Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

Qianqian Lu, Haisheng Han, Wenjuan Sun, Xingfei Zhang, Weiwei Wang, Bilan Zhang, Wensheng Chen, Qin Zou

International Journal of Minerals, Metallurgy, and Materials ›› 2024, Vol. 31 ›› Issue (6) : 1198-1207. DOI: 10.1007/s12613-023-2697-3

Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite

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Abstract

Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate. A new acid leaching–flotation process for fluorite is proposed in this work. This innovative process raised the fluorite’s grade to 97.26wt% while producing nanoscale calcium carbonate from its leachate, which contained plenty of calcium ions. On the production of nanoscale calcium carbonate, the impacts of concentration, temperature, and titration rate were examined. By modifying the process conditions and utilizing crystal conditioning agents, calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511 µm were produced. The influence of the impurity ions Mn2+, Mg2+, and Fe3+ was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution. The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources, thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.

Keywords

fluorite / calcite / nanoscale calcium carbonate / waste recovery

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Qianqian Lu, Haisheng Han, Wenjuan Sun, Xingfei Zhang, Weiwei Wang, Bilan Zhang, Wensheng Chen, Qin Zou. Preparation of high-purity fluorite and nanoscale calcium carbonate from low-grade fluorite. International Journal of Minerals, Metallurgy, and Materials, 2024, 31(6): 1198‒1207 https://doi.org/10.1007/s12613-023-2697-3

