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Effect of harmful elements on the coke ratio of blast furnace

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DOI: 10.1080/03019233.2017.1368955

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Effect of harmful elements on the coke ratio of

blast furnace

Y. J. Wang, X. J. Ning, J. L. Zhang, K. X. Jiao & C. Wang

To cite this article: Y. J. Wang, X. J. Ning, J. L. Zhang, K. X. Jiao & C. Wang (2017): Effect
of harmful elements on the coke ratio of blast furnace, Ironmaking & Steelmaking, DOI:
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 IRONMAKING & STEELMAKING, 2017
https://doi.org/10.1080/03019233.2017.1368955

Effect of harmful elements on the coke ratio of blast furnace

Y. J. Wang, X. J. Ning, J. L. Zhang, K. X. Jiao and C. Wang
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing, China

ABSTRACT ARTICLE HISTORY

The circulation and accumulation of harmful elements in the blast furnace leads to a decrease in gas Received 23 June 2017
utilisation and an increase in heat consumption, which can cause the increase of coke ratio. In this Accepted 25 July 2017
paper, the effect of harmful elements on the coke ratio was quantitatively studied using the Rist
KEYWORDS
diagram. The results show that the effect degree of each harmful element on the coke ratio varies. Blast furnace; harmful
The influence orders of accumulation times and loads of harmful elements on the coke ratio are elements; Rist operation
Na > K>Zn and Zn > Na > K, respectively. The increase of heat consumption has more effect on the diagram; gas utilisation; heat
Downloaded by [University of Science & Technology Beijing] at 21:48 18 September 2017

coke ratio than the decrease of gas utilisation. The total increase of coke ratio by the effect of K, Na consumption; coke ratio
and Zn is 14.2, 35.8 and 9.3 kg/tHM, respectively, of which the effect of heat consumption accounts
for 55.9, 60.9, 60.9%, respectively.

Introduction excess heat that is consumed to reduce the harmful elements

Some impurity elements, such as K, Na and Zn, are commonly
found in iron ore and coke. These impurity elements are called
harmful elements, because they can cause operational pro-
blems in the blast furnace [1–8]. The adverse effect of
harmful elements on the blast furnace production has been
extensively studied. Yang and Gao [6] studied the distributions
and accumulations of alkali in the blast furnace by dissecting an
experimental BF with a volume of 55 m3. According to the
experimental results, the main reason of formation of scaffold
on the furnace wall is the circulation and accumulation of
alkali. Jiao et al. [7] established a model of zinc solution beha-
viours among the slags and hot metals. The results show that
zinc is saturated in hot metal and bosh gas. This could lead
to the accumulation of zinc, and cause severe damage, in the
blast furnace bottom brick and tuyere refractory due to the
expansion of refractory. Li et al. [8] studied the composition
of tuyere coke by the sampling analysis. The research shows
that the accumulation of zinc in tuyere coke may cause coke
degradation in the blast furnace.
To reduce the adverse impact of harmful elements on blast
furnace operations, it is necessary to control the loads of
harmful elements in the blast furnace. Currently, there is no
uniform standard of loads of harmful elements [9,10]. In
China, the maximum load of alkali metal oxide (K2O + Na2O)
and zinc are 3 and 0.15 kg/tHM, respectively. However, BF
operators determine the lack of unified quantitative research
methods on the effect degree of harmful elements, based on
blast furnace production and operational experience, which
leads to significant difference in loads of harmful elements
between different furnaces. In China, the alkali load is gener-
ally in the range of 2.0–12 kg/tHM, the average load of zinc is
0.5 kg/tHM [11–13].
Jiao et al. [14] studied the effects of harmful elements on
the fuel consumption in a quantitative way. The results
show that the circulation and accumulation of harmful
elements in the blast furnace resulted in a decrease in gas util-
isation and an increase in fuel consumption. However, the
is not considered. Therefore, the effect of harmful elements
on the coke ratio that is based on gas utilisation and heat con-
sumption was quantitatively studied in this paper.
The behaviour of harmful elements in the blast
furnace
Alkalis in iron ore and coke exist in the form of complex sili-
cates and aluminosilicates [15], respectively. These alkali min-
erals enter the blast furnace with burden and are reduced to
potassium and sodium vapours at the high temperature in the
bosh and hearth regions of the blast furnace because of the
lower boiling point of alkali. The ascending alkali vapours
are oxidised by CO2 to produce silicates. The silicates move
downwards with burden and re-reduced during their
descent, which leads to alkali circulation within the furnace
[16]. The oxidation and reduction of alkali can be expressed
with the following equations. In addition, there is a circulation
of alkali carbonates in the upper part of the blast furnace [17].
K2 SiO3 + CO = 2K(g) + SiO2 + CO2 (g)
(1)
DH1⊖ = 137520 J mol−1
Na2 SiO3 + CO = 2Na(g) + SiO2 + CO2 (g)
(2)
DH2⊖ = 162420 J mol−1
2K(g) + SiO2 + CO2 (g) =K2 SiO3 + CO(g) (3)
2Na(g) + SiO2 + CO2 (g) = Na2 SiO3 + CO(g) (4)
Similar to alkali, zinc also circulates inside the furnace [18].
Zinc is present in the blast furnace as a constituent of burden
in the form of oxides (ZnO). ZnO is reduced to zinc vapours in
the lower part of the furnace. The gasified zinc is oxidised and
part of ZnO is deposited on burden. The reaction of zinc can
be expressed with the following equations.
ZnO + CO = Zn + CO2 (5)

