Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime

doi:10.1016/S1004-9541(13)60626-6

Chin.J.Chem.Eng. ›› 2013, Vol. 21 ›› Issue (11): 1303-1312.DOI: 10.1016/S1004-9541(13)60626-6

• ENERGY, RESOURCES AND ENVIRONMENTAL TECHNOLOGY • Previous Articles Next Articles

Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime

DENG Licong^1,2, ZHANG Yifei¹, CHEN Fangfang¹, CAO Shaotao¹, YOU Shaowei^1,2, LIU Yan^1,2, ZHANG Yi¹

1 Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
2 Graduate University of Chinese Academy of Sciences, Beijing 100049, China

Received:2012-07-30 Revised:2012-12-17 Online:2013-11-26 Published:2013-11-28
Contact: ZHANG Yifei, CHEN Fangfang
Supported by:
Supported by the National High Technology Research and Development Program of China (2011AA060701) and the National Water Pollution Control and Management Science Program of China (2009ZX07529-005).

Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime

邓立聪^1,2, 张亦飞¹, 陈芳芳¹, 曹绍涛¹, 游韶玮^1,2, 刘艳^1,2, 张懿¹

1 Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
2 Graduate University of Chinese Academy of Sciences, Beijing 100049, China

通讯作者: ZHANG Yifei, CHEN Fangfang
基金资助:
Supported by the National High Technology Research and Development Program of China (2011AA060701) and the National Water Pollution Control and Management Science Program of China (2009ZX07529-005).

Abstract

Abstract: The present work focused on the recycle of the sulfate and the metal ions from acidic wastewater discharged by nonferrous metallurgical industry. The effects of the temperature, the reactant concentration, the stirring speed and the metal ions on the reactive crystallization process of calcium sulfate between sulfuric acid and lime were systematically investigated. The morphology of the precipitated crystals evolved from platelet-like and needle-like shape to rod-like shape when the temperature was increased from 25 to 70 ℃. An increase in the agglomeration of calcium sulfate was found with increasing lime concentration. Metal ions markedly retard the rate of crystallization of calcium sulfate dihydrate. The crystallization of gypsum was slowed with the existence of Mg²⁺ in the solution, and the morphology of gypsum was transformed from platelet-like shape to rod-like shape when Mg²⁺ concentration reached 0.08 mol·L^-1. The amorphous ferric hydroxide was coated on the calcium sulfate after the co-precipitation process while Zn²⁺ and Al³⁺ ions in the solution enhanced the agglomeration of the calcium sulfate by absorbing on the surface of the crystals. Comprehensive acidic wastewater containing heavy metals was efficiently purified by the two stage lime neutralization technology, and highly agglomerated gypsum precipitates with needle-like shape were obtained. The precipitates could be purified by sulfuric acid washing, and the metal ions were effectively separated from the calcium sulfate by-products.

Key words: reactive crystallization, acidic wastewater, lime milk, calcium sulfate dihydrate

摘要： The present work focused on the recycle of the sulfate and the metal ions from acidic wastewater discharged by nonferrous metallurgical industry. The effects of the temperature, the reactant concentration, the stirring speed and the metal ions on the reactive crystallization process of calcium sulfate between sulfuric acid and lime were systematically investigated. The morphology of the precipitated crystals evolved from platelet-like and needle-like shape to rod-like shape when the temperature was increased from 25 to 70 ℃. An increase in the agglomeration of calcium sulfate was found with increasing lime concentration. Metal ions markedly retard the rate of crystallization of calcium sulfate dihydrate. The crystallization of gypsum was slowed with the existence of Mg²⁺ in the solution, and the morphology of gypsum was transformed from platelet-like shape to rod-like shape when Mg²⁺ concentration reached 0.08 mol·L^-1. The amorphous ferric hydroxide was coated on the calcium sulfate after the co-precipitation process while Zn²⁺ and Al³⁺ ions in the solution enhanced the agglomeration of the calcium sulfate by absorbing on the surface of the crystals. Comprehensive acidic wastewater containing heavy metals was efficiently purified by the two stage lime neutralization technology, and highly agglomerated gypsum precipitates with needle-like shape were obtained. The precipitates could be purified by sulfuric acid washing, and the metal ions were effectively separated from the calcium sulfate by-products.

关键词: reactive crystallization, acidic wastewater, lime milk, calcium sulfate dihydrate

DENG Licong, ZHANG Yifei, CHEN Fangfang, CAO Shaotao, YOU Shaowei, LIU Yan, ZHANG Yi. Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime[J]. Chin.J.Chem.Eng., 2013, 21(11): 1303-1312.

邓立聪, 张亦飞, 陈芳芳, 曹绍涛, 游韶玮, 刘艳, 张懿. Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime[J]. Chinese Journal of Chemical Engineering, 2013, 21(11): 1303-1312.

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Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime

Reactive Crystallization of Calcium Sulfate Dihydrate from Acidic Wastewater and Lime

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