MineralsEngineering,Vol.10, No. 12,pp.

1395-1404,1997
Pergamon 0892-6875(97)00129-5 1997 Publishedby Elsevier Science Ltd All fights reserved. Printedin Great Britain 0892-6875/97 $17.00+0.00

A NEW' COLLECTOR FOR RARE EARTH MINERAL FLOTATION

J. REN ~*, S. LU t, S. SONG* and J. NIU ~

University of Science and Technology Beijing, College of Resources Engineering, 30 College Road, Beijing 100083, China. E-mail: licylxj@public.bta.net.cn v Baotou Iron and Steel Corporation, Baotou, Innermongolian 014010, China Universidad Autonoma de San Luis Potosi, Instituto de Metallurgia, San Lius Potosi, S.L.P, C.P. 78240, Mexico Ministry of Metallurgical Industry of P.R. China, Beijing 100044, China (Received 29 September 1996; accepted 16 June 1997)

ABSTRACT

A new coUectorfor bastnaesite flotation - modified hydroxamic acid (MOHA) has been developed through several years laboratory research. The experimental results offlotation of pure bastnaesite mineral and rare earth ores, and the application experience in flotation plants showed that MOHA is an efficient collector for bastnaesite flotation. MOHA .lugs stronger collector ability and higher selectivity compared to the other commonly used collectors. Through the measurements of zeta-potential, adsorption and infrared adsorption spectrum and in terms of the electronegativity theory of reagent groups, the flotation mechanism has been discussed. It was concluded that the adsorption of MOHA on bastnaesite surfaces is chemical adsorption in nature through three oxygen atoms in the polar group of MOHA chelating the surface Ce(lll) of bastnaesite to form a pentagon-cycle chelate: O-C--N-O-Ce(III)-O. Additionally, the chemisorption is accompanied with the multilayer and non-homogeneous physical adsorption of the MOHA molecules, The MOHA adsorption equation at the surfaces of bastnaesite can be expressed as: I" = 6.76x10-2CI/1.02, while the adsorption rate constant k is: k = 2.64x105 min-lmot"lm 2. 1997 Published by Elsevier Science Lid
Keywords Flotation collectors; froth flotation

INTRODUCTION

Due to the rapid development of superconducting, magnetic, functional and fluorescent materials the demand for rare earth materials in the world is continuously increasing. Bastnaesite (CeCO3F) is one of the main rare earth minerals, which contains approximately 75% Ce. At the present time, about 60-70% of the rare earth (RE203) in the world is extracted from bastnaesite. There is little literatures concerned with the flotation of bastnaesite [1-8]. Various reagents, such as oleic acid, oxidized OP-100, alkylhydroxamic acid, naphthenic acid, sodium dodecylsulfate, N-hydroxyl phthalicimide and styrophosphonic acid have been investigated as collectors for bastnaesite flotation. Presentedat MineralsEngineering '96, Brisbane,Australia, August26-28, 1996
1395

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J. Ren et al.

Hydroxamic acid is a chelating agent commonly used in chemical analysis. Due to its high selectivity to rare earth element ions in the weak alkaline region, hydroxamic acid has been used as the collector in rare earth mineral flotation. In our previous papers [9,10], we described experimental studies on the flotation of monazite and bastnaesite from rare earth ores by using a combination of modified hydroxamic acid (MOHA) and proper modifiers. MOHA (R-OHCOONH2) is characterized by its two polar groups; in addition to the hydroxamic group a hydroxyl group is introduced, both polar groups being connected to the non-polar chain of the reagent molecule. The structure of MOHA is similar to salicylic hydroxamic acid, but instead of a benzene ring the non-polar part in the MOHA molecule is a naphthalene ring. In this paper, the collector behaviours of MOHA in bastnaesite flotation and its commercial application in three flotation plants are described. Furthermore, the collector mechanism of MOHA is discussed in terms of the data obtained through zeta-potential, adsorption and infrared absorption spectrum measurements and from the point of view of electronegativity theory of reagent groups. MATERIALS AND EXPERIMENTAL METHODS The pure bastnaesite sample used in this study is taken from Maoniuping mine, Sichuan Prov., China. The specimen was cut by hammer and purified by hand-sorting, then with gravity concentration and magnetic separation in deionized water. After that, the purified samples were ground and classified into several size fractions, and the size fraction 37-100 larn was used for the tests. Tbe purity of the bastnaesite sample was 98.13%, and its specific surface area the 0.2011 m2/g. The bastnaesite ore samples used for the flotation tests were from Maoniuping (MNP) mine, Weishan (WS) mine and Beiyunebo (BYEB) mine, China. The main composition of the samples is given in Table 1. The -741am fraction in the ore samples was 67% for MNP ore and 71% for WS ore, respectively. The gangue minerals are barite, fluorite and silicate minerals.
TABLE 1 The composition of the rare earth ores (%)

