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Materials Transactions, Vol. 50, No. 1 (2009) pp.

171 to 176
#2009 The Mining and Materials Processing Institute of Japan

Removal of Trace Impurity from Limestone Using Flotation Techniques


Masami Tsunekawa1; * , Yugo Honma1 , Kyoungkeun Yoo2 , Naoki Hiroyoshi1 and Mayumi Ito1
1
Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
2
Korea Institute of Geoscience & Mineral Resources, Daejeon 305-350, Korea

High grade limestone was obtained by removing trace impurities through reverse and carrier otation techniques. A simple method for
measuring the impurity content of limestone was developed by correlating the amount of impurities and the turbidity of suspensions of residue
from limestone dissolved in 20% acetic acid.
Impurity removal more than 50% with limestone recovery better than 85% was obtained under suitable conditions by both reverse otation
and carrier otation using sodium oleate (NaOl) and dodecylammonium acetate (DAA) as collectors. Limestone containing more than
0.15 mass% impurity was used as the carrier. These results suggest that limestone treated by otation can be used as high quality limestone in
paper manufacturing. [doi:10.2320/matertrans.M-MRA2008839]

(Received January 23, 2008; Accepted October 7, 2008; Published December 3, 2008)
Keywords: trace impurity, limestone, reverse otation, carrier otation

1. Introduction 2. Materials and Experimental Procedures

A large amount of limestone (CaCO3 ) is used widely in 2.1 Materials


various industries such as cement, plastic, and paper, due to Two samples of limestone from the Kawara mine in
its low cost.13) However, high grade limestone deposits are Fukuoka, Japan were used and the impurity contents were
being depleted and low grade deposits need to remove their determined to be 0.13 mass% and 0.15 mass% by the method
impurities before they can be utilized.3) described below in 2.2. The sample with 0.13 mass%
Limestone to be used as ller for paper requires strict impurity was ground with a ball mill (UBM-2L, Masuda
quality control in properties such as particle size and Co. Ltd., Japan) and the ground product was used as feed for
whiteness.2) Limestone containing more than 0.1 mass% of the otation tests. The median diameter of the ground product
trace impurities is dicult to use, because the impurities was 9.45 mm and the 90% of cumulative undersize (D90 )
decrease the whiteness of paper and the durability of the particle diameter was 40.54 mm. The limestone with
equipment used in paper manufacturing. Here, the impurities 0.15 mass% impurity was used as carrier in the otation
are dened as materials not dissolved by acetic acid through a tests, because aside from it can adsorb the impurities, it can
method developed in this study. Due to this, limestone with be used for cement and has little eect on the grade of the
more than 0.1 mass% impurities is only used for cement. The concentrate.
establishment of a method to remove trace impurities from Impurity particles in the limestone were collected by
limestone with impurity contents above 0.1 mass% is dissolving limestone in 20% acetic acid (Wako Pure Chemi-
important to be able to utilize such resources as ller for cal Industries, Ltd.) at 5 mass% pulp density and centrifuging
paper manufacturing. the suspension at 17600  g centrifugal acceleration for
Flotation is the most important and versatile mineral 10 min in a RS-18III high speed refrigerated centrifuge
processing technique for ne particle processing and upgrad- (TOMY SEIKO Co. Ltd., Japan). The precipitate was dried
ing of ore. Both uses and applications of otation are being at 65 C overnight and characterized by the method described
expanded to treat greater tonnages and to cover new areas.4) in 2.3.
There are various otation researches related to lime-
stone:3,510) (1) calcite or limestone is removed as a gangue 2.2 Quantitative analysis of impurity in the limestone by
to recover uorite,5,6) apatite,7) or phosphate ore;9,10) (2) turbidity measurement
limestone is beneciated to use for cement or paper The impurity particles in limestone collected from the
manufacturing;1114) and (3) silica is removed from limestone centrifuge tube by the method described in 2.1 (residue
using an emulsion otation technique.12) However, there obtained by dissolving limestone with 20% acetic acid) were
have been no papers reporting the removal of trace impurities added to a mixture of 25 cm3 of glycerol and 25 cm3 of
from limestone using otation, obtaining high grade lime- distilled-deionized water (DDW). After agitation, the sus-
stone as ller in paper manufacturing. pension was introduced into a glass cell, and the turbidity of
The present study characterized trace impurities in a the suspension in the glass cell was measured with a
limestone by X-ray diractometry and X-ray uorescence turbidimeter (SEP-PT-201, Nihon Seimitsu Kagaku Co.,
analysis, then determined the turbidity using 20% acetic acid Ltd., Japan).
and glycerol, and the trace impurities were removed by a
modied otation technique. 2.3 Characterization of the impurities
The impurity particles obtained using the method describ-
*Corresponding author, E-mail: tunekawa@eng.hokudai.ac.jp ed in 2.2 were analyzed with an X-ray diractometer (XRD,
172 M. Tsunekawa, Y. Honma, K. Yoo, N. Hiroyoshi and M. Ito

