Please wait a minute...
Shopping Cart Email List Chinese
Advanced Search Fig/Tab
Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

Featured Articles  |  Most Downloaded  |  Most Reading
Online Submission Subscribe to Our RSS Content Feed
Front. Chem. Sci. Eng.    2020, Vol. 14 Issue (5) : 902-912    https://doi.org/10.1007/s11705-019-1887-z
RESEARCH ARTICLE
Coextraction of vanadium and manganese from high-manganese containing vanadium wastewater by a solvent extraction-precipitation process
Zishuai Liu1,3,4,5, Yimin Zhang1,3,4,5(), Zilin Dai2, Jing Huang1,3,4,5, Cong Liu1,3,4,5
1. School of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China
2. Guangdong Research Institute of Rare-Metal, Guangzhou 510650, China
3. State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control, Wuhan University of Science and Technology, Wuhan 430081, China
4. Hubei Collaborative Innovation Center for High Efficient Utilization of Vanadium Resources, Wuhan University of Science and Technology, Wuhan 430081, China
5. Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resources, Wuhan University of Science and Technology, Wuhan 430081, China
 Download: PDF(1147 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

High-manganese containing vanadium wastewater (HMVW) is commonly produced during the vanadium extraction process from vanadium titano-magnetite. HMVW cannot be reused and discharged directly, and is harmful to the environment and affect product quality due to heavy metals in the wastewater. The wastewater is usually treated by lime neutralization, but valuable metals (especially V and Mn) cannot be recovered. In this study, an efficient and environmentally friendly method was developed to recover valuable metals by using a solvent extraction-precipitation process. In the solvent extraction process, 98.15% of vanadium was recovered, and the V2O5 product, with a purity of 98.60%, was obtained under optimal conditions. For the precipitation process, 91.05% of manganese was recovered as MnCO3 which meets the III grade standard of HG/T 2836-2011. Thermodynamic simulation analysis indicated that MnCO3 was selectively precipitated at pH 6.5 while Mg and Ca could hardly be precipitated. The results of X-ray diffraction and scanning electron microscopy demonstrated that the obtained V2O5 and MnCO3 displayed a good degree of crystallinity. The treated wastewater can be returned for leaching, and resources (V and Mn) in the wastewater were utilized efficiently in an environmentally friendly way. Therefore, this study provides a novel method for the coextraction of V and Mn from HMVW.
Keywords high-manganese containing vanadium wastewater      solvent extraction      carbonate precipitation      vanadium titano-magnetite      valuable metal recovery     
Corresponding Author(s): Yimin Zhang   
Just Accepted Date: 04 September 2019   Online First Date: 15 January 2020    Issue Date: 25 May 2020
 Cite this article:   
Zishuai Liu,Yimin Zhang,Zilin Dai, et al. Coextraction of vanadium and manganese from high-manganese containing vanadium wastewater by a solvent extraction-precipitation process[J]. Front. Chem. Sci. Eng., 2020, 14(5): 902-912.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1887-z
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I5/902
Fig.1  Principle flowsheet of vanadium extraction from vanadium titano-magnetite.
Element V VO2+ VO2+ Mn Mg Ca Fe Al P Si
Concentration /(mg?L?1) 1150 1111 39 15240 6150 455 34 47 16 120
Tab.1  Chemical composition of HMVW
Fig.2  Effect of equilibrium pH on the extraction of V and Mn.
Fig.3  Potential-pH diagram for V-Mn-H2O systems at 25°C.
Fig.4  Extraction isotherm of vanadium.
Items Concentration/(mg?L?1) Extraction efficiency /% Distribution ratios Separation coefficient
V Mn V Mn V Mn
Loaded organic phase 3420 2100 99.13 4.60 327.00 0.14 2335.71
Raffinate 10 14540 0.87 95.40
HMVW 1150 15240 100.00 100.00
Tab.2  Results of a three stages countercurrent simulation experiment
Element V Mn Mg Ca Fe Al P Si
Concentration/(mg?L?1) 10 14540 6010 432 23 44 24 116
Tab.3  Chemical composition of raffinate
Fig.5  Effect of H2SO4 concentration on the stripping of V and Mn.
Fig.6  Stripping isotherm of vanadium.
Items Concentration/(mg?L?1) Stripping efficiency/%
V Mn V Mn
Stripped vanadium solution 16953 549 99.14 5.23
Barren organic phase 147 9951 0.86 94.77
Loaded organic phase 3420 2100 100.00 100.00
Tab.4  Results of four-stage countercurrent stripping
Time of recycle 0 1 2 3 4 5 6
Extraction efficiency 99.14 99.27 99.18 99.36 99.20 99.17 99.08
Tab.5  Results of regeneration of barren organic phase
Fig.7  Effect of equilibrium pH on MnCO3 precipitation.
