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LOW IRON SILICA SAND FOR GLASSMAKING

Conference Paper · January 2011

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 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760

LOW IRON SILICA SAND FOR GLASSMAKING

A. Valchev1, M. Marinov1, I. Grigorova2, I. Nishkov2

1 Kaolin AD, 7038 Senovo, Rousse distr., Bulgaria

2 University of Mining and Geology “St.Ivan Rilski”, Department of Mineral Processing and

Recycling, 1700 Sofia, Bulgaria

ABSTRACT
The Bulgarian deposits of quartz-kaolin raw materials are localized in the eastern part of the Danube
plain. This raw material is a mixture of quartz sand and kaolin in a ratio approximately 4:1 and is mine
in open pits. After wet separation the quartz-kaolin sand yields two products – washed kaolin
(different grades) and silica sand (different grades).
Research and development program has started to improve silica sand quality for glass industry by
reducing the amount of impurities, especially iron and titanium, which color glass. For all glasses, the
consistence of the chemical components and size characteristics are important to producing high
quality glass. The three main chemical contaminates in silica sand are usually the iron content
expressed as Fe2O3, the alumina content expressed as Al2O3 and titanium expressed as TiO2. In an
effort to reduce the cost of collectors and change the flotation pH-range from 2.5 to 7, various
alternative collectors have been considered as replacements for the existing suite of Cytec promoters.
A series of laboratory and pilot tests were conducted to compare the performance of different
separation alternatives – attrition scrubbing, desliming, reverse flotation and high intensity magnetic
separation. The experimental results show that there are possibilities to obtain the silica sand for
glassmaking with low content of Fe2O3 - below 0.015 %. On the basis of test results new technology for
silica sand treatment was developed.

