Article pubs.acs.org/IECR
Influence of Preparation Conditions on Characteristics, Reactivity, and Operational Life of Microsized Fe/Cu Bimetallic Particles Bo Lai,* Yun-Hong Zhang, Yue Yuan, Zhao-Yu Chen, and Ping Yang Department of Environmental Science and Engineering, School of Architecture and Environment, Sichuan University, Chengdu, Sichuan 610065, China S Supporting Information *
ABSTRACT: The effect of the preparation conditions on the physicochemical characteristics, operating life, and reactivity of Fe/Cu bimetallic particles was studied significantly by using a model pollutant (p-nitrophenol), scanning electron microscopy− energy dispersive spectrometry, and X-ray diffraction spectrometry. The results suggest that the higher reactivity and longer operating life of Fe/Cu bimetallic particles were obtained under the optimal preparation conditions. Furthermore, under the optimal preparation conditions, Cu was not easily dropped from the Fe0 particle, and the weight ratio of Cu on the surface of the Fe/Cu bimetallic particles increased significantly. Moreover, their optimal theoretical Cu mass loading could be decreased from 0.89 to 0.41 g Cu/g Fe, which favors the reduction of production costs. In addition, two batch experiments with Fe/Cu bimetallic particles prepared under optimal and nonoptimal conditions were set up to comparatively investigate the improvement of operating life and reactivity of Fe/Cu particles when optimized preparation conditions were carried out. As a result, it was proven that the reactivity and operating life of Fe/Cu bimetallic particles could be improved significantly through the optimization of preparation conditions.
1. INTRODUCTION In recent years, there has been increasing interest in the study of the degradation of toxic and refractory pollutants in industrial wastewater by zerovalent iron (ZVI), Fe/GAC, and Fe/Cu bimetallic systems, which are environmental physicochemical processes based on the in situ generation of Fe2+, atomic hydrogen (•H, anoxic conditions), or hydroxyl radical (•OH, oxic conditions).1−4 On one hand, under the anoxic conditions, both the newly generated Fe2+ and atomic hydrogen are strong reductants that could reduce the pollutants in wastewater.4−6 On the other hand, under the oxic conditions, the generated hydroxyl radical is the second strongest oxidant known after fluorine, with a high standard oxidation potential that can nonselectively mineralize the pollutants (i.e., overall conversion into CO2, H2O, and inorganic ions).7−10 ZVI and Fe/GAC systems have been used to treat toxic and refractory industrial wastewater including dye wastewater,8 pharmaceutical wastewater,11 pesticide wastewater,12 and ABS resin wastewater.13,14 Despite the widespread studies on these treatment technologies, their practical applications are still suffering from many limitations.14,15 Recently, it has been shown that the micron-scale Fe/Cu bimetallic particles prepared by planting Cu on the iron surface can significantly enhance the reduction rates of the pollutants.4,5 In our previous work, it was also proven that the planted Cu could improve the reactivity of Fe0 remarkably.6 Meanwhile, the reduction reactions with high efficiency occurred even in a much wider range of pH (3.0−9.0) when the p-nitrophenol (PNP) aqueous solution was treated by the prepared Fe/Cu bimetallic particles.6 Also, the Cu distributional characteristics on the surface of Fe0 significantly affected the reactivity of the prepared Fe/Cu bimetallic particles.5,6 Furthermore, the preparation conditions, such as temperature, mixing intensity, Cu 2+ © 2014 American Chemical Society
concentration, and pH, might have an influence on the distributional characteristics of Cu. Therefore, the reactivity of Fe/Cu bimetallic particles might be affected by the preparation conditions. In the previous studies, however, the effect of these preparation conditions was not studied yet. In other words, the previous preparation process of Fe/Cu bimetallic particles was too simple. In particular, after the CuSO4 solution was added to the iron particles, the slurry was mixed manually, and then the prepared Fe/Cu bimetallic particles were deposited, cleared, and dried.4−6 Therefore, it is necessary to investigate the effect of the preparation conditions on the reactivity of Fe/Cu bimetallic particles. In this study, PNP was used as a model pollutant to investigate the reactivity of Fe/Cu bimetallic particles that were prepared under different conditions. Also, the Cu distributional characteristics on the surface of Fe0 were observed by using scanning electron microscope (SEM) and energy dispersive spectrometry (EDS). Furthermore, the optimal preparation conditions were obtained based on the results of PNP removal efficiency and SEM-EDS analysis. Finally, the reactivity and operational life of Fe/Cu bimetallic particles prepared under optimal conditions were compared with those of Fe/Cu bimetallic particles prepared under nonoptimal conditions.
