JFE TECHNICAL REPORT

No. 28 (Sep. 2022)

Reduction of CO2 Emissions from Blast Furnace with

Carbon Recycling Methane
KAWASHIRI Yuki*1  NOUCHI Taihei*2  KASHIHARA Yusuke*3

Abstract: nologies for reducing CO 2 emissions have been devel-

In order to reduce of CO 2 emissions from blast fur- oped to date, including burden distribution control
nace, a carbon recycling blast furnace, in which methane techniques and small coke mixed charging, CO 2 emis-
synthesized from CO 2 in the blast furnace gas (CN sion reduction by operational technologies is approach-
methane) is used again in the blast furnace, was studied. ing its limit 3,4). With this background, moves to convert
As a result of the evaluation by the Rist diagram, it was energy sources from coal (carbon) to hydrogen which
shown that CN methane reduced CO 2 emission mainly doesn’t discharge CO 2 in order to realize a drastic
by the following two functions. (1) To decrease direct reduction in CO 2 emissions can be seen in Japan and
reduction by increasing the amount of reducing gas. (2) other countries. As examples, a one tuyere hydrogen
To supply heat by reacting with oxygen in front of the injection test at ThyssenKrupp’s Duisburg No. 9 blast
tuyere. In this study, the carbon recycling blast furnace furnace and the COURSE50 project in Japan may be
was found to have the possibility of reducing CO 2 emis- mentioned 5,6). In recent years, CCU (Carbon dioxide
sions by 30 % or more compared with the conventional Capture and Utilization) has attracted attention as a
blast furnace. It was also found that oxygen blowing and method for effectively utilizing CO 2 by producing
heating gas injection from the shaft upper level were products using CO 2 captured from the atmosphere or
effective for maximizing the amount of CN methane from industrial exhaust gases as a feedstock. Utilizing
injection. captured CO 2 to produce products that were originally
made from fossil fuels will contribute to low carboniza-
tion, and CO 2 will not be emitted while it is fixed in the
1. Introduction
product. Although CO 2 emissions from manufacturing
The 21 st Conference of the Parties to the United process are allowed in CCU, there is currently an
Nations Framework Convention on Climate Change imbalance between the demand for products that can
(COP21) held in November 2015 adopted the Paris be produced using CO 2 emitted by the steel industry
Agreement on emissions of greenhouse gases (GHG), and the amount of those emissions. For example, Japan
beginning with CO 2 1). Steel works which mainly use the imports an average of about 1.7 million tons of metha-
blast furnace process produce large amounts of steel by nol each year, but considering the fact that 0.7 tons of
consuming coal as a primary energy source. In 2019, methanol can be produced from 1 ton of CO 2, conver-
the Japanese steel industry emitted 150 million tons of sion of all the CO 2 emitted by the steel industry to
CO 2, or approximately 14 % of the country’s total methanol is not realistic, since the supply of methanol
annual CO 2 emissions of 1.1 billion tons (actual results would vastly exceed demand. 7)
for 2019) 2). Thus, reducing CO 2 emissions is an urgent Therefore, the authors attempted to solve the
challenge for the steel industry as a CO 2 emission-in- above-mentioned market problem by reusing a product
tensive industry. Although various energy-saving tech- produced by CCU as a reducing agent in the steel

† *2
Originally published in JFE GIHO No. 49 (Feb. 2022), p. 8−14 Dr. Eng.,
Senior Researcher General Manager,
Ironmaking Research Dept.
(currently, Environmental Process Research Dept),
Steel Res. Lab., JFE Steel

*1 *3
 enior Researcher Deputy Manager,
S Dr. Eng.,
Ironmaking Research Dept., Senior Researcher Manager,
Steel Res. Lab., Ironmaking Research Dept.,
JFE Steel Steel Res. Lab., JFE Steel