1. INTRODUCTION
The main raw material mined in the open pits of KAOLIN AD and processed in the company ’s
plants is quartz-kaolin sands. They are mined from several deposits situated in the eastern
part of the Danube plain. This raw material is a mixture of quartz sand and kaolin in a ratio
approximately 4:1.
The geological structure of quartz-kaolin sand consists of carbonate sediments from the
early Cretaceous period. In the subsequent raising, the erosion revealed Barramian and
Aptian rocks on the earth’s surface. These limestones formed a large pleokarstics complex
with vast drops. As a result of some adjacent areas erosion, the lowerings were gradually with
quartz and feldspar grains. The chemical weathering transformed this material into the now-
existing weakly cemented quartz-kaolin sands. A layer of Quaternary red clay and loess covers
all of these materials.
KAOLIN AD is a company which main line of business is mining of industrial minerals. The
company is a leader in industrial minerals production in Bulgaria. The main manufactured
products are: different grades of kaolin, silica sand, chamotte, feldspar, carbonate fillers and
ceramic read body. KAOLIN AD is the first sand producer in Eastern Europe and the forth
largest producer of sand in Europe. The company controls 1 % of the world’s kaolin reserves
and is the first kaolin producer in South-Easter Europe and the second chamotte producer in
Europe.
For a many years, the quartz-kaolin sand separation has been performing by water
washing technology. After wet separation the raw material yields two products – washed
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760
kaolin (different grades) and quartz sand (different grades). The manufacturing process
includes: disintegration; three stages spiral classification; two stages hydrocyclone
classification and dewatering of kaolin grades; hydroclassification; several stages sizing using
drum screens, glass sand reverse flotation and dewatering of quartz sand grades.
The grades of silica sand produced by the company are: silica sand for glass industry,
ground sand for sanitary ware, silica sand for moulding, dry silica sand and gladded sand.
Silica sand is the most common ingredient in glass. Whether the glass is container glass,
window glass, boro-silicate glass, fiberglass or water glass (sodium silicate), silica sand makes
up approximately 60 – 70 % of the glass batch and therefore has a significant affect on the
glass quality.
The glass industry has established different standard specifications for the silica sand
intended for seven types of glass. For all glasses, the consistency of the chemical components
and size characteristics are important to producing high quality glass. The three main
chemical contaminates in silica sand are usually the iron content expressed as Fe2O3, the
alumina content expressed as Al2O3 and titanium expressed TiO2.
The presence of metallic oxides in glassmaking sands usually results in colored glass. If iron
is present, the resulting glass is colored green or brown. The iron level is consequently the
most critical parameter in determining whether particular sand can be used to make clear
glass. In ascending order of permitted iron content, the three most commonly produced
categories of glass are: colorless container glass (or `flint' glass); clear flat glass (or `float'
glass) and colored container glass.
Many processing techniques are used in processing silica sand. The techniques consist of
both wet and dry processes, and at times, process combinations to produce an acceptable
product (Sekulic et al., 2004; Bayat and Akarsu, 2002; Mowla et al., 2008).
• Washing is the simplest and lowest cost method of cleaning silica sand. In some of the
very pure deposits that are void of heavy minerals, high amounts of clay and silt, and no
surface staining, washing is sufficient to produce acceptable grade product.
• Attrition scrubbing is used when the clay or silts are more tightly bound to the silica
grains, or clay particles are similar in size to the silica grains. This process gives a possibility
for removing iron hydroxide coats from the quartz grains. For proper attrition scrubbing, it is
important that the solid percentage of slurry be within a range of 72-75 % solids. At this
content, there is good particle-to-particle contact and the viscosity of the slurry is low enough
to allow the slurry to move freely in the attrition-scrubbing tank. Typical scrubbing times are
approximately 5 minutes. However, the actual retention time can vary considerably
depending on the amount and type of material that needs to be liberated.
• Disliming is the process that removes the fines These slimes are generally clay type
minerals, fine iron hydroxide coats or very fine silica that is detrimental to the glass making
process. Although there are many different methods of desliming, only two are widely used in
the industry – cyclones and hydrosizers. Cyclones are low cost and effective in removing the
fines from silica sand when the “– 100 µm” material does not exceed 3 wt%. Typically,
cyclones remove 80 - 90 % of the “– 100 µm” fraction in the feed. For feeds that have more
than 4 -5 wt% “– 100 µm” material, or when there is a need to remove all or part of the “– 150
µm” material, the best equipment is the hydrosizer.
• Sizing for glass sand is extremely critical in order to make high quality glass product.
Normally ranging between 0.1 and 0.5 mm in diameter, that in the case of glassmaking sands.
Sizing to provide a sand product that is less than 0.5 mm is typically conducted with a screen
or hydrosizer. The allowable material above 0.5 mm has been greatly reduced in the last 25 -
30 years. It was not uncommon in the past for the glass producers to allow 5 wt% “+0.5 mm”
in the specifications for glass sands. Today, they are pushing the limit to 0 percent on “+0.5
mm” with specification now being proposed with limits on the 0.4 mm screen. High frequency
screens supplied by companies like Derrick or Rotex are generally used to make the 0.5 mm
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760
separation. The high capacity screens employ several screen decks within one machine unit.
The system employees a feed distribution system that evenly feeds all screen decks
simultaneously.
• Gravity separation for glass sands are limited to spirals since other gravity separation
processes, such as enhanced gravity separators are too expensive to operate or processes
such shaking tables that are too low capacity for glass sands, are not cost effective. Spirals are
capable of separating heavy mineral particles from glass sands to lower the iron content.
Generally, specific gravity differences of greater than o.5 to 1.0 units are required to make an
effective separation.
• Froth flotation is primarily used to remove the iron bearing minerals and hydroxides
coats removed after attrition scrubbing from quartz grains. A reverse flotation method is
applied to separate tailings containing iron bearing minerals and hydroxides coats from silica
sand concentrate using several cleaning stages. In this process, the pH is generally in the 2 – 3
range and the most widely used reagents for acid circuit flotation are anionic petroleum
sulfonate promoters.
Research and development program has started to improve the quality of glass silica sand
by decreasing the iron impurities and reduce the manufacturing costs. This paper describes
the results on an experimental work in the frame of the research program.

2. EXPERIMENTAL
The quartz-kaolin raw material in Kaolinovo site, Shumen region, Bulgaria is mined in two
open pits.
The silica-kaolin sand separation has been performing by water washing technology in the
processing plant Kaolinovo.
After wet separation two products are obtained: kaolin for porcelain-faience and ceramic
industries and silica sand for glass and sanitary ware industries. The flotation technology is
used in two cleaning stages to produce glass silica sand with low iron content. The production
flow sheet of glassmaking sand is given in Fig.1.
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760

