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Production of metallurgical-grade silicon from Egyptian quartz

Article in Journal of the Southern African Institute of Mining and Metallurgy · February 2018
DOI: 10.17159/2411-9717/2018/v118n2a7

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 http://dx.doi.org/10.17159/2411-9717/2018/v118n2a7

Production of metallurgical-grade
silicon from Egyptian quartz
by H.H.M. Ali*, M.H. El-Sadek*, M.B. Morsi*, K.A. El-Barawy*,
and R.M. Abou-Shahba†

2SiO2 (s, l) + SiC (s) →

#16(-4- 3SiO (g) + CO (g) [2]
Metallurgical-grade silicon (MG-Si) was successfully produced by ΔH2000°C =1364 kJ/mol
carbothermic reduction-smelting of Egyptian quartz using a mixture of
carbonaceous materials in a locally made semi-pilot submerged arc furnace. SiO2 (s, l) + Si (l) → 2SiO (g) [3]
The effects of different technical parameters such as the carbon to silica ΔH2000°C = 599 kJ/mol
ratio, smelting time, power input, and weight ratio of carbon sources were
investigated. The MG-Si product was characterized by X-ray diffraction
SiO (g) + SiC (s) → 2Si (l) + CO (g)
(XRD), X-ray fluorescence (XRF), and scanning electron microscopy (SEM). [4]
A maximum silicon recovery of about 75% at a product purity of about 97% ΔH2000°C = 167 kJ/mol
was achieved under the optimum experimental conditions of 80 minutes’
smelting time, 48 kW power input, and a carbon/silica ratio of 0.39. The slowest of these three reactions are
:5 63,- probably the SiO(g)-producing reactions [2]
metallurgical- grade silicon, carbothermic reduction, quartz, charcoal, coke, and [3], which consume a major part of the
petroleum coke. input electrical energy. Silicon can be produced
through reaction [4] at temperatures above
1811°C. The SiO gas travels upwards in the
furnace and is recovered either by reaction
91736,.07461 with the carbon material (Equation [5]) or by
Metallurgical-grade silicon (MG-Si) is an condensation where the temperature is
important metal which has a range of diverse sufficiently low (< l800°C) (reactions [2 rev.]
industrial applications such as a deoxidizer in and [3 rev.]).
steelmaking industry, alloying element in the
aluminum industry, the preparation of SiO(g) + 2C(s) → SiC(s) + CO(g)
[5]
organosilanes, and the production of hyper- ΔH2000°C = -78 kJ/mol
pure ‘electronic grade’ silicon (>99.99% Si),
which is used in the electronics industry as 3SiO (g) + CO (g) →
well as solar cells (PV Education. 2013; Aasly, 2SiO2(s,l) + SiC(s) [2 rev.]
2008). ΔH2000°C = -1380 kJ/m.ol
MG-silicon is produced by the carbothermic
reduction-smelting process, in which silica is
2SiO (g) → SiO2(s,l) + Si(l) [3 rev.]
reduced by carbon in a submerged arc furnace
at temperatures between 1300 and 2000°C ΔH2000°C = -606 kJ/mol
under atmospheric pressure. The charge
materials include a silicon source (quartz, The condensate-producing reactions
sand, or quartzite) and a typical reductant [2 rev.) and [3 rev.] are strongly exothermic
blend comprising coke, coal, charcoal, and and are the main factors that contribute to the
wood chips. The reduction process occurs upwards heat transport in the furnace.
according to the following reaction: The temperature at the top of the furnace
can vary between 1000 and 1700°C. Typical
SiO2 (s) + 2C(s) → Si(s,l) + 2CO (g) [1] industrial silicon yields are around 85% in a
ΔH2000°C = 687 kJ/mol
This overall reaction is the sum of different
reactions inside the furnace, which can be
specified according to the temperature range.
The furnace environment is divided into two * Central Metallurgical Research and Development
zones; high temperature (approx. 2000°C) and Institute (CMRDI), Egypt.
low temperature (< 1811°C) zones, in which † Faculty of Science, Al-Azhar University, Egypt.
different reactions dominate. In the high- © The Southern African Institute of Mining and
temperature zone around the electrode tip, the Metallurgy, 2018. ISSN 2225-6253. Paper received
following reactions occur: Jun. 2017; revised paper received Nov. 2017.