9
Copyright © 2022 JFE Steel Corporation. All Rights Reserved.
 Reduction of CO 2 Emissions from Blast Furnace with Carbon Recycling Methane

industry, in other words, by “carbon recycling” to the

3. Evaluation by Model
steel manufacturing process. It should be noted that
this approach has the advantage of not contributing to
3.1 Heat and Mass Balance Model
CO 2 emissions, as the carbon that originates from the
carbon-recycling reducing agent is repeated recycled in The potential amount of CO 2 emission reduction in
the steel manufacturing process, and is not discharged a blast furnace process using the carbon recycling tech-
outside the system. This paper reports on a study nology was studied with a Rist diagram 10,11). In a Rist
aimed at maximizing the reduction of CO 2 emissions diagram, the heat and mass balance is considered by
from the blast furnace process by utilizing carbon recy- separating the blast furnace into upper and lower parts
cling technology. by the temperature of the thermal reserve zone T R
(temperature at which heat rise and reduction stagnate).
A typical example of a Rist diagram is shown in Fig. 2,
2. Carbon Recycling Technology
where the horizontal axis shows (O+H 2) / (C+H 2), the
Figure 1 shows a conceptual diagram of the blast vertical axis shows (O+H 2) / Fe and the operational
furnace process using carbon recycling technology. condition of the blast furnace (Rist operating line) is
The coke used in the production of 1 ton of molten represented by the line RP. Point W shows the reduc-
pig iron (coke ratio) is reduced by injecting the product tion equilibrium condition of wustite-Fe at T R, and
synthesized from CO 2 (carbon neutral reducing agent) point P is a point determined from the heat balance in
from the tuyeres of the blast furnace in the same man- the lower part of the furnace. Actual operation passes
ner as pulverized coal, which has long been used in through point R, which is separated from point W by
blast furnaces. As the reducing agent synthesized from some distance. At this time, GR/GW is defined as shaft
CO 2, methane (CH 4) was selected in this study. The efficiency and is used as an index of reduction effi-
technology for synthesizing methane from CO 2 and ciency, which is determined by the reactivity of the raw
hydrogen, which is called methanation, was discovered materials, the burden distribution and other factors.
by Sabatier at the beginning of the 20 th century 8). As Point Y d expresses the reduction amount (direct reduc-
shown by the chemical reaction equation and heat of tion amount) by the apparent C in the coke. The slope
reaction expressed by the following Eq. (1), this is an of line RP, (C+H 2) / Fe, shows the specific reducing gas
exothermic reaction accompanied by comparatively volume necessary to produce 1 t of molten pig iron. In
large heat generation. this study, the CO 2 emission reduction rate of the blast
furnace using the carbon recycling technology was
CO 2 + 4H 2 = CH 4 + 2H 2O + 165 kJ/mol…… (1) evaluated on a conventional Rist diagram, considering
operational constraints. The CO 2 emission of the blast
Since 2013, a commercial methanation plant has furnace was calculated from the unit consumption of
been in operation using CO 2 separated from biogas and carbon charged to the blast furnace (specific carbon
hydrogen produced by electrolysis of water by Eto- consumption). In calculations of specific carbon con-
Gas 9). sumption, it should be noted that the carbon content

Fig. 1 Schematic of blast furnace process with carbon

recycling Fig. 2 Rist diagram

10 JFE TECHNICAL REPORT No. 28 (Sep. 2022)

 Reduction of CO 2 Emissions from Blast Furnace with Carbon Recycling Methane

of the carbon-neutral reducing agent (CN methane)

and the carbon contained in the injected preheating gas
(described below) were not counted in the specific car-
bon consumption because both are recirculated in the
system.

