砷的还原热力学及纳米零价铁除砷初步探究

doi:10.11894/iwt.2020-0667

摘要/Abstract

摘要：

基于工业废酸废水的处理现状，提出在溶液体系直接还原沉淀单质砷的工艺，采用纳米零价铁直接处理铜冶炼含砷（Ⅲ）废酸。结果表明：酸性溶液体系中As（Ⅲ）、As（Ⅴ）以H₃AsO₃及H₃AsO₄形式存在，AsO₃^3-与AsO₄^3-存在于强碱性溶液体系中。热力学计算表明溶液体系中的砷可被直接还原为单质砷。纳米零价铁可将铜冶炼废酸中的As（Ⅲ）还原为As（0）。

关键词: 砷, 纳米零价铁, 还原

Abstract:

Based on the treatment status of industrial waste acid wastewater, it was proposed a process of directly reducing and precipitating elemental arsenic from the solution system, and adopting nano zero-valent iron directly treated copper smelting waste acid containing arsenic(Ⅲ). The results showed that As(Ⅲ) and As(Ⅴ) in the acidic solution system existed as H₃AsO₃ and H₃AsO₄, respectively, while AsO₃^3- and AsO₄^3- existed in the strong alkaline solution system. Thermodynamic calculations showed that arsenic in the solution system could be directly reduced to elemental substances arsenic. Nano zero-valent iron could reduce As(Ⅲ) in waste acid from copper smelting to As(0).

Key words: arsenic, nano zero-valent iron, reduction

中图分类号:

X703

李梦醒,潘瑞,徐冰洁,邱奔,韩召. 砷的还原热力学及纳米零价铁除砷初步探究[J]. 工业水处理, 2021, 41(4): 37-42, 112.

Mengxing Li,Rui Pan,Bingjie Xu,Ben Qiu,Zhao Han. Preliminary study on the reduction thermodynamics of arsenic and removal of arsenic by nano zero-valent iron[J]. Industrial Water Treatment, 2021, 41(4): 37-42, 112.

https://www.iwt.cn/CN/Y2021/V41/I4/37

图/表 11

参考文献 16

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反应式	Δ_rG_m^Θ/（kJ·mol^-1）	Δ_rH_m^Θ/（kJ·mol^-1）	Δ_rS_m^Θ/（kJ·mol^-1）
H₃AsO₄（aq）+2e+2H⁺=H₃AsO₃（aq）+H₂O（l）	-110.796	-125.578	-0.050
H₂AsO₄^-（aq）+2e+3H⁺=H₃AsO₃（aq）+H₂O（l）	-123.588	-118.462	0.017
HAsO₄^2-（aq）+2e+4H⁺=H₃AsO₃（aq）+H₂O（l）	-162.383	-121.811	0.136
HAsO₄^2-（aq）+2e+3H⁺=H₂AsO₃^-（aq）+H₂O（l）	-110.030	-94.605	0.052
HAsO₄^2-（aq）+2e+2H⁺=HAsO₃^2-（aq）+H₂O（l）	-46.638	-68.650	-0.074
AsO₄^3-（aq）+2e+3H⁺=HAsO₃^2-（aq）+H₂O（l）	-112.683	-86.650	0.087
AsO₄^3-（aq）+2e+2H⁺=AsO₃^3-（aq）+H₂O（l）	-36.190	-61.325	-0.084
H₃AsO₃（aq）+3e+3H⁺=As（s）+3H₂O（l）	-72.025	-115.115	-0.145
H₂AsO₃^-（aq）+3e+4H⁺=As（s）+3H₂O（l）	-124.378	-142.324	-0.060
HAsO₃^2-（aq）+3e+5H⁺=As（s）+3H₂O（l）	-187.774	-168.276	0.065
AsO₃^3-（aq）+3e+6H⁺=As（s）+3H₂O（l）	-264.267	-193.601	0.237