2. EXPERIMENTAL SECTION 2.1. Reagents. Zero valent iron powders, CuSO4 (analytical reagent), CuCl2 (analytical reagent), Na2SO4 (analytical reagent), and PNP (99%) from Chengdu Kelong chemical Received: Revised: Accepted: Published: 12295
April 29, 2014 July 13, 2014 July 22, 2014 July 22, 2014 dx.doi.org/10.1021/ie501756m | Ind. Eng. Chem. Res. 2014, 53, 12295−12304
Industrial & Engineering Chemistry Research
Article
Figure 1. Effect of preparation parameters on the reactivity of Fe/Cu bimetallic particles: (a) temperature, (b) Cu2+ concentration (CuSO4), (c) Cu2+ concentration (CuCl2), (d) pH of planting solution, (e) mixing speed, and (f) TMLCu.
(i.e., 1, 2, 3, 4, 6, 8, and 12 g/L). Meanwhile, to investigate the effect of copper salt, two typical copper salts (i.e., CuSO4 and CuCl2) were used to prepare planting solutions. Furthermore, under the above optimal conditions, the preparation processes were performed in the planting solutions with different initial pH (i.e., 3.0, 4.0, 4.6, and 5.0). Moreover, the effect of stirring speed (i.e., 100, 200, 250, 300, and 400 rpm) was further investigated under other optimal conditions. Additionally, under the above optimal conditions, the effect of TMLCu (i.e., 0.03, 0.05, 0.11, 0.24, 0.41, 0.62, 0.89, 1.26, and 1.81 g Cu/g Fe) was investigated. Finally, to observe the effect of the preparation conditions on the physicochemical characteristics of the prepared Fe/Cu bimetallic particles, these particles obtained under different preparation conditions were analyzed using SEM-EDS.
reagent factory were used in the experiment. The zerovalent iron powders have mean particle size of approximately 120 μm, and their iron content reaches approximately 97%. Other chemicals used in the experiment were of analytical grade. 2.2. Preparation of Fe/Cu Bimetallic Particles. The Fe/ Cu bimetallic particles were prepared through the Fe−Cu displacement reaction in aqueous solution, and the main preparation process was the same as that in our previous work.6 In this study, the main preparation conditions including temperature, mixing intensity, initial pH, Cu2+ concentration of planting solution, types of copper salt, and theoretical Cu mass loading (TMLCu) were optimized thoroughly. First, the Fe/Cu bimetallic particles were prepared under different temperatures (i.e., 25, 40, 55, 70, and 85 °C). Next, under the obtained optimal temperature, the Fe/Cu bimetallic particles were prepared under different Cu2+ concentrations 12296
dx.doi.org/10.1021/ie501756m | Ind. Eng. Chem. Res. 2014, 53, 12295−12304
Industrial & Engineering Chemistry Research
Article
Figure 2. Characteristics of the prepared Fe/Cu bimetallic particles under the optimal conditions: (a) SEM image of Fe/Cu bimetallic particles; (b) EDS spectrum of area in the purple frame of the SEM in panel a; (c) SEM image of Fe/Cu bimetallic particles; (d) EDS spectrum of area in the purple frame of the SEM in panel c; (e, f) EDS spectra of points 2 and 3 in the SEM in panel c. (Optimal conditions: temperature, 40 °C; mixing speed, 250 rpm; Cu2+ concentration, 3 g/L (CuSO4); TMLCu, 0.41 g Cu/g Fe; and pH of planting solution, 4.6.)