CONTACT Kexin Jiao jiaokexin_ustb@126.com School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing
100083, China
© 2017 Institute of Materials, Minerals and Mining
 2 Y. J. WANG ET AL.

the following equations.

DH3 ⊖ = 182400 J mol−1
2 · w[Si]/28
Zn + CO2 = Zn + CO (6) ySi = (9)
w[Fe]/56
The mechanism of alkali and zinc reduction, oxidation and w[Mn]/55
circulation in the blast furnace is illustrated in Figure 1. yMn = (10)
w[Fe]/56
2.5 · w[P]/31
yP = (11)
Rist operation diagram w[Fe]/56

The Rist operation diagram describes the oxygen transfer in w(S) · U/32
yS = (12)
Fe–C–O system, which is generally used to analyse the 1000w[Fe]/56
energy utilisation in the blast furnace [19]. In this study, the where w[i] is the weight percent of specie i in hot metal, w(S)
Rist operation diagram is used to analyse the effect of is the weight percent of S in slag, U is slag volume.
harmful elements on the coke ratio.
(3) Oxygen atoms come from hot blast
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The ordinate n(O)/n(Fe) The moles of oxygen atoms consumed by carbon combus-
The main sources of oxygen that reacted with carbon are iron tion in front of tuyere for producing 1 mol of metal iron: yb can
oxides, other oxides and hot blast. be calculated by the following equation.
n(O) V · w(O2 ) × 2/22.4
(1) Oxygen atoms come from iron oxides yb = = (13)
n(Fe) 1000w[Fe]/56

Iron oxides in burden exist in the form of FeO, Fe2O3 and where V is the blast volume, m3/tHM, w(O2 ) is the volume
Fe3O4. Fe3O4 consists of equal moles of FeO and Fe2O3 for cal- percent of oxygen in blast.
culating easily. The moles of oxygen atoms removed from iron
oxides for producing 1 mol of metal iron: yA can be calculated
by the following equation. The abscissa n(O)/n(C)
n(O) w(Fe2 O3 ) × 3/160 + w(FeO) × 1/72 The ratio of oxygen to carbon can be calculated approxi-
yA = = (7) mately by Equation (14) according to the composition of
n(Fe) w(TFe)/56
top gas.
where n(O) is the number of moles of oxygen atoms in the
ore, n(Fe) is the number of moles of iron atoms in the ore, n(O) 2w(CO2 ) + w(CO)
xA = = (14)
w(Fe2 O3 ) is the weight percent of Fe2O3 in the ore, w(FeO) n(C) w(CO2 ) + w(CO)
is the weight percent of FeO in the ore, w(TFe) is the grade where w(CO) and w(CO2 ) are the CO and CO2 contents of the
of iron ore. top gas, %, respectively.

