Farrokhrouz M., Haghi H.

: THE APPLICATION OF HALLIMOND TUBE FOR FLOATABILITY STUDY OF PURE GALENA

FROM NAKHLAK MINE

THE APPLICATION OF HALLIMOND TUBE FOR FLOATABILITY STUDY

OF PURE GALENA FROM NAKHLAK MINE

Mohsen FARROKHROUZ 1, Hamed HAGHI 2

1 Iran Central Oil Fields Co., 22 Esfandiar Ave., Vali-Asr St., Tehran, Iran
2 Tehran University, School of Mine North Kargar St, Jalal Al Ahmd Hwy, Tehran, Iran
mfarrokhrouz@gmail.com, hhaghi@mines.ut.ac.ir

Abstract
Floatation kinetics of Galena of Nakhlak Mine in center of Iran was under study. Since lead
and silver has been extracted for several years from this underground mine, the remaining
cannot be recovered using conventional mining methods. Designing a flotation factory for
remaining portion of the mine is under study.
The sample was grinded in three mesh size and flotation process was simulated in Hallimond
tube for pure Galena. The results of the tests showed that -75+45 grain size with pH in the
range of 7.5-8.5 can give the highest recovery with linear trend. In the next step, analysis of the
test results and obtaining kinetic rate constant and the equation of modeling design was under
investigation.
Using linear and non-linear methods, some correlations were obtained with some discrepancies.
Recoveries greater than 100 or smaller than cumulative recovery are some of these illogical
observations. To modify these errors, LSD method with the ability to insert these limitations was
employed and better result attained. Finally, for time optimization, statistical analyses applied and
minimum duration of flotation time with highest recovery were investigated. Throughout all these
steps, medium grain size (-75+45 micron) and intermediate pH (7.5-8.5) showed the best results.
This range of grain size does not cost too much of crushing and grinding. In addition, the range of
pH is nearly neutral and is accessible in normal water. Conclusively, designing flotation factory
for this mine is economically optimized and suggestive.

Keywords: Galena, Hallimond Tube, flotation cell, flotation kinetics, regression methods

Introduction
To analyze a flotation circuit, some affecting parameters should be considered before designing and
improvement: the kind of additives and their amounts to float special mineral; additives which should
depress the gangue minerals and just intended minerals can be floated; and the most important of all how
long this circuit should be active; meaning that the optimum duration of floatation to improve the grade of
pulp while increasing the recovery factor.
In industrial models economical and time limitations prevent flotation process to be streamed for long
time. Therefore, the ideal circuit is desired with minimum time and maximum recovery. Theoretically,
during this period flotation kinetics is linear and of first order. The graph is obtained using the points from
cumulative percentage of floated material versus time until the point where it is linear. Note that the
sample using in these tests should be the target ore without any impurity.
There have been many different methods of testing floatability and characterizing flotation
performance reported in the literature over the past forty years. These include but are not limited to
release analysis, test-tube floatability, film flotation, frothless flotation, locked-cycle tests, contact angle
measurements, Hallimond tube flotation, and the use of novel cell designs such as the dissolved air
Hallimond tube.

