酸性含汞溶液中電沉積回收汞的研究

李子良; 徐志峰; 張溪; 昝苗苗; 劉志樓

doi:10.13374/j.issn2095-9389.2020.03.15.001

酸性含汞溶液中電沉積回收汞的研究

doi: 10.13374/j.issn2095-9389.2020.03.15.001

李子良¹,
徐志峰^{1, 2},
張溪¹,
昝苗苗¹,
劉志樓^{1, 2, ,}

1.
江西理工大學材料冶金化學學部，贛州 341000
2.
綠色冶金與過程強化研究所，贛州 341000

基金項目: 國家自然科學基金資助項目（51804139）；中國博士后面上基金資助項目（2019M652275）；江西理工大學清江青年英才支持計劃資助項目（JXUSTQJYX2019003）

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通訊作者:
E-mail: lzl8786489@163.com

中圖分類號: TF819.1
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出版歷程
- 收稿日期: 2020-03-15
- 刊出日期: 2020-09-11

Mercury recovery from acidic mercury solution using electrodeposition

LI Zi-liang¹,
XU Zhi-feng^{1, 2},
ZHANG Xi¹,
ZAN Miao-miao¹,
LIU Zhi-lou^{1, 2
, ,}

1.
Faculty of Materials Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
2.
Green Metallurgy and Process Intensification Research Institute, Ganzhou 341000, China

More Information

Corresponding author: E-mail: lzl8786489@163.com

摘要

摘要: 針對有色金屬冶煉煙氣中濕法脫汞過程產生的硫脲汞溶液難處置的問題，研究提出了電沉積從硫脲汞溶液中回收汞的新工藝。采用線性電位掃描法得到汞電沉積過程的陰極極化曲線，考察了不同雜質離子對硫脲汞溶液陰極極化曲線的影響。結果顯示，在控制陰極電位為?0.55～?0.45 V的條件下，溶液中的汞可選擇性沉積，溶液中Fe³⁺、Cu²⁺和H₂SO₃并不會影響溶液中汞的電沉積，即汞選擇性電沉積的電位為?0.55～?0.45 V。采用控電位技術對硫脲汞溶液電解回收汞工藝進行研究，探究了電解質種類和濃度、電解液溫度、攪拌速率、電解時間等因素對汞回收效率的影響。得到在陰極材料為銅片的條件下，最佳的電解工藝參數：電解質為0.24 mol·L^?1 Na₂SO₄，電解液溫度為30～40 ℃，攪拌速度為100～300 r·min^?1，$ {\rm{SO}}^{2-}_{3}$濃度為8 mmol·L^?1，電解時間為5 h。最佳工藝條件下，溶液中汞的回收效率可達98%以上。對陰極電解產物進行分析，陰極上的汞為單質汞，且純度超過99%。
- 酸性溶液 /
- 硫脲 /
- 電沉積 /
- 汞回收 /
- 控電位
Abstract: Mercury, a heavy metal, can seriously harm human bodies and the environment due to its characteristics of high toxicity, biological enrichment, and long-range migration. The non-ferrous metal smelting industry is one of the main sources of atmospheric mercury pollution in China. Therefore, controlling atmospheric mercury emissions from non-ferrous smelting plants is very important. The wet cleaning process has been widely applied in the purification of smelting flue gas because of its advantages such as a high removal efficiency, stable operation, and low cost. During the wet purification process, thiourea is usually added because it can reduce the oxidation potential of mercury and react with mercury to form stable coordination ions, resulting in the high-efficiency removal of mercury from high-sulfur smelting flue gas. However, mercury recovery from scrubbing solutions containing mercury and thiourea obtained from the wet cleaning process is difficult. In this study, a novel technology to recover mercury from the thiourea mercury solution via electrodeposition was proposed and investigated. The linear potential scanning method was applied to obtain the reduction potential of mercury. It was determined that the optimal potential of the mercury electrodeposition process should be controlled between ?0.55 V and ?0.45 V because the presence of ferric ions, copper ions, and sulfite ions did not seriously affect the electrodeposition of mercury. Controlled potential electrolysis was employed to efficiently recover mercury from thiourea mercury solution, and the effects of key parameters, including electrolyte type and concentration, electrolyte temperature, stirring rate, and electrolytic time, on the mercury recovery efficiency were explored. The optimal process conditions are as follows: a cathode material of copper sheet, electrolyte of 0.24 mol·L^?1 Na₂SO₄, electrolyte temperature of 30–40 ℃, stirring speed of 100–300 r·min^?1, $ {\rm{SO}}^{2-}_{3} $ concentration of 8 mmol·L^?1, and electrolytic time of 5 h. Under the optimal process conditions, the mercury recovery efficiency mercury is over 98%. The electrolytic products on the cathode are elemental mercury, and the corresponding purity is over 99%.
- acid solution /
- thiourea /
- electrodeposition /
- mercury recovery /
- controlled potential

