湿法磷酸体系磷石膏结晶过程与机理研究

doi:10.19964/j.issn.1006-4990.2021-0655

Abstract

Abstract:

Calcium sulfate crystallization restricts the quality of phosphogypsum in the process of wet process phosphoric acid.Fine calcium sulfate crystallization can not only improve the phosphorus yield，but also be conducive to the resource utilization of phosphogypsum.Aiming at the regulation of calcium sulfate crystallization in the process of phosphogypsum formation，the variation of phase morphology of calcium sulfate with reaction time was systematically investigated under the condition of adding n-octanol.The crystal structure change and growth law of phosphogypsum were studied comprehensively.The results showed that the residual phosphorus in phosphogypsum at 7 h was 0.36%，in which the aqueous soluble phosphorus was 0.18%，and the yield of phosphorus was 98.79%.Phosphogypsum was growed with（002） as the main crystal plane，and the crystallization process was divided into three stages：phosphate rock acidolysis，calcium sulfate crystal particle growth，crystal crushing and secondary crystallization.Uniform calcium sulfate dihydrate slab crystallization was helpful to improve the washing performance and washing effect of phosphogypsum.By studying on the crystallization regulation and change process of phosphogypsum.It was provided reference and basic support for the selection of process parameters and the control of calcium sulfate crystal form in the actual production of wet phosphoric acid.

Key words: wet process phosphoric acid, phosphogypsum, calcium sulfate crystallization, regulation

CLC Number:

TQ126.35

HE Lei,ZHU Ganyu,ZHENG Guangming,WU Wenfen,ZhANG Jianbo,LI Fang,LI Huiquan,CHEN Wen. Study on crystallization process and mechanism of phosphogypsum in wet process phosphoric acid system[J]. Inorganic Chemicals Industry, 2022, 54(7): 110-116.