JEOL JDX-3500), an energy diusive type X-ray uores- 2.4 Flotation


cence analyzer (XRF, JEOL JSX-3210A), a CHN-corder Reverse otation and carrier otation were conducted to
(Yanako, Japan), a microscope, and a particle size analyzer remove the impurities from the limestone. The limestone,
(Microtrac MT3000, Brookhaven Instruments Co.). The ground as in section 2.1, with 0.13 mass% impurity and
XRD data were obtained with a monochromator under the 9.45 mm median diameter was used as feed for the otation
following conditions: radiation, Cu K, 30 kV, 200 mA; step tests. All otation experiments were performed using a
scanning; time constant 0.5 seconds; and angle range 060 otation tester (FT-1000, Heiko Seisakusho Ltd.): otation
degree/2. The XRF was measured under the following cell 8 cm long, 8 cm wide, and 12 cm high, and with a 5 cm
conditions: Rh, 30 kV; time 300 seconds. Before analyzing diameter impeller blade. The pH of the suspensions was
the particle size, the impurity particles were conditioned to adjusted with 1 kmolm3 of NaOH or H2 SO4 . All reagents
disperse fully by ultrasonic treatment for 30 seconds. were of analytical grade.
The zeta potentials of the impurities were analyzed with a The removal ratio was calculated by determining the
zeta potential analyzer (Zeta-Plus, Brookhaven Instruments dierences between the amount of impurities in 3 g of
Co., USA). limestone before and after the otation tests.

impurity amount before otationimpurity amount after otation


removal ratio  100
impurity amount before otation
The recovery ratio was determined by the following equation:
amount of limestone in non-froth product
recovery ratio  100
limestone amount of feed

2.4.1 Reverse otation


A 40 g of limestone feed was added to 340 cm3 of distilled- 20
deionized water (DDW). With a magnetic stirrer, the
R2 = 0.9758
suspension was agitated at 600 rpm for 5 min, then
0.015 cm3 methyl isobutyl carbinol (MIBC, Nippon Kasei 15
Turbidity / -

