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Adsorption of Cd (II) and Pb (II) Using Physically Pretreated Camel Bone Biochar

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Adsorption of Cd (II) and Pb (II) Using Physically Pretreated Camel Bone Biochar Advanced Journal of Chemistry-Section A, 2019, 2(4), 347-364 http://ajchem-a.com Research Article Adsorption of Cd (II) and Pb (II) Using Physically Pretreated Camel Bone Biochar Mohamed Nageeb Rashed* , Allia Abd-Elmenaim Gad, Nada Magdy Fathy Faculty of Science, Aswan University, 81528 Aswan, Egypt A R T I C L E I N F O A B S T R A C T Received: 15 April 2019 In this study, low-cost biochar adsorbent originated from camel Revised: 06 May 2019 bone was prepared by physical treatment, and the prepared camel Accepted: 05 June bone biochar for the removal of Cd2+ and Pb2+ from aqueous Available online: 10 June solutions was examined. The characterization of the prepared biochar adsorbent before and after the treatment with the metal DOI: 10.33945/SAMI/AJCA.2019.4.8 solutions was done by using XRD, SEM, FT-IR, and BET surface isotherm. The bone sample was pyrolyzed at temperature 500, 600, 800, and 900 °C. Adsorption efficiency of Pb and Cd were optimized K E Y W O R D S by varying different parameters viz., pH, pHz, contact time, initial Wastewater metal concentration, adsorbent dosage, and temperature. Nature of Lead the adsorption process is predicted by using adsorption kinetic, Cadmium isotherms, and thermodynamic models. The results revealed that the Camel Bone effective pyrolysis of camel bone achieved at 800 °C which possess Biochar high removal capacity. The maximum adsorption removal percentage for Cd and Pb were 99.4 and 99.89%, respectively at contact time of 1 h, adsorbent dosage of 1 g, pH=5, and initial metal concentration 10 mg/L of both metal salts. The kinetic results of cadmium and lead adsorption obeyed a pseudo-second-order model and fitted well with the Langmuir isotherm. G R A P H I C A L A B S T R A C T * Corresponding author's E-mail address: [email protected] M. N. Rashed et al. Introduction wastewater. The aim of this study is to prepare low cost, Aquatic pollution by heavy metals is a great effective and eco-friendly camel biochar problem. The presence of heavy metals in the adsorbent from camel bone by physical aquatic environment is the most problem activation (carbonization) and applying the effects the health of humanity, as it is non- developed adsorbent for the removal of two degradability and, so it's toxic in water [1]. heavy metals (Pb and Cd) from the polluted The existence of low levels of the heavy metals water. in water resources will accumulate in the food chain and lead to its contamination with toxic Experimental heavy metals [2]. Several techniques are available for the Reagents and standards treatment of heavy metals pollution from The reagents and chemicals used were polluted water viz., catalysis, ion exchange, of analytical grade (Merk and BDH). reverse osmosis, precipitation adsorption, Deionized water was used throughout the and coagulation. Among these technologies, study to carry out all the experiments. adsorption has a wide application. The Metal (Cd and Pb) standard solutions were adsorption of heavy metal depends on the prepared by using analytical grade samples nature of the adsorbents which prepared from [Pb(NO3)2, Cd(NO3)2]. pH was adjusted to several sources which include natural the suitable values for each experiment by resources, including tree ferns and pH meter using solutions of HNO or NaOH. composites [3], plants, industrial waste, clays, 3 activated carbon, sludges, algae, wheat bran, Camel bone collection and pretreatment shells [4], agricultural wastes and cork Yohimbe bark wastes [5], tire rubber [6-7]. Discarded Camel bones were purchased Bone char is an adsorbent consisting of from local butchers shops. In order to 90% calcium phosphate and 10% carbon and remove the fat and flesh from the Camel's is produced by two main treatments which bone, it is washed with hot deionized water include chemical treatment by several several times; then the bones were left to chemicals, and physical treatment by dry in the open air. The air-dried bones are carbonization of bones. The structure of bone oven dried in an oven at 110 °C overnight. char is calcium phosphate in the The dried bones were crushed, sieved to hydroxyapatite form (Ca10(PO4)6(OH)2, HAp) particle size (<63 µm) and stored in dry which is known for its more effective containers which may be used to carry out adsorption properties which can adsorb the experiments. divalent heavy metals [8]. Camel bone char was applied widely for Biochar adsorbent preparation the treatment of polluted water with heavy The dried bone was calcinated at 500 °C metals. Alqadami et al. [9] prepared magnetic up to 900 °C by varying time (1, 2 and 3 h) nanocomposite from camel bones and used it in a muffle furnace with a limited supply