Pergamon

Minerals Engineering, Vol. 10, No. I1, pp. 1291-1295, 1997

0892--6875(97)00115-5

Allrighu~

1997 Elsevier Science Ltd 0892--6875/97 $17.00+0.00

l'nntedin Greatnritain

TECHNICAL NOTE FLOTATION CONCENTRATION OF A XENOTIME PRE-CONCENTRATE

C.A. P E R E I R A j a n d A.E.C. P E R E S t

Dept. of Mining, UFOP, CAMPUS Morro do Cruzeiro, 35400-000 Ouro Preto, MG, Brazil. E-mail: aecperes@dedalus.lcc.ufmg.br of Dept. of Metallurgical Engineering, UFMG, Rua Espirito Santo, 35 30160-030 Belo Horizonte, MG, Brazil (Received 17 April 1997; accepted 25 July 1997)

ABSTRACT

The worm market for rare-earths elements is increasing due to the development of new products and applications, resulting in the need for technology to treat deposits having highly complex mineralogy, such as that of Pitinga, AM, Brazil, with estimated reserves of 146,960 t of rare-earths oxides (REO), including Y203. Mineralogically the mine of Pitinga is very rich. The initial and major target of the company Paranapanema was the production of tin concentrates from placer deposits and later from primary ore. However, geological studies identified several other minerals of potential economical importance, such as: columbite-tantalite, zircon, cryolite and xenotime, the objective of the present investigation. The response of a pre-concentrate sample of the non-conducting fraction from Pitinga " s electrostatic separator to laboratory scale physical concentration methods was very poor. Another possibility for the selective separation of xenotime and zircon (the major associated mineral) is flotation. Microflotation experiments were performed in a modified HaUimond tube with pure samples of xenotime and zircon, in the presence of hydroxamate as collector and five different reagents as depressants. 1997 Elsevier Science Ltd The zeta potential of xenotime and zircon was determined in the presence of electrolyte and hydroxamate.
Keywortb Flotation reagents; flotation depressants; flotation collectors

supporting

INTRODUCTION

The rare-earths represent a group of 17 elements (lanthanides, scandium and yttrium) that have similar properties in aqueous solution. Despite the designation "rare-earths", these elements are widely distributed in the earth's crust, although the known deposits are scarce [1]. Among the 70 known minerals which contain rare-earth elements, only bastnaesite, monazite and xenotime are employed as commercial sources.
Presented at Complex Ores '97, Bulawayo, Zimbabwe, March 1997

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C.A. Pereiraand A. E. C. Peres

The world supply of rare-earths is dominated by the production of bastnaesite in Mountain Pass, California, USA, and Bayan Obo (Baotou), in China, as a by-product of iron ore concentration. The known reserves of rare-earths in Brazil are distributed in the states of: Amazonas (mineral xenotime (146,960 t of REO, including Y203)); Minas Gerais, Espirito Santo and Bahia, (mineral monazite (82,710 t of REO)) [2]. Bastnaesite is also present in the deposit of Morro do Ferro, Pocos de Caldas, MG. The concentration of this ore has proved to be extremely difficult [3]. The major product of Paranapanema's Pitinga concentrator is cassitefite concentrate obtained from placer and primary ores. Several other minerals of potential economical importance have been identified, such as: columbite-tantalite, zircon, cryolite and xenotime (yttrium phosphate - - YPO4). A pre-concentrate containing xenotime, contaminated by zircon, assaying 0.74% Y203 is produced in the concentrator. The response of this product to physical concentration methods (magnetic and electrostatic separation) is very poor (Y203 recovery of 32% at a grade of 9.2%). An alternative method for the concentration of this product is flotation. Sodium oleate collector has been utilised in previous investigations dealing with xenotime. Aiming at better selectivity, a commercial hydroxamate was chosen for the present work. Five different depressants were employed. Zeta potential determinations were performed, not only due to its relevance to the flotation process but also because the surface charge of sparingly soluble minerals is sensitive to impurities occasionally present.

