<<

Journal of Ecological Engineering Volume 17, Issue 2, Apr. 2016, pages 38–42 DOI: 10.12911/22998993/62284 Research Article

THE METHOD OF REMOVAL (III) AND (III) FROM DILUTE AQUEOUS SOLUTIONS

Olga Lobacheva1, Natalia Dzhevaga1, Aleksandr Danilov1

1 National Resources University (Mining University), Vasil’evsky Island, 21 line 2, Saint-Petersburg, 199106 Russia, e-mail: [email protected], [email protected], [email protected]

Received: 2015.12.22 ABSTRACT Accepted: 2016.03.04 Yttrium (III) and ytterbium (III) cations flotation from diluted aqueous solutions Published: 2016.04.01 in the presence of using sodium dodecyl as collector agent were studied. Y (III) and Yb (III) distribution and recovery coefficients as a function of aqueous рН value at different concentrations were received. Yttrium (III) and ytterbium (III) chloro and hydroxo complexes instability constants were calculated. The calculation of separation coefficient at рН specified values- de pending on chloride ion concentration was conducted. Maximum separation coeffi-

cient was observed when chloride concentration of 0.01 M is 50 at рН 7.8. Ksep is minimal in medium ans is 3 at рН 7.0. At sodium chloride concentration of

0.05 М Ksep is 9 at рН 7.8. Keywords: ion flotation, sodium dodecyl sulfate, distribution coefficient, separation coefficient, removal.

INTRODUCTION all Russian rare-earth deposits are part of com- plex deposits, whose processing does not include Ion flotation is a process based on adsorption recovering rare-earth elements. For example, a at liquid-gas phase boundary of surfactant and joint-stock company ‘Apatite’ is a large mining inorganic compound ions reaction products. The complex whose sphere of activity are booty and method is widely used for recovering substances enriching of apatite-nephelites ores of Hibiny de- from solutions with concentrations of 10-2 – 10-8 posits, production apatite and nephelite concen- mol/l. Ion flotation is based on recovering ion at- trates, and also other mineral concentrates – sy- traction by oppositely charged collector ions that enite, titaniummagnetite. A nephelite concentrate had attached to the surface of air or gas bubbles containing no less than 28,5 percent of Al2О3 is that are let through the solution [Gol’man 1982]. used for the production of aluminum, soda, pot- Various classes of surfactants are used as collec- ash, cement, phosphoric-potassium fertilizers, co- tor agents. Ion flotation method permits recover- agulants of containing an , brick wares, ing non-ferrous, rare-earth and heavy cat- wares, rare-earth elements, different salts of ions from diluted aqueous solutions and industrial aluminium and other foods outside a joint-stock waste . company ‘Apatite’ [Danilov et al. 2015]. Rare-earth elements are widely used in differ- Multipurpose use of mineral raw materials is ent branches of industry. Thus , the most important direction for resource-saving and yttrium are used for manufacturing glass, ce- in new millennium. Separated pure rare-earth el- ramics, catalysts; is used while manu- ements have extrinsic value. That is why an in- facturing magnets and ; is used crease in efficiency of separation of rare-earth -el when manufacturing luminophor; and ements with similar properties is a pressing prob- are used when manufacturing lem, permitting decreasing the cost of individual and in nuclear industry. It should be noted that rare-earth elements and their , and expand

