Performance and mechanism of the amino methylene phosphonic acid chelating resin (D418) for the efficient removal of Cu(II)
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摘要: 为阐明氨基磷酸螯合树脂(D418)在水体中高效去除Cu(II)的作用机制，通过吸附实验系统考察了pH、离子强度、接触时间、温度等因素对D418树脂去除Cu(II)的影响，并通过吸附动力学模型、等温吸附模型和位点能量分布理论分析其去除机制。研究结果表明：Cu(II)溶液初始pH=9.00时，Cu(II)最大去除率达到97.20%，且Zeta电位变化对Cu(II)去除率影响符合Boltzmann模型。离子强度在0~0.10 mol/L增加，有利于促进D418树脂去除Cu(II)。根据线性相关系数大小比较，D418树脂吸附Cu(II)过程最符合颗粒内扩散模型和Sips模型。以Sips模型计算热力学参数和吸附位点能量分布，D418树脂对Cu(II)的去除为自发进行的吸热过程。Cu(II)先占据D418树脂高能量位点，再占据低能量位点。基于XPS和FTIR数据分析，D418树脂去除Cu(II)的机制主要是静电吸引、化学沉淀和内层络合作用。Abstract: In order to elucidate the adsorption mechanism of the amino methylene phosphonic acid chelating resin (D418) with high efficiency for removal of Cu(II) from wastewater, the influence of pH, ionic strength, contact time and temperature were detailly investigated by adsorption experiment. Meanwhile, adsorption kinetics, adsorption isotherms and site energy distribution theory were used to explain the removal mechanism of Cu(II) on the D418 resin. The results demonstrate that the optimal removal rate of Cu(II) on the D418 resin reaches to 97.20% at the initial pH=9.00, and the change of zeta potential on the influence of removal rate is well compatible with Boltzmann model. Furthermore, the removal efficiency of Cu(II) increases with the ionic strength at the range of 0-0.10 mol/L. According to the comparisons of the linear correlation coefficient values, the data of the adsorption kinetics fits well to the intra-particle diffusion while isotherm model data fits well to the Sips model. Based on the Sips model, the isotherm parameters and the energy distributions of adsorption sites were also conducted, and the result shows that the process of the Cu(II) adsorption on the D418 resin is spontaneous and endothermic. Cu(II) is preferentially adsorbed to the high- energy sites and to the low-energy sites. Based on the XPS and FTIR analysis, the adsorption mechanism of the Cu(II) ions is mainly attributed to the electrostatic interaction, the chemical precipitation and the inner-sphere complexation.
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Key words:
- Cu(II) /
- chelate resins /
- adsorption /
- model /
- site energy distribution
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图 1 氨基磷酸螯合(D418)树脂实物光学照片 (a)、XRD图谱和SEM图像 (b)
Figure 1. Photograph (a) , XRD pattern and SEM image of amino methylene phosphonic acid chelating resin (D418) resin (b)
图 2 溶液初始pH对Cu(II)去除率η的影响(ρ0=20 mg/L, I=0 mol/L, T=298 K, m=0.1 g, V=50 mL) (a)、Cu(II)在水溶液中分布形态(T=298 K) (b)、不同pH条件下D418树脂的zeta电位 (c)、Zeta电位变化对η的影响 (d)
