Modification of coconut shell biochar by ball milling with an alkali for enrofloxacin adsorption
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摘要: 为了高效吸附水中的恩诺沙星(EFA)，本文通过球磨法和KOH活化对椰壳进行改性制备椰壳生物炭(BM-KOH-BC)，并在吸附EFA方面进行深入研究。通过扫描电子显微镜、傅里叶变换红外光谱和X射线衍射等方法对BM-KOH-BC进行表征，结果揭示了KOH活化和球磨改性显著提高了BM-KOH-BC的孔隙结构和比表面积。在优化条件下(初始EFA浓度为80 mg·L−1时，在pH值为7，温度为25℃，吸附剂剂量为0.14 g·mg·L−1，搅拌速度为200 r/min、接触时间为35 h的条件下，BM-KOH-BC表现出良好的吸附性能，去除率达77.4%，最大吸附容量为481.1 mg·g−1。吸附过程符合二级动力学模型和Freundlich等温线模型。此外，BM-KOH-BC在5次吸附-解吸循环后仍保持高效的EFA去除率。这一低成本、高效吸附和可循环利用的特性使得BM-KOH-BC在处理水体中的EFA方面展现出潜在的应用前景。Abstract: In order to efficiently adsorb enrofloxacin (EFA) in water, coconut shell biocharC(BM-KOH-BC) was prepared by modifying coconut shell through ball milling and KOH activation, and in-depth research was conducted on the adsorption of EFA. BM-KOH-BC was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The results revealed that KOH activation and ball milling modification significantly improved the pore structure and specific surface area of BM-KOH-BC. under optimized conditions (initial EFA concentration is 80 mg·L−1, pH value is 7, temperature is 25°C, adsorbent dosage is 0.14 g·mg·L−1, stirring speed is 200 r/min, contact time Under the conditions of 35 h), BM-KOH-BC showed good adsorption performance, with a removal rate of 77.4% and a maximum adsorption capacity of 481.1 mg·g−1. The adsorption process is consistent with the second-order kinetic model and Freundlich isotherm model. In addition, BM-KOH-BC still maintains efficient EFA removal rate after 5 adsorption-desorption cycles. This low-cost, efficient adsorption and recyclability feature makes BM-KOH-BC show potential application prospects in treating EFA in water bodies.
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Key words:
- ball-milling /
- biochar /
- coconut shell /
- enrofloxacin /
- adsorption
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图 1 恩诺沙星(EFA)在不同吸附剂上的吸附能力
Figure 1. Adsorption capacities of enrofloxacin (EFA) on different adsorbents
图 2 生物炭(BC)、碱活化生物炭(KOH-BC)、球磨生物炭(BM-BC)和球磨-碱活化生物炭(BM-KOH-BC)的SEM图像
Figure 2. SEM images of biochar(BC), alkali-activated biochar (KOH-BC), ball milled biochar( BM-BC), and ball milled and alkali-activated biochar(BM-KOH-BC)
图 3 生物炭结构的表征。(a) EFA吸附前后BM-KOH-BC的FTIR光谱；(b) BC、KOH-BC、BM-BC和BM-KOH-BC的FTIR光谱；(c)XRD谱图
Figure 3. Characterization of the biochar. (a) FTIR spectra of BM-KOH-BC before and after EFA adsorption; (b) FTIR spectra of BC, KOH-BC, BM-BC and BM-KOH-BC; (c) XRD patterns
图 5 (a)不同EFA初始浓度的影响；(b)pH值对BM-KOH-BC吸附EFA的影响
Figure 5. (a) Effects of different initial concentrations of EFA; and (b) the effect of the pH value on EFA adsorption by BM-KOH-BC
图 6 BM-KOH-BC去除EFA的吸附等温线：(a)Langmuir、(b)Freundlich(c)EFA吸附的Van't Hoff图
Figure 6. Adsorption isotherms of EFA removal by BM-KOH-BC:(a) Langmuir, (b)Freundlich (c)Van’t Hoff plot of EFA adsorption
图 7 EFA 在BM-KOH-BC上吸附的动力学模型：(a) 准一级，(b) 准二级
Figure 7. Kinetics models for the adsorption of EFA onto BM-KOH-BC:(a) pseudo-first-order, and (b) pseudo-second-order
表 1 BC、KOH-BC 和BM-KOH-BC 的 BET 分析
Table 1. BET analysis of BC, KOH-BC, and BM-KOH-BC
Material BET surface area/(m2·g−1) Pore volume/(cm3·g−1) Element mass fraction /wt% C O H N BC 775.99±2.53 0.424163±0.008 79.78±3.53 9.85±0.42 1.34±0.35 0.31±0.02 BM-BC 1559.12±1.83 0.604902±0.005 71.09±2.47 18.29±0.28 1.79±0.33 0.56±0.01 KOH-BC 2,277.28±1.02** 1.238911±0.002** 60.85±2.53 28.04±0.45 3.37±0.28 0.58±0.03 BM-KOH-BC 2,620.49±0.21* 1.433558±0.001* 60.51±2.38 29.89±0.57 3.53±0.21 0.65±0.03 Notes: *, P< 0.05; **, P< 0.01. 
