energies

Article
Thermodynamic Study on Reduction of Iron Oxides
by H2 + CO + CH4 + N2 Mixture at 900 ◦C
Guanyong Sun 1,2 , Bin Li 3 , Hanjie Guo 1,2, *, Wensheng Yang 1,2 , Shaoying Li 1,2
and Jing Guo 1,2
1 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing,
Beijing 100083, China; sunguanyong@xs.ustb.edu.cn (G.S.); b20160095@xs.ustb.edu.cn (W.Y.);
b20170108@xs.ustb.edu.cn (S.L.); guojing@ustb.edu.cn (J.G.)
2 Beijing Key Laboratory of Special Melting and Preparation of High-End Metal Materials, University of
Science and Technology Beijing, Beijing 100083, China
3 College of Metallurgical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China;
libin@xauat.edu.cn
* Correspondence: guohanjie@ustb.edu.cn; Tel.: +86-010-62334964




Received: 23 July 2020; Accepted: 22 September 2020; Published: 25 September 2020


Abstract: The reduction gas used in the gas-based direct reduction iron-making process contains CH4
in different concentrations, which has an important effect on the gas and heat needed for the reduction
of iron oxide. To investigate the influence of CH4 on gas utilization rate and heat needed at 900 ◦ C,
the initial conditions are set as H2 % + CO% = 90, CH4 % + N2 % = 10, gas pressure 1–9 atm, and 0.5 mol
Fe2 O3 , and the equilibrium state composition is calculated using the minimum free energy method.
The utilization rate of total gas can be improved, and gas demand can be decreased by increasing
CH4 concentration or H2 concentration or reducing gas pressure. For the production of per ton of Fe
from 25 ◦ C to 900 ◦ C, 6.08–7.29 m3 of reduction gas, and 7.338–8.952 MJ of gas sensible heat can be
saved by increasing 1 m3 CH4 , while 10.959–11.189 MJ of reaction heat is increased. Compared with
3390.828–3865.760 MJ of the total heat of per ton of Fe for the reduction by H2 + CO, 2.174–3.703 MJ
of total heat is increased by increasing 1 m3 CH4 , and the increase ratio is 0.065–0.096%. This study is
helpful to improve the gas efficiency and lower the pursuit of higher concentration of H2 + CO in
reduction gas.

Keywords: thermodynamic model; gas-based direct reduction ironmaking; gas utilization rate; CH4
conversion; minimized Gibbs free energy principle; equilibrium state; heat needed; reaction enthalpy

1. Introduction
The gas-based direct reduction iron-making process is a kind of non-blast furnace iron-making
process which does not use coke and produces solid iron through gas–solid reaction. It is a rapidly
developing iron-making process due to its short technological process, high cleanliness, and low CO2
emission [1]. The basic composition of a gas-based direct reduction iron-making process can be divided
into two parts: the gasification process and reduction process [2–6]. The gasification process provides
available and clean reduction gas, which requires the concentration ratio of H2 + CO greater than
85%, the concentration ratio of CO2 + H2 O less than 5%, the concentration ratio of CH4 less than 3%,
the concentration ratio of H2 S less than 0.1%, and the residual is N2 .
H2 and CO are highly efficient in reducing gases. The gas utilization rates of H2 and CO in
the reduction of Fe2 O3 at 900 ◦ C are 37.575% and 31.460%, respectively, which is the upper limit of
the utilization rates of these two gases at 900 ◦ C. Therefore, the reduction utilization rate of the H2
+ CO mixture is between 31.460% and 37.575% [7]. In the presence of CO2 and H2 O, the reduction

Energies 2020, 13, 5053; doi:10.3390/en13195053 www.mdpi.com/journal/energies

Energies 2020, 13, 5053 2 of 18

utilization rate of the H2 + CO + CO2 + H2 O mixture is further lower. N2 is often recognized as a heat
carrier and does not participate in the reduction reaction in a reduction atmosphere [8]. CO2 can be
removed by pressure swing adsorption or polyamine adsorption, and H2 O can be removed by low
temperature or desiccants, while CH4 + N2 will stay in the reduction gas [9].
The reduction gas generated from CH4 conversion and coal gasification contain CH4 in different
concentrations, as shown in Table 1 [9–13]. The difference in the concentration of CH4 between input
and output is used to calculate reduction gas demand [11]. In addition, 1 mol CH4 is often considered
to be equivalent to 4 mol H2 + CO, according to CH4 conversion Formulas (9) and (10). The chemical
reactions in which CH4 participates in the reduction of Fe2 O3 are complex and reversible, as shown
in Table 2. The main reactions between Fe2 O3 and H2 + CO + CH4 + N2 include reduction reactions
by H2 or CO or CH4 , CH4 conversion reactions, carburizing reactions, carbon deposition reaction,
water gas shift reaction, gasification reaction, etc. The determination of the equilibrium state containing
11 components requires detailed calculation. It is not reliable to calculate gas demand by only these
two chemical equations. Therefore, a specific thermodynamic analysis of the influence of CH4 on
the reduction reaction of Fe2 O3 is required.

Table 1. The gas composition used for the reduction of iron oxide (volume fraction, %).

Species CH4 Conversion Coal Gasification

HYL III MIDREX BG/L Texaco Shell HT-L Two-Stage
H2 /% 61.8 55–58 27.9 30.78 25.6 30 29.36
CO/% 23.5 34–37 58.93 39.35 65.1 60 62.38
H2 O/% 0.6 3–4 - 16.43 - - 1.5
CO2 /% 3.0 1.5–2.5 3.03 11.43 0.8 3.5 2.76
CH4 /% 4.0 0.5–3 6.13 0.04 0.01 <1 0.26
N2 /% 7.1 0.5–1 3.35 0.49 8.03 6.2 4.87
H2 S(COS)/% - - - 0.88 0.07 0.02 0.37

Table 2. The main reactions between Fe2 O3 and H2 + CO + CH4 mixture.