38 3  Me  3DS Me(DS)3 (1) 3  Me  3DS Me(DS)3 (1) i.e. it is 0.003 M (DS- - dodecyl sulfate ion). Sodium chloride was also added to initial solution at a i.e. it is 0.003 M (DS- - dodecyl sulfate ion). Sodium chloride was also added to initial solution at a rate corresponding to the concentration of 0.01 and 0.05 mol/l. The received froth and chamber rate corresponding to the concentration of 0.01 and 0.05 mol/l. The received froth and chamber products were separated and analyzed. The froth was destroyed by using 1 М sulphuric acid. Rare- products were separated and analyzed. The froth was destroyed by using 1 М sulphuric acid. Rare- earth elements concentration wasJournal determined of Ecological by photometricEngineering Vol. method 17(2), 2016 with arsenazo III [4]; chloride earth elements concentration was determined by photometric method with arsenazo III [4]; chloride ions concentration – by mercurimetric titration method with mixed indicator (0.5 mass % of the possibility of their use.ions When concentration employing –ion by mercurimetrickov 1976]; dodecyl titration sulfate method ion concentration with mixed – by indicator (0.5 mass % of flotation high separationdiphenylcarbazide factors for rare-earth alcohol el- solutionpotentiometric and 0.05 titration mass method % of bromphenolby 0.002 М cetblue)- [5]; dodecyl sulfate ion diphenylcarbazide alcohol solution and 0.05 mass % of bromphenol ) [5]; dodecyl sulfate ion ements are not observedconcentration [Chirkst et al.– by 2009a]. potentiometric yltrimethylammonium titration method chloride by 0.002 solution М with cetyltrimethylammonium ion- chloride Studying of chloride ionsconcentration influence on – ion by flotapotentiometric- selective titration , method consisting by of0.002 -chloride- М cetyltrimethylammonium chloride tion process is of interest.solution with ion-selective EVL-1MЗ, electrode, put consisting into NaDS of and silver NaCl-chloride solution,-EVL and -1MЗ, put into NaDS and solution with ion-selective electrode, consisting of silver- -chloride-EVL-1MЗ, put into NaDS and NaCl solution, and membrane,membrane, selective selective to DS- ion.to DS The ion. membrane The membrane was manufactured by Ionometry - MATERIALS AND METHODSNaCl solution, and membrane,was selective manufactured to DS by ion. Ionometry The membrane Laboratory was of manufactured by Ionometry Laboratory of St. PetersburgSt. Sta Petersburgte University State Department University of Department Physical ofChemistry [6]. Solutions рН Laboratory of St. Petersburg State University Department of Physical Chemistry [6]. Solutions рН Ion flotation processvalue was ranges conducted from in 4 mark to 9 inPhysical increments Chemistry of 0.5 [Timofeev and adjusted et al. 1978]. by nitric The acid or sodium 137 V-FL laboratory flotationvalue rangesmachine fromwith a 4 cell to 9 invalue increments of pH solutions of 0.5 рН and value adjusted ranges from by nitric4 to 9 acid or sodium hydroxide of 1 dm3 for 5 minutes.solution. Chemically pure 0.001 in increments of 0.5 and adjusted by or solution. sodium hydroxide solution. mol/l yttrium and ytterbium cations solutions distribution coefficients between froth and chamber products were calculated Metals cations distribution coefficients be- were used as standard test solutions.Metals cations Solution distribution coefficients between froth and chamber products were calculated by [Ме3+] concentration in thetween froth froth product and chamber relative productsto [Ме3+ were] concentration calcu- in chamber residue in volume was 200 ml. Dry sodium3+ dodecyl sulfate 3+ 3+ combining both collectorby and [Ме foaming] concentration agent prop- in latedthe froth by [Ме product] concentration relative to in [Ме the froth] concentration product in chamber residue in accordance with formula [7] 3+ erties with general formula С Н OSO Na was relative to [Ме ] concentration in chamber resi- accordance12 25 with3 formula [7] used as a surfactant. Its concentration conformed due in accordance with Cformula [Zolotov 2004]: D  org (2) to stoichiometry of the following reaction: Corg D  Caq (2) (2) 3  Me  3DS Me(DS)3 (1) (1) Caq and separation coefficient - and separation coefficient i.e. it is 0.003 M (DS- - dodecyli.e. itsulfate is 0.003 ion). M (DS Sodium –and dodecyl chlorideseparation sulfate wa coefficientsion). also So added- to initial solution at a dium chloride was also added to initial solution at DMe K  1 (3) rate corresponding to the concentrationa rate corresponding of 0.01 to andthe concentration 0.05 mol/l. Theof 0.01 received froth and chamberMe1 DMe Me D 1 K 2  Me2 and 0.05 mol/l. The received froth and chamber Me1 (3) products were separated and analyzed. The froth was destroyed by using 1 М sulphuric acid. RareMe2 - D products were separated and analyzed. The froth In Figures 1 and 2 distributionMe2 coefficients as (3) earth elements concentrationwas was destroyed determined by usingby photometric 1 М sulphuric method acid. withRa- arsenazoa function III of[4 ];рН chloride at different sodium chloride con-