         
VOLUME 118   
 143
Production of metallurgical-grade silicon from Egyptian quartz
well -operated furnace. The SiO gas will only be captured by by a flowing current of water. The furnace is tilted on its
reactions [2 rev.] and [3 rev.]. The temperature has a major horizontal axis to pour the molten silicon metal at the end of
effect on the equilibrium conditions for these two reactions each experiment. The quartz sample was mixed thoroughly
Much work has been done in recent years to define the with predetermined amounts of carbonaceous materials
reaction zones inside the silicon furnace (Myrhaug, 2003; according to the following relationship.
Tangstad et al., 2010; Ringdalen and Tangstad, 2012; Asen The reduction experiments were carried out by
2012; Tangstad, 2012; Schei, Tuset, and Tvei, 1998). introducing about 10 kg of the mixture through the feeder
In Egypt, tremendous resources of high-quality sands into the furnace. After smelting, the extent of the reduction
and quartz (the average content of SiO2 is 99%) exist in Sinai process was calculated according to the following formula:
and in the Eastern Desert. Despite the huge silica resources Extent of reduction % = [(Sip/ Si0] × 100
and the availability of reductants, there is no silicon industry
where Si0 is the initial silicon content in quartz and Sip is the
in Egypt. In this paper we investigate the possibility of
produced Si metal
utilizing the local quartz resource for the production of MG-Si
by studying the factors affecting the production process, such
as carbon/silica ratio, reduction time, power input, and 5-.+7-821,8,4-0.--461
weight ratio of carbon sources. The data obtained and technical parameters affecting the
carbothermic reduction smelting of quartz to produce MG-
$"(534&5172+ silicon metal are discussed in the following sections

   

One ton of quartz from the Al Faleg area, Marsa Alam, #"#!"   !# #! "
Eastern Desert was subjected to a series of crushing cycles
To ensure a high silicon recovery, it is necessary to maintain
using a pilot jaw crusher. The particle size between 16 mm
the carbon/silica weight ratio of the charge at the required
and 2 mm was used for the production of MG-Si. XRF
stoichiometric value. A series of experiments was carried out
analysis showed that quartz consists mainly of SiO2
using mixtures of the pure crushed quartz sample with
(99.94%), with minor amounts of Fe2O3 (0.02 %), Al2O3
different proportions of coal, petroleum coke, charcoal, and
(0.02%), and MgO (0.02%).Trace amounts of other oxides
wood chips. Different ratios of fixed carbon to silica (C/SiO2)
such as CaO (0.002%), K2O (0.003%), and TiO2 (0.0002%)
ranging from 0.30 to 0.45 (i.e. from 1.5 to 2.25 molar ratio of
were detected. XRD analysis was conducted to determine the
fixed carbon to silicon dioxide) were used in this study. The
phase composition of the quartz. Figure 1 shows that all the
charges were smelted in the EAF at constant conditions of
peak positions match the standard quartz phase.
current (about 0.8 kA), voltage (about 45 V), and power
Different carbon sources such as charcoal, coal, petroleum
input (about 36 kW) for a constant smelting time of 60
coke, and wood chips (with a fixed carbon content of 45%)
minutes. The extent of reduction of silica as a function of the
were used as reductants. Table I shows the approximate
carbon/silica ratio is depicted in Figure 2. It is clear that the
chemical analysis of the carbonaceous materials.
reduction extent increases from 15% to about 30% as the
   carbon/silica ratio increases from 0.3 to 0.39 (i.e. from 1.5 to
1.95 molar ratio of fixed carbon to silicon dioxide). The
Reduction-smelting tests were performed in a locally-made
maximum recovery of MG-Si was about 30%. Increasing the
electric arc furnace (EAF). The furnace is a submerged
C/SiO2 ratio above 0.39 was accompanied by a decrease in
single-electrode (125 kW) furnace powered by five
reduction extent. It can be concluded that the optimum C/SiO2
transformers. Smelting tests were conducted in a graphite
weight ratio is about 0.39 (1.95 molar ratio of C/SiO2), which
hearth of 35 cm diameter which acts as the earth conductor,
is in good agreement with the published results (Dosaj et al.,
with a graphite rod 10 cm in diameter and 120 cm in length,
1992; Arvidson, Dosaj, and May, 1991).
located in the center of the graphite hearth, acting as the live
XRD characterization of the product metal was conducted
electrode. The graphite electrode is connected to the terminal
to ascertain the reasons for these trends. Figure 3 shows the
of the power transformer through a pure copper tube cooled
presence of the silicon carbide phase behind silicon metal in
the product from a charge containing a C/SiO2 weight ratio of

Table I

)5&402+8212+-4-886/87)58,4//5351787(5-86/
023!618.-5,82-835,.07217-

23!6187(5
62+ 57806 5 )23062+8

Moisture 0.5 0.43 3.6

Volatile matter 19.8 14.6 12.9
Ash 8.4 0.38 2.86
Fixed carbon 71.3 84.6 80.6
'4*.358%8-(5073.&86/87)58.237


144   
 VOLUME 118          

Production of metallurgical-grade silicon from Egyptian quartz

charcoal, and wood chips). In order to estimate the optimum

reductant recipe, we varied the mass of each type of
carbonaceous materials while keeping the masses of the
other types constant. The mass ratio of fixed carbon to silica
was kept constant (0.39) in all the experiments.