Chemical Co., Ltd.) as frother and 0.0150.03 cm3 kerosene


(Wako Pure Chemical Industries, Ltd.) as collector were
added. The suspension was agitated for conditioning at 10
600 rpm for 5 min. After conditioning, the suspension was
introduced into the otation cell, and 60 cm3 of DDW was
added to adjust the pulp density to 10 mass%, and the pH of 5
the suspension was adjusted to a desired value. Flotation
was conducted under the following conditions: air ow
rate, 1,200 cm3 min1 ; otation time, 5 to 30 min; impeller 0
speed, 1200 rpm. The impurities were removed as froth, and 0 2 4 6 8
the froth and the non-froth product were dried at 105 C for
one day, then weighed and their impurity contents were The amount of impurities / mg
measured.
2.4.2 Carrier otation combined with reverse otation Fig. 1 Turbidities (arbitrary) of suspensions containing various amount of
impurities, where the impurities were collected as residue by dissolving
The limestone with 0.15 mass% impurity was used as the limestone with 20% acetic acid.
carrier. Carrier otation was conducted using sodium oleate
(NaOl) or dodecylammonium acetate (DAA) as collectors
under the following conditions: for the limestone, suspension simple and accurate method was developed to determine
30 g of limestone feed was added to 270 cm3 of DDW; for the trace amounts of impurities by dissolving limestone in 20%
carrier suspension, 10 g of carrier was added to 90 cm3 of acetic acid solution. Figure 1 shows the turbidity of suspen-
DDW. Each suspension was agitated at 600 rpm for 10 min sions containing known amounts of impurities. There was a
with a magnetic stirrer and then for another 3 min after good correlation between the turbidity and the amount of
adding a desired amount of collector. The two suspensions impurities (R2 0:9758). The trace amount of impurities
were mixed and conditioned in a otation cell at 1700 rpm was determined by this method using the calibration curve
for 5 min after adding 0.015 cm3 of MIBC, 0.015 cm3 of shown in Fig. 1.
kerosene (or isooctane), and 40 cm3 of DDW, and adjusting Figure 2 shows the XRD pattern of the impurities with
the pH. Flotation was conducted for 10 min under the same peaks for quartz and calcite observed; some calcite remains
conditions as in the reverse otation. after dissolving the limestone with 20% acetic acid. As can
be seen in Table 1, the results of the XRF analysis indicate
3. Results and Discussion that the major components of the impurities are Si and Ca,
agreeing with the results of XRD. The impurities were
The impurity content of the limestone is extremely low. A analyzed with a CHN-corder to measure the carbon content
Removal of Trace Impurity from Limestone Using Flotation Techniques 173

100
3000
Intensity/counts

80

Cumulative / %
2000 Q Ca
60

1000 40
Q Ca Q
Ca
20
0
10 20 30 40 50 60
2 / Deg. 0
1 10 100 1000
Fig. 2 XRD pattern of impurities collected from the limestone dissolved
with 20% acetic acid. Q, quartz; Ca, calcite. Particle size / m
Fig. 4 Cumulative undersize distribution of impurities collected from the
Table 1 Composition of the impurities analyzed with XRF, where the dissolved limestone.
impurities were collected as residue by dissolving limestone with 20%
acetic acid.

Element Ca Si Fe P Al Mg Zn Cr Recovery and removal ratio / %


w/w% 39.8 34.8 10.2 6.8 4.0 2.6 1.3 0.5 100

80
Table 2 Amounts of C, H, and N in the impurities determined by CHN-
corder, where the impurities were collected as residue by dissolving
limestone with 20% acetic acid.
60
Element C H N
w/w% 10.5 0.7 Not detected
40

Recovery ratio
20
Removal ratio

0
0 10 20 30 40

Flotation time / min


Fig. 5 Limestone recovery and impurity removal ratios with increasing
otation time in reverse otation. Conditions: suspension vol. 400 cm3 ;
pulp concentration 5%; MIBC 0.0015 cm3 ; kerosene 0.0015 cm3 .

50 m
Because the impurities are coated partly with carbon, it is
expected that they can be removed by otation using
Fig. 3 Microscopic observation of impurities collected from the dissolved
kerosene as a collector for carbon. This otation technique
limestone.
was conducted to obtain high grade limestone as the non-
froth product, therefore this is termed as reverse otation.
and the result is shown in Table 2. The carbon content other Figure 5 shows the removal ratio of the impurities and the
than CaCO3 is 10.5 mass% in the impurities, showing that recovery ratio of the limestone as a function of otation time.
quartz is a main component of the impurities. As shown in The removal ratio increases from 21.0% at 5 min to 65.7%
Fig. 3, microscopic observation indicated that the silicate at 30 min, while the recovery ratio is almost constant and
particles are partly coated with carbon components. higher than 97%. To obtain high removal ratio, longer
Figure 4 shows the particle size distribution of the impu- otation time is needed due to low collision probability of air
rities. The cumulative undersize of 10, 50, and 90% were bubbles and few amount of impurities. Figure 6 shows the
obtained as 8.39 mm, 44.35 mm, and 158.70 mm, respectively. relation between the removal ratio and the recovery ratio to
Because 90% of the impurities were coarser than 9 mm, about kerosene addition with otation time kept at 10 min in the
90% of the impurities could be liberated by grinding reverse otation. The removal ratio increases from 34.2 to
limestone to ner than 10 mm. 58.8% with increase in the amount of kerosene and the
174 M. Tsunekawa, Y. Honma, K. Yoo, N. Hiroyoshi and M. Ito
Recovery and removal ratio / %
100 140
120
Silica with DAA

