Ferrite Nanocomposite (Rice Straw-CoFe2O4) as New Chemical Modified of for Treatment of Heavy Metal from Waste Water
Received Date: Feb 13, 2019 / Accepted Date: Mar 11, 2019 / Published Date: Mar 20, 2019
The agricultural by-products such as Rice Straw (RS) has widely investigated as an efficient alternative for current costly methods of removing heavy metals from waste water. RS were modified by CoFe2O4, results of adsorption indicated that RS treated with CoFe2O4 spinel ferrite nanoparticles appeared to be more efficient to remove heavy metals from waste water. Where the percentage removal of Fe, Mn, are 84.25%, 92.45% respectly and Cu, Cd, Zn, Ni, Pb are 100% removal. The prepared samples were characterized using different analytical techniques, X-ray diffraction (XRD), FTIR, Transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Atomic Absorption Spectrometer (AAS) using in determination of concentrations of heavy metals.
Keywords: Rice Straw (RS); Cobalt ferrite nanoparticles; Agricultural waste; Waste water treatment
Water Pollution defined as Change of chemical, physical and biological properties of water which restricts its use in the various applications . The effluents no disperse in water systems and so change water quality has happen. The contamination of heavy metal in waste water streams from various industries such as wire drawing, printed circuit boards, metallic coatings, mining and agricultural sources where fertilizers and fungicides are widely using . Lignocelluloses one of the malignant wastes in the world is Rice Straw. Before wheat and maize, the most third important grain crop in the world production is rice. Chemical composition of Rice Straw contains lignin (5-24%), hemicellulose (19-27%) and cellulose (32-47%) . Phenomenon of black cloud is released when Rice Straw burning, affecting on human health, visibility, and global climate by emitting gaseous pollutants. binding sites of rice straw able remove metal on aqueous solution by adsorption like activated carbon . On the surface of rice straw have functional groups, binding characteristic may tack up metals from waste water. Rice straw advantage with low-cost bio-adsorbent in removal heavy metals from water and waste water .
Large ratios between surface and volume of fabrication of nonmaterial is very important in treatment of pollutants. Nanotechnology have role in our environment, by production new materials, sensors and treatment techniques for monitoring purposes . The contaminants removal from the environment is occurred so rapidly, efficiently and within low costs framework. Thus, the novel nanomaterial field in Nanotechnology with increased affinity, selectivity and capacity for heavy metals. The nanoparticles (NPs) are ultra-fine particles in the size of nanometre order. In many cases, the particles from 1 to 100 nm are generally called as nano particles. The nano sized magnetic materials show many novel properties, especially, magnetisation behavior different than bulk magnetic material. Recently, the use of nano-sized magnetic material as adsorbents has happen increasing interest due to their high surface area and unique super paramagnetism. These properties lead to high adsorption efficiency and high removal rate of contaminants . The stability of magnetic nanoparticles is utmost important for their applications. This can be greatly improved by preventing their oxidation and aggregation. Modification of the surface of magnetic nanoparticles by attaching organic or inorganic materials is proven to be greatly enhances the stability and prevents aggregation. Further these attached groups have specially function group that can ion selective uptake .
Magnetic oxides, such as Fe3O4, acting as adsorbents (nano) to removal of many metal ions from waste water, such as Ni2+, Cu2+, Co2+ and Pb2+. the mainly properties of Magnetic nanoparticles are large surface /volume ratio, bind with chemicals and then they be removed using a magnet. In water problems, nanotechnology of nanoparticles is useful for treatment of water contaminants including bacteria, viruses, and heavy metals like, Nickel, chromium, etc. . Cobalt ferrites one subject of researchers interests due to its high saturation magnetization and coactivity. Cobalt ferrite materials are known to exhibit very high cubic magneto crystalline anisotropy. The magnetic properties of the Cobalt ferrites are very good are known to be mainly attributed to the Co ions in a spinal lattice . Cobalt ferrite (CoFe2O4) belongs to opposite spinel structure in which half of Fe3+ ions occupy tetrahedral sites and the other half occupy the octahedral sites with Co2+ ions. In the inverse spinel structure the magnetic moment of Fe3+ in the tetrahedral sites is aligned in opposite direction to that of Fe3+ in the octahedral sites and hence the net magnetic moment produced from Fe3+ is zero. So the net magnetic moment of CoFe2O4 is due to the magnetic moment of Co2+ in the octahedral sites . Many synthetic methods to prepare highly crystalline and uniformly sized magnetic nanoparticles of Cobalt-Ferrites have been studied such as the precipitation method . The solvo thermal method . the co-precipitation method , the hydrothermal method  and the sol-gel method . Sol-gel is a simple way to produce ultra-fine powders due to their simple synthesis equipment and process. The reason behind studying and opting for this sol-gel route is that the reactants used for the process are cost effective, safe and environmentally friendly . Adsorption capacities of native plant materials usually show lower maximum. Nevertheless, these capacities can be significantly increased with a suitable method such as treatment with various hydroxides, acids; carbonization and hydrolysis have been reported recently. Combination of nonmagnetic powdered material with magnetic nano or microparticles results in a formation of magnetically responsive (bio) composites which exhibit response to external magnetic field .
