Solid-phase carbon reduction of ferrioxide-silicate materials have been investigated on example of sedimentary
iron ores of Kerch deposit. It was shown that nanochemical iron oxide reduction to sponge iron
with flux-mineralizers is accomplished due to ferric carbide and nanocarbon mostly, which are being
formed out of initial carbon powdered material by carbide mechanism.
Obtained results caused development of iron ore direct reduction method which is much better of
SL/RN method used in industry.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3555

Ilyashov, M.A.

Kovzun, I.G.

Oleinik, V.O.

Panko, A.V.

Protsenko, I.T.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 3, 03AET10(3pp) (2013)   2304-1862/2013/2(3)03AET10(3) 03AET10-1  2013 Sumy State University Nanochemical Processes In Solid-Phase Reduction Of Ferrioxide-Silicate Materials  V.O. Oleinik1, A.V. Panko1,*, I.G. Kovzun1, M.A. Ilyashov2, I.T. Protsenko1,†  1 Institute of Biocolloidal Chemistry named after F.D.Ovcharenko, National, Academy of Sciences of Ukraine, 42, Vernadskogo Blvd., Kyiv, Ukraine, 03680 2 Private joint-stock company «Donetsksteel» – metallurgical plant», 122, I. Tkachenko Str., Donetsk, Ukraine, 83062  (Received 14 June 2013; published online 01 September 2013)  Solid-phase carbon reduction of ferrioxide-silicate materials have been investigated on example of sed-imentary iron ores of Kerch deposit. It was shown that nanochemical iron oxide reduction to sponge iron with flux-mineralizers is accomplished due to ferric carbide and nanocarbon mostly, which are being formed out of initial carbon powdered material by carbide mechanism.  Obtained results caused development of iron ore direct reduction method which is much better of SL/RN method used in industry.   Keywords: Ferrioxide-silicate materials, Nanocarbon, Mineralizers, Nanochemical reduction, Sponge iron.    PACS numbers: 81.07. – b, 81.05.Bx, 81.05.U –, 82.33.Pt, 82.70.Dd                                                           * wiz@list.ru † protsenkoit@ukr.net 1. INTRODUCTION  The problem of iron and steel production enhance-ment from iron ores production technology was and still remains as actual globally due to permanent need in high-quality and relatively low-price steel and iron semi-finished and finished products at different branches of industry. Extensive scientific and scientific-technical investigations in this sphere have led to development (till the end of 20th century) of various cost-effective technologies of ferrioxide materials direct reduction with gaseous hydrogen and single-oxide carbon obtained from natural gas [1]. However, availability of such technolo-gies is being constantly decreased due to increasing costs for natural gas, while interest in methods of solid state reduction of ferrioxide materials with carbon and their scientific substantiation using achievements in nanosci-ence and nanotechnology is constantly growing [2-4]. Thus, current investigation is devoted to development of conceptions of such processes.  2. EXPERIMENTALS  Sediment ferrioxide-silicate ores with manganese additive from Kerch deposit are used at experimental part of the work. Their solid state reduction at 1000-1200°C with carbon powdered material, with and with-out mineralizers presence has been investigated using roentgen-phase, thermogravimetric, electronmicroscop-ic and chemical methods.  