Fig.8  Speciation distribution of Mn, Mg, and Ca in aqueous carbonic acid solution at 25°C. (a) [Mn] = 0.28 mol/L, [Mg] = 0.26 mol/L, [Ca] = 0.014 mol/L, [CO32?] = 0.28 mol/L; (b) [Mn] = 0.28 mol/L, [Mg] = 0.26 mol/L, [Ca] = 0.014 mol/L, [CO32?] = 0.32 mol/L.
Fig.9  Effect of reaction time on MnCO3 precipitation.
Element V Mn Mg Ca Fe Al Si
Concentration /(mg?L?1) 5 1301 5830 419 15 18 87
Tab.6  Chemical composition of treated wastewater
Fig.10  SEM-EDS and XRD images of the V2O5 product.
Elements V2O5 Si Fe P S As K2O+ Na2O
Product 98.60 0.015 0.008 0.006 0.002 ? 0.75
YB/T 5304-2017 ≥98.0 ≤0.2 ≤0.25 ≤0.03 ≤0.1 ≤0.02 ≤1.0
Tab.7  Purity of the V2O5 product a)
Fig.11  SEM and XRD images of the MnCO3 product.
Elements Mn Cl? SO42? SiO2 Al K Na Ca Mg Pb
Product 44.80 0.001 0.30 0.03 0.26 0.002 0.005 0.10 0.25 0.0001
HG/T 2836-2011 ≥43 ≤0.03 ≤0.50 ≤0.05 ≤0.05 ≤0.02 ≤0.03 ≤1.0 ≤0.50 ≤0.01
Tab.8  Purity of the MnCO3 product a)
Fig.12  A process flowsheet for coextracting V and Mn from HMVW.
1 R R Moskalyk, A M Alfantazi. Processing of vanadium: A review. Minerals Engineering, 2003, 16(9): 793–805
https://doi.org/10.1016/S0892-6875(03)00213-9
2 H Y Li, H X Fang, K Wang, W Zhou, Z Yang, X M Yan, W S Ge, Q W Li, B Xie. Asynchronous extraction of vanadium and chromium from vanadium slag by stepwise sodium roasting-water leaching. Hydrometallurgy, 2015, 156: 124–135
https://doi.org/10.1016/j.hydromet.2015.06.003
3 S S Liu, Y F Guo, G Z Qiu, T Jiang, F Chen. Solid-state reduction kinetics and mechanism of pre-oxidized vanadium-titanium magnetite concentrate. Transactions of Nonferrous Metals Society of China, 2014, 24(10): 3372–3377
https://doi.org/10.1016/S1003-6326(14)63479-8
4 X W Wang, D X Gao, B F Chen, Y Q Meng, Z B Fu, M Y Wang. A clean metallurgical process for separation and recovery of vanadium and chromium from V-Cr-bearing reducing slag. Hydrometallurgy, 2018, 181: 1–6
https://doi.org/10.1016/j.hydromet.2018.08.008
5 P C Hu, Y M Zhang, J Huang, T Liu, Y Z Yuan, N N Xue. Eco-friendly leaching and separation of vanadium over iron impurity from vanadium-bearing shale using oxalic acid as a leachant. ACS Sustainable Chemistry & Engineering, 2018, 6(2): 1900–1908
https://doi.org/10.1021/acssuschemeng.7b03311
6 P Hu, Y Zhang, T Liu, J Huang, Y Yuan, N Xue. Source separation of vanadium over iron from roasted vanadium-bearing shale during acid leaching via ferric fluoride surface coating. Journal of Cleaner Production, 2018, 181: 399–407
https://doi.org/10.1016/j.jclepro.2018.01.226
7 H Lin, G Y Li, Y B Dong, J Li. Effect of pH on the release of heavy metals from stone coal waste rocks. International Journal of Mineral Processing, 2017, 165: 1–7
https://doi.org/10.1016/j.minpro.2017.05.001
8 A Akcil, F Vegliò, F Ferella, M D Okudan, A Tuncuk. A review of metal recovery from spent petroleum catalysts and ash. Waste Management (New York, N.Y.), 2015, 45: 420–433
https://doi.org/10.1016/j.wasman.2015.07.007
9 J R Kumar, S M Shin, H S Yoon, C W Nam, K W Chung, J Y Lee, J T Park. Separation and recovery of vanadium from synthetic leach liquor solutions containing iron, calcium, sodium, aluminum, and manganese by the solvent extraction technique. Separation Science and Technology, 2014, 49(6): 819–828
https://doi.org/10.1080/01496395.2013.863925
10 Z L Cai, Y L Feng, Y Z Zhou, H R Li, W D Wang. Selective separation and extraction of vanadium (V) over manganese (II) from co-leaching solution of roasted stone coal and pyrolusite using solvent extraction. JOM: the journal of the Minerals Metals & Materials Society, 2013, 65(11): 1492–1498
https://doi.org/10.1007/s11837-013-0768-z
11 P N Remya, M L Reddy. Solvent extraction separation of titanium(IV), vanadium(V) and iron(III) from simulated waste chloride liquors of titanium minerals processing industry by the trialkylphosphine oxide Cyanex 923. Journal of Chemical Technology and Biotechnology (Oxford, Oxfordshire), 2004, 79(7): 734–741