Preparation of adsorbent materials
Rice Straw (RS): By-product Straw remained after Rice being harvested was gathered from local market.
1. Washed well to remove water soluble and dirt substances via soaking suitable amount of RS into a detergent solution for 50 minutes, followed by extensive washing 4-5 times with tap water for 1 hour and left till next day in tab water, finally washed with de-ionized water and squeezed.
2. RS cut to small pieces, dried in oven at 65°C to 2 hours (constant weight). For preservation, RS kept in plastic bags and preserved in desiccators until the time of use to minimize contact with humidity .
3. The Raw RS was characterized using different techniques such as FTIR and SEM.
Synthesis of cobalt- ferrites nanoparticles
The process for synthesis of mono disperse CoFe2O4 with super paramagnetic behavior at room temperature was carried out as following:
1. 10.8 g of FeCl3.6H2O (MW 270.32) was mixed with 3.3 g of Co Cl2.2H2O (M.W 165.9) and dissolved in 50 ml de-ionized water (2:1 molar ratio) according to the stoichiometric proportion of Co and Fe in CoFe2O4. 1.28 g of Citric acid (M.W 192.124) was added as gelling agent (3:1 molar ratio).
2. 4M ammonia solution (NH4OH) was added in order to keep the pH of the solution to 7.0 with continuous stirring using a magnetic stirrer.
3. Continuous stirring for 9 hours at 85°C, the clear sol. was completely turned to a gel.
4. Dried in oven at 80°C till constant weight and grinded to fine powder, the powder was calcined at 550°C for 5 hours in furnace under air atmosphere .
Preparation of RS-CoFe2O4 ferrite nanocomposite
For increasing adsorption capacities of adsorbent use RS in modified form.
1. 5 g of RS was added to 0.5 g of Cobalt- Iron Oxide nanoparticles.
2. Refluxed with 30 ml Ethyl Alcohol and 30 ml NaOH (2.5%) at 85°C for 3 hours.
3. Filtrated and washed for several times with HCl (0.1 N) then by deionized water. Then, the modified RS was dried at 105°C till constant weight . A photograph of prepared RS-CoFe2O4 nanocomposite was shown in Figure 1. where RS/CoFe2O4 Nanocomposite used in the adsorption study was characterized by using FTIR and SEM.
Characterization methods and instruments
The FTIR, XDR, SEM, TEM, AAS analyzed at the analytical Laboratory, The City of Scientific Research and Technological Applications (SRTA-City), Borg Al Arab, Egypt using Bruker Tensor 37 FT/IR, LabX XRD-6100 shimadzu, JEOL JSM-6360LA, FEI TECNAI SPIRIT, PerkinElmer (PinAAcle 900 T respectably)
Method of treatment (removal of heavy metals): The sewage water samples were collected from Zarkon drain El-Mahmodya Station, Beheria Government, Egypt. Where some Precautions taken:
1. The samples were transferred to laboratory in closed bottles.
2. Distributed in sixteen 2-liter beakers, each of them had 1-liter water volume. Beakers were subdivided into 4 treatments with each adsorbent for 24 hour and 4 treatments with each adsorbent for 72 hours.
