Arabian Journal of Chemistry (2013) xxx, xxx–xxx
King Saud University
Arabian Journal of Chemistry www.ksu.edu.sa www.sciencedirect.com
SPECIAL ISSUE: ENVIRONMENTAL CHEMISTRY
Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems Kumars Seifpanahi Shabani a,*, Faramarz Doulati Ardejani a, Khashyar Badii b, Mohammad Ebrahim Olya b a b
Faculty of Mining, Petroleum and Geophysics, Shahrood University of Technology, Shahrood, Iran Department of Environment, Institute for Color Science and Technology, Tehran, Iran
Received 1 April 2013; accepted 1 December 2013
KEYWORDS Diatomite; Perlite; Mineral nanoparticles; Heavy metals adsorption; Aqueous solution
Abstract Results of studies of the sorption activity of diatomite nanoparticles, diatomite–perlite composite nanoparticles and perlite nanoparticles that was provided from internal resource at Iran, with respect to Fe(II), Cu(II), Mn(II) and Cr(III) ions are presented. Thus, diatomite nanoparticles, diatomite–perlite composite nanoparticles and perlite nanoparticles were modified and prepared via particle size decreasing and characterized by XRD, XRF, BET, SEM, TEM and FT-IR. In the batch system the influence of pH, adsorbent dosage, temperature and ions initial concentration was investigated. The results of isotherm and kinetics studies show that the Langmuir isotherm and pseudo-second order kinetic showed better correlation with the experimental data. Calculations of thermodynamic parameters show the negative DG values or spontaneous reaction, the enthalpy (DH) change shows the endothermic process and values of DS indicate low randomness at the solid/solution interface during the uptake of ions. Finally, three adsorbents were packed inside a glass column as a continuous system and the breakthrough curves were obtained. All results show that the ion affinity to adsorption onto adsorbents is as follows: Cu(II) > Fe(II) > Mn(II) > Cr(III). So, these abundant, locally available cheap minerals showed a greater efficiency for the removal of metal ions from the aqueous solution, also can be utilized for other water pollutants. Crown Copyright ª 2013 Published by Elsevier Ltd. All rights reserved.
1. Introduction * Corresponding author. Tel.: +98 9187807644. E-mail address:
[email protected] (K. Seifpanahi Shabani). Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
Contamination of water by heavy metals is a global problem (Danil de Namor et al., 2012) accordingly nowadays everybody knows that heavy metal ions consist of iron, lead, manganese, zinc, copper, chromium, nickel and so on that lead to many problems for human and water environment. In the environment two main sources of heavy metals are natural
1878-5352 Crown Copyright ª 2013 Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.arabjc.2013.12.001 Please cite this article in press as: Seifpanahi Shabani, K. et al., Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.12.001
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background derived from parent rocks and anthropogenic contamination, including mineral industrial wastes, Agrochemicals and other output of industrial activities and factories (Li et al., 2012). Several conventional methodologies such as precipitation (Martins et al., 2010), ion exchange (Yuan et al., 2010), filtration membrane technology (Song et al., 2011), electrochemical processes (Karami, 2013) and adsorption process (Chiban et al., 2011) are available for heavy metal removal and other pollutants from wastewaters. Generally, they are expensive or ineffective sometimes, especially when the metal concentration is higher than 100 mg/l (Miretzky et al., 2006; Schiewer and Volesky, 1995). Among all the treatments proposed, adsorption using sorbents is one of the most popular methods. It is now recognized as an effective, efficient and economic method for water decontamination applications and for separation for pilot purpose (Niu et al., 2007). Nowadays, the adsorption of pollutants by natural materials has been widely reported such as diatomite (Caliskan et al., 2011), perlite (Ghassabzadeh et al., 2010), red mud (Lopes et al., 2012), chitosan (Kyzas et al., 2013), orange skin (Lugo-Lugo et al., 2012), soy meal hull (Badii et al., 2008), almond skin (Doulati Ardejani et al., 2008), sawdust (Pehlivan and Altun, 2008), zeolite (Egashira et al., 2012) and clay (Sheikhhosseini et al., 2013). These adsorbents have a natural base and they are environmentally friendly and it is possible to regenerate most of them or be applied in different products, but less researches have focused on metal ions adsorption by natural