Pergamon

Minerals Engineering, Vol. 9, No. 3, pp. 357-366, 1996 Copyright 1~ 1996 Published by Elsevier Science Lid Printed in Great Britain. All rights reserved PII: S0892--6875(96)00020-9 0892~g75/96 $15.00+0.00

TECHNICAL NOTE ADSORPTION OF OLEATE AND OCTYL-HYDROXAMATE ON TO RARE-EARTHS MINERALS O. P A V E Z , P . R . G . B R A N D A O t a n d A . E . C . P E R E S t Dept. of Metallurgy, Universidad de Atacama, Casilla 240--Copiapo, Chile t Dept. of Mining Engineering, UFMG, Rua Espirito Santo, 35/702, 30160-030 Belo Horizonte, MG, Brazil (Received 16 June 1995; accepted 18 October 1995) ABSTRACT

The adsorption of sodium oleate and potassium octyl-hydroxamate onto the rare-earths minerals monazite and bastnaesite was investigated through microflotation experiments, zeta potential determinations and infrared spectroscopy. The monazite and bastnaesite samples were purified in the laboratory reaching, respectively, final grades of 68. 7 and 45.3% RE203 + ThO2. The results confirm that sodium oleate chemisorbs onto bastnaesite and suggest a physical adsorption mechanism of this reagent onto monazite. Despite the lack of a full confirmation from FTIR spectrometry, there is a possibility of oleate chemisorption onto monazite in the pH range above the isoelectric point. A chemical adsorption mechanism was established for the interaction between octylhydroxamate and both minerals.
Keywords Flotation reagents; flotation collectors; industrial minerals INTRODUCTION Bastnaesite and monazite are the most important rare-earths bearing minerals in the world. Sodium oleate adsorption onto these minerals has been reported in the literature. Gerdel and Smith [1] observed that sodium oleate abstraction by basmaesite is significant above the isoelectric point--IEP, indicating chemisorption of the reagent onto the mineral surface. Viswanathan and Majumdar [2] investigated, via infrared spectroscopy, oleate adsorption onto monazite, arriving at the conclusion that a chemisorbed layer is formed on the mineral surface. Zakharov et al. [3] suggested that monazite flotation with sodium oleate depends on the reactions between the collector and thorium and rare-earths elements, with the formation of the corresponding metal oleate. Hydroxamic acids adsorption has been attributed to their ability of complexing metallic cations. According to Bogdanov [4], they form stable complexes with the cations of rare-earths elements. Fuerstenau and Pradip [5] presented a model based on equations to explain the chemical interaction between potassium octyl-hydroxamate and bastnaesite. A similar model was proposed by Jiake and Xiangyong [6] for the chemisorption of hydroxamic acid onto bastnaesite and monazite. Poster presentationat MineralsEngineering '95, St. Ires, Cornwall,England,June 1995

357

358

Technical Note

The present investigation studies the mechanisms of sodium oleate and potassium octyl-hydroxamate adsorption onto the rare-earths bearing minerals monazite and bastnaesite.

MATERIALS AND METHODS The monazite sample was supplied by SAMITRI--SA Mineracao da Trindade, from Sao Goncalo do Sapucai, MG, Brazil in the size range - 2 1 0 +105 /~m. The sample was purified by using a Frantz isodynamic magnetic separator, washed with distilled water and dried at 80 C. Basmaesite was extracted from a sample of the rare-earths ore obtained from Pocos de Caldas, MG, Brazil, supplied by MINEGRAL SA. After crushing (rolls crusher), a hand picking operation, under a stereoscopic microscope, provided grains rich in bastnaesite. A fraction - 2 1 0 + 74/zm was produced by grinding and further purified in a Frantz isodynamic magnetic separator and in a Magstream apparatus. The material was ground to 100% - 3 7 / ~ m , washed with distilled water and dried at 80 C. The chemical analyses of the two samples was as follows:

Sample

Re203 + ThO 2 % 68.7 45.3

SiO 2 % 1.15 11.64

A1203 % 0.92 9.83

P %

CaO % 0.96

Fe %

monazite bastnaesite The reagents utilised were: i.

12.1

15.12

potassium octyi hydroxamate--CH3(CH2)6CONHOK--synthetised according to a method reported by Fuerstenau and Pradip [5]; sodium oleate--CH3(CH2)7CH =CH(CH2)TCOONa--analytical grade; potassium hydroxide and hydrochloric acid, analytical grade, for pH control; potassium chloride, analytical grade, as indifferent electrolyte; nitrogen, as gas in the microflotation experiments.

ii. iii. iv. v.