3. RESULTS CONSIDERATON  Radiographs (Fig. 1) of cakes, obtained from mixture of ore and carbon, have verified availability of metal iron and magnetite in them. Wustite and magnetite are available in cake, obtained at 1000 ºС, while in cake, obtained at 1050ºС, their amount is considerably lower, and the main component of cake, obtained at 1200°С is a metal iron. Quantity of the last is 1.5-2 times higher in case of application of mineralizers, and a phase of nsut-ite [MnO (OH)] forms. Amount of ferrous silicate Fe2SiO4 (fayalite) in cake obtained at 1000ºС and 1050ºС-1200ºС remains constant. It shows that its amount depends on quantity of highdispersed silica in charge mixture which reacts generating highdispersed and nanodispersed fay-alite under the following scheme:   2FeO + SiO2 → Fe2SiO4 (1)  According to obtained thermogravimetric analysis data (Fig.2) the processes of iron ore reduction with car-bon begin at temperature above 450ºС generating mag-netite, which partly reduced to wustite at temperature above 1000ºС. The latter coexists with magnetite and metallic iron up to 1050ºС (Fig.1). At higher tempera-tures (1150-1215ºС) sponge iron with fayalite Fe2SiO4 admixture covered with nanocarbon particles is present.  Experiments with addition of salts-mineralizers show that along with traditional direct iron reduction chemical processes proceeding with the basic reactions:    3Fe2O3 + C → 2Fe3O4 + CO  (2)  Fe3O4 + C → 3FeO +CO (3)  FeO + C → Fe + CO (4)  intermediate reaction of unstable highdispersed cement-ite formation is proceeding actively:   3Fe + C → Fe3C (5)  dissociating into sponge iron and nanocarbon particles easily. Formed cementite is actively interacting with the ironoxide materials at specially selected conditions (op-timal ratio of charge components, their dispersion, availability of mineralizers) due to the availability of nanocarbon in its structure and due to the high disper-sion of cementite itself under the following schemes:   V.O. OLEINIK, A.V. PANKO, ET AL. PROC. NAP 2, 03AET10 (2013)   03AET10-2   Fig. 1 – X-ray diffractogram of Kerch deposit ore (a) and products of its reducing firing at 1000°С (b) and at 1200 °С (c) mixed with carbon powder in 4:1 ratio    Fig. 2 – Thermograms of Kerch deposit ore (a) and its mixture with carbon powder in 4:1 ratio (b)      Fig. 3 – Electronmicroscopic image of nanocarbon (a) and carbonized silicate (b) extracted from sponge iron obtained at 1215°С   100 нм c b a  NANOCHEMICAL PROCESSES IN SOLID-PHASE REDUCTION… PROC. NAP 2, 03AET10 (2013)   03AET10-3  Fe2O3 + 3Cnano → 2Fe + 3CO (6)  Fe2O3 + 3Fe3C → 8Fe + 3CO (7)  Fe3O4 + 4Fe3C → 15Fe + 4CO (8)  FeO + Fe3C → 4Fe + CO (9) The process is accompanied with partial dissolution of solid sponge iron microparticles in cementite melt formed at 1160-1180°С, which provides for further liq-uid metal microdroplets formation. Those microdroplets are purified from adhesively bound silicate inclusions under the influence of flux-mineralizers regulating the surface tension and droplet size as well as their reactiv-ity. After consumption of excess carbon in those drop-lets for active recovery processes, they are being hard-ened, transformed mainly again into sponge iron of higher purity, than the original one. This can be repre-sented by following scheme:    .  (10)   The method of direct sponge iron and cast iron mate-rials reduction from ironoxidesilica materials has been developed and patented based on results obtained. This method is 1.5-2 times exceeding the SL/RN method [1] used now in the industry at its economic efficiency. 4. CONCLUSIONS  Thus, colloid-chemical foundations of direct solid iron oxide materials reduction have been considered, and the determining role of nanoscience achievements and nanotechnological colloidal elements in these pro-cesses has been shown.  REFERENCES  1. Yu.S. Yusfin, N.F. Pashkov, Metallurgiya zheleza (Metal-lurgy of Iron) (Moscow: IKTs Akademkniga, 2007).  2. M.A. Ilyashov, V.O. Oleinik, I.G. Kovzun, A.V. Panko, I.T. Protsenko, Naukovedenie No1, 29ТВН113 (2013). publ.naukovedenie.ru. 3. Nanoscience. Colloidal and Interfacial Aspects (Ed. V.M. Starov (London-New York: CRC Press: 2010). 4. G.B. Sergeev, Nanohimija (Nanochemistry) (Moscow: MSU Publishing House, 2003).  

