Minerals Engineering 23 (2010) 1–9

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Evaluation of flotation technology for the trona industry

O. Ozdemir a,b, A. Jain a, V. Gupta a, X. Wang a, J.D. Miller a,*
a
Department of Metallurgical Engineering, University of Utah, 135 S. 1460 E., 412 WBB, Salt Lake City, UT, USA
b
School of Chemical Engineering, The University of Queensland, Brisbane, Queensland 4072, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Trona ore consists mainly of trona, sodium sesquicarbonate dihydrate (Na2CO3NaHCO32H2O), including
Received 2 July 2009 minor undesirable insoluble materials. With the present industrial practice, there is no particle separa-
Accepted 21 August 2009 tion process to remove these insoluble minerals prior to thermochemical processing. In this current
Available online 9 October 2009
research appropriate conditions for trona flotation technology were established from exploratory
bench-scale experiments, and the conditions obtained from the bench-scale experiments were also
Keywords: applied to pilot scale flotation tests. In this regard various process variables such as amine dosage, flota-
Trona
tion percent solids, amine to oil ratio, pH of amine solution, collector structure, brine composition, feed
Soda ash
Soluble minerals
particle size, etc. were studied to establish the preferred conditions and operating variables for pilot-
Flotation plant testing. Additional information regarding the mineralogy of the system and collector characteristics
is also reported to provide further analysis and explanation.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction is the most widely practiced by industry. The schematic flowsheet

Soda ash (sodium carbonate) is a most important commodity
used by many industries such as the glass industry, chemical
industry, soap and detergents, pulp and paper, and water treat-
ment industries (Kostick, 2004). Soda ash is traditionally produced
from trona ore in the USA, and most of the soda ash production in
the US comes from the Green River Basin in Wyoming which is the
largest known trona ore deposit in the world. The estimated trona
reserves in the USA are 23 billion tons. Considering that the world
trona reserves are about 24 billion tons, it can be said that the tro-
na deposits in the USA will be the most significant source of soda
ash in the years to come, and it is estimated that these reserves
of trona could satisfy the world’s demand for many centuries (Ko-
stick, 1994). Other trona deposits are not so common, and signifi-
cant deposits are only found at a few locations in the world:
Turkey, Botswana, and Mexico. None of these trona resources com-
pare to the vast trona deposit of the Green River Basin in the US.
The trona beds occur with layers of oil shale, marlstone, and
sandstone/mudstone. These insoluble contaminants include a
number of double carbonate salts in addition to dolomitic shale,
quartz and clays (Garrett, 1991). In the industry, there are two
commercial processes to remove the insolubles and produce soda
ash from the trona ore; the sesquicarbonate process and the mono-
hydrate process. Of these two processes the monohydrate process
* Corresponding author. Fax: +1 801 581 4937.
E-mail addresses: orcey@yahoo.com (O. Ozdemir), Jan.Miller@utah.edu (J.D.
Miller).
for the monohydrate process is presented in Fig. 1.
As seen from Fig. 1, the trona is converted to soda ash in a multi-
step purification process; calcination, dissolution, clarification, fil-
tration, and crystallization. The treatment processes for trona ore
are not only chemically expensive but also energy-intensive. Pro-
duction of soda ash has a significant energy demand due to the cal-
cination and crystallization operations. In this regard, processing
costs, particularly energy costs, are higher than desired and these
costs have a significant impact on the cost of production. Hence,
the production of high purity trona concentrate at lower energy
and operating cost is of considerable interest to the trona industry.
Removal of insoluble gangue minerals from trona by particle
separation processes is not practiced by industry. Nevertheless, re-
search and development efforts have been made to find an appro-
priate particle separation process for the removal of insoluble
gangue minerals prior to traditional thermochemical processing.
Some researchers have suggested that gangue minerals can be sep-
arated from the trona ore prior to further processing. For example
studies on magnetic separation (Wold et al., 1999), electrostatic
separation (Brison and Webber, 1982; Imperto and Hillard 1983),
particle size separation (Smith, 1966), and even optical sorting
(Graves and Sopchak, 1974) have been reported in the literature.
It is also believed that removal of gangue minerals from the trona
plant feed might be accomplished by froth flotation. Such a prepro-
cessing strategy at ambient temperature and pressure has been
limited by the lack of satisfactory flotation technology. Some
researchers (Garrett and White, 1970; Rosar et al., 1974; Rosar
et al., 1976; Brison and Gathje, 1981; Datta and Salotti, 1990)
claimed to be able to float the insoluble minerals. Nevertheless,