反应式	Δ_rG_m^Θ/（kJ·mol^-1）	Δ_rH_m^Θ/（kJ·mol^-1）	Δ_rS_m^Θ/（kJ·mol^-1）
H₃AsO₄（aq）+2e+2H⁺=H₃AsO₃（aq）+H₂O（l）	-110.796	-125.578	-0.050
H₂AsO₄^-（aq）+2e+3H⁺=H₃AsO₃（aq）+H₂O（l）	-123.588	-118.462	0.017
HAsO₄^2-（aq）+2e+4H⁺=H₃AsO₃（aq）+H₂O（l）	-162.383	-121.811	0.136
HAsO₄^2-（aq）+2e+3H⁺=H₂AsO₃^-（aq）+H₂O（l）	-110.030	-94.605	0.052
HAsO₄^2-（aq）+2e+2H⁺=HAsO₃^2-（aq）+H₂O（l）	-46.638	-68.650	-0.074
AsO₄^3-（aq）+2e+3H⁺=HAsO₃^2-（aq）+H₂O（l）	-112.683	-86.650	0.087
AsO₄^3-（aq）+2e+2H⁺=AsO₃^3-（aq）+H₂O（l）	-36.190	-61.325	-0.084
H₃AsO₃（aq）+3e+3H⁺=As（s）+3H₂O（l）	-72.025	-115.115	-0.145
H₂AsO₃^-（aq）+3e+4H⁺=As（s）+3H₂O（l）	-124.378	-142.324	-0.060
HAsO₃^2-（aq）+3e+5H⁺=As（s）+3H₂O（l）	-187.774	-168.276	0.065
AsO₃^3-（aq）+3e+6H⁺=As（s）+3H₂O（l）	-264.267	-193.601	0.237

反应式	lgK^Θ	K^Θ
H₃AsO₄（aq）+2e+2H⁺=H₃AsO₃（aq）+H₂O（l）	20.29	1.95×10²⁰
H₂AsO₄^-（aq）+2e+3H⁺=H₃AsO₃（aq）+H₂O（l）	22.63	4.27×10²²
HAsO₄^2-（aq）+2e+4H⁺=H₃AsO₃（aq）+H₂O（l）	29.74	5.50×10²⁹
HAsO₄^2-（aq）+2e+3H⁺=H₂AsO₃^-（aq）+H₂O（l）	20.15	1.41×10²⁰
HAsO₄^2-（aq）+2e+2H⁺=HAsO₃^2-（aq）+H₂O（l）	8.54	3.47×10⁸
AsO₄^3-（aq）+2e+3H⁺=HAsO₃^2-（aq）+H₂O（l）	20.65	4.47×10²⁰
AsO₄^3-（aq）+2e+2H⁺=AsO₃^3-（aq）+H₂O（l）	6.63	4.27×10⁶
H₃AsO₃（aq）+3e+3H⁺=As（s）+3H₂O（l）	13.19	1.55×10¹³
H₃AsO₃（aq）+3e+3H⁺=As（s）+3H₂O（l）	22.78	6.03×10²²
HAsO₃^2-（aq）+3e+5H⁺=As（s）+3H₂O（l）	34.39	2.45×10³⁴
AsO₃^3-（aq）+3e+6H⁺=As（s）+3H₂O（l）	48.39	2.45×10⁴⁸

反应式	lgK^Θ	K^Θ
H₃AsO₄（aq）+2e+2H⁺=H₃AsO₃（aq）+H₂O（l）	20.29	1.95×10²⁰
H₂AsO₄^-（aq）+2e+3H⁺=H₃AsO₃（aq）+H₂O（l）	22.63	4.27×10²²
HAsO₄^2-（aq）+2e+4H⁺=H₃AsO₃（aq）+H₂O（l）	29.74	5.50×10²⁹
HAsO₄^2-（aq）+2e+3H⁺=H₂AsO₃^-（aq）+H₂O（l）	20.15	1.41×10²⁰
HAsO₄^2-（aq）+2e+2H⁺=HAsO₃^2-（aq）+H₂O（l）	8.54	3.47×10⁸
AsO₄^3-（aq）+2e+3H⁺=HAsO₃^2-（aq）+H₂O（l）	20.65	4.47×10²⁰
AsO₄^3-（aq）+2e+2H⁺=AsO₃^3-（aq）+H₂O（l）	6.63	4.27×10⁶
H₃AsO₃（aq）+3e+3H⁺=As（s）+3H₂O（l）	13.19	1.55×10¹³
H₃AsO₃（aq）+3e+3H⁺=As（s）+3H₂O（l）	22.78	6.03×10²²
HAsO₃^2-（aq）+3e+5H⁺=As（s）+3H₂O（l）	34.39	2.45×10³⁴
AsO₃^3-（aq）+3e+6H⁺=As（s）+3H₂O（l）	48.39	2.45×10⁴⁸

时间/min	5	15	30	60	90	120	150	180	210	240
mZVI对As去除率/%	15.85	18.24	19.46	28.42	32.01	33.70	33.81	33.04	—	—
nZVI对As去除率/%	54.86	58.49	58.88	59.55	60.69	60.50	63.85	65.57	64.81	66.43

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