mineral adsorbents with nano size particles. The comparison of adsorption capacity of different adsorbents for different ion sorption was showed in Table 1. Based on Table 1 we can see that these adsorbents have a suitable adsorption capacity in adsorption process. The results of evaluating the performance of nano-mineral with other materials reported in the literature show that nanominerals have a higher performance than raw or natural minerals, because of particle size reduction and increase in the surface area of particles and also more adsorption. So, the objective of the present study is focused on the development of diatomite and perlite nanoparticles separately and as composite for removal of four heavy metal ions Fe(II), Mn(II), Cu(II) and Cr(III) ions that because of their environmental significance were selected. Iron is a vital ion for human but its existence at water resource in higher than the standard concentration (0.3 mg/l (USEPA, 2012)) leads to many problems that were reported by researchers already (Das et al., 2007; Songyan et al.,
Table 1
2009; Tekerlekopoulou and Vayenas, 2007). Manganese is another metal found in wastewaters that its concentration in the discharging water must be less than the standard values (0.05 mg/l) to prevent the death of living organisms (USEPA, 2012). Copper is one of the applicable metals in the industry which is considered as a potential source of surface and groundwater contamination (Seifpanahi Shabani et al., 2011). Copper is one of the biologically essential ions but is only required at low concentrations and concentrations higher than 1.3 mg/l (USEPA, 2012) in water lead to environmental and health problems (Danil de Namor et al., 2012). Chromium compounds are extensively used in many industrial processes such as tanning, plating, dyeing, refractory technologies and others. The presence of chromium species in higher than 0.1 mg/l concentration (USEPA, 2012) in water has serious environmental implications and consequently produces a detrimental effect on human health (Guru et al., 2008). The use of diatomite and perlite mineral adsorbents for the removal of heavy metal ions particularly Cu(II) and Cr(III) ions from water have been the subject of numerous publications in recent years (see Table 2). In view of that potentially low cost materials for the sorption of heavy metals have been discussed. The present study is focused on the development, modification and preparation of diatomite and perlite nanoparticles separately and as composite with equal ratio for removal of Fe(II), Mn(II), Cu(II) and Cr(III) ions. So, in the batch system the effects of pH, adsorbent dosage, initial concentration and temperature on the adsorption capacity were investigated. Since optimization of parameters, the characterization of isothermal adsorption and adsorption kinetics was also studied in order to provide a new method and theoretical evidences for wastewater treatment. Also, the column of adsorbent was tested for all ions and obtaining the breakthrough curves. Finally, thermo-dynamic parameters of adsorption process were considered. 2. Materials and methods 2.1. Materials In this research the raw diatomite and raw perlite samples were obtained from internal sources, Zanjan mine at North West of Iran (Fig. 1). All other chemicals consist of sodium hydroxide, chloridric acid, iron (II) chloride, manganese (II) sulfate, copper (II) chloride and potassium dichromate were purchased from Merck Company.
Comparison of adsorption capacity (mg g1) of different adsorbents for different ion sorption.
Adsorbent
Ion
Adsorption capacity (mg g1)
Refs.
Diatomite Perlite Red Mud Chitosan Orange Skin Soy Meal Hull Almond Skin (mixture, external and internal shells) Sawdust Zeolite Clay
Zn(II) Ag(I), Cu(II) and Hg(II) As(V) Cr(VI) and As(V) Cr(III) and Fe(III) Direct dye Direct Red 80 dye
3.2 8.46, 1.95 and 0.35 3.3 175 and 208 9.43 and 18.19 15.3 20.5, 16.96 and 16.4
Caliskan et al. (2011) Ghassabzadeh et al. (2010) Lopes et al. (2012) Kyzas et al. (2013) Lugo-Lugo et al. (2012) Badii et al. (2008) Doulati Ardejani et al. (2008)
Cr(VI) Cu(II), Zn(II) and Mn(II) Ni(II), Cd(II), Zn(II) and Cu(II)
8.01 11.3, 3.7 and 6.11 2.7, 2.9, 3.6 and 10.53
Pehlivan and Altun (2008) Egashira et al. (2012) Sheikhhosseini et al. (2013)
Please cite this article in press as: Seifpanahi Shabani, K. et al., Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.12.001
Preparation and characterization of nano-mineral for removal of heavy metals Table 2
3
Summary of adsorption of heavy metal ions on natural diatomite and natural perlite.