3.2 Constraints on Blast Furnace Operation

3.2.1 Theoretical flame temperature in front

of tuyere
Fig. 3 Relationship between O 2 concentration in blast with
In a blast furnace, hot blast is blown into the fur- specific hot blast volume (relative value)
nace from the tuyeres, and the reducing agent which is
injected at the same time and high temperature coke
present in front of the tuyere react with the oxygen in ture oxygen with the hot blast. Figure 3 shows the rela-
the hot blast to produce a reducing gas. The tempera- tionship of the O 2 concentration in the hot blast and
ture of the reducing gas after this reaction is called the specific hot blast volume (unit consumption of hot
theoretical flame temperature (TFT) in front of the blast) for the case where the specific O 2 volume is con-
tuyere and is used as a control index in actual opera- stant. The specific hot blast volume decreases when the
tion. If TFT is too high, a large amount of SiO gas will O 2 concentration in the blast increases.
be generated in the raceway, and may cause high Si in
the hot metal, scaffolding on the furnace wall and other 3.3 Operational Limits of Blast Furnace
trouble 12). On the other hand, if TFT is too low, heat
transfer to the molten iron will be insufficient, resulting 3.3.1 Thermal reserve zone temperature and
in a drop in the hot metal temperature. Here, the upper shaft efficiency
and lower limits of TFT were set at 2 300˚C and In a Rist diagram, the blast furnace is divided into
2 000˚C, respectively, based on actual results. TFT is upper and lower parts at the thermal reserve zone,
calculated assuming 100 % of the elements C, H, N which is determined by the gasification starting tem-
and O contained in the hot blast, injected reaction perature of the coke. The reduction equilibrium gas
agent and coke react to the form of CO, H 2 and N 2. composition is found on the precondition that the tem-
The temperature of the coke in front of the tuyere was perature of the thermal reserve zone and the wustite-Fe
set at 0.75 times TFT following Ramm’s equation 13). reduction starting temperature are the same, and the
reduction equilibrium constraints in blast furnace
3.2.2 Top gas temperature operation is considered. However, according to
A low top gas temperature will cause poor blast fur- Miyashita et al., the heat-flow ratio (ratio of thermal
nace operation due to problems such as condensation capacity of a solid and thermal capacity of a gas)
of the moisture in the top gas. Here, the lower limit of increases as the O 2 concentration in the blast is
the top gas temperature was set at 100˚C. One tech- increased, heating of the burden in the upper shaft
nique for raising the top gas temperature is injection of becomes inadequate, and the thermal reserve zone dis-
preheating gas from the upper shaft, which has also appears when the O 2 concentration is raised to 35 % or
been proposed for the oxygen blast furnace 14). In this more 15). This means the reduction equilibrium tem-
study, if the top gas temperature decreases to 100˚C or perature cannot be determined under high O 2 concen-
less, preheated gas at a temperature of 1 000˚C by par- tration conditions, and analysis by the Rist diagram is
tial combustion of the top gas is injected into the fur- inappropriate. On the other hand, in an experiment
nace from the upper shaft to maintain a top gas tem- with a small-scale blast furnace, Ohno et al. demon-
perature of 100˚C. strated an oxygen blast furnace process in which pre-
heating gas was injected in the upper shaft together
3.2.3 Blast temperature with the oxygen blast 14). As a result, a quasi-thermal
An upper limit of the oxygen concentration in the reserve zone where the temperature stagnates was
blast that passes through the hot stove is set consider- formed in the vicinity of the preheating gas injection
ing the risk to the equipment. Here, the upper limit of level, and the temperature could be controlled by the
the oxygen concentration of the gas passing through temperature and flow rate of the preheating gas. In
the hot stove was set to 29 %. When the oxygen con- addition, the ore had been reduced to wustite at the
centration of the blast is raised, the blast temperature preheating gas injection level. Based on these results,
was determined assuming mixture of normal tempera- Ohno et al. analyzed the operation of the experimental

JFE TECHNICAL REPORT No. 28 (Sep. 2022)11

 Reduction of CO 2 Emissions from Blast Furnace with Carbon Recycling Methane

FeO + H 2 = F + H 2O − 24 kJ/mol … ……… (3)

FeO + C = Fe + CO − 155 kJ/mol… ……… (4)

Because direct reaction is an extremely large endo-

thermic reaction in comparison with the other two
reactions, reducing the ratio of direct reduction leads
to a decrease in the amount of coke combustion in
front of the tuyere, and in turn, a decrease in the CO 2
emission from the blast furnace. Since direct reduction
cannot take a negative value, the theoretical lower limit
is 0 %. This means the Rist operating line cannot enter
the region to the lower right of the coordinate (1, 0).

3.4 Calculation Results

Operation of a blast furnace using the carbon recy-
cling technology was studied with a Rist diagram under
the assumptions up to section 3.3. As common condi-
tions, shaft efficiency of 0.9, unit heat loss of 420 MJ/
t-HM and a hot metal and slag temperature of 1 500˚C
were set. Since pulverized coal is injected from the
tuyeres as an injected reducing agent in conventional
Fig. 4 Themal reserve zone temperature of conventional blast furnaces, a representative pulverized coal ratio of
blast furnace and oxygen blast furnace 150 kg/t-HM was assumed. During CN methane injec-
tion, pulverized coal was not injected, and the CN
blast furnace by a Rist diagram, using the gas tempera- methane injection rate was manipulated in the range
ture at the preheating gas injection level as the tempera- from 0 to 200 kg/t-HM. When the reducing agent is
ture of the thermal reserve zone. Figure 4 shows a con- injected from the tuyeres, TFT decreases for reasons
c e p t u a l d i ag ra m o f t h e t h e r m a l re s e r ve z o n e such as an increase in the volume of gas due to gas
temperature of a conventional blast furnace and the injection. However, TFT can be increased by increasing
oxygen blast furnace. The results of this operational the O 2 concentration in the blast, which reduces the
analysis confirmed that the shaft efficiency of the oxy- energy required to heat nitrogen in the blast. In this
gen blast furnace process is substantially constant, even study, the O 2 concentration in the blast was manipu-
though the thermal reserve zone temperature is lated in the range of 25 % to 100 %, and operational
decreased by approximately 200˚C from that of the parameters which satisfied the heat and mass balance
conventional blast furnace. were obtained as calculation results.
Based on this knowledge, in the present study, we
assumed that the thermal reserve zone temperature
decreases linearly from the blast O 2 concentration of
35 % to 100 %, so that the thermal reserve zone tem-
perature, which is 1 000˚C when blowing hot blast
decreases to 800˚C. In addition, shaft efficiency was
assumed to be constant, independent of the blast O 2
concentration, due to preheating gas injection.