Figure 1. Glassmaking sand production flow sheet

After scavenger classification in mechanical classifier the silica sand with 0.024 % Fe 2O3
and 75 – 80 wt% solids is introduced to an attrition scrubber. Additional water is added in
attrition-scrubbing tank to reduce the pulp density to 68 – 70 wt%. The attrition time is 4
minutes. Before desliming the solid pulp density is reduced with additional water. Desliming
process for remove the fines is realized in 250 mm hydrocyclone. The overflows are pumped
via tailings pool. The underflow sand is introduced to a conditioning tank.
The pulp pH is adjusted to 2.5 -2.7 using concentrated sulfuric acid. Two Cytec promoters are
added in solution 10 %. The conditioning time is 12 min at pulp density - 40 wt% solids. Then,
the reverse flotation is realized in two stages. After conditioning the feed is introduced into
two flotation machines, consecutively. The floated iron bearing minerals from the both stages
are final tails. The froth products are neutralized to pH 7 using 10 % sodium carbonate and
are pumped via tailings pool.
The low iron content silica sand recovered by flotation is neutralized to pH 7 using 10 %
Na2CO3 and then goes to spiral classifier for dewatering. The final product – glassmaking silica
sand is with low content of Fe2O3 – less 0.015 %.
In an effort to reduce the cost of collectors and change the flotation pH-range from 2.5 to 7,
various alternative collectors have been considered as replacements for the existing suite of
Cytec promoters. A series of laboratory and pilot tests using the KAOLIN AD experimental
facilities were conducted to compare the performance of different separation alternatives –
attrition scrubbing, desliming and reverse flotation and high intensity magnetic separation.
A bulk silica sand sample for glassmaking Grade A3 was taken from Kaolinovo processing
plant to reduce the iron content. The particle size distribution was determined by wet sieving
using vibratory sieve shaker Analysete 3, FRITSCH. The sample chemical analysis was
performed by an Inductively Coupled Plasma Spectrometer (ICP-AES).
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760
Two different combinations of processing techniques were carried out to produce acceptable
grade glassmaking sand.
• Attrition scrubbing and magnetic separation
Attrition scrubbing experiments were conducted in the laboratory using Netzsch PE5
dissolver under the predetermined optimum conditions up to 70 wt% solid pulp density, 850
rpm motor speed and 5 min attrition time. After attrition scrubbing the silica sand sample was
treated by wet magnetic separation using Carpco® Wet Laboratory High-Intensity Magnetic
Separator Model 3x4 L with coil current of 3.8 A and spheres of 12.5 mm.
• Attrition scrubbing and reverse flotation
Silica sand flotation is primarily used to remove the iron bearing heavy minerals and
hydroxide coats removed after attrition scrubbing from quartz grains. To reduce the cost of
collectors and change the flotation pH-range from 2.5 to 7, various collectors have been tested
as replacements for the existing suite of Cytec promoters. The reverse flotation (collecting
gangue into froth) tests were conducted using a Sl-135-Fl laboratory flotation machine in a
2.8 dm3 cell. Tap water was used throughout the experiments at pH - 7. Conditioning and
flotation time were 12 and 15 min, respectively.

3. RESULTS AND DISCUSSIONS

The chemical analyses data and the particle size distribution data of silica sand sample Grade
A3 are presented in Tables 1 and 2.

Table 1. Silica sand chemical composition.

Grades Content, %
SiO2 99.32
Al2O3 0.31
Fe2O3 0.024
TiO2 0,072
CaO 0,026
MgO 0,006
K2O 0,022
Na2O 0,012
L.o.i. 0.24

Table 2. Silica sand particle size distribution and Fe2O3 grade.

Particle size Yield, Grade of
fraction, wt% Fe2O3,
µm %
+ 500 0.40 0.034
- 500 + 315 16.99 0.017
- 315 + 250 27.15 0.016
- 250 + 160 44.62 0.020
- 160 + 125 7.69 0.051
- 125 3.15 0.12
Total 100.00 0.024

The data of particle size distribution clearly demonstrate that the silica sand Grade A3 fit into
known quality standard specifications. The pointed granulometry is suitable for all types of
glass production. The performed chemical analysis shows that the iron content in silica sand
is too high – 0.024 % Fe2O3. The iron is concentrate in the fines (- 125 µm) and in coarser
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760
grains (+ 500 µm), respectively 0.12 % and 0.034 % Fe2O3. The lowest iron content is in the
fraction “- 315 + 250 µm” - 0.016 % Fe2O3.
The attrition scrubbing and magnetic separation test data of silica sand sample Grade A3
are presented in Table 3.

