.86 9.53 10.20 10.75 11.01 11.01 11.01 11.01 Removal of MB, % 50.75 61.75 70.75 85.72 91.76 96.75 99.05 99.05 99.05 99.05

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Table 5.7 Adsorption isotherm for the adsorption of MB on MSF Time=420min, pH=9, T= 299 2 K, MFS= 450 mg, agitation speed= 180 rpm Ce 0.95 2.97 5.62 9.91 15.44 36.17 49.20 72.52 167.70 243.41 q 11.01 16.33 21.59 26.98 31.62 34.87 38.98 45.76 48.03 50.73

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Table 5.8 Langmuir isotherm for adsorption of MB on MSF Time=420min, pH=9, T= 299 2 K, MFS= 450 mg, agitation speed= 180 rpm Ce 0.95 2.97 5.62 9.91 15.44 36.17 49.20 72.52 167.70 243.41 Ce/q 0.086 0.182 0.260 0.373 0.488 1.037 1.262 1.585 3.492 4.798

Table 5.9 Langmuir constant for the adsorption of MB on MSF

qm (mg/g) 51.81

KL(1/mg) 0.101

R2 0.997

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Table 5.10 Freundlich adsorption isotherm for the adsorption of MB on MSF Time=420min, pH=9, T= 299 2 K, MFS= 450 mg, agitation speed= 180 rpm log Ce -0.022 0.473 0.750 0.996 1.189 1.558 1.692 1.861 2.225 2.286 log qe 1.042 1.213 1.334 1.431 1.500 1.543 1.591 1.661 1.682 1.705

Table 5.11 Freundlich constant for the adsorption of MB on MSF

Kf 12.72

n 3.556

R2 0.964

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Table 5.12 Pseudo first order model for the adsorption of MB on MSF MB=100 mg/dm3, pH=9, T= 299 2 K, MFS=450 mg, agitation speed= 180 rpm t min 0 30 60 120 180 240 300 360 log (qe-qt) 1.0418 0.881 0.736 0.542 0.263 -0.041 -0.569 -1.398

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Table 5.13 Pseudo second order model for the adsorption of MB on MSF MB=100 mg/dm3, pH=9, T= 299 2 K, MFS=450 mg, agitation speed= 180 rpm t 0 30 60 120 180 240 300 360 420 t/qt 0 8.798 10.791 15.936 19.608 23.762 27.933 32.817 38.147

Table 5.14 Kinetic parameters for the adsorption of MB on MSF Pseudo first order qe exp. (mg/g) 11.01 k1x103 (min1) 6.40 qe calc. (mg/g) 17.02 0.932 6.26 R2 Pseudo second order k2 x103 qe calc. (mg/g) 12.64 0.991 R2

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Table 5.15 Intraparticle diffusion for the adsorption of MB on MSF MB=100 mg/dm3, pH=9, T= 299 2 K, MFS=450 mg, agitation speed= 180 rpm t 1/2 5.477 7.746 10.955 13.417 15.492 17.321 18.974 20.494 qt 3.410 5.560 7.530 9.180 10.100 10.740 10.970 11.010

Table 5.16 Study of intraparticle diffusion of adsorption of MB on MSF kid (mg g1 min1) 0.512 0.942 R2

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Table 5.17 Effect of temperature on amount of MB adsorbed on MSF MB=700 mg/dm3, Time=420 min, MFS= 450 mg, pH=9, agitation speed= 180 rpm TK 303 308 313 318 323 Amount adsorbed, q mg/g 53.05 56.03 59.03 60.57 61.85

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Table 5.18 Van't Hoff plots for the adsorption of MB on MSF MB=700 mg/dm3, Time=420 min, MFS= 450 mg, pH=9, agitation speed= 180 rpm 1/T 0.00330 0.00324 0.00319 0.00314 0.00309 lnKc 1.563 1.618 1.671 1.696 1.717

Table 5.19 Thermodynamic parameters of adsorption of MB on MSF TK 303 308 313 318 323 G kJ/mol -3.938 -4.143 -4.348 -4.484 -4.611 0.746 4.034 H kJ/mol S J/mol k

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Table 5.20 Comparison of adsorption capacity of MSF with other adsorbents Adsorbent Natural zeolite Raw kaolin Calcined raw kaolin Gypsum Amberlite XAD-2 Fe(III)/Cr(III) hydroxide Polyacrylic acid-bound iron oxide magnetic nanoparticles Halloysite nanotubes Multiwalled carbon nanotubes containing oxygen 0.85% 2.16%, 7.07% Silica nano-sheets Oil palm wood activated carbon Sunflower oil cake activated carbon Impregnation with 0.85 H2SO4 Impregnation with 1.90 H2SO4 Straw carbon Rice husk carbon Groundnut shell carbon Coconut shell carbon Bamboo dust carbon Dehydrated wheat bran carbon 61.10 36.62 25.62 11.77 90.9 10.21 16.43 15.798 42.60 37.57 7.50 8.16 7.20 82.00 [35] [35] [35] [36] [47] [48] [48] [48] [49] [49] [49] [49] [49] [53] 0.199 84.32 [31] [34] qm (mg/g) 16.37 27.49 13.44 36 16.8 22.8 Reference [19] [24] [24] [25] [27] [28]

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271

Activated coir pith carbon Cotton stalk Cotton dust Cotton waste Natural wheat straw Rice husk ash Spent coffee grounds residue Parthenium hysterophorus Coconut bunch waste C. racemosa var. cylindracea Neem tree Mahogany Fruit Shell