3. Adsorbent weight (1 to 4 g) mixed with polluted water (sewage water) to investigate the effect of adsorbent weight on removal efficiencies of different investigated metals and contact time (24 hour to 72 hour) to investigate the effect of contact period on removal efficiencies of different investigated metals.
4. Samples were placed in a shaker for 24 hour or 72 hours at 120 rpm at room temperature . Adsorption was performed for initial heavy metal concentrations of 1.9 and 1.0 mg/L for Fe, 0.53 and 0.3 mg/L for Mn, 0.013 and 0.015 mg/L for Cu, 0.01 and 0.008 mg/L for Cd, 0.18 and 0.1 mg/L for Zn, 0.12 and 0.1 mg/L for Ni as well as 0.163 and 0.1 mg/L for Pb. Metal ions remaining in aqueous solution were determined by AAS. The amount of metal ion adsorbed was calculated as: % Adsorption=((Ci- Cf)/Ci) × 100.
Where Ci: initial concentration and Cf: final concentrate of the metal ions in the solution (mg/L).
Desorption and reusability: Nanocomposites (RS/CoFe2O4) are undergoing under several investigate as reusability of the adsorbent, regeneration and desorption. Adsorbent (RS/CoFe2O4) was separated from adsorption process is performed into process which include:
1. To remove any un adsorbed metal ions, washing with de -ionized water.
2. Mixing resultant metal-loaded adsorbent with 20 mL of 0.10 M HNO3.
3. Stripping agent in water shaker bath for one hour.
4. The drying adsorbent.
These process was repeated three times .
Results and Discussion
Characterization of biosorbent
FTIR of RS before and after treatment: Figure 2 shows the FT-IR spectra of RS-CoFe2O4 Ferrite Nano particles Composite. terms of intensity of the bands and disappearance of bands after treatment. However, slight changes were found for some functional groups. For instance, Broad absorption band at 3436 cm-1 became broader in Figure 1 and shifted to a lower wave number value 3171 cm-1. Also, strong sharp beaks appeared at 1625 cm-1 and 1404 cm-1. Absorbt on band appear at 642 cm-1 which belongs to the stretching vibration of the metal-oxygen. The difference indicated that the structure of RS was changed after treatment which indicate the successful modification process.
XRD: Figure 3 shows the X-ray diffraction pattern of the calcinated cobalt ferrite nanoparticles. This pattern matches well with the standard diffraction data of CoFe2O4 crystals. Using XRD, it is confirmed that the samples were cubic structure in nature. All peaks of the prepared sample and its position at 2θ scale are completely compatible with the characteristic peaks of cubic spinel CoFe2O4 and they are matched with the XRD card no.22-1086. The CoFe2O4 peaks are particularly sharp. Other oxides or impurity phases are not detected which indicate that we have pure cubic spinel CoFe2O4 .
TEM: The TEM analysis presented in Figure 4 reveals mildly agglomerate pseudo spherical particles with a grain size ranging between 42.9-86.7 nm. TEM imaging has permitted the precise view regarding the size and shape of theobtained particles. Particles have two shapes; common one is spherical and elongated as shown in the TEM images.
SEM: Figure 5 shows the SEM images of RS -CoFe2O4 nanocomposite. SEM images show that the CoFe2O4 nanoparticles are presented on the surface of RS.
Removal efficiencies of heavy metals by using raw rice straw
Concentrations of different investigated metals such as Fe, Mn, Cu, Cd, Zn, Ni and Pb were measured in sewage water samples before and after being treated with different dosages of RS. Also, different retention time 24 and 72 hour. relation between contact time and removal efficiency is linearly proportional . Their removal efficiencies were detected, and the results were as follow in Tables 1 and 2 where: in Table 1 as the weight of adsorbent increase, the heavy metal percentage treated increase at 24 hours. in sample 1 the Fe, Mn, Cu, Cd, Zn, Ni and Pb, are measured, the large heavy metal treated was Ni was 55.29% in weight of adsorbent 4 g in sample 1, when in sample 2 was Zn was 70%, while the least one treated was Fe in sample 1 and 2 were 21.05 and 38.42% respect. As same time Mn, Pb and Zn were half percentage treated.
|Percentage of removal (%) by Rice straw|
|24 hours||72 Hours|
Table 1: The percentage removal of heavy metals (Fe, Mn, Cu, Cd, Zn, Ni and Pb) which treated by rice straw.
|Rice Straw-CoFe4O Percentage of removal (%) by Ferrite Nanocomposite|
|24 hours||72 hours|
|Sample 1||1||12.97||22.45||92.3||58||45.56||35.67||33.7||20.45||30.4||100||100||70||62.5||51. 3|
Table 2: The percentage removal of heavy metals (Fe, Mn, Cu, Cd, Zn, Ni and Pb) which treated by CoFe2O4/RS.
