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砷(As)是一种广泛存在于自然环境中的有毒类金属,砷污染问题已成为全球关注的问题。世界卫生组织(WHO)和美国环境保护局(USEPA)已将饮用水中砷的最大污染物水平(MCL)从50 μg·L−1降低到10 μg·L−1[1-3]。水中的砷一般以三价砷As(Ⅲ)和五价砷As(Ⅴ)两种价态存在。As(Ⅲ)的毒性是As(Ⅴ)的60倍左右,移动性强且具有亲水性[4]。而常规给水处理工艺对砷的去除能力有限,故采取有效的方法强化去除饮用水中的砷非常必要[5]。
相较于膜法、生物法、离子交换法和混凝法等,吸附法因其操作简单、经济高效且再生能力强等优点,因而被小型社区和农村分散式砷去除工艺普遍采用[3-5]。近年来的研究表明,单质铁及其氧化物与水体中的砷存在很强的亲和力,且来源丰富、绿色高效,更适合大规模应用于水体除砷工艺[6-7]。但一方面铁氧化物与中性分子形式存在的As(Ⅲ)结合力相对较弱,对As(Ⅲ)去除效果并不理想[8];另一方面铁氧化物尤其是吸附性能良好的水合铁氧化物粒径极细甚至为纳米级粒径,致使其在实际应用时水头损失过大,固液分离困难[9-10],易造成构筑物管道或设备堵塞,因而限制了其工业化应用。
活性炭具有较大的比表面积,对污染物吸附能力强,是常用的吸附剂。然而,单纯使用活性炭无法有效去除As(Ⅲ),为了获得理想的除砷效果,有必要对活性炭加以改性处理。因此,绿色安全地应用活性炭和水合氧化铁的吸附性能,同时又解决水合氧化铁固液分离的难题,成为强化吸附除砷的研究热点。有研究表明,采用FeSO4浸渍和H2O2氧化的组合[8]、FeSO4浸渍和NaClO氧化的组合[11]以及FeCl3浸渍和NaClO氧化的组合[12]所制备出的载铁活性炭,对水中的As均能达到良好的去除效果。这些研究为铁盐浸渍和氧化组合方式进行活性炭改性负载铁氧化物研究提供了理论基础和技术借鉴,但利用氧化性和吸附性良好的高铁酸钾(K2FeO4),经过适当的改性处理,将原位生成的多种吸附性能优良的铁氧化物负载在多孔材料活性炭上,制备出吸附和固液分离性能良好的载铁活性炭复合材料还鲜有研究。基于上述背景,本研究利用FeSO4和少量K2FeO4通过恒温浸润的方式,制备获得原位铁氧化物载铁活性炭(AFPAC)。研究AFPAC对水中As(Ⅲ)的吸附特性,并结合系列表征分析以阐明其除As(Ⅲ)机理,以期为地下水除砷治理技术的探索提供参考。
原位铁氧化物载铁活性炭的制备及其对水中As(III)的去除性能
Preparation of in situ iron oxides-loaded activated carbon and its performance on arsenite removal from water
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摘要: 针对水中三价砷As(III)毒害大、难去除的问题,本研究采用FeSO4/K2FeO4组合处理方式以恒温浸润法对活性炭进行改性,制备获得原位铁氧化物载铁活性炭(AFPAC),利用负载的铁氧化物的吸附性能,耦合活性炭的吸附和有效的固液分离功能,实现了As(Ⅲ)的高效去除。结果表明,当AFPAC投加量1 g·L−1时,对初始质量浓度1 mg·L−1的As(Ⅲ)的去除率达到99.5%以上,吸附容量达到6.17 mg·g−1;其吸附行为属于非均质表面吸附,以化学吸附为主。AFPAC表面原位生成的铁氧化物形态和物种丰富,具有较强的络合和吸附能力,对As(Ⅲ)的去除呈现出配位络合、静电吸附及氧化还原等多重协同作用机制。Abstract: In view of the problem that arsenic trivalent As(Ⅲ) in water is highly toxic and difficult to remove, in this study, the in-situ ferric oxide ferric-loaded activated carbon (AFPAC) was prepared by the dipping method at constant temperature with FeSO4/K2FeO4 combined treatment mode, and As (Ⅲ) could be efficiently removed by coupling the adsorption ability of loaded iron oxides with the adsorption and effective solid-liquid separation abilities of activated carbon. The results showed that at AFPAC dosage of 1 g·L−1, the removal rate of As(Ⅲ) at the initial concentration of 1 mg·L−1 was above 99.5%, and the corresponding adsorption capacity reached 6.17 mg·g−1. The adsorption behavior of As(Ⅲ) was heterogeneous surface adsorption, mainly belonged to chemical adsorption. The iron oxides generated in situ on the surface of AFPAC were rich in form and species with strong complexation and adsorption capacity for As(Ⅲ) removal. Multiple synergistic mechanisms for As(Ⅲ) removal were ligand complexation, electrostatic adsorption and adsorption and oxidation reduction.
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Key words:
- iron-loaded activated carbon /
- in-situ iron oxide /
- ferrate /
- arsenite /
- ligand complexation
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表 1 不同组合改性后的活性炭除砷效果
Table 1. Arsenic removal effect of activated carbon modified by different combinations
不同铁盐和氧化剂组合 As(Ⅲ)的去除率/% 铁含量/% 原始新鲜活性炭 33.00 — 酸预处理活性炭 35.80 — 碱预处理活性炭 32.60 — FeCl3+K2FeO4 85.50 3.20 FeSO4·7H2O+ K2FeO4 99.50 4.50 注:吸附剂投量为1 g·L−1;As(Ⅲ)初始质量浓度为1 mg·L−1。 表 2 不同研究中载铁活性炭除砷效果
Table 2. Arsenic removal effect of iron-loaded activated carbon in different studies
表 3 吸附动力学模型拟合结果与参数值
Table 3. Adsorption kinetics model fitting results and parameter values
拟一级吸附动力学模型 拟二级吸附动力学模型 R2 q/(mg·g-1) K1 R2 q/(mg·g-1) K2 0.954 7 0.675 5 0.002 8 0.996 0 1.020 4 0.014 6 表 4 吸附等温线拟合结果与参数值
Table 4. Adsorption isotherm fitting results and parameter values
T/℃ Freundlich吸附等温线模型 Langmuir吸附等温线模型 n KF R2 qm/(mg·g−1) KL R2 25 3.155 3.687 0.899 7 6.169 1.416 0.970 3 35 5.397 4.395 0.953 7 6.274 8.810 0.989 6 45 6.974 5.248 0.968 7 6.329 23.939 0.990 7 -
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