Aqueous

Research Article pubs.acs.org/journal/ascecg

High-Performance Recovery of Vanadium(V) in Leaching/Aqueous Solution by a Reusable Reagent-Primary Amine N1519 Xiaohua Jing,†,‡ Pengge Ning,*,† Hongbin Cao,† Jianyou Wang,‡ and Zhi Sun† †

Beijing Engineering Research Centre of Process Pollution Control, Key Laboratory of Green Process and Engineering, Division of Environment Technology and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, No. 1, Beier Street, Zhongguancun, Haidian District, Beijing 100190, China ‡ College of Environmental Science and Engineering, Nankai University, 38 Tongyan Road, Haihe Education Park, Jinnan District, Tianjin 300350, China S Supporting Information *

ABSTRACT: Efficient extraction and stripping for recovering vanadium(V) from the leaching/aqueous solution of chromiumbearing vanadium slag (V−Cr slag) are essential to the reuse of heavy metals. The performance characteristics of a new reagent, primary amine N1519, were first reported for extracting vanadium. With a phase ratio of organic to aqueous up to 1:1, 99.7% of vanadium(V) can be effectively extracted from the leaching/ aqueous solution, and powder of NH4VO3 was obtained through the stripping with ammonia. The new reagent can be recyclable in use for sustainable reuse after stripping. Different extraction conditions, e.g., the initial pH of the leaching/aqueous solution and the molar quantity of N1519 were investigated. The powder of vanadium-organic compounds (VOC) with N1519 formed in the process of extraction was obtained and purified through threesteps of solvent-out crystallizations. The hydrogen bond association mechanism of extraction was illustrated with the structure of VOC and the enthalpy change in extraction process. The fast extraction process and slow stripping procedure for recovering vanadium(V) are suitable for use in annular centrifugal contactors with very short contact/resident times and mixed-settler extractors with very good mass transfer, respectively. The results offer significant advantages over conventional processes. KEYWORDS: Extraction of vanadium, Hydrogen bond association, Vanadium-organic compound, Primary amine N1519, The enthalpy change

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INTRODUCTION To reduce efficiently the volume of high-pollution waste, the main components of V−Cr slag, that is, recyclable vanadium (about 1.2% in mass) and chromium (about 0.6% in mass), can be recovered by reprocessing.1,2 Moreover, vanadium is a significant strategic resource that is extensively used as constituent of several catalysts, alloys, and pigments due to its physical properties of tensile strength, hardness, fatigue resistance.3 The current method for disposing commercial V−Cr slag is a salt roasting process including procedures of salt roasting, leaching, crystallization, purification, solvent extraction, stripping and precipitation, etc.2 It was originally developed to extract vanadium for industrial application.1 In the salt roasting process, a very important step is to extract vanadium from the leaching/aqueous solution with primary amine N1923.1,2,4−6 Within the current disposing of method, vanadium separation has been conventionally achieved through the use of extraction process with primary amine as extractant.1 In last 2 decades, considerable efforts have been made to investigate many reagents of vanadium(V) extraction in the leaching/aqueous solution in order to improve separation © 2017 American Chemical Society

technology. Various reagents have been utilized for implementing solvent-extraction process, e.g., phosphinic acids (CYANEX 272),7 hydroxyoximes (LIX 63),8 primary amines (Primene JMT),9 tertiary amines (Alamine 336),10 trialkylamine,11 and phosphorus−oxygen extractants (TBP).12 The extraction mechanism of vanadium with mixtures of D2EHPA−TBP was evaluated based on the slope analysis method.13 N235 was able to extract vanadium(V) of anionic form through ionexchange type reaction.14 The metal ion of vanadium was extracted by primary amine N1923 by hydrogen bond association (as shown in the following equation).2,15 + x RNH 2(o) + y V4O12(a)4 − + 4y H(a)

⇔ (RNH 2)x ·(H4V4O12 )y(o)

(1)

where, (o)-organic phase, (a)-aqueous phase, x,y-parameters for mass balance. Received: November 18, 2016 Revised: January 21, 2017 Published: February 3, 2017 3096