Reaction Type Chemical Reaction Equation

3Fe2 O3 + CO = 2Fe3 O4 + CO2 ∆H298K
= −43.221 kJ/mol (1)
Fe3 O4 + CO = 3FeO + CO2 ∆H298K
= 19.288 kJ/mol (2)
CO Reduction reaction
FeO + CO = Fe + CO2 ∆H298K
= −10.920 kJ/mol (3)
Fe2 O3 + 3CO = 2Fe + 3CO2 ∆H298K
= −23.389 kJ/mol (4)
3Fe2 O3 + H2 = 2Fe3 O4 + H2 O ∆H298K
= −2.071 kJ/mol (5)
Fe3 O4 + H2 = 3FeO + H2 O ∆H298K
= 60.438 kJ/mol (6)
H2 Reduction reaction
FeO + H2 = Fe + H2 O ∆H298K
= 30.229 kJ/mol (7)
Fe2 O3 + 3H2 = 2Fe + 3H2 O ∆H298K
= 100.060 kJ/mol (8)
CH4 + H2 O = 3H2 + CO ∆H298K
= 206.083 kJ/mol (9)
CH4 conversion reaction
CH4 + CO2 = 2H2 + 2CO ∆H298K
= 247.233 kJ/mol (10)
CH4 cracking reaction CH4 = C + 2H2 ∆H298K
= 74.810 kJ/mol (11)
CH4 + FeO = Fe + 2H2 + CO ∆H298K
= 236.312 kJ/mol (12)
CH4 reduction reaction
Fe2 O3 + 3CH4 = 2Fe + 6H2 + 3CO ∆H298K
= 718.309 kJ/mol (13)
3Fe + 2CO+ = Fe3 C + CO2 ∆H298K
= −149.829 kJ/mol (14)
3Fe + CO + H2 = Fe3 C + H2 O ∆H298K
= −108.679 kJ/mol (15)
Carburizing reaction 3Fe + CH4 = Fe3 C + 2H2 ∆H298K
= 97.404 kJ/mol (16)
3FeO + 5CO = Fe3 C + 4CO2 ∆H298K
= −182.590 kJ/mol (17)
3Fe + C = Fe3 C ∆H298K
= 22.594 kJ/mol (18)
Carbon deposition reaction 2CO = C + CO2 ∆H298K
= −172.423 kJ/mol (19)
Water-gas shift reaction CO + H2 O = H2 + CO2 ∆H298K
= −41.150 kJ/mol (20)
Gasification reaction C + H2 O = H2 + CO ∆H298K
= 131.273 kJ/mol (21)

The aim of this study is to investigate the effects of CH4 concentration, gas pressure, H2 or CO
concentration on reduction gas needed, and reaction enthalpy at 900 ◦ C with CH4 concentration
 10%. This study is helpful to understand the relationship between H2 + CO and CH4 in
ss of reducing Fe2O3 and even to improve the utilization rate of reducing gas by increasing
ntration of CH4.
Energies 2020, 13, 5053 3 of 18

thods
less than 10%. This study is helpful to understand the relationship between H2 + CO and CH4 in
the process of reducing Fe2 O3 and even to improve the utilization rate of reducing gas by increasing
arameters Settings
the concentration of CH4 .

2. Methods
The initial state and the equilibrium state are shown in Figure 1. The reaction system
2.1.and
osed of solid Parameters
gas.Settings
The initial solid is 0.5 mol Fe2O3, and other gangue in the iron ore
The initial state and the equilibrium state are shown in Figure 1. The reaction system is composed
onsidered in the reaction system. The initial gas volume fraction is as shown in Table 3.
of solid and gas. The initial solid is 0.5 mol Fe2 O3 , and other gangue in the iron ore are not considered
me fraction of Hreaction
in the 2 + CO is fixed
system. atgas90%;
The initial volumenamely,
fraction is asCO%
shown in+Table
H2% = 90,
3. The volumewhich
fraction is
of a common
H2 + CO is fixed at 90%; namely, CO% + H2 % = 90, which is a common gas composition requirement.
osition requirement. For comparison, CO2 gas and H2O gas in initial states are neglected in
For comparison, CO2 gas and H2 O gas in initial states are neglected in the mixed gas. The volume
d gas. The volume
fraction offraction of CH
CH4 gas increase 4 gas
from 0% toincrease
10%, and thefrom 0% to 10%, and the N2 is residual.
N2 is residual.

Initial state：
Solid：0.5 mol Fe2O3；
Gaseous：H2，CO，CH4，N2

Tempeature：900 ℃；
Pressure：ptotal=1~9 atm
ΔH r

Equilibrium state：
Solid：Fe2O3，Fe3O4，Fe0.95 O，Fe，Fe3C，C；
Gaseous：H2，CO，H2O，CO2，CH4，N2

Figure 1. The initial and equilibrium state of the reaction system.

Figure 1. The initial and equilibrium state of the reaction system.
Table 3. The given volume fraction of each component of initial gas.

H2 /%given volume
Table 3. The CO/% fraction /% each component
CH4of N2 /% Σ/%
of initial gas.
0 90
15 75
H2/% CO/% 30 60
CH4/% N2/% Σ/%
0–10, increment 1
0 90 45
60
45
30
Residual 100

15 75 75 15
90 0
30 60
45 The 0–10,
45reaction temperature is 900 increment
◦ C, which 1 MIDREX process and
is used in the Residual
HYL/Energiron 100
process [9,13]. The total gas pressure ptotal increases from 1 atm 9 atm, and 1 atm (atmosphere) or 1 p
60 30
is 101,325 Pa. The total pressure of the reaction system is set to remain unchanged before and after
75 15In fact, the gas pressure decreases from bottom to top of the shaft furnace due to the solid
reactions.
bulk layer.
90 0

The reaction temperature is 900 °C, which is used in the MIDREX process and HYL/Energ

ss [9,13]. The total gas pressure

ptotal increases from 1 atm 9 atm, and 1 atm (atmosphere
Energies 2020, 13, 5053 4 of 18

The amount of the initial gas is 10 mol, which exceeds the amount of gas required for reduction.
For the reduction of 0.5 mol Fe2 O3 , the demand for reduction gas, composed of different concentrations
of H2 + CO, are 4.0–4.7 mol, which has been calculated by the minimum Gibbs free energy method [7].
For the H2 + CO + CH4 + N2 gas mixture, the gas demand needs to be calculated under different
conditions by the minimum Gibbs free energy method.