Figures/Tables 5

Fig.1

Table 1

Fig.2

Fig.3

Fig.4

References 40

1	ZHAO Jingcai， SONG Xingfu， SUN Yuzhu，et al.Study on crystallization of calcium carbonate from calcium sulfate and ammonium carbonate in the presence of magnesium ions［J］.Crystal Research and Technology，2015，50（4）：277-283.
2	董泽，翟延波，任志威，等.磷石膏建材资源化利用研究进展［J］.无机盐工业，2022，54（4）：5-9.
	DONG Ze， ZHAI Yanbo， REN Zhiwei，et al.Research progress on phosphogypsum utilization in building materials［J］.Inorganic Che-
	Industry micals，2022，54（4）：5-9.
3	AMRANI M， TAHA Y， KCHIKACH A，et al.Phosphogypsum recycling：New horizons for a more sustainable road material application［J］.Journal of Building Engineering，2020，30.Doi：10.1016/j.jobe.2020.101267 . doi: 10.1016/j.jobe.2020.101267
4	YANG Lin， CAO Jianxin， LUO Tong.Effect of Mg²⁺，Al³⁺，and Fe³⁺ ions on crystallization of type α hemi-hydrated calcium sulfate under simulated conditions of hemi-hydrate process of phosphoric acid［J］.Journal of Crystal Growth，2018，486：30-37.
5	EL-SHALL H， RASHAD M M， ABDEL-AAL E A.Effect of phosphonate additive on crystallization of gypsum in phosphoric and sulfuric acid medium［J］.Crystal Research and Technology，2002，37（12）：1264-1273.
6	张利珍，吕子虎，张永兴，等.磷石膏提质降杂实验研究［J］.无机盐工业，2021，53（6）：171-173，184.
	ZHANG Lizhen， Zihu LÜ， ZHANG Yongxing，et al.Experimental study on improving quality and reducing impurity of phosphogypsum［J］.Inorganic Chemicals Industry，2021，53（6）：171-173，184.
7	ABU-EISHAH S I， ABU-JABAL N M.Parametric study on the production of phosphoric acid by the dihydrate process［J］.Chemical Engineering Journal，2001，81（1/2/3）：231-250.
8	POLAT S， SAYAN P.Characterization and kinetics of calcium sulfate dihydrate crystallization in the presence of trimesic acid［J］.Asia-Pacific Journal of Chemical Engineering，2017，12（3）：391-399
9	RASHAD M M， MAHMOUD M H H， IBRAHIM I A，et al.Crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production in the presence of aluminum and magnesium ions［J］.Journal of Crystal Growth，2004，267（1/2）：372-379
10	ZHU Zhilong， PENG You， HATTON T A，et al.Crystallization of calcium sulphate during phosphoric acid production：Modeling particle shape and size distribution［J］.Procedia Engineering，2016，138：390-402.
11	FU Hailu， JIANG Guangming， WANG Hao，et al.Solution-mediated transformation kinetics of calcium sulfate dihydrate to α-calcium sulfate hemihydrate in CaCl₂ solutions at elevated temperature［J］.Industrial & Engineering Chemistry Research，2013，
	52（48）：17134-17139.
12	HAMDONA S K， HADAD U A AL.Crystallization of calcium sulfate dihydrate in the presence of some metal ions［J］.Journal of Crystal Growth，2007，299（1）：146-151.
13	JIANG Guangming， FU Hailu， SAVINO K，et al.Nonlattice cation-
	SO 42 ^- ion pairs in calcium sulfate hemihydrate nucleation［J］.Crys-
	tal Growth & Design，2013，13（11）：5128-5134.
14	KRUGER A， FOCKE W W， KWELA Z，et al.Effect of ionic impurities on the crystallization of gypsum in wet-process phosphoric
	acid［J］.Industrial & Engineering Chemistry Research，2001，
	40（5）：1364-1369.
15	MAO Xiulong， SONG Xingfu， LU Guimin，et al.Effects of metal ions on crystal morphology and size of calcium sulfate whiskers in aqueous HCl solutions［J］.Industrial & Engineering Chemistry Research，2014，53（45）：17625-17635.
16	YANG Liuchun， WU Zhongbiao， GUAN Baohong，et al.Growth rate of α-calcium sulfate hemihydrate in K-Ca-Mg-Cl-H₂O systems at elevated temperature［J］.Journal of Crystal Growth，2009，
	311（20）：4518-4524.
17	RABIZADEH T， STAWSKI T M， MORGAN D J，et al.The effects of inorganic additives on the nucleation and growth kinetics of calcium sulfate dihydrate crystals［J］.Crystal Growth & Design，2017，17（2）：582-589.
18	HASSON D， ADDAI-MENSAH J， METCALFE J.Filterability of gypsum crystallized in phosphoric acid solution in the presence of ionic impurities［J］.Industrial & Engineering Chemistry Research，1990，29（5）：867-875.
19	孙祥斌，窦焰，方羊，等.铝离子对二水硫酸钙晶体结晶性能的影响［J］.过程工程学报，2017，17（3）：613-618.
	SUN Xiangbin， DOU Yan， FANG Yang，et al.Effect of aluminium ion on crystallization performance of calcium sulfate dihydrate［J］.The Chinese Journal of Process Engineering，2017，17（3）：613-618
20	WANG Fulin， DAVIS T E， TARABARA V V.Crystallization of calcium sulfate dihydrate in the presence of colloidal silica［J］.Industrial & Engineering Chemistry Research，2010，49（22）：11344-11350.
21	李绪，朱干宇，宫小康，等.Si/F/K/Na杂质对硫酸钙结晶过程的影响［J］.过程工程学报，2018，18（4）：815-820.
	LI Xu， ZHU Ganyu， GONG Xiaokang，et al.Effects of Si/F/K/Na impurities on the crystallization of calcium sulfate［J］.The Chinese Journal of Process Engineering，2018，18（4）：815-820.
22	DOĞAN Ö， AKYOL E， ÖNER M.Polyelectrolytes inhibition effect on crystallization of gypsum［J］.Crystal Research and Technology，2004，39（12）：1108-1114.
23	杨丽庭，吕慧，李彦涛，等.硫酸钙晶须的制备及其改性聚丙烯性能的研究［J］.华南师范大学学报：自然科学版，2020，52（2）：24-30.