Figure 2. Effect of initial pH on Cu(II) removal rate η (ρ0=20 mg/L, I=0 mol/L, T=298 K, m=0.1 g, V=50 mL) (a), speciation diagram for the Cu(II)–H2O system(T=298 K) (b), zeta potential of D418 resin at different pH values (c), effect of zeta potential on η (d)
图 3 离子强度对Cu(II)吸附影响(ρ0=20 mg/L, pH=5.86, T=298 K, m=0.1 g, V=50 mL) (a)、 D418树脂吸附Cu(II)前后FTIR图谱 (b)
Figure 3. Effect of initial pH value on the adsorption of Cu(II) (a), FTIR spectra of D418 resin before and after Cu(II) adsorption (ρ0=20 mg/L, pH=5.86, T=298 K, m=0.1 g, V=50 mL) (b)
图 4 D418树脂对Cu(II)吸附的动力学曲线(ρ0=20 mg/L, pH=5.86, T=298 K, m=0.1 g, V=50 mL) (a)、颗粒内扩散模型拟合曲线 (b)
Figure 4. Kinetic studies of Cu(II) adsorption on D418 resin(ρ0=20 mg/L, pH=5.86, T=298 K, m=0.1 g, V=50 mL) (a), plot of intraparticle diffusion (b)
图 5 不同等温模型对D418树脂吸附Cu(II)的非线性拟合
Figure 5. Nonlinear fitting curves of Cu(II) absorption onto D418 resin under different models
图 6 不同温度下Cu(II)溶解度 (a)、不同温度条件下D418树脂对Cu(II)的位点能量分布 (b)
Figure 6. Cu(II) solubility in water at different temperatures (a) , site energy distributions of Cu(II) on D418 resin at different temperatures (b)
图 7 D418树脂吸附Cu(II)后的XPS图谱 (a)、Cu 2p XPS能谱 (b)、O 1s XPS能谱 (c)、N 1s XPS能谱 (d)
Figure 7. XPS survey spectra (a) of Cu(II) onto D418 resin and high resolution XPS spectra of Cu 2p (b) , O 1s (c) and N 1s (d)
图 9 D418树脂吸附Cu(II)的机制
Figure 9. Schematic of adsorption mechanism of Cu(II) by D418 resin
表 1 D418树脂吸附Cu(II)的动力学参数和拟合的线性相关系数
Table 1. Kinetic parameters and correlation coefficient for Cu(II) adsorption onto D418 resin
Kinetic model Parameter Result Pseudo-first order qe,c/(mg·g−1) 9.75 k1/h−1 0.3070 R2 0.8908 Pseudo-second order qe,c/(mg·g−1) 12.57 k2/(g·(mg·h)−1) 0.0239 R2 0.8349 Intra-particlediffusion kp1; kp2/(mg·(g·h0.5)−1) 5.0101; 0.9932 C1; C2 −3.672; 6.1511 R2; R2 0.9948; 0.8795 Notes: qe,c—Adsorbed amount of Cu(II) at a given time and the equilibrium concentration; k1, k2 and kp—Rate constants for the pseudo-first order, pseudo-second order and intraparticle diffusion, respectively; R2—Coefficient of determination; C—Dsorption constant. 
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表 2 D418树脂吸附Cu(II)的等温模型参数
Table 2. Isotherm parameters of Cu(II) adsorption onto D418 resin at varying temperatures