2.2. The Minimum Gibbs Free Energy Method

The minimum Gibbs free energy method can be used to calculate the amount of the components
in the equilibrium state [7,14,15], which can be obtained from the initial state conditions (amount,
temperature, and pressure). Based on the principle of minimum free energy; that is, the sum of Gibbs
free energy of each component in the equilibrium state is the smallest, and a calculation model is
established, as shown in Formulas (22) and (23). By solving the non-linear equations with constraints,
the amount of each component in the equilibrium state could be received.

N
X N
X  
min.Gall = ni Gi = ni G
i
+ RT ln a i (22)
i=1 i=1

N
X
s.t. αie ni = ne (e = 1, 2, · · · , M) (23)
i=1

In this two formulas, i, e, represent the components and elements in the equilibrium state,
respectively; N, M, represent the number of components and the number of elements in the equilibrium
state, respectively; ni , ne , are the amounts of the components i and elements e in the equilibrium
state, respectively, mol; Gi , G i
, represent the Gibbs free energy and the standard Gibbs free
energy of the components i, respectively, J/mol; pi , ptotal , p , represent the partial pressure of
the components i, the total pressure of all gas, and the standard atmospheric pressure, respectively,
Pa, and p = 1atm = 101,325 Pa; αie represents the number of element e in the component i; T,
represents the thermodynamic temperature of the system, K; R, is the ideal gas constant, which is equal
p n p
to 8.314, J/(mol·K); ai represents the activity, when i is a gaseous state ai = p i = P ni · total
p
, when i is a
i
solid-state ai = 1. The software LINGO is used in the mathematics calculation of minimum values for
nonlinear equations.

2.3. Reaction Enthalpy and Sensible Heat

For reaction enthalpy of chemical reactions and sensible heat of substance with temperature
changing, these calculation formulas are the same, which are the difference between the final state
and the initial state, as shown in Formula (24).

N
X M
X
∆H = ni Hi, T − n j H j, T (24)
i j
i=1 j=1

where ∆H represents the enthalpy change, kJ/mol, and a negative value is exothermic, a positive value
is endothermic; i, j, signify the components after and before the state change, respectively; N and M
represent the number of components after and before the state change, respectively; ni and nj represent
the number of components after and before the state change, respectively, mol; Ti and Tj represent
the thermodynamic temperature of components after and before the state change, respectively, K; Hi, T
i
and H j, T , represent the standard molar enthalpy of component i at the thermodynamic temperature
j
Ti and the component j at the thermodynamic temperature Tj , respectively, kJ/mol. The standard molar
enthalpy and standard molar Gibbs energy of pure matter are derived from the specific heat capacity
data provided by previous literatures [16].
Energies 2020, 13, 5053 5 of 18

2.4. Related Definitions

All equilibrium compositions are calculated by the minimum Gibbs free energy method based
on the initial conditions. According to the amount of each component in the initial and equilibrium
state, some definitions are made out to search the thermodynamic law in the reduction of iron oxide by
reduction gas within CH4 at 900 ◦ C.
CO2 /(CO + CO2 ) and H2 O/(H2 O + H2 ) are used to show the equilibrium gas ratio and the utilization
rate of CO and H2 in the reduction of iron oxide, which is shown in Formulas (25) and (26), respectively.
nCO2 ,equilibrium
equilibrium gas ratio of CO2 = (25)
nCO,equilibrium + nCO2 ,equilibrium

nH2 O,equilibrium
equilibrium gas ratio of H2 O = (26)
nH2 ,equilibrium + nH2 O,equilibrium
where in the n expresses the amount of the component, and the subscript equilibrium and initial express
the equilibrium state and the initial state, respectively.
However, when CH4 is in the reduction gas, Formulas (25) and (26) are meaningless. According
to the mass balance of gas–solid reactions, the lost oxygen in iron oxide is the same as the increased
oxygen in gas. The deoxygenation rate of Fe2 O3 and the utilization rate of total gas are defined
as Formulas (27) and (28), respectively. Furthermore, the gas demand can be got by Formula (29).
The amount of O in iron oxide is 1.5 mol for 0.5 mol Fe2 O3 , and 600 m3 for Fe2 O3 including 1 t Fe. CH4
can save the volume of reduction gas and increase the reaction enthalpy, compared with the reduction
gas H2 + CO, the saving volume of total gas per mol CH4 and increased reaction enthalpy per mol are
defined in Formulas (30) and (31), respectively.

the amount of lost oxygen in Fe2 O3

deoxygenation rate of Fe2 O3 = × 100% (27)
the amount of oxygen in Fe2 O3

the amount of lost oxygen in Fe2 O3

utilization rate of total gas = × 100% (28)
the amount of the initial gas
the amount of O in iron oxide
the amount of gas needed = (29)
the utilization rate of total gas
the amount of saving volume
saving volume of total gas per mol CH4 = (30)
the amount of CH4
(∆HCO