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圖 1 硫脲體系Hg²⁺還原的陰極極化曲線

Figure 1. Cathodic polarization curve of Hg²⁺ reduction in thiourea system

下載: 全尺寸圖片幻燈片

圖 2 Fe³⁺對電沉積過程陰極極化曲線的影響

Figure 2. Effect of Fe³⁺ on cathodic polarization curve in electrodeposition process

下載: 全尺寸圖片幻燈片

圖 3 Cu²⁺對電沉積過程陰極極化曲線的影響

Figure 3. Effect of Cu²⁺ on the cathodic polarization curve in the electrodeposition process

下載: 全尺寸圖片幻燈片

圖 4 H₂SO₃對電沉積過程陰極極化曲線的影響

Figure 4. Effect of H₂SO₃ on the cathodic polarization curve in the electrodeposition process

下載: 全尺寸圖片幻燈片

圖 5 不同電解質及濃度對汞回收效率的影響

Figure 5. Effect of different electrolytes and concentrations on mercury recovery efficiency

下載: 全尺寸圖片幻燈片

圖 6 電解液溫度（a）和攪拌速度（b）對汞回收效率的影響

Figure 6. Effect of the temperature of mercury electrolytes (a) and rotate speed (b) on mercury recovery efficiency

下載: 全尺寸圖片幻燈片

圖 7 電流效率隨時間（a）和${\rm{SO}}_3^{2-} $濃度（b）的變化

Figure 7. Change in current efficiency with electrolysis time and ${\rm{SO}}_3^{2-} $ concentration

下載: 全尺寸圖片幻燈片

圖 8 電位為?0.5 V下電解1 h后的石墨陰極（a）和銅片陰極（b）的掃描電鏡圖

Figure 8. SEM image of graphite cathode (a) and copper cathode (b) under a constant potential of ?0.5 V and electrolysis time of 1 h

下載: 全尺寸圖片幻燈片

表 1 模擬洗滌凈化液的主要化學組成（質量濃度）

Table 1. Elemental composition of simulated cleaning solution mg·L^?1

Hg²⁺	Zn²⁺	Pd²⁺	Cu²⁺	Cd²⁺
70	125	10	10	10

Fe²⁺	F^?	Cl^?	As³⁺	H₂SO₄
30	200	600	80	500

下載: 導出CSV

表 2 石墨電極和銅片電極不同區域能量色散X射線光譜元素分析結果

Table 2. Results of EDX elemental analysis in different areas of graphite cathode and copper cathode

Element	Mass fraction (graphite electrode)/%			Mass fraction (copper sheet electrode)/%
Element	Area 1	Area 2	Area 3	Area 1	Area 2
Na	11.68	10.77	2.49	0	0
Cl	13.11	14.86	4.90	0	0
S	53.07	35.43	14.53	0.54	0.34
Hg	22.15	38.94	78.09	99.46	99.66

下載: 導出CSV

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