Nanochemical Processes In Solid-Phase Reduction Of Ferrioxide-Silicate Materials

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 3, 03AET10(3pp) (2013) 
 
 
2304-1862/2013/2(3)03AET10(3) 03AET10-1  2013 Sumy State University 
Nanochemical Processes In Solid-Phase Reduction Of Ferrioxide-Silicate Materials 
 
V.O. Oleinik1, A.V. Panko1,*, I.G. Kovzun1, M.A. Ilyashov2, I.T. Protsenko1,† 
 
1 Institute of Biocolloidal Chemistry named after F.D.Ovcharenko, National, Academy of Sciences of Ukraine, 42, 
Vernadskogo Blvd., Kyiv, Ukraine, 03680 
2 Private joint-stock company «Donetsksteel» – metallurgical plant», 122, I. Tkachenko Str., Donetsk, Ukraine, 83062 
 
(Received 14 June 2013; published online 01 September 2013) 
 
Solid-phase carbon reduction of ferrioxide-silicate materials have been investigated on example of sed-
imentary iron ores of Kerch deposit. It was shown that nanochemical iron oxide reduction to sponge iron 
with flux-mineralizers is accomplished due to ferric carbide and nanocarbon mostly, which are being 
formed out of initial carbon powdered material by carbide mechanism.  
Obtained results caused development of iron ore direct reduction method which is much better of 
SL/RN method used in industry.  
 
Keywords: Ferrioxide-silicate materials, Nanocarbon, Mineralizers, Nanochemical reduction, Sponge iron. 
 
  PACS numbers: 81.07. – b, 81.05.Bx, 81.05.U –, 
82.33.Pt, 82.70.Dd 
 
 
                                                        
* wiz@list.ru 
† protsenkoit@ukr.net 
1. INTRODUCTION 
 
The problem of iron and steel production enhance-
ment from iron ores production technology was and still 
remains as actual globally due to permanent need in 
high-quality and relatively low-price steel and iron semi-
finished and finished products at different branches of 
industry. Extensive scientific and scientific-technical 
investigations in this sphere have led to development 
(till the end of 20th century) of various cost-effective 
technologies of ferrioxide materials direct reduction with 
gaseous hydrogen and single-oxide carbon obtained from 
natural gas [1]. However, availability of such technolo-
gies is being constantly decreased due to increasing costs 
for natural gas, while interest in methods of solid state 
reduction of ferrioxide materials with carbon and their 
scientific substantiation using achievements in nanosci-
ence and nanotechnology is constantly growing [2-4]. 
Thus, current investigation is devoted to development of 
conceptions of such processes. 
 
2. EXPERIMENTALS 
 
Sediment ferrioxide-silicate ores with manganese 
additive from Kerch deposit are used at experimental 
part of the work. Their solid state reduction at 1000-
1200°C with carbon powdered material, with and with-
out mineralizers presence has been investigated using 
roentgen-phase, thermogravimetric, electronmicroscop-
ic and chemical methods. 
 
3. RESULTS CONSIDERATON 
 
Radiographs (Fig. 1) of cakes, obtained from mixture 
of ore and carbon, have verified availability of metal iron 
and magnetite in them. Wustite and magnetite are 
available in cake, obtained at 1000 ºС, while in cake, 
obtained at 1050ºС, their amount is considerably lower, 
and the main component of cake, obtained at 1200°С is a 
metal iron. Quantity of the last is 1.5-2 times higher in 
case of application of mineralizers, and a phase of nsut-
ite [MnO (OH)] forms. Amount of ferrous silicate Fe2SiO4 
(fayalite) in cake obtained at 1000ºС and 1050ºС-1200ºС 
remains constant. It shows that its amount depends on 
quantity of highdispersed silica in charge mixture which 
reacts generating highdispersed and nanodispersed fay-
alite under the following scheme: 
 
 2FeO + SiO2 → Fe2SiO4 (1) 
 
According to obtained thermogravimetric analysis 
data (Fig.2) the processes of iron ore reduction with car-
bon begin at temperature above 450ºС generating mag-
netite, which partly reduced to wustite at temperature 
above 1000ºС. The latter coexists with magnetite and 
metallic iron up to 1050ºС (Fig.1). At higher tempera-
tures (1150-1215ºС) sponge iron with fayalite Fe2SiO4 
admixture covered with nanocarbon particles is present.  
Experiments with addition of salts-mineralizers show 
that along with traditional direct iron reduction chemical 
processes proceeding with the basic reactions:  
 