(2) Oxygen atoms come from other oxides

In this study, other oxides SiO2, MnO, P2O5 and sulphur
oxides are included. The total moles of oxygen atoms
removed from SiO2, MnO, P2O5 and desulphurisation for pro-
ducing 1 mol of metal iron: yf can be calculated by the follow-
ing equation.
n(O)
yf = = ySi + yMn + yP + yS
n(Fe)
where ySi , yMn , yP , yS are the moles of oxygen atoms removed
from SiO2, MnO, P2O5 and desulphurisation for producing
1 mol of metal iron, respectively, and can be calculated by
The restriction of thermal equilibrium on the Rist
operation diagram
According to the energy utilisation in the blast furnace, the
fuel consumption is determined by thermal equilibrium in
the high-temperature zone. Therefore, the circulation of
alkali carbonates in the upper part of the blast furnace is
(8) not considered. In this study, the high-temperature zone
boundary condition is assumed to be tburden = 950◦ C,
tgas = 1000◦ C. The coordinate of point P, reflecting the
effect of thermal equilibrium on the Rist operation diagram,
can be determined as follows.

Figure 1. The mechanism of alkali and zinc reduction, oxidation and circulation.
 IRONMAKING & STEELMAKING 3

Table 1. Composition of raw materials and fuel (wt-%). Table 3. Composition of hot metal (wt-%).
Compositions TFe FeO Fe2O3 w(C)K w(C)M Compositions Fe C Si Mn P S THM (°C)
Values 56.65 7.71 71.26 85.63 77.48 Values 94.56 4.57 0.36 0.36 0.12 0.03 1505

The source of heat in the high-temperature zone is carbon 1000w[Fe]

combustion, and the heat is consumed by the reduction of K = ( tan a × 12 × + 1000w[C]
56
iron oxides and other oxides as well as melting ore and (23)
1
slag. According to the carbon combustion reaction shown in − M · w(C)M ) ·
w(C)K
Equation (15), one carbon atom requires one oxygen atom
to form CO, thus the oxygen atom consumed is equal to the where K is the coke ratio, kg t−1, M is the pulverised coal injec-
carbon atom consumed in front of tuyere. The thermal equili- tion rate, kg t−1, w(C)K is the carbon content of coke,%, w(C)M
brium in the high-temperature zone can be expressed as is the carbon content of coal, %, w[C] is the carbon content of
Equation (16) or (17). hot metal,%.

2C + O2 = 2CO (15)
Effect of harmful elements on the coke ratio
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yb · qb = yd · qd + Q
yb qd
= (17)
yd + Q/qd qb
where yd is the degree of direct reduction, qd is the heat
consumed by reducing 1 kg FeO molecule, which is deter-
mined by the heat effect of Equation (18). Here, qd is
153,200 kJ kg−1. Q is the heat that is consumed by the
reduction of other oxides, desulphurisation and melting
ore and slag. qb , the effective heat produced by combusting
1 kg carbon atom in front of tuyere, is given by Equation
(19).
FeO + C = Fe + CO
(9800w(C)blast + vblast · cblast · tblast − vgas · cgas · tgas )
qb =
w(C)blast /12
where w(C)blast is the mass of carbon combusted in front of
tuyere for producing 1 t of metal iron, kg/tHM, vblast is the
volume of blast for producing 1 t of metal iron, m3/tHM,
cblast is the specific heat capacity of blast, kJ (m3 K)−1,
tblast is the blast temperature, °C, vgas is the volume of
gas for producing 1 t of metal iron, m3/tHM, cgas is the
specific heat capacity of gas, kJ (m3 K)−1, tgas is the gas
temperature, °C.
The coordinate of point P is determined by the following
equations according to the similar triangle principle.
qd
xP =
qd + qb