DOI: 10.1021/acssuschemeng.6b02797 ACS Sustainable Chem. Eng. 2017, 5, 3096−3102

Research Article

ACS Sustainable Chemistry & Engineering In the above-mentioned reagents, primary amine N1923 is always used in the industrial process. However, the extracting mechanism of vanadium with primary amine N1923 was not investigated by reliable methods but only speculated as hydrogen bond association.2,15 Several metal−organic compounds are formed simultaneously in the extraction process when various species of vanadium16,17 contact with the extractant of primary amine N1923. High purity of metal− organic compound was difficult to obtain by common separation methods (e.g., recrystallization, column separation, and membrane separation). It is difficult or impossible to obtain the single crystal of the metal−organic compound, and the combination way of vanadium and primary amine N1923 is unable to observe directly. Therefore, obtaining purified powder of the metal−organic compounds and investigating their structures is essential to study the mechanism of extraction.18,19 In this paper, we reported a new organic mixed reagent, N1519, which belongs to a homologue of N1923 and have been demonstrated an impressive ability for extracting vanadium(V) from the leaching/aqueous solution. Additionally, the reagent N1519 has some advantages: easy to obtain, high activity, and less cost. Moreover, the reagent N1519 can also be reused without increasing the volume of the waste at the end. The powder of the VOC with N1519 has been obtained by solventout crystallization. Its average chemical composition was illustrated by the methods of elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), and inductive couple plasma-optical emission spectrometer (ICP). Its structure was determined through the spectra of NMR and IR. The mechanism of vanadium extraction from the leaching/aqueous solution by primary amine N1519 was studied based on the structure of the VOC, which can be used for further investigating the essence of the separation process.

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Figure 1. Negative mode ESI-MS spectra of N1519. with magnetic stirring and then the powder of VOC form and settlement; (3) filter the organic phase and then soak and scrub the power of VOC; (4) drying the VOC in vacuum oven at the temperature of 303.15 K. The procedure of recrystallizaiton for the VOC was the same as the solvent-out crystallization. The powders of the VOC or the loaded organic phase contained vanadium were back-extracted using ammonia solution at the temperature of 318.15 K. Instrumental Analysis. The concentration of each metal in the leaching/aqueous solution was determined by inductive couple plasma-optical emission spectrometry (ICP-OES, PerkinElmer Optima 6300DV), and the metal concentration in the loaded organic phase was calculated from mass balance. The pH value of the aqueous phase was measured using a Mettler-Toledo Delta 320 pH meter. Highresolution 1H NMR was measured using Bruker Varian ARX 700 NMR spectrometer at a frequency of 700 MHz. FT-IR spectra were carried out on SEPCTRUM GX1 (PerkinElmer, USA) at room temperature. Electrospray ionization mass spectrometry (ESI-MS) was measured on a Bruker HCT/Esquire instrument. An elemental analyzer (Flash EA 1112) was adopted to analyze C, H, and N in the compounds. The valence of vanadium in the VOC was determined through X-ray photoelectron spectroscopy (XPS, Thermo Scientific, K-Alpha, using Al Kα monochromatic radiation). Treatment of Data. The extraction percentage (EV) and distribution ratio (DV) were calculated as follows:

EXPERIMENTAL SECTION

Materials. The simulated leaching/aqueous solutions of vanadium(V) and chromium(VI) were used for systematic experiments and they were prepared by dissolving NaVO3 (2.93g, 0.024 mol) and Na2CrO4· 4H2O (2.81g, 0.012 mol) in deionized water (100 mL). The concentrations of V(V) and Cr(VI) in the simulated aqueous solution were in accord with the concentrations of two metals in the leaching solution of the V−Cr slag.2 The extractant of primary amine N1519 with diluent (n-hexane) were used for extraction experiments. Primary amine N1519 (Figure 1) was C 15 −C 19 secondary long-alkyl primary amines (i.e., C15H31NH2, C17H35NH2, and C19H39NH2), with a purity of 98% and the molar concentration of −NH2 being 3.15 mol/L. All the chemicals (Table S1-S1) used in these experiments were all of analytical grade without further purification. The water used in all experiments was ultrapure water with specific resistance more than 18.2 MΩ·cm (Millipore Milli-Q). The initial pH values of the simulated leaching/aqueous solution were modulated with 9.2 mol/L H2SO4 solution. Experiment Methods. With a 1:1 phase ratio of organic to aqueous and a contact time of 30 min, extraction experiments were carried out in separatory funnels fixed in an oscillator with a speed of 200r/min under the temperature of 293.1 ± 0.5 K. The molar ratio of primary amine to vanadium(V) was 1:1, and the initial pH value of aqueous solution was 1.5 ± 0.1 unless stated differently. The powders of the VOC with primary amine N1519 were obtained through solvent-out crystallization from the organic phase. Further purification of the VOC was carried out through several recrystallizations. The solvent-out crystallization were carried out by four steps: (1) scrubbing the loaded organic phase with water and then phaseseparation; (2) put the acetone slowly into the loaded organic phase