MATERIALS AND METHODS A small amount of material assaying approximately 95% xenotime and 5% zircon was selected from the concentration plant of Pitinga's mine. Samples of the minerals xenotime and zircon, as pure as possible, were produced by hand picking, with the help of pincers, under a microscope. The reagents utilised were: Collector: Hydroxamate - Flotinor V3759 ( Hoechs0 Depressants: lignin sulphonate*, quebracho*, conventional corn starch (RMB), amylopectin (SIGMA), sodium metasilicate PA - weight ratio SiO2:Na20 = 1:1 (J. T. Baker) * unknown supplier

The microflotation experiments were performed with mineral samples weighing 1 g, in the size range -212 }~m+106 }~m,at room temperature, in two sequences: collector only; collector and depressant. The nitrogen flowrate was 60 mL/min and the flotation time was 1 rain. The pH of the depressant and collector solutions was ajusted to 10 0.05. The conditioning times were 5 min for the depressant and 3 min for the hydroxamate. An extension was inserted to the Hallimond tube to prevent the entrainment of fine particles, increasing its volume from 190 mL to 350 mL. The samples for zeta potential and zero charge condition determinations were ground in an agate mortar to -38 pro. A solution of NaC1 lxl0 -2 molar was employed as supporting electrolyte and a solution lxl0 -3 molar of hydroxamate was utilised in the tests to check the effect of this reagent on the zeta potential. The pH was adjusted with NaOH and HC1. A Rank Brothers microelectrophoretic apparatus was employed for zeta potential determinations. The conditioning time was 3 rain ~and the suspension was kept under rest condition for 2 min, before the velocities of individual particles inthe cell were determined, the value for each point being the arithmetic mean of 20 determinations, the polarity of the cell being reversed after each measurement. The procedure followed in the determination of the zero charge condition according to the Mular & Roberts method was:

Flotation concentration of a xenofime pre~concentrate

1293

adding to 10 beakers (100 mL) 1.0 g of xenotime suspended in a supporting electrolyte at an ionic strength of lxl0 -3 molar; adjusting the pH to different arbitrary values pHi; dissolving an amount of dry supporting electrolyte increasing the ionic strength to lxl0 -2 molar and measuring pHf; determining ApH = pHi - pHf.

RESULTS AND DISCUSSION The floatability of xenotime in the absence of depressant was determined for hydroxamate concentrations in the range between 10 mg/L and 60 mg/L, at pH = 10 + 0.05. From 20 mg/L to 50 mg/L the floatability remained constant at a level of approximately 98%. There is a trend towards recovery decrease at both extremes of the range. The collector concentration of 35 mg/l was chosen for the tests, aiming at the selective depression of zircon, due to the fact that it represents an adequate condition for xenotime flotation. The results of xenotime and zircon microflotation in the narrow size range -212 tun +106 tun, with commercial hydroxamate as collector (concentration of 35 mg/L), in the presence of the depressants (concentration of 100 mg/L): calcium lignin sulphonate, starch, sodium silicate, amylopectin and quebracho, presented in Figure 1, show that quebracho and amylopectin yield xenotime recoveries inferior to 90%. Sodium silicate, starch and lignin sulphonate affect only slightly the floatability of xenotime (recoveries above 90%) and lead to zircon recoveries of 21.6%, 30.8% and 51.1%, respectively.

100 90 80 =~ 70 60 50 40 30 20 10 0

tO
-

Depressant
Fig.1

="

Floatabilities of xenotime and zircon with hydroxamate [35 mg/L] and depressants (lignin sulphonate, sodium silicate, starch, amylopectin, quebracho) [100 mg/L].

A study on the floatability of xenotime and zircon [4] reports recoveries of 95.9% and 42.9%, respectively, achieved in the pH range between 5 and 6, in the presence of oleic acid [70 mg/L] as collector and sodium metasilicate [65 rag/L] as depressant.

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C.A. Pereira and A. E. C. Peres

The floatability of xenotime and monazite was investigated in a modified Hallimond tube and by means of a technique that measures the particle/bubble adhesion force, utilising sodium oleate as collector [5]. The maximum floatability regions for xenotime and monazite were determined in the pH ranges of 7.0 to 8.0 and 8.5 to 9.0, respectively. The enhanced floatability above the zero charge condition (pH = 3.0 for xenotime and pH = 5.3 for monazite) suggests a chemisorption mechanism for the collector. Curves of zeta potential as a function of the pH were determined from microelectrophoretic experiments for xenotime in the presence of supporting electrolyte and hydroxamate (Figure 2). In the absence of collector a zero charge condition was observed at pH = 2.3. This value is lower than those measured by Scorzelli [4] pH = 4.0; Silva [6] pH = 5.0 and Cheng et al. [5] pH = 3.0. The hydroxamate does not significantly change the zeta potential above the pH corresponding to the zero charge condition. The major role of this reagent is to keep the zeta potential negative in the pH range between 2.0 and 3.0, around the zero charge condition, indicating a chemisorption mechanism. The zero charge condition of xenotime was also determined according to the Mular & Roberts method, leading to a pH value of 3.0, identical to one report from the literature (Cheng et al. [5]).