#"#! #!"!#!  "#

Charcoal was found to be the best reductant due to its high
reactivity, low ash content, and high electrical resistivity,
which has a positive influence on the furnace electrical
efficiency and process chemistry. A series of experiments was
carried out using charges of quartz mixed with constant
weights of coal, petroleum coke, and wood chips with
different weights of charcoal. The carbon/silica ratio was
'4*.358%$//50786/8023!61-4+40283274686187)585"751786/8#4 35,.07461 maintained at 0.39, and the applied electrical power was
about 36 kW with a smelting time of 60 minutes. Figure 4
shows the variation of the extent of silica reduction as a
function of the ratio of charcoal to silica in the charge. The
extent of reduction increased with increasing charcoal content
in the charge up to 30% by mass, and then decreased. The
initial increase in the extent of reduction is due to the high
reactivity of charcoal, which enhances the reduction process
and leads to the formation of excess silicon carbide. However,
further charcoal additions accelerate the formation of silicon
monoxide gas in the outer zone of the furnace, which escapes
from the surface of reaction and leads to a decrease in the
extent of reduction and lower recovery of silicon metal
(Vaish, 2012; Kuhlmann, 1965)

#"#! #"
#"#!  "

A series of experiments was performed in which the ratio of
petroleum.coke to quartz was varied while keeping the
'4*.358 %8(277531-86/8(36,.078/36&80)23*58061724141*8023!61#4 carbon/silica ratio constant at 0.39. The applied electrical
32746-86/8 821,8
power was about 36 kW and the smelting time 60 minutes.
Figure 5 shows the variation in the extent of reduction as a
function of the petroleum coke/quartz ratio.
0.45, which indicates that the reaction is not complete. The extent of reduction increased with increasing
However, with the charge containing a C/SiO2 weight ratio of petroleum coke additions up to about 28% by mass, after
0.39 (1.95 molar ratio of C/SiO2), only the silicon metal which further increases in petroleum coke decreased the
phase was detected. Smelting with an excess of carbon extent of reduction and the yield of silicon metal. Although
promoted the formation of an excess of silicon carbide, which petroleum coke plays an important role in the reduction
lowered the amount of silicon produced. Subsequently, process, it contains ash with a low iron content and much
silicon carbide accumulated and filled the hearth of the finer material. The introduction of these fines into the
furnace, which made it necessary to raise the electrode,
which increased the temperature in the outer zone of the
furnace. This will lead to an increase in the electrode
consumption. Therefore, it is important for efficient furnace
operation that the furnace is kept in carbon balance (Dosaj et
al., 1992).

#"#!"##"#   #" "#!#"!

!"   !# #! "#
There is no doubt that the carbonaceous reductant in the mix
should have a minimum ash content, large reactive surface,
low volatile matter content, high electrical resistance, and
sufficient mechanical strength for achieving a good silicon
yield with acceptable purity. A primary factor affecting the
efficiency of the silica reduction process is the reactivity of
the carbon reductants. Based on reactivity, purity, and the
cost of the reductant, we investigated mixtures of different
'4*.358 %$//50786/80)23062+8768.2378327468278061-72178023!61-4+402
types of carbonaceous materials (coal, petroleum coke, 3274686187)585"751786/835,.074618


         
VOLUME 118   
 145
Production of metallurgical-grade silicon from Egyptian quartz
20% to 75% as the power input was increased from 30 to 48
kW. With further increases in power, silicon recovery
decreased, falling to about 30% at 60 kW power input.
The optimum recovery of about 75% of MG-Si was
obtained at a power input of 48 kW. This may be due to the
power input being sufficient to increase the furnace
temperature to a level that enhances the reaction between SiO
gas and SiC to form silicon metal. Higher power inputs, and
higher temperatures, lead to the formation of excess SiO gas

'4*.358 %$//50786/8(5736+5.&806 58768.2378327468278061-7217

023!61-4+40283274686187)585"751786/835,.074618

furnace results in poor furnace efficiency because it reduces

the porosity of the charge, leading to the entrainment and
subsequent blowing out of the fines with the furnace off-gas
(Kuhlmann, 1965).

