NaCl溶液浓度对磷石膏制备α-半水石膏转晶行为的影响

doi:10.19964/j.issn.1006-4990.2023-0409

Abstract

Abstract:

In order to improve the utilization rate and added value of phosphogypsum by-products discharged from wet phosphoric acid process，α-hemihydrate phosphogypsum materials were prepared in NaCl solution by the atmospheric pressure hydrothermal synthesis method，and the effects of NaCl solution concentration on crystal water content，crystallization behavior，mineral phase composition and microscopic morphology of α-hemihydrous phosphogypsum were studied.The results showed that the crystalline water content of phosphogypsum was gradually decreased with the prolongation of reaction time in 10.0%~20.0% NaCl solution at a temperature of 95 ℃ and leveled off after decreasing to about 6%.Combined with XRD and SEM analysis，it was concluded that phosphogypsum could be dehydrated and recrystallized to form stable α-hemihydrous gypsum with hexagonal columnar shape in 10.0%~20.0% NaCl solution at 95 ℃.At the same time，the dehydrated transcrystallization rate of phosphogypsum was increased slowly at first，then rapidly，and finally gradually tended to be gentle，which was a typical growth-nucleation dynamic process.With the increase of NaCl concentration，the induced nucleation time and crystal growth time of α-hemihydrous phosphogypsum were gradually accelerated，and the total crystallization time was gradually shortened.Among them，the completely dehydrated transcrystallization time of phosphogypsum in 20.0%NaCl solution was only 0.5 h，and which was shortened by 1.38 h compared with 15.0%NaCl solution.Therefore，it was concluded that the increase of NaCl solution concentration accelerated the dehydration and crystallization efficiency of phosphogypsum，which could provide guidance for the actual large-scale production of α-hemihydrate gypsum.

Key words: phosphogypsum, α-hemihydrate gypsum, transcrystallization behavior, hydrothermal synthesis, NaCl solution

CLC Number:

TQ126.3

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.