Q
yP = yU + xP (yV − yU ) = yf + xP
qd
The slope of the Rist operation diagram is given by the fol-
lowing equation.
m(O)/m(Fe)
tan a =
m(O)/m(C)
Considering the carbon dissolved in hot metal and existed in
coal, the certain relationship between the slope of the Rist
operation diagram and coke ratio is expressed as the follow-
ing equation.
(16)
In this study, the effect of harmful elements on the coke ratio
is researched on a commercial blast furnace with an inner
volume of 1780 m3. Tables 1–6 [14] show the compositions
of raw materials and fuel, blast furnace operating parameters,
the compositions of hot metal, slag and gas as well as the
loads and accumulation times of harmful elements, respect-
ively. Based on the results of dissection study of the blast
furnace, the accumulation times of K, Na and Zn are
assumed to be 50, 50 and 80, respectively.
The Rist operation diagram is obtained according to the
above method, as shown in Figure 2.
The oxides of harmful elements are reduced by CO in the
(18) lower part of furnace and oxidised by CO2 in the upper part
of furnace, which leads to a decrease in gas utilisation and
an increase in heat consumption. As a result, the positions
of A and P in the Rist operation diagram are changed accord-
(19)
ing to the following equations:
Xi Yi
2V(CO2 ) + V(CO) − Vm
m(O) Mi
xA′ = = (24)
m(C) V(CO2 ) + V(CO)
⎛ ⎞
Xi · Yi · DHi ⊖ /Mi
⎜ Q + ⎟
1000w[Fe]/56
yP′ = yf + xP ⎜
⎝ − yf ⎟
⎠ (25)
qd
where Xi is the load of harmful elements, kg/tHM, Yi is the
accumulation times of harmful elements, Mi is the molar
mass of specie i, V(CO) and V(CO2 ) are the volumes of CO
(20)
and CO2 in the top gas, m3.
Figure 3 shows the impact of harmful elements on the Rist
− yf (21) operation diagram. The line AE is the Rist operation diagram
current condition, and the line A′ E′ is the Rist operation
diagram under ideal condition that no harmful elements
into blast furnace. It is concluded that harmful elements can
lead to an increase in the slope of Rist operation diagram,
(22) which means that the coke ratio increases. The calculation
results show that the loads and accumulation times of K, Na
and Zn under current condition lead to an increase in the
coke ratio by 14.2, 35.8, 9.3 kg/tHM compared to the ideal con-
dition. It is clear that harmful elements have significant impact
on the coke ratio in the blast furnace.

Table 2. Blast furnace operating parameters.

Parameters Productivity t (d m3)−1 Blast m3 min−1 Oxygen rate % Moisture % Tblast °C Coal rate kg t−1
Values 2.60 4175 2.19 1.5 1239 172
 4 Y. J. WANG ET AL.

Table 4. Composition of slag (wt-%).

Compositions SiO2 CaO MgO S Al2O3 R2 Slag volume (kg)
Values 34.42 38.65 7.74 0.8 15.89 1.12 412

Table 5. Composition of top gas (%).

Compositions CO CO2 Gas utilisation (%)
Values 26.00 22.80 46.72

Table 6. Loads and accumulation times of harmful elements.

Elements K2O Na2O Zn
Loads (kg/tHM) 1.4 2.1 0.35
accumulation times 50 50 80
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Effect of harmful elements accumulation times on the

coke ratio Figure 3. Effect of harmful elements on the Rist operation diagram.
The accumulation times of harmful elements are the enrich-
ment of harmful elements in the blast furnace. Figures 4
and 5 show the effect of accumulation times of harmful
elements on gas utilisation and heat consumption, respect-
ively. Gas utilisation decreases and heat consumption
increases proportional with the increase of accumulation
times of each element. The increase of accumulation times
means that more harmful elements are reduced in the
lower part of the blast furnace, leading to a CO transfer by
the reduction reaction in the blast furnace. As a result, gas util-
isation decreases and heat consumption increases. The effect
of each element on gas utilisation decreases and heat con-
sumption increases in the order of Na, K, and Zn. This
means that the circulation and accumulation of Na can
cause maximum increase in the coke rate in the blast furnace.
Figure 6 shows that the effect of accumulation times of
harmful elements on the coke ratio. With an increase in the
accumulation times, a linear increase in the coke ratio is Figure 4. Effect of accumulation times of harmful elements on gas utilisation.
observed. The effect degree of each harmful element on the
coke ratio varies. Table 7 shows the effect degree of each
harmful element accumulation times on the coke ratio (the slopes of the lines as presented in Figure 6). As shown in
Figure 6 and Table 7, the influence orders of harmful elements
accumulation times are Na > K > Zn. Thus, it is important to
improve the capacity of removing alkali metals of slag to
decrease the coke ratio.