References

[[1]]
Basiev TT, Doroshenko ME, Konyushkin VA, et al.. Fluoride optical nanoceramics. Russ. Chem. Bull., 2008, 57(5): 877,
CrossRef Google scholar
[[2]]
Kan WH, Thangadurai V. Challenges and prospects of anodes for solid oxide fuel cells (SOFCs). Ionics, 2015, 21(2): 301,
CrossRef Google scholar
[[3]]
Shah FA. Fluoride-containing bioactive glasses: Glass design, structure, bioactivity, cellular interactions, and recent developments. Mater. Sci. Eng. C, 2016, 58: 1279,
CrossRef Google scholar
[[4]]
Němec D. Fluorine in lamprophyre and lamproid rocks. Geochim. Cosmochim. Acta, 1968, 32(5): 523,
CrossRef Google scholar
[[5]]
Sadykov VA, Simonov MN, Bespalko YN, et al.. Design and characterization of nanocomposite catalysts for biofuel conversion into syngas and hydrogen in structured reactors and membranes. Kinet. Catal., 2019, 60(5): 582,
CrossRef Google scholar
[[6]]
Shi CB, Cho JW, Zheng DL, Li J. Fluoride evaporation and crystallization behavior of CaF2–CaO–Al2O3–(TiO2) slag for electroslag remelting of Ti-containing steels. Int. J. Miner. Metall. Mater., 2016, 23(6): 627,
CrossRef Google scholar
[[7]]
Sun RF. . Effect and Mechanism of Metal Ions on Calcite Inhibitors in Fluorite Flotation System, 2022 Kunming Kunming University of Science and Technology 12
[[8]]
Z.Y. Gao, C. Wang, W. Sun, Y.S. Gao, and P.B. Kowalczuk, Froth flotation of fluorite: A review, Adv. Colloid Interface Sci., 290(2021), art. No. 102382.
[[9]]
H.P. Zhou, Z.Z. Yang, Y.B. Zhang, F.X. Xie, and X.P. Luo, Flotation separation of smithsonite from calcite by using flax-seed gum as depressant, Miner. Eng., 167(2021), art. No. 106904.
[[10]]
J.W. Huang, Q.W. Zhang, H.C. Li, and C. Wang, Difficulties and recent achievements in flotation separation of fluorite from calcite—An overview, Minerals, 12(2022), No. 8, art. No. 957.
[[11]]
R.L. Wang, H.S. Han, W. Sun, A.V. Nguyen, W.J. Sun, and Z. Wei, Hydrophobic behavior of fluorite surface in strongly alkaline solution and its application in flotation, Colloids Surf. A: Physicochem. Eng. Aspects, 609(2021), art. No. 125661.
[[12]]
D.Q. Wang, D. Liu, Y.B. Mao, R.F. Sun, R.T. Liu, and S.M. Wen, Effect of fluoride ion on the separation of fluorite from calcite using flotation with acidified water glass, Minerals, 11(2021), No. 11, art. No. 1203.
[[13]]
Lin QQ, Gu GH, Wang H, Zhu RF, Liu YC, Fu JG. Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching. Int. J. Miner. Metall. Mater., 2016, 23(5): 491,
CrossRef Google scholar
[[14]]
El-Sheikh SM, Rabah MA. Optical properties of calcium chromate 1D-nanorods synthesized at low temperature from secondary resources. Opt. Mater., 2014, 37: 235,
CrossRef Google scholar
[[15]]
Luo XP, Song XW, Cao YW, Song L, Bu XZ. Investigation of calcium carbonate synthesized by steamed ammonia liquid waste without use of additives. RSC Adv., 2020, 10(13): 7976, pmcid: 9049945
CrossRef Pubmed Google scholar
[[16]]
I. Korkut, A. Civas, and M. Bayramoglu, Effects of ultrasound and process parameters on the precipitation of CaCO3 polymorphs from synthetic soda ash industry liquid waste, Chem. Eng. Process., 168(2021), art. No. 108584.
[[17]]
Han JS, Jung SY, Kang DS, Seo YB. Development of flexible calcium carbonate for papermaking filler. ACS Sustainable Chem. Eng., 2020, 8(24): 8994,
CrossRef Google scholar
[[18]]
Wu W, Zhang XQ, Chen JF, Shen SL. Synthesis of nano-CaCO3 composite particles and their application. J. Univ. Sci. Technol. Beijing, 2008, 15(1): 67,
CrossRef Google scholar
[[19]]
Cao ML, Ming X, He KY, Li L, Shen S. Effect of macro-, micro- and nano-calcium carbonate on properties of cementitious composites—A review. Materials, 2019, 12(5): 781, pmcid: 6427187
CrossRef Pubmed Google scholar
[[20]]
Lin H, Dong YB, Jiang LY. Preparation of calcium carbonate particles coated with titanium dioxide. Int. J. Miner. Metall. Mater., 2009, 16(5): 592,
CrossRef Google scholar
[[21]]
X.Y. Zhou, R. Yu, J.H. Jiang, et al., PEEK composite resin with enhanced intumescent flame retardancy loaded with Octaphenylsilsesquioxane and nano calcium carbonate and its application in fibers, Polym. Degrad. Stab., 202(2022), art. No. 110042.
[[22]]
C.C. Zeng, H.M. Hu, X.H. Feng, K. Wang, and Q.W. Zhang, Activating CaCO3 to enhance lead removal from lead-zinc solution to serve as green technology for the purification of mine tailings, Chemosphere, 249(2020), art. No. 126227.
[[23]]
Chang Y, Han HJ, Liu TT, et al.. Cell-tailored calcium carbonate particles with different crystal forms from nanoparticle to nano/microsphere. RSC Adv., 2020, 10(70): 43233, pmcid: 9058178
CrossRef Pubmed Google scholar
[[24]]
L.T. Kang, M.W. Cui, F.Y. Jiang, et al., Nanoporous CaCO3 coatings enabled uniform Zn stripping/plating for long-life zinc rechargeable aqueous batteries, Adv. Energy Mater., 8(2018), No. 25, art. No. 1801090.