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The Hallimond tube is a fairly well accepted method of testing floatability despite some serious
shortcomings. In the original version, the test sample is placed as a loose bed of particles on top of a
porous septum. Air is pushed through the bed and into contact with the particles. Since the particles are
restricted in their movement, it is generally easier for the bubbles to attach themselves to the mineral
particles than is the case in an industrial flotation cell. As a result, particles which would not float under
industrial conditions may float in a Hallimond tube (Klassen and Makrousov, 1963). The introduction of a
stirrer in a later version of the tube appeared to minimize this problem; however, some shortcomings still
remain. These include (i) incomplete flotation chemistry (i.e., no frother is added), (ii) inability to
generate real grade vs. recovery data, and (iii) unrealistic flow conditions (Chudacek and Fichera, 1991).
Therefore the Hallimond tube test is not considered representative of industrial flotation.
The dissolved-air flotation micro-cell test is carried out in a modified Hallimond tube adapted to
use the dissolved-air technique (Figure 1). The dissolved-air procedure involves introducing
pressurized water into a cell through a needle valve. When the pressure is released as the water enters
the cell, fine bubbles (-120 micron) “precipitate” out (Matis and Mavros, 1991). These fine bubbles
increase the recovery rate by improving bubble-particle collision efficiency (Yoon et al., 1989).
In a typical test a 200 ml suspension is produced with a pulp density of 0.5% and a particle size range
of 25 × 10 microns. The suspension is conditioned with a xanthate collector and appropriate pH
modifiers. Pressurized water is then introduced into the cell and the release of pressure produces the
very fine bubbles. A concentrate is then collected and analyzed. The main advantage of this test is
that the experiments are performed under conditions similar to those in large-scale flotation cells. For
example, laminar flow conditions are prevalent in the collection and flotation areas of these cells, due
mainly to the relatively slow bubble rise velocity (Matis and Mavros, 1991).
This improves the rate of particle adhesion which in turn improves the flotation efficiency.
Other advantages of this test are that it provides the capability of conducting floatability tests with small-
size bubbles, a release analysis procedure can easily be adapted to it, and it allows for fast experiments
with low mineral consumption.

Figure 1: Schematic diagram of the Hallimond tube flotation cell.

Unfortunately, the test still possesses some of the disadvantages of the original Hallimond tube
including incomplete flotation chemistry, low operating solids range, and unrealistic flow conditions as
compared to conventional flotation. Therefore, this test is generally not used for characterizing flotation
behavior on an industrial basis. But the results of the tests can be good estimators for modifying linear
portion of kinetics and it is still under consideration for such purposes.

Tests Performance
To perform flotation tests in Hallimond tube, the sample should be pure. The pure Galena sample was
taken from Nakhlak mine in Iran. It is grinded into three grain sizes: -150+75, -75+45 and -45+37 micron.

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 Farrokhrouz M., Haghi H.: THE APPLICATION OF HALLIMOND TUBE FOR FLOATABILITY STUDY OF PURE GALENA
FROM NAKHLAK MINE

Tests are grouped into two main categories: grain size control tests and pH control tests. Grain size
control tests are performed in pH=7.5 and pH control tests are done in three values of pH: 7.5, 8.5 and 10
while the grain size is constant.
Hallimond tube is filled with water up to 50 cm3 and 3 grams of sample is poured into the tube.
To homogenize the pulp, the setup should be run for two minutes. Collector and frother are added to the
pulp at this time. The conventional amount of these materials is 50 g/t Amyle Potassium Xantate as
collector (should be scaled down) and 10 g/t frother which will be very little amount in 3 grams of the
sample and it is ignored in the test. The pump is switched on and works for one minute. Then, according
to Table 1 the flotation is performed during five minutes. Based on the best result during grain size
control tests, pH control tests carried out. Industrial grain size range for flotation of different kinds of
galena can be between 20-100 micron and 37-240 in laboratory tests (Fuerstenau, 1980). Flotation
activity falls off very rapidly above the optimum particle size, due to the lesser degree of liberation of the
minerals and because of decreasing ability of the bubbles to lift the coarse particles. It can be seen that the
floated material is composed of a fast floating fraction in the medium-size range and a more reluctant
fraction comprising un-liberated coarse material and fines. In a commercial flotation circuit the fast
floating material will be recovered in the roughing section, while the more reluctant fraction is recovered
by scavenging (Wills and Napier-Munn, 2006).

