磷石膏浮选-常压盐溶液转晶制备α-半水石膏

doi:10.19964/j.issn.1006-4990.2023-0063

Abstract

Abstract:

In order to realize the high value utilization of phosphogypsum，froth flotation-atmospheric Na₂SO₄ solution crystallization method was used to convert phosphogypsum sampled from Hubei province into α-hemihydrate gypsum.The morphology，composition and mechanical strength of the product were characterized through various characterization methods（like SEM-EDS，XRF，XRD，FT-IR，TG-DSC，whiteness test and mechanical strength test）.Experimental data revealed that the final product had uniform particle size with aspect ratio of 1.50±0.271.Whiteness and purity（based on CaSO₄） of the product was found to be around 84.6% and 95%，respectively.Most of the Si，F and P impurities was removed during the treatment，and final impurity level met the requirement of Grade I phosphogypsum in the National Standard GB/T 23456—2018 as the raw material of gypsum building materials.The compressive and 2 h flexural strength of hardened body of the crystallized product were higher than 36.3 MPa and 7.7 MPa，respectively，which met the requirements of the relevant national and industrial standards for the mechanical strength grade of high strength gypsum.The research was illustrated that α-hemihydrate gypsum with high whiteness，high purity，and high mechanical strength could synthesize by the process，and could be considered as a potential option for phosphogypsum.

Key words: phosphogypsum, α-hemihydrate gypsum, flotation, saline solution, crystal modifier

CLC Number:

TQ177.3

LIU Chao, FAN Chuigang, LIU Runguo, YU Dongxue, LI Songgeng. Preparation of α-hemihydrate gypsum from phosphogypsum by flotation and atmospheric trans-crystallization in solution[J]. Inorganic Chemicals Industry, 2023, 55(11): 107-114.