of for adsorption of toxic metals from water. oxygen. The resulted biochar bone Hassan et al. [10] prepared camel bone adsorbents were grounded with agate charcoal and applied it for the removal of mortar, sieved to particle size (<63 µm) and mercury ions from wastewater. Ramavandi et stabilized to the further experiments. al. [11] reported the efficiency of camel bone powder for the removal of copper from Adsorbate preparation 348 Adv J Chem A 2019, 2(4), 347-364 Adsorption of Cd (II) and Pb (II) using… 1000 mg/L Pb and Cd stock standard camel biochar adsorbent dosage (g) and V solutions are prepared by using deionized solution volume (L). water. The working metal ions solution was Removal percentage of the heavy metal prepared from the stock solution by ions were calculated: dilution. Ci−Ce Removal % = ×100 Batch adsorption experiments Ci Characterization of Camel bone biochar Batch adsorption experiments adsorbent performed such as ZpHc, pH, initial metal ions concentration, adsorbent dosage, X-ray diffraction (XRD) spectra of camel temperature and contact time. bone and the prepared camel biochar The effect of camel biochar dose on the adsorbents were characterized using a adsorption of the metal was studied by Bruker D8 Advance diffraction system, with carrying out using different masses of the Cu Ka radiation in theta/theta reflection camel biochar in a range between 0.01 and geometry. The surface morphology of the 1 g. The effect of contact time on the prepared camel biochar adsorbents was adsorption of Cd and Pb onto camel biochar investigated by scanning electron were verified with 30, 60, 120, and 180 microscope (SEM, JEOL_ JSM-6400). FTIR minutes. For the effect of initial metal spectra of both original and prepared concentration on adsorption, the metal adsorbents were performed by Bomem ions (Cd and Pb) concentration were varied MB100 FTIR spectrometer recorded in the from 10 to 70 mg/L. For studying the effect 4000–400 cm−1 region. The specific surface of pH, the values of pH were in a range from area and pore size distributions of the 3 up to 9. The final and initial pH values in adsorbent were determined by applying the ZpHc were measured in which a 50 mL the adsorption-desorption BET method solution of 0.1 M NaCl was in contact with using nitrogen as an adsorbate, at 77 K. 0.1 of camel biochar bone. From plotting initial pH and final pH, the point of the Results and discussion intersection gave the ZpHc [12]. Characterization of Camel bone biochar Analytical measurement of heavy metals XRD Heavy metal concentrations in the X-ray diffraction (XRD) patterns (Figure filtrate were determined after each 1 a, b) show morphology of the camel bones experiment by atomic absorption before and after calcination from the spectrometer (AAS) [THERMO SCIENTIFIC Figures, it was noticed that the camel bones Ice 3000]. sample displays the same characteristic The adsorption capacities of Cd2+ and peaks as standard hydroxyapatite, where it Pb2+ were calculated by the following shows three intense peaks at 31.8°, 32.22° equation: and 33.01° corresponding to Miller indices q=V (Ci− Ce)/W (211), (112) and (300) respectively, less intense peaks at 2θ of 25.9°, 39.8°, Where q is adsorption capacity (mg/g), Ce 46.73°and at 2θ=49.48°-53.24° also at metal concentration at equilibrium (mg/L), 2θ=28.13°-29.02°. X-ray diffraction spectra Ci initial metal concentration (mg/L), W of the adsorbents (camel biochar) show the crystalline structure of hexagonal calcium 349 Adv J Chem A 2019, 2(4), 347-364 M. N. Rashed et al. hydroxyapatite (Ca10(PO4)6(OH)2 or (1100-900 cm-1) and the absorption bands calcium phosphate hydroxide (Figure 1 b) at 720 cm-1 suggest the presence of CO32- in While the camel bone before activation hydroxyapatite structure. Moreover, a shows the approximately amorphous phase broad and strong band of calcium of Ca2+ of hydroxyapatite with very low-intensity was observed at (550-610 cm-1) that peaks as shown in (Figure 1 a). indicated the structure of calcium hydroxyapatite. After carbonization FTIR (CB800) (Figure 2 b), no peaks were noticed due to protein and collagen (C=N, The FTIR study of the camel bone C=O, C=C), while the peaks due to OH group biochar provided us with information (3000-3600 cm-1) and hydrocarbon of -CH about the mechanism of adsorption. FTIR stretching (2853-2923 cm-1) were reduced spectrum of the camel bone biochar before after calcination. However, the main calcination (CB) (Figure 2 a) indicates functional groups, phosphate and calcium presence of hydrocarbon groups peaks of - peaks remain unchanged. Elliot [13] CH stretching at 2853-2923 cm-1, the large reported in bone IR spectrum strong split peak located at 3000-3600 cm-1 assigned to phosphate (PO 3-) bands in the range 1, the crystallization water (OH groups), the 4 100–1, 000 cm-1 (stretching mode) and absorption bands due to C=N, C=O, C=C 500–600 cm-1.
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