ores MNp WS BYEB

9.5O 6.14 7.91

sao 28.73 II.89 22.25 10.11 6.58 14.88

F 6.7l 1.06 9.56

Fe,,t 12.54 4.5O 9.84 2.30 24.28

SiOz co2 p 3, 13.74 7.37 O.35 30.63 7.93 0.20 9.18 5.12

Pb
6-53 1.02

0.78 0.053

The modified hydroxamic acid (MOHA) used in this study was prepared in our laboratory, and was 90.16% pure. Modifiers-water glass and H103 are industrial products. Reagent H03, which consists mainly of an alcoholic organic complex, is a by-product of the synthesis of MOHA. The experiment with pure bastneasite was conducted in a 50 ml XFG-36 flotation cell. Initially 2.0g of the pure sample was conditioned with distilled water for 1 min, then MOHA was added and agitated for 5 min before flotation for 5 min. The flotation results were reproducible, the absolute error being between +1.5% of flotation recovery. The ore flotation tests were conducted in a laboratory 500 ml XJK flotation cell. Initially 150g of the ore sample was conditioned with tap water for 1 min, then Na2SiO 3, MOHA and H103 were added in sequence and agitated for 5 min, 5 min, 1 rain, respectively, flotation being for 6 min. Both laboratory flotation cells were mechanically agitated. The XJK flotation cell is a type of self-aerating and mechanically agitated flotation machine, which has a flat bladed impeller with 6 blades, perpendicular to the direction of rotation, and a stator with 18 blades, installed underneath a horizontal round plate with several circulating holes and at an angle to the direction of rotation. The XJK flotation cell is widely used in the flotation plants in China. Zeta-potential was measured with a MRK micro-electrophoretic meter, made in Japan. The MOHA adsorption was measured with a UV-3000 ultra-violent spectrophotometer, Shimazu Co., Japan. The structure of adsorption product at the mineral surfaces were estimated with a 74-FI-IR infrared-spectrometer, Nicolet Co., USA. The procedure of measurement consisted of the following steps:first add MOHA to the mineral sample of -21am and agitate for half an hour, then separate the solid from liquid by centrifugation,

A new collectorfor rare earth mineral flotation

1397

then dry the sediment at a temperature lower than 30C, then press the dried sample into small cake for IR analysis.

F L O T A T I O N RESULTS Flotation Tests of Pure Bastnaesite The flotation recovery of bastnaesite with MOHA vs. the pH value and the concentration of MOHA is shown in Figures 1 a and b, respectively. As seen in Figure 1, with increase in pH flotation recovery sharply rises until pH=8.5. At pH 8.5 - 9.5, the flotation recovery reaches its maximum and then decreases in strong alkaline media. The flotation recovery increases with increase of concentration of MOHA. Flotation recovery reached 90% at 1.0xl03mol/1 of MOHA, and 95% at 5.0x10"3mol/1 of MOHA.
100 8 le
U o

1N

i"
m a 6. $ 6 7 Ca O
11 13

N-

40-

m-

-6

.4

-42

.4

Fig. 1 The effects of pH value and MOHA concentration on the flotation recovery of bastnaesite Flotation test of Bastnaesite ores The effects of pH value and MOHA dosage on the flotation results of three bastnaesite ores are shown in Figures 2a and 2b, respectively. It can be seen that the best flotation results were obtained at pH 8.5-9.5. Three ore samples were then tested under the optimum pH condition in a closed flotation circuit with one step rougher flotation and one step cleaning, reagents added being MOHA, Na2SiO 3 and H103. The results of the closed flol:ation circuit are shown in Table 2. TABLE 2 Flotation performance of three bastnaesite ores Ores Coneealrate Teili~ Feed Concentrate l"ailings Feed Concenlnte Middlinss Tailiass Feed

Ye

%
REO 63.78 0.75 9.51 56.13
1.31

MNP

WS

BYEB

13.87 86.13 I00.00 9.05 90.95 100.00 7.91 3.31 88.78 100.00

~ % BaO 2.13 33.01 28.73

3.96

CaO 7.75 12.58

i

11.89 9.04

Reeove~ % BaO CaO 1.03 8.83 6.88 98.97 91.17 100.00 1 0 0 . 0 0 100.00 REO 93.12
81.01 1.61 8.09

6.27 60.13 19.51

2.58

24.07 22.25 1.89

10.22 10.11 9.04

18.99 100.00 61.82

8.44 29.74

9839 91.91 1 0 0 . 0 0 100.00 2.27 2.57

7.70

6.58

14.88

100.00

1 0 0 . 0 0 100.00

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J. Ren et al.