3.3.2 Direct reduction ratio

The reduction reaction of ore that occurs in a blast
furnace can be broadly divided into three reactions:
reduction by CO gas, reduction by H 2 gas and direct
reduction by reaction with the apparent C content of
the coke. The chemical reaction equations and heat of
reaction of these respective reactions are shown in the
following Eq. (2) to Eq. (4).
Fig. 5 Change of theoretical flame temperature in front
of tuyere (TFT) with O 2 concentration in blast and
FeO + CO = Fe + CO 2 + 17 kJ/mol ………… (2) CN methane injection

12 JFE TECHNICAL REPORT No. 28 (Sep. 2022)

 Reduction of CO 2 Emissions from Blast Furnace with Carbon Recycling Methane

Fig. 6 Change of top gas temperature (TGT) with O 2

concentration in blast and CN methane injection
Fig. 7 Change of specific carbon consumption reduction
ratio with O 2 concentration in blast and CN methane
Figure 5 shows the change of TFT by manipulation injection
of the CN methane injection ratio and the O 2 concen-
tration in the blast. Although there is an upper limit for Table 1 Operation condition of conventional blast furnace
injection of CN methane because TFT decreases as the and carbon recycling blast furnace
CN methane injection ratio is increased, the CN meth- Conventional Carbon
ane injection volume can be increased by raising TFT BF recycling BF
by increasing the O 2 concentration in the blast to Shaft efficiency ( ) 0.9
reduce the energy required to heat nitrogen in the blast. Heat loss (MJ/t-HM) 420
Similarly, the change in the top gas temperature Coke rate (kg/t-HM) 354 341
(TGT) is shown in Fig. 6. TGT decreases when the O 2 Pulverized coal rate (kg/t-HM) 150
concentration in the blast is increased. This is due to CN methane rate (kg/t-HM) 145
the increased heat-flow ratio when the amount of
Blast volume (Nm 3/t-HM) 1 014 317
nitrogen in the blast is decreased, and in the region
O 2 concentration in blast (%) 24 100
where the methane injection ratio is low and the O 2
Blast temperature (˚C) 1 200 25
concentration in the blast is high, TGT decreases to the
Heating gas vol. (Nm 3/t-HM) 160
lower limit of 100˚C or less. Therefore, in this region, it
Heating gas temperature (˚C) 1 000
is necessary to recover TGT by injection of preheating
gas. B gas volume (Nm 3-dry/t-HM) 1 540 1 030

Figure 7 shows the change of the specific carbon B gas calorie (MJ/Nm ) 3
3 400 7 100
consumption reduction ratio, together with the permis- Carbon consumption (kg/t-HM) 425 293
sible range (upper/lower limits) of TFT and the region CO 2 emissions reduction (%) 31
where injection of preheating gas is necessary. Basically, CO reduction ratio (%) 61 61
specific carbon consumption can be reduced signifi- H 2 reduction ratio (%) 9 35
cantly by massive injection of CN methane. Therefore, Direct reduction ratio (%) 30 4
at the same O 2 concentration in the blast, the specific
carbon consumption reduction ratio increase as TFT
decreases. In addition, preheating gas injection is also blast) is not linear, and the temperature of the thermal
necessary in order to reduce specific carbon consump- reserve zone decreases as the O 2 concentration in the
tion by 20 % or more. From these results, it was shown blast increases.
that oxygen blowing and preheating gas injection from Table 1 shows the conditions of the carbon recycling
the upper shaft are effective for maximizing the volume blast furnace at the maximum CO 2 emission reduction
of CN methane injection. Here, it may be noted that rate, that is, the conditions of oxygen blowing and CN
the specific carbon consumption reduction rate takes a methane injection to the lower limit of TFT, in com-
minimum value with respect to the O 2 concentration in parison with the conditions of the conventional blast
the blast due to the assumptions that the relationship furnace. The specific carbon consumption of the car-
between the O 2 concentration in the blast and the spe- bon recycling blast furnace is 293 kg/t-HM, showing
cific hot blast volume (i.e., sensible heat of the hot the possibility of reducing specific carbon consumption