When removal of metal ions from solution the time of equilibrium is effective factor. Increasing of contact time is accompanied with enhancing of uptake of both metal ions as due to the decreased coefficient of mass transfer for diffusion-controlled reaction between the metal ions and the adsorbent . which indicate in retention time 72 hour, in sample 1 and 2 the large heavy metal treated was Cu was 100% that clear that active dose is 3 g so 4 g become waste. while Fe metal still the least metal treated except if removal percentage increases by retention time increase. The rest of metals have more than half percentage treatment in dose 4 g of rice straw.
Removal efficiencies of heavy metals by using modified RS (CoFe2O4/RS)
In Table 2 use modified RS (CoFe2O4/RS) with different dose and retention time different to study the percentage removal of heavy metals such as Fe, Mn, Cu, Cd, Zn, Ni and Pb Concentrations of different investigated metals such as Fe, Mn, Cu, Cd, Zn, Ni and Pb were measured in sewage water samples before and after being treated with different dosages of RS. Also, different retention time 24 and 72 hours. relation between contact time and removal efficiency is linearly proportional . Their removal efficiencies were detected, and the results were as follow in Table 2 where: The heavy metal percentage treated increase at 24 hours. in sample 1 measure Fe, Mn, Cu, Cd, Zn, Ni and Pb which indicate that more heavy metal treated were Cu and Cd was 100% in weight of adsorbent 2 g and 4 g in sample 1 and 2, while the least heavy metal treatment percentage was Fe at sample 1 and 2 were 40.45 and 74.1. The rest of metals percentage near to 100%, that indicate the efficiency of CoFe2O4/RS which appeared in small dose. In retention time 72 hours clear that in weight of adsorbent 4 g all measure element was 100% except Fe and Mn except if they near to 100% (84.25 and 92.45 respectively).
Effect of adsorbent weight: The adsorbent weight is an important parameter in adsorption studies because it determines the capacity of adsorbent for a given initial concentration of metal ion solution. The amount of adsorbent decides the extent of available surface binding sites for adsorption. Hence, the percentage removal of adsorbate increases with adsorbent dosage. The effect of variation of adsorbent amount on the removal of metal ions by raw and modified RS was studied by varing adsorbent amount from (1 to 4 g).
Effect of contact time: The rate of ion sorption is faster of metal ion at initial as cause to large number of available sorption sites for adsorption. For the initial blank surface, adsorption proceeded with a high rate. At the end. The adsorption rate is slower probably due to active sites become saturation and equilibrium is stabilized . The effect of adsorbent weight and contact time on removal efficiencies of heavy metals by RS-CoFe2O4 Ferrite Nanocomposite. In adsorption the most factors have great affect is surface area since with a decrease in particle size is accompanied with more number of binding sites for adsorption. From that mean there are directly relation between Surface area and Adsorption. Waste surface of Agriculture is porous and which contain meso pores, micro pores, and macro pores. Along with volume, area and diameter of pores are also influencing factors. Degree or extent of diffusion is determined by volume and diameter pore for pollutant molecules into the pores. Diffusion is depended on the pore diameter and size of the molecule. If the diameter of adsorbat molecule is smaller than the pore diameter, then the molecule diffuses deeper into the pore. From that finding the surface area is influenced on the number of sorption site . Cellulose of RS can provide binding sites for heavy metals, so it is potential adsorbent for heavy metals when used as adsorbent without Coating the CoFe2O4, but the yield of removal is low and difficult separation of adsorbent from solution. Other site removal of heavy metal with RS-Coating CoFe2O4 nanoparticles is higher yield of heavy metals because of the high surface area to volume ratio of RS-CoFe2O4 nanocomposites .