Table 1: Obtained data from different tests

Size range Time Floated PbS Non-cumulative Cumulative
Type pH
(microns) (min) (g) Recovery (%) Recovery (%)
-150 +75 7.5 0.5 0.06 2.00 2.00
-150 +75 7.5 1 0.08 2.67 4.67
Case -150 +75 7.5 2 0.03 1.00 5.67
I -150 +75 7.5 3 0.04 1.33 7.00
-150 +75 7.5 4 0.07 2.33 9.33
-150 +75 7.5 5 0.05 1.67 11.00
-75 +45 7.5 0.5 1.66 55.33 55.33
-75 +45 7.5 1 0.34 11.33 66.67
Case -75 +45 7.5 2 0.19 6.33 73.00
II -75 +45 7.5 3 0.09 3.00 76.00
-75 +45 7.5 4 0.07 2.33 78.33
-75 +45 7.5 5 0.04 1.33 79.67
-45 +37 7.5 0.5 0.05 1.67 1.67
-45 +37 7.5 1 0.12 4.00 5.67
Case -45 +37 7.5 2 0.12 4.00 9.67
III -45 +37 7.5 3 0.12 4.00 13.67
-45 +37 7.5 4 0.11 3.67 17.33
-45 +37 7.5 5 0.1 3.33 20.67
-75 +45 8.5 0.5 0.37 12.33 12.33
-75 +45 8.5 1 0.29 9.67 22.00
Case -75 +45 8.5 2 0.34 11.33 33.33
IV -75 +45 8.5 3 0.16 5.33 38.67
-75 +45 8.5 4 0.1 3.33 42.00
-75 +45 8.5 5 0.06 2.00 44.00
-75 +45 10 0.5 0.03 1.00 1.00
-75 +45 10 1 0.09 3.00 4.00
Case -75 +45 10 2 0.04 1.33 5.33
V -75 +45 10 3 0.07 2.33 7.67
-75 +45 10 4 0.09 3.00 10.67
-75 +45 10 5 0.08 2.67 13.33

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Kinetics Investigations
Most of models for flotation kinetics are designed based on similarity with a chemical reaction.
It is assumed that bubble contact with hydrophobic mineral is equal to molecular contacts of reactants in
a chemical reactor. Modeling design, based on this assumption, is usually considered to be linear and
classic and it is proposed like below (Laskowski, 2001):

C = C o e − kt (1)

Where C is the concentration of the mineral at time t, C0 is initial concentration and k is kinetics rate
constant. This formula is derived from integration of the Equation (2):
dc (2)
= − kc
dt
A number of different modeling equations have been proposed, but it seems that Equation (3)
(classical model with first order) is the best kinetic model for flotation recovery and it used in this study.

(
R = R∞ 1 − e − kt ) (3)
In the flotation kinetic equations, k is a complex function involving (among other things) particle and
bubble sizes, reagent concentration, and flotation cell hydrodynamics. Although it is generally accepted
that flotation recovery follows first-order kinetics (Bushel, 1962), experimental evidence suggests that the
order of the process may vary (Bogdanov et al, 1959; Arbiter, 1951; Ahmed and Jameson, 1989).
Using Equation (3) as the base equation, two regression methods have suggested using Curve-Expert
1.37 software: non-linear regression and linear regression. In non linear regression suggested model obeys
above form. In linear regression using excel software proposed model obeys the form of Equation (4).

⎛R −R⎞
Ln⎜⎜ ∞ ⎟⎟ = − kt (4)
⎝ R∞ ⎠
Table 2 summarizes this data output. Since this software performance is based on statistical data, some
deviations from logical results are observed. For example R∞ in some cases is more than 100% or less
than cumulative recovery which is not logically correct. In non-linear method, final recovery is assumed
to be 100% and reaction rate modeling is anticipated. In linear methods, considering R∞ to be constant
(100, 95, 90, 85), the relation is solved to obtain k. Because of difference in particle size and chemical
environment R∞ will not be a constant value. In all, this method does not seem to be perfect and output
results are not reliable enough.

