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ISSN 1067 8212, Russian Journal of Non Ferrous Metals, 2011, Vol. 52, No. 6, pp. 481484.

Allerton Press, Inc., 2011. Original Russian Text V.I. Zhuravlev, 2011, published in Izvestiya VUZ. Tsvetnaya Metallurgiya, 2011, No. 6, pp. 2125.

METALLURGY OF NONFERROUS METALS

Study of Sorption Purification of Lithium Hydroxide Solutions from Aluminum by Resin ANB 11g
V. I. Zhuravlev
National University of Science and Technology, Moscow Institute of Steel and Alloys MISiS, V 49, Leninskii pr. 4, Moscow, 252660 Russia e mail: vgurawlew@mail.ru AbstractThe results of studying the main regularities of the sorption of aluminum on complexing resin ANB 11g from lithium hydroxide solutions are given. The sorbent contains functional groups of methylglu cosylamine (N methylglucamine) and is produced by amination of chloromethylated copolymer of styrene and divinylbenzene by methylglucosylamine. Tests of its chemical and thermal stability in solutions contain ing 48 g/dm3 LiOH showed that ANB 11g retains sorption properties after 30 days contact with it. Heating of the studied sorbent in this solution to 373 K doesnt lead to a change in IR spectrathey are identical to the original. It was established on constructing the sorption isotherms of aluminum from solutions with 12 96 g/dm3 LiOH that an increase of the resins capacity for aluminum is observed with increasing content of the alkali in the original solution. The sorbent is regenerated by a diluted solution of the alkali with heating of the eluent to T = 323363 K. As a result of pilot industrial testing of sorption purification of lithium hydrox ide solutions to remove aluminum, the content of metal in them decreased by 12 orders of magnitude in them depending on the volume of solutions that passed through the resin. The degree of aluminum desorption was 99.5%. Keywords: alkaline solution, aluminum, lithium hydroxide, sorbent, sorption, resin ANB 11g, elution. DOI: 10.3103/S1067821211060174

Lithium and its compounds are used widely in var ious technologies [1].In hydrometallurgy of lithium, methods of producing salts of this metal with the use of solutions of alkalis are frequently employed. The LiOH solutions produced during processing of lithium raw material contain a considerable amount of alumi num impurities, which negatively affects the proper ties of the finished product. Thus, for example, at one of the chemical enterprises the Al content in lithium hydroxide monohydrate reaches 0.030.06%, and according to the requirements of State Standard GOST 8595 for brand LGO 1 this index should not exceed 0.01% and for LGO 3, 0.05%. Technologies of extracting Al from alkaline solu tions by converting it into insoluble compounds are widely used in practice [2]. However, the conventional methods of precipitating Aldecomposition and car bonization [2]are ineffective from the viewpoint of removing an impurity of this metal from solutions. Precipitation of aluminum by decomposition is char acterized by a low degree of its recovery and long time of the process, and the use of carbonization is related to neutralization of almost all alkali. The problem of purifying lithium hydroxide from aluminum can be solved by the sorption method, espe cially under conditions of low concentrations of the impurity in solutions [3].

This article gives the results of studying the main regularities of sorption of Al on resin AN 11g from LiOH solutions. As the sorbent for extracting aluminum we used the complexing resin synthesized at the Plastics Research Institute (Moscow). The sorbent contains functional groups of methylglucosylamine (N methylglucamine) and is produced by amination of chloromethylated copolymer of styrene and divinylbenzene by methyl glucosylamine. ANB 11g has the structure
R N C6H11O5 , CH3

where R is the sorbent matrix. An experimental batch of this resin was produced at NPO Plastmassy (Moscow). Experiments were conducted on synthetic solu tions under static and dynamic conditions. The ratio of the mass of the sorbent (in terms of the mass (g) of air dry resin) to the volume of the solution (ml) was 1 : 100. In the first stage we investigated the chemical and thermal stability of ANB 11g in an alkaline medium. Three batches of resin were placed for 30 days in indi vidual solutions containing, g/dm3: 48 LiOH, 80 NaOH, and 112 KOH, which corresponds to dou ble molar concentrations of solutions of the alkali.

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Table 1. Initial data and results of calculating the ionization constants of functional groups of sorbent ANB 11g in solutions with ionic strength = 0.1 pH 6.90 7.10 9.25 0.562 0.500 0.125 log/(1 ) 0.108 0.000 0.845 n 2.47 2.47 2.47 pK 6.834 6.900 6.924 Average 6.886 K 1.3 107