0892-6875/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2009.08.006
2 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9

TRONA ORE DRY

MINING CRUSHING DISSOLUTION
CALCINATION

WATER
WATER & HEAT SETTLERS
CARBON DIOXIDE
WATER HEAT INSOLUBLES
WATER
TO WASTE

MONOHYDRATE CARBON
DEHYDRATION CENTRIFUGATION TREATMENT
CRYSTALLIZATION
DENSE & FILTRATION
SODA
ASH HEAT

STORAGE &
SHIPPING

Fig. 1. Schematic flowsheet for the monohydrate process (Garrett, 1991).

an appropriate flotation technique for trona recovery has not yet
been commercialized. More recently, a unique flotation procedure
was discovered at the University of Utah (Wang et al., 2002). Re-
sults from laboratory research show that run-of-mine trona ore
can be treated using a special flotation procedure to separate the
gangue minerals and make a trona concentrate of 99% purity with
a recovery of 97% (Wang et al., 2002).
Trona is a complex salt of sodium carbonate (Na2CO3) and so-
dium bicarbonate (NaHCO3). Despite many studies regarding the
flotation of soluble salts, there are few studies about the flotation
of carbonate salts. Microflotation experiments with pure Na2CO3
and NaHCO3 salts showed that excellent flotation of NaHCO3 can
be achieved with both anionic and cationic collectors. On the other
hand flotation of Na2CO3 is generally difficult (Ozcan and Miller,
2002). Studies with carbonate salts suggest that their flotation re-
sponse seems to be related mostly to the viscosity of the brine and
interfacial water structure. Based on the analysis of interfacial
water structure in saturated brines, Na2CO3 was found to act as a
strong water structure maker, whereas NaHCO3 acts as a weak
water structure maker (Ozdemir et al., 2006a,b, 2007; Du et al.,
2008). Also because trona (Na2CO3NaHCO32H2O) is a structure
maker, flotation is generally difficult with 12C collectors. Finally,
it was concluded that due to the structure making effect of Na2CO3
in the brine and at the trona surface, the direct flotation of trona
from its brine is difficult (Ozdemir et al., 2009). These facts support
the use of a reverse flotation strategy to float the gangue minerals
by flotation and thus prepare a trona concentrate. In this case, the
flotation circuit could be installed after the crushing process and
before the dissolution process. Then, the high quality trona concen-
trate could be sent onto the existing plant for conversion to soda
ash and/or be marketed as a new product.
This paper evaluates the reverse flotation technology for the
production of a trona concentrate. The results help to provide a fur-
ther basis for the development of improved flotation technology
for the trona industry.
2. Materials and methods
2.1. Experimental materials
2.1.1. Trona ore
Trona samples for flotation tests were obtained from the plant
operated by General Chemical, which processes trona ore from the
Green River Formation, Wyoming. First, the samples (specific gravity
of trona feed, 2.2 g/cm3; and bulk density, 0.97 g/cm3) were taken
from the crushing circuit before calcination. Then, they were classi-
fied into different particle size fractions by laboratory screening.
Fig. 2 shows the total mass distribution and insoluble content of
the trona ore with respect to particle size for the 2 mm material ta-
ken from the feed to calcination. As seen from the figure, the insolu-
ble content of the trona ore decreases as the particle size decreases,
particularly at particle size less than 600 lm. About 26% of the total
mass is distributed in the 75 lm fraction with only 1–2% insoluble
content. Since the 75 lm material contains only 1–2% insoluble,
this size fraction can be used directly as a trona concentrate. The
overall insoluble content for this feed material is about 11.3%.
2.1.2. Insoluble minerals
The insoluble minerals in the trona ore were isolated after dis-
solution and analyzed by X-ray diffraction (XRD) for identification.
XRD analyses indicate that the insoluble minerals are composed of
mostly quartz, calcite, shortite, dolomite and feldspar. The chemi-
cal compositions of the insoluble minerals are given in Table 1.

