See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/324836553

Influence of Thermal Stability of Quartz and the Particle Size distribution of

Burden Materials on the Process of Electrothermal Smelting of
Metallurgical Silicon

Article in Oriental Journal Of Chemistry · April 2018

DOI: 10.13005/ojc/340265

CITATIONS READS

7 891

5 authors, including:

Zobnin Nikolay
Ansa Silicon
6 PUBLICATIONS 11 CITATIONS

SEE PROFILE

All content following this page was uploaded by Zobnin Nikolay on 23 September 2019.

The user has requested enhancement of the downloaded file.

 ISSN: 0970-020 X
ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG
An International Open Free Access, Peer Reviewed Research Journal
2018, Vol. 34, No.(2):
Pg. 1120-1125
www.orientjchem.org

Influence of Thermal Stability of Quartz and the Particle

Size distribution of Burden Materials on the Process
of Electrothermal Smelting of Metallurgical Silicon
NIKOLAY NIKOLAYEVICH ZOBNIN*, ANATOLIY KORNEYEVICH TORGOVETS,
IRINA ANATOLYEVNA PIKALOVA,YULIYA SERGEYEVNA YUSSUPOVA,
and SERGEY ASIFOGLY ATAKISHIYEV

Karaganda State Industrial University, Kazakhstan, 101400, Temirtau, Republic Avenue, 30

Tau-Ken-Temir LLP, Kazakhstan, 100018, Karaganda,Oktyabrsky district, Accounting
quarter 018, building 133, Kazakhstan.
*Corresponding author E-mail: [email protected]

http://dx.doi.org/10.13005/ojc/340265

(Received: December 26, 2018; Accepted: February 01, 2018)

ABSTRACT

The article describes the thermal stability of quartz deposits in Kazakhstan-Aktas and
Sarykul. It is established that the quartz of the Aktas deposit is a raw material with low thermal
stability, and quartz is of medium-durability at Sarykul deposit. The complex influence of the
thermal stability of this raw material on the technological parameters of smelting of technical silicon
under experimental industrial conditions of electrothermal melting in a furnace with a capacity of 30
MVA was studied at LLP “Tau-Ken-Temir” (Kazakhstan). A new method for optimizing the smelting
of commercial silicon has been developed, even when using raw materials with low thermal
stability. The main idea of the method is that the less thermally stable quartz is used, the more the
initial size of its pieces should be. Optimum values of the average size of pieces of quartz-Aktas-
(85-95 mm) and Sarykul-(30-40 mm) are obtained.

Keywords: Thermal stability, Quartz, Technical silicon, Smelting.

INTRODUCTION in the process of smelting of technical silicon, when

quartz is loaded into the furnace. This is explained
Many researchers have studied the by phase transitions. The leading role here belongs
phenomenon of change in the granulometric to the conversion of quartz into its modification -
composition of natural quartz as a result of thermal crystobalite5. This transformation is accompanied
shock1-4. This phenomenon is observed practically by a change in the volume of the material. The

This is an Open Access article licensed under a Creative Commons Attribution-NonCommercial-ShareAlike

4.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/ ), which permits unrestricted
NonCommercial use, distribution and reproduction in any medium, provided the original work is properly cited.
 ZOBNIN et al., Orient. J. Chem., Vol. 34(2), 1120-1125 (2018) 1121