Adsorbent
Ion
Refs.
Raw diatomite
Cr(III) Cu(II) Cu(II), Pb(II) and Zn(II) Cr(III) Cr(III) Cr(III) Cu(II) Cu(II) U Zn(II) Pb(II)
De Castro Dantas et al. (2001) Tengjaroenkul et al. (2004) Murathan and Benli (2005) Guru et al. (2008) Puszkarewicz (2009) Li et al. (2009) Thippraphan et al. (2010) Sljivic et al. (2010) Sprynskyy et al. (2010) Caliskan et al. (2011) Knoerr et al. (2011)
Raw perlite
Cu(II) Cd(II) Cu(II) and Pb(II) Cu(II) Cu(II), Co(II) and Ni(II) Ag(I), Cu(II) and Hg(II) As(V)
Alkan and Dogan (2001) Mathialagon and Viraraghavan (2002) Sari et al. (2007) Hasan et al. (2008) Swayampakula et al. (2009) Ghassabzadeh et al. (2010) Thanh et al. (2011)
Nanodiatomite Nanoperlite
Fe(II), Mn(II), Cu(II) and Cr(III) Fe(II), Mn(II), Cu(II) and Cr(III)
This study This study
Table 3 The chemical analysis of modified DNPs, DPCNPs and PNPs.
Figure 1 Diatomite and perlite reservoirs in the Zanjan mines, North West of Iran.
Constituent
DNPs (wt.%)
DPCNPs (wt.%)
PNPs (wt.%)
SiO2 K2O Al2O3 Na2O Fe2O3 CaO ZrO2 MgO SO3 TiO2 MnO2
65.88 4.42 21.36 0.30 3.03 3.24 0.06 0.34 0.57 0.80 0.0
60.98 12.39 19.54 1.37 2.74 1.88 0.09 0.29 0.37 0.28 0.07
56.87 17.70 18.36 2.61 2.53 0.96 0.19 0.20 0.27 0.17 0.13
Thanh et al., 2011). So, raw diatomite and raw perlite were washed five times with deionized water and then dried at 100 C for 8 h. Next the samples were crushed by the laboratory planetary ball mill (Fritsch Pulverisette 6 model) consisting of distilled water in 250 RPM for 5 h. Finally, slurry samples were dehumidifying by spray dryer (B-290 model) in 180 C and prepared for characterization and investigation of the adsorption processes. 2.3. Adsorbent characterization
2.2. Adsorbent modification In assessing the potential applications of diatomite and perlite as nanoparticles for the removal of heavy metal ions from aqueous solution, the modification of the material is an important issue to address. A variety of methodologies can be used to modify the diatomite and perlite surface such as calcination (Ediz et al., 2010; Ghassabzadeh et al., 2010; Jing et al., 2011), and functionalization (Fowler et al., 2007;
The chemical composition of the modified diatomite nanoparticles (DNPs), diatomite–perlite composite nanoparticles (DPCNPs) and modified perlite nanoparticles (PNPs) which were determined by XRF (XRF-1800 model) is given in Table 3. DNPs, DPCNPs and PNPs are mainly composed of silica as SiO2. The hydroxyl species and acid sites on DNPs, DPCNPs and PNPs surfaces and hydroxyl species on perlite structure were
Please cite this article in press as: Seifpanahi Shabani, K. et al., Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.12.001
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identified as a function of adsorption process. Thus various hydroxyl species including isolated hydroxyl groups, H-bonded hydroxyl groups and water uptake have been identified for diatomite and perlite. In addition, acid sites found on the diatomite surface generally result from clay impurities present in diatomaceous earth (Yuan et al., 2004). Generally, hydroxyl groups are classified according to their coordination with the silicon atom that is shown in Fig. 2. The BET (Quantachrome 2200e model) specific