氯盐体系下阳离子对脱硫石膏晶须水热结晶的影响及其机理

doi:10.16085/j.issn.1000-6613.2022-0099

化工进展 ›› 2022, Vol. 41 ›› Issue (7): 3957-3965.DOI: 10.16085/j.issn.1000-6613.2022-0099

氯盐体系下阳离子对脱硫石膏晶须水热结晶的影响及其机理

汪潇¹(), 金彪¹, 张小婷¹, 张建武¹, 王宇斌², 苑冬冬¹, 杨留栓¹

^1.河南城建学院材料与化工学院，河南平顶山 467036
^2.西安建筑科技大学资源工程学院，陕西西安 710055

收稿日期:2022-01-13 修回日期:2022-03-10 出版日期:2022-07-25 发布日期:2022-07-23
通讯作者: 汪潇
作者简介:汪潇（1975—），男，博士，副教授，研究方向为固体废物资源化利用。E-mail：wx407@126.com。
基金资助:
国家自然科学基金面上项目(51674097);河南省重大公益专项(201300311000);河南城建学院工业副产石膏资源化创新团队资助项目(K-X2020020)

Effect of cation on hydrothermal crystallization of desulfurized gypsum whiskers in chloride system and its mechanism

WANG Xiao¹(), JIN Biao¹, ZHANG Xiaoting¹, ZHANG Jianwu¹, WANG Yubin², YUAN Dongdong¹, YANG Liushuan¹

^1.School of Chemical & Material Engineering, Henan University of Urban Construction, Pingdingshan 467036, Henan, China
^2.School of Resources Engineering, Xi’an University of Architecture & Technology, Xi’an 710055, Shaanxi, China

Received:2022-01-13 Revised:2022-03-10 Online:2022-07-25 Published:2022-07-23
Contact: WANG Xiao

摘要/Abstract

摘要：

为探索阳离子对水热制备脱硫石膏晶须结晶调控的影响，本文以预处理后的脱硫石膏为原料，NaCl、CuCl₂、AlCl₃为添加剂采用水热法制备脱硫石膏晶须，重点研究Cl^-存在条件下阳离子对脱硫石膏晶须结晶的影响及其作用机理。结果表明，Na⁺、Cu²⁺、Al³⁺对脱硫石膏晶须的显微结构、长径比和品质均有一定的影响，其中Cu²⁺影响最为显著。Cu²⁺可在晶须的(200)、(400)和(020)晶面发生化学吸附形成CuSO₄膜层，使其径向生长受阻；同时，少量Cu²⁺可取代Ca²⁺，促进Ca²⁺的去溶剂化，使晶须长径比增大至200。Na⁺和Al³⁺均通过物理吸附作用于脱硫石膏晶须(200)、(400)和(020)晶面而阻碍其径向生长。此外，Al³⁺与溶液中的OH^-通过羟基化反应生成Al(OH)²⁺和Al(OH)₂⁺，吸附在带负电的(200)、(400)和(020)晶面，降低这些晶面的表面能，从而促进脱硫石膏晶须沿c轴生长。

关键词: 脱硫石膏, 氯盐体系, 晶须, 阳离子, 作用机理

Abstract:

Using pretreated desulfurized gypsum as raw material, and NaCl, CuCl₂ and AlCl₃ as additives, desulfurized gypsum whiskers were prepared by hydrothermal method in order to explore the effect of cations on their crystallization regulation. The study focused on the effect of cations on the crystal of desulfurized gypsum whiskers in the presence of Cl^- and their mechanism. The results showed that Na⁺, Cu²⁺, Al³⁺ could affect the microstructure, aspect ratio and quality of desulfurized gypsum whiskers, but the effect of Cu²⁺ was more significant. Cu²⁺ could chemically adsorb on (200), (400) and (020) crystal faces of the crystal of whisker to form a CuSO₄ film, which hindered its radial growth. At the same time, a little of Cu²⁺ could replace Ca²⁺, thereby promoting the desolvation of Ca²⁺, which caused an increase of the whisker aspect ratio to 200. However, both Na⁺ and Al³⁺ acted on (200), (400) and (020) crystal faces through physical adsorption and hindered the radial growth of desulfurized gypsum whiskers. In addition, Al³⁺ reacted with OH^- in the solution to generate Al(OH)²⁺ and Al(OH)₂⁺, and they were adsorbed on the (200), (400) and (020) planes with negative charges, which reduced surface energy of the above planes and also promoted the growth of desulfurized gypsum whiskers along the c-axis.

Key words: desulfurization gypsum, chloride system, whisker, cation, mechanism

中图分类号:

O611

汪潇, 金彪, 张小婷, 张建武, 王宇斌, 苑冬冬, 杨留栓. 氯盐体系下阳离子对脱硫石膏晶须水热结晶的影响及其机理[J]. 化工进展, 2022, 41(7): 3957-3965.

WANG Xiao, JIN Biao, ZHANG Xiaoting, ZHANG Jianwu, WANG Yubin, YUAN Dongdong, YANG Liushuan. Effect of cation on hydrothermal crystallization of desulfurized gypsum whiskers in chloride system and its mechanism[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3957-3965.

图/表 11

表1 预处理前后脱硫石膏的化学组成（质量分数）单位：%

处理方式	CaO	SO₃	Al₂O₃	SiO₂	Fe₂O₃	MgO	TiO₂	K₂O	Na₂O
预处理前	33.23	37.23	2.86	5.18	0.64	1.24	0.10	0.21	0.01
预处理后	31.02	43.98	1.06	2.48	0.32	0.15	0.05	0	0

图1 不同阳离子作用下水热制备脱硫石膏晶须的SEM照片

图2 不同阳离子作用下水热制备的脱硫石膏晶须的长径比

图3 脱硫石膏晶须的XRD衍射图谱和主要晶面窄谱图

图4 脱硫石膏水热产物的红外光谱图和局部放大图

图5 不同阳离子作用下SO42-官能团的红外分峰拟合图

图6 脱硫石膏晶须XPS全谱图

图7 不同阳离子作用下脱硫石膏晶须样品中氧元素的XPS窄谱图

表2 氧的价键形式及其分布

添加剂	面积				面积百分比/%
添加剂	Ca―O―S	H―O	R―O	合计	Ca―O―S	H―O	R―O
无	435646.30	193732.74	—	629379.04	69.22	40.78	—
NaCl	296950.41	94892.78	—	378005.79	75.78	24.22	—
CuCl₂	240580.59	55997.44	35539.94	332117.97	72.44	16.86	10.71
AlCl₃	150731.44	39263.23	38190.37	228185.04	66.06	17.21	16.74

图8 pH与Cu2+和Al3+成分分布系数图

图9 不同阳离子作用下试样羟基官能团的红外分峰拟合图

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氯盐体系下阳离子对脱硫石膏晶须水热结晶的影响及其机理

Effect of cation on hydrothermal crystallization of desulfurized gypsum whiskers in chloride system and its mechanism

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