Adsorption mechanism: It can be seen in Figure 6 that the attraction is done between -OH groups (negative charge) of the RS and CoFe2O4 nanoparticles (a partial positive charge) . On the other hand, for adsorption of heavy metal ions by RS/ CoFe2O4 nanocomposite, CoFe2O4 nanoparticles act as a magnet when the metal ions approach to the composite, their surface change from positive charge change to a negative charge they since CoFe2O4 nanoparticles is acted as temporary dipole, it means there will be cationic interaction between CoFe2O4 nanoparticles and metal ions. So, its interaction is physical interaction. The nanoparticles are acted as superior accessible active sites could be the main roles for the higher removal of metal ions by RS/ CoFe2O4 nanocomposite than with raw RS. The nanoparticles are acted as superior accessible active sites could be the main roles for the higher removal of metal ions by RS/ CoFe2O4 nanocomposite than with raw RS. The dispersion of nanoparticles sites on the surface of RS is better which provides more available of adsorption for heavy metal ions. After adsorption, the CoFe2O4 nanoparticles on the surface of RS separated to adsorbent super paramagnetism as magnetic separation [21,26-28].
This study shows that the adsorption of metal ions by the modified RS was suitable as compared with the unmodified adsorbent from waste water. Modification of RS with (CoFe2O4) Nanoparticles, and practically use on adsorption ions from waste water, as it gives higher adsorption than unmodified RS. The adsorption study showed that physically attraction between different charges as was responsible for metal ions removal. High surface area of nanoparticles cause to capacity is high of adsorption. The results show RS/CoFe2O4 Nanocomposite is given elimination with highly efficiency for of heavy metal ions as good adsorbent from waste water. From these studies we obtained the optimum conditions for the removal by adsorption mechanism involved mainly is electrostatic attraction as Figure 6.
- Taha A, El-Mahmoudi A, El-Haddad I (2004) Pollution sources and related environmental impacts in the new communities southeast Nile Delta, Egypt. Emirates Journal for Engineering Research 9: 35-49
- Kadirvelu K, Thamaraiselvi K, Namasivayam C (2001) Removal of heavy metals from industrial wastewaters by adsorption onto activated carbon prepared from an agricultural solid waste. Bioresource Technology 76: 63-65.
- Saha BC (2003) Hemicellulose bioconversion. Journal of Industrial Microbiology and Biotechnology 30: 279-291.
- El-Sayed G, Dessouki H, Ibrahim S (2010) Biosorption of Ni (II) and Cd (II) ions from aqueous solutions onto RS. Chem Sci J 9: 1-11.
- Osmania HE, Badwy RK, Ahmad HF (2010) Usage of some agricultural by-products in the removal of some heavy metals from industrial wastewater. Journal of Phytology.
- Hillie T, Munasinghe M, Hlope M, Deraniyagala Y (2006) Nanotechnology, water and development. Meridian Institute, Washington.
- Ambashta RD, Sillanpää M (2010) Water purification using magnetic assistance: a review. Journal of Hazardous Materials 180: 38-49.
- Girginova PI, Daniel-da-Silva AL, Lopes CB, Figueira P, Otero M, et al. (2010) Silica coated magnetite particles for magnetic removal of Hg2+ from water. Journal of Colloid and Interface Science 345: 234-240.
- Hu J, Lo IM, Chen G (2007) Comparative study of various magnetic nanoparticles for Cr (VI) removal. Separation and Purification Technology 56: 249-256.
- Balakrishnan P, Veluchamy P (2015) Synthesis and characterization of CoFe2O4 magnetic nanoparticles using sol-gel method. Int J ChemTech Res 8: 271-276.
- Zhang D, Zhang X, Ni X, Song J, Zheng H (2006) Synthesis and characterization of CoFe2O4 octahedrons via an EDTA-assisted route. Journal of Magnetism and Magnetic Materials 305: 68-70.
- Houshiar M, Zebhi F, Razi ZJ, Alidoust A, Askari Z (2014) Synthesis of cobalt ferrite (CoFe2O4) nanoparticles using combustion, coprecipitation, and precipitation methods: A comparison study of size, structural, and magnetic properties. Journal of Magnetism and Magnetic Materials 371: 43-48.