Figures/Tables 9

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References 20

1	杨再银.中国工业副产石膏利用现状及“十四五” 展望［J］.硫酸工业，2021（7）：1-4，23.
	YANG Zaiyin.Utilization status of industrial by-product gypsum in China and its prospect in the 14th Five-Year Plan［J］.Sulphuric Acid Industry，2021（7）：1-4，23.
2	周妙琴，陶雪，廖迅，等.磷石膏产排情况及资源化利用研究进展［J］.云南化工，2022，49（12）：4-8.
	ZHOU Miaoqin， TAO Xue， LIAO Xun，et al.Production and discharge of phosphogypsum and research progress on its resource utilization［J］.Yunnan Chemical Technology，2022，49（12）：4-8.
3	黄照昊，罗康碧，李沪萍.磷石膏中杂质种类及除杂方法研究综述［J］.硅酸盐通报，2016，35（5）：1504-1508.
	HUANG Zhaohao， LUO Kangbi， LI Huping.Types of impurity in phosphogypsum and the method of removing impurity research review［J］.Bulletin of the Chinese Ceramic Society，2016，35（5）：1504-1508.
4	顾青山，林喜华，赵士豪，等.不同预处理工艺对磷石膏性能的影响［J］.无机盐工业，2022，54（4）：17-23.
	GU Qingshan， LIN Xihua， ZHAO Shihao，et al.Effect of different pretreatment processes on properties of phosphogypsum［J］.Inorganic Chemicals Industry，2022，54（4）：17-23.
5	LU Wenda， MA Baoguo， SU Ying，et al.Preparation of α-hemihydrate gypsum from phosphogypsum in recycling CaCl₂ solution［J］.Construction and Building Materials，2019，214：399-412.
6	张峻，解维闵，董雄波，等.磷石膏材料化综合利用研究进展［J］. 材料导报，2023，37（16）：167-178.
	ZHANG Jun， XIE Weimin， DONG Xiongbo，et al.Research progress on comprehensive utilization of phosphogypsum for materials：A review［J］.Materials Reports，2023，37（16）：167-178.
7	JIN Zihao， CUI Chengjia， XU Zihao，et al.Recycling of waste gypsum from αlpha-hemihydrate phosphogypsum：Based on the atmospheric hydrothermal process［J］.Construction and Building Materials，2023，377：131136.
8	胡成，向玮衡，陈平，等.丁二酸对水热合成α-半水脱硫石膏微晶形貌及力学强度的影响［J］.无机盐工业，2021，53（4）：76- 80.
	HU Cheng， XIANG Weiheng， CHEN Ping，et al.Effects of succinic acid on crystallite morphology and mechanical strength of α-hemihydrate desulfurized gypsum synthesized by hydrothermal method［J］.Inorganic Chemicals Industry，2021，53（4）：76-80.
9	LI Xianbo， HE Yuqi.Preparation of α-hemihydrate gypsum from phosphogypsum in glycerol and Na₂SO₄ mixed solutions under atmospheric pressure［J］.Journal of Crystal Growth，2021，568/569：126184.
10	YANG Liuchun， GUAN Baohong， WU Zhongbiao.Characterization and precipitation mechanism of α-calcium sulfate he-mihydrate growing out of FGD gypsum in salt solution［J］.Science in China Series E：Technological Sciences，2009，52（9）：2688-2694.
11	李显波，叶军建，王贤晨，等.盐介质对磷石膏常压盐溶液法制备α半水石膏的影响研究［J］.矿产保护与利用，2017（6）：79-86.
	LI Xianbo， YE Junjian， WANG Xianchen，et al.Effect of salt medium on preparation of α-hemihydrate from phosphogypsum using salt solution method［J］.Conservation and Utilization of Mineral Resources，2017（6）：79-86.
12	杨润，陈德玉，米阳，等.常压无氯复合盐溶液磷石膏制备α-半水石膏［J］.非金属矿，2019，42（4）：1-5.
	YANG Run， CHEN Deyu， MI Yang，et al.Preparation of α-semi hydrated gypsum from phosphogypsum in atmospheric pressure chlorine-free complex salt solution［J］.Non-Metallic Mines，2019， 42（4）：1-5.
13	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 Chemi-Industry cals，2017，49（11）：54-58.
14	杨后文，刘丰，江郡，等.常压水热法制备半水脱硫石膏的工艺因素研究［J］.矿产综合利用，2021（1）：140-143，198.
	YANG Houwen， LIU Feng， JIANG Jun，et al.Research on process condition on the preparation of hemihydrate desulfurization gypsum with hydrothermal method under atmospheric pressu-re［J］.Multipurpose Utilization of Mineral Resources，2021（1）：140-143，198.
15	刘先锋，舒渝艳，魏桂芳，等.盐溶液浓度对常压水热法制备α-半水脱硫石膏的影响［J］.科学技术与工程，2012，12（16）：3877-3879，3888.
	LIU Xianfeng， SHU Yuyan， WEI Guifang，et al.The effect of salt solution concentration on the preparation of α-calcium sulfate hemihydrate from FGD gypsum using the hydrothermal method under atmospheric pressure［J］.Science Technology and Engineering，2012，12（16）：3877-3879，3888.
16	陈平，田宇，胡成.盐溶液种类和浓度对α-半水脱硫石膏合成的影响［J］.无机盐工业，2020，52（10）：130-134.
	CHEN Ping， TIAN Yu， HU Cheng.Effect of type and concentration of salt solution on synthesis of α-semi-water desulfurization gypsum［J］.Inorganic Chemicals Industry，2020，52（10）：130- 134.
17	玉霞.磷石膏半液相法制备α-半水石膏中转晶剂的作用机理研究［D］.宜昌：三峡大学，2021.
	YU Xia.Mechanism of transforming agent in the semi-liquid method for preparation of α-hemihydrate gypsum by phosphogypsum［D］.Yichang：China Three Gorges University，2021.
18	SKRDLA P J.Crystallizations，solid-state phase transformations and dissolution behavior explained by dispersive kinetic models based on a Maxwell-boltzmann distribution of activation energies：Theory，applications，and practical limitations［J］.The Journal of Physical Chemistry A，2009，113（33）：9329-9336.
19	SKRDLA P J.Kinetics and thermodynamics of efficient chiral symmetry breaking in nearly racemic mixtures of conglomerate crystals［J］.Crystal Growth & Design，2011，11（5）：1957-1965.
20	毛经纬.脱硫石膏溶液结晶法制备α-半水石膏过程中的稳定性及结垢研究［D］.杭州：浙江大学，2013.
	MAO Jingwei.Metastability of α-calcium sulfate hemihydrate during preparation from FGD gypsum in salt solution and anti-fouling research［D］.Hangzhou：Zhejiang University，2013.

NaCl溶液质量分数/%	诱导成核时间/h	晶体生长时间/h	总转晶时间/h
10.0	3.82	10.84	14.66
12.5	2.02	8.81	10.83
15.0	0.54	1.34	1.88
17.5	0.30	0.73	1.03
20.0	0.15	0.35	0.50

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Inorganic Acid-Base-Salt Committee of CIESC

Effect of NaCl solution concentration on transcrystallization behavior of α-hemihydrate gypsum from phosphogypsum

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