5.87 4.52 8.33 9.75 60.66 18.15 18.70 39.68 70.92 5.23 8.76 51.81

[54] [60] [60] [60] [63] [66] [71] [74] [78] [87] [96] Present work

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272

CH3 N H3 C

Cl S N

CH3 N CH3

Fig. 5.1 Structure of methylene blue dye

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273

40

36 Transmitance (%)

896 1733 1434 1372 1250 2923


609

32

28

1626

24 4000

3400 3500 3000 2500 2000


-1

1500

1048 1000

Wavenumber (cm )

Fig. 5.2 FTIR spectrum of MSF

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608 500

Chapter 5

274

A
896 609 1733 1434 1372

Transmitance (%)

1250

1048

1626

B
886

1508 1488 1423 1396 1383 1356 1330 1248 1182 1142

889

1601

609 C

1736

1620 1602

1800

1500

1200 900 -1 W avenum ber (cm )

Fig. 5.3 FTIR spectrum of (A) MSF, (B) MB, (C) MB adsorbed on MSF

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609

1051

600

Chapter 5

275

Fig.5.4 (A) SEM image before adsorption of MB

Fig.5.4 (B) SEM image after adsorption of MB

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100 80

0 2 4

60 6 40 8 20 0 0 2 4 6 8 10 12 10 12

pH

Fig. 5.5 Effect of pH on removal, % and amount of MB adsorbed, mg/g MB=100 mg/dm3, Time = 420 min, T= 299 2 K, MSF=450 mg, agitation speed= 180 rpm

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

Amount adsorbed of MB, mg/g

Rmoval of MB, %

Chapter 5

277

120 100

0 2 4 6 8 10 12
0 200 400 600 800

80 60 40 20 0

time, min

Fig. 5.6 Effect of shaking period on removal, % and amount adsorbed, mg/g of MB MB=100 mg/dm3, pH=9, T= 299 2K, MFS=450 mg, agitation speed= 180 rpm

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

Amount adsorbed of MG, mg/g

Removal of MB, %

Chapter 5

278

100

60 50 40

80

60 30 40 20 20 10 0 0 200 400 600


3

800

Initial conc. MB, mg/dm

Fig. 5.7 Effect of initial concentration of MB on amount adsorbed, mg/g and removal, % of MB Time= 420 min, pH=9, T= 299 2 K, MFS= 450 mg, agitation speed= 180 rpm

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

Amount adsorbed of MB, mg/g

Removal of MB, %

Chapter 5

279

100

0 2 4

80

60 6 40 8 20 10 12 0 100 200 300 400 500

Adsorbent dose, mg

Fig. 5.8 Effect of adsorbent dosage on removal, % and amount adsorbed, mg/g on MB MB = 100mg/dm3, Time= 420 min, pH=9, T= 299 2 K, agitation speed= 180 rpm

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

Amount adsorbed of MB, mg/g

Removal of MB, %

Chapter 5

280

100

80

2 4

60 6 40 8 20 10

0 50 100 150 200

12 250

rpm

Fig. 5.9 Effect on agitating speed on removal, % and amount adsorbed, mg/g of MB MB=100 mg/dm3, Time=420 min, T= 299 2 K, MFS= 450 mg, pH=9

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

Amount adsorbed of MB, mg/g

Removal of MB, %

Chapter 5

281

60 50 40

qe mg/g

30 20 10 0 0 50 100 150 200


3

250

300

Ce mg/dm

Fig. 5.10 Adsorption isotherm for adsorption of MB on MSF Time=420 min, T= 299 2 K, MFS= 450 mg, pH=9, agitation speed= 180 rpm

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

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282

6 5 4

Ce /qe

3 2 1 0 0 50 100 150 200 250 300

Ce

Fig. 5.11 Langmuir isotherm for adsorption of MB on MSF Ttime=420 min, T= 299 2 K, MFS= 450 mg, pH=9, agitation speed= 180 rpm

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283

1.6

1.2

log qe

0.8

0.4

0 -0.5 0 0.5 1 1.5 2 2.5

log C e

Fig. 5.12 Freundlich adsorption isotherm for adsorption of MB on MSF Time=420 min, T= 299 2 K, MFS= 450 mg, pH=9, agitation speed= 180 rpm

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284

1.5 1 0.5

log (qe -qt)

0 0 -0.5 -1 -1.5 -2 100 200 300 400

t min

Fig 5.13 Pseudo-first order plot for adsorption of MB on MSF MB=100 mg/dm3, T= 299 2 K, MFS= 450 mg, pH=9, agitation speed= 180 rpm

REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST ADSORBENTS

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285

50

40

30

t/qt
20 10 0 0 100 200 300 400 500

t min

Fig. 5.14 Pseudo-second order plot for adsorption of MB on MSF MB=100 mg/dm3, T= 299 2 K, MFS= 450 mg, pH=9, agitation speed= 180 rpm

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286

14 12 10 8

qt

6 4 2 0 0 5 10 15 20 25

1/2

Fig. 5.15 Intraparticle diffusion plot for adsorption of MB on MSF MB=100 mg/dm3, T= 299 2 K, MFS= 450 mg, pH=9, agitation speed= 180 rpm

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287

65

Amount adsorbed of MB, mg/g

60

55

50

45

40 300 305 310 315 320 325

TK

Fig. 5.16 Effect of temperature on amount adsorbed of MB on MSF MB=700 mg/dm3, Time=420 min, MFS= 450 mg, pH=9, agitation speed= 180 rpm

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288

1.76

1.72

1.68

ln Kc

1.64

1.6

1.56

1.52

0.00305

0.0031

0.00315

0.0032

0.00325

0.0033

0.00335

1/T

Fig. 5.17 Van't Hoff plots for adsorption of MB on MSF MB=700 mg/dm3, Time=420 min, MFS= 450 mg, pH=9, agitation speed= 180 rpm

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