change in volume leads to a violation of the integrity MATERIAL AND METHOD

of quartz crystals and the conversion of lump
material into dust. The stability of natural quartz to The traditional method for determination
similar transformations was called - thermal stability. of thermal stability of quartz includes heating it in a
The formation of dust disrupts the silicon reduction furnace to a temperature of 1300 0C and keeping
process in the furnace. This violation is caused by siliceous pieces of material sized 20-30 mm for one
the removal of dust particles from the furnace by hour there 1-3 . If, after cooling,we can notice
rising gas flows. At the same time, the specific energy substantial destruction of material, then this product
consumption becomes higher than 12 MW * h / t, is considered to be of poor quality for the
the recovery of silicon decreases below 80-85%, metallurgical process. If this does not happen, then
and the yield of siliceous dust becomes more than we shall continue with the rotation of raw quartz in a
500 kg / t of technical silicon. Most of the earlier drum (for 2 min. with the drum rotation speed of 40
studies were carried out on a laboratory scale. The RPM) with the subsequent classification of
study of the effect of quartz thermal stability on the investigated material on sieves sized of 20 mm, 10
quartz melting indices in industrial conditions is mm, 4 mm and 2 mm. If there is extensive destruction
complex in terms of organization and a costly (much of the material was less than 10 mm), this
experiment. However, it is necessary to find ways stuff will work in an ore-thermal furnace worse than
to solve the problems that arise when using quartz heat-resistant quartz. Source5 results data for the
with low thermal stability. study of thermal stability of silica raw material only
by using heating of samples without subsequent
machining in a rotating drum.
Probably the effect of thermal stability of
quartz should be considered in conjunction with LLP “Tau-Ken-Temir” (Kazakhstan) has
the granulometric composition of the raw materials. problems with optimization of the process of
There are different opinions about the size of the production of technical silicon. The company has
raw material particles necessary to achieve optimal been working since 2010 in Karaganda. The raw-
melting points. In the literature, there are indications material base of the enterprise is the deposit of
that quartz particles, for melting in furnaces with a quartz “Aktas”, located in Ulytau region of
capacity of 6.5 MVA - 22.5, should be 20-80 mm4, 6; Karaganda oblast, 130 km north-west of
the source6 claims that the size of the quartz particles Zhezkazgan. The quartz from this deposit is of high
should be 20-100 mm, and the rest of the text has a purity, making it the most attractive raw material for
recommendation for quartz 4-100 mm and 10-100 smelting technical silicon of the highest marks. Total
mm. The particle size of green coke should be 2-15 stock of quartz on the field is over 4 million tons,
with an annual production volume of 72 thousand
mm according to one author8, and in another6 -8-25
tons of veined quartz8.
mm and here6 0-80 mm. For charcoal, the size of
the fraction should be 6-80 mm 6, according to In addition, the state deposits balance of
another source - 580 mm8. Coal is recommended the Republic of Kazakhstan as on 01.01.2011 takes
in fraction 0-80 mm6, chip size - 30 * 100 mm8. The into account information about the holdings of 19
greatest divergence is observed with granulometric deposits of rock crystal and quartz raw materials, of
composition of quartz and green coke. The most which 3 are Akshoky-JSC “SPK” , Saryarka
common ideas are about the granulometric “(Karaganda Oblast) and Sarykul-quartz” LLP
composition of charcoal. Doubts arise because the (Almaty region). Balance reserves of quartz raw
recommended limits for these materials allow materials as on 01.01.2011 on amount of categories
varying the particle size in 10-12 times. Probably, A+B+C1 are: Crysorber -1679.9 t, piezooptic quartz
the optimal granulometric composition of raw -1891 kg/monoblock, rock crystal-591.1 t, milky white
materials is not a constant value and depends on veined quartz -8082.01thousand t, granulated
the design features of the furnace smelting space, quartz-104 thousand t.; category C2: Crysorber-
electrical parameters of the furnace transformer and 1203.2 t, piezooptic quartz -1432 kg/monoblock,
the thermal stability of quartz. In each case, it is rock crystal-168.2 t, milky white veined quartz- 621.4
necessary to optimize the particle size distribution. thousand t9.
1122 ZOBNIN et al., Orient. J. Chem., Vol. 34(2), 1120-1125 (2018)

On LLP “Tau-Ken-Temir”reportingfor 2016, pieces. In this case, the raw materials will manage
annual techno-economic indexes of silicon smelting to pour down fromthe throat into the zone of
from Aktas quartz were the following: the intensive chemical reactions before they
technological consumption of electricity per silicon disintegrate into dust. Laboratory research was
fractions 0-300 mm-16.0 MW*h/t, extraction of
conducted on thermal stability of quartz from Aktas
silicon in metal-64.8%, silica fume outlet-1 t/t silicon.
Such indicators significantly worsened the and Sarykul deposits and industrial research of the
production economy. The basic idea of the planned influence of the particle size distribution of burden
study was that the lower the thermal resistance of materials on technical-economic indicatorsof the
quartz is, the greater must be the original size of its production when using quartz from these deposits.
Table 1: The chemical composition of quartz from Sarykul and Aktas deposits for the
period of studies

The name of quartz Chemical composition,%

SiO2 Fe2O3 Al2O3 CaO TiO2

Aktas 99.88 0.03 0.08 0.004 0.003
Sarykul 99.91 0.06 0.01 0.01 0.001

Laboratory studies on the thermal stability highly influencing the specific energy consumption.
of quartz was conducted in strict accordance with “SMS Demag” has optimized the high current line
the manufacturer’s recommendations, ore-thermal system in such a way that minimizes the reactance
furnaces installed in LLP “Tau-Ken-Temir”- SMSDemag of the system and reducing the off-times due to
(Germany). The company “SMS Demag” gives maintenance purposes Figure.1.11.
granulometric curves obtained from the tests on
the quartz with low, medium and high temperature
resistance (unpublished data).

These curves allow judging the suitability

of thequartz raw material,validated with this
technique, for smelting technical silicon.