Microflotation tests with monazite ( - 2 1 0 + 74 txm) were performed in a modified Hallimond tube similar to that described by Fuerstenau, Metzger and Seele [7]. A tube similar to that described by Siwek, Zembala and Pomianowski [81 was utilised for the finer ( - 3 7 #m) bastnaesite sample. Zeta potential determinations were carried out using a Rank Brothers Mark II apparatus with a 1 mm flat microelectrophoretic cell. Each point represented an average of 20 determinations. The mineral samples were ground to - 3 7 tzm in a porcelain mortar. A l x l 0 -3 M KC1 solution was employed as indifferent electrolyte and pH was controlled with 5 % w/v HC1 and KOH solutions. The infrared absorption spectra were obtained through the KBr pellet method in a Fourier transform infrared spectrometer Perkin Elmer FT-IR 1760X, controlled through an interface connected to a Professional Computer Perkin Elmer 7700. The data acquisition and spectra processing and displaying programmes were the regular ones (CDS package), supplied by Perkin Elmer. The monazite and bastnaesite samples were previously ground in an agate mortar for eight hours. The specific surface areas, as determined by BET technique, using a Quantasorb instrument, were 5.05 m2/g for monazite and 8.47 m2/g for bastnaesite.

Technical Note

359

In this infrared study the following spectra were compared: (a) mineral exposed to water at the desired pH; (b) mineral exposed to the collector solution at the desired pH.

RESULTS Floatability curves as a function of pH for monazite and bastnaesite in the presence of sodium oleate and potassium octyl-hydroxamate are presented in Figure 1. In the presence of 152 mg/l sodium oleate, monazite showed high floatability at pH=3 and the range between 6 and 10, showing a minimum around pH=4.

< 0

..J U.

monmdte 152 m~l oleate monmz~m3O0 mgn hydroxam~e

0 []
0.~
2.00
' 1 I '

badnaesit~ 200 m ~ hydroxamate b~neesite 60 m ~ oleete

I ' I '

4.~

8.~

8.~

10.~

12.~

pH

Fig. 1 Floatability of monazite and bastnaesite with sodium oleate and potassium octyl-hydroxamate as a function of pH Viswanathan, Madhavan and Majumdar [9] reported a high floatability of monazite in the presence of 200 mg/l sodium oleate in the pH range between 3 and 10. Dixit and Biswas [10], investigating the floatability of beach sand minerals, observed a maximum monazite floatability in the pH range 8.5-8.7 (2.66 x 10 -4 M sodium oleate). The pH range 5 to 10 proved to be the most adequate for the flotation of monazite with 300 mg/l potassium octyl hydroxamate (70 to 80% floated). Bastnaesite presented floatability maxima around pH =9 with both collectors sodium oleate (60 mg/l) and potassium hydroxamate (200 mg/l).

360

Technical Note

A high floatability of bastnaesite with oleate at pH = 8 was reported by Gerdei and Smith [ 1]. The maximum around p H = 9 (the pK a range reported for hydroxamic acids is 8.5 to 9.5) is characteristic for hydroxamates in adsorption and flotation studies, according to Fuerstenau and Pradip [5]. Zeta potential curves of monazite and bastnaesite as a function of pH, in the absence of both collectors and in the presence of sodium oleate and potassium octyl-hydroxamate, are presented in Figure 2. The isoelectric point stays at p H = 5 . 2 for monazite and p H = 4 . 9 for bastnaesite. The presence of collector displaces the IEP towards the more acidic region. In the pH region above the IEP the collector shifts the zeta potential to more negative values.

80.00 M - ~ B - bulmaesite + 40.00 C) [] 0

0.00 0. M no

collector

M 300 mg4 hydroxamate M 30 m o ~ B no collecto( B 240 mg/I hydroxamate B 152 mg/1oleate

I
8.OO

pH

12 00

.<

-40.00

-80.00
1 x 10-3 M KCI

-120.00

Fig.2 Zeta potential of monazite and bastnaesite as a function of pH in the absence/presence of sodium oleate (SO) and potassium octyl-hydroxamate (POH) Infrared absorption spectra of the systems: monazite, bastnaesite, sodium oleate and potassium octyl hydroxamate are illustrated in Figures 3, 4, 5 and 6. Figures 3, 4 and 5 describe: (a) spectrum of the mineral in distilled water at the desired pH; (b) spectrum of the mineral after exposed to a collector solution at the desired pH; (c) spectrum corresponding to the difference between (a) and (b). An abscissa expansion, in a certain wavenumber range, is presented for the spectrum shown in (c). Two spectra of this type are displayed in Figure 6.