EV =

DV =

VSCS(V) − VR C R(V) VSCS(V)

× 100 (2)

CS(V) − C R(V) C R(V)

(3)

where VS and VR are the volumes of the stock and raffinate solution, respectively. CS(V), CR(V) are the concentrations of vanadium in the stock and raffinate solution, respectively.

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RESULTS AND DISCUSSION Influence of Various Conditions on Extraction Process. Influence of Initial pH value on EV and DV. As shown in Figure 2, with a contact time of 30 min, the initial pH of 0.5, only 23.64% of vanadium(V) was extracted when the molar ratio of N1519 to vanadium(V) is 1:1. 99.66% of vanadium(V) was extracted when the initial pH was 1.5. The EV and DV were first increased and then reduced when the initial pH value changed from 0.5 to 7.0. The maximal values of EV and DV were 99.66% and 290.56 when the pH value was 1.5. Influence of Molar Ratio of N1519 to Vanadium on EV and DV. As shown in Figure 3, with a 1:1 molar ratio of N1519 to vanadium(V), EV was reached to 99.66% when the initial pH 3097


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ACS Sustainable Chemistry & Engineering

Figure 2. Effect of initial pH value on EV and DV.

Figure 5. Crystallization process of VOC.

Figure 3. Effect of molar quantity of N1519 on EV and DV.

Figure 6. V 2p spectra of VOC with N1519.

combine with H3VO4, H3V3O9 and H6V10O28,16 and at higher acid concentration the different species of vanadic acid were prone to be formed, thus resulting in a higher extraction percentage. The high-purity powder of NH4VO3 can be obtained by stripping process with ammonia solution. The chemical reaction between VOC of C17H35NH2V3O9H3 and ammonia solution can form H2O, thus suggesting that the stripping might go through the acid−base neutralization. Effect of Molar Ratio of N1519 on the V(V) and Cr(VI) Selective Separation. From Figure 4, the values of βV/Cr first increased and then decreased with increase of the molar ratio of N1519 to sum of V(V) and Cr(VI) under the same extraction conditions, e.g., the initial pH value of 1.5, a contact time of 30 min. The maximum value of βV/Cr was 510.52 under a 0.66:1 molar ratio of N1519 to sum of V(V) and Cr(VI). It can be concluded that the appropriate molar quantity of extractant was important to selective extraction of V(V) and Cr(VI). Possible Structure of VOC with N1519. To confirm further the above-mentioned mechanism, powders of VOC with N1519 were obtained by a novel crystallization process. XPS Spectrum of VOC with N1519. Powders of the VOC were obtained from vanadium-loaded organic phase through solvent-out crystallization. As shown in Figure 5, the color of the compound was yellow. Compared with the yellow color of the leaching/aqueous solution containing vanadium before extraction, it was concluded that the valence of vanadium in the compound was not changed in extraction process. To confirm the above-deduction, the spectra of the VOC collected from the V 2p core region are shown in Figure 6. Significant bands appeared at binding energy of 517.56−524.95 eV, which corresponded to V 2p3/2 orbital assigned at 517.56

Figure 4. Effect of molar ratio of N1519 on the selective separation.