+H
− ∆HCO

)
2 +CH4 +H 2 T,P
increased reaction enthalpy per mol CH4 = (31)
the amount of CH4
CH4 conversion is defined as shown in Formula (32). According to the element balance,
the possible product from CH4 are C, Fe3 C, H2 , CO, CO2 , and H2 O. Other hydrocarbons, carbon
hydroxide, and carbonates are not considered. CH4 conversion reflects the utilization rate of CH4
under specific conditions.
nCH4 ,equilibrium
CH4 conversion rate = (1 − ) × 100% (32)
nCH4 ,initial
 Energies 2020, 13, x FOR PEER REVIEW 6 of 18
Energies 2020, 13, 5053 6 of 18

3. Results and Discussion

3. Results and Discussion
3.1. The
3.1. The Equilibrium
Equilibrium Composition
Composition
The collection
The collection of
of settings
settings are
are taken
taken as
as an
anexample
exampletotodisplay
displaythe
thelaw
lawofofreduction
reductionofof
FeFe
2O3 by H2
2 O3 by
+ CO + CH4 + N2 mixtures: the initial gas concentration is H2% = 45, CO% = 45, CH4% = 3.0, N2% = 7,
H2 + CO + CH4 + N2 mixtures: the initial gas concentration is H2 % = 45, CO% = 45, CH4 % = 3.0,
the total pressure is 4 atm, and the reaction temperature is 900 °C. Figure 2 shows some rules, such as
N2 % = 7, the total pressure is 4 atm, and the reaction temperature is 900 ◦ C. Figure 2 shows some rules,
equilibrium products, equilibrium gas ratio, deoxygenation rate of iron oxide, gas utilization rate,
such as equilibrium products, equilibrium gas ratio, deoxygenation rate of iron oxide, gas utilization
and CH4 conversion.
rate, and CH4 conversion.

(a) (b)

(c) (d)
Figure2.2. The
Theinitial
initialgas
gasconcentration
concentrationisisHH 2%==45, CO%==45,
45,CO% 45,CH %== 3,
CH44% 3, N %=
N22% = 7, the total
total pressure
pressure
Figure 2%
isis44atm,
atm,and
andthe
thetemperature
temperatureisis900 ◦ C. (a)
900°C. (a)the
theamount
amountof ofequilibrium
equilibriumproducts;
products;(b)
(b)equilibrium
equilibriumgas
gas
ratio; (c) deoxygenation rate of Fe
ratio; (c) deoxygenation rate of Fe2 O3 2O 3 and utilization rate of total gas; (d) CH
gas; (d) CH4 4 conversion rate.

Figure
Figure2a2ashows
showsthe amount
the amountand kinds
and of equilibrium
kinds products
of equilibrium with with
products increasing the amount
increasing of initial
the amount of
reduction gas at the
initial reduction gascurrent
at the setting,
current which
setting,demonstrates that the composition
which demonstrates of equilibrium
that the composition products
of equilibrium
isproducts
significantly affected by
is significantly the quantity
affected by theof reduction
quantity gas. Withgas.
of reduction the With
increasethe of reduction
increase gas, the iron
of reduction gas,
oxide follows
the iron oxidethe law ofthe
follows gradual
law ofreduction,
gradual reduction, O3 →Fe
that is, Fe2that 3 O24O
is, Fe 3→Fe
→Fe 4→Fe0.95O→Fe.
3OO→Fe.
0.95 When the initial
When the
amount of reduction
initial amount gas is 1.5–2.5
of reduction gas ismol and the
1.5–2.5 molinitial
and iron oxide is
the initial 0.5 oxide
iron mol Feis2 O0.5
3 , the
molequilibrium
Fe2O3, the
state is Fe0.95 O→Fe
equilibrium state isstage. Also, any
Fe0.95O→Fe twoAlso,
stage. stagesany
cannot
two exist at the
stages cannotsameexist
timeatin the
thermodynamics.
same time in
Under the current initial
thermodynamics. Underconditions,
the currentFeinitial
3 C andconditions,
C have not Febeen generated.
3C and C haveThe notcomplete reductionThe
been generated. of
Energies 2020, 13, 5053 7 of 18

iron oxide is shown in Figure 2a that product Fe0.95 O gradually decreases to 0, and the corresponding
amount of product Fe gradually increases to a maximum of 1mol and then remains unchanged. There is
a certain amount of reduction gas that is just enough for the iron oxide to be completely reduced,
and the more amount of reduction gas is not needed. Besides, attention should be paid to the fact that
the content of CH4 in Figure 2a is close to 0.
Figure 2b shows the equilibrium gas ratio with increasing the amount of initial reduction gas in
the current setting. In the reduction stage of Fe0.95 O→Fe stage at 900 ◦ C, the equilibrium concentration
ratios of H2 O/(H2 + H2 O) and CO2 /(CO + CO2 ) are 37.581% and 31.450%, respectively, which are
the same as that of the reduction of iron oxide by pure H2 and pure CO. The two equilibrium
concentration ratios are a function of temperature, regardless of whether CH4 exists or not, or how
much CH4 exists.
Figure 2c shows the deoxygenation rate of Fe2 O3 and the utilization rate of total gas with increasing
the amount of initial reduction gas at the current setting. In the presence of CH4 , the equilibrium
concentrations of H2 O/(H2 + H2 O) and CO2 /(CO + CO2 ) cannot represent the utilization rate of
the gas. The ratio of the amount of oxygen loss to the amount of reduction gas should be adopted
to display the utilization rate of reduction gas. In the reduction stage of Fe0.95 O→Fe, the utilization
rate does not change with the increase of the deoxygenation rate of Fe2 O3 . Therefore, this rule can be
used to calculate the reduction gas utilization rate under different settings, such as gas concentration,
gas pressure, etc.
Figure 2d shows the CH4 conversion rate with increasing the amount of initial reduction gas at
the current setting. In the reduction stage of Fe0.95 O→Fe, the CH4 conversion rate remains unchanged
with the increase of the reduction gas. The increased CH4 has reacted with the increased H2 O and CO2
obtained from the reduction of Fe0.95 O, which is shown in Figure 2a. At any reduction stage of
iron oxide, CH4 is almost completely decomposed, and the conversion rate of CH4 is ≥99.982%.
When the amount of reduction gas is more than needed, the CH4 conversion rate decreases rapidly,
and the reason is that the amount of CO2 and H2 O generated from the reduction of iron oxide do
not increase.