DISCUSSION Regarding the infrared spectra of the adsorbed collectors, in all cases of this investigation, the bands in the 3000-2700 c m - : were always clearly observed. Those bonds correspond to the stretching vibrations of the CH 2 (mainly) and CH 3 groups of the hydrocarbon chains of either oleate or hydroxamate collectors. This prove that the collectors were really adsorbed onto the minerals' surfaces; however, those bonds do not give any information on the adsorbed species, and it is necesary to rely on the bands in the 1800-1400 cm-1 range for this kind of information.

Technical Note

361

100 ~

"k

,-,:,.,t .0

' I00

'

,'

so -

"t
-t
-

I00
eo

't

'oo1_4__:~

,oi-,,,

U ~. L~,I,o

~_~

, . ~ . , 4 o
_,
- " " 20

1,o

or
.o
0
40(20

rI
i
I
3500 ~
--

,, v
-~!
-

"f

Z S O 0 _2)0n 1 7 5 0

I I 1500 11250

I
I000

0 400

750

WAVENUMBER (crn- 1)

100

100

"~ '01- \

.oI_ \ / "F_ \d ';r"' ~

1800 1/'50

~.o
1450

1 '

~-1.0
I;
1650

1700

1600

1550

1500

1400

W A V E N U M B E R (era -l)
Fig.3 Infrared spectra of the system monazite-sodium oleate (304 rag/l); pH=3; contact time= 15 mJn; (a) monazite; (b) monazite after adsorption from sodium oleate aqueous solution; (c) difference spectrum (b)-(a); (d) abscissa expansion in the range 1800-1400 cm-1 of (c) spectrum
ME 9:3-F

362

Technical Note

1(30 ~

.o I- v

/k

'

I00

r,~ I

80 60 40
20 100

80 60 40
20 I00

8 6O
20

0
Xl

~
"

80 60

(c) I
750

OL I ! I 1 I I I I 40C0 3~:)0 ~000 Z:~I~O 2~XX) 17'301500 IP.50 I000

400

40 20

WAVENUMBER(cm*I)

too I ~

,/.,.~.~

too

60
"t
o ~ ,

- 60
V
, ,,._,

~
, ,

"
, , ,

- "
o

WAVENUMBER (cm"1)
Fig.4 Infrared spectra of the system monazite-sodium oleate (304 mg/l); pH = 8; contact time = 180 rain; (a) monazite; (b) monazite after adsorption from sodium oleate aqueous solution; (c) difference spectrum (b)-(a); (d) abscissa expansion in the range 1800-1300 cm - l of (c) spectrum

Technical Note

363

100

.or\,f "r~

"

\ & 1.0 Y'-.'I~I "

.o'r,.,
ZO 100
oo
I I I I I I I I i

2O I O0
oo

~ 60
:;

" "
-

"

:lz
I1

- 60
40 20 0 400

4oZO 0 4000

(c)
I ~X) I J 3000 2~0 J 2000 I I T?~O rJO0 m I 12501000 I 750

W A ~ E R

(cm"1)

o~

40

.of
20 0
moo rrso' TmO 1650

,,,

\/

, to
40 20 0
~.0

1.0

mOO

~SSO

~00

W A ~ E R

(m -l)

Fig.5 Infrared spectra in the system bastnaesitc-sodium olcate (608 rag/l); pH =9; contact time= 180 min; (a) bastna~site, (b) bastnaesite after adsorption from sodium olea(c aqueous solution; (c) difference spectrum Co)-(a); (d) abscissa expansion in the range 1800-1400 cm -I of (c) spectrum

364

Technical Note

100
60

6080I 14,) 40 20

- 60 - 40 -- 20

I .I I , I I I l I I 1700 1480 1460 1640 1620 1400 18410 84S0 1540 1520 1500

WAVENUMBER(m-1)