re-earth elements concentrationOn wasFigs determined. 1 and 2 distributioncentrations coefficie for yttriumnts and as aytterbium function cations of рН are at different sodium chloride ions concentration – by mercurimetric titration method with mixed indicator (0.5 mass % of by photometric method with arsenazoOn Figs .III 1 [Savin and 2 distributionshown. coefficients as a function of рН at different sodium chloride concentrations for yttrium and ytterbium cations are shown. diphenylcarbazide alcohol solution1966]; chlorideand 0.05 ions mass concentration % of bromphenol – by mercu blue)- [5]; dodecylWhen flotating sulfate ioyttriumn (III) cations in acidic rimetric titration methodconcentrations with mixed for indicator yttrium andmedium ytterbium at NaCl cations concentration are shown. of 0.01 M in the Fig. 1 Yttrium Kdistr. as a function of рН at different chloride concentrations concentration – by potentiometric(0.5 mass titration % of diphenylcarbazidemethod by 0.002 alcohol М cetyltrimethylammonium solu- range of рН < 6.7 chloride the recovery is near zero. The Fig. 1 Yttrium Kdistr. as a function of рН at different chloride concentrations tion and 0.05 mass % of bromphenol blue) [Kresh- abrupt jump of K is observed at рН 6.7. Max. solution with ion-selective electrode, consisting of silver-chloride-EVL-1MЗ, put into NaDSdistr and

- Fig. 2 Ytterbium K as a function of рН at different chloride concentrations NaCl solution, and membrane, selective to DS ion. The membrane was manufactureddistr. by Ionometry Fig. 2 Ytterbium K as a function of рН at different chloride concentrations When flotating yttrium (III)distr. cations in acidic medium at NaCl concentration of 0.01 M in the Laboratory of St. Petersburg State University Department of Physical Chemistry [6]. Solutions рН When flotating yttrium (III) cations in acidic medium at NaCl concentration of 0.01 M in the range of рН < 6.7 the recovery is near zero. The abrupt jump of K is observed at рН 6.7. Max. value ranges from 4 to 9 in increments of 0.5 and adjusted by nitric acid or sodium hydroxide distr range of рН < 6.7 the recovery is near zero. The abrupt jump of K is observed at рН 6.7. Max. K is 379 at рН 7.8, and 856 in nitrate medium at рН 6.95. Chloridedistr ions suppress yttrium (III) solution. distr K is 379 at рН 7.8, and 856 in nitrate medium at рН 6.95. Chloride ions suppress yttrium (III) cationsdistr recovery to froth and shift рН of maximum recovery to the region of high values from 6.95 Metals cations distribution coefficients between froth and chamber products were calculated cations recovery to froth and shift рН of maximum recovery to the region of high values from 6.95 3+ in nitrate medium3+ to 7.8 at NaCl concentration of 0.01 M. When increasing sodium chloride by [Ме ] concentration in the froth product relative to [Ме ] concentration in chamber residue in in nitrate medium to 7.8 at NaCl concentration of 0.01 M. When increasing sodium chloride concentration up to 0.05 M, yttrium (III) cations recovery to froth increases significantly. In the accordance with formula [7] concentration up to 0.05 M, yttrium (III) cations recovery to froth increases significantly. In the range of рН 4.0-9.0 the K doesn't exceed 10. рН of maximum recovery at C distr D  rangeorg of рН 4.0 - 9.0 the K distr doesn't exceed(2) 10. рН of maximum recovery at chlorides 2 Caq 2 and separation coefficient D K  Me1 Me1 Me D 2 Me2 (3) Figure 1. Yttrium K as a function of рН at different chloride concentrations distr.

On Figs. 1 and 2 distribution coefficients as a function of рН at different sodium chloride 39 concentrations for yttrium and ytterbium cations are shown.

Fig. 1 Yttrium Kdistr. as a function of рН at different chloride concentrations

Fig. 2 Ytterbium Kdistr. as a function of рН at different chloride concentrations When flotating yttrium (III) cations in acidic medium at NaCl concentration of 0.01 M in the range of рН < 6.7 the recovery is near zero. The abrupt jump of Kdistr is observed at рН 6.7. Max.