The chemical composition of Aktas quartz

used during this study is listed in Table 1. The Fig. 1. Simulation of high current system
content of solid carbon: semi-coke -85-88%, including electrodes11
coal -48-52%, charcoal-89-92%. Ash content of all
reducing agents ranged from 1.5% to5.5%. Table 2 shows the electrical characteristics
The composition of the burden: quartz-700 kg, of the furnace transformers used in the study. The
charcoal-214 kg, coal from Shubarkul deposits -118 kg, working stage of the transformer was the 14th stage.
Karaganda green coke -70 kg, wood chips-253 kg. Electric smelting process mode: rated secondary
voltage - 215 in (102-105 in with the “landing”),
The study was carried out on one of the operating current electrode 70-75 kA, active power
two three-electrode ore-thermal furnaces with furnace 17-18, MVA, cos(ϕ)= 0.70 -0.75. Thanks to
capacity of 30 MVA. The furnace is powered by the innovative scheme for connecting transformers,
three furnace transformers with capacity of 10 MVA the value of the phase current is ƒ3 times higher
each. The transformers are connected individually than the nominal value in Table 2.
to each electrode, and each transformer is
Geometrical parameters: the diameter of
connected via two electrodes. This means, for
a smelting bath-6900 mm, total bath depth -3246
example, that there is no possibility of increasing
capacity at only one electrode by increasing mm, height of graphite blocks of crucible part-1400
capacity on one transformer. The design and the mm, diameter of graphite electrodes-1272 mm,
material for the high current line, including the distance between the axis of the electrodes-2900
electrode column as well as for the furnace roof are 3250 mm (during the tests it reached maximum).
 ZOBNIN et al., Orient. J. Chem., Vol. 34(2), 1120-1125 (2018) 1123

Table 2: Electrical characteristics of the furnace transformers

Stage Power, kV*A High voltage side Low voltage side

Voltage, V Current, A Voltage, V Current, A

1 7088 202.5 145.0

2 7352 210.1 150.4
3 7617 217.6 155.8
4 7882 225.2 161.3
5 8147 232.8 166.7
6 8411 240.3 172.1

48880
7 8876 247.9 177.5
8 8941 255.5 182.9
9 9206 263.0 188.3
10 9470 270.6 193.8
11 9735 278.1 199.2
12 204.6
35000

13a
13b 210.0 47619
13c
14 215.4 46422
15 220.8 45283
16 226.3 44199
10000

17 231.7 43165
18 237.1 42179
285.7

19 242.5 41237
20 247.9 40336
21 253.3 39474
22 258.8 38647
23 264.2 37855
24 269.6 37094
25 275.0 36364

The furnace bath provides the rotation maintenance of the grain-size composition of
speed of 5-15 days to one turn. Granulometric carbonaceous reducing agents at a constant level
composition of other materials is maintained at a has been one of the most technically complex tasks
constant level. The relevant data are shown in Table in this study.
3. The usedwood chips size is 35 * 100 mm. The
Table 3: Granulometric parameters of carbonaceous reducing agents taken in the
research process

Material Granulometric parameters

designation The main Exit of “trivia” Exit of “trivia” with Average logarithmic diameter
fraction with diameter less diameter less than the of particles at the endpoint
mm than the lower limit lower limit at the endpoint of burden batching, mm
on input data,% of burden batching,%

Coal from 10-15 3.4 15.8 11.6

Shubarkul
deposits
Charcoal 5-100 4.9 32.5 36.5
Karaganda
semi-coke 5-20 1.9 11.3 18.3
1124 ZOBNIN et al., Orient. J. Chem., Vol. 34(2), 1120-1125 (2018)

RESULTS AND DISCUSSION The speed of these processes should be

roughly equal. In our case, melting of the surface of
Figure. 2 presents comparative granulometric quartz particles has led to their merging into a single
curves according to “SMS Demag” and the results mass, and to overfilling the throat withsolid slag
of the laboratory study of thermal Aktas and Sarykul with a high concentration of silicon oxide.Sufficient
Quartz. As can be seen from the data presented, organizational work was carried out with raw
Aktas quartz with fractions 2-10 mm, obtained as material suppliers, and several batches of quartz
the result of research work, can be called raw from both deposits with different fractional
materials with high thermal durability. However, its composition were formed. Several experimental
indicators deviatein the direction of quartz with low smelting campaigns were held, during which an
strength, and in the area of 20 mm they cross the average logarithmic diameter of quartz pieces was
characteristic curve of the quartz with the lowest ranged.
indicators. Sarykul quartz with fractions of 2-10 mm
could be called raw materials with high thermal The results of the study are presented in
stability but its temperature resistance can be Fig.3. On the basis of these results, it can be
assessed as intermediate between medium and concluded that adjusting the granulometric
high. As can be seen from the results of the analysis parameters of quartz during electrothermal smelting
of the particle size distribution curves of quartz ofsilicon, onecan achieve good results not
subjected to study on heat resistance, using Sarykul depending on the thermal stability of raw materials.
quartz for smelting silicon will provide a significant It is crucial to find the conditions under which the
improvement in the process. quartz particles reach the zone of intensive
Further industrial investigations were chemical reactions until the spillage and carryover
carried out. The first campaign of smelting using from the furnace in the form of dust. For more heat-
Sarykulquartz during 5 days, failed. Purchased resistant Sarykulquartz, optimum particle size (30-
quartz with fraction of 20-300 mm and medium 40 mm) is less than for less heat-resistant
logarithmicparticle diameter of 158 mm was Aktasquartz (85-95 mm).
used.As a result the throat was overfilled with solid
slag with a high concentration of silicon oxide.
Average logarithmic value was calculated from here
onwards because of the significant differences
between upper and lower limit dimensions. From
this it could be concluded that the particle of quartz
during smelting is subjected to two oppositely
directed processes – melting of the surface of quartz
with the subsequent aggregation on the one hand,
and thermal decay on the other hand.

Fig. 2. Granulometric characteristics of Quartz Fig. 3. Dependence of specific power

with different heat resistance according to “SMS consumption and silicon extraction into metal
Demag” and the results of the study of quartz on the average logarithmic diameter of particles
deposits Aktas and Sarykul of Sarykul and Aktasquartz
 ZOBNIN et al., Orient. J. Chem., Vol. 34(2), 1120-1125 (2018) 1125

CONCLUSIONS heat-resistant Sarykulquartz, optimum particle size

(30-40 mm) is less than for less heat-resistant
Probably, optimization of particle size Aktasquartz (85-95 mm).
distribution of carbon reducing agents is also
interesting from a scientific point of view. In practice,
ACKNOWLEDGEMENT
however, the fine adjustment of average logarithmic
diameter of particles on carbonaceous materials is
The authors of the article thank the
technically very complicated due to their significant
self disintegration during their movement on the management and employees of LLP “Tau-Ken
tracts of burden batching complexes. Therefore, of Temir” for the opportunity to realize their ideas on
practical significance is only optimization industrial equipment, organizational and technical
ofgranulometric composition of quartz raw materials support during the research. We hope to continue
in metallurgical siliconsmelting. For more our long-term and mutually beneficial cooperation.

REFERENCES

1. Kallfelz, P.L.,Quartz for Production of Silicon G-Global [Electronic resource]. 2017, Access
Metal - Criteria for the Right Choice. Internal report. mode:http://group-global.org/ru/publication/
Elkem ASA, Silicon Division., 2000, 34. 346-355. 45890-issledovanie-processa-vyplavki-kremniya
2. Malvik, T.; Lund, B., Problems involved with -s-primeneniem-dlinnoplamennyh-ugley
quartzite as a raw material for FeSi and Si 8. Silicon production.«Ukrbas» test information
metal production. Process Mineralogy IX, The web-Por tal [Electronic resource]. 2017,
Minerals, Metals & Materials Society. 1990., Access mode: http://ukrbascompany.at.ua/
IX, 499-508 index/proizvodstvo_kremnija/0-52
3. Birkeland, R.,Optimal quartz properties - 9. About the company. Tau-Ken-Temir
method evaluation part 1, report no F10/03. Manufacturing of Silicon [Electronic
Internal Report, with permission from Elkem resource]. 2017, Access mode: http://tks-
(in Norwegian)., 2004, 25. 215-225 temir.kz/?ctrl=info&name=company
4. The basic raw materials for obtaining Silicon. 10. About quartz. The Ministry of investment and
Irkutsk National Research Technical development of the Republic of Kazakhstan.
University [electronic resource]. 2017, Access Committee of geology and subsurface use
mode: http://www.istu.edu/structure/57/3944/ [electronic resource]. 2014, Access
5. Ringdalen, E., Changes in Quartz During mode:http://geology.gov.kz/ru/presstsentr/
Heating and the Possible Effects on Si blog-predsedatelya/vopros-otvet/entry/
Production. JOM., 2015, 67. 100-105 kasatelno-kvartsa
6. Shkolnikov, A.R.; Fillipov, A.V.; Skornyakov, 11. Degel,R.; Fröhling, Ch.; Kalisch, M.; Hecker,
V.I.; Veselkov, V.V.; Chernykh, E.A.; Zelberg, E.; Oterdoom H., Innovative electric smelter
B.I.,Silicon production. Saint Petersburg., solutions of the SMS group for the silicon
2001, 269. 150-161. industry. The Four teenth International
7. Baysanov, S.O.; Isagulov, A.Z.; Mehdiyev, Ferroalloys Congress Energy efficiency and
A.D.; Azbanbaev, E.M., Study of Silicon environmental friendlinessare the future of the
smelting process using high volatile coal. global Ferroalloy industry., 2015, 4, 122-132.

View publication stats