--6--~

i.

--~--M --il.-III --O--M --O--M

I'

$
1W b
M

J~4

le

12

~A2 --A--m

i[.
1E

--D-M --n--B1 --O--A1

0
L5 1 1.S 2 ~ 3 ~LS 4

ucx~
Fig.2 Flotation results of bastnaesite ores as a function of (a) pH and (b) collector concentration (ARecovery, B-Grade, 1-MNP ore, 2-WS ore, 3-BYEB ore)

Industrial Application On the basis of the laboratory tests, the reagent combination mentioned above has been applied in the plants of Maoniuping (MNP) mine and Beiyunebo (BYEB) mine with 2.8m3 X3K flotation cells. With one-step rougher flotation and one-step cleaning flotation, high quality bastnaesite concentrates are obtained. The flotation parameters and results in the plants are listed in Table 3 and Table 4. TABLE 3 The operating parameters of bastnaesite flotation in plants

~,,p ~ a t
~ , t / d Size of Feed (-74pro), % Solid dmmity, % T ~ of Pulp, C pH
75 72.78

BYEnl~at
' 300 95.66

vomse o f N . ~ . ]qr/t v o s ~ of MOH~ ~S/t

HI03, I~/t

4,~M 28-32 8-9 3.76 O.68

4~-,~ 30-,35 8.5--9.5 3.19 1.34

o.2~

o~1

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TABLE 4 The results of bastnaesite flotation in plants

Yeed
MNP plant B Y~B plant Coneenerate Tailing Feed Con~ Teil~18 Feed 14.92 85.08 100.00 il.97 88.03 100.00

GnU% m oaaoc
,,,

mxMy,%
sio Fe
-

aa0

sio
,,

Fe

60.81 2.33 7.97 2.10 0.83 29.488.41 23.26 9.78 25.43 8.34 20.10 50.190.98 9.53 1.14 6.84 2.91 7.71 15.39 10.35 27.81 8.64 6.91 14.69 9.25 25.30

92.77 1.37 14.26 1.56 7.23 98.63 85.74 98.44 !00.00 100.00 100.00 100.00 70.37 1.74 7 . 7 6 1.51 3.24 29.63 ~ . ~ 92.24 98.49 96.76 100.00 100.00 100.00 100.00 100.00

The data obtained in the industrial practice and from the laboratory tests demonstrate that MOHA is an efficient collector for bastnaesite flotation.

THEORETICAL STUDY Figure 3 illustrates the relationship between zeta potential of bastnaesite and pH. The iso-electde~l point of bastnaesite in pure water is pH 8.0. However, in the presence of MOHA the zeta potential curve of bastnaesite shifts left, and the i.e.p, becomes pH 5.9. Moreover, a peak of negative zeta potential appears at pH 9.0.
4e

4111

12

Fig.3 Relationship between zeta potential and pH (A2-In water, B2-In MOHA)

Figures 5 and 6 illustrate the adsorption (F) of MOHA at the surface of bastnaesite as a function of MOHA concentration ( C ) as well as adsorption time (t), respectively. The relationships between the adsorption of MOHA at the surfaces of bastnaesite and the pH value is given in Figure 4. It can be seen that the maximum adsorption occurs in the range of pH 8.0 - 10.0, and when the pH value becomes greater than 11, the adsorption dramatically reduces, being in agreement with the flotation results' dependence on pH value (Figure la). The infrared absorption spectra of MOI-IA, untreated bastnaesite and bastnaesite treated with MOHA are shown in Figure '7. It can be seen that the infrared absorption bands of the active groups of MOHA are at

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J. Ren et al.