Samples of sorbent ANB 11g from the indicated resin batches were preliminarily saturated with aluminum under static conditions from the indicated solutions of hydroxides containing 1.0 g/dm3 Al each. The alumi num capacity of the resin, calculated from the results of a chemical analysis of equilibrium solutions, was, mg/g: 25 for sorption from the LiOH solution, 15.2 for NaOH, and 14.9 for KOH. After holding the sorbent in the alkaline solutions for 30 days, the resin samples were saturated again with aluminum under analogous conditions. The sorption capacity of all three ANB 11g batches stayed at the same level. It is necessary to note that the half life in a solution with 40 g/dm3 NaOH of the longest lived of the aromatic glycosylamines, N p chlorophenyl D glucosylamine, is 45 h 31 min [4], i.e., the duration of alkaline treatment of sorbent ANB 11g is completely sufficient for determining the chemical stability of functional groups of glucosylamine. An analysis of the resin by IR spectroscopy didnt reveal differences in the IR spectra of samples that underwent long alkaline treatment and without such. Heating ANB 11g in a solution containing 48 g/dm3 LiOH to 373 K also didnt lead to a change in the IR spectra. The increase in chemical stability of functional groups of methylglucosylamine in the sorbent com pared with its low molecular weight (LMW) analogue (the half life of LMW N methyl D glucosylamine is only 3 h) [5] can be explained by the mesomeric effect [6], which the high molecular weight matrix of the copolymer of styrene and divinylbenzene has on the glucosylamine molecule fixed on it. The mesomeric effect manifests itself to various degrees in all aromatic amines [6]. The shift of the vacant electron pair of the nitrogen atom toward the benzene ring of the hydro carbon matrix of the sorbent caused by it prevents hydrolysis of the functional groups of methylglucosy lamine. On the basis of the tests conducted, a conclusion can be made about high indices of the chemical and thermal stability of ANB 11g in alkaline media.
1 The

mesomeric effect is a shift of electron density of the chemi cal bond with respect to bonds, when the initial system over laps with the system or p orbital of the substituent, as a result of which redistribution of the electron density occurs.

The conventional method of potentiometric titra tion was used for determining the ionization constants (K) of functional groups of the sorbent and its capacity for ion exchange [7]. It was established that the resin has one group capable of ion exchangenitrogen, occurring in the structure of the functional groups, which at pH 79 splits off H+. In an acidic medium, nitrogen is in a protonated form and acquires a positive charge and capacity for exchange of anions, and in an alkaline medium is in a deprotonated form. Thus, the complexing properties of the resins functional groups are realized in an alkaline solution during sorption of aluminate ions. Transition of the amino group of methylglucosylamine from a protonated to a deproto nated form can occur only provided that the pH of the solution exceeds the pK value of ionization of the resins functional groups, which can be calculated by the HendersonHasselbalch equation [8]: pK = 14 pH nlog/(1 ), where is the degree of ionization of the functional groups; n is a parameter related to electrostatic inter action of adjacent groups, determined as the slope of the tangent line in coordinates pHlog/(1 ). The maximum capacity of the amino group of methylglucosylamine with respect to ion H+ and degree of its ionization were found experimentally, and the value of n was also determined. Then the pK values were calculated by the proposed equation. The initial data and calculation results are given in Table 1. During construction of the sorption isotherms of aluminum from solutions with a LiOH content of 12, 48, and 96 g/dm3 (Fig. 1), it wasnt possible to reach a plateau of the curves. This is related to the dependence of the solubility of aluminate ions in lithium hydroxide solutions on its concentration. The graphs have a con vex character, which indicates a good affinity of the resins functional groups for aluminum. The sorbents capacity for Al increases considerably with increasing content of alkali in the initial solutions (see Fig. 1). Under conditions of a higher alkali concentration and lower solvent (water) concentration in the sorbent phase compared with the external solution, an increase in the degree of dehydration of the aluminum hydroxo complexes present in the resin phase occurs and the probability of their interaction with functional groups both due to the formation of a hydrogen bond between the dehydrated hydroxo complexes and OH
Vol. 52 No. 6 2011

RUSSIAN JOURNAL OF NON FERROUS METALS

STUDY OF SORPTION PURIFICATION OF LITHIUM HYDROXIDE SOLUTIONS 40 Sorption capacity for Al, mg/g Sorption capacity for aluminum, mg/g 30

483

30 2 20 1 10

1 20

10

2 3

0 290

0.5

1.0

1.5

2.0

2.5

320 350 Solution temperature, K

380

Equilibrium concentration of Al in solution, g/dm3


Fig. 1. Sorption isotherms of aluminum from solutions containing (1) 12,(2) 48, and (3) 96 g/dm3 LiOH.