surface area analysis was done for DNPs, DPCNPs, PNPs, raw diatomite and raw perlite. The specific surface areas of DNPs, DPCNPs, PNPs, raw diatomite and raw perlite are shown in Table 4. According to Muller (2010) research the increase in surface area by decreasing the particle size of the diatomite and perlite resulted in a higher uptake of heavy metal ions by the smaller particles relative to the larger ones. X-ray diffraction (XRD) patterns for DNPs, DPCNPs and PNPs were obtained by XMD300-Unisantis X-ray diffractometer that are shown in Fig. 3. Scanning electron microscopy (SEM) LEO-1455VP model was used to study the morphology and homogeneity of the DNPs, DPCNPs and PNPs. The SEM images in Fig. 4 show the pristine DNPs and DPCNPs and pure PNPs, respectively. Fig. 4(A) shows that pure DNPs were spherical in shape that are arranged closely with an average diameter of Mn(II) > Fe(II) > Cu(II), implying that, temperature has a more important influence on Cr(III)-Mn(II)-Fe(II)-Cu(II) uptake, respectively. The positive low values of DS indicate low randomness at the solid/solution interface during the uptake of Fe(II), Mn(II), Cu(II) and Cr(III) onto DNPs, DPCNPs and PNPs adsorbents. Since, DH > 0 and DS > 0, thus enthalpy and entropy are unfavorable and favorable agent, respectively, scilicet entropy cause to the adsorption processes was done to more adsorption and enthalpy cause to the adsorption processes was done to less adsorption. So, theses adsorption processes are bilateral and can be done spontaneously. Also, at the reactions that enthalpy and entropy are inversely, the temperature is determinant agent, hence at higher temperatures the entropy is predominant agent and at lower temperatures the enthalpy is effective agent.
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Table 9 The values of parameters obtained from different kinetic models for the adsorption of Fe(II), Mn(II), Cu(II) and Cr(III) ions onto DNPs, DPCNPs and PNPs adsorbents. Adsorbent
DNPs
Kinetic model
Pseudo-first order
Pseudo-second order
Intra-particle diffusion model
DPCNPs
Pseudo-first order
Pseudo-second order
Intra-particle diffusion model
PNPs
Pseudo-first order
Pseudo-second order
Intra-particle diffusion model
Parameters
Ions Fe(II)
Mn(II)
Cu(II)
Cr(III)
K1 (min ) qe (mg g1) R2 K2 (g mg1 min1) qe (mg g1) R2 Ki R2 qe Exp. (mg/g)
0.023 8.254 0.983 0.005 12.5 0.993 2.361 0.992 12.48
0.03 12.86 0.983 0.011 12.2 0.999 2.82 0.985 12.11
0.018 799.1 0.948 0.007 26.316 0.992 9.347 0.975 26.301
0.012 0.017 0.902 0.0001 3.05 0.997 0.446 0.912 3.01
K1 (min1) qe (mg g1) R2 K2 (g mg1 min1) qe (mg g1) R2 Ki R2 qe Exp. (mg/g)
0.039 0.117 0.984 0.013 7.63 0.986 0.696 0.992 7.60
0.042 0.024 0.916 0.023 7.25 0.966 0.853 0.916 7.21
0.042 0.484 0.842 0.017 13.9 0.932 1.24 0.842 13.82
0.01 1.45*E-7 0.133 0.103 1.6 0.957 0.155 0.957 1.57
K1 (min1) qe (mg g1) R2 K2 (g mg1 min1) qe (mg g1) R2 Ki R2 qe Exp. (mg/g)
0.023 0.0035 0.931 0.024 5.39 0.985 0.419 0.947 5.34
0.025 0.011 0.988 0.026 4.37 0.998 0.42 0.99 4.34
0.048 0.004 0.952 0.041 5.40 0.996 0.469 0.927 5.38
0.007 4.9*E-12 0.174 0.483 1.25 0.997 0.134 0.957 1.23
1
Figure 14 The mass transport of ions and concentration profile of adsorbent (Choy et al., 2004).