Kdistr is 379 at рН 7.8, and 856 in nitrate medium at рН 6.95. Chloride ions suppress yttrium (III) cations recovery to froth and shift рН of maximum recovery to the region of high values from 6.95 in nitrate medium to 7.8 at NaCl concentration of 0.01 M. When increasing sodium chloride concentration up to 0.05 M, yttrium (III) cations recovery to froth increases significantly. In the range of рН 4.0-9.0 the Kdistr doesn't exceed 10. рН of maximum recovery at chlorides 2

Journal of Ecological Engineering Vol. 17(2), 2016

Figure 2. Ytterbium Kdistr. as a function of рН at different chloride concentrations

Kdistr is 379 at рН 7.8, and 856 in nitrate medium at kov 1976]. At maximum recovery рН of 7,0 at

рН 6.95. Chloride ions suppress yttrium (III) cat- chloride ions concentration of 0.05 М Y(OH)2 DS + ions recovery to froth and shift рН of maximum goes into the froth, because рНcompl Me(OH)2 is recovery to the region of high values from 6.95 7.0, and pHhydr is 7.2 [Gol’man 1982]. in nitrate medium to 7.8 at NaCl concentration of Ytterbium (III) hydroxo dodecyl

0.01 M. When increasing sodium chloride con- YbOH(DS)2 go into the froth up to рНcompl + centration up to 0.05 M, yttrium (III) cations re- Me(OH)2 6.3, ytterbium (III) digidroxo dodecyl covery to froth increases significantly. In the range sulfates Yb(OH)2 DS in the range of рН from + of рН 4.0–9.0 the Kdistr does not exceed 10. рН of рНcompl Me(OH)2 6,3 to pHhydr 6.6 and ytterbium maximum recovery at chlorides concentration of (III) at рН > pHhydr 6.6 [Chirkst et 0.05 M shifted insignificantly to the region of high al. 2009c]. In the range of maximum recovery values from 6.9 in nitrate medium up to 7.0. Ytterbium (III) cations recovery at NaCl con- Table 1. Rare-earth metals distribution coefficients as centration of 0.01 M starts at рН 5.9 and reaches a function of recovery рН and sodium chloride con- centration the highest value of 48 at рН 7.4. Maximum Kdistr at chloride ions concentration of 0.05 M is 12 at Parameter Y(III) Yb(III)

2+ рН 6.7. In the range of рН values from 4 to 6 and рН compl MeOH 6.3 5.8 from 7.5 to 9 recovery is near zero. + рН compl Me(OH)2 7.0 6.3

pH hydr 7.2 6.6 C = 0 RESULTS NaCl Distribution coefficient 855.6 403.7 In Table 1 the results of yttrium and ytterbium рН of maximal recovery 6.9 8.3 cations distribution coefficients calculations be- рН of the start of recovery 6.1 6.0 tween froth pulp and chamber residue, onset and CNaCl = 0.01 M maximum recovery pH value, complexing and Distribution coefficient 379.5 48.3 hydrating рН are shown. рН of maximal recovery 7.8 7.4 Yttrium recovery in the absence of chloride рН of the start of recovery 6.7 5.9 ions at maximum recovery рН of 6.9 occurs in a CNaCl = 0.05 M form of YOH(DS)2, and at chloride concentrations Distribution coefficient 9.4 12.4 of 0.01 M in a form of Y(OH)3, because рНhydr рН of maximal recovery 7.0 6.7 and pHcompl are 7.2 and 6.3 respectively [Kresh- рН of the start of recovery 6.4 6.0

40 concentration of 0.05 M shifted insignificantly to the region of high values from 6.9 in nitrate medium up to 7.0. concentration concentration of 0.05 M shifted of 0.05 insignificantly M shifted insignificantly to the region to of the high region values of from high 6.9 values in nitrate from 6.9 in nitrate Ytterbium (III) cations recovery at NaCl concentration of 0.01 M starts at рН 5.9 and reaches medium up to medium7.0. up to 7.0. the highest value of 48 at рН 7.4. Maximum K at chloride ions concentration of 0.05 M is 12 at Ytterbium (III)Ytterbium cations recovery (III) cations at NaCl recovery concentration at NaCl concentrationof 0.01 M starts of at0.01distr рН M 5.9 starts and atreaches рН 5.9 and reaches the highest value of 48 at рН 7.4.рН Maximum 6.7. In the Krangedistr at of chloride рН values ions from concentration 4 to 6 and fromof 0.05 7.5 M to is 9 12recovery at is near zero. the highest value of 48 at рН 7.4. Maximum Kdistr at chloride ions concentration of 0.05 M is 12 at

рН 6.7. In the рНrange 6.7. of In рН the values range from of рН 4 valuesto 6 and from from 4 to7.5 6 to and 9 recoveryfrom 7.5 isto near9 recovery zero. is near zero.