was 1.5. With a 2:1 molar ratio, EV can be reached to 99.99%. The EV and DV were increased when the molar ratio of N1519 to vanadium(V) changed from 0.5 to 2. Considering the cost of extraction process, the suitable molar ratio was between 1.0 and 1.5. Additionally, after contact with the vanadium-loaded leaching/aqueous phase, the organic solution became yellow in color, thus indicating that vanadium(V) might be combined with N1519 during the extraction. Similar to the organic amine reagents, such as N1923, 7301, and N235 reported in previous studies,2,15 in the pH range of 1.5−7, the extraction percentage of vanadium(V) increased with the increase of acid concentration in the leaching/aqueous solution, thus suggesting that the fast extraction might go through a hydrogen bond association mechanism. N1519 as an organic base might 3098


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Figure 9. Possible structure of (C17H35NH2)2V3O9H3.

can be extracted with primary amine N1519 and then formed metal−organic compounds. According to elemental analysis, the average mass percentages of elements (i.e., C, H, N, V) in the VOC were 49.44%, 9.41%, 3.42%, and 19.40%, respectively. Based on the valence of vanadium in the VOC, the composition of the VOC with N1519 was C17H35NH2V1.57O4.73H1.59, which was near the chemical structure of (C17H35NH2)2V3O9H3. Based on previous paper,16 the specific composition of C17H35NH2V1.57O4.73H1.59 can be divided two parts: about 4.6% of C17H35NH2 V3O9H3 and 95.4% of (C17H35NH2)2V3O9H3. In other words, the main component of VOC was (C17H35NH2)2V3O9H3. 1 H NMR Spectra of VOC. High-resolution nuclear magnetic resonance (NMR) spectroscopy is a powerful tool in obtaining useful information on the details of compound structure. The 1 H NMR spectra of the VOC are shown in Supporting Information (Figure S2−S1). Spectra of the VOC can be analyzed for 1H NMR (700 MHz, Pyr) δ 4.00−3.82 (m, 1H), 2.47−2.20 (m, 2H), 2.09 (s, 2H), 1.81 (t, J = 45.1 Hz, 2H), 1.71−1.56 (m, 2H), 1.57−1.04 (m, 22H), 0.95−0.78 (m, 6H). The total numbers of H atoms in the VOC were 37 except active hydrogen, which was consistent with the total number of H atoms in N1519. It was concluded that the organic part of the VOC was not changed in the process of extraction reaction. FT-IR Spectra of VOC. FT-IR spectra of NaVO3, N1519, and (C17H35NH2)2V3O9H3 are shown in Figure 7. As shown in Figure 7A,B, the spectra of NaVO3 exhibited a number of absorption bands in the 500−1000 cm−1 region. The strong and sharp bands at 916 and 962 cm−1 were assigned to asymmetric and symmetric VO stretching vibrations.21 The peak at 547 cm−1 was attributed to VO stretching vibration. Characteristic peaks about 1463, 1377, 2956, 2854, 2930, and 1618 cm−1 in the spectra of N1519 were assigned to δ asym (−CH 2 ), δ sym (−CH 3 ), ν asym (−CH 3 ), ν sym (−CH 3 ), νasym(−CH2), and δsym(−NH2) bands, respectively. Via comparison of the VOC ((C17H35NH2)2V3O9H3) and N1519 spectra, the peak of δsym(−NH2) was shifted from 1618 cm−1 to a low wavenumber of 1610 cm−1, indicating that a hydrogen bond (i.e., CN···H) was formed between N1519 and V3O9H3. As for the VOC, a broad band between 725 and 840 cm−1 with maxima at 725 and 785 cm−1 and a strong and sharp band at 594 cm−1 were attributed to asymmetric and symmetric (VOV) stretching of the vanadium oxide chains.21 Peak about 3464 cm−1 was assigned to symmetric OH stretching.

Figure 7. FT-IR spectra of the metal−organic compound.