- Baykal A, Deligöz H, Sozeri H, Durmus Z, Toprak MS (2012) Triethylene glycol stabilized CoFe2O4 nanoparticles. Journal of Superconductivity and Novel Magnetism 25: 1879-1892.
- Zhao D, Wu X, Guan H, Han E (2007) Study on supercritical hydrothermal synthesis of CoFe2O4 nanoparticles. The Journal of Supercritical Fluids 42: 226-233.
- Sivakumar M, Kanagesan S, Babu RS, Jesurani S, Velmurugan R, et al. (2012) Synthesis of CoFe2O4 powder via PVA assisted sol–gel process. Journal of Materials Science: Materials in Electronics 23: 1045-1049.
- Bortnic RA, Goga F, Mesaroş A, Nasui M, Vasile BS, et al. (2016) Synthesis of Cobalt Ferrite Nanoparticles Via A Sol-Gel Combustion Method. Studia Universitatis Babes-Bolyai, Chemia 61: 4.
- Yavuz CT, Prakash A, Mayo JT, Colvin VL (2009) Magnetic separations: from steel plants to biotechnology. Chemical Engineering Science 64: 2510-2521.
- Al-Nagaawy AM, Shalaby NI (2009) Efficiency of two agricultural wastes for removing copper and lead from wastewater. In Proceedings of the 2nd Global Fisheries and Aquaculture Research Conference, Cairo International Convention Center, 24-26 October, 2009. Massive Conferences and Trade Fairs, pp: 39-51.
- Mostafa KM, Samarkandy AR, El-Sanabary AA (2012) Harnessing of chemically modified rice straw plant waste as unique adsorbent for reducing organic and inorganic pollutants. International Journal of Organic Chemistry 2: 143.
- Parker C (1972) Water analysis by atomic absorption spectroscopy. Varian Techtron.
- Khandanlou R, Ahmad MB, Masoumi HR, Shameli K, Basri M, et al. (2015) Rapid adsorption of copper (II) and lead (II) by rice straw/Fe3O4 nanocomposite: optimization, equilibrium isotherms, and adsorption kinetics study. PloSONE 10: e0120264.
- Buasri A, Chaiyut N, Ponpatcharasakul N, Artsalee P, Potisook S (2007) Factors affecting the removal of copper (II) and zinc (II) from aqueous solutions with clinoptilolite. J Res Eng Technol 4: 1-7.
- Pehlivan E, Altun T, Parlayıcı S (2009) Utilization of barley straws as biosorbents for Cu2+ and Pb2+ ions. Journal of Hazardous Materials 164: 982-986.
- Nguyen TA, Ngo HH, Guo WS, Zhang J, Liang S, et al. (2011) Applicability of agricultural waste and by-products for adsorptive removal of heavy metals from wastewater. Bioresource Technology 148: 574-585.
- Ding Y, Jing D, Gong H, Zhou L, Yang X (2012) Biosorption of aquatic cadmium (II) by unmodified rice straw. Bioresource Technology 114: 20-25.
- Feng J, Zhang DD, Liu YF, Bai Y, Chen QD, et al. (2010) Magnetic nanofilm of Fe3O4 for highly efficient organic light-emitting devices. The Journal of Physical Chemistry C 114: 6718-6721.
- Sharma HB, Singh NG, Singh SB, Devi TH (2014) Synthesis and Characterization of Cobalt Ferrite (CoFe2O4) Nanoparticles by Sol-Gel Autocombustion Method. Invertis Journal of Science & Technology 7: 78-84.
- Wang X, Zhao C, Zhao P, Dou P, Ding Y, et al. (2009) Gellan gel beads containing magnetic nanoparticles: an effective biosorbent for the removal of heavy metals from aqueous system. Bioresource Technology 100: 2301-2304.
Citation: Alia AE, Salema WM, Younes SM, Elabdeen AZ (2018) Ferrite Nanocomposite (Rice Straw-CoFe2O4) as New Chemical Modified of for Treatment of Heavy Metal from Waste Water. Hydrol Current Res 10:311.
Copyright: © 2019 Alia AE, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
Select your language of interest to view the total content in your interested language
Share This Article
- Total views: 649
- [From(publication date): 0-0 - Nov 21, 2019]
- Breakdown by view type
- HTML page views: 576
- PDF downloads: 73