RESULTS In Table 1 the results of yttrium and ytterbium cations distribution coefficients calculations RESULTS RESULTS between froth pulp and chamber residue, onset and maximum recovery pH value, complexing and In Table 1 theIn results Table of1 theyttrium results and of ytterbium yttrium and cations ytterbium distribution cations coefficients distribution calculations coefficients calculations hydrating рН are shown. between froth betweenpulp and froth chamber pulp residue,and chamber onset residue,and maximum onset and recovery maximum pH value,recovery complexing pH value, and complexing and Table 1. Rare-earth metals distribution coefficients as a function of recovery рН and sodium hydrating рН arehydrating shown .рН are shown. chloride concentration Table 1. Rare-Tableearth metals1. Rare distribution-earth metals coefficients distribution as coefficients a function of as recovery a function рН of and recovery sodium рН and sodium chloride concentration Yttrium recoverychloride in the concentrationabsence of chloride ions at maximum recovery рН of 6.9 occurs in the   Journal of Ecological Engineering Vol. 17(2), 2016 Yttrium recoveryYttrium in the recovery absenceform ofin of the YOHchloride absenceDS ions2 ,of and atchloride maximum at chlori ionsde recovery at concentrationsmaximum рН of recovery 6.9 of occurs 0.01 рН inMof the 6.9in theoccurs form in ofthe Y (OH)3 , because form of YOHDS2 , and at chloriрНhydrde and concentrations pHTablecompl are 2. Yttrium 7.2 of 0.01and and 6.3 M ytterbium inrespectively the form chloro of[8 ].andY At(OH hydroxo maximum)3 , because complexes recovery instability рН of 7,0 constants at chloride ions form of YOHDS2 , and at chloride concentrations of 0.01 M in the form of Y(OH)3 , because 0 0 Compound K ∆ G Compound + K ∆ G рНhydr and pHcompl are 7.2 and 6.3concentration respectively of [8 0.05]. At Мmaximum Y(OH) recoveryDS gon into рН the of 7,0froth,compl at chloridebecause298 рНionscompl Me(OH)2 is 7.0, andn pHhydr compl 298 рНhydr and pHcompl are 7.2 and 6.3 respectively [8].2 At maximum recovery рН, kJ/mol of 7,0 at chloride ions , kJ/mol - YCl2+ 0.054 + - 7.22 Y(OH)2+ 1.56×10 8 - 44.56 concentration of 0.05 М Y(OH)is DS7.2 [7].go into the froth, because рНcompl Me(OH)2 is 7.0, and pH+ hydr concentration of 0.052 М Y(OH) DS go into the froth, because рНcompl Me(OH)2 is 7.0, and pHhydr 2 2+ - 2+ × -9 - YbCl 0.110 5.46  Yb(OH) 4.99 10 47.39 is 7.2 [7]. is 7.2 [7]. Ytterbium (III) hydroxo dodecyl sulfates YbOH DS 2 go into the froth up to рНcompl + Ytterbium (III) hydroxo dodecyl sulfates YbOHDS go into the froth up to рНcompl Ytterbium (III)Me(OH) hydroxo2 6.3, dodecyl ytterbium sulfates (III) 2 digidroxoYbOHDS dodecyl go sulfates into the Yb froth(OH up)2 DS to in рН thecompl range of рН from рН of 6.7 ytterbium (III) goes2 into the froth in + + CONCLUSIONS + Me(OH)2 6.3, ytterbium (III) рН digidroxocompl Me(OH) dodecyl2 6,3 sulfates to pH Ybhydr( OH6.6) 2andDS ytterbiumin the range (III) of hydroxides рН from at рН > pHhydr 6.6 [8]. In the Me(OH)2 6.3, ytterbium (III) the digidroxo form of dodecyl Yb(OH) sulfates3, because Yb (рНOHhydr)2 DSis 6.6. in theрН range of рН from + of recovery onset 6.0 lies in the range of рН 1. During ytterbium ion flotation when adding рНcompl Me(OH)2 6,3 to pHhydr+range 6.6 andof maximum ytterbium recovery(III) hydroxides рН of 6.7 at ytterbiumрН > pH hydr(III) 6.6 goes [8]. complinto In the froth in the form of Yb(OH)3 , рНcompl Me(OH)2 6,3 to pHhydr 6.6 and2+ ytterbium (III) hydroxides+ at рН > pHhydr 6.6 [8]. In the MeOH 5.8 and рНcompl Me(OH)2 6.3 [Chirkst chloride ions a tendency to Kdistr decreasing and 3+ 2+ range of maximum recovery рНbecause of 6.7 ytterbiumрНhydr is 6.6.(III) рН goes of intorecovery the froth onset in 6.0 the lies form in ofthe Ybran(geOH of)3 рН, compl MeOH 5.8 and рНcompl range of maximum recovery рНet of al. 6.7 2010], ytterbium therefore, (III) goes Yb into is the recovered froth in inthe a form of shiftingYb(OH ) maximum3 , recovery to the region of + form of YbOH (DS)3+ . 