Zeta potential / mV
80 100
80
Impurity with DAA
60
60 40
20
40 0
-20 Impurity without DAA
Recovery ratio
-40
20
Removal ratio -60
Silica without DAA
-80
0 -100
0 0.01 0.02 0.03 0.04 5 6 7 8 9 10 11 12
Amount of collector added / cm3 pH
Fig. 6 Limestone recovery and impurity removal ratios with increasing
Fig. 7 Zeta potential of the impurities collected from the dissolved
amounts of collector added in the reverse otation: pulp concentration 5%;
limestone (circle) and silica (rhombus) with (open) and without (solid)
MIBC 0.0015 cm3 ; otation time 10 min.
0.0001 moldm3 DAA.

recovery ratio is always higher than 95%. Generally, as a collector. For simplicity, the carrier otation using DAA
kerosene adsorbs on surfaces of hydrophobic particles such is termed as DAA-carrier otation in the succeeding
as carbon and it accelerates adhesion of particles on the paragraphs.
bubbles and improves otation performance. This would be Prior to the DAA-carrier otation experiments, the zeta
the reason why the removal ratio of impurities increases with potentials of the impurities and silica with and without
increasing amounts of kerosene. 0.0001 moldm3 DAA were determined to conrm if the
As stated above, the reverse otation using kerosene as a potential of the impurities is similar to that of silica. The
collector is an eective method to remove impurities in result is shown in Fig. 7. Here, silica was used as the
limestone, but the removal ratio of impurities is not sucient substitute for the main component of the impurities, i.e.
when kerosene amounts are low and otation times are short: quartz. The zeta potentials of the impurities without DAA
for example the removal ratio is only 21.0% with 5 min of agree well with the reported values20,21) for quartz and the
otation time and 0.015 cm3 kerosene addition. curve shapes of the impurities and silica were similar. Both
There are two reasons for the low removal ratio of the zeta potentials of the impurities and silica with DAA
impurities in the reverse otation: (1) when the surface changed from negative to positive and are close to each other.
coverage of silica particles with carbon is small due to low This suggests that the surfaces of the impurities behave like
carbon content, the particles behave as hydrophilic and this the silica surface and that DAA can be adsorbed.
causes the low oatability of particles. In this case, addition Carrier otation using 0.001 moldm3 DAA as a collector
of collector, which will change the silica surface to hydro- and 0.015 cm3 isooctane as an accelerator was performed.
phobic, may be eective to improve the removal of silicate Figure 8 shows that the removal and the recovery ratios
impurities; (2) because the inertia of very ne impurities is decrease with the increase in pH from 9 to 11. The
very small, they move together with the uid and the dissociation constant of dodecylammonium ions is 10.63,22)
probability of collision between particles and bubbles is low. and above pH 10.6 the capability of DAA as a collector
To overcome this, carrier otation combined with reverse would decrease. The highest removal ratio of 58.3% was
otation was applied, where carrier particles of sizes obtained at pH 9.
suciently large to collide with bubbles were introduced in The eect of DAA concentration on the recovery and the
the otation pulp. The carrier attaches to the ne particles, removal ratios was investigated at pH around 10. As shown
then adsorbs on bubbles and oats. It has been widely in Fig. 9, with increasing DAA addition, the removal ratio
reported that carrier otation is eective to remove ne increases and the recovery ratios decreases sharply. The
particles in small amounts15) with coal,16) anatase,17) and cationic collector DAA adsorbs on the negatively charged
gold.18) In the carrier otation, a low-grade limestone with surface of impurities and carrier, and both collide and
0.15 mass% impurities and of 106149 mm particle size was adhere to each other mainly due to hydrophobic bond, then
used as the carrier, because the low-grade limestone is easily oat. Because DAA acts both as a collector and a frother, the
obtained in situ and the carrier/impurity mixture recovered increase in DAA addition produces an abundant froth
by the otation can be expected to nd usage in cement volume, causing the decrease in the recovery of limestone
production. as non-froth product.
The quartz surface is negatively charged over a wide pH Sodium oleate (NaOl) acts as a collector for quartz23,24) in
range and with a cationic surfactant (DAA) it can be expected the presence of Ca2 ions. The preliminary experiment
to adsorb on silica surfaces by electrical attraction19) and act results of bubble pick-up tests for the impurity showed that
Removal of Trace Impurity from Limestone Using Flotation Techniques 175
Recovery and removal ratio / %