40

: 20
~

NaCI
Hydrox

10

11 pH

12

"~-20
i-

-40

n..
Q 0 l~

-60

80

-100
Fig.2 Microelectrophoretic determination of the zeta potential of xenotime as a function of pH in the presence of NaC1 and hydroxamate solutions.

Curves of zeta potential as a function of pH were also determined from microelectrophoretic measurements for zircon in the presence of supporting electrolyte and hydroxamate (Figure 3). In the absence of collector a zero charge condition was observed at pH = 4.0. This value is lower than those obtained by ScorzeUi [4] pH = 4.7 and Silva [6] pH = 6.0, being the same as one report from the literature (Pavez [3]). The hydroxamate significantly reduces the zeta potentialin the full pH range investigated making it impossible to reach a zero charge condition, indicating a chemisorption mechanism. The zero charge condition of zircon was also determined according to the Mular & Roberts method, leading to a pH value of 5.8, close to one report from the literature (Silva [6]). The difference between the values of the pH omresponding to the zero charge condition of zircon determined in the present investigation by the microelectrophoretic and the Mular & Roberts methods is difficult to explain. It might arise from impurities in the, samples.

Rotation concentration of a xenotime pre-concentrate

1295

40 20
I

NaCI .. t r . Hydrox.
I ~ I I I I I I I

2 -20 L0
D . m

4 ~5

10

11

_ -6o
'13.
. . . . . . . D . o ..

|-so
I1. N

ooot3. ~
~ "

-100 -120
-140 -160

~1~,. ",..

""-..(3..... .rn

Fig.3

Microelectrophoretic determination of the zeta potential of zircon as a function of pH in the presence of NaC 1 and hydroxamate solutions. CONCLUSIONS

The mieroflotation experiments showed that the floatability level of xenotime in the presence of commercial hydroxamate is high in the concentration range between 20 mg/L and 50 rag/L, decreasing for lower and higher levels. In the presence of commercial hydroxamate as collector and of the depressants sodium silicate and starch, the recovery of xenotime in microflotation experiments reached 93.9% and 96.5%, respectively. Utilising the same reagents an effective depression of zircon was possible, resulting in floatabilities of 21.6% and 30.8%, respectively. The zero charge condition was'determined by mieroelectrophoresis (xenotime - - pH = 2.3; zircon - - pH = 4.0) and Mular & Roberts method (xenotime m pH = 3.0; zircon m pH = 5.8). Hydroxamate renders the zeta potential of xenotime negative near and below the pH of zero charge condition. In the case of zircon the whole curve of zeta potential as a function of pH is shifted negatively in the presence of the collector.
REFERENCES
.

2. 3. 4. 5. 6.

Hedrick, J.B., Rare-earths elements and yttrium. In: The Bureau of Mines Minerals Yearbook. Washington: U.S. Department of Interior / Bureau of Mines, (1985). Silva, M.B.F., Mineral Summary, 14, 96-97, DNPM, (1994). (in Portuguese). Pavez, O.F.M., Flotation of rare-earths bearing minerals. Ph.D. Thesis, UFMG, 362 p., (1993). (in Portuguese). Scorzelli, I.B., Contribution to the study of the separation xenotime/zireon by flotation. M.Sc. Thesis, PUC / RJ, 150 p., (1994). (in Portuguese). Cheng, T.W. et al., Froth flotation of monazite and xenotime, Minerals Engineering, 6 (4), 341-351 (1993). Silva, M.L.S., Studies on the flotation of cassiterite, zircon and xenotime from the primary ore from Pitinga. M.$c. Thesis, COPPFJUFRJ, 109 p., (1988). (in Portuguese).