Table 2: Result of obtained model with regression method

Method Parameters Case I Case II Case III Case IV Case V
R∞ 13.93 76.658 48.94 45.523 72.803
regressio
linear

k 0.28 2.373 0.11 0.65 0.04

Non-

Standard Error 0.841 2.898 0.556 0.322 0.689

Correlation Coefficient (R2) 0.973 0.959 0.998 1.000 0.990
k 0.0247 0.4069 0.0476 0.1388 0.0283
R∞ =100
R2 0.928 0.288 0.994 0.827 0.987
k 0.0261 0.4612 0.0504 0.1486 0.0298
regression

R∞ =95
Linear

R2 0.929 0.363 0.995 0.834 0.988

k 0.0276 0.5382 0.0535 0.1599 0.0316
R∞ =90
R2 0.930 0.468 0.995 0.841 0.988
k 0.0294 0.6649 0.057 0.1731 0.0336
R∞ =85
R2 0.930 0.630 0.995 0.849 0.988

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 Farrokhrouz M., Haghi H.: THE APPLICATION OF HALLIMOND TUBE FOR FLOATABILITY STUDY OF PURE GALENA
FROM NAKHLAK MINE

Because of some discrepancies in regression method, it is tried to minimize sum of difference squares
to obtain real and calculated recovery using test results and model predictions, respectively. Solver option
in Excel software is used for minimization of Least Square Differences (LSD) by changing k and R∞ in
three modes:
1. Calculation of R∞ and k under no condition.
2. R0 presumed as a constant value in all situations and k is calculated.
3. Two preliminary conditions are assumed: R∞ cannot be greater than 100 (R∞ ≤ 100) and should be
greater or equal to maximum recovery of test results (R∞ ≥ Max{Rcum}).
Finally, in all suggested modes, correlation coefficient for predicted and calculated models should be
investigated to choose the most logical value. The final output of these calculations is presented in Table 3.

Table 3: Results of calculated model with minimization of Least Square Difference (LSD)
Conditions Parameters Case I Case II Case III Case IV Case V
R∞ 83.848 76.657 88.744 45.521 101.146
No Limitation k 0.0296 2.373 0.0546 0.6496 0.0279
R2 0.961 0.993 0.995 0.999 0.987
k 0.0249 0.8505 0.0477 0.1484 0.0283
R∞ =100 R2 0.943 0.861 0.994 0.921 0.987
k 0.0263 1.111 0.0505 0.1596 0.0298
R∞ =95 R2 0.96 0.915 0.995 0.924 0.987
k 0.0278 1.4028 0.0537 0.1727 0.0316
R∞ =90 R2 0.961 0.954 0.995 0.929 0.987
k 0.0295 1.7205 0.0572 0.1882 0.336
R∞ =85 R2 0.961 0.979 0.995 0.934 0.987
R∞ 13.949 79.667 49.0105 45.5211 90.6077
R∞ ≤ 100
k 0.2799 2.112 0.1093 0.6496 0.0313
R∞ ≥ Rcum Max
R2 0.971 0.991 0.997 0.999 0.987

Finally historical data design (a type of response surface method) for analysis of variance (ANOVA)
of Cumulative recovery and multivariate linear regression were applied. For evaluating the effect of each
parameter on the optimization criteria, the collected data were analyzed by DX 7.0 and Minitab14.0
softwares. Also all calculations were controlled with Excel software. Considering confidence interval of
95% in this study, p-values less than 0.0500 indicate model terms are significant. For cumulative
recovery, A, B and C are significant model terms. The Model F-value of 205.01 implies that the model is
significant. There is only a 0.01% chance that "F-Value Model" with this value is occurred due to noise.
R-Squared (R2) of this model is 0.9693. ANOVA table for cumulative recovery as response is presented
in Table 4.

Table 4: Analysis of variance (ANOVA) for cumulative recovery based on historical data design
Source SS DOF MS F Value p-value
Model 38567.09 4 9641.77 205.01 < 0.0001
A-pH 20123.85 1 20123.85 427.89 < 0.0001
B-Time (cum) 1253.12 1 1253.12 26.64 < 0.0001
C-Particle Size range 26166.20 2 13083.10 278.18 < 0.0001
Residual (Error) 1222.80 26 47.03
Total 39789.89 30

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Due to ANOVA table, flotation conditions like pH and particle size range have a large impact on
floatability of pure galena. Regarding the obtained tests, the best particle size range is -75 +45 microns.
After ANOVA, the optimization process was carried out and the results of this process in constant pH
(7.5 and 8.5) are presented in Table 5 and Table 6. As test results and predictions, statistical studies
confirm that the highest recovery with minimum time in cell is -75+45 micron. It should be noted that
these results are obtained for a sample with no impurity and no secondary ore like Sphalerite.
Medium particle size range (-75 +45 microns) was selected for multivariate linear regression study
implemented by Mintab14. After calculations Equation (5) were suggested for cumulative recovery with
variety of pH and cumulative recovery. R-Squared (R2) of this model is 0.925. Figure 2 shows predicted
values for cumulative recovery of pure galena in the medium particle size range.