Figure 5. Effect of accumulation times of harmful elements on heat

Figure 2. The Rist operation diagram under current condition. consumption.
 IRONMAKING & STEELMAKING 5

Figure 8. Effect of loads of harmful elements on heat consumption.

Figure 6. Effect of accumulation times of harmful elements on the coke ratio.
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Table 7. Effect degree of accumulation times of harmful elements on the coke

ratio.
Elements K2O Na2O Zn
Values 0.29 0.71 0.12

Effect of loads of harmful elements on the coke ratio

As shown in Figures 7 and 8, the effect trend of loads of
harmful elements is consistent with that of accumulation
times of harmful elements on gas utilisation and heat con-
sumption. However, at fixed load, the effect of Zn on gas util-
isation and heat consumption is more significant than those
of K and Na.
Figure 9 shows that the effect of loads of harmful elements Figure 9. Effect of loads of harmful elements on the coke ratio.
on the coke ratio. The influence orders of loads of harmful
elements are Zn > Na > K. Table 8 shows the effect degree
of each harmful element load on the coke ratio (the slopes Table 8. Effect degree of loads of harmful elements on the coke ratio.
of the lines as presented in Figure 9). It can be seen that the Elements K2O Na2O Zn
increase of loads of harmful elements has significant impact Values 10.2 16.9 27.3
on the coke ratio. Many studies have shown that the
adverse impact of K on blast furnace operations is higher
than those of Na and Zn. However, according to the results From the above discussion, the effect of harmful elements
in the paper, the effect of Na and Zn on gas utilisation and on the coke ratio is quantitatively studied using the Rist
heat consumption is more significant than that of K. Therefore, diagram, which can be described by the following equation.
it is important to restrict the loads of Na and Zn in the blast
furnace.
DK = 0.21XK YK + 0.34XNa YNa + 0.34XZn YZn (26)

Figure 7. Effect of loads of harmful elements on gas utilisation. Figure 10. The coke rate increased by the effect of harmful elements.
 6 Y. J. WANG ET AL.
where DK is the increments of coke ratio by the effect of
harmful elements, kg/tHM.
Figure 10 shows that the calculation results of this paper
compared with Jiao’s results. The increase of heat consump-
tion has more effect on the coke ratio than the decrease of
gas utilisation. The total increase of the coke ratio by the
effect of K, Na and Zn is 14.2, 35.8, 9.3 kg/tHM, respectively,
of which the effect of heat consumption accounts for 55.9,
60.9, 60.9%, respectively.
Conclusions
(i) The oxides of harmful elements are reduced by CO in the
lower part of furnace and oxidised by CO2 in the upper
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part of furnace, which leads to a decrease in gas utilis-
ation and an increase in heat consumption. As a result,
the coke ratio increases.
(ii) The effect degree of each harmful element on the coke
ratio varies. The influence orders of accumulation times
and loads of harmful elements on the coke ratio are
Na > K > Zn, Zn > Na > K, respectively. Therefore, it is
important to restrict the loads of K, Na and Zn in the
blast furnace.
(iii) The increase of heat consumption has more effect on the
coke ratio than the decrease of gas utilisation. The total
increase of coke ratio by the effect of K, Na and Zn is
14.2, 35.8, 9.3 kg/tHM, respectively, of which the effect
of heat consumption accounts for 55.9, 60.9, 60.9%,
respectively.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was financially supported the National Science Foundation for
Young Scientists of China (51704019) and the Key Program of the National
Natural Science Foundation of China (No. U1260202) and the 111 Project
(No. B13004).
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