3.2. The Utilization Rate of Reduction Gas

The utilization rate of reduction gas for the full reduction of iron oxide is the same as that of
the partial reduction stage of Fe0.95 O→Fe. Therefore, the initial amount of reduction gas is set as
2 mol. The initial gas concentration is H2 % + CO% = 90, CH4 % = 0–10, the residual is N2 , and these
given initial gas concentration (volume fraction) are listed in Table 3. The total pressure is 1–9 atm
and the reaction temperature is 900 ◦ C.
The Figure 3a,b show the relationship between the utilization rate of total gas and the total gas
pressure, and the former fixes the initial concentrations of both H2 and CO at 45%, the latter fixed
the initial concentration of CH4 at 2%. As can be seen from these two figures, no matter what the initial
gas concentration is, the gas utilization rate decreases with the increase of the total gas pressure, expect
for single gas reduction. However, the influence of pressure on the gas utilization rate is not significant.
The change of gas utilization rate from 1 atm to 9 atm is less than 1.70%, as shown in Figure 4. Also,
when initial H2 % = 60, the pressure has the greatest effect on gas utilization, which is close to 1.70%.
Energies 2020, 13,
Energies 2020, 13, 5053
x FOR PEER REVIEW 88 of
of 18
18

(a) (b)

(c) (d)
Figure
Figure 3. 3. The
The relationship
relationship between
between thethe utilization
utilization rate
rate of
of total
total gas
gas and other initial
and other initial conditions
conditions at 900
at 900
°C.
◦ C. (a)
(a) the
the x-axis
x-axis is
is the
the total
total gas
gas pressure,
pressure, and
and initial H22%
initial H %==45,
45,CO%
CO%==45,
45,CH 4% = 0–10; (b) x-axis is
CH 4 % = 0–10; (b) x-axis
the total gas pressure, and initial H 2% + CO% = 90, CH4% = 2; (c) x-axis is the initial CH4 volume
is the total gas pressure, and initial H2 % + CO% = 90, CH4 % = 2; (c) x-axis is the initial CH4 volume
fraction, and initial
initialHH2%% = 45, CO% = 45; (d) x-axis is the total gas pressure, and initial H2% + CO% =
fraction, and 2 = 45, CO% = 45; (d) x-axis is the total gas pressure, and initial H2 % + CO% = 90,
90, CH
CH % = 2.4% = 2.
4

Figure 3c shows the relationship between the utilization rate of total gas and the the initial
initial CH
CH44
fraction. It can
volume fraction. can bebe seen
seenfromfromthese
thesetwotwofigures,
figures,nonomatter
matterwhat what the
the initial
initial gasgas concentration
concentration is,
is, the gas utilization rate decreases with the increase of the total gas pressure.
the gas utilization rate decreases with the increase of the total gas pressure. In other words, increasing In other words,
increasing the concentration
the concentration of CH4improve
of CH4 can greatly can greatly improve
the gas the gas
utilization rate.utilization
Besides, therate. Besides,
lines under the lines
different
under different
pressures pressures
are nearly are According
parallel. nearly parallel.
to theAccording
calculation toofthethecalculation
slope, for of the 1%
every slope, for every
increase in CH1%4
increase in CH4the
concentration, concentration,
gas utilization therate
gascan
utilization rate can
be improved by be improved by 2.03–2.07%.
2.03–2.07%.
Figure 3d
3dshows
showsthe the relationship
relationship between
between the the utilization
utilization rate ofrate of gas
total totalandgas
theand theHinitial
initial 2 volume H2
volume fraction. As can be seen
fraction. As can be seen from the figure, from the figure, the gas utilization rate increases as the
gas utilization rate increases as the initial H2 concentration initial H2
concentration
increases also increases
decreasesalsoas thedecreases
initial COas concentration
the initial CO concentration
increases. Also, increases.
the two Also,
ends ofthealltwo endsare
curves of
all curves are approximately
approximately coincident, thatcoincident,
is, when the that
gasis,concentration (H2 % = 90, CHis4 %
when the gasis concentration (H=2%2)=and CH4%== 90,
90, (CO% 2)
CH4 % = 2), the pressure has little effect on the gas utilization. For other H2 concentrations, the higher2
and (CO% = 90, CH 4% = 2), the pressure has little effect on the gas utilization. For other H
concentrations, the lower
the pressure is, the higherthe theutilization
pressure of is,the
thegas
lower the utilization
is. Based on the slope of the gas is. Based
calculation, everyon 1%the slope
increase
calculation, every 1%can
in H2 concentration increase
improve in Hthe2 concentration
gas utilization canrate
improve
by about the 0.06%.
gas utilization rate by about 0.06%.
Table 4 lists the utilization rate of total gas of the selected nine groups of gas concentrations
under different pressure. For single reduction gas (CO% = 90, N2% = 10) and (H2% = 90, N2% = 10),
 0 90 5 38.635 38.633 38.631 38.627 38.623 38.617 38.611 38.603 38.595
45 45 0 31.058 31.040 31.011 30.971 30.919 30.855 30.78 30.695 30.598
45 45 2 35.189 35.169 35.136 35.089 35.030 34.957 34.872 34.774 34.663
45 45 5 41.386 41.362 41.322 41.267 41.195 41.108 41.006 40.889 40.757
90 0 0 33.823 33.823 33.823 33.823 33.823 33.823 33.823 33.823 33.823
90 2020, 13,
Energies 0 5053 2 37.954 37.951 37.946 37.938 37.929 37.918 37.904 37.889 37.872
9 of 18
90 0 5 44.151 44.143 44.130 44.111 44.088 44.059 44.025 43.987 43.943

Therelationship
relationshipbetween
betweenthe
the rangeability ◦C
Figure
Figure 4.4. The rangeability of of
thethe utilization
utilization raterate of total
of total gas gas at °C
at 900 900and
and the initial
the initial H2 volume
H2 volume fraction.
fraction.