1610 cm "~, 1150 cm .1 and 1050 cm ~, respectively, the infrared absorption bands of bastnaesite are in the region of 1550 - 1350 cm m and 950 - 800 cm l. After adsorption of MOHA, the infrared absorption bands at 1550 cm "1 and 1100 cm "l were much enhanced and become wider.
'12

!.
S 2 4 I pH | 'IB '12

Fig.4 Relationship between pH and the adsorption of M O H A on bastnaesite surface

.4,

.4,

t
j4

.7

~lci 4

.4

Fig.5 The adsorption of M O H A on surface vs. the concentration of M O H A

DISCUSSIONS Origin of S u r f a c e C h a r g e s oil Bastuaesite In aqueous solution, Ce(III) ion is hydrolyscd, the hydrolysis equations being as follows: ki = Ce(OH) 2+ + H +

Ce 3+ + H 2 0

k! = 10s'9

(1)

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1401

Ce(OH) 2+ + H20 ,, Ce(OH)2 + + H + k3 = Ce(OH)3 + H +

k2 = 105-8

(2)

Ce(OH)2 + + H 2 0

k3=104.3

(3)
(4)

k4
Ce(OH) 3 + H20 = Ce(OH)4 + H
t6
I$

k4=103-1

'114
II

5 3 I 0 4 $

tni

$2

tS

29

Fig.6 The adsorption of MOHA at bastnaesite surface vs. adsorption time 1

I
m

tm wmmw

total

Fig.7

The inl~ared spectra of MOHA, bastnaesite and bastnaesite treated MOHA (1-MOHA, 2-bastnaesite, 3-adsorbed MOHA on bastnaesite)

Based on the stable constants of hydrolysis of Ce(III) in Equations 1, 2, 3, 4111], the pC-pH diagram for Ce 3+ hydrolyses iin aqueous solution has been calculated and the results are shown in Figure 8. It can be seen from the comparison of Figure 3 with Figure 8 that the negative electrokinetic potential of bastnaesite in water is probably due to the adsorption of O H and Ce(OH)4- on the surface of bastnaesite in the high pH region; whereas the positive zeta-potential of bastnaesite observed in the region of pH< 8.0 is due to

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J. Ren et al.

the adsorption of H and Ce 3+. After the adsorption of MOHA, the ~-pH curve moves toward a negative value (the i.e.p, moves from pH 8.0 to pH 5.9), this trend being in good accordance with the F- pH curve. This is obviously caused by the adsorption of MOHA anions at the bastnaesite surfaces. The experimental result show that even if the pH > i.e.p., MOHA, an anionic collector, can still adsorb on bastnaesite surface regardless of its negative charges and the bastnaesite surface becomes more negative because of the MOHA adsorption. Accordingly, it is reasonable to propose that MOHA anions are chemically adsorbed on bastnaesite surfaces, or it is essentially the specific adsorption.
-3

..4 I ,6

g 4
-7

.4 0 2 4 tt 8

lO

12

Fig.8 Logarithmic concentration diagram of Ce 3+ hydrolysate (10 -4 mol/1) (1-Ce3 , 2-Ce(OH) 2 , 3-Ce(OH)2 + , 4 -Ce(OH) 3, 5-Ce(OH)4-)

Adsorption Equation

The adsorption curve lgF-lgC shown in Figure 5 is a linear one, and can be simulated by the following equation:
1 I'--6.76x 10-2C 1.02

(5)

Obviously, the adsorption of MOHA on the bastnaesite surfaces obeys the Freundich adsorption formula
1

F = k C n . Thus, the MOHA adsorption at the bastnaesite surface can be considered as a multilayer and non-homogeneous adsorption. An adsorbed layer is chemically connected with the surface and directly situated on it, further there exists a physically adsorbed MOHA multilayer, which is associated with the chemisorbed layer. In Equation 5, n = 1.02, indicating that the adsorption of MOHA at bastnaesite surfaces is relatively stable. From the adsorption kinetic curve shown in Figure 6, the adsorption rate of MOHA at the bastnacsite surfaces can be described by the follow equation:

A new collector for rare earth mineral flotation

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1 t - 2.tMxlOSx(1.64x10_6) 2 + 1.64x10~

(6)

Evidently, it is a second order equation with a general form such as:

P kl-,2 P..

Thus the adsorption

rate constant of MOHA, obtained from equation (6) is: k = 2.64x105 minlmol4m2. Properties of MOHA Chelated with Surface Ce(IH) The chelating action of MOHA to Ce(III) mainly depends on the character of its active groups. Based on the theory of eleA:tronegativity of reagent active groups, an attempt has been made to find the bonding atoms of MOHA. In our considerations, the Pauling standardization of electronegativity and a calculating method suggested by W.'mg [12] were used, and only the first atom C which directly connects with polar group in the naphthalene ring was taken into account.