Figures/Tables 16

Fig.1

Table 1

Fig.2

Table 2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

Fig.11

Fig.12

Table 3

Fig.13

References 25

1	LI Xibing， DU Jing， GAO Li，et al.Immobilization of phosphogypsum for cemented paste backfill and its environmental effect［J］.Journal of Cleaner Production，2017，156：137-146.
2	杨兆娟，向兰.磷石膏综合利用现状评述［J］.无机盐工业，2007，39（1）：8-10.
	YANG Zhaojuan， XIANG Lan.Review of comprehensive utilization of phosphogypsum［J］.Inorganic Chemicals Inoustry，2007，39（1）：8-10.
3	TIAN Tian， YAN Yun， HU Zhihua，et al.Utilization of original phosphogypsum for the preparation of foam concrete［J］.Construction and Building Materials，2016，115：143-152.
4	YANG Lin， CAO Jianxin， LI Caiyu.Enhancing the hydration reactivity of hemi-hydrate phosphogypsum through a morphology-controlled preparation technology［J］.Chinese Journal of Chemical Engineering，2016，24（9）：1298-1305.
5	CHERNYSH Y， YAKHNENKO O， CHUBUR V，et al.Phosphogypsum recycling：A review of environmental issues，current trends，and prospects［J］.Applied Sciences，2021，11（4）：1575.
6	DU Mingxia， WANG Jinming， DONG Faqin，et al.The study on the effect of flotation purification on the performance of α-hemihydrate gypsum prepared from phosphogypsum［J］.Scientific Reports，2022，12：95.
7	MA Baoguo， JIN Zihao， SU Ying，et al.Utilization of hemihydrate phosphogypsum for the preparation of porous sound absorbing material［J］.Construction and Building Materials，2020，234：117346.
8	韩青，罗康碧，李沪萍，等.磷石膏开发利用现状［J］.化工科技，2012，20（1）：53-58.
	HAN Qing， LUO Kangbi， LI Huping，et al.Development and utilization status on the phosphogypsum［J］.Science & Technology in Chemical Industry，2012，20（1）：53-58.
9	RU Xiaohong， MA Baoguo， HUANG Jian，et al.Phosphogypsum transition to α-calcium sulfate hemihydrate in the presence of omongwaite in NaCl solutions under atmospheric pressure［J］.Journal of the American Ceramic Society，2012，95（11）：3478-3482.
10	胡宏，何兵兵，薛绍秀. α-半水石膏的制备与应用研究进展［J］.新型建筑材料，2015，42（4）：44-48.
	HU Hong， HE Bingbing， XUE Shaoxiu.Research progress on preparation and application of α-calcium sulfate hemihydrate［J］.New Building Materials，2015，42（4）：44-48.
11	MAO Jingwei， JIANG Guangming， CHEN Qiaoshan，et al.Influences of citric acid on the metastability of α-calcium sulfate hemihydrate in CaCl₂ solution［J］.Colloids and Surfaces A：Physicochemical and Engineering Aspects，2014，443：265-271.
12	王鑫，纪利俊，陈葵，等.pH与Ca²⁺浓度对磷石膏常压制备α-半水硫酸钙的影响［J］.无机盐工业，2017，49（11）：54-58.
	WANG Xin， JI Lijun， CHEN Kui，et al.Effects of pH and Ca²⁺ concentration on formation of α-hemihydrate calcium sulfate by phosphogypsum under atmospheric pressure［J］.Inorganic Chemicals Industry，2017，49（11）：54-58.
13	陈金文，易芸，张慧，等.蒸压参数与杂质对磷石膏制备α-半水石膏的影响［J］.无机盐工业，2022，54（3）：91-96.
	CHEN Jinwen， YI Yun， ZHANG Hui，et al.Effect of autoclave parameters and impurities on preparation of α-hemihydrate gypsum from phosphogypsum［J］.Inorganic Chemicals Industry，2022，54（3）：91-96.
14	丁峰，窦焰，郑之银，等.常压盐溶液-丁二酸转晶体系中pH对α-CaSO₄·0.5H₂O的影响［J］.无机盐工业，2020，52（1）：82-86，98.
	DING Feng， DOU Yan， ZHENG Zhiyin，et al.Effect of pH on α-CaSO₄·0.5H₂O in salt solution at atmospheric pressure-succinic acid crystal transfer system［J］.Inorganic Chemicals Industry，2020，52（1）：2-86，98.
15	FELDMANN T， DEMOPOULOS G P.Influence of impurities on crystallization kinetics of calcium sulfate dihydrate and hemihydrate in strong HCl-CaCl₂ solutions［J］.Industrial & Engineering Chemistry Research，2013，52（19）：6540-6549.
16	马保国，茹晓红，邹开波，等.常压水热Ca-Na-Cl溶液中用磷石膏制备α-半水石膏［J］.化工学报，2013，64（7）：2701-2707.
	MA Baoguo， RU Xiaohong， ZOU Kaibo，et al.Preparation of α-calcium sulfate hemihydrate from phosphogypsum in Ca-Na-Cl solutions under atmospheric pressure［J］.CIESC Journal，2013，64（7）：2701-2707.
17	KONG Xia， LUO Kangbi， LI Huping，et al.Removing impurity fluorine from phosphogypsum by sulfuric acid leaching method［J］.Chemical Engineering，2012，40（8）：65-68.
18	KONG Bao， GUAN Baohong， YATES M Z，et al.Control of α-calcium sulfate hemihydrate morphology using reverse microemulsions［J］.Langmuir，2012，28（40）：14137-14142.
19	陈燕，岳文海，董若兰.石膏建筑材料［M］.2版.北京：中国建材工业出版社，2012.
20	POWELL D A.The α- and β-forms of calcium sulphate hemihydrate［J］.Nature，1960，185（4710）：375-376.
21	CLIFTON J R.Thermal analysis of calcium sulfate dihydrate and supposed a and forms of calcium sulfate hemihydrate from 25 to 500 C［J］.Journal of Research of the National Bureau of Standards Section A：Physics and Chemistry，1972，76A（1）：41.
22	POWELL D A.Transformation of the α- and β-forms of calcium sulphate hemihydrate to insoluble anhydrite［J］.Nature，1958，182（4638）：792.
23	LI Xianbo， ZHANG Qin.Effect of molecular structure of organic acids on the crystal habit of α-CaSO₄·0.5H₂O from phosphogypsum［J］.Crystals，2020，10（1）：24.
24	SHAO Duoduo， ZHAO Bin， ZHANG Hongqi，et al.Preparation of large-grained α-high strength gypsum with FGD gypsum［J］.Crystal Research and Technology，2017，52（7）：1700078.
25	陈星宇，陈德玉，米阳，等.丁二酸对磷石膏制备α-半水石膏晶体生长的影响［J］.四川建材，2022，48（1）：22-23.
	CHEN Xingyu， CHEN Deyu， MI Yang，et al.Effect of succinic acid on crystal growth of α-hemihydrate gypsum prepared from phosphogypsum［J］.Sichuan Building Materials，2022，48（1）：22-23.

检测项目	检测技术	仪器与设备	表征手段
表面形貌	SEM	JSM-7001F型热场发射扫描电子显微镜	将样品研磨成粉体，60 ℃烘干，进行喷金，于镜下观察
表面元素	EDS	INCAX-MAX型能谱仪	加速电压调节至15 kV后进行高真空能谱测试
晶相组成	XRD	Smartlab（9）型X射线衍射仪	将样品研磨至粉末，烘干制样，扫描范围为2θ=5°~90°
化学成分	XRF	AXIOS max型X射线荧光分析仪	将样品与硼酸混合，压片制样，进行组分分析
热分析	TG-DSC	STA-449C型综合热分析仪	T_初始=30 ℃，T_最终=600 ℃，升温速率为10 ℃/min，载气为氮气（50 mL/min），保护气为氩气（20 mL/min）
白度分析	标准比色法	WSD-3U型白度计	将白度计预热30 min，然后进行仪器矫正，压片，测量白度
稠度分析	标准稠度用水量	CHD-50型石膏稠度仪	参考GB/T 17669.4—1999《建筑石膏净浆物理性能的测定》
强度分析	烘干抗压强度及2 h抗折强度	WDW-50G型电子万能实验拉伸机	参考GB/T 17669.3—1999《建筑石膏力学性能的测定》、JC/T 2038—2010《α型高强石膏》