Rcum. = 242.18 − 25.082 × pH + 4.663 × timeCum. (5)

Table 5: Optimized level of parameters for flotation in pH=7.5.

Time particle size Predicted cum.

Target Desirability
cum. (min) (microns) Recovery (%)

5 -75 +45 74.81 0.938

Max. Cum. Recovery 4.1 -75 +45 71.17 0.892
all parameters in range 5 -45 +37 23.00 0.280
5 -150 +75 18.17 0.218
5 -75 +45 74.81 0.938
Max. Cum. Recovery 2.74 -75 +45 65.65 0.907
Min. pH 5 -45 +37 23.00 0.529
Other parameters in range 4 -45 +37 18.91 0.477
5 -150 +75 18.17 0.467
0.5 -75 +45 56.58 0.841
Max. Combustible recovery 0.5 -75 +45 49.12 0.782
Min. Time 2.28 -45 +37 12.00 0.291
Other parameters in range 2.83 -45 +37 14.20 0.285
3.12 -150 +75 10.56 0.225
7 -75 +45 82.91 1.000
Max. Combustible recovery
7 -45 +37 31.10 0.383
flotation time (cum.)= 7min
7 -150 +75 26.27 0.321
10 -75 +45 95.06 1.000
Max. Combustible recovery
10 -45 +37 43.26 0.537
flotation time (cum.)= 10min
10 -150 +75 38.42 0.476
11 -75 +45 99.11 1.000
Max. Combustible recovery
11 -45 +37 47.31 0.589
flotation time (cum.)= 11min
11 -150 +75 42.47 0.527
Max. Combustible recovery 15 -45 +37 63.51 0.795
flotation time (cum.)= 15min 15 -150 +75 58.68 0.733
Max. Combustible recovery 20 -45 +37 83.76 1.00
flotation time (cum.)= 20min 20 -150 +75 78.93 0.991
Max. Combustible recovery 24 -45 +37 99.96 1.00
flotation time (cum.)= 24min 24 -150 +75 95.13 1.00

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 Farrokhrouz M., Haghi H.: THE APPLICATION OF HALLIMOND TUBE FOR FLOATABILITY STUDY OF PURE GALENA
FROM NAKHLAK MINE

Table 5: Optimized level of parameters for flotation in pH=8.5.

Time particle size Predicted cum.

Target Desirability
cum. (min) (microns) Recovery (%)

Max. Cum. Recovery

5 -75 +45 51.17 0.638
all parameters in range
Max. Combustible recovery
0.5 -75 +45 32.94 0.637
Min. Time
11 -75 +45 75.47 0.947
Max. Combustible recovery
11 -45 +37 23.67 0.288
flotation time (cum.)= 11min
11 -150 +75 18.84 0.227
15 -75 +45 91.68 1.000
Max. Combustible recovery
15 -45 +37 39.87 0.494
flotation time (cum.)= 15min
15 -150 +75 35.04 0.433
Max. Combustible recovery 20 -45 +37 60.12 0.752
flotation time (cum.)= 20min 20 -150 +75 55.29 0.690
Max. Combustible recovery 24 -45 +37 76.33 0.96
flotation time (cum.)= 24min 24 -150 +75 71.49 0.90

Figure 2: Predicted cumulative recovery of pure galena in (-75 +45 microns) particle size range.

