多孔球状活性氧化镁的制备及除氟效能研究

doi:10.19965/j.cnki.iwt.2022-0017

摘要/Abstract

摘要：

为解决含氟废水中氟离子浓度超标的问题，采用均匀沉淀法制备多孔球状活性氧化镁（PSAM），考察了影响PSAM除氟性能的制备因素，得到其最佳制备条件。通过静态吸附实验和除氟前后PSAM的SEM、BET、EDS、XRD等表征分析，探讨了PSAM的除氟机理和再生效果，分析了PSAM对实际含氟废水的处理效果。结果表明：在n〔CO（NH₂）₂〕∶n（MgCl₂·6H₂O）=4.5∶1，V（PEG400）∶V（溶剂）=3∶20，110 ℃反应2 h，450 ℃煅烧2 h的条件下制备的PSAM除氟性能最佳，在初始氟离子质量浓度为9.9 mg/L时，其对氟离子的吸附量达到18.72 mg/g，除氟率达到86.14%；PSAM的pH_pzc=11.82，当pH在2~7之间时PSAM对于氟具有较好的吸附去除性能，吸附过程符合Freundlich吸附等温式和准二级动力学模型，为多层非均匀化学吸附；氟离子主要通过取代PSAM表面的活性位点并与PSAM形成化学键而被去除；PSAM对实际含氟废水的除氟率较传统氧化镁除氟率提高了83.19%，达到了95.83%；经过5次再生循环后，PSAM对氟离子的吸附容量由13.31 mg/g降低到8.35 mg/g。

关键词: 含氟废水, 多孔球状活性氧化镁, 吸附, 吸附等温线, 吸附动力学, 再生

Abstract:

In order to solve the problem of excessive fluorine ion in fluorine-containing wastewater，porous spherical activated MgO（PSAM） defluorination agent was prepared by using homogeneous precipitation. The preparation factors effecting the fluorine removal performance of PSAM were investigated and the optimum preparation conditions were obtained. Through the static adsorption experiment and characterization analysis by SEM、EDS、BET、XRD before and after defluorination， the fluorine removal mechanism and regeneration effect of PSAM was discussed，and the treatment effect of PSAM on actual fluorine-containing wastewater was analyzed. The experimental results showed that，the PSAM had the best defluorination performance when prepared in the conditions of n〔CO（NH₂）₂〕∶n（MgCl₂·6H₂O）=4.5∶1，V（PEG400）∶V（溶剂）=3∶20，reaction at 110 ℃ for 2 h，and calcination at 450 ℃ for 2 h. When the initial fluorine ion mass concentration was 9.9 mg/L，the adsorption capacity was 18.72 mg/g，the defluorination rate could reach 86.14%. The pH_pzcof PSAMwas 11.82，that meant it had high fluorine removal performance with pH range from 2 to 7. The adsorption was well described by Freundlich equation and the pseudo-second order kinetic model. The defluorination process of PSAM was multi-layer heterogeneous chemisorption，and the fluorine ions were removed by replacing active points on the surface of PSAM by ion exchange method to form chemical bonds. PSAM had a better treatment effect on actual fluorine-containing wastewater，and the fluorine removal rate was increased by 83.19% and reached 95.83% compared with that of traditional magnesium oxide. After 5 cycles of regeneration，the adsorption capacity decreased from 13.31 mg/g to 8.35 mg/g.

Key words: fluorine-containing wastewater, porous spherical activated MgO, adsorption, adsorption isotherm, adsorption kinetics, regeneration

中图分类号:

康宁, 由昆, 徐丽, 刘振鹏, 黄殿男, 高振东, 刘琦, 曹凯. 多孔球状活性氧化镁的制备及除氟效能研究[J]. 工业水处理, 2022, 42(11): 65-75.

Ning KANG, Kun YOU, Li XU, Zhenpeng LIU, Diannan HUANG, Zhendong GAO, Qi LIU, Kai CAO. Research on porous spherical activated MgO preparation and its defluorination efficacy[J]. Industrial Water Treatment, 2022, 42(11): 65-75.

https://www.iwt.cn/CN/Y2022/V42/I11/65

图/表 17

图1 n〔CO（NH₂）₂〕∶n（MgCl₂·6H₂O）对PSAM除氟性能的影响

Fig. 1 Effect of n〔CO（NH₂）₂〕∶n（MgCl₂·6H₂O） on fluoride removal performance of PSAM

图2 PEG400添加量对PSAM除氟性能的影响

Fig. 2 Effect of PEG400 addition on fluoride removal performance of PSAM

图3 反应温度对PSAM除氟性能的影响

Fig. 3 Effect of reaction temperature on fluoride removal performance of PSAM

图4 反应时间对PSAM除氟性能的影响

Fig. 4 Effect of reaction time on fluoride removal performance of PSAM

图5 煅烧温度对PSAM除氟性能的影响

Fig. 5 Effect of calcination temperature on fluoride removal performance of PSAM

图6 煅烧时间对PSAM除氟性能的影响

Fig. 6 Effect of calcination time on fluoride removal performance of PSAM

图7 吸附F^-前后PSAM的SEM

Fig.7 SEM analysis of PSAM before and after fluoride ion adsorption

图8 PSAM的粒径分布

Fig.8 Particle size distribution of PSAM

图9 PSAM的EDS表征

Fig.9 EDS analysis of PSAM

图10 PSAM的XRD

Fig.10 XRD patterns of PSAM

图11 pH对PSAM除氟效果的影响

Fig. 11 Effect of pH on fluoride removal by PSAM

图12 PSAM吸附氟离子的等温拟合曲线

Fig. 12 Isothermal fitting curve of adsorption of fluorine ion by PSAM

表1 吸附等温线拟合参数

Table 1 Fitting parameters of adsorption isotherm

T/K	Langmuir			Freundlich
T/K	q _max/ （mg·g^-1）	B ₁/ （L·mg^-1）	R ²	B ₂/（mg·g^-1·（mg·L^-1）^（-1/ ⁿ ^））	1/n	R ²
298.15	56.63	0.35	0.908 2	18.56	0.36	0.998 4
308.15	60.39	0.38	0.938 0	20.42	0.35	0.998 7
318.15	64.59	0.36	0.937 8	21.50	0.36	0.997 1

图13 PSAM吸附氟的动力学及其拟合曲线

Fig. 13 Kinetics and fitting curve of fluorine adsorption by PSAM

表2 吸附动力学参数

Table 2 Adsorption kinetic parameters

F^-/（mg·L^-1）	准一级动力学			准二级动力学
F^-/（mg·L^-1）	q _e/（mg·g^-1）	k ₁/（min^-1）	R ²	q _e/（mg·g^-1）	k ₂/（g·mg^-1·min^-1）	H/（mg·g^-1·min^-1）	R ²
5	7.52	0.18	0.994 9	7.81	0.045	2.73	0.996 8
10	12.24	0.17	0.984 4	12.75	0.025	4.10	0.998 2

图14 PSAM和传统氧化镁对实际含氟废水处理的效果

Fig. 14 Effect of PSAM and traditional MgO on the treatment of actual fluoride-containing wastewater

图15 再生循环实验

Fig. 15 Regeneration cycle experiment

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