Solvent extraction mechanism and precipitation stripping of bismuth (III) in hydrochloric acid medium by tributyl phosphate

Abstract

Tributyl phosphate (TBP) was employed for the Bi(III) extraction from hydrochloric acid medium. The effects of extraction time and material concentration were examined. The replacement mechanism between the anion (Cl⁻) and TBP was proposed for extraction. The results show the species extracted into the organic phase were found to be mainly BiCl₃·xTBP (x=2 or 3). Thermodynamic parameters of the extraction reaction were obtained from the thermodynamics analysis, which illustrates that higher temperatures show a negative effect on the extraction. Extraction isotherm was obtained with 2.16 mol/L TBP for a typical solution containing 0.1 mol/L of bismuth and 1.0 mol/L of hydrochloric acid. About 98.5 % of bismuth has been extracted from the leaching solution under the optimum condition. Moreover, oxalate was explored as a precipitation stripping agent for BiCl₃·xTBP (x=2 or 3) complexes, by which Bi(III) was stripped in the form of Bi₂(C₂O₄)₃·7H₂O. A stripping efficiency of 99.3% was obtained in only one stage at the phase ratio of 1 and TBP also could be recycled. Therefore, the method is an efficient, effective and highly selective approach to extract Bi(III) and to recover metal bismuth.

Keywords

solvent extraction / bismuth (Bi) / tributyl phosphate (TBP) / precipitation stripping / extraction mechanism

References

[1] RohrO. Bismuth—The new ecologically green metal for modern lubricating engineering [J]. Industrial Lubrication & Tribology, 2002, 54(4): 153-164

[2] ZhanJ, WangZ-j, ZhangC-f, HwangJ-y, XiaC-ping. Separation and extraction of bismuth and manganese from roasted low-grade bismuthinite and pyrolusite: Thermodynamic analysis and sulfur fixing [J]. JOM, 2015, 67(5): 1114-1122

[3] YangJ-g, TangC-b, YangS-h, HeJ, TangM-tang. The separation and electrowinning of bismuth from a bismuth glance concentrate using a membrane cell [J]. Hydrometallurgy, 2009, 100(1/2): 5-9

[4] HaT K, KwonH B, ParkK S, MohapatraD. Selective leaching and recovery of bismuth as Bi₂O₃ from copper smelter converter dust [J]. Separation & Purification Technology, 2015, 142: 116-122

[5] KunterR S, BedalW E. Chloride process treatment of smelter flue dusts [J]. JOM, 1992, 44(12): 35-38

[6] WangC-y, QiuD-f, JiangP-hai. Bismuth hydrometallurgy technology in China [J]. Nonferrous Metals, 2001, 53(4): 15-18

[7] FlynnC M, GarnahanT G, LindstromR ERecovery of bismuth from chloride process solutions: US, 4285912[P], 1981

[8] KimD K, LeeseT A, SaitoM N, YoungB R, WeidnerC J. Use of solvent extraction to remove bismuth and antimony from copper electrolyte at the San Manuel Refinery [C]. CROWSON A. Proceedings of Sessions and Symposia, the TMS Annual Meeting, 1998San AntonioEPD Congress301-315

[9] DreinsigerD B, LeongB J Y, BailintB J, BeyadM H. The solvent extraction of As, Sb and Bi from copper refining electrolytes using organophosphorus reagents [C]. Proceedings of International Solvent Extraction Conference, 1993LondonElsevier Applied Science1271-1278

[10] SzymanowskiJ. Removal of toxic elements from copper electrolyte by solvent extraction [J]. Miner Process Extr Metall Rev, 1998, 18(3/4): 389-418

[11] WangC, JiangK, LiuD, WangH. Purification of copper electrolyte with Cyanex 923 [C]. International Solvent Extraction Conference, 20021039-1044

[12] YangJ-g, YangJ-y, TangM-t, TangC-b, LiuWei. The solvent extraction separation of bismuth and molybdenum from a low grade bismuth glance flotation concentrate [J]. Hydrometallurgy, 2009, 96(4): 342-348

[13] TyerJ N, DhadkeP M. Solvent extraction and separation studies of antimony (III) and bismuth (III) by using Cyanex-925 [J]. Ind J Chem Technol, 2003, 10(6): 665-669

[14] AbdarA K, VanjaraA K. Solvent extraction and separation of Bi(III) and Sb(III) from HCl and HBr media using tri-n-octyl phosphine oxide (TOPO) [J]. Ind J Chem Technol, 2001, 8(4): 239-243

[15] KokateS J, ShelarY S, AherH R, KuchekarS R. Liquid-liquid extraction and recovery of bismuth(III) from hydrochloric acid media using n-octylaniline in chloroform [J]. Bulg Chem Commun, 2010, 42(2): 107-112

[16] MoriyaY, SugaiM, NakataS, OgawaN. Extraction of bismuth(III) with 2-bromoalkanoic acid in nondonating solvent from highly acidic aqueous solution [J]. Anal Sci, 2001, 17(2): 297-300

[17] SarkarS G, DhadkeP M. Solvent extraction separation of antimony (III) and bismuth (III) with bis (2, 4, 4-trimethylpentyl) monothiophosphinic acid (Cyanex 302) [J]. Separation & Purification Technology, 1999, 15(2): 131-138

[18] SongN-z, LiW-j, JiaQiong. Solvent extraction of bismuth with 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester and 2,2'-bipyridyl [J]. Separation & Purification Technology, 2013, 104: 64-67

[19] PatnaikP, BabaA A, NathsarmaK C, SarangiK, SubbaiahT. Separation of iron and zinc from manganese nodule leach liquor using TBP as extractant [J]. Mineral Processing and Extractive Metallurgy, 2013, 122(3): 179-185

[20] KumbasarR A. Separation and concentration of cobalt from aqueous thiocyanate solutions containing cobalt-nickel by emulsion liquid membranes using TBP as extractant [J]. Journal of Membrane Science, 2009, 338(1): 182-188

[21] SarangiK, ParhiP K, PadhanE, PalaiA K, NathsarmaK C, ParkK H. Separation of iron(III), copper(II) and zinc(II) from a mixed sulphate/chloride solution using TBP, LIX 84I and Cyanex 923 [J]. Separation & Purification Technology, 2007, 55(1): 44-49

[22] WuJ, WeiC, LiX-b, WangS-f, WangM-s, LiC-xiong. Selective extraction of Mo using Cyanex-272 and tributyl phosphate from low grade Ni-Mo ore leach liquor [J]. Separation & Purification Technology, 2012, 99(41): 120-126

[23] GagliardiF M, CashionJ D. Solvation of gold and rare earths by tributyl phosphate [J]. Hyperfine Interactions, 2012, 207(1/2/3): 13-17

[24] AhnJ W, LeeJ C. Separation of Sn, Sb, Bi, As, Cu, Pb and Zn from hydrochloric acid solution by solvent extraction process using TBP (tri-n-butylphosphate) as an extractant [J]. Materials Transactions, 2011, 52(12): 2228-2232

[25] ChenJ-yongHandbook of hydrometallurgy [M], 2005, 124–131: 1297-1327