[[25]]
A.S.A. Mohammed, A. Carino, A. Testino, M.R. Andalibi, and A. Cervellino, In situ liquid SAXS studies on the early stage of calcium carbonate formation, Part. Part. Syst. Char., 36(2019), No. 6, art. No. 1800482.
[[26]]
B. Wang, Z.H. Pan, H.G. Cheng, Z.E. Zhang, and F.Q. Cheng, A review of carbon dioxide sequestration by mineral carbonation of industrial byproduct gypsum, J. Cleaner Prod., 302(2021), art. No. 126930.
[[27]]
Y. Wei, H. Xu, S.M. Xu, et al., Synthesis and characterization of calcium carbonate on three kinds of microbial cells templates, J. Cryst. Growth, 547(2020), art. No. 125755.
[[28]]
Katsman A, Polishchuk I, Pokroy B. On the mechanism of calcium carbonate polymorph selection via confinement. Faraday Discuss., 2022, 235: 433,
CrossRef Pubmed Google scholar
[[29]]
Ma M, Wang YH, Cao XF, Lu WP, Guo YC. Temperature and supersaturation as key parameters controlling the spontaneous precipitation of calcium carbonate with distinct physicochemical properties from pure aqueous solutions. Cryst. Growth Des., 2019, 19(12): 6972,
CrossRef Google scholar
[[30]]
J. Wang, J.Z. Song, Z.Y. Ji, et al., The preparation of calcium carbonate with different morphologies under the effect of alkanolamide 6502, Colloids Surf., A, 588(2020), art. No. 124392.
[[31]]
X.H. Mei, Q. Zhao, Y.M. Li, et al., Phase transition and morphology evolution of precipitated calcium carbonate (PCC) in the CO2 mineralization process, Fuel, 328(2022), art. No. 125259.
[[32]]
Korchef A, Touaibi M. Effect of pH and temperature on calcium carbonate precipitation by CO2 removal from iron-rich water. Water Environ. J., 2020, 34(3): 331,
CrossRef Google scholar
[[33]]
Korchef A. Effect of iron ions on the crystal growth kinetics and microstructure of calcium carbonate. Cryst. Growth Des., 2019, 19(12): 6893,
CrossRef Google scholar
[[34]]
Konrad F, Purgstaller B, Gallien F, Mavromatis V, Gane P, Dietzel M. Influence of aqueous Mg concentration on the transformation of amorphous calcium carbonate. J. Cryst. Growth, 2018, 498: 381,
CrossRef Google scholar
[[35]]
Goncharuk VV, Bagrii VA, Bashtan SY, Chebotareva RD, Nanieva AV. Crystalization of calcium carbonate in magnetized water in the presence of ions of iron and manganese. J. Water Chem. Technol., 2011, 33(3): 160,
CrossRef Google scholar
[[36]]
Kontoyannis CG, Vagenas NV. Calcium carbonate phase analysis using XRD and FT-Raman spectroscopy. Analyst, 2000, 125(2): 251,
CrossRef Google scholar
[[37]]
A. Gomez-Flores, G.W. Heyes, S. Ilyas, and H. Kim, Prediction of grade and recovery in flotation from physicochemical and operational aspects using machine learning models, Miner. Eng., 183(2022), art. No. 107627.
[[38]]
Ševčík R, Pérez-Estébanez M, Viani A, Šašek P, Mácová P. Characterization of vaterite synthesized at various temperatures and stirring velocities without use of additives. Powder Technol., 2015, 284: 265,
CrossRef Google scholar
[[39]]
Xia X, Chen JW, Shen J, Huang D, Duan PZ, Zou GH. Synthesis of hollow structural hydroxyapatite with different morphologies using calcium carbonate as hard template. Adv. Powder Technol., 2018, 29(7): 1562,
CrossRef Google scholar
[[40]]
N. Mehta, J. Gaëtan, P. Giura, T. Azaïs, and K. Benzerara, Detection of biogenic amorphous calcium carbonate (ACC) formed by bacteria using FTIR spectroscopy, Spectrochim. Acta, Part A, 278(2022), art. No. 121262.
[[41]]
Avaro JT, Ruiz-Agudo C, Landwehr E, Hauser K, Gebauer D. Impurity-free amorphous calcium carbonate, a preferential material for pharmaceutical and medical applications. Eur. J. Mineral., 2019, 31(2): 231,
CrossRef Google scholar
[[42]]
Goldsmith JR, Heard HC. Subsolidus phase relations in the system CaCO3–MgCO3. J. Geol., 1961, 69(1): 45,
CrossRef Google scholar
[[43]]
T.Y. Chen, S. Honarparvar, D. Reible, and C.C. Chen, Thermodynamic modeling of calcium carbonate scale precipitation: Aqueous Na+–Ca2+–Cl−–HCO–CO2−–CO2 system, Fluid Phase Equilib., 552(2022), art. No. 113263.
[[44]]
Bénézeth P, Dandurand JL, Harrichoury JC. Solubility product of siderite (FeCO3) as a function of temperature (25–250°C). Chem. Geol., 2009, 265(1–2): 3,
CrossRef Google scholar
[[45]]
Johnson KS. Solubility of rhodochrosite (MnCO3) in water and seawater. Geochim. Cosmochim. Acta, 1982, 46(10): 1805,
CrossRef Google scholar
[[46]]
Dean JA. . Lange’s Handbook of Chemistry, 1985 New York McGraw-Hill Professional Publishing
[[47]]
Mills JV, Barnhart HA, DePaolo DJ, Lammers LN. New insights into Mn2+ and Mg2+ inhibition of calcite growth. Geochim. Cosmochim. Acta, 2022, 334: 338,
CrossRef Google scholar
[[48]]
Zeller EJ, Wray JL. Factors influencing precipitation of calcium carbonate. AAPG Bull., 1956, 40(1): 140

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