2.4.2. Continuous mode adsorption studies After characterization, preparation and batch mode adsorption studies, the three adsorbents were packed inside a glass column, where it was used for the adsorption/removal of Fe(II), Mn(II), Cu(II) and Cr(III) ions from aqueous solution. A schematic view of glass column is shown in Fig. 17. The length and diameter of glass column are 20 and 2 cm, respectively. A known amount of three nanoadsorbents was
packed inside a glass column separately and Fe(II), Mn(II), Cu(II) and Cr(III) ion solutions were allowed to flow inside the column with a certain flow rate. The metal ion concentration was determined before and after the treatment using atomic absorption spectroscopy (PG-990 model). So, the column of adsorbent was tested for all ions and obtaining the breakthrough curves. The breakthrough curves that are obtained for Fe(II), Mn(II), Cu(II) and Cr(III) ions adsorption by DNPs, DPCNPs and PNPs adsorbents are shown in Fig. 18. In the breakthrough curve if Cinlet (ion concentration at the inlet) = Coutlet (ion concentration at the outlet), then the saturation of adsorbent at column is occurring. The saturation time for ions adsorption onto DNPs, DPCNPs and PNPs are shown in Table 11. The following discussion is the results of the illusion of metal ions using three types of adsorbents at temperature 25 C. Elution of the metal ions did not occur at the same rate (Table 5). The results show that the ease of selection of ions through the adsorption column depends on the metal – OH bond stability. Metal ions weakly retained by the adsorbents eluted first and strongly retained metal ions eluted last, as expected (Fig. 18). The elution profile for Fe(II), Mn(II), Cu(II) and Cr(III) ions and DNPs, DPCNPs and PNPs adsorbents are presented in Fig. 18. The results show that elution values for Cu(II), Fe(II), Mn(II) and Cr(III) ions for DNPs, DPCNPs and PNPs adsorbents are (169, 137, 117 and 69), (148, 105, 101 and 64) and (131, 119, 87 and 53), respectively. So, similar
Please cite this article in press as: Seifpanahi Shabani, K. et al., Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.12.001
Preparation and characterization of nano-mineral for removal of heavy metals
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Figure 15 Sorption of Fe(II), Mn(II), Cu(II) and Cr(III) ions onto DNPs, DPCNPs and PNPs as a function of square root of time for intra-particle diffusion rate constant determination (metal ion concentration, pH, adsorbent dos base on Table 5 at T: 25 C).
Figure 16 Boyd plot for the adsorption of Fe(II), Mn(II), Cu(II) and Cr(III) ions onto DNPs, DPCNPs and PNPs: (metal ion concentration, pH, adsorbent dos base on Table 5 at T: 25 C).