https://doi.org/10.1002/jctb.1046
12 P N Remya, J Saji, M L Reddy. Solvent extraction and separation of vanadium (V) from multivalent metal chloride solutions by Cyanex 923. Solvent Extraction and Ion Exchange, 2003, 21(4): 573–589
https://doi.org/10.1081/SEI-120022522
13 J Thomas, G D Surender, M L Reddy. Solvent extraction separation of vanadium(V) from multimetal chloride solutions using tributylphosphate. Separation Science and Technology, 2003, 38(15): 3761–3774
https://doi.org/10.1081/SS-120024228
14 H Liu, Y M Zhang, J Huang, T Liu, N N Xue, K Wang. Selective separation and recovery of vanadium from a multiple impurity acid leaching solution of stone coal by emulsion liquid membrane using di-(2-ethylhexyl)phosphoric acid. Chemical Engineering Research & Design, 2017, 122: 289–297
https://doi.org/10.1016/j.cherd.2017.04.026
15 Q H Shi, Y M Zhang, J Huang, T Liu, H Liu, L Wang. Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A. Separation Science and Technology, 2017, 181: 1–7
16 H I Kim, G Moon, I Choi, J Y Lee, R K Jyothi. Hydrometallurgical process development for the extraction, separation and recovery of vanadium from spent desulfurization catalyst bio-leach liquors. Journal of Cleaner Production, 2018, 187: 449–458
https://doi.org/10.1016/j.jclepro.2018.03.247
17 G Z Zhang, D S Chen, W Zhao, H X Zhao, L N Wang, D Li, T Qi. A novel synergistic extraction method for recovering vanadium (V) from high-acidity chloride leaching liquor. Separation Science and Technology, 2016, 165: 166–172
18 M R Tavakoli, D B Dreisinger. Separation of vanadium from iron by solvent extraction using acidic and neutral organophosporus extractants. Hydrometallurgy, 2014, 141: 17–23
https://doi.org/10.1016/j.hydromet.2013.10.008
19 X B Li, C Wei, Z G Deng, M T Li, C X Li, G Fan. Selective solvent extraction of vanadium over iron from a stone coal/black shale acid leach solution by D2EHPA/TBP. Hydrometallurgy, 2011, 105(3-4): 359–363
https://doi.org/10.1016/j.hydromet.2010.10.006
20 G P Hu, D S Chen, L N Wang, J C Liu, H X Zhao, Y H Liu, T Qi, C Q Zhang, P Yu. Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA. Separation Science and Technology, 2014, 125: 59–65
21 A Cheraghi, M S Ardakani, E K Alamdari, D H Fatmesari, D Darvishi, S K Sadrnezhaad. Thermodynamics of vanadium (V) solvent extraction by mixture of D2EHPA and TBP. International Journal of Mineral Processing, 2015, 138: 49–54
https://doi.org/10.1016/j.minpro.2015.03.011
22 A A Baba, L Ibrahim, F A Adekola, R B Bale, M K Ghosh, A R Sheik, S R Pradhan, O S Ayanda, I O Folorunsho. Hydrometallurgical processing of manganese ores: A review. Journal of Minerals & Materials Characterization & Engineering, 2014, 2(3): 230–247
https://doi.org/10.4236/jmmce.2014.23028
23 C Y Cheng. Purification of synthetic laterite leach solution by solvent extraction using D2EHPA. Hydrometallurgy, 2000, 56(3): 369–386
https://doi.org/10.1016/S0304-386X(00)00095-5
24 J Pakarinen, E Paatero. Effect of temperature on Mn-Ca selectivity with organophosphorus acid extractants. Hydrometallurgy, 2011, 106(3-4): 159–164
https://doi.org/10.1016/j.hydromet.2011.01.003
25 H K Haghighi, D Moradkhani, M M Salarirad. Separation of zinc from manganese, magnesium, calcium and cadmium using batch countercurrent extraction simulation followed by scrubbing and stripping. Hydrometallurgy, 2015, 154: 9–16
https://doi.org/10.1016/j.hydromet.2015.03.007
26 W S Zhang, C Y Cheng. Manganese metallurgy review. Part II: Manganese separation and recovery from solution. Hydrometallurgy, 2007, 89(3-4): 160–177
https://doi.org/10.1016/j.hydromet.2007.08.009
27 J Pakarinen, E Paatero. Recovery of manganese from iron containing sulfate solutions by precipitation. Minerals Engineering, 2011, 24(13): 1421–1429