Table 3. Attrition scrubbing and magnetic separation test data.

Product Content, %
Al2O3 Fe2O3 TiO2
Head quartz sand 0.31 0.024 0.072
sample
Quartz after 0.18 0.012 0.031
attrition scrubbing
and magnetic
separation

The results show that there is decreasing of Al2O3, Fe2O3 and TiO2 grades after attrition
scrubbing and high intensity magnetic separation. The content of Fe2O3 is decreased from
0.024 % to 0.012 %. This drop is overage 50 % compared to the head sand samples. The same
trend applies to the grade of TiO2.
Laboratory reverse floatation (collecting gangue into froth) tests were conducted after
silica sand attrition scrubbing. The best results are obtained using the reagent kindly supplied
by COGNIS for this study – fatty acid sulfonate and rapeseed fatty acid with low erucic content.
The optimum reagent dosage rates were established. The flotation test data of silica sand
samples are presented in Table 4.

Table 4. Attrition scrubbing and flotation test data.

Product Content, %
Al2O3 Fe2O3 TiO2
Head quartz 0.31 0.024 0.072
sand sample
Quartz after 0.15 0.010 0.026
attrition
scrubbing and
reverse flotation

The results show that there are possibilities to reduce the amount of iron impurities using
attrition scrubbing and reverse flotation at pH -7. The reduction of Fe2O3 content is about 58
% compared to the head silica sand sample. The same trend applies to the grades of TiO2 and
Al2O3.

4. APPLICATION RANGE
Based on the characterization data of silica sand Grade A3 and the laboratory study results a
silica sand deferrization flotation technology at pH -7 was developed.
The flowsheet silica sand treatment is given in Fig.2.
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760

Figure 2. New glassmaking sand production flow sheet

The silica sand Grade A3 is introduced to an attrition scrubber machine. The iron content of in
silica sand Grade A3 is 0.024 % Fe2O3 and the pulp density is 75 – 80 wt% solids. Additional
water is added in attrition-scrubbing tank to reduce the pulp density to 68 – 70 wt%. At this
content, there is good particle-to-particle contact and the viscosity of the slurry is low enough
to allow the slurry to move freely in the attrition-scrubbing tank. The attrition time is 4
minutes. The process gives a possibility for removing iron hydroxide coats from the quartz
grains. Then the solid pulp density is reduced with additional water.
Desliming process for remove the fines is realized in 250 mm hydrocyclone. The overflows
are pumped via tailings pool. The underflow sand is introduced to a conditioning tank. The
required amount of flotation reagents are added at pH - 7.
The conditioning time is 12 min at pulp density - 40 wt% solids. Then, the reverse flotation
collecting gangue into froth is realized in two stages. After conditioning the feed is introduced
into two flotation machines, consecutively. The floated iron bearing minerals from the both
stages are final tails. The froth products are pumped via tailings pool. The low iron content
silica sand recovered by reverse flotation goes to spiral classifier for dewatering. The final
product – glassmaking silica sand is with low content of Fe2O3 – less 0.015 %.
 Proc. of XXII World Mining Congress, Vol. III, Istanbul, Turkey, 2011, pp. 755-760

5. CONCLUTIONS
From the results obtained in laboratory and plant trials, the following conclusions are
deduced:
The flotation recovery-grade data (Fe2O3 content of the silica sand concentrate) for new
collectors is better than those of the existing collectors and the combination of attrition
scrubbing and magnetic separation.
Since the cost of the exiting collectors is much higher than the new collectors, there is a
significant cost advantage.
Consequently, the company has decided to introduce the new collectors at pH 7 in new
silica sand treatment technology.

ACKNOWLEDGEMENT
Financial support for this studies and permission to publish this paper from KAOLIN AD is
gratefully acknowledged.

REFERENCES
Sekulic, Z., Canic, N., Bartulovic, Z., Dakovic, A. (2004). Application of different collectors in the
flotation concentration of feldspar, mica and quartz sand. Minerals Engineering, 17, 77-80.
Bayat, O., Akarsu, H. (2002). Evaluation of new collectors for silica/glass sand and statistical analysis of
plant trials. Minerals Engineering, 15, 293-296.
Mowla, D., Karimi, G., Ostadnezhas, K. (2008). Removal of hematite from silica sand ore by reverse
flotation technique. Separation purification technology, 58, 419-423.

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