Preparation of Fly Ash Modified with Manganese Dioxide to Enhance As(Ⅲ) and As(Ⅴ) Adsorption from Groundwater
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摘要: 高砷地下水在我国广泛分布，开发绿色高效的除砷材料对于促进地区发展和保障居民饮用水安全具有重要意义.采用共沉淀法结合NaOH水热处理技术制备了二氧化锰改性粉煤灰吸附材料MFA150，并研究其对地下水中As（Ⅲ）和As（Ⅴ）的吸附特性.结果表明，NaOH水热处理破坏了原始粉煤灰的玻璃体结构，且在这一过程中生成沸石相，粉煤灰比表面积由1.30 m2/g增加至40.26 m2/g.在负载MnO2后，MFA150比表面积达到148.82 m2/g.此外，吸附材料表面-OH的含量显著增加，为As（Ⅲ）和As（Ⅴ）提供了更多的吸附活性位点.MFA150对As（Ⅲ）和As（Ⅴ）的吸附过程符合Elovich模型和Freundlich模型.在中性条件下MFA150对As（Ⅴ）和As（Ⅲ）的吸附量分别达到2.55 mg/g和9.71 mg/g，酸性条件更有利于吸附.溶液中共存的HCO3‒和PO43‒会抑制As（Ⅲ）和As（Ⅴ）的吸附，而SO42‒对As（Ⅲ）和As（Ⅴ）的去除具有轻微促进作用.在模拟地下水中，MFA150对总砷的去除率达到91.90%.MFA150制备方法简单，制备原料廉价易得，吸附性能好有望用于含砷地下水处理.Abstract: High arsenic groundwater is widely distributed in China, and it is of great significance to develop green and efficient arsenic removal materials for the sake of regional development and safety of drinking water for residents. In this study, the fly ash modified with manganese dioxide (MFA150) was prepared using co-precipitation method combined with NaOH hydrothermal process, to investigate its adsorption of As(Ⅲ) and As(Ⅴ) in groundwater. The results show that the vitreous structure of the raw fly ash was destroyed to generate zeolite phase in NaOH hydrothermal process, and the specific surface area of fly ash increased from 1.30 m2/g to 40.26 m2/g. After loading MnO2, the specific surface area of the adsorbent further increased to 148.82 m2/g, and the content of -OH on the surface was significantly increased to provide more adsorption sites for As(Ⅲ) and As(Ⅴ). The adsorption of As(Ⅲ) and As(Ⅴ) was in accordance with the Elovich model and the Freundlich model. The adsorption capacities of MFA150 for As(Ⅴ) and As(Ⅲ) under neutral condition were 2.55 mg/g and 9.71 mg/g, respectively, and showed stronger adsorption ability under acidic condition. Coexisting HCO3‒ and PO43‒ inhibited the adsorption of As(Ⅲ) and As(Ⅴ), while SO42‒ slightly promoted the removal of As(Ⅲ) and As(Ⅴ). In simulated groundwater, the removal rate of total As reached 91.90% by MFA150. Since preparation of MFA150 is simple and the raw material is cheap and easy to obtain, MFA150 is expected to be used in the treatment of the high arsenic groundwater owing to the better adsorption performance for As(Ⅴ) and As(Ⅲ).
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Key words:
- high arsenic /
- groundwater /
- fly ash /
- manganese oxide /
- adsorption /
- resource utilization /
- environmental geology
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图 1 粉煤灰及其改性材料SEM图像和EDS分析
a.FA; b.NFA; c.MFA150
Fig. 1. SEM image and EDS of fly ash and the modified materials
图 4 FA以及不同MnO2负载量的MFA对As(Ⅴ)和As(Ⅲ)的去除率
Fig. 4. Removal rates of As(Ⅴ) and As(Ⅲ) by FA and MFA with different MnO2 loads
图 5 初始浓度对As(Ⅴ) (a)和As(Ⅲ) (b)吸附去除影响
Fig. 5. Effect of initial concentration on adsorption removal of As(Ⅴ) (a) and As(Ⅲ) (b)
图 8 初始pH对MFA150吸附去除As(Ⅲ)和As(Ⅴ)的影响
a. As（Ⅲ）和As（Ⅴ）去除率随pH变化；b. MFA150零电荷点测定；c. 锰元素浸出量
Fig. 8. Effect of initial pH of on As(Ⅲ) and As(Ⅴ) removal
图 9 共存阴离子（HCO3‒、SO42‒、PO43‒）对MFA150吸附去除As(Ⅴ) (a)和As(Ⅲ) (b)的影响
Fig. 9. Effect of coexisted ion (HCO3‒, SO42‒ and PO43‒) on As(Ⅴ) (a) and As(Ⅲ) (b) removal by MFA150
图 10 MFA150吸附去除模拟地下水中的砷
a. As(T); b. As(Ⅲ); c. As(Ⅴ)
Fig. 10. Removal of arsenic from simulated groundwater over MFA150
表 1 粉煤灰重金属元素浸出量
Table 1. Leaching amount of heavy metals from fly ash
元素 Cr Ni Cu Zn As Cd Hg Pb 浸出量(μg/g) 1.330 0.034 0.003 0.009 0.044 0.004 0.019 0.008 
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表 2 FA、NFA和MFA150的比表面积和孔结构参数
Table 2. Specific surface area and pore structure parameters of FA, NFA and MFA150
材料 BET比表面积(m2/g) 孔容(cm3/g) 平均孔径(nm) FA 1.30 6.14×10‒3 28.47 NFA 40.26 1.59×10‒1 10.78 MFA150 148.82 2.00×10‒1 7.82
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表 3 MFA150吸附As(Ⅴ)和As(Ⅲ)的动力学拟合参数
Table 3. The kinetic parameters of adsorption As(Ⅲ) and As(Ⅴ) over MFA150
qe, exp 准一级动力学模型 准二级动力学模型 Elovich模型 qe, cal k1 R2 qe, cal k1 R2 α β R2 As(Ⅲ) 0.86 0.79 0.062 0.6557 0.82 0.124 0.8603 8.290 14.690 0.9928 As(Ⅴ) 0.86 0.79 0.023 0.7900 0.82 0.038 0.8616 0.164 9.953 0.9800 颗粒内扩散模型 第一阶段 第二阶段 第三阶段 kd1 C1 R12 kd2 C2 R22 kd3 C3 R32 As(Ⅲ) 0.020 0.437 0.8834 0.010 0.556 0.9757 0.001 0.797 0.9257 As(Ⅴ) 0.037 0.171 0.9842 0.014 0.374 0.9804 0.003 0.687 0.9949
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表 4 MFA150吸附As(Ⅲ)和As(Ⅴ)吸附等温线拟合参数
Table 4. The Langmuir and Freundlich parameters of adsorption As(Ⅲ) and As(Ⅴ) over MFA150
Langmuir Freundlich qmax（μg/g） KL（L/μg） R2 1/n Kf（μg/g） R2 As(Ⅲ) 9 713.9 0.000 1 0.945 9 0.246 9 262.68 0.986 3 As(Ⅴ) 2 545.1 0.002 1 0.944 1 0.537 7 38.77 0.980 4
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