 3Fe2O3 + C → 2Fe3O4 + CO  (2) 
 Fe3O4 + C → 3FeO +CO (3) 
 FeO + C → Fe + CO (4) 
 
intermediate reaction of unstable highdispersed cement-
ite formation is proceeding actively: 
 
 3Fe + C → Fe3C (5) 
 
dissociating into sponge iron and nanocarbon particles 
easily. 
Formed cementite is actively interacting with the 
ironoxide materials at specially selected conditions (op-
timal ratio of charge components, their dispersion, 
availability of mineralizers) due to the availability of 
nanocarbon in its structure and due to the high disper-
sion of cementite itself under the following schemes: 
 
 V.O. OLEINIK, A.V. PANKO, ET AL. PROC. NAP 2, 03AET10 (2013) 
 
 
03AET10-2 
 
 
Fig. 1 – X-ray diffractogram of Kerch deposit ore (a) and products of its reducing firing at 1000°С (b) and at 1200 °С (c) mixed 
with carbon powder in 4:1 ratio 
 
 
 
Fig. 2 – Thermograms of Kerch deposit ore (a) and its mixture with carbon powder in 4:1 ratio (b) 
 
   
 
Fig. 3 – Electronmicroscopic image of nanocarbon (a) and carbonized silicate (b) extracted from sponge iron obtained at 1215°С 
  
100 нм 
c 
b 
a 
 NANOCHEMICAL PROCESSES IN SOLID-PHASE REDUCTION… PROC. NAP 2, 03AET10 (2013) 
 
 
03AET10-3 
 Fe2O3 + 3Cnano → 2Fe + 3CO (6) 
 Fe2O3 + 3Fe3C → 8Fe + 3CO (7) 
 Fe3O4 + 4Fe3C → 15Fe + 4CO (8) 
 FeO + Fe3C → 4Fe + CO (9) 
The process is accompanied with partial dissolution 
of solid sponge iron microparticles in cementite melt 
formed at 1160-1180°С, which provides for further liq-
uid metal microdroplets formation. Those microdroplets 
are purified from adhesively bound silicate inclusions 
under the influence of flux-mineralizers regulating the 
surface tension and droplet size as well as their reactiv-
ity. After consumption of excess carbon in those drop-
lets for active recovery processes, they are being hard-
ened, transformed mainly again into sponge iron of 
higher purity, than the original one. This can be repre-
sented by following scheme:  
 
 .  (10) 
 
 
The method of direct sponge iron and cast iron mate-
rials reduction from ironoxidesilica materials has been 
developed and patented based on results obtained. This 
method is 1.5-2 times exceeding the SL/RN method [1] 
used now in the industry at its economic efficiency. 
4. CONCLUSIONS 
 
Thus, colloid-chemical foundations of direct solid 
iron oxide materials reduction have been considered, 
and the determining role of nanoscience achievements 
and nanotechnological colloidal elements in these pro-
cesses has been shown. 
 
REFERENCES 
 
1. Yu.S. Yusfin, N.F. Pashkov, Metallurgiya zheleza (Metal-
lurgy of Iron) (Moscow: IKTs Akademkniga, 2007).  
2. M.A. Ilyashov, V.O. Oleinik, I.G. Kovzun, A.V. Panko, 
I.T. Protsenko, Naukovedenie No1, 29ТВН113 (2013). 
publ.naukovedenie.ru. 
3. Nanoscience. Colloidal and Interfacial Aspects (Ed. 
V.M. Starov (London-New York: CRC Press: 2010). 
4. G.B. Sergeev, Nanohimija (Nanochemistry) (Moscow: MSU 
Publishing House, 2003). 
 


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Nanochemical Processes In Solid-Phase Reduction Of Ferrioxide-Silicate Materials

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