Performance and mechanism of biochar loaded magnetic nanocarbon hydroxyapatite(CHAP-γ-Fe2O3/BC) for the removal of U(VI) from water
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摘要: 针对利用功能材料去除水中U(Ⅵ)的效率与纳米颗粒易团聚的问题，利用玉米秸秆、蛋壳以及磁性γ-Fe2O3，采用动态油热法和浸渍法，制备了生物炭负载磁性纳米碳羟基磷灰石(CHAP-γ-Fe2O3/BC)复合材料，试验考察了其性能并用于水中U(Ⅵ)的去除。当U(Ⅵ)初始浓度为5 mg/L，CHAP-γ-Fe2O3/BC投加量为0.1 g/L，pH值为6，温度30°，反应时间1 h时，试验结果表明：CHAP-γ-Fe2O3/BC对U(Ⅵ)的最大吸附容量达324.4 mg/g，去除率达95.93%。拟二级动力学模型和Langmuir模型可较好拟合CHAP-γ-Fe2O3/BC对U(Ⅵ)的吸附过程，表明以单分子层化学吸附为主。材料通过表面改性技术，实现了减弱团聚的目的。复合材料在磁场中其表现出良好的分离回收和循环利用性。FTIR、XPS等表征结果证明该材料对铀的去除机制主要包括离子交换、溶解-沉淀的化学吸附作用和表面络合作用。Abstract: To address the efficiency of removing U(VI) from water using functional materials and the susceptibility of nanoparticles to agglomeration, biochar-loaded magnetic nanocarbon hydroxyapatite (CHAP-γ-Fe2O3/BC ) composites were prepared by dynamic oil-heating and impregnation methods using corn stover, egg shells, and magnetic γ-Fe2O, and the experiments were carried out to investigate the performances and used for the removal of U(Ⅵ) from water. When the initial concentration of U(Ⅵ) is 5 mg/L, the dosage of CHAP-γ-Fe2O3/BC is 0.1 g/L, the pH value is 6, the temperature is 30°, and the reaction time is 1 h, the experimental results show that the maximum adsorption capacity of CHAP-γ-Fe2O3/BC for U(Ⅵ) reaches 324.4 mg/g, and the removal rate reaches 95.93%. The proposed secondary kinetic model and Langmuir model could fit the adsorption process of CHAP-γ-Fe2O3/BC on U(Ⅵ) better, indicating that the monomolecular layer chemisorption is dominated. The materials are realized to attenuate the agglomeration by surface modification technique. The composite material shows good separation recovery and recyclability in the magnetic field. The characterization results of FTIR and XPS prove that the removal mechanism of uranium by this material mainly includes ion exchange, dissolution-precipitation chemisorption and surface complexation.
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Key words:
- uranium(U(Ⅵ)) /
- biochar(BC) /
- carbon hydroxyapatite(CHAP) /
- γ-Fe2O3 /
- chemical adsorption /
- magnetic nanocomposite
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图 1 不同烧制温度和不同质量比生物质制备的生物炭负载磁性纳米碳羟基磷灰石(CHAP-γ-Fe2O3/BC)复合材料去除U(Ⅵ)预实验
Figure 1. Different firing temperatures and different mass ratios biomass prepared by the biochar-loaded magnetic nanocarbon hydroxyapatite (CHAP-γ-Fe2O3/BC) composites pre-experiment for U(VI) removal
图 2 BC和CHAP-γ-Fe2O3/BC的外表面(a)、(d),横切面(b)、(e)的SEM图；BC和CHAP-γ-Fe2O3/BC的EDS-Mapping图(c)、(f)；BC和CHAP-γ-Fe2O3/BC吸附U(VI)前后的EDS图谱(g)、(h)和(i)
Figure 2. SEM maps of BC and CHAP-γ-Fe2O3/BC on the outer surfaces (a), (d), and cross sections (b), (e); EDS-Mapping of BC and CHAP-γ-Fe2O3/BC (c), (f); EDS maps of BC and CHAP-γ-Fe2O3/BC before and after adsorption of U(VI) (g), (h), and (i)
图 3 CHAP和CHAP-γ-Fe2O3/BC吸附U(VI)前后的XRD图谱
Figure 3. XRD patterns of CHAP and CHAP-γ-Fe2O3/BC before and after U(VI) adsorption
图 4 BC(a)和CHAP-γ-Fe2O3/BC(b)的N2吸附-脱附等温线和孔径分布
Figure 4. N2 adsorption-desorption isotherms and pore size distribution of BC (a) and CHAP-γ-Fe2O3/BC (b)
图 7 CHAP-γ-Fe2O3/BC吸附U(VI)：(a)pH值的影响；(b)投加量的影响
Figure 7. U(VI) adsorption by CHAP-γ-Fe2O3/BC: (a)Effect of pH value;(b) Effect of dosing amount
图 8 CHAP-γ-Fe2O3/BC吸附U(VI) :(a)干扰离子的影响；(b)NaCl离子强度的影响
Figure 8. U(VI) adsorption by CHAP-γ-Fe2O3/BC: (a) Effect of interfering ions; (b) Effect of NaCl ion intensity
图 9 CHAP-γ-Fe2O3/BC吸附U(VI): (a)时间的影响; (b)拟一级动力学; (c)拟二级动力学; (d)颗粒内扩散
Figure 9. U(VI) adsorption by CHAP-γ-Fe2O3/BC: (a) Effect of time; (b) Proposed primary dynamics; (c) Proposed secondary dynamics;(d) Intraparticle diffusion
图 10 CHAP-γ-Fe2O3/BC吸附U(VI): (a)吸附等温线；(b)lnKL与1/T线性关系图
Figure 10. U(VI) adsorption by CHAP-γ-Fe2O3/BC: (a) Adsorption isotherm;(b) linear plot of lnKL vs 1/T.