Conclusions and Recommendations

1. In a flotation cell, +75 micron and -45 micron are typically considered as coarse material and lime,
respectively. The results of these tests showed that -75+45 micron is a good range of grain size and
the highest recovery of the mineral was obtained inside this range.
2. Suitable pH value for flotation process was pH = 7.5 which is the pH of natural water meaning
economical justification for industrial design. In practice, during industrial designing a range of pH
is introduced. In this case, pH = 8.5 showed the good recovery after initial phase. Therefore, pH
range of 7.5-8.5 can be mentioned as practical variety of pH.

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3. To scale up the Hallimod tube for flotation cells, accurate flotation kinetics has been calculated.
The most practical and logical results were obtained using LSD method with limitations (R∞ ≤ 100,
R∞ ≥ Max {Rcum}). Based on this case, the value of R∞ = 79.67 and k = 2.11 for lower limit
(pH = 7.5) and R∞ = 45.52 and k = 0.65 for upper limit (pH = 8.5) are the best test results with
good correlation (R2). This is another confirmation of suggestive grain size and pH range: -75+45
grain size and pH = 7.5-8.5.
4. For time considerations in flotation cells, some analyses were done. In pH = 7.5, different
parameters were chosen to obtain best results. In all cases, predicted grain size (-75+45) shows the
highest recovery and minimum time in range. Even in a desired constant time (t = 7, 10, 11min)
this grain size range has better recovery than the others. Given time extension up to 24 minutes in
this pH can lead the flotation process to 99% and 95% of cumulative recovery for -45+37 and
-150+75 micron grain size, respectively.
5. To control the effect of pH in desired range, the upper limit (pH = 8.5) nominated for statistical
analysis. In this phase of experiments, -75+45 still shows good results; recovery more than 90%
after 15 minutes of flotation time. If flotation time increased up to 24 minutes, cumulative recovery
in the range of -150+75 and -45+37 grain size will be 76 and 71, respectively. These results are in
the second order of desirability.
6. Totally, it was observed that extending the time of flotation up to 15, 20 and 24 minutes, the other
grain sizes can give good output. In this case -45+37 grain size shows better results than -150+75.
This extension in flotation time is a suitable option for lime ore flotation to increase the recovery of
mineral or coarse mineral flotation if grinding process is restricted under any condition.

Reference
[1] Ahmed, N., Jameson, G.J., Frothing in Flotation Gordon and Breach, Flotation kinetics,
In: J.S. Laskowski (ed.), London, 1989, pp. 77-100.
[2] Arbiter, N., Flotation rates and flotation efficiency, Trans AIME, 190, 1951, p 791.
[3] Bogdanov, O.S., Podnek, A.K., Khayman, V.J., Yanis, N.A., Theoretical and technological
problems of flotation, Trans. Mekhanobr, Leningrad, 124, 1959.
[4] Bushell, C.H.G., Kinetics of flotation, Trans SME/AIME, 223, 1962, p 266.
[5] Chudacek, M.W., Fichera, M.A., The relationship between the test-tube flotability test and batch cell
flotation, IN: Minerals engineering; New York, Pergamon Press, v.4, n.1, 1991, p. 25-35.
[6] Fuerstenau, D.W., Fine Particle Processing, in P. Somasundaran (ed.), SME/ AIME, New York,
1980, p 669.
[7] Klassen, V.I., Mokrousov, V.A., an Introduction to the Theory of Flotation, Butterworths, 2nd ed.,
London, 1963.
[8] Laskowski, J.S. (editor), Coal Flotation and Fine Coal Utilization, Developments in Mineral
Processing, Vol 14, 2001, pp226-232.
[9] Matis, K.A., Mavros, P., Foam/froth flotation: part II removal of particulate matter, separation and
purification methods, vol 20, no 2, 1991, pp 163-198.
[10] Wills, B.A., Napier Munn, T., an Introduction to the Practical Aspects of Ore Treatment and Mineral
Recovery, Elsevier Science and Technology Books, 7th ed., 2006.
[11] Yoon, A.H., Luttrell, G.H., Adel, G.T., In-plant testing of micro-bubble column flotation,
DOE/PC/89909-T2, Virginia Center for Coal and Minerals Processing, Blacksburg, VA (USA), 1989.

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