30
Trona Ore and Insoluble Wt %

Trona Ore Wt % Insoluble Content, %

25

20

15

10

0
2.0×1.7 1.7×1.18 1.18×0.85 0.85×0.6 0.6×0.425 0.425×0.25 0.25×0.18 0.18×0.15 0.15×0.75 0.75
Particle Size Fraction (mm)

Fig. 2. Total mass distribution and insoluble content of trona ore with respect to particle size (sample taken from calcination feed material; 2 mm).
 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9
Table 1
Insoluble minerals in trona identified by X-ray diffraction.
Mineral Formula
Dolomite CaCO3MgCO3
Feldspar (K,Na)OxAl2O3ySiO2
Quartz SiO2
Calcite CaCO3
Shortite Na2CO32CaCO3
2.1.3. Reagents
Armeen 12D (Dodecylamine, C12H27N), a commercial reagent
manufactured by Akzo Nobel Surface Chemistry LLC, was used
for the flotation experiments. Kerosene purchased from a local
company, Hi-Valley Chemical, Inc., was also used to extend the
hydrophobic effect of the amine collector.
2.2. Methods
2.2.1. Collector preparation and characterization
Dodecylamine hydrochloride (DAH) as a surfactant, and kero-
sene for the oil phase were selected for collector characterization
tests. In this study, four different concentrations of aqueous amine
solutions were prepared, i.e., 1%, 2%, 3%, and 4% (4.51  102 M,
9.02  102 M, 1.35  101 M, and 1.80  101 M, respectively).
The emulsions were prepared by adding the oil to the amine solu-
tion and using a Cole Parmer laboratory mixer (2 min, 1500 rpm).
The weight ratio of the amine reagent to oil was 1:12 for each
experiment. In each case, the emulsion was equilibrated for
2 min. A sample of emulsion was collected and immediately placed
on a Burker plate for microscopic analysis. An optical microscope,
model AXIOPLAN (ZEISS, Germany) and microscopic slide with
master scale were used. Ten photos of each sample were taken
and the droplet sizes were determined. Droplets (500–700) were
counted to obtain the size distribution curve (five photographs
were selected for each distribution and every droplet on each pho-
tograph was counted). From the time the emulsion was prepared
to the time the digital pictures were taken, no coalescence was ob-
served. However, coalescence was observed after 1 h.
Eq. (1) was used to calculate the sauter diameter of the droplets
(Becher, 1965). The sauter mean diameter is an index of the disper-
sity of the emulsion, which is defined as the surface mean diameter
of a distribution with surface area equal to the mean surface area
of all the droplets in the emulsion.
X .X
x ¼ 6V=S ¼ x3i ni x2i ni
where V is the volume of dispersed phase, S is the total interfacial
area, ni is the number of droplets of diameter xi.
In the case of flotation tests, a 3% by weight amine solution
(Armeen 12D) was prepared in distilled water at pH 3. The solution
was then stirred using a mixer at 1200–1500 rpm for an hour to
completely dissolve the amine. Since the amine is not very soluble
in water, the solution was heated to 70 °C in order to obtain a clear
solution. The solution was then cooled down for an hour before
preparation of the collector emulsion in the next step. The emul-
sion was prepared by dispersing kerosene in the 3% aqueous amine
solution in the ratio of 1:12 (amine to kerosene) by weight using a
mixer at 1500 rpm for 2 min. The mixing speed of 1500 rpm was
established after using different speeds to see the effect on emul-
sion properties. In this way a collector emulsion (oil-in-water)
was prepared and used to float the insoluble minerals from the tro-
na ore. The density of the amine solution and kerosene were
0.98 g/cm3 and 0.75 g/cm3, respectively.
3
2.2.2. Brine preparation
Since trona is soluble in water, a saturated solution of trona was
used for the flotation tests to prevent solubilization of the trona
particles to be separated from the gangue mineral particles. The
preparation of the saturated brine solution for the flotation exper-
iments is very important. At room temperature, the solubility of
trona in water is about 20 wt.%. Due to sensitivity of the salt solu-
tions, more than the required amount of ground trona was placed
in water (40% solids + 60% water) and stirred for over 10 h to reach
the saturation (light yellow colored solution). Then, the saturated
solution was stored overnight to ensure that suspended solids
had settled completely. The solution was then decanted, and trans-
ferred to another container. Finally the solution was filtered to re-
move fine particles before use in the flotation experiments. The
density of the trona saturated solution (brine) was 1.21 g/cm3.
2.2.3. Analytical techniques
The analytical method for insoluble mineral analysis of flotation
products (concentrate and tailing) was as follows: After drying and
weighing, a representative sample (25–30%) of product was ta-
ken for insoluble mineral analysis. This representative sample
was mixed with water and stirred for 1 min. Then it was decanted
after 5 min. This process was repeated several times until all solu-
ble salts (light yellow color) were dissolved completely. Only the
insoluble minerals (dark brown color) remained. These insoluble
minerals were then transferred onto a Pyrex glass plate and heated
at 40–50 °C for a few minutes followed by cooling at room temper-
ature. The dry sample was then weighed, and the insoluble mineral
content was determined.
2.2.4. Bench-scale flotation tests
Bench-scale flotation tests were conducted in a bench-scale
Denver flotation machine. In addition, a Denver conditioning ma-
chine was used for the conditioning process. The flotation tests
were carried out with 150 g of dry trona feed. First, the feed sample
was conditioned in the conditioning tank by adding 25–30 mL sat-
urated trona solution for 30 s. Then, the collector emulsion was
added for further conditioning. The conditioning time was 2 min
at 75% solids (trona feed). The conditioned sample was transferred
to the flotation cell, and then diluted with saturated solution. Final-
ly flotation was carried out. The flotation time was about 4–5 min.
The water-insoluble material in both float and sink products was
determined by gravimetric analysis. Fig. 3 shows the flowsheet
for the bench-scale flotation tests.
ð1Þ
Trona Feed
Screening Oversize
Undersize
Saturated Solution
& Conditioning
Emulsion
Saturated Solution Flotation Float (Insolubles)
Sink
(Trona Concentrate)
Fig. 3. Procedure for bench-scale flotation experiments.
4 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9
Fig. 4. Trona flotation pilot-plant circuit.
2.2.5. Pilot scale flotation tests
In the case of the pilot scale flotation tests, the flotation ma-
chine shown in Fig. 4 was used in order to find the preferred con-
ditions for the continuous pilot-plant system. The pilot circuit seen
in Fig. 4 was installed for flotation tests at the University of Utah.
As seen from the figure, the system includes a vibratory feeder
with a pipe to transfer feed material to the conditioning tank (1),
a conditioning tank with an impeller for stirring (2), a dilution tank
(3), and a flotation machine (4).
The bench-scale flotation procedure was also followed for the
pilot scale flotation tests. The trona ore was fed to the conditioning
tank through the vibratory feeder at a calculated solids flow rate
(50 kg/h). In the conditioning step, the calibrated amount of re-
agents and saturated solutions were also added to obtain 75% sol-
ids conditioning. The slurry was conditioned about 2 min in the
conditioning tank and then discharged by gravity into the dilution
tank where the slurry was diluted to about 15% solids with the
addition of fresh saturated trona solution and pumped to the flota-
tion equipment. The slurry flow rate was adjusted with the control
valve. Each test lasted for at least 30 min during which time oper-
ating variables were kept constant at desired values. Samples of
float and sink products were dried, weighed and analyzed for insol-
uble mineral content. The water-insoluble material in both float
and sink products was determined by gravimetric analysis.
3. Results
3.1. Collector emulsion for reverse flotation
3.1.1. Collector composition and characterization
The droplet size distributions of emulsions were also measured
by optical microscopy. The micrographs for these emulsion drop-
lets (DAH and kerosene) are shown in Fig. 5. As seen from the
micrographs, the droplet sizes do not change in 1% and 2% DAH
solutions. It can be observed in Fig. 5 that after 2% the droplet size
becomes smaller.
Fig. 6 shows the droplet size distributions of emulsions (dodecyl
amine hydrochloride and kerosene). The results show that the
droplet size distributions become narrower and smaller in size as
the amine concentration increases. Average diameters of the drop-
lets were also calculated using Eq. (1), and the results are pre-
sented in Table 2. The results indicate that the size of the
droplets decreases with an increase in amine concentration. The
diameter of droplet sizes at 3% amine concentration is about
9 lm. There is excellent agreement between these results and
the flotation results with different amine concentrations (Fig. 9e).
As shown in Fig. 9e, the separation gets better at 3% than those ob-
tained with 1% and 2%. It means that the finely dispersed emul-
sions in 3% or 4% amine solutions improve the trona flotation.
The high surface energy of the small oil droplets appears to provide
for the fast and stable wetting on the insoluble minerals. On the
other hand, the conditioning process is also a very important step
for flotation at high salt concentration because of the wetting/
spreading phenomena. Since the insoluble minerals are negatively
charged, the positively charged hydrophobic collector (emulsion)
will adsorb (cover) on the insoluble minerals such as quartz, dolo-
mite, and feldspar, and makes the insolubles hydrophobic which is
the favorable condition for flotation. Since the electrostatic interac-
tion between the particle and collector will be very weak at high
salt concentrations due to a compressed electrical double layer,
the high solid conditioning is necessary for wetting of insolubles
by the emulsion. Traditional phosphate flotation is a good example
for this case, which involves aerofloc formation with the insoluble
fatty acid/fuel oil collector (Wang et al., 2006). The significance of
the wetting/spreading phenomena and the necessity of high solids
conditioning have also been reported by Lu et al. (1997). The low
flotation recovery for large scale (30 L) flotation tests can be attrib-
uted to the failure of the conditioning or wetting/spreading
process.
3.1.2. Electrokinetic studies
Electrokinetic properties of the insolubles as revealed from zeta
potential measurements provide important information for the
understanding of flotation separation processes. In this regard, zeta
potential measurements for the insoluble minerals were per-
formed in water and brine to determine the electrophoretic mobil-
ity of such samples. Fig. 7 presents the zeta potential results of
floor and roof shale as a function of pH. As seen from Fig. 7, the
pzc values (point of zero charge) for floor and roof shale in water
were found to be between pH 2 and 3. Thus, the surface charge
of these shales is negative and their negative character arises from
the relative abundance of Si4+, Al3+, Ca2+ and Mg2+ species and their
preferential dissolution from shale as well as dissociation of sur-
face acid groups.
 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9 5

Fig. 5. Photomicrographs of the dispersed drops in DAH emulsions.

Fig. 6. Comparison of droplet diameter distributions for oil emulsions at different DAH concentrations.

Table 2 Fig. 8, the electrophoretic mobility values for the insolubles de-
Sauter mean diameter (lm) for DAH emulsion of kerosene. crease with an increase in the salt concentration. The important
DAH concentration Sauter mean Standard finding is that the sign of the samples are negative even in a satu-
(%) diameter (lm) deviation (lm) rated solution of trona. This high salt concentration appears to
1 16.03 ±1.15 make significant changes on the surface charge of the particles.
2 17.60 ±1.11
3 9.07 ±1.08
4 9.12 ±1.07 3.2. Reverse flotation experiments

3.2.1. Bench-scale tests

Since the trona flotation process must be carried out in its sat- Bench-scale flotation experiments were conducted in order to
urated solution, equilibrium electrophoretic measurements were establish appropriate flotation conditions and operating variables
also accomplished for floor and roof shale in brine. As seen from for pilot-plant testing. It was determined that the successful
6 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9

10 3.2.1.2. Percent solids. The effect of flotation percent solids on the

flotation performance is presented in Fig. 9b. The bench-scale
experiments with the 600  75 lm size fraction as a function of
0 flotation percent solids showed that when the flotation tests were
carried out in suspensions of 15% solids or more, the flotation re-
sponse of insoluble minerals increases. At 15% solids, trona concen-
-10 trate with a purity of almost 99% trona at a recovery of more than
75% was obtained. The results show that 15% solids is the optimum
Zeta Potential, mV

for the trona flotation.

-20
3.2.1.3. Flotation time. The flotation tests were carried out with
600  75 lm size fraction to investigate the effect of flotation time.
-30 The results in Fig. 9c showed that most of the insoluble minerals
(75% of the insoluble minerals) float in 2 min. However; for suc-
cessful flotation, 4 min of flotation time was necessary to float all
-40 Floor Shale insoluble minerals from the trona.
Roof Shale
3.2.1.4. Amine dosage. The flotation experiments were carried out
-50 to determine the effect of amine dosage for different feed grades.
0 2 4 6 8 10 12 14
pH Reagent dosages were varied from 2 kg/t to 5 kg/t. Fig. 9d shows
the results from flotation experiments using feed material with dif-
Fig. 7. Zeta potential of insoluble minerals as a function of pH in water. ferent levels of insoluble contents (600  75 lm at 8.21% insoluble,
600  75 lm at 13.73% insoluble and 500  75 lm at 26.65% insol-
uble). The flotation results with different amine dosages showed
0.0 that a large amount of amine is needed to achieve a specified grade
for the trona product. As is evident from the results presented,
even with an insoluble content as high as 27%, an excellent flota-
-0.5 tion separation is still possible. In this case, a dosage of 5 kg/t of
Electrophoretic Mobility, (µ/sec)/(V/cm)

amine was selected for further flotation tests.

-1.0
3.2.1.5. Amine concentration. A few experiments were performed
under the same operating conditions mentioned above with differ-
ent amine concentrations (1%, 2%, 3% and 4%). Excellent separation
-1.5
was obtained with 3% amine solutions. It can be seen in Fig. 9e that
grades with 3% were better than those obtained with 1%, 2% and
slightly better than 4%. It is interesting to note that even though
-2.0
the sauter means for 3% and 4% amine solutions are almost the
same, their flotation response was slightly different. At high con-
centration the amine is insoluble and a colloidal dispersion forms.
-2.5
Floor Shale For example, at a concentration of 3% amine, the collector is insol-
Roof Shale uble and a lot of colloidal amine appears. When the concentration
of amine is increased to 4%, even more colloidal amine appears. At
-3.0 this point the collector selectivity decreases and as a result, the
0 20 40 60 80 100
Saturation, % insoluble content in the trona product increases. Therefore, in this
case, the amine concentration is very critical.
Fig. 8. Electrophoretic mobility of insoluble minerals in brine.

3.2.1.6. Amine/oil ratio. The effect of dry amine to oil ratio (A/O) on
flotation of insoluble gangue minerals such as dolomite, dolomitic the flotation of trona was investigated. Flotation results with dif-
shale, quartz, shortite and clays is possible by proper control of the ferent amine to oil ratios indicate that the best concentrate grade
flotation variables such as particle size, percent solids, collector is obtained for an A/O ratio of 1:12 for the emulsion. At a dosage
chemistry and dosages including collector structure, amine dosage, of 5 kg/t of amine and 1:12 for the A/O ratio, a concentrate grade
amine to oil ratio and flotation time etc. Some of our flotation re- of about 99.5% was obtained with 91% recovery of trona (Fig. 9f).
sults have already been previously presented (Jain et al., 2006). Photographs of the trona concentrate and the insoluble tailings
The results for the flotation tests are summarized as follows. product are presented in Fig. 10. It is evident that almost all colored
impurities were removed from the trona ore in the flotation
separation.
3.2.1.1. Particle size. Flotation experiments with respect to particle
size of the flotation feed shows that the fine particles play an 3.2.2. Pilot scale tests
important role in the flotation of insolubles from trona ore. It can The pilot scale flotation experiments were carried out in the
be seen from the Fig. 9a, in the presence of fine fraction, particu- mineral processing laboratory at the University of Utah. The trona
larly 75 lm, flotation is not effective. The best separation was flotation circuit was installed in such a way as to insure that effi-
achieved for coarse particle size material. For this reason, the cient and reliable flotation experiments could be carried out. The
75 lm fraction was removed from the flotation feed. In this case, results obtained from this test showed that a trona concentrate
600  75 lm size fraction was used for the flotation tests in order of 98% purity (trona content of the feed was 82.2%) was obtained
to increase the flotation recovery. with a recovery of 75.2% using commercial amine with pilot scale
 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9 7

(a) (d) 10 100

5 100

8 80
4 80

Insoluble Content ( %)
Insoluble Content;
Insoluble Content; Insol.
Insol. 8%8%

Trona Recovery (%)

Insoluble Content (%)

3 60 6 Insoluble Content;
Insoluble Content; Insol.
Insol. 14%
14% 60

Recovery (%)
Insoluble Content;
Insoluble Content; Insol.
Insol. 27%
27%
Trona Recovery;Insol.
Trona Recovery; Insol.
8%8%
Trona Recovery;Insol.
Trona Recovery; Insol.
14% 14%
2 40 4 Trona Recovery;Insol.
Trona Recovery; Insol.
27% 27% 40

1 20 2 20
Insoluble Content (%)
Recovery(%)
Recovery (%)

0 0 0 0
50 75 100 125 150 1 2 3 4 5 6
Amount of Reagent (kg/t)
Undersize Cut Point (microns)

(b) 5 100 (e) 5 100

4 80
4 80
Insoluble Content (%)

Insoluble Content (%)

3 Insoluble Content (%) 60 Insoluble content (%)

Recovery (%)

3 60

Recovery (%)
Recovery(%)
Recovery (%) Recovery (%)

2 40 2 40

1 20 1 20

0 0 0 0
0 5 10 15 20 25 1% 2% 3% 4%
Flotation Percent Solids (%) Amine Concentration (%)

(c) 4 100
(f) 3.0 100

80 2.5
80
3
InsolubleContent
Insoluble Content(%) (%)
Insoluble Content (%)
Insoluble Content (%)

2.0
Recovery(%)(%)
Recovery (%)

Recovery
60 60
Insoluble Content (%) Recovery (%)
2 1.5
Recovery (%)
Recovery (%)

40 40
1.0

1
20 20
0.5

0 0 0.0 0
0 1 2 3 4 5 1:8 1:10 1:12 1:14 1:16
Flotation Time (min) Ratio of Amine/Kerosene

Fig. 9. Effect of (a) particle size, (b) percent solids, (c) flotation time, (d) amine dosage, (e) amine concentration, (f) amine/oil ratio.

flotation equipment. Figs. 11 and 12 show the facility for the emul- 4. Summary and conclusions
sion preparation process and the conditioning step, respectively.
Photographs presented in Figs. 13 and 14 show the flotation Results from bench-scale and pilot scale tests are compared in
concentrate product (trona) and the flotation separation of gangue Table 3. The results indicate that reverse flotation for trona recov-
minerals in the flotation cell, respectively. ery is excellent for the bench-scale system (1 L), and that it is
8 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9

Fig. 10. The pictures of flotation products: (a) Trona concentrate, (b) insoluble impurities.

Fig. 11. Facility for emulsion preparation. Fig. 13. Concentrate product.

Fig. 14. Flotation of gangue minerals.

Fig. 12. Conditioning process in trona flotation.

possible to produce a trona concentrate of 99.75% purity with a Table 3 indicate that the insoluble content of the trona feed can be
recovery of 85.5%. The reverse flotation system also works for large reduced to 2% from 17.8% with a recovery of 75.2% in pilot scale
scale batch (30 L) and continuous operation. The flotation results in batch experiments. In addition, the insoluble content of the trona
 O. Ozdemir et al. / Minerals Engineering 23 (2010) 1–9
Table 3
Comparison of trona flotation results for bench-scale, pilot scale and continuous operation.
System Cell volume (L) Trona (%)
a
Laboratory bench-scale 1 86.3
Pilot batch scaleb 30 82.2
Pilot continuous scalec 30 85.7
a
Flotation conditions: 600  75 lm feed, 75% conditioning pulp density, 3% amine concentration, 2 min conditioning time, 4 min flotation time, 1:12 amine/oil by weight,
15% flotation percent solids, 5 kg/t amine dosage.
b
Flotation conditions: 600  75 lm feed, 75% conditioning pulp density, 3% amine concentration, 2 min conditioning time, 4 min flotation time, 1:12 amine/oil by weight,
15% flotation percent solids, 4 kg/t amine dosage.
c
Flotation conditions: 600  75 lm feed, 70% conditioning pulp density, 3% amine concentration, 2–4 min conditioning time, 1:12 amine/oil by weight, 10% flotation
percent solids, 4–5 kg/t amine dosage.
feed can be reduced to 3.93% from 14.3% with a recovery of 72.1%
in pilot scale continuous experiments.
It must be pointed out that although the bench-scale experi-
ments were very good, the flotation separation was not successful
for large scale and continuous pilot-plant tests. In fact, there are
many factors, such as the flotation machine and processing vari-
ables (solids concentration, size distribution or reagent dosage)
that can affect the flotation process from small scale to large scale.
In our case, the conditioning parameters, such as particle size dis-
tribution, conditioning strength, and uniformity were well con-
trolled when the bench-scale experiments were conducted. In
the large scale flotation tests, we used the parameters obtained
from the bench-scale flotation experiments. For scale up, some of
the conditions might not have been satisfied. In addition, during
the conditioning a lot of fine particles might be generated in the
large scale flotation experiments.
It was thought that this new flotation technology could be eas-
ily integrated into the traditional sesquicarbonate process which
uses trona ore typically containing 80% trona. In this case, the high
quality trona concentrate (2–4% insolubles) from the flotation pro-
cess could be sent to the existing plant so that the existing process
efficiency and capacity would be increased significantly. It can be
concluded from these results that reverse flotation of trona can
be used for the production of a high quality trona concentrate
(more than 99%) under optimum operating conditions. The present
flotation process can yield a trona concentrate composed of up to
96% or even 99% trona. These results may indicate that the flotation
response of the insolubles in trona brine mostly depends on the
conditioning process or wetting/spreading of the emulsion on the
insoluble surface. In order to prove this, the solution chemistry
for the trona system must be considered in more detail to improve
flotation technology for the trona industry. In addition, the scale up
problem is not clear and more research work should be conducted
to optimize the scale up parameters.
As a result, improvement of this new technology could allow for
better productivity and the development of a new product for the
marketplace.
Acknowledgements
The authors wish to recognize the financial support provided by
CAST (Center for Advanced Separation Technologies) and the Office
of Basic Sciences, DOE. In addition, General Chemical is highly
appreciated for their support during this project. Finally, apprecia-