Fig. 2. Dependence of sorption capacity of resin for alumi num on temperature of solutions. Content, g/dm3: (1) 48 LiOH, (2) 80 NaOH, (3) 112 KOH; initial Al concen tration in solutions, 0.76 g/dm3; phase contact time, 24 h.

group of the D glucose radical and due to coordina tion of the central Al+ ion near the electron donor nitrogen atom increases. Experiments were conducted under static condi tions to determine the effect of temperature on the capacity indices of ANB 11g for aluminum during its recovery from solutions of lithium, sodium, and potas sium hydroxides. It is seen from the character of the curves (Fig. 2) that an increase in temperature of the solution above 333 K leads to a decrease of aluminum sorption and at T = 363 K the process of sorption of aluminate ions by the resin completely ceases. Its Al sorption capacity depends strongly on the nature of the cation of the alkali and changes in the series LiOH > NaOH > KOH. The decrease in recovery of aluminum at T > 333 K, complete cessation of Al sorption at T = 363 K, and reduction of the sorption capacity of ANB 11g for alu minum with decreasing content of alkali in the initial solutions (see Fig. 2) allowed the assumption that the saturated sorbent can be regenerated by diluted solu tions of the alkali at an elevated temperature. There fore, the Al saturated resin was eluted by a solution with a LiOH concentration of 2.4 g/dm3 under dynamic conditions in a 7 mm diameter column. The volume of the sorbent was 10 ml, which corresponded to an air dry resin mass of 3.85 g; the specific flow rate of the eluent was 0.5 h1 and the temperature of con ducting desorption was 363 K. Figure 3 shows the dependence of the degree of aluminum recovery on the ratio of the volumes of elu ate and sorbent (Vel/Vsorb). As is seen, the resin is regenerated almost completely by nine volumes of the LiOH solution. It should be noted that elution occurs
RUSSIAN JOURNAL OF NON FERROUS METALS

sufficiently effectively with a diluted LiOH solution and at a lower temperature (323 K). On the basis of the data obtained in laboratory experiments, pilot industrial testing of sorption purifi cation of lithium hydroxide solution was carried out in the lithium fluoride production department of one of the chemical industry enterprises. The solution being purified, containing 55 g/dm3 LiOH, was passed through a column 0.985 m high and 0.10 m in diame ter. The flow rate was 10 dm3/h; the volume of sorbent ANB 11g was 5 dm3, or 1.92 kg (in terms of the mass of air dry resin); the fill factor of the column with sor bent was 0.7.
100 Degree of Al recovery in eluate, % 80 60 40 20

10

Vel/Vsorb
Fig. 3. Dependence of degree of aluminum recovery in elu ate on ratio of eluate volume to resin volume. Vol. 52 No. 6 2011

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Table 2. Initial data and results of pilot industrial testing of sorption purification of lithium hydroxide solutions from alu minum Amount of solution passed, dm3 Initial 250 530 810 1075 1.7 103 1.1 103 4.4 104 5.5 104 Al concentration, wt % After purification 6 105 6 105 3 104 2.2 104

The initial data and results of the pilot industrial tests are given in Table 2. As is seen, as a result of sorp tion purification of lithium hydroxide solutions, the aluminum content in them was reduced by 12 orders of magnitude depending on the volume of the solu tions that passed through the resin. The sorbent that was saturated during the tests was regenerated in the same column at a temperature of the process of 323328 K. Heating was done by an external electric heater. A solution containing 3 g/dm3 was used as the eluent. The degree of aluminum des orption was 99.5%. CONCLUSIONS Thus, the ANB 11g sorbent used in this work showed good results in tests for chemical and thermal stability in highly basic alkaline solutions. High indices of its capacity characteristics with respect to aluminum in alkaline media as well as simplicity and effectiveness of regeneration brought about pilot industrial testing of resin ANB 11g under plant conditions. Positive results of sorption purification of lithium hydroxide solutions from aluminum were obtained: the content of the metal in them was reduced by 12 orders of magnitude

depending on the volume of the solutions that passed through the sorbent. REFERENCES
1. Kulifeev, V.K., Miklushevskii, V.V., and Vatulin, I.I., Litii (Lithium), Moscow: MISiS, 2006. 2. Moskvitin, V.I., Nikolaev, B.A., and Fomin, B.A., Metal lurgiya legkikh metallov (Metallurgy of Light Metals), Moscow: Intermet Inzhiniring, 2005. 3. Strizhko, V.S., Zhuravlev, V.I., Redkin, S.A., et al., USSR Inventors Certificate 1178463, 1985. 4. Volkova, E.N., Stepanenko, B.N., and Chentsova, M.G., Khimiya i biokhimiya uglevodov (Carbohydrate Chemistry and Biochemistry), Moscow: Nauka, 1969, pp. 4145. 5. Stepanenko, B.N. and Greshnykh, R.D., Khimiya i biokhimiya uglevodov (Carbohydrate Chemistry and Biochemistry), Moscow: Nauka, 1969, pp. 3640. 6. Petrov, A.A., Balyan, Kh.V., and Trishchenko, A.G., Organicheskaya khimiya (Organic Chemistry), Mos cow: Vyssh. Shk., 1973. 7. Polyanskii, N.G., Gorbunov, G.V., and Polyanskii, N.L., Metody issledovaniya ionitov (Methods of Investigating Ion Exchangers), Moscow: Khimiya, 1976. 8. Tulupov, P.E., Stoikost ionoobmennykh materialov (Resistance of Ion Exchange Materials), Moscow: Khimiya, 1984.

RUSSIAN JOURNAL OF NON FERROUS METALS

Vol. 52

No. 6

2011

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