图 11 不同循环次数的CHAP-γ-Fe2O3/BC吸附-解吸效率
Figure 11. Adsorption-desorption efficiency of CHAP-γ-Fe2O3/BC with different number of cycles
图 12 CHAP-γ-Fe2O3/BC的XPS图谱：(a)全谱：(b) U4f；(c) C1s；(d) O1s；(e) Ca2p；(f) P2p；(g) Fe2p
Figure 12. XPS maps of CHAP-γ-Fe2O3/BC: (a) full spectrum: (b) U4f; (c) C1s; (d) O1s; (e) Ca2p; (f) P2p; (g) Fe2p
表 1 CHAP-γ-Fe2O3/BC吸附U(VI)的动力学参数
Table 1. Kinetic parameters of U(VI) adsorption by CHAP-γ-Fe2O3/BC
C0/(mg·L−1) 5 10 15 qe,exp/(mg·g−1) 48.02 90.027 125.9 Pseudo-first-order model K1/min−1 0.049 0.189 0.039 qe,cal/(mg·g−1) 8.218 0.711 1.082 R 2 0.529 0.417 0.491 Pseudo-second-order model K2/min−1 0.0077 0.0229 0.158 qe,cal/(mg·g−1) 48.15 89.928 125.3 R 2 0.999 1 0.999 Intraparticle diffusion model Kd1/(mg·(g·min0.5)−1) 0.947 0.648 3.714 C1 44.08 88.471 121.6 R1 2 0.968 0.269 0.584 Kd2/(mg·(g·min0.5)−1) 0.121 0.163 0.327 C2 46.97 90.245 131.3 R2 2 0.486 0.504 0.939 Notes: qe,exp-calculated adsorption equilibrium; qe,cal-actual adsorption equilibrium; K1 and K2-first-order and second-order rate constants; Kd1, Kd2-particle diffusion constants; C-constant; R2-linear correlation coefficient. 
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表 2 CHAP-γ-Fe2O3/BC对U(VI)的吸附等温线拟合参数
Table 2. Adsorption isotherm fitting parameters of CHAP-γ-Fe2O3/BC for U(VI)
T/K Langmuir model Freundlich model qmax/(mg·g−1) KL/(L·mg−1) R 2 KF/(L·mg−1) n R 2 293 315.86 0.413 0.988 107.54 2.92 0.947 303 324.415 0.456 0.991 137.30 3.70 0.928 313 350.93 0.412 0.983 117.17 2.78 0.969 Notes: qmax-maximum adsorption capacity; KL and KF-Langmuir and Freundlich adsorption equilibrium constants; n-Freundlich equation constant; R2-linear correlation coefficient.
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表 4 不同材料对U(VI)吸附效果的比较
Table 4. Comparison of the adsorption effect of different materials on U (VI)
Material T/K pH qmax/(mg·g−1) Reference Magnetic biochar 298 6 17.24 [30] CA-PO4 298 5.5 150.3 [31] HAP microspheres 298 3 199 [32] P-pFGO-7 298 4 266.7 [33] M-α-FeOOH 298 5 127.73 [24] CHAP-γ-Fe2O3/BC 303 6 324.4 This work Notes：CA-PO4—phosphorylated carbon aerogel; HAP—hydroxyapatite; P-pFGO-7—phytic acid functionalized graphene oxide; M-α-FeOOH—goethite (α-FeOOH) and Fe2+-modified magnetic goethite.
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表 3 CHAP-γ-Fe2O3/BC吸附U(VI)的热力学参数
Table 3. Thermodynamic parameters of U(VI) adsorption by CHAP-γ-Fe2O3/BC
T/K ΔG/(kJ·mol−1) ΔH/(kJ·mol−1) ΔS/(J·(mol·K)−1) 393 −12.49 16.393 98.574 303 −13.46 313 −14.46 Notes：ΔG—free energy; ΔH—enthalpy change; ΔS—entropy change.
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