Recovery and removal ratio / %


100
100

80
80
Recovery ratio
60
60 Removal ratio

40
40

Recovery ratio 20
20
Removal ratio
0
0
149-210 210-297 297-590 590-850
9 10 11

pH Carrier size / m
Fig. 10 The eect of carrier size on limestone recovery and impurity
Fig. 8 The eect of pH on limestone recovery and impurity removal ratios removal ratios in the NaOl-carrier otation. Conditions: suspension vol.
in the DAA-carrier otation. Conditions: suspension vol. 400 cm3 ; pulp 400 cm3 ; pulp concentration 5%; MIBC 0.015 cm3 ; kerosene 0.015 cm3 ;
concentration 5%; MIBC 0.0015 cm3 ; isooctane 0.0015 cm3 ; DAA NaOl 0.0004 moldm3 ; otation time 10 min; pH 8.08.4.
0.0001 moldm3 ; otation time 10 min.
Recovery and removal ratio / %

100 100 100

Product Recovery (%)


80 80
80
Removal (%)

60 56.3% 60
60
40 40
40
20 20
Carrier Size:-210 +150 m
-4
NaOl: 3.74 10 M
20 0 0
3 4 5 6 7 8 9 10 11 12 13
0 pH
0 0.0004 0.0008 0.0012 Removal (%) Product Recovery (%)
collector concentration / moldm-3 Fig. 11 The eect of pH on limestone recovery and impurity removal
ratios in the NaOl-carrier otation. Conditions: suspension vol. 400 cm3 ;
Fig. 9 The eect of DAA concentration added on limestone recovery and pulp concentration 5%; MIBC 0.015 cm3 ; kerosene 0.015 cm3 ; NaOl
impurity removal ratios in the DAA-carrier otation. Conditions: 0.0004 molm3 ; otation time 10 min.
suspension vol. 400 cm3 ; pulp concentration 5%; MIBC 0.015 cm3 ;
isooctane 0.015 cm3 ; otation time 10 min; pH 10.0. The symbols are the
same as in Fig. 9.
Figure 11 shows the eect of pH on the removal ratio in
the NaOl-carrier otation. The highest ratio (56.3%) with
the impurity particles became hydrophobic with NaOl, thus 85.2% recovery was obtained in the pH region between 10
carrier otation using NaOl was conducted and is termed as and 11, where activation of the quartz by calcium species
NaOl-carrier otation. dissolved from limestone is expected to occur.23,24) This
The eect of particle size of the carrier in NaOl-carrier activation is explained by the formation of Ca-oleate salts in
otation was investigated with these carrier size fractions: solution or in the vicinity of the quartz surface followed by
149210 mm, 210297 mm, 297590 mm, and 590850 mm. adsorption. This adsorption mechanism requires the presence
Figure 10 shows that the removal ratio decreases with of Ca(OH) ions in solution, which only becomes signicant
increasing carrier size, while the recovery ratio remains near pH 11.23) At pH values lower than 11, concentrations of
almost constant. This could be explained from the fact that Ca(OH) decrease, and this would cause a decrease in the
smaller sized carriers have larger specic surface areas and adsorption amount of the collector on the quartz surface and
adsorb more impurity particles such as quartz and carbon. a decrease in its oatability.
The 149210 mm carrier was used in the succeeding experi- As discussed above, the impurity removal ratio of more
ments. than 50% with limestone recovery higher than 85% was
176 M. Tsunekawa, Y. Honma, K. Yoo, N. Hiroyoshi and M. Ito

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