Figure 8. Effect of temperature on extraction of vanadium(V) (0.24 mol/L C17H35NH2 in n-hexane, pH = 2.4, [V3O9H3] = 0.08 mol/L, A:O = 1:1).

eV for V2O5, and the bands at 524.95 eV were correspond to the V 2p1/2 orbital.20 The results implied that the valence of vanadium in the VOC was +5, i.e., the valence of vanadium had not changed. The result provided a sufficient evidence for unchanged valence of vanadium in the extraction process. Composition of VOC. In the extraction process of our work, the pH value was changed from 1.5 to 7.9 and concentration of V(V) in the simulated aqueous solution was changed from 0.024 to 8.64 × 10−5 mol/L. According to diagram for V(V)− OH− species with different V(V) concentrations and pH values,9 speciation of vanadium compounds in acid media (aqueous solution) were H2V10O284−, HV10O285−, V10O286−, V4O124−, V3O93−, H2VO4−, and HVO42−. These V(V) species 3099


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Figure 10. Reaction mechanisms of extraction and stripping.

assumed to be constant at a particular temperature under the experimental conditions. The values of log Kex at different temperatures were calculated based on eq 5. The plot of log Kex versus 1000/T is presented in Figure 8, the extraction percentage decreased with the increase of temperature throughout the studied temperature range. A positive of slope of 0.6749 was obtained. The change of Gibbs free energy, ΔG°, and the change of entropy, ΔS°, of the system at 298.15 K can be obtained as eqs 7, 8: ΔG° = −2.303RT log Kex

(7)

ΔG° = ΔH ° − T ΔS ° ⇒ ΔS ° =

Enthalpy Change in Extraction Process. According to the above conclusion, the VOC formed in extraction process was mainly composed of (C17H35NH2)2V3O9H3, so the extraction reaction was described by the following eq 4: 3H+(aq) + V3O93 −(aq) + 2C17 H35NH 2(org) (4)

where “aq” and “org” denote the aqueous and organic phase, respectively. Neglecting the activity coefficient for the chemical reaction in organic and aqueous phases, the apparent equilibrium constant Kex can be described by eq 5: Kex =

(C17H35NH 2)2 V3O9H3(org) [V3O93 −]· [H+]3 · [C17H35NH 2(org)]2

(8)

The values of ΔH°, ΔG°, and ΔS° at 298.15 K were −12.92 kJ· mol−1, −115.31 kJ·mol−1, and 343.42J·(mol−1·K−1), respectively, which indicate that the extraction reaction was exothermic and spontaneous. To our interest, the value of ΔH° in the extraction process means the intermolecular forces between primary amine N1519 (mainly including C17H35NH2) and V3O9H3 in the organic phase. The binding energy of 12.92 kJ·mol−1 was less than the values of 20−25 kJ·mol−1, which corresponded to most associated energies of hydrogen bonds (with a few exceptions, usually involving fluorine).24 The results (i.e., the value of ΔH° and the change of FT-IR spectra) provided sufficient evidence for the existence of hydrogen bond of N···H in the VOC. Possible Structure of VOC. According to several analysis methods for the VOC, it was concluded that several functional groups (e.g., VOV, VO, −CH3, −CH2, RH2N···H, −OH) were in the (C17H35NH2)2V3O9H3, and the vanadium oxide chains were composed of (V3O93−) unites linked by (V OV) bonds.21 The possible structure of the VOC can be shown in Figure 9. The combination way of primary amine N1519 and H3V3O9 was hydrogen bond of N···H. Reaction Mechanisms of Extraction and Stripping. To our knowledge, the reactions between organic base and inorganic acid are common, e.g., the reaction between triethylamine and hydrochloric acid, the reaction between phenethylamine and hydrochloric acid.25 The combination way of the organic base and the inorganic acid is hydrogen bond in the nonpolar solvents. As shown in Figure 10, the mechanism of extracting vanadium(V) with primary amine N1519 is hydrogen bond association, which is a RH2N···H bonding between the organic amine and V3O9H3.

Figure 11. Effect of recycle number of N1519 on EV (a contact time of 30 min, the initial pH of 1.5 and a 1:1 molar ratio of N1519 to vanadium).