Model and parameter 298 K 308 K 318 K Langmuir nonlinear fit ${q_{\rm{e,c}}} = \dfrac{{{\rm{4}}{\rm{.63}}{\rho _{\rm{e}}}}}{{1 + 0.1{\rm{238}}{\rho _{\rm{e}}}}}$ ${q_{\rm{e,c}}} = \dfrac{{{\rm{6}}{\rm{.55}}{\rho _{\rm{e}}}}}{{1 + 0.{\rm{1734}}{\rho _{\rm{e}}}}}$ ${q_{\rm{e,c}}} = \dfrac{{{\rm{1}}{\rm{.82}}{\rho _{\rm{e}}}}}{{1 + 0.{\rm{0458}}{\rho _{\rm{e}}}}}$ R2 0.9284 0.9615 0.9866 Freundlich nonlinear fit ${q_{\rm{e,c}}} = 14.96{\rho _{\rm{e}}}^{0.3272}$ ${q_{\rm{e,c}}} = 1{\rm{6}}{\rm{.01}}{\rho _{\rm{e}}}^{0.327{\rm{8}}}$ ${q_{\rm{e,c}}} = 1{\rm{5}}{\rm{.84}}{\rho _{\rm{e}}}^{0.3{\rm{420}}}$ R2 0.8272 0.8745 0.8414 Toth nonlinear fit ${q_{\rm{e,c}}} = \dfrac{{{\rm{380}}{\rm{.05}}{\rho _{\rm{e}}}}}{{{{\left( {{\rm{43}}{\rm{.4256}} + {\rho _{\rm{e}}}^{{\rm{1}}{\rm{.2572}}}} \right)}^{{\rm{1}}{\rm{.2572}}}}}}$ ${q_{\rm{e,c}}} = \dfrac{{{\rm{226}}{\rm{.93}}{\rho _{\rm{e}}}}}{{{{\left( {{\rm{24}}{\rm{.3591}} + {\rho _{\rm{e}}}^{{\rm{1}}{\rm{.2572}}}} \right)}^{{\rm{1}}{\rm{.2572}}}}}}$ ${q_{\rm{e,c}}} = \dfrac{{{\rm{2}}{\rm{.83}} \times {\rm{1}}{{\rm{0}}^{\rm{7}}}{\rho _{\rm{e}}}}}{{{{\left( {{\rm{1820}}{\rm{.9799}} + {\rho _{\rm{e}}}^{2.1442}} \right)}^{2.1442}}}}$ R2 0.9349 0.9770 0.9346 Sips nonlinear fit $q_{\rm{e,c}}^{} = \dfrac{{{\rm{2}}{\rm{.49}}{\rho _{\rm{e}}}^{{\rm{1}}{\rm{.4237}}}}}{{1 + {\rm{0}}{\rm{.0780}}{\rho _{\rm{e}}}^{{\rm{1}}{\rm{.4237}}}}}$ ${q_{\rm{e,c}}} = \dfrac{{{\rm{3}}{\rm{.18}}{\rho _{\rm{e}}}^{{\rm{1}}{\rm{.5502}}}}}{{1 + {\rm{0}}{\rm{.0974}}{\rho _{\rm{e}}}^{{\rm{1}}{\rm{.5502}}}}}$ ${q_{\rm{e,c}}} = \dfrac{{{\rm{1}}{\rm{.1814}}{\rho _{\rm{e}}}^{{\rm{2}}{\rm{.4557}}}}}{{1 + {\rm{0}}{\rm{.0458}}{\rho _{\rm{e}}}^{{\rm{2}}{\rm{.4557}}}}}$ R2 0.9386 0.9826 0.9866
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表 3 不同种类螯合树脂对Cu(II)的去除效果
Table 3. Cu(II) adsorption by different chelating resins
Number Sorbent Reaction condition Adsorption capacity/(mg·g-1) Reference 1 R-AC pH=5.0, C0=3 mmol/L, T=298 K 77.31 [4] 2 MMARS pH=5.0, C0=0.1 mmol/L, T=283 K, t=720 min 28.99 [6] 3 DTC pH=7-9, ρ0 =16 mg/L, T=293 K 10.25 [7] 4 PS-AMPY pH=5.0, C0=1 mmol/L, T=318 K, t=480 min 78.08 [27] 5 PSA pH=4.0, C0= 0.1 mmol/L, T=298 K, t=72 h 16.13 [28] 6 Si-AMPY-1 pH=4.0-5.0, C0=1.0 mmol/L, T=328 K, t=90 min 28.16 [29] 7 PV-g-PS pH=5.0, C0=4.0 mmol/L, T=298 K, t=240 min 53.12 [30] 8 D418 resin pH=5.68, ρ0=100 mg/L, T=318 K, t=360 min 39.76 Present study
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表 4 D418树脂吸附Cu(II)的热力学参数
Table 4. Thermodynamic parameters for the adsorption of Cu(II) onto D418 resin
T/K ΔG/(kJ·mol−1) ΔH/( kJ·mol−1) ΔS/(J·mol−1·K) 298 −46.88 — — 308 −53.91 597.02 2 144.60 318 −89.77 — — Notes: T—Temperature; ΔG—Gibbs free energy; ΔH—Change in enthalpy during adsorption; ΔS—Adsorption process entropy change.
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