Xs=0.31(n*+l)+0.5
?.

(7)

Xt+l n*=(N-P)+E2mox~+xa~-~" oXn+XX-~ 2m,+S,(~)a, A+E nt X

-Xt

(8)

where, X g is the electronegativity of group; r is the covalent radius; n* is the number of covalent electrons; P is the number of electrons bonded by neighbour atoms; X is the atom electronegativity; i is ordinal number of the atom in group ( 0, 1, 2 ..... i = 0 for atom A, i = 1 for atom B); m i is the number of electron couples with a separation distance i from the bonded atom A; m o is the number of electron couples at A-B bond; S i is the number of non-bonded electrons with a separation distance i from the bonded atom A; So is the number of non-bonded electrons of atom B; a i is the coefficient of partition, aF2.7 in our case. The calculated electronegativities of atoms N and O are noted in the reagent structural formula as follows:

H (3.so)
N--OH
(4.03)

--OH (3.s5)
(3.69)

It is clear that atom N in the naphthalene ring has a higher electron affinity than atom O, so atom O loses electrons more easily than atom N. Therefore, based on the theory of coordinate chemistry, two atoms O in the hydroxamic group of MOHA molecule donate electrons to surface Ce(III), forming stable pentagoncycle chelate:

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J. Ren et al.

on the bastnaesite surface, therefore making the surface hydrophobic. The infrared spectrum shown in Figure 7 have further proved that the bonds C-O-Ce and N-O-Ce indeed exist on the bastnaesite surfaces treated with MOHA.

CONCLUSIONS MOHA is a selective and efficient collector for bastnaesite flotation due to its specific affinity to the surface Ce(III) of bastnaesite. The optimum pH value of bastnaesite flotation with MOHA is in the pH range 8 9.5. MOHA, chemical adsorbed on the bastnaesite surfaces through its oxygen atoms to chelate surface Ce(III) of bastnaesite, can form a pentagon-cycle chelate on it. The chemically adsorbed layer is accompanied with the non-homogeneous and physically adsorbed MOHA multilayer. It is the surface Ce(III) of bastnaesite which dominates the flotation behavior of bastnaesite with MOHA as a collector.

REFERENCES
.

2. 3.

5.

7. 8. 9. 10. 11. 12.

Ren, J., Flotation behavior and mechanism of bastnaesite with N-hydroxyl phthalicimide. Acta Matallugica Sinica, 29(6) B241-245 (1993). Zhang, X., Research on the flotation of rare earth minerals with isohydroxamic acid. Rare Earth and Niobium, 3, 24-27 (1975). ( in Chinese). Zhang, X., Research upon the separation of bastnaesite and monazites concentrates from Baotou rare earth rough concentrates, Multipurpose Utilization of Mineral Resources, 1, 13-18 (1984). (in Chinese). Huang, L. & Wu, X., The manufacture of isohydroxamic acid collectors and its flotation experiment on rare earth minerals. Rare Earth, 3, 1-7 (1985). (in Chinese). Zhang, X. & Li, L., Principles and mechanism of bastnaesite and monazite separation by flotation. Proceedings of l st International Conference on Metallurgy and Material Science of Ti, RE and Sb., Changsha, China (1988). Fuerstenau, D.W. & Pradip, Mineral flotation with hydroxamate collectors. Trans. Inst. Min. Metall., Sect. C 161-168 (1984). Zhang, J. & Jian, B., Research on the flotation of Weishan rare earth minerals with Styrenephosphate acid. Mining and Metallurgical Engineering, 2(2), 26--30 (1981). (in Chinese). Mukai, S., Imanishi, N., Kumamoto, J. & Okamoto, K., Flotation of rare earth minerals. Flotation, 31(3), 209-214 (1984). (in Japanese). Ren, J., The practice of rare earth mineral flotation and process improving in Baotou mine. Nonferrous Metal, 6, 15-19 (1989). (in Chinese). Ren, J., Zhang, W. & Zhang, X., Study on the flotation of rare earth minerals from the co-existing ferrite ores in Balyunebo. Nonferrous Metal, 4, 16-19 (1990). (in Chinese). Bass, C.F. & Messmer, R.E., The hydrolysis of cations, Wily,New York (1976). Wang, D., Structure and Properties of Flotation Reagents, Metallurgical Industry Press, Beijing (1982). (in Chinese).