#"#! #"!#!  "

Coal has a high electrical resistance and negligible quantities '4*.358%$//50786/8062+8768.2378327468278061-72178/4"5,8023!61-4+402
of volatile matter, but contains undesirable impurities such as 3274686187)585"751786/835,.074618
iron. Figure 6 shows the extent of reduction as a function of
the coal/quartz ratio. The extent of reduction increases with
increasing coal additions until about 28% yield, beyond
which the yield decreases with further coal additions. This
may be due to the coal containing from about 5 to 15% ash
(25% of which is iron oxide). The iron partitions into the
silicon metal and affects the purity of the product (Kuhlmann,
1965).
From these results, the optimum charge composition was
determined to be 64.63 wt.% quartz, 4.08 wt.% coal, 12.6
wt.% charcoal, 11.77 wt.% petroleum coke, and 6.92 wt.%
wood chips.

   

A series of smelting experiments was conducted on charges
containing 64.63 wt.% quartz, 4.08 wt.% coal, 12.6 wt.%
charcoal, 11.77 wt.% petroleum coke, and 6.92 wt.% wood '4*.358%$//50786/8-&5+741*874&586187)585"751786/835,.074618
chips at a C/SiO2 ratio of 0.39 and power input of 36 kW,
while varying the smelting time from 60 to 90 minutes. It
was found (Figure 7) that the recovery of silicon metal
increased from 28 to 40% as the smelting time was increased
from 60 to 80 minutes. Further increases in smelting time up
to 90 minutes decreased the silicon recovery to about 20%.
This sharp decrease is due to the evaporation of the silicon
metal product in the form of silica fumes as a result of the
long smelting time. The optimum smelting time of 80
minutes yielded a silicon recovery of about 40%.



The smelting process was investigated at different power
inputs ranging from 30 to 60 kW using charges having a
C/SiO2 ratio of 0.39 and a constant smelting time of 80
minutes. Figure 8 illustrates the variation in silicon recovery
with power input. Silicon recovery was increased from about '4*.358%$//50786/8-&5+741*8(6 5386187)585"751786/835,.074618


146   
 VOLUME 118          

Production of metallurgical-grade silicon from Egyptian quartz
and consequently increase the silica loss (Mitsuhiro and """#
Hirasawa, 2000).
Scanning electron microscopy (SEM) images of the MG-
   silicon product are shown in Figure 11. A general distribution
of silicon metal grains with traces of iron at the grain
Figure 9 displays photographs of the MG-silicon product
boundaries is evident.
obtained at the optimum reduction-smelting conditions
(carbon/silica mass ratio 0.39, smelting time 80 minutes, and
power input 48 kW). The microstructure and chemical 610+.-461-
composition were investigated using XRD, SEM, and XRF. MG-Si was produced from Egyptian quartz using a locally
made submerged arc furnace, with a recovery of about 75%
 !# ! "#  and product purity of about 97% silicon.
Figure 10 shows the XRD spectrum of the MG-Si produced The optimum conditions for production of MG-Si are
under optimum conditions, which indicates the presence of summarized as follows:
silicon metal only.  Carbon/silica weight ratio (C/SiO2) 0.39
 Charge composition quartz 64.63 wt.%, coal 4.08 wt.%,
 !#"# 
charcoal 12.6 wt.%, petroleum coke 11.77 wt.%, and
The MG-silicon was chemically analysed by XRF to determine wood chips 6.92 wt.%
its purity. The results are summarized in Table II. The MG-  Smelting time 80 minutes
silicon product contained about 97% Si and 1.15% Fe, with  Power input 48 kWh
traces of other elements. It is clear that the MG-Si product  Electrical energy consumption approx. 19 kWh/kg of
had low traces of P, and it is noteworthy that no boron was silicon metal produced
detected. It is known that most impurities such as Fe, Al, and  Electrode consumption 0.11 kg/kg of silicon metal
Ti, contained in the raw materials are transferred to the MG- produced
silicon product.  Silicon metal purity about 97%.

5/535105-
AASLY, K. 2008. Properties and behavior of quartz for the silicon process PhD
dissertation, Norwegian University of Science and Technology,
Trondheim.

'4*.358%)676*32()-86/8 #48(36,.07

'4*.358%8-(5073.&86/8 -4+40618(36,.05,82786(74&.&
061,47461- '4*.358%#$ 8&4036*32()-86/87)58 -4+40618(36,.07

Table II

'8212+-4-86/8 #48(36,.078 7

#4 + '5 2 2 4  1 . #
4

96.94 0.393 1.153 1.085 0.013 0.035 0.028 0.028 0.102 0.012 0.186


         
VOLUME 118   
 147
Production of metallurgical-grade silicon from Egyptian quartz
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