Table 4 lists the utilization rate of total gas of the selected nine groups of gas concentrations
3.3. The Saving Volume of Reduction Gas per m3 CH4
under different pressure. For single reduction gas (CO% = 90, N2 % = 10) and (H2 % = 90, N2 % = 10),
The reduction
the utilization rate gas needed
of total gas for the full
at 900 reduction
◦ C is 28.305%of iron
and oxide torespectively.
33.823%, produce 1 ton of metallic
Increasing CHFe4
can be calculated
concentration and by the utilization
decreasing rate ofcan
the pressure reduction
improvegas. Forutilization
the gas H2% = 45, rate.
CO%At = the
45, same
CH4%temperature
= 0–10, gas
pressure
and is 1–9 pure
pressure, atm, the
H2 reduction gas required
has the highest for a ton ofrate,
gas utilization iron while
is shown
purein CO
Figure
has5.the
As can be seen
lowest gas
from Figure
utilization 5, the amount of reduction gas required per ton of iron decreases with the increase of
rate.
CH4 content. For example, when the initial CH4% is 0, the reduction gas (H2% = 45, CO%45, N2% =
Table
10, gas 4. The4utilization
pressure rate of
atm) needed total gas of
is 1937.319 m3the selected
; when the nine groups
initial CH4%ofisgas
5, concentration under
that is 1453.959 m3, the
different pressure.
reduction gas required decreases by 483.36 m . 3

Initial Gas
Total Gas Pressure/Atm
Concentration/%
H2 CO CH4 1 2 3 4 5 6 7 8 9
0 90 0 28.305 28.305 28.305 28.305 28.305 28.305 28.305 28.305 28.305
0 90 2 32.438 32.437 32.436 32.435 32.435 32.434 32.433 32.431 32.430
0 90 5 38.635 38.633 38.631 38.627 38.623 38.617 38.611 38.603 38.595
45 45 0 31.058 31.040 31.011 30.971 30.919 30.855 30.78 30.695 30.598
45 45 2 35.189 35.169 35.136 35.089 35.030 34.957 34.872 34.774 34.663
45 45 5 41.386 41.362 41.322 41.267 41.195 41.108 41.006 40.889 40.757
90 0 0 33.823 33.823 33.823 33.823 33.823 33.823 33.823 33.823 33.823
90 0 2 37.954 37.951 37.946 37.938 37.929 37.918 37.904 37.889 37.872
90 0 5 44.151 44.143 44.130 44.111 44.088 44.059 44.025 43.987 43.943

3.3. The Saving Volume of Reduction Gas per m3 CH4

The reduction gas needed for the full reduction of iron oxide to produce 1 ton of metallic Fe
can be calculated by the utilization rate of reduction gas. For H2 % = 45, CO% = 45, CH4 % = 0–10,
gas pressure is 1–9 atm, the reduction gas required for a ton of iron is shown in Figure 5. As can be
seen from Figure 5, the amount of reduction gas required per ton of iron decreases with the increase of
CH4 content. For example, when the initial CH4 % is 0, the reduction gas (H2 % = 45, CO%45, N2 % = 10,
gas pressure 4 atm) needed is 1937.319 m3 ; when the initial CH4 % is 5, that is 1453.959 m3 , the reduction
gas required decreases by 483.36 m3 .
 Energies 2020, 13, 5053 10 of 18

Energies 2020,
Energies 2020, 13,
13, xx FOR
FOR PEER
PEER REVIEW
REVIEW 10 of
10 of 18
18

Figure5.
Figure
Figure 5. Therelationship
5.The
The relationshipbetween
relationship betweenthe
between thevolume
the volumefor
volume fortotal
for totalgas
total gasneeded
gas neededfor
needed forper
for perton
per tonFe
ton Feand
Fe andinitial
and initialCH
initial CH444
CH
volumefraction
volume
volume fractionat
fraction at900
at 900 ◦
900°C
°CCwith
withthe
with theinitial
the initialH
initial H22%
H %===45
2% 4545and
and CO%== =
andCO%
CO% 4545
45 under
under
under 1–9
1–9
1–9 atm.
atm.
atm.

Thereduction
The
The reductiongas
reduction gasdemand
gas demandcan
demand canbe
can besaved
be savedby
saved byincreasing
by increasingCH
increasing CH444into
CH intothe
into themixture,
the mixture,and
mixture, andthe
and thespecific
the specific
specific
effectcan
effect
effect canbe
can becalculated
be calculatedby
calculated byFormula
by Formula(30),
Formula (30),which
(30), whichis
which isisshown
shownin
shown ininFigure
Figure6.
Figure 6.6.As
Ascan
As canbe
can beseen
be seenfrom
seen fromthe
from thefigure,
the figure,
figure,
the saving
the saving
the effect
saving effect decreases
effect decreases with
decreases with the
with the increase
the increase of
increase ofthe
of theinitial CH
the initial
initial CH concentration,
CH44 concentration,
4 and
concentration, and the decreasing
and the trend
the decreasing
decreasing
is obvious
trend is
trend with
is obvious the
obvious with increase
with the of
the increase the
increase of pressure.
of the However,
the pressure.
pressure. However,the range
However, the of
the range these
range of savings
of these due
these savingsto pressure
savings duedue to to
and CH concentration is small, with a maximum of just 0.008 m 3 /m3 . Therefore, it can be considered
pressure and
pressure 4 and CHCH44 concentration
concentration is is small,
small, withwith aa maximum
maximum of of just
just 0.008
0.008 m m /m
3
3 /m .. Therefore,
3
3 Therefore, itit can
can be be
that for reduction
considered
considered that forgas
that for (H2 % =gas
reduction
reduction 45,(H
gas CO%
(H % ===45,
22% 45, N2 %===45,
45,CO%
CO% 10,N
45, Nand% ==the
22% 10,pressure
10, and the
and is 1–9 atm),
the pressure
pressure is 1–9
is 1–9
3 CH can
1 matm),
atm), 141 m
m33
save
CH
CH 6.64–6.65
can
44 can save m3 totalm
save 6.64–6.65
6.64–6.65 mreduction gas.
total reduction
33 total reduction gas.
gas.

