利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究

doi:10.11949/j.issn.0438-1157.20181536

化工学报 ›› 2019, Vol. 70 ›› Issue (6): 2377-2385.DOI: 10.11949/j.issn.0438-1157.20181536

• 材料化学工程与纳米技术 • 上一篇下一篇

利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究

孙燕^1,²(),蓝际荣^1,²,郭莉^1,²,孙朋^1,²,叶恒朋^1,²,杜冬云^1,²(),占伟^1,²

1. 中南民族大学资源与环境学院，湖北省重金属污染防治工程技术研究中心，湖北武汉430074
2. 民族地区资源绿色转化与利用国家民委-教育部重点实验室，湖北武汉430074

收稿日期:2019-01-02 修回日期:2019-03-07 出版日期:2019-06-05 发布日期:2019-06-05
通讯作者: 杜冬云
作者简介:<named-content content-type="corresp-name">孙燕</named-content>（1994—），女，硕士研究生，<email>YanSun0123@163.com</email>
基金资助:
国家科技支撑计划项目(2015BAB01B03);中南民族大学中央高校项目(CZT18022)

Preparation of As(Ⅲ) adsorbent material by electrolytic manganese slag and its properties

Yan SUN^1,²(),Jirong LAN^1,²,Li GUO^1,²,Peng SUN^1,²,Hengpeng YE^1,²,Dongyun DU^1,²(),Wei ZHAN^1,²

1. Hubei Province Engineering Research Center for Control and Treatment of Heavy Metal Pollution, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074, Hubei, China
2. Key Laboratory of Resources Green Conversion and Utilization of the State Ethnic Affairs Commission & Ministry of Education, Wuhan 430074, Hubei, China

Received:2019-01-02 Revised:2019-03-07 Online:2019-06-05 Published:2019-06-05
Contact: Dongyun DU

摘要/Abstract

摘要：

通过对工业废弃物电解锰渣(electrolytic manganese residues, EMRs)进行改性制备As(Ⅲ)吸附材料（改性EMRs），探究了NaOH用量、超声及微波对其表面结构及吸附性能的影响。结果表明：该工业废渣在固液比M(EMRs)∶V(NaOH, aq) = 1∶10(C _NaOH，aq = 2.0 mol·L^-1)条件下，经超声反应（200 W）2 h脱除大部分Si、S、Ca后，再微波（700 W）反应5 min以使Fe、Mn等活性吸附基团在其表面沉积，最后经105℃烘干制得改性EMRs。SEM结果表明，EMRs改性后表面形成片层纳米结构，对砷具有良好的吸附性能，可将初始As(Ⅲ)浓度为50 mg·L^-1废水出水中砷降至0.042 mg·L^-1，符合国家地表水环境质量标准Ⅰ类水质量要求(GB 3838—2002)；同时，经3% NaOH溶液再生处理后可继续使用。XPS结果表明，改性EMRs吸附砷性能与其表面Fe₃O₄、FeOOH、MnO₂等对As(Ⅲ)具有吸附作用或氧化作用的活性物种的增多密切相关。

关键词: 电解锰渣, 除砷, 微波, 再生, 吸附剂

Abstract:

As(Ⅲ) adsorbent (called modified EMRs) was prepared by modifying the industrial waste electrolytic manganese residues (EMRs). The effects of NaOH dosage, ultrasonic and microwave on its surface structure and adsorption performance were investigated. The results showed that most of the Si, S and Ca were removed by ultrasonic reaction (200 W) for 2 h with solid-liquid ratio M (EMRs)∶V(NaOH, aq) = 1∶10 (C _{NaOH, aq} = 2.0 mol·L^-1). Fe, Mn and other active adsorption groups were deposited on the surface after the microwave (700 W) was reacted for 5 min. Finally, the adsorbent dried at 105℃. The SEM results show that the surface of the material has a lamellar nanostructure and good adsorption performance for arsenic. The initial As(Ⅲ) concentration of 50 mg·L^-1 wastewater effluent can be reduced to 0.042 mg·L^-1. The national surface water environmental quality standard Class I water quality requirements (GB 3838—2002), at the same time, can be continued after being regenerated by 3% NaOH solution. XPS results show that the adsorption of arsenic by modified EMRs is closely related to the increase of active species such as Fe₃O₄, FeOOH and MnO₂ on As(Ⅲ) adsorption or oxidation.

