Inorganic Chemicals Industry >

2022 , Vol. 54 >Issue 7: 110 - 116

DOI: https://doi.org/10.19964/j.issn.1006-4990.2021-0655

Environment·Health·Safety

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

  • Lei HE ,
  • Ganyu ZHU ,
  • Guangming ZHENG ,
  • Wenfen WU ,
  • Jianbo ZhANG ,
  • Fang LI ,
  • Huiquan LI ,
  • Wen CHEN
Expand
  • 1.Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
    2.CAS Key Laboratory of Green Process and Engineering, National Engineering Research Center of green recycling for strategic metal resources, Institute of Process Engineering, Chinese Academy of Sciences
    3.Yidu Xingfa Chemical Co. , Ltd.
    4.School of Chemical Engineering, University of Chinese Academy of Sciences

Received date: 2021-10-27

  Online published: 2022-07-14

Fold

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

Cite this article

Lei HE , Ganyu ZHU , Guangming ZHENG , Wenfen WU , Jianbo ZhANG , Fang LI , Huiquan LI , Wen CHEN . Study on crystallization process and mechanism of phosphogypsum in wet process phosphoric acid system[J]. Inorganic Chemicals Industry, 2022 , 54(7) : 110 -116 . DOI: 10.19964/j.issn.1006-4990.2021-0655

References

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.
2 DONG Ze， ZHAI Yanbo， REN Zhiwei，et al.Research progress on phosphogypsum utilization in building materials［J］.Inorganic Che-
2 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 .
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.
6 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，
11 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-
13 SO 42 - ion pairs in calcium sulfate hemihydrate nucleation［J］.Crys-
13 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
14 acid［J］.Industrial & Engineering Chemistry Research，2001，
14 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，
16 311（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.
19 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.
21 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 DO?AN ?， AKYOL E， ?NER 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.
23 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-
25 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， AVC? 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.
30 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.
31 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-
33 fill［J］.Journal of Hazardous Materials，2020，399.Doi：10.1016/j.jhazmat.2020.122993 .
34 SINDELAR M E， WOLKOWSKI R P.Reducing water-soluble pho-
34 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.
35 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.
Options
Outlines

/

〈 〉



Copyright © 2021 Editorial Office of Inorganic Chemicals Industry

Add:No.3 Road Dingzigu,Hongqiao District,Tianjin,China

E-mail：book@wjygy.com.cn 违法和不良信息举报电话: 022-26689297