batch state, in continuous stat DNPs > DPCNPs > PNPs and adsorption processes for ions as Cu(II) > Fe(II) > Mn(II) > Cr(III). Also, in Table 12 we can see that the removal percent of ions after 100 min at the glass column that was adsorbed on nano minerals is as follow:
2.4.3. Reusing the adsorbents Reusing the DNPs, DPCNPs and PNPs is an important factor which aims to utilize the adsorbent in wastewater treatment. So, in this paper we collected the three utilized adsorbents and firstly were washed with NaCl 1 M for 2 h, then the NaCl/adsorbent mixture was filtered. Secondly the adsorbent
Please cite this article in press as: Seifpanahi Shabani, K. et al., Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.12.001
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Table 10 Values of thermodynamic parameters for the adsorption of Fe(II), Mn(II), Cu(II) and Cr(III) ions on DNPs, DPCNPs and PNPs adsorbents. Adsorbent
Ion
DH (kJ mol1)
DS (J mol1 K1)
DG (kJ mol1) 298.15 K
318.15 K
338.15 K
DNPs
Fe(II) Mn(II) Cu(II) Cr(III)
0.2079 0.2744 0.0831 0.74
0.0249 0.0249 0.0333 0.0748
7.2290 9.8327 7.1625 17.0368
7.7279 10.4979 7.6614 18.2009
8.2268 11.1630 8.1603 19.3649
DPCNPs
Fe(II) Mn(II) Cu(II) Cr(III)
0.5571 0.5238 0.1247 1.2222
0.0249 0.0249 0.0333 0.1081
6.9131 9.7912 6.8798 19.4742
7.4120 10.4563 7.3787 20.8045
7.9108 11.1215 7.8776 22.1349
PNPs
Fe(II) Mn(II) Cu(II) Cr(III)
2.2615 0.8315 0.1663 2.8602
0.0333 0.0333 0.0333 0.1829
9.0844 9.7496 7.6543 51.0523
9.7496 10.4147 8.3195 54.5444
10.4147 11.0799 8.9846 58.0365
Metal Ion Solution
Inlet
Frits
Adsorbent = 20cm
Outlet
Figure 17 DNPs, DPCNPs and PNPs adsorbents packed inside a glass column.
was washed with NH4OH 1 M for 2 h. Finally after filtration for expelling the NHþ 4 that sits on the OH function, the adsorbent was washed with deionized water and then heated in 300 C for 2 h. This work has been done four times for three adsorbents after using and the adsorption process was considered for Fe(II), Mn(II), Cu(II) and Cr(III) ions. The results of DNPs, DPCNPs and PNPs reusing Fe(II), Mn(II), Cu(II) and Cr(III) ions for adsorption are shown in Fig. 19.
According to Fig. 19 the adsorption of Fe(II), Mn(II), Cu(II) and Cr(III) ions by reactivating DNPs, DPCNPs and PNPs for four times kind of decreased that is due to reduction of the adsorbents specific surface area because of coagulation and agglomeration of adsorbent particles and the lack of quite clean absorbent that was collected and reactivated from previous steps. 3. Conclusions The surface properties and potential use of diatomite nanoparticles (DNPs), diatomite-perlite composite nanoparticles (DPCNPs) and perlite nanoparticles (PNPs) as a sorbent for iron (II), manganese (II), copper (II) and chromium (III) were studied. Thus, DNPs, DPCNPs and PNPs that were prepared from internal resource (Zanjan mine, North West of Iran) firstly were modified and then characterized by XRD, XRF, SEM, TEM, FT-IR and BET analysis. XRD and XRF show that the main component is SiO2 (Nearly 60%). The FT-IR shows the positive effect of the OH function in SiO2, also Fig. 6 shows the FT-IR spectra of DNPs, DPCNPs and PNPs before and after Fe(II), Mn(II), Cu(II) and Cr(III) ions adsorption processes it is obvious that the band B5 has OH weaken after Fe(II), Mn(II), Cu(II) and Cr(III) ions adsorption processes than before adsorption that is due to OH function saturating by Fe(II), Mn(II), Cu(II) and Cr(III) ions. The BET shows specific surface area 119.5 m2/gr for DNPs, 102.1 m2/gr for DPCNPs, 89.7 m2/gr for PNPs, 8.3 m2/gr for raw diatomite, and 3.5 m2/gr for raw perlite. In the batch mode after parameters optimization, the results of isotherm and kinetic studies show that the Langmuir isotherm and pseudo-second order kinetic have a good correlation with adsorption processes. Also, the maximum adsorption values for DNPs, DPCNPs and PNPs for Fe(II), Mn(II), Cu(II) and Cr(III) ions is as: 111.11, 100, 142.857, 33.2, 21.739, 15.625, 83.33, 1.718, 16.667, 11.111, 15.152 and 1.427, respectively. According to Fig. 15 the intra-particle/pore diffusion is not the singular rate-limiting step in the adsorption process. The initial curved part is attributed to boundary layer (film) diffusion, the linear, to the intra-particle diffusion and chemical reaction. From Fig. 16, it was observed that the plots were linear but do not
Please cite this article in press as: Seifpanahi Shabani, K. et al., Preparation and characterization of novel nano-mineral for the removal of several heavy metals from aqueous solution: Batch and continuous systems. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.12.001
Preparation and characterization of nano-mineral for removal of heavy metals
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Figure 18 The breakthrough curves of Fe(II), Mn(II), Cu(II) and Cr(III) ions adsorption by DNPs (- - - -), DPCNPs (...) and PNPs (––––) for pH = 3.2 and time 180 min, at three different flow rates (flow rate = 1 mL/min = , flow rate = 3 mL/min = , flow rate = 5 mL/min = d).