https://doi.org/10.1016/j.mineng.2011.06.004
28 A M Silva, F L S Cruz, R M F Lima, M C Teixeira, V A Leão. Manganese and limestone interactions during mine water treatment. Journal of Hazardous Materials, 2010, 181(1-3): 514–520
https://doi.org/10.1016/j.jhazmat.2010.05.044
29 A M Silva, E C Cunha, F D R Silva, V A Leão. Treatment of high-manganese mine water with limestone and sodium carbonate. Journal of Cleaner Production, 2012, 29–30: 11–19
https://doi.org/10.1016/j.jclepro.2012.01.032
30 Z L Cai, Y L Feng, H R Li, Y Z Zhou. Selective separation and extraction of vanadium(IV) and manganese(II) from co-leaching solution of roasted stone coal and pyrolusite via solvent extraction. Industrial & Engineering Chemistry Research, 2013, 52(38): 13768–13776
https://doi.org/10.1021/ie401635m
31 B F Chen, S Huang, B Liu, Q Ge, M Y Wang, X W Wang. Separation and recovery of vanadium and chromium from acidic leach solution of V-Cr-bearing reducing slag. Journal of Environmental Chemical Engineering, 2017, 5(5): 4702–4706
https://doi.org/10.1016/j.jece.2017.09.001
32 B F Chen, S Huang, B Liu, Q Ge, S S Xie, M Y Wang, X W Wang. Thermodynamic analysis for separation of vanadium and chromium in V(IV)-Cr(III)-H2O system. Transactions of Nonferrous Metals Society of China, 2018, 28(3): 567–573
https://doi.org/10.1016/S1003-6326(18)64689-8
33 T D Nguyen, A Whitehead, G G Scherer, N Wai, M O Oo, A Bhattarai, G P Chandra, Z J Xu. The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery. Journal of Power Sources, 2016, 334: 94–103
https://doi.org/10.1016/j.jpowsour.2016.10.017
34 Y M Zhang, S X Bao, T Liu, T J Chen, J Huang. The technology of extracting vanadium from stone coal in China: History, current status and future prospects. Hydrometallurgy, 2011, 109(1-2): 116–124
https://doi.org/10.1016/j.hydromet.2011.06.002
35 D R Lide. Handbook of Chemistry and Physics. 78th. Florida: CRC Press, 1997, 198–200
36 E L Dromgoole, L M Walter. Iron and manganese incorporation into calcite: Effects of growth kinetics, temperature and solution chemistry. Chemical Geology, 1990, 81(4): 311–336 doi:10.1016/0009-2541(90)90053-A
37 R C Patel, F Garland, G Atkinson. Dynamics of magnesium-bicarbonate interactions. Journal of Solution Chemistry, 1975, 4(2): 161–174
https://doi.org/10.1007/BF00649156
38 F J Millero, V Thurmond. The ionization of carbonic acid in Na-Mg-Cl solutions at 25°C. Journal of Solution Chemistry, 1983, 12(6): 401–412
https://doi.org/10.1007/BF00646393
39 Y J Lee, R J Reeder, R W Wenskus, E J Elzinga. Structural relaxation in the MnCO3-CaCO3 solid solution: A Mn K-edge EXAFS study. Physics and Chemistry of Minerals, 2002, 29(9): 585–594
https://doi.org/10.1007/s00269-002-0274-2
40 L Puigdomenech. Medusa Software, KTH University, Sweden, 2015
41 V Prigiobbe, M Mazzotti. Precipitation of Mg-carbonates at elevated temperature and partial pressure of CO2. Chemical Engineering Journal, 2013, 223: 755–763
https://doi.org/10.1016/j.cej.2013.03.033
42 M Lindner, G D Saldi, G Jordan, J Schott. On the effect of aqueous barium on magnesite growth—A new route for the precipitation of the ordered anhydrous Mg-bearing double carbonate norsethite. Chemical Geology, 2017, 460: 93–105
https://doi.org/10.1016/j.chemgeo.2017.04.019
43 YB/T 5304—2017, Vanadium pentoxide. China: Ministry of Industry and Information Technology of the People’s Republic of China, 2017 (in Chinese)
44 HG/T 2836–2011, Manganese carbonate for soft ferrite use. China: Ministry of Industry and Information Technology of the People’s Republic of China, 2011 (in Chinese)
[1] Yunzhao Li,Xingfu Song,Guilan Chen,Shuying Sun,Yanxia Xu,Jianguo Yu. Extraction of hydrogen chloride by a coupled reaction-solvent extraction process[J]. Front. Chem. Sci. Eng., 2015, 9(4): 479-487.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed