Production of Special Coke
Production of Special Coke
Production of Special Coke
Original Russian Text © V.M. Strakhov, 2008, published in Koks i Khimiya, 2008, No. 9, pp. 44–49.
COKE
Abstract—The fundamental principles in the production of coke and semicoke characterized by high reactivity
and electrical resistivity and developed pore structure are considered. The laws governing the formation of these
properties are established as a function of the initial coal components and the pyrolysis conditions. A production
technology for carbon reducing agents that may be used in electric furnaces is developed, and its prospects for
application in Russia are discussed.
DOI: 10.3103/S1068364X08090068
Coke production traditionally focuses on blast-fur- pyrolytic conditions so as to obtain effective carbon
nace coke, which must be strong and in large chunks, reducing agents characterized by high reactivity and elec-
above all [1]. However, coke used in other industrial trical resistivity and a developed pore structure. Contribu-
processes must satisfy different requirements. In partic- tors to this research have included N.S. Gryaznov,
ular, coke is also used as a reducing agent in electric V.I. Sukhorukov, G.I. Nechaeva, P.Ya. Nefedov,
furnaces, for the production of ferroalloys, calcium car- O.G. Unterberger, V.D. Glyanchenko, M.B. Shkoller,
bide, and phosphorus [2–4]. Currently, various size V.M. Dinel’t, and S.P. Rod’kin, as well as the author.
classes gleaned from gross coke are used for these pur-
poses: mainly coke nuts of the 25–10 mm class or, where The variation in reactivity, electrical resistivity, and
those are unavailable, coke of size class 25–40 mm, pore structure of coke within the metamorphic series of
which is broken down to a chunk size of 20–5 mm. coal is of great interest [18–22]. The highest values of
these parameters are obtained in coke from the extreme
The main requirements on coke for electric furnaces components of the series: long-flame, gas, poorly clin-
are as follows [5]: kering, and lean coal. On switching to coke that is pro-
high carbon content (80–85%); duced using coal from the middle of the metamorphic
minimal content (in the mineral component) of ele- series (coke-group and bituminous coal), the reactivity
ments impairing product content; and resistivity decline sharply. This may be attributed to
high reactivity; the characteristics of the initial coal and the pyrolytic
conditions. The following patterns may be identified.
a developed pore structure;
high electrical resistivity; With increase in metamorphic stage of the coal, the
adsorptivity and chemical activity reach a minimum at
a small yield of volatiles, without tar residues; the middle of the series (bituminous and coke-group
sufficient mechanical strength, but less than for coal).
blast-furnace coke; and
In coal of intermediate metamorphism, the actual
optimal size (5–20 mm). density, porosity, and internal surface are a minimum.
The coke currently employed does not meet these The number of oxygen-bearing polar functional groups
requirements, especially in terms of their physicochem- also decreases on switching from long-flame and gas
ical properties: it is characterized by low reactivity and coal to bituminous and coke-group coal. In both cases,
low electrical resistivity [6–9]. In this context, there has the result is reduced chemical activity of the coal.
been extensive research on the production of special
types of reducing agents that meet electric-furnace The internal surface and adsorptive properties of the
requirements to the maximum possible extent [10–17]. coal increase again for poorly clinkering and lean coals,
on account of the increase in porosity and microcrack-
The Eastern Coal-Chemistry Institute (ECCI) and ing that accompanies degassing and shrinkage during
its Kuznetsk Center have conducted systematic the metamorphic process.
research (on the laboratory, semiindustrial, and indus-
trial scale) into the physicochemical properties of coke Since coke inherits the microporous structure of the
as a function of the initial coal batch and the conditions coal, the ratio of sorptional and reactive properties in
of batch preparation and coking. Theoretical principles coke samples will be the same as in the initial coal
have been established for the selection of coal and the batches.
364
PRODUCTION OF SPECIAL COKE FOR USE IN ELECTRIC FURNACES 365
The increase in the structural density of coke from fact, it does not even cover the shortage of carbon
bituminous and coke-group coal on account of their reducing agents.
greater clinkering properties improves the electrical The production of carbon reducing agent in exter-
resistivity and, in turn, reduces the chemical activity of nally heated vertical furnaces during the coking of coal
the coke. pieces is of interest. In the 1970s, this technology was
As the clinkering properties of the coal deteriorate, developed at ECCI using Kuznetsk SS coal in furnaces
the contact between the residual material from the ini- at the Slantsy shale-processing plant (Kokhtla-Yarve)
tial coal grains or the petrographic microcomponents [28]. Tests show that the coke obtained is one of the
within a single grain becomes less secure, more struc- best reducing agents for phosphorus production.
tural defects appear in the coke, and its reactivity and Currently, externally heated chamber furnaces oper-
electrical resistivity increase. ate at the Slantsy plant. However, they are only used to
Coke with a less orderly structure is obtained from roast oil-industry coke. In 1997, New Zealand long-
coal that has poor or nonexistent clinkering properties flame coal was coked in these furnaces, to produce
(ranks D, G, SS, and T) and is petrographically nonuni- high-quality coke as a carbon reducing agent [29].
form. Correspondingly, the coke is characterized by Regrettably, more than 70% of the chamber furnaces at
greater chemical activity and electrical resistance. the Slantsy plant are no longer operating and are in a
state of cold conservation.
On the basis of these findings, we conclude that the
most promising raw material for reducing agents used Semicoke production in gas generators at the
in electrofurnaces is coal characterized by poor or non- Slantsy plant proves relatively efficient. These genera-
existent clinkering properties, petrographic nonunifor- tors have been adapted for semicoking on an experi-
mity, and a low metamorphic stage. mental basis. They offer significant benefits over other
semicoking furnaces. The unit power of the gas gener-
Accordingly, D, G, SS, and T coal from the Kuz- ators is twice that for Pinch furnaces, and they are con-
netsk Basin predominantly but also from other deposits siderably simpler to design and operate than three-zone
has been investigated at ECCI’s Kuznetsk Center with vertical Lurgi furnaces.
a view to producing coke and semicoke of the required
quality. A technology using D, DG, and SS coal has been
tested at the Slantsy plant [30–33]. The quality of the
Given the requirements on carbon reducing agents, semicoke fully satisfies electrofurnace requirements
semicoke is of most interest. The production of semi- (Table 1). Industrial tests of semicoke at Russian, Nor-
coke from different coals has been tested industrially at wegian, and Kazakh ferroalloy plants resulted in excel-
various enterprises, in collaboration with specialized lent furnace productivity [31, 32].
research institutes.
The use of chain gratings for coal pyrolysis is a
In vertical Lurgi furnaces with internal heating, long-established idea. In these conditions, pyrolysis is
semicoke has been obtained from D coal extracted in oxidative, on account of the combustion of volatiles
Cheremkhovsk and Kuznetsk mines. The quality of the above the fuel layer. Accordingly, this is sometimes
semicoke depends on the material composition of the described as an autothermal or autogenic process. It
coal and the operational parameters of the furnaces. may be used to produce either coke or semicoke.
However, the semicoke is characterized by excellent In Russia, analogous technology for coal chunks
physicochemical properties [16]. was developed at Mendeleev Moscow Chemical-Engi-
Semicoke from Cheremkhovsk coal (often referred neering Institute and then at the ECCI. In recent years,
to as Angarsk semicoke) obtained in Lurgi furnaces was with the participation of ECCI’s Kuznetsk Center, the
widely used (up to 500000 t/yr) at Siberian, Ural, and process has been further developed and introduced in
Kazakh ferroalloy plants in the 1970s and 1980s, with Kazkahstan [34–36]. This method is widely used in
great technological and economic benefits. Its use sig- Canada, the United States, Germany, South Africa, and
nificantly improves ferroalloy production [23, 24]. The India.
use of semicoke in the industrial production of phos- In Russia, the coking of Kuznetsk Basin G, D, and
phorus sponge and calcium carbide proved successful SS coal on chain gratings was investigated in industrial
[25, 26]. Unfortunately, the Angarsk semicoke plant conditions. The properties of the coke obtained are suit-
has closed, and the Russian ferroalloy industry has suf- able for electric furnaces [37]. It is found that coking on
fered considerable losses, for lack of satisfactory reduc- chain gratings is inexpensive and highly productive and
ing agents. permits the use of various coals to obtain reducing
In the past, semicoke from long-flame Kuznetsk agents of high quality. Unfortunately, thermooxidative
coal has been produced in Pinch furnaces at the Len- coking of coal on chain gratings has not been adopted
insk-Kuznetsk semicoking plant and used in ferroalloy in Russia on an industrial scale. However, in recent
smelting. Semicoking of a mixture of D and SS coal is years, there has been renewed interest in this technol-
also possible [27]. However, the plant is equipped with ogy, and a few boilers in the Kuznetsk Basin and the
furnaces of unsatisfactory design and outdated equip- Altaisk region are producing semicoke from D and SS
ment. Its semicoke output is small (~60000 t/yr); in coal in small quantities.
Table 1
Semicoke
from Kuznetskii Basin coal Coke nuts
Characteristic from Shum- from Kuznetskii
from from
barkol’skii coal coking coal
Colombia coal Pechorskii coal Bachatskii Kedrovskii
(Kazakhstan)
mine mine
Rank of coal DG D D 1SS 2SS
Technical analysis, %:
Wr 32.2 24.8 9.4 18.0 20.3 10.7
Ad 2.6 27.13 7.0 7.4 10.4 11.5
Vdaf 11.4 9.79 7.1 7.70 9.91 1.70
Sd 0.54 1.93 0.30 0.20 0.17 0.42
Pd 0.003 0.037 0.043 0.029 0.034 0.039
Fixed-carbon content Cfix, % 86.6 65.7 86.4 85.4 80.7 87.0
Reactivity with CO2 at 1.35 2.19 2.83 2.28 2.23 0.47
1000°C, cm2/g s
Electrical resistivity, Ω cm 3.6 × 102 1.4 × 105 68.4 1.3 × 106 4.3 × 102 2.9
Density, g/cm3:
actual 1.607 1.785 1.744 1.633 1.843 1.897
apparent 0.753 1.090 1.108 1.031 1.087 1.033
Porosity, % 53.1 38.9 36.5 36.9 41.0 45.5
Total pore volume, cm3/g 0.706 0.357 0.329 0.358 0.377 0.441
Structural strength, % 71.0 78.0 82.8 75.5 82.1 83.7
Thermal stability, % 96.2 – 78.1 91.4 96.4 99.2
Granulometric composition
(%) by class, mm:
>50 – – – 4.7 11.5 –
50–25 33.6 22.2 3.8 33.2 38.7 7.4
25–15 34.3 48.6 31.2 13.5 41.8 88.6
15–5 20.6 19.0 23.0 42.7 6.0 2.5
<5 11.5 10.2 42.0 5.9 2.0 1.5
The thermal processing of coal undertaken as an to the best available carbon reducing agents for electro-
industrial pilot process at ZAO Karbonika-F (Krasno- furnaces (Table 2).
yarsk) is of great practical interest. Essentially, this In 2006, the industrial production of semicoke from
involves bed gasification of coal with an air blast, in lignite extracted from the Berezovsk mine in the Kan-
which the volatiles are gasified. The degree of gasifica- sko-Achinsk Basin was introduced at OOO Sibtermo,
tion of the solid carbon residue is regulated by the blast in a standard KTVS-20 boiler. This technology
conditions [38–40]. (Termokoks-KS technology) is based on coal pyrolysis
This is a single-stage autothermal process. Drying, in a fluidized bed with partial combustion of the vola-
pyrolysis, thermal decomposition of the volatiles, and tiles released and entrainment of finely disperse coal,
cooking of the semicoke are combined within a single which undergoes final combustion in the space below
apparatus. The process is currently being debugged in the furnace roof [41]. The calculated semicoke output
the production of lignite semicoke from Kansko- of the unit is 30 000 t/yr. Finely disperse (<5 mm) lig-
Achinsk coal; the semicoke output is ~10000 t/yr. The nite semicoke with high chemical activity is obtained
production of moderate-temperature coke from Kuz- (Table 2).
netsk and Shubarkol’skii (Kazakhstan) long-flame coal Annular furnaces may be used to produce coke or
is undergoing tests [39]. The coke obtained corresponds semicoke from all types of solid fuel. Coal pyrolysis in
Table 2
Karbonika-F technology Sibtermo technology
Characteristic Kansko-Achinsk Mokhovskii mine Shubarkol’skii Berezovskii min
Basin (KAB) (Kuznetskii Basin) mine (Kazakhstan) (KAB)
Rank of coal B D D B
Technical analysis, %: 8.6
Ad 8.3 8.8 5.0 9.2
Vdaf 0.12 2.8 3.8 9.5
Sd 0.12 0.19 0.30 0.20
Fixed-carbon content Cfix, % 83.8 88.6 91.4 82.1
Reactivity with CO2 at 1000°C, cm2/g s 6.5 2.7 2.2 3.7
Electrical resistivity (6–3 mm class), Ω cm – 29.5 19.0 –
Density, g/cm3:
actual 1.846 1.814 1.850 2.023
apparent 0.924 0.665 0.880 –
Porosity, % 49.9 63.3 52.4 –
Total pore volume, cm3/g 0.540 0.953 0.596 –
Structural strength, % 3.2 73.0 79.3 –
Granulometric composition (%) by class, mm:
>20 – 13.5 25.0 –
20–5 2.5 78.2 69.0 –
<5 97.5 8.3 6.0 100.0
annular furnaces involves heating a relatively thin layer Energy Institute and ECCI specialists (employed at Yekat-
(50–200 mm) of coal charge on a moving hearth to erinburg cogeneration plant) [22].
specified temperature. Depending on the fuel and the
requirements on the final product, chunks or powder Note that Kazakhstan is considerably ahead of Rus-
may be loaded on the annular hearth [22, 42]. sian coke and semicoke producers in this respect, with
the recent introduction of three new coal-processing
Germany has the most experience with powerful technologies producing special types of coke and semi-
annular furnaces (diameter up to 25 m) using lignite. coke on chain gratings, in outdoor and vertical fur-
Such furnaces produce lignite semicoke at a rate of naces. Two of these technologies have been adopted in
115000 t/yr (Ad = 9%; Vdaf = 3%; porosity 48.6%; spe- China [43].
cific surface 300 m2/g). In the United States, annular
furnaces (diameter 5 and 8 m) with a coke output of up Note, in conclusion, that considerable quantities of
to 28 t/day are employed. The coke is used in electro- high-quality coke and semicoke are required for elec-
furnace production of ferroalloys and phosphorus. trofurnace production. It follows from theoretical data
and industrial-test data regarding various coal-process-
In Russia, industrial tests of coking in 5-m annular ing technologies that there are real prospects for the
furnaces were undertaken at OAO NTMK and Moscow production of special carbon reducing agents in Russia.
Coke Plant. Regrettably, this equipment is no longer in Given foreign experience and Russian research, all that
operation. is required is adequate investment and active collabora-
tion of the producers and consumers of special coke and
Other Russian processing technologies for solid fuel semicoke.
have reached the stage of industrial testing but have not
been adopted in production conditions. Notable among
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