Key words: electrolytic manganese residues, arsenic removal, microwave, regeneration, sorbents

中图分类号:

X 75

孙燕, 蓝际荣, 郭莉, 孙朋, 叶恒朋, 杜冬云, 占伟. 利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究[J]. 化工学报, 2019, 70(6): 2377-2385.

Yan SUN, Jirong LAN, Li GUO, Peng SUN, Hengpeng YE, Dongyun DU, Wei ZHAN. Preparation of As(Ⅲ) adsorbent material by electrolytic manganese slag and its properties[J]. CIESC Journal, 2019, 70(6): 2377-2385.

图/表 16

表1 电解锰废渣主要组成成分

Table 1 Main components of EMR/%

Si	Al	Ca	Mg	Fe	S	Mn
23.99	2.1	10.53	1.95	7.24	25.92	4.82

图1 EMRs改性过程

Fig.1 Schematic diagram of preparation process of adsorbent

图2 不同改性方法获得的不同改性EMRs产品产率及其除砷性能

Fig.2 Effect of different modification methods on material yield and arsenic removal performance

表2 不同改性方法获得的各改性EMRs样品的主要含量变化

Table 2 Main content changes of EMRs samples with different modification methods/%(mass)

Element	EMRs	EMRs+ NaOH	EMRs+ NaOH+ ultrasound	EMRs + NaOH+ ultrasound+ microwave
Ca	8.53	6.12	3.89	3.91
S	15.02	12.56	0.24	0.12
Mn	4.82	3.78	3.95	5.57
Fe	7.24	4.24	3.85	8.17
Si	23.99	13.22	7.13	7.51
O	40.23	42.25	43.22	41.25

图3 不同NaOH浓度碱浸对改性EMRs除砷性能的影响

Fig.3 Effect of different NaOH concentrations on arsenic removal performance of materials

图4 NaOH物质的量与硫(a)、钙(b)和硅(c)物质减少量的关系

Fig.4 Relationship between amount of NaOH substances and reduction of sulfur (a), calcium (b) and silicon (c) substances

图5 超声反应时间(a)和微波反应时间(b)对改性EMRs除砷性能的影响

Fig.5 Effect of ultrasonic reaction time(a), and microwave reaction time(b) on arsenic removal performance

图6 不同固液比对改性EMRs除砷性能的影响

Fig.6 Effect of different solid-liquid ratio on arsenic removal performance of modified materials

图7 不同改性方法材料表面形貌特征

Fig.7 Surface morphology characteristics of different modification methods

图8 材料的XPS表征

Fig.8 XPS representation of material

图9 改性EMRs对As(Ⅲ)的吸附平衡

Fig.9 Modified EMRs equilibrium of materials for As(Ⅲ)

图10 利用不同浓度NaOH溶液和HNO3溶液再生改性EMRs

Fig.10 Recycling modified EMRs using different concentrations of NaOH solution and HNO3 solution

图11 改性EMRs重复利用情况

Fig.11 Modified EMRs recycling

表3 模拟废水在改性EMRs吸附后出水性质

Table 3 Characteristics of synthesis wastewater after treated with material as compared with that shown in GB 3838—2002

Item

Fe/

(mg·L^-1)

Mn/

(mg·L^-1)

Si/

(mg·L^-1)

Ca/

(mg·L^-1)

Na/

(mg·L^-1)

SO₄ ^2?/

(mg·L^-1)

As/

(mg·L^-1)

Chromaticity (dilution factor)

after material treatment

图12 不同方法对As(Ⅲ)的去除情况

Fig.12 Removal rate of As(Ⅲ) by different methods

图13 吸附机理图

Fig.13 Adsorption mechanism diagram of As(Ⅲ)

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利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究

Preparation of As(Ⅲ) adsorbent material by electrolytic manganese slag and its properties

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