tion is extended to Ms. Dorrie Spurlock for diligent review of the
manuscript.
9
Feed insoluble (%) Concentrate insoluble (%) Trona recovery (%)
13.7 0.25 85.5
17.8 2.00 75.2
14.3 3.93 72.1
References
Becher, P., 1965. Emulsions: Theory and Practice. Reinhold Publishing Corporation,
New York, NY.
Brison, R.J., Gathje, J.C., 1981. Beneficiation of Trona by Flotation. Application: US
4283,277. Stauffer Chemical Co., USA, 5 pp.
Brison, R.J., Webber, M.E., 1982. Soda Ash. Application: US 4341,744. Stauffer
Chemical Co., USA, 12 pp (Cont-in-part of US Ser No 5644, abandoned).
Datta, R.S., Salotti, C.A., 1990. Process for Beneficiating Oil Shale using Froth
Flotation. Application: US 4968,413. Chevron Research Company, USA, 6 pp.
Du, H., Liu, J., Ozdemir, O., Nguyen, A.V., Miller, J.D., 2008. Molecular features of the
air/carbonate solution interface. Journal of Colloid and Interface Science 318 (2),
271–277.
Garrett, D.E., 1991. Natural Soda Ash; Occurrences, Processing, and Use. Van
Nostrand Reinhold, NewYork.
Garrett, D.E., White, W.R., 1970. Method for Separating Chloride, Sulfate and
Carbonate Salts, and the Like. Application: US. 3525,434, 3 pp.
Graves, C.A., Sopchak, P., 1974. Process for the Preparation of Soda Ash from Trona
Ore. Application: US 3819,805. Allied Chemical Corporation, USA, 7 pp.
Imperto, E.G., Hillard, O.H., 1983. Electrostatic Enrichment of Trona and Nacholite
Ores. Application: US 4375,454. Intermountain Research and Development
Corporation, USA, 14 pp.
Jain, A., Ozdemir, O., Wang, X., Miller, J.D., 2006. In: Acarkan, N., Onal, G., Celik, M.S.
(Eds.), Evaluation of reverse flotation for the trona industry, vol. XXIII. IMPC,
Istanbul, Turkey.
Kostick, D.S., 1994. Mineral Commodity Summaries. US Geological Survey.
Kostick, D.S., 2004. Soda Ash, United Stated Geological Survey Minerals Yearbook.
Lu, Y., Drelich, J., Miller, J.D., 1997. Wetting of francolite and quartz and its
significance in the flotation of phosphate rock. Minerals Engineering 10 (11),
1219–1231.
Ozcan, O., Miller, J.D., 2002. Flotation of sodium carbonate and sodium bicarbonate
salts from their saturated brines. Minerals Engineering 15 (8), 577–584.
Ozdemir, O., Nguyen, A.V., Nickolov, Z., Celik, M.S., Miller, J.D., 2006a. Surface
chemistry aspects of trona flotation, vol. XXIII. IMPC, Turkey.
Ozdemir, O., Karakashev, S.I., Nguyen, A.V., Miller, J.D., 2006b. Adsorption of
carbonate and bicarbonate salts at the air–brine interface. International Journal
of Mineral Processing 81 (3), 149–158.
Ozdemir, O., Celik, M.S., Nickolov, Z.S., Miller, J.D., 2007. Water structure and its
influence on the flotation of carbonate and bicarbonate salts. Journal of Colloid
and Interface Science 314 (2), 545–551.
Ozdemir, O., Karaguzel, C., Nguyen, A.V., Celik, M.S., Miller, J.D., 2009. Contact angle
and bubble attachment studies in the flotation of trona and other soluble
carbonate salts. Minerals Engineering 22 (2), 168–175.
Rosar, E.C., Hobaugh, J.R., Lepetic, V.M., 1974. Froth flotation method of separating
nacholite from ores containing nacholite. Application: US 3806,044. Industrial
Resources, Inc., USA, 4 pp.
Rosar, E.C., Hobaugh, J.R., Lepetic, V.M., 1976. Froth flotation process. Application:
US 3973,734. Industrial Resources, Inc., USA, 23 pp.
Smith, L.K., 1966. Method of producing crude soda ash from crude trona ore with
selective pulverization. Application: US 3244,476. Intermountain Research and
Development Corporation, USA, 3 pp.
Wang, X., Li, M., Miller, J.D., 2002. Flotation as a process alternative for the
treatment of trona resources, SME Annual Meeting, Phoenix, Arizona.
Wang, X., Nguyen, A.V., Miller, J.D., 2006. Selective attachment and spreading of
hydroxamic acid–alcohol collector mixtures in phosphate flotation.
International Journal of Mineral Processing 78 (2), 122–130.
Wold, J.S., Hazen, W.C., Pruzsko, R., Schmidth, R., Denham, J., Dale. L., 1999. Method
for Purification and Production of Saline Minerals from Trona. Application: US
5911,959. Environmental Projects, Inc., USA, 10 pp.