Therelationship
Figure6.6.The relationshipbetween
betweenthethe saving
saving volume
volume per m333 CH
per m CH and
andinitial
initialCH
CH44volume
volumefraction
fractionat
at
Figure
Figure 6. The relationship between the saving volume per m CH444and initial CH 4 volume fraction at
900 ◦ C with the initial H2 % = 45 and CO% = 45 under 1–9 atm.
900 °C
900 °C with
with the
the initial
initial H
H22%
% == 45
45 and
and CO%
CO% == 45
45 under
under 1–9
1–9 atm.
atm.
Energies 2020, 13, x FOR PEER REVIEW 11 of 18

Energies 2020, 13, 5053 11 of 18

Figure 7 shows the relationship between saving volume of total gas per m3 CH4 and the initial H2
concentration. It can be seen from Figure 7 that the saving volume per m 3 CH4 decreases linearly with
Figure 7 shows the relationship between saving volume of total gas per m3 CH4 and the initial H2
the increaseconcentration.
of the initial H2 concentration. Since CH4 concentration has little influence on the savings
It can be seen from Figure 7 that the saving volume per m3 CH4 decreases linearly with
effect of CHthe
4, the points
increase of thein initial
Figure H2 7concentration.
are coincide, and
Since CHthe coordinate
4 concentration hasvalues of theonmain
little influence nodes have been
the savings
effect
marked in the of CHFor
figure. 4 , thegas
points in Figure 7 arefrom
concentration coincide,
(H2and
% =the 0, coordinate
CO% = 90) values
to (H of 2the
% =main
90, nodes
CO%have = 0), the saving
been marked in the figure. For gas concentration from (H 2 % = 0, CO% = 90) to (H 2 % = 90, CO% = 0),
effect of CH4 is decreased from 7.29 m /m to 3 3 6.08 m /m . Compared with pressure and CH4
3 3
the saving effect of CH4 is decreased from 7.29 m3 /m3 to 6.08 m3 /m3 . Compared with pressure and CH4
concentration, H2 concentration
concentration, has a more
H2 concentration significant
has a more significanteffect
effect on thesavings
on the savings effect
effect of CHof4 . CH4.

Figure 7. The relationship between the saving volume per m3 CH4 and initial H2 volume fraction at
Figure 7. The
900relationship
◦ C under 4 atm.between the saving volume per m CH4 and initial H2 volume fraction at
3

900 °C under 4 atm.

It is important to note that the volume saving per m3 CH4 cannot be calculated according to
Formula (9) and (10). According to Formula (9), the reaction between CH4 and H2 O can produce
It is important
3 m3 H2 + 1tom3noteCO by that1 m3the
CH4volume
. Accordingsaving per (10),
to Formula m3 CH 4 cannot be calculated according to
the reaction between CH4 and CO2
Formula (9)canand get(10).
2 m According
3 H2 + 2 m COto3 byFormula
1 m CH4 .(9),
3 the reaction
In other words, the between
reaction of CH anddeoxidized
CH44 with H2O can produce 3
products H O and CO results in a mixture of 4 m 3 H + CO. However, this algorithm for saving effect
m H2 + 1 m CO by2 1 m CH
3 3 3 2 4. According to Formula 2 (10), the reaction between CH4 and CO2 can
without the iron oxide reduction system is not correct, due to the gas utilization rate for reduction is
get 2 m3 H2neglected.
+ 2 m3 CO by 1 m3 CH4. In other words, the reaction of CH4 with deoxidized products
In the gas system composed of CH4 + H2 O + H2 + CO2 + CO, five kinds of gases. H2 O + H2 ,
H2O and CO and results
2 CO 2 + CO in
are a mixture
also of 4 m3 H2 + CO. However, this algorithm for saving effect
in equilibrium.
without the iron oxide reduction system is not correct, due to the gas utilization rate for reduction is
neglected. In the gas system composed of CH4 + H2O + H2 + CO2 + CO, five kinds of gases. H2O + H2,
and CO2 + CO are also in equilibrium.

3.4. The Reaction Enthalpy

The reaction enthalpy of reduction of iron oxide can be calculated by Formula (24). Figure 8
shows the relationship between the reaction enthalpy and the initial gas amount, and the oblique
line shows the full reduction of iron oxide. The curve that demonstrates the reduction by gas
 Energies 2020, 13, 5053 12 of 18

3.4. The Reaction Enthalpy

The reaction enthalpy of reduction of iron oxide can be calculated by Formula (24). Figure 8
shows the relationship between the reaction enthalpy and the initial gas amount, and the oblique line
shows the full reduction of iron oxide. The curve that demonstrates the reduction by gas without
CH4 is at the bottom of all curves and reaches a maximum value of 8.3 kJ/mol when the iron oxide
is completely reduced; due to reverse reaction of Formulas (9) and (10), the curve starts to go down.
For the reduction by gas included CH4 , the reaction enthalpy increases with the increase of the amount
of reduction
Energies 2020, gas. REVIEW
13, x FOR PEER 12 of 18

