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Introduction
It has been suggested by Sebba1-3 that, under certain conditions, bubbles bearing a charge
determined by adsorption of surfactant collector ions can be used to collect ions of opposite
charge (colligend ions) from aqueous solutions. These conditions may be satisfied by introducing
a surfactant of the appropriate ionic nature to the aqueous solution through which a stream of
bubbles is ascending. The adsorbed ions are concentrated by the breaking froth to form a scum
(the sublate). Aluminium and beryllium form negatively charged complexes with oxalate ions
as ligands; their different chemical properties can be utilised in an ion-flotation process to achieve
a separation of the two elements.
Experimental
Flotation reagents
The distilled grade of long-chain amines, Armeens, supplied by Armour Industrial Chemical
Co., Chicago, was used in the present work. The aminium chlorides were prepared by bubbling
dry hydrogen chloride gas into an anhydrous ether solution of the amine. The precipitated
hydrochlorides were dried in vacuum and stored over phosphorus pentoxide. The reagent was
dissolved in methanol before use.
Potassium trioxalatoaluminate trihydrate K, [Al(C,O,), ],3H,O and sodium binoxalato-
beryllate monohydrate Na, [Be(C,O,), ],H,O were prepared by accepted procedures4 The salts
were crystallised and analysed quantitatively before use. Stock solutions of the trioxalato-
aluminate salt containing approximately 1 mg. of A1 per C.C. and of the binoxalatoberyllate
containing approximately 0.16 mg. of Be per C.C. were prepared by dissolving the appropriate
amounts of each salt in water: these solutions were standardised (with respect t o A1 and Be)
before use.
All other reagents used were of analytical grade.
Apparatus
(1) Flotation circuit (Fig. 1)
Pure nitrogen was allowed to enter a visual rate indicator (water bubbler), A, through a
reduction unit governed by a sensitive needle valve, B. Gas at the required pressure then
entered a buffer chamber, C, which consisted of an empty bottle fitted with an outlet tube
incorporating a thin capillary, D. A mercury manometer, E, was connected across the cell
outlet and the flotation cell, F, was supported above a catchwater, G, fitted with a spring-drawn
tap which could be vented to atmosphere. All joints were made gas tight.
Results
The influence of the chain length of the alkylamine is shown in Fig. 2. Dense and stable
foams were produced with decyl- and dodecyl-amine hydrochloride over a wide range of con-
centration and these collectors were not investigated further. Fig. 3 shows the variation of
recovery of aluminium and beryllium with pH., and Fig. 4 the percentage recovery of aluminium
and beryllium from a solution of the oxalato complexes kept at a constant molar ratio of 2-0:l.
I I I I
_____
A, toncn I" fl0Of lYlUllO"
"0 2 L 6
COLLECTOR, rnmoles PER I. OF SOLUTION
The mole ratio of aluminium in solution to the collector added (tetradecylamine) was kept to
0.29, the optimum indicated by experiment.
The effect of increasing beryllium concentration while keeping that of aluminium constant is
shown in Table I.
Table I
b'aviatzorts in collectiiirz caused by incveasiuig bevyllium coriccnivafiorz
I;lotatiuri conditions: 111 concentration, 1.1 minole per 1.: pH 4.0: tetradecylamine hydrochloride collector,
3-8inmole per 1.; gas flow rate approx. 1400 C.C.of nitrogenlmin.; temperature 23"
Sublate
- 00 8
MOLARITY OF Na2[BclC20c 41 x lo -'
L I I I
0 10 20
MOLARITY OF K3 [AIIC20c)3]x 10.'
Temperatures in excess of about 25" caused excessive foaming and prevented quantitative
removal of sublate. The effect of temperature below 25" on systems containing varying ratios of
aluminium to beryllium are summarised in Table 11.
Table I1
Variation in collection caused by temperature
Flotation conditions: collector, tetradecylamine hydrochloride, 3.8 mmoles per 1. of solution; flow rate approx.
1400 C.C. of nitrogen/min.; pH 4.0; A1 concentration constant a t 1.1 mmole per 1.
Sublate
Discussion
The trioxalato-complex of beryllium is a weak one which dissociates on dilution: it has a
stability constant comparable with that of [CU(NH,),]~+.The studies of Sidgwick & Lewis*
on the ionic form of beryllium in oxalate solutions were supported by ion-exchange work
reported elsewhere. In this work, solutions of aluminium and beryllium oxalato-complexes in the
concentration range 0.1-1.0 mmole per litre were adjusted to p H 4-0 and allowed to percolate
through a 20-C.C.bed of IRA-400 anion-exchange resin: the effluents were analysed for aluminium
and beryllium, the amount retained by the resin corresponding t o the anionic form. The results
showed that although aluminium was quantitatively retained, in the case of beryllium an
equilibrium mixture of uncharged oxalate, oxalato-complex anions and beryllium cations exists
in aqueous solutions containing the complex (Table 111). No such behaviour was detected for
oxalato-aluminates, which have been shown by other methods t o be stable towards
Table I11
with concentration at p H 4.0
I*aviationof oxionic fovm of [Be(C,0,),]2-
Molarity of Na,Be(C,O,), 7; anionic form
1.5 :.. 10-4 40
6 61
12 72
15 90
20 90
Tetradecylaniine hydrochloride was the best collector although excess appears to reduce
recuvery: this is due to the effect of excess of solvent used to introduce the collector. The
concentration of solvent should not exceed 2.5 vol.-% of solution t o be floated. Collection of
oxalato-aluminate ion is nearly stoicheiometric, 7.0 mmoles of tetradecylamine being required to
collect 2.3 mmoles of aluminium.
Since sulphate interferes badly in recovery, it is understandable that amounts of sulphuric
acid in excess of those required to adjust the solution pH to the optimum value of 4.0 cause
rapid decrease in recovery. Competition between SO,2- or HS0,- ions and the complex anions is
resolved in favour of the former: the anions are said to be stable in dilute acid solution. On the
alkaline side of pH 4.0 a fall and subsequent rise in recovery is presumably an indication of
hydrolysis of the complex to form monovalent binoxalatoaluminatell which is then floated.
Beryllium however is floated in increasing amounts at pH values above 5.5 because of the
hydrolysis of the binoxalatoberyllate ion and the subsequent formation of cationic polyvalent
liydroxy compound^.^^^^^
Beryllium collection even under widely varying conditions is surprisingly small (Table 11),
although Al/Be ratios should not vary outside the limits 0.5-1.3 if undesirably high berylliutn
contamination of the sublate is to be avoided. The results indicate that, because of the lesser
tendency of beryllium to form anionic complexes, a selective flotation of aluminium from solutions
containing the two elements is possible, provided the concentration of beryllium is kept low.
Some information on the nature of beryllium oxalate-tri-isooctylamine complexes has been
obtained by de Bruin and co-workersl4 in solvent extraction studies. The effect of competing
ahminiurn ions was not described but the general conclusions are of the form reported here.
Acknowledgments
One of the authors (J.A.L.) wishes to acknowleage the award of a Kesearch Bursary from
the South African Council for Scientific K. Industrial Research.
Dept. of Chemistry,
ITniversityof the Witwatersrand,
Johannesburg, South ilfrica
Received 12 February, 1965;
amended manuscript 16 August, 1965
References
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~ ~ ~ Lusher,
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