2+ lower рН values is observed. Yttrium Kdistr also because рНhydr is 6.6. рН of recoveryMe(OH) onset2 6.3 6.0 [ 9lies], therefore in the ran Yb ge of is2 рНrecoveredcompl MeOH in the form5.8 and of рНYbOHcompl2+ DS  . because рНhydr is 6.6. рН of recoveryThe onset influence 6.0 lies of in chloridethe range ions of рНoncompl the MeOHdistri- 5.8 anddecreases,2 рНcompl and maximum recovery рН at chlo- + 3+ + 3+ Me(OH)2 6.3 [9], therefore Yb is recoveredChloridebution in ions the coefficientforminfluence of YbOH on distribution wasDS 2 explained. coefficient by was comparing explained ride by concentration comparing chloroof 0.01 and М shifts to the region Me(OH)2 6.3 [9], therefore Yb is recovered in the form of YbOHDS2 . of high values, compared to nitrate medium. hydroxo complexeschloro instability and hydroxo constants complexes (table2). instability The first conones- were calculated using the following Chloride ions Chlorideinfluence ions on distributioninfluence on coefficient distribution was coefficient explained was by comparingexplained bychloro comparing and chloro and stants (Table 2). The first ones were calculated 2. At maximum recovery рН yttrium goes into hydroxo complexes instability constantsformula: (ta ble2). The first ones were calculated using the following hydroxo complexes instability constantsusing the (tafollowingble2). The formula: first ones were calculated using thethe following froth at chloride concentration of 0.01 М formula:  G0 MeCl2   G0 Me3   G0 Cl  inR aT formln K of Y(OH) , and at chloride ions con- formula: f 298 aq f 298 aq f 298 aq n 3 (4) 0 2 0 3 0  centration of 0.05 М the Y(OH) DS goes into   0 2   0 3   0   (4) 2 f G 298  MeCl aqGby fevaluatingGMeCl298Meaq instability Gf G 298Me constantCl aq R fromGT  lntheClK equation,n  R  T  lnthe K f 298 aq f 298 aq f 298 aq (4)n froth. (4) Ytterbium (III) hydroxides are recov- by evaluating instability constant from  the G fol0 - ered into the froth at maximum recovery рН at by evaluating instability constant from the equation, the  compl 298 by evaluating instability constant from the equation, the RT lowing equation:  NaCl concentration of 0.01 M, because pHhydr 0 Kn e complG 298 0 (5)  complG 298 6.6 [8]. In the maximum recovery рН range of RT   RT Gibbs energy K n eof chloro K complexes e and cations (5) formation 6.7 with in aqueous sodium solution chloride was concentration of 0.5 n (5) (5) М ytterbium (III) goes into the froth in a form accepted according to the database [10]. Hydroxo complexes instability constants were accepted Gibbs energy ofGibbs chloro energy complexes of chloro and complexes lanthanideGibbs energy and cations lanthanide of formationchloro cations complexes in aqueous formation and solution lantha in aqueous- was solution was of Yb(OH)3. according to datanide [1cations1]. formation in was ac- accepted accordingaccept ed to theaccording database to [ the10]. database Hydroxo [ 10 complexes]. Hydroxo instability complexes constants instability were constants accepted were accepted cepted according to the database [Database3 TKB]. Acknowledgements according to data [11]. according to data [11]. Hydroxo complexes instability constants were ac- cepted3 according to3 data [Chirkst et al. 2009]. The work is done according to the grant of When adding chlorides, part of the President of the Russian Federation for state binds into non-floating chloro complexes. De- support of young Russian scientists Project crease in hydroxo complexes part to flota- 14.Z56.15.6262-YC “Investigation of the meth- tion suppression and maximum recovery value ods effective adsorption-bubble recovery and shifting to higher pH values range. As a result, separation of rare earth elements with the use of conditions for yttreum and ytterbium separation surface-active substance from multicomponent are provided. solutions of poor technogenic raw materials”. Yttrium (III) cations are bonded into strong The studies were performed using equip- non-floating chloro complex, therefore, -a sig ment CCU of the Mining University: atomic ab- nificant decrease of distribution coefficients is sorption spectrometer AA 6300 of the company observed. Because of comparatively high value Shimadzu, optical emission spectrometer with of ytterbium (III) chloro complex instability con- parallel action ICPE-9000 inductively coupled stant, a decrease of recovery onset рН value and plasma of the company Shimadzu, spectropho- maximum recovery рН value when increasing tometer UV-VIS Specord 200 of the company chlorides concentration is observed. Analytik Jena. Because of chloro and hydroxo complexes different stability, different shift of recovery рН REFERENCES and flotation suppression occur, and, therefore, the conditions for yttrium and ytterbium separa- 1. Chirkst D.E., Lobacheva O.L., Berlinskiy I.V. and Su- tion appear. The stronger the chloro complex and limova M.A. 2009a. Extraction and separation of ions weaker the hydroxo complex are, the greater shift Ce3+ and Y3+ from aqueous solutions by ion flotation. towards higher recovery рН values is. Journal of Applied Chemistry, 82(8), 1370–1374.