↔ (C17H35NH 2)2 V3O9H3(org)

ΔH ° − ΔG° T

(5)

The enthalpy change associated with the extraction of vanadium(V), ΔH0, can be calculated from the slope of log Kex against 1/T using the Van’t Hoff equation.22,23 ∂(log Kex ) ΔH ° ΔH ° 1 =− orlog Kex = − +C ∂(1/T ) 2.303R 2.303R T (6)

where R is the universal gas constant 8.314J/(mol·K), T is the absolute temperature, and C is an integration constant that is 3100



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The loaded organic phase contained 9.8−12 g/L of V(V) was stripped with 25%−28% (v/v) of ammonia solution at the temperature of 318.5 K for more than 21 min. The molar ratio of vanadium(V) in the organic phase to NH3·H2O was 1:1.3, and the stirring speed was 50−200 rpm. As shown in Figure 10, powder of NH4VO3 was obtained by acid−base neutralization between the VOC and NH3·H2O. Separation Efficiency of Recycled Primary Amine N1519. The effect of recycle number of extractant primary amine N1519 on EV is shown in Figure 11. In the recycle number of 1−3, the average EV was 99.64, which was near the value of 99.66 with the fresh primary amine N1519. In our lab experiments, the efficiency of reutilization of primary amine N1519 was good.

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CONCLUSIONS

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ASSOCIATED CONTENT

REFERENCES

(1) Ning, P.; Lin, X.; Wang, X.; Cao, H. High-efficient extraction of vanadium and its application in the utilization of the chromiumbearing vanadium slag. Chem. Eng. J. 2016, 301, 132−138. (2) Ning, P.; Lin, X.; Cao, H.; Zhang, Y. Selective extraction and deep separation of V(V) and Cr(VI) in the leaching solution of chromium-bearing vanadium slag with primary amine LK-N21. Sep. Purif. Technol. 2014, 137, 109−115. (3) Moskalyk, R. R.; Alfantazi, A. M. Processing of vanadium: a review. Miner. Eng. 2003, 16 (9), 793−805. (4) Ning, P.; Cao, H.; Liu, C.; Li, Y.; Zhang, Y. Characterization and prevention of interfacial crud produced during the extraction of vanadium and chromium by primary amine. Hydrometallurgy 2009, 97 (1−2), 131−136. (5) Ning, P.; Cao, H.; Lin, X.; Zhang, Y. The crud formation during the long-term operation of the V(V) and Cr(VI) extraction. Hydrometallurgy 2013, 137, 133−139. (6) Ning, P.; Cao, H.; Zhang, Y. Stability of the interfacial crud produced during the extraction of vanadium and chromium. Hydrometallurgy 2013, 133, 156−160. (7) Tavakoli, M. R.; Dreisinger, D. B. Separation of vanadium from iron by solvent extraction using acidic and neutral organophosporus extractants. Hydrometallurgy 2014, 141, 17−23. (8) Nguyen, T. H.; Lee, M. S. Recovery of molybdenum and vanadium with high purity from sulfuric acid leach solution of spent hydrodesulfurization catalysts by ion exchange. Hydrometallurgy 2014, 147−148, 142−147. (9) Nekovár,̌ P.; Schrötterová, D. Extraction of V(V), Mo(VI) and W(VI) polynuclear species by primene JMT. Chem. Eng. J. 2000, 79 (3), 229−233. (10) Lozano, L. Comparative study of solvent extraction of vanadium from sulphate solutions by primene 81R and alamine 336. Miner. Eng. 2003, 16 (3), 291−294. (11) Chen, Y.; Feng, Q.; Shao, Y.; Zhang, G.; Ou, L.; Lu, Y. Investigations on the extraction of molybdenum and vanadium from ammonia leaching residue of spent catalyst. Int. J. Miner. Process. 2006, 79 (1), 42−48. (12) Ojo, J. O. Separation of simulated mixed Mo(VI) and V(V) From HNO3 and HCl solutions by selective extraction and stripping with Tri-N-Butyl phosphate as extractant. Sep. Sci. Technol. 2013, 48 (10), 1577−1584. (13) Cheraghi, A.; Ardakani, M. S.; Keshavarz Alamdari, E.; Haghshenas Fatmesari, D.; Darvishi, D.; Sadrnezhaad, S. K. Thermodynamics of vanadium (V) solvent extraction by mixture of D2EHPA and TBP. Int. J. Miner. Process. 2015, 138, 49−54. (14) Yang, X.; Zhang, Y.; Bao, S.; Shen, C. Separation and recovery of vanadium from a sulfuric-acid leaching solution of stone coal by solvent extraction using trialkylamine. Sep. Purif. Technol. 2016, 164, 49−55. (15) Yu, S.; Meng, X.; Chen, J. Solvent extraction of vanadium(V) from aqueous solutions by primary amines. Sci. China, Ser. B: Chem. 1982, 25 (2), 113−123. (16) Liu, F.; Ning, P. G.; Cao, H. B.; Zhang, Y. Measurement and modeling for vanadium extraction from the (NaVO3+H2SO4+H2O) system by primary amine N1923. J. Chem. Thermodyn. 2015, 80, 13− 21. (17) Lozano, L. J.; Juan, D. Solvent extraction of polyvanadates from sulphate solutions by primene 81R. its application to the recovery of vanadium from spent sulphuric acid catalysts leaching solutions. Solvent Extr. Ion Exch. 2001, 19 (4), 659−676. (18) Xian, L.; Tian, G.; Beavers, C. M.; Teat, S. J.; Shuh, D. K. Glutarimidedioxime: a complexing and reducing reagent for plutonium recovery from spent nuclear fuel reprocessing. Angew. Chem., Int. Ed. 2016, 55 (15), 4671−4673. (19) Krumeich, F.; Muhr, H. J.; Niederberger, M.; Bieri, F.; Schnyder, B.; Nesper, R. ChemInform abstract: morphology and topochemical reactions of novel vanadium oxide nanotubes. ChemInform 1999, 30 (51), DOI: 10.1002/chin.199951239.