等级	2 h抗折强度/MPa	烘干抗压强度/MPa
α25	3.5	25.0
α30	4.0	30.0
α40	5.0	40.0
α50	6.0	50.0

[1]	LENG Manxi, ZHU Yu, YAN Jikang, XIE Ke, ZOU Yongjie. Study on crystallization characteristics and mineral flotation performance of industrial waste phosphogypsum [J]. Inorganic Chemicals Industry, 2025, 57(3): 108-115.
[2]	TAN Shanyi, WEN Huizi, HE Shuyu, ZHANG Liwen, CHEN Shaohua, XI Benjun. Study on leaching behavior and kinetics of phosphorus from phosphogypsum [J]. Inorganic Chemicals Industry, 2025, 57(2): 105-112.
[3]	TANG Kaijing, LIU Chuanbei, LI Yingding, JIANG Yong, WU Junnan, ZHANG Tao. Research on preparation and mechanism of superhydrophobic phosphogypsum products [J]. Inorganic Chemicals Industry, 2025, 57(1): 97-102.
[4]	WANG Rui, ZHAO Hui, ZHAO Yuhang. Comparative study on decarbonization of aluminum extraction residue from fly ash by roasting and flotation [J]. Inorganic Chemicals Industry, 2024, 56(9): 136-141.
[5]	TANG Xuemei, WANG Meibo, XU Li, ZHANG Xujie, TAI Shijun, YI Xianmei, LIU Hongjuan, PAN Linyi. Study on whitening of phosphogypsum by low⁃temperature calcination [J]. Inorganic Chemicals Industry, 2024, 56(8): 110-115.
[6]	SUN Lan, CHEN Shiying, YANG Liuxu, NIU Yiming, ZHAO Aonan. Basic study on fixing soluble phosphorus in phosphogypsum with magnesium slag [J]. Inorganic Chemicals Industry, 2024, 56(8): 92-98.
[7]	HU Cheng, LIU Meng, XIANG Weiheng, CHEN Ping, WANG Neng, LU Guanju, ZHOU Jinlan. Preparation of α-hemihydrous gypsum from CaCl₂ and MgCl₂ and their composite solution [J]. Inorganic Chemicals Industry, 2024, 56(7): 112-117.
[8]	HU Dian, GUO Ze, ZHANG Hanquan, LU Manman. Research on effects of roasting process and typical impurities on reduction and decomposition process of phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(7): 88-95.
[9]	HU Cheng, LIU Meng, XIANG Weiheng, DUAN Pengxuan, LI Shunkai, MING Yang, WANG Neng, LU Guanju. Effect of NaCl solution concentration on transcrystallization behavior of α-hemihydrate gypsum from phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(6): 87-93.
[10]	TU Yanping, BAI Dengxian, CHENG Shukai, XIE Junjie, HUANG Zhiliang, CHEN Guofu. Effect of high temperature modification of mineral powder and quicklime on properties of phosphogypsum cement based materials [J]. Inorganic Chemicals Industry, 2024, 56(6): 94-101.
[11]	WANG Mingshun, AO Xianquan, YUAN Xing, DONG Wenyan, CHEN Qianlin. Study on effect of crystallizer on preparation of anhydrous calcium sulfate from phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(5): 101-107.
[12]	DENG Fuli, XIA Zhixiang, LONG Bingwen, ZHANG Yi, DAI Yafen, WANG Bin, DING Yigang. Study on purification process of phosphogypsum by reverse flotation [J]. Inorganic Chemicals Industry, 2024, 56(5): 115-120.
[13]	WANG Peixiong, GONG Xiaomei, DING Jiaqi, CAO Hong. Effect of crystal modifier on preparation of α-hemihydrates gypsum from industrial gypsum [J]. Inorganic Chemicals Industry, 2024, 56(4): 112-117.
[14]	CHEN Feng, FENG Kang, LI Ming, SHEN Haojie, TIAN Chengtao, TANG Yuan, LI Zhili, HE Dongsheng. Application of organically modified calcium sulfate whiskers in asphalt modification [J]. Inorganic Chemicals Industry, 2024, 56(3): 125-130.
[15]	WANG Ruting, ZHAO Xiaorong, HUANG Xuquan, WANG Haojie, XUE Fei, CAI Jiawei. Research on preparation and early performance of mixed phase phosphogypsum-based cementing materials [J]. Inorganic Chemicals Industry, 2024, 56(3): 98-104.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Preparation of α-hemihydrate gypsum from phosphogypsum by flotation and atmospheric trans-crystallization in solution

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 16

References 25

Related Articles 15

Metrics

Comments

Recommended 0