[,,T.I

100

' i

"'i

100

ilO

80

41I 'J "(b,

o t I

g
I I

."
I

-:,
I

"! 40 I -1 ,o
I 0

1.o

1100

1650

164)0

1550

1500

1450

1400

WAVENUMBER(m-1)
Fig.6 Infrared spectra of the systems monazite and basmaesite-potassium octyl-hydroxamate (1000 mg/l) corresponding to the difference of spectra of the mineral prior and after collector adsorption from aqueous solution, presented respectively in the ranges of abscissa expansion of 1700-1500 c m - I and 1700-1400 c m - ] ; (a) monazite; pH = 9; contact time = 300 min; (b) bastnaesite; p H = 9 . 3 ; contact time=60 min The floatability of monazite with oleate reached maxima at pH =3 and in the pH range between 6 and 10, as shown in Figure 1. The monazite infrared spectra after oleate adsorption at pH =3 and pH = 8 present absorption bands: (a) at 1713 cm -1 corresponding to the stretching vibration of the C = O group, characteristic of the physical adsorption of oleic acid, as a dimer, such as in aqueous emulsions; (b) at 2923 and 2853 c m - s attributed to stretching vibrations of C - H bonds from the oleate hydrocarbon chain; (c) at 1558 and 1467 c m - 1 corresponding, respectively, to the asymmetric and symmetric stretching vibrations of the carboxilate group. The surface charge of monazite, at pH---3, in the absence of sodium oleate, is positive. Despite the fact that at this pH level the collector is not ionised, its presence shifts the curve of zeta potential as a function of pH to the left. A physical oleate adsorption is suggested, involving dipole/positively charged surface interactions, with lateral interactions between the hydrocarbon chains via van der Waals bonds. The zeta potential decrease might be attributed to H3 O+ withdrawal from the surface as a consequence of collector adsorption. On the other hand, electrokinetic and microflotation results at p H = 8 show that the oleate/monazite interaction is strong enough to surpass the electrostatic repulsion between the negatively charged surface and the anion. The fact that the collector renders the surface more negative indicates adsorption under electrostatic repulsion conditions. The infrared spectroscopy results show an absorption band at 1558 cm -1, characteristic of a bond between the collector polar group and a metallic cation,

Technical Note

365

suggesting the possibility of chemisorption. Nevertheless the asymmetric stretching band of sodium oleate is located at 1561 cm -1 , making it difficult to confirm chemisorption via infrared spectroscopy. At pH =8 physical adsorption of the collector onto the mineral surface is also possible, indicated by the oleic acid band at 1713 c m - 1. In the system monazite/potassium octyl-hydroxamate flotation occurs in a pH range above the IEP. Collector adsorption takes place under strong electrostatic repulsion conditions. The infrared spectrum of monazite after octyl-hydroxamate adsorption shows the following adsorption bands: (a) at the 2700 - 3050 cm -1 range, corresponding to the hydrocarbon chain axial deformation vibrations; (b) at 1607 cm -1, corresponding to the stretching vibration of the C = O bond, which is located at 1622 c m - 1 in the potassium octyl hydroxamate spectrum. A shift to the region of smaller wavenumbers indicates hydroxamate chemisorption, with formation of a metallic hydroxamate. The maximum bastnaesite floatability is achieved at pH =9 (oleate, 60 mg/1) and pH =9.3 (hydroxamate, 200 mg/l). The isoelectric point of bastnaesite is located at pH =4.9. Both collectors adsorb onto the mineral under strong electrostatic repulsion conditions and render the surface more negative, suggesting a chemisorption mechanism. In the pH region bellow the IEP, neither oleate nor hydroxamate adsorbed onto the mineral, showing that physical adsorption does not play a role in this system. Infrared spectroscopy of bastnaesite after oleate adsorption, at p H = 9 , presented the following bands: (a) at 2924 and 2854 c m - 1, corresponding to axial deformation vibrations of the oleate hydrocarbon chain C-H bonds; (b) at 1585 and 1466 c m - 1, corresponding to the carboxilate group axial stretching vibrations. Specially important is the asymmetric mode, for its frequency is characteristic of a metallic cation bonded to the collector polar group. In this case the band at 1585 cm - l indicates that the adsorbed species is a rare-earth carboxylate. Therefore, there was evidence of chemisorption by the reaction between oleate and rare-earth elements onto bastnaesite surface (mainly Ce 3 and La 3 +). In the system bastnaesite/potassium octyl-hydroxamate, after collector adsorption at pH = 9.3, the following adsorption bands were observed: (a) at 1621 and 1467 cm-1, that corresponded to original hydroxamate bands; (b) at 1604 and 1538 cm -1, which were new bands, i.e. formed after adsorption, therefore proving that chemisorption has occurred. Tentatively the new bands could be assigned to streching vibrations of the C---O bonds, in the following way: 1604 cm -1, amide I band (originally at 1622 c m - l ) ; and 1538 cm -1, amide II band (originally at 1553 c m - l ) . It is possible that chelate type complexes were formed between the collector and the mineral. The presence of original hydroxamate bands is an evidence that some amount of physically adsorbed collector was also present at the surface. There is a good agreement between values of adsorption bands for complexes hydroxamate/rare-earths elements reported by Jiake and Xiangyong [6], Agrawal and Kapoor [11] and Agrawal and Shukla I12] and those obtained in the present investigation.