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表 2 BM-KOH-BC吸附 EFA 的 Langmuir 和 Freundlich 吸附等温线参数
Table 2. Langmuir and Freundlich adsorption isotherm parameters for EFA adsorption by BM-KOH-BC
T(K) Langmuir Freundlich $ {Q}_{\mathrm{m}\mathrm{a}\mathrm{x},\mathrm{e}\mathrm{x}\mathrm{p}} $/(mg·g−1) $ {Q}_{\mathrm{m}\mathrm{a}\mathrm{x},\mathrm{c}\mathrm{a}\mathrm{l}} $/(mg·g−1) KL/(mg·g−1) R2 1/n KF/(mg·g−1) R2 298 481.1 476.1 2.1 0.8644 0.0318 410.9617 0.9982 308 492.6 476.1 1.75 0.885 0.0366 411.4551 0.9978 318 504.4 500 1.5384 0.8979 0.0402 414.2211 0.9957 Notes：Qmax — Maximum sorption capacity; KL — Adsorptive constant of Langmuir model; 1/n — Empirical parameter varied with the degree of heterogeneity of adsorbing sites; KF — Adsorptive constant of Freundlich model; R2 — The Correlation coefficient of Langmuir and Freundlich models.
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表 3 不同吸附剂对EFA的吸附容量
Table 3. EFA adsorption capacities of different adsorbents
Adsorbent SBET/ (m2·g−1) Qmax/
(mg·g−1)Reference Montmorillonite 32 239.7 [30] Illite 22 81.6 [30] Kaolinite 10 7.2 [30] Ca-montmorillonite nd 144.4 [31] Na-montmorillonite nd 163.4 [31] Ligno-cellulosic substrate
from wheat bran11 ± 3 3.56 [32] Chemically activated carbon derived from industrial paper sludge 4514 44.4 [33] Chemically activated carbon developed from green coconut shell 1005.76 12.3 [17] Ball milling-alkali activated green coconut shell biochar 2,620.49 481.1 本研究 Notes：Qmax — Maximum sorption capacity；SBET—BET surface area
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表 4 不同EFA初始浓度下BM-KOH-BC吸附EFA的动力学参数
Table 4. Kinetic parameters for EFA adsorption by BM-KOH-BC at different initial EFA concentrations
Initial concentration/
(mg·L−1)Qe,exp/
(mg·g−1)Pseudo-first-order Pseudo-second-order k1 $ {Q}_{e,cal} $ R2 k2 $ {Q}_{e,cal} $ R2 80 2.50 0.0031 0.98 0.8647 0.0094 2.54 0.9994 120 2.56 0.0031 1.07 0.8836 0.0080 2.60 0.9992 160 2.61 0.0034 0.86 0.90536 0.0119 2.65 0.9996 Notes：Qe,exp — Equilibrium sorption capacity obtained from experiment; k1—First-order apparent sorption rate constants; Qe,calu — Equilibrium sorption capacity calculated by pseudo-first order kinetics or pseudo-second order kinetics; k2 — Second-order apparent sorption rate constants; R2 — The Correlation coefficient of pseudo-first order kinetics or pseudo-second order kinetics.
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表 5 BM-KOH-BC吸附EFA的热力学参数
Table 5. Thermodynamic parameters of EFA adsorption by BM-KOH-BC
Temperature/°C △G/(kJ·mol−1) △H/(kJ·mol−1) △S/(kJ·mol−1) 25 −3.1012 2.8176 0.02 35 −3.2946 45 −3.4944 Notes：ΔG°—Gibbs free energy; ΔH°—enthalpy; ΔS°—entropy.
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