JFE TECHNICAL REPORT No. 28 (Sep. 2022)13

 Reduction of CO 2 Emissions from Blast Furnace with Carbon Recycling Methane

by more than 30 % in comparison with the conven- in comparison with the conventional blast furnace.
tional blast furnace.
4.2 Change of Heat Balance
Next, the conventional blast furnace and the carbon
4. Discussion
recycling blast furnace were compared in terms of the
heat balance. Figure 9 shows the necessary heat
4.1 Change of Rist Operating Line
(demand) and supplied heat (supply) for production of
A comparison of the Rist diagrams of the conven- 1 ton of hot metal by the respective processes. As
tional blast furnace and the carbon recycling blast fur- shown in Table 1, in the carbon recycling blast furnace,
nace is shown in Fig. 8. In the carbon recycling blast the amount of heat necessary for the reduction reaction
furnace, the W point, which is the reduction equilib- is small due to the small amount of direct reduction,
rium constraint, shifts further to the oxidation gas side which is a large endothermic reaction. Therefore, the
due to the decrease in the temperature of the thermal heat demand for production of 1 ton of hot metal is
reserve zone. Furthermore, because massive injection reduced by approximately 1 000 MJ/t-HM in compari-
of CN methane is possible under the condition of oxy- son with the conventional blast furnace process. In
gen blowing, the specific reducing gas volume per ton addition, the amount of heat supplied by combustion
of hot metal increases, and the slope of the corre- of coke is also reduced because heat is supplied by the
sponding operating line becomes larger. As a result of reaction of CN methane and oxygen in front of the
these changes, the point of intersection between the tuyeres. Because this effect cannot be obtained by
operating line and the Y axis at X = 1 shifts downward, blowing hydrogen directly into the blast furnace, this
and the direct reduction amount Y d decreases greatly can be considered an advantage of the carbon recycling
blast furnace, in which hydrogen is converted to a
chemical compound.

4.3 Change of Carbon Consumption Balance

Figure 10 shows the breakdown of the carbon con-
sumption in the conventional blast furnace and the car-
bon recycling blast furnace. In the conventional blast
furnace, carbon is mainly consumed in the reaction
with oxygen in front of the tuyeres, in the direct reduc-
tion reaction and the hot metal carburization reaction.

Fig. 8 Rist diagrams of conventional blast furnace and Fig. 10 Breakdown of carbon consumption of conventional
carbon recycling blast furnace blast furnace and carbon recycling blast furnace

Fig. 9 Heat balance of conventional blast furnace and carbon recycling blast furnace

14 JFE TECHNICAL REPORT No. 28 (Sep. 2022)

 Reduction of CO 2 Emissions from Blast Furnace with Carbon Recycling Methane

Among these reactions, in the carbon recycling blast (1) U

 se of carbon neutral (CN) methane reduces
furnace, carbon consumption by direct reduction the CO 2 emission of the blast furnace by the fol-
decreases greatly. Carbon consumption by combustion lowing two effects.
in front of the tuyeres to compensate for the decrease i) C N methane decreases the amount of direct
in the sensible heat of the blast is larger in the carbon reduction, which is a large endothermic reac-
recycling blast furnace than in the conventional blast tion, by increasing the amount of reducing
furnace, but because part of this carbon consumption gas.
is carbon in the CN methane, the amount of coke con- ii) C  N methane supplies heat by reaction with
sumed in front of the tuyeres is approximately the same oxygen in front of the tuyeres.
as that in the conventional blast furnace. (2) I t is possible to reduce CO 2 emissions more than
30 % at a maximum by using CN methane in the
4.4 Technologies to be Developed and Issues for blast furnace.
Realization (3) I n maximizing CN methane injection, oxygen
When examining the operating parameters by the blowing and preheating gas injection from the
Rist diagram in this study, several calculation assump- upper shaft level are effective.
tions were made based on past knowledge, for example,
the transition of the thermal reserve zone temperature References
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JFE TECHNICAL REPORT No. 28 (Sep. 2022)15

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