CONCLUSIONS Electrokinetic, microflotation and infrared spectroscopy studies suggest the following types of adsorption for the systems rare-earths mineral/collector: monazite/sodium oleate: physical adsorption at pH =3. physical adsorption at pH = 8 (with a possibility of chemisorption, wich was detected via infrared spectroscopy, but could not be unambiguosly proven by this technique). ii. monazite/potassium octyl hydroxamate: chemisorption at pH =9.

366 iii.

Technical Note bastanaesite/sodium oleate: chemisorption plus physical adsorption at pH =9. bastnaesite/potassium octyl-hydroxamate: chemisorption at pH=9.3

iv

ACKNOWLEDGEMENTS The authors are thankful to CNPq and to Fapemig for the scholarships awarded to O. Pavez.

REFERENCES . Gerdel, M.A. & Smith, R.W., The role of lignin sulfonate in flotation of bastnaesite from barite, Rare Earth Extraction, Preparation and Application, (R. G. Bautista & M. M. Wong eds), The Minerals, Metals & Materials Society, Warrendale, UK, 35 (1988). Viswanathan, K.V. & Majumdar, K.K., Infrared adsorption studies on beach sand minerals under conditions of soap flotation, Bhabha At. Res. Cent. 391, Bombay, India, 12 (1969). Zakharov, A.E., Ilie, P., Pol'kin, S.I. & Solnyshkin, V.I., Reaction of sodium sulfide with pyrochlore, zircon, and monazite in flotation with sodium oleate, Flotation Properties of Rare Metals Minerals, (I. N. Plaksin ed.), Primary Sources, New York, USA, 71 (1967). Bogdanov, O.S., Reagents chemisorption on minerals as a process of formation of surface compounds with a coordination, XII International Mineral Processing Congress, MME/DNPM, Sao Paulo, Brasil, 2, 280 (1977). Fuerstenau, D.W. & Pradip, Mineral flotation with hydroxamate collectors, Reagents in Mineral Industry, (M. J. Jones & R. Oblatt eds), IMM, London, UK, 161 (1984). Jiake, L. & Xiangyong, C., Research into the recovery of high grade rare-earth concentrate from Baotou complex iron ore, China, Minerals Processing and Extractive Metallurgy, (M. J. Jones & P. Gill eds), IMM, London, UK, 663 (1984). Fuerstenau, D.W., Metzger, P.H. & Seele, G.D., Hallimond tube for better flotation testing, Eng. Min. J., 158(3), 93 (1957). Siwek, B., Zembala, M. & Pomianowski, A.A., A method for determination of fine-particle floatability, Int. J. Miner. Process., 8(1), 85 (1981). Viswanathan, K.V., Madhavan, T.R. & Majumdar, K.K., Selective flotation of beach sand monazite, Min. Mag., 113(1), 17 (1965). Dixit, S.G. & Biswas, AK., pH-Dependence of the flotation and adsorption properties of some beach sand minerals, Trans. Am. Inst. Min. Eng., 224(2), 173 (1969). Agrawal, Y.K. & Kapoor, H.L., Studies on hydroxamic acids: part II, gravimetric determination and separation of praseodymium and neodymium with N-m-tolyl-m-nitrobenzohydroxamic acid by direct weighing, J. Indian Chem. Soc., 53(1), 174 (1976). Agraval, Y.K. & Shukla, J.P., N-phenyl-benzohydroxamic acid as donor, J. Indian Chem. Soc., 51(2), 373 (1974).

2.

3.

4.

6.

7.

8. 9. 10. 11.

12.