41 Journal of Ecological Engineering Vol. 17(2), 2016

2. Chirkst D.E., Lobacheva O.L., Berlinskiy I.V. and nal of Ecological Engineering, 16(5), 9–14. DOI: Sulimova M.A. 2009b. Thermodynamic proper- 10.12911/22998993/60448 ties of hydroxocompounds and mechanism of ion 6. Database TKB. Parameters and definitions // http:// flotation cerium, europium and yttrium. Journal of www.chem.msu.su Physical Chemistry, 83(12), 2022–2027. 7. Gol’man A.M. 1982. Ion flotation. Nedra, pp. 144. 3. Chirkst D.E., Lobacheva O.L. and Berlinskiy I.V. 8. Kreshkov A.P. 1976. Fundamentals of analytical 2009c. Gibbs Energies of formation of hydroxides of lanthanides and yttrium. Journal of Physical chemistry. Theoretical basis. Quantitative analysis. Chemistry, 84(12), 2047–2050. Chemistry, pp. 480. 4. Chirkst D.E., Lobacheva O.L., Berlinskiy I.V. and 9. Savin S.B. 1966. Arsenazo III. Atomizdat, pp. 265. Cheremisina O.V. 2010. Thermodynamic investi- 10. Timofeev S.V., Materova V.A., Arkhangelskiy L.K. gation of the ytterbium ion flotation. Bulletin of St. 1978. Vestnik LGU. A Series of Physics, Chemis- Petersburg State University, 4(2), 137–142. try, 3(16), 139–141. 5. Danilov A.S., Smirnov Y.D. and Pashkevich 11. Zolotov Y.A. (Ed.) Fundamentals of Analytical M.A. 2015. Use of biological adhesive for effec- Chemistry. Book 1. General questions. Methods of tive dust suppression in mining operations. Jour- separation. Higher School, 2004, pp. 360.

42