Table 11 The saturation time of adsorbent at columns for Fe(II), Mn(II), Cu(II) and Cr(III) ions adsorption onto DNPs, DPCNPs and PNPs adsorbent, optimal pH, temperature 25 K and concentration according to Table 5. Adsorbent
Ion
Flow rate (ml/min)
Saturation time (min)
DNPs
Fe(II) Mn(II) Cu(II) Cr(III)
1 3 5 1
137 117 169 69
DPCNPs
Fe(II) Mn(II) Cu(II) Cr(III)
3 5 1 3
105 101 148 64
PNPs
Fe(II) Mn(II) Cu(II) Cr(III)
5 0.5 1 1.5
119 87 131 53
pass through the origin, suggesting that the adsorption process is controlled by film diffusion. It can be assumed that the diffusion of the solute inside the DNPs, DPCNPs and PNPs is more important for the adsorption rate than the external mass transfer. So we can say that the Fe(II), Mn(II), Cu(II) and Cr(III) ions removal process involving DNPs, DPCNPs and PNPs follows the pseudo-second order model, with the intraparticle diffusion as the limiting factor. Calculations of thermodynamic parameters show that the negative DG values at three different temperatures suggest that the sorption of all metal ions was spontaneous. Change in DH for all ions show the endothermic process, as ion uptake increased with increase in temperature. Values of DS indicate low randomness at the solid/solution interface during the uptake of both for all ions
Table 12 The removal percent of ions after 100 min at the glass column. Ion
Flow rate mL/min
PNPs
DPCNPs
DNPs
Fe(II)
1 3 5
3.9 0 0
18.46 0 0
51.39 12.83 0
Mn(II)
1 3 5
0 0.2 0
8.5 0 0
27.8 4.45 0
Cu(II)
1 3 5
55.83 12.68 0
55.16 18.19 0
71.84 49.84 7.18
Cr(III)
1 3 5
0 0 0
0 0 0
0 0 0
by adsorbents. In the long run, the DNPs, DPCNPs and PNPs nanoparticles were packed inside a glass column and used for the removal of four ions from aqueous solution in several flow rates and obtaining the breakthrough curves. After reusing the adsorbents the adsorption of Fe(II), Mn(II), Cu(II) and Cr(III) ions by reactivating DNPs, DPCNPs and PNPs for four times kind of decreased that is due to reduction of the adsorbents specific surface area because of coagulation and agglomeration of adsorbent particles and the lack of quite clean absorption sites of adsorbents that were collected and reactivated from previous steps. All results show that the ion affinity to adsorption onto adsorbents is as follows: Cu (II) > Fe (II) > Mn (II) > Cr (III). Also, the results show that the affinity of adsorption for three adsorbents is DNPs > DPCNPs > PN Ps. The high selectivity in the bonding of iron (II), manganese
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Figure 19
Reusing the DNPs, DPCNPs and PNPs for Fe(II), Mn(II), Cu(II) and Cr(III) ions adsorption.
(II), copper (II) and chromium (III) suggests that DNPs, DPCNPs and PNPs may be useful for removal of these toxic heavy metal ions and probably other heavy metal ions from wastewaters. This ability can be explored in treatment technologies since diatomite and perlite are cheap, abundant, and locally available resources.
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