高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (3): 473-480.doi: 10.7503/cjcu20190486

• 研究论文:无机化学 • 上一篇    下一篇

阴离子在脱硫石膏晶须水热结晶中的作用机理

汪潇1,金彪1,王宇斌2,*,徐卓越1,张鲁2,张小婷1,杨留栓1   

  1. 1. 河南城建学院材料与化工学院, 平顶山 467036
    2. 西安建筑科技大学资源工程学院, 西安 710055
  • 收稿日期:2019-09-11 出版日期:2020-02-17 发布日期:2019-12-31
  • 通讯作者: 王宇斌
  • 作者简介:王宇斌, 男, 博士, 副教授, 主要从事矿物材料方面的研究. E-mail: wangyubin1972@sohu.com
  • 基金资助:
    国家自然科学基金(Nos.51674097);国家自然科学基金(Nos.51974218);河南省科技厅基金(Nos.152102210090);河南省科技厅基金(Nos.172102310729);河南城建学院学术技术带头人资助项目(No.YCJXSJSDTR201706);河南城建学院青年骨干教师基金资助(No.G2015002)

Interaction Mechanism of Anions in Hydrothermal Crystallization of Desulfurization Gypsum Whiskers

WANG Xiao1,JIN Biao1,WANG Yubin2,*,XU Zhuoyue1,ZHANG Lu2,ZHANG Xiaoting1,YANG Liushuan1   

  1. 1. School of Chemical & Material Engineering, Henan University of Urban Construction, Pingdingshan 467036, China
    2. School of Resources Engineering, Xi’an University of Architecture & Technology, Xi’an 710055, China
  • Received:2019-09-11 Online:2020-02-17 Published:2019-12-31
  • Contact: Yubin WANG
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.51674097);† Supported by the National Natural Science Foundation of China(Nos.51974218);the Science and Technology Department of Henan Province, China(Nos.152102210090);the Science and Technology Department of Henan Province, China(Nos.172102310729);the Henan University of Urban Construction(HUUC) Academic and Technical Leaders Funded Projects, China(No.YCJXSJSDTR201706);the Youth Key Teacher Fund Project of Hennan University of Urban Construction, China(No.G2015002)

摘要:

以经预处理的烟气脱硫石膏为原料, 分别以氯化铜、 硫酸铜和硝酸铜为添加剂, 采用水热法制备了脱硫石膏晶须; 通过傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)和X射线衍射(XRD)等对晶须进行了表征; 并探讨了不同阴离子及其作用下的Cu 2+在晶体结晶过程中的作用机理. 结果表明, Cu 2+存在条件下阴离子对脱硫石膏的溶解特性和晶须的结晶形貌均有显著影响, 且其作用强于Cu 2+, 并会影响Cu 2+在晶须表面的吸附状态. N O 3 - 可促进脱硫石膏的溶解, Cl -次之, 而S O 4 2 - 则阻碍了脱硫石膏的溶解. 在Cl -作用下, 晶须样品直径均匀, 长径比较大, 在S O 4 2 - 作用下晶须样品中颗粒状产物含量较多, 而在N O 3 - 作用下晶须样品粗化. 在不同阴离子作用下Cu 2+化学吸附的程度不同, 导致样品表面S O 4 2 - 的反对称伸缩振动吸收峰向低波数方向漂移并发生窄化; 并导致晶须表面氧元素电子结合能的减小幅度及Cu—O结合能的大小出现差异, 其在N O 3 - 作用下最大, S O 4 2 - 作用下次之, Cl -作用下最弱.

关键词: 脱硫石膏, 晶须, 添加剂, 表面特性, 溶解

Abstract:

Desulfurization gypsum whiskers were prepared by hydrothermal method using purified flue gas desulfurization(FGD) gypsum as raw materials, CuCl2, CuSO4 or Cu(NO3)2 as additive. The crystal samples were characterized by FTIR, XPS, XRD, etc. to discuss the mechanism of Cu 2+ under different anions and these anions in crystal crystallization. The results show that the solubility characteristics of FGD gypsum and the crystal morphology of whiskers are affected by the anions under the effect of Cu 2+. The effect of anions is stronger than that of Cu 2+, and the adsorption state of Cu 2+ on whisker surfaces is affected by anions. The N O 3 - promotes the dissolution of FGD gypsum, the Cl - takes the second place, and the S O 4 2 - hinders the dissolution of FGD gypsum. The whiskers with uniform diameter and large aspect ratio are prepared under the effect of Cl -, the whisker samples with high content of granular products can be prepared under the effect of S O 4 2 - , and the whisker samples are coarsened under the effect of N O 3 - . The degree of chemical adsorption of Cu 2+ is different under the effect of different anions, which leads to the right drift and narrowing of the antisymmetric stretching vibration absorption peak of S O 4 2 - on the surface of the sample, and the differences of the decrease extent of electron binding energy of oxygen elements on whisker surface and the intensity of Cu—O binding energy. The intensity of Cu—O binding energy is the highest under the effect of N O 3 - , the second under the effect of S O 4 2 - , and the weakest under the effect of Cl -.

Key words: Desulfurization gypsum, Whisker, Additive, Surface characteristics, Dissolution

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