2.3. Batch Experiments. In the experimental process, PNP was used as a model pollutant to evaluate the reactivity of the prepared Fe/Cu bimetallic particles. A 500 mg/L PNP aqueous solution was prepared by simple dissolution in deionized water, filtered by the 0.45 μm glass fiber membranes, and stocked in amber bottles. The Na2SO4 as an electrolyte (50 mmol/L) was added into the PNP aqueous solution. Furthermore, the PNP stock solutions were not buffered, and the initial pH was adjusted to approximately 6.7. In each batch experiment, 6 g of Fe/Cu bimetallic particles and 300 mL of PNP aqueous solution (500 mg/L) were added into a 500 mL beaker and the slurry was stirred by a mechanical stirrer with a stirring speed of 400 rpm. The whole experiment process was performed at a running temperature of 25 ± 1 °C
through water bath heating. Then, the Fe/Cu bimetallic particles obtained under different preparation conditions were used to treat the 500 mg/L PNP aqueous solution at the same operating conditions. The reactivity of the prepared Fe/Cu bimetallic particles could be evaluated through the PNP removal efficiencies. Samples (1 mL) were taken at 5 min intervals for 30 min, diluted by deionized water, and filtered through a PTFE syringe filter disc (0.45 μm). Finally, the PNP concentration of the influent and effluent were measured by reversed-phase high-performance liquid chromatography (HPLC) chromatography (Agilent, U.S.). 2.4. Analytical Methods. The concentration of PNP in the samples was achieved by reversed-phase HPLC chromatography (Agilent U.S.) equipped with the Eclipse XDB C-18 (5 12297
dx.doi.org/10.1021/ie501756m | Ind. Eng. Chem. Res. 2014, 53, 12295−12304
Industrial & Engineering Chemistry Research
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Figure 3. Operating life of the Fe/Cu bimetallic particles prepared under optimal or nonoptimal conditions: (a) optimal conditions, (b) nonoptimal conditions, and (c) correlation of kobs and number of batch experiments. (Optimal conditions: temperature, 40 °C; mixing speed, 250 rpm; Cu2+ concentration, 3 g/L (CuSO4); TMLCu, 0.41 g Cu/g Fe; and pH of planting solution, 4.6. Nonoptimal conditions: temperature, 25 °C; mixed by hand; Cu2+ concentration, 8 g/L (CuSO4); TMLCu, 0.41 g Cu/g Fe; and pH of planting solution, 4.5.)
min−1 when the preparation temperature increased from 25 to 40 °C. The kobs decreased gradually from 0.08821 to 0.06203 min−1 when the preparation temperature further increased from 40 to 85 °C. The results suggest that the optimal preparation temperature was 40 °C, as the lower or higher preparation temperature would be unfavorable to the reactivity of Fe/Cu bimetallic particles. In the literature, it is noted that the accelerating temperature usually could enhance the masstransfer rate and overcome the activation energy barrier to improve the heterogeneous chemical reaction at the surface or the diffusion of reactant and product.19−22 Therefore, the displacement reaction rate between Fe0 and Cu2+ could be accelerated significantly with the preparation temperature increase. Subsequently, the high or low displacement reaction rate might have a negative effect on the distribution of Cu on the surface of Fe0 particles, which would limit the reactivity of Fe/Cu bimetallic particles. 3.2. Effect of Cu2+ Concentration. Previous authors usually used CuCl2 or CuSO4 to support Cu2+ for the displacement reaction.17,23,24 However, the Fe−Cu displacement reaction rate might be affected by Cu2+ concentration and type of copper salt, which would indirectly affect the Cu distribution characteristics on the surface of Fe0. Figure 1b shows that high kobs (0.10754−0.11858 min−1) were obtained when the Cu2+ concentration of planting solution was below 3 g/L. kobs decreased sharply from 0.11858 to 0.02272 min−1 when the Cu2+ concentration of planting solution increased from 3 to 12 g/L. The results suggest that the reactivity of the
μm, 250 × 4.6 mm2).6 The surface morphologies and elementary composition of the prepared Fe/Cu bimetallic particles were observed by an S-3500N scanning electron microscope (Hitachi, Japan) and an energy dispersive spectrometer (Oxford Instruments).16 On the basis of the elemental composition analysis of the prepared Fe/Cu bimetallic particles by EDS, its compound composition was further investigated by X-ray diffraction (XRD) analysis.6,16 2.5. Kinetics Analysis. The removal efficiency of PNP in aqueous solution by the Fe/Cu bimetallic system was treated by a pseudo-first-order equation: ln
C = −Kobst C0
(1)
where C0 is the initial concentration of PNP in aqueous solution (mg/L), C the residual PNP concentration in aqueous solution after the treatment (treatment time is t), kobs the measured rate constant (min−1), and t the treatment time (min). The kobs were calculated by the method of linear regression.