To conclude, we have reported a new primary amine, N1519, for extracting vanadium(V) in the simulated leaching/aqueous solution. With the molar ratio of N1519 to vanadium(V) of 1:1, 99.7% of vanadium(V) was extracted under the initial pH of 1.5. N1519 will be a promising extractant for deep disposing wastewater containing vanadium and recovering vanadium from the leaching/aqueous solution of V−Cr slag. Both the experimental phenomenon and the structure of the VOC with N1519 provided sufficient evidence of the formation of hydrogen bond between primary amine N1519 and V3O9H3 in the process of extraction, and this conclusion had been further illustrated with the enthalpy change in the separation process. The hydrogen bond association (RH2N···H) mechanism of extracting vanadium(V) and the acid−base neutralization of stripping vanadium(V) will guide further development of novel methods for heavy metals recovery. The loaded-vanadium extractant, through stripping, can be reused for extracting vanadium. Recycled utilization of reagent is in accord with the thought principles of sustainable development.

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.6b02797. Detailed descriptions of chemicals used in this work (source and purity) and 1H NMR spectra of vanadiumorganic compounds (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (P. Ning). ORCID

Hongbin Cao: 0000-0001-5968-9357 Zhi Sun: 0000-0001-7183-0587 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation (Grant No. 51425405) and National Key Technology Support Program of China (No. 2015BAB02B05). 3101


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ACS Sustainable Chemistry & Engineering (20) Wu, Q. H.; Thißen, A.; Jaegermann, W. XPS and UPS study of Na deposition on thin film V2O5. Appl. Surf. Sci. 2005, 252 (5), DOI: 10.1016/j.apsusc.2005.03.134. (21) Khan, M. I.; Yohannes, E.; Doedens, R. J.; Golub, V. O.; O’Connor, C. J. Templated synthesis of a chiral solid: synthesis and characterization of {Co(H2N(CH2)2NH2)3}[V3O9]·H2O, containing a new type of chiral vanadium oxide chain. Inorg. Chem. Commun. 2005, 8 (9), 841−845. (22) Senturk, H. B.; Ozdes, D.; Gundogdu, A.; Duran, C.; Soylak, M. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: equilibrium, kinetic and thermodynamic study. J. Hazard. Mater. 2009, 172 (1), 353−362. (23) Dai, Y. Y.; W, Q.; Zhang, J. Complex Extraction Technology of Organics; Chemical Industry Press: Beijing, 2003. (24) Muller, P. Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994). Pure Appl. Chem. 1994, 66, 1077− 1184. (25) Xing, Q. Y.; Xu, R. Q.; Pei, J. Basic organic chemistry; Higher Education Press: Beijing, 2005.

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