	YANG Liting， Hui LÜ， LI Yantao，et al.Preparation of calcium sulfate whisker and properties of polypropylene/calcium sulfate whisker composites［J］.Journal of South China Normal University：Natural Science Edition，2020，52（2）：24-30.
24	LIOLIOU M G， PARASKEVA C A， KOUTSOUKOS P G，et al.Calcium sulfate precipitation in the presence of water-soluble polymers［J］.Journal of Colloid and Interface Science，2006，303（1）：164-170.
25	FELDMANN T， DEMOPOULOS G P.Effects of crystal habit mo-
	difiers on the morphology of calcium sulfate dihydrate grown in strong CaCl 2 -HCl solutions［J］.Journal of Chemical Technology & Biotechnology，2014，89（10）：1523-1533.
26	TITIZ-SARGUT S， SAYAN P， AVCı B.Influence of citric acid on calcium sulfate dihydrate crystallization in aqueous media［J］.Crystal Research and Technology，2007，42（2）：119-126.
27	HE Hua， DONG Faqin， HE Ping，et al.Effect of glycerol on the preparation of phosphogypsum-based CaSO₄·0.5H₂O whiskers［J］.Journal of Materials Science，2014，49（5）：1957-1963.
28	MU Xinru， ZHU Ganyu， LI Xu，et al.Effects of impurities on CaSO₄ crystallization in the Ca（H₂PO₄）₂-H₂SO₄-H₃PO₄-H₂O system［J］.ACS Omega，2019，4（7）：12702-12710.
29	WANG Xiao， YANG Liushuan， ZHU Xinfeng，et al.Preparation of calcium sulfate whiskers from FGD gypsum via hydrothermal crystallization in the H₂SO₄-NaCl-H₂O system［J］.Particuology，2014，17：42-48.
30	赵红涛，王树民，刘志江，等.磷石膏矿化固定CO₂制备高纯高白CaCO₃ ［J］.材料导报，2019，33（18）：3031-3034，3042.
	ZHAO Hongtao， WANG Shumin， LIU Zhijiang，et al.Preparation of high-purity and high-white CaCO₃ by phosphogypsum mineralization for CO₂ capture［J］.Materials Reports，2019，33（18）：3031-3034，3042.
31	张品，陈以明.湿法磷酸装置总磷收率降低的原因分析和应对措施［J］.磷肥与复肥，2021，36（3）：24-26.
	ZHANG Pin， CHEN Yiming.Reasons analysis and countermeasures for reduction of total phosphorus yield of a WPA plant［J］.Phosphate & Compound Fertilizer，2021，36（3）：24-26.
32	KOOPMAN C， WITKAMP G J.Ion exchange extraction during continuous recrystallization of CaSO₄ in the phosphoric acid production process：Lanthanide extraction efficiency and CaSO₄ particle shape［J］.Hydrometallurgy，2002，63（2）：137-147.
33	ZHOU Shitong， LI Xibing， ZHOU Yanan，et al.Effect of phosphorus on the properties of phosphogypsum-based cemented back- doi: 10.1016/j.jhazmat.2020.122993
	fill［J］.Journal of Hazardous Materials，2020，399.Doi：10.1016/j.jhazmat.2020.122993 . doi: 10.1016/j.jhazmat.2020.122993
34	SINDELAR M E， WOLKOWSKI R P.Reducing water-soluble pho-
	sphorus in soil through flue gas desulfurization gypsum application：Year of application effects at multiple sites in Wisconsin［J］.Journal of Environmental Quality，2019，48（3）：654-659.
35	吴佩芝.湿法磷酸［M］.北京：化学工业出版社，1987.
	WU Peizhi.Wet process phosphoric acid［M］.Beijing：Chemical Industry Press，1987.
36	WITKAMP G J， SECKLER M M， BRUINSMA O S L，et al.Recrystallization of calcium sulfate in phosphoric acid solutions；batchwise operation［J］.Journal of Crystal Growth，1990，99（1/2/3/4）：1117-1123.
37	INOUE M， HIRASAWA I.The relationship between crystal morphology and XRD peak intensity on CaSO₄·2H₂O［J］.Journal of Crystal Growth，2013，380：169-175.
38	MACEDO PORTELA DA SILVA N， RONG Yi， ESPITALIER F，et al.Solvothermal recrystallization of α-calcium sulfate hemihydrate：Batch reactor experiments and kinetic modelling［J］.Journal of Crystal Growth，2017，472：46-53.
39	SHUKLA J， MEHTA M J， KUMAR A.Effects of aliphatic alcohols on solubility，physicochemical properties，and morphology of calcium sulfate dihydrate（gypsum） in aqueous sodium chloride solution at 35 ℃［J］.Journal of Chemical & Engineering Data，2019，64（2）：536-544.
40	YE Changwen， LI Jun.Wet process phosphoric acid purification by solvent extraction using n-octanol and tributylphosphate mixtures［J］.Journal of Chemical Technology & Biotechnology，2013，88（9）：1715-1720.

[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]	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.
[5]	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.
[6]	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.
[7]	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.
[8]	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.
[9]	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.
[10]	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.
[11]	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.
[12]	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.
[13]	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.
[14]	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.
[15]	ZHANG Guidong, YANG Xuejiao, GUO Xudong, YANG Lin. Study on hydration properties of type Ⅱ anhydrite prepared by calcination and atmospheric acidification [J]. Inorganic Chemicals Industry, 2024, 56(2): 104-110.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on crystallization process and mechanism of phosphogypsum in wet process phosphoric acid system

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 40

Related Articles 15

Metrics

Comments

Recommended 0