3. RESULTS AND DISCUSSION 3.1. Effect of Preparation Temperature. In previous work, the preparation process of Fe/Cu bimetallic particles usually was performed at room temperature (25 ± 3 °C),4,17,18 and the effect of preparation temperature on the reactivity of Fe/Cu bimetallic particle has not yet been investigated. Figure 1a shows that kobs increased sharply from 0.04842 to 0.08821 12298
dx.doi.org/10.1021/ie501756m | Ind. Eng. Chem. Res. 2014, 53, 12295−12304
Industrial & Engineering Chemistry Research
Article
Figure 4. Characteristics of Fe/Cu bimetallic particles after 5 batch experiments. (a) SEM image of Fe/Cu bimetallic particles prepared under optimal conditions. (b) EDS spectrum of area in the purple frame of the SEM in panel a. (c) SEM image of Fe/Cu bimetallic particles prepared under nonoptimal conditions. (d) EDS spectrum of area in the purple frame of the SEM in panel c. (e) SEM image of casting of the Fe/Cu prepared under nonoptimal conditions. (Optimal and nonoptimal conditions are the same as those in Figure 3).
favorable to the Cu deposition on the surface of Fe0. (b) Cl− could significantly accelerate the corrosion rate of Fe0,25,26 and the rapid corrosion of Fe0 was harmful to the Cu deposition on the surface of Fe0. Therefore, the reactivity of Fe/Cu bimetallic particles prepared by using CuSO4 was much higher than that prepared by using CuCl2 when the Cu2+ concentration of the planting solution was below 3 g/L. 3.3. Effect of Initial pH of the Planting Solution. Figure 1d indicates the effect of initial pH of the planting solution on the PNP degradation by the prepared Fe/Cu bimetallic particles. It is clear that kobs of the PNP degradation increased gradually from 0.09381 to 0.11858 min−1 with increasing pH from 3.0 to 4.6. Then it decreased to 0.10910 min−1 when the pH further increased to 5.0. When the pH was above 5.0, Cu2+ precipitated in the form of Cu(OH)2. Therefore, the effect of the higher pH (>5.0) was not be investigated in this study. Additionally, the Fe−Cu reaction time increased rapidly from 1.7 to 6.5 min with increasing pH from 3.0 to 5.0. The results suggest that the decrease of the initial pH of the planting
prepared Fe/Cu bimetallic particles would be improved by using a lower Cu2+ concentration planting solution (3 g/ L) would significantly decrease its reactivity. Figure 1c shows the effect of CuCl2 on the reactivity of Fe/ Cu bimetallic particles. Their kobs maintained between 0.05642 and 0.08112 min−1 when the Cu2+ concentration increased from 1 to 12 g/L. It is clear that if the Fe/Cu bimetallic particles were prepared at a lower Cu2+ concentration (