Figure 8. Figure 8. The relationship

the relationship between
between the the reactionenthalpy
reaction enthalpy and
andthethe
initial gas amount
initial at 900 ◦at
gas amount C under 4 under
900 °C
atm with H2 % = 45, CO% = 45, CH4 % = 0–10.
4 atm with H2% = 45, CO% = 45, CH4% = 0–10.
Figure 9 shows the relationship between the reaction enthalpy and the initial CH4 concentration.
Figure 9 shows
As shown the relationship
in the figure, reaction enthalpy between
is linearlythe reaction
correlated with enthalpy
the initial CHand the initial CH4
4 concentration.
The initial
concentration. As reduction
shown in gasthe
volume is setreaction
figure, as 1.5 mol,enthalpy
2.0 mol, and is 2.5 mol, respectively,
linearly correlated so the
withequilibrium
the initial CH4
state is in the stage of Fe0.95 O→Fe. According to the calculation by Formula (33), the change of reaction
concentration. The initial reduction gas volume is set as 1.5 mol, 2.0 mol, and 2.5 mol, respectively,
enthalpy brought by 1 mol CH4 is the same at the same pressure. Increasing the pressure can reduce
so the equilibrium state is in the stage of Fe0.95O→Fe. According to the calculation by Formula (33),
the change value of reaction enthalpy. The change of reaction enthalpy caused by 1 mol CH4 at 4 atm,
the change of reaction
5 atm, and 6 atmenthalpy brought
is 249.79 kJ/mol, 249.31bykJ/mol,
1 moland CH 4 is the
248.72 same
kJ/mol, at the same pressure. Increasing
respectively.
the pressure can reduce the change value of reaction enthalpy. The change of reaction enthalpy
slope of reaction enthalpy
caused by 1 mol CH4 at 4 atm, ∆H51173K
atm,= and 6 atm is 249.79 kJ/mol, 249.31 kJ/mol, and 248.72 (33) kJ/mol,
increment of the initial amount of CH4
respectively.

slope of reaction enthalpy

ΔH1173 K = (33)
increment of the initial amount of CH 4
the pressure can reduce the change value of reaction enthalpy. The change of reaction enthalpy
caused by 1 mol CH4 at 4 atm, 5 atm, and 6 atm is 249.79 kJ/mol, 249.31 kJ/mol, and 248.72 kJ/mol,
respectively.

slope of reaction enthalpy

ΔH1173 K = (33)
Energies 2020, 13, 5053 increment of the initial amount of CH 4 13 of 18

Energies 2020, 13, x FOR PEER REVIEW 13 of 18

(a)

(b)

(c)

Figure 9.
Figure 9. The
The relationship
relationship between
between the
the reaction
reaction enthalpy
enthalpyand
andthe
theinitial
initialCH
CH4 4volume
volumefraction
fractionatat900
900°C
◦C
withHH2%% = 45, CO% = 45. (a) the total pressure is 4 atm; (b) total pressure is 5 atm; (c) total pressure is 6
with 2 = 45, CO% = 45. (a) the total pressure is 4 atm; (b) total pressure is 5 atm; (c) total pressure is
atm.
6 atm.

3.5. The Increased Reaction Enthalpy Per m3 CH4

Comparing the reduction of iron oxide by gas within CH4 and by gas without CH4, the reaction
enthalpy increases under the same initial concentration of H2 and CO and pressure.
Energies 2020, 13, 5053 14 of 18

3.5. The Increased Reaction Enthalpy Per m3 CH4

Comparing the reduction of iron oxide by gas within CH4 and by gas without CH4 , the reaction
enthalpy increases under the same initial concentration of H2 and CO and pressure.
Figure 10 shows the relationship between the increased reaction enthalpy per m3 CH4 and the total
gas pressure and the initial H2 concentration. As shown in the figure, the increased reaction enthalpy
decreases with the increase of the total gas pressure, or with the increase of the initial H2 concentration.
For the gas (H2 % = 0, CO% = 90, the pressure is 1atm), the increased reaction enthalpy per m3 CH4 is
the maximum of 11.189 MJ/m3 . For the gas (H2 % = 90, CO% = 0, the pressure is 9atm) the increased
Energies 2020, 13, x FOR PEER REVIEW 14 of 18
reaction enthalpy per m3 CH4 is the smallest of 10.959 MJ/m3 .

(a) (b)
Figure 10.
Figure 10. The
The increased
increased reaction
reactionenthalpy
enthalpyper permm33CH
CH44 at
at 900
900with %++ CO%
withHH22% CO% == 90. (a) the x-axis is
is
the total
the total gas
gas pressure;
pressure; (b)
(b) x-axis
x-axis is
is the
the initial
initialH fraction.
H22 volume fraction.

For the gas (H

According % =reduction
to 2the 0, CO% =reaction = 10),
90, N2 % and the reaction
methane enthalpy
conversion for producing
reaction, a ton of
the reaction iron is
between
−330.280
CH4 and MJ.ironFor the gas
oxide (H2 % = 90,
is obtained CO% = 0, N
by coupling, as2 % = 10),inand
shown the reaction
Formulas (34) enthalpy
and (35). for
Thethe production
released heat
of 3 CH in the gas phase can make the reaction
of achemical
ton of iron is 568.471
reaction in theMJ. The addition
production of 30ofmFe
of 1 mol with 4 CO is 18.445 kJ, the absorption heat of
enthalpy
chemical of the former
reaction gas
in the system zero,
production of 1and
moltheoflatter gas H
Fe with system morekJ,
2 is 31.747 heat
andsupply needed. heat of
the absorption
According
chemical to the
reaction reduction
in the reaction
production of 1 and
mol methane
of Fe withconversion reaction,
CH4 is 373.061 kJ. the reaction between CH4
and iron oxide is obtained by coupling, as shown in Formulas(34) and (35). The released heat of
Fe2O3 +of3CO
chemical reaction in the production 1 mol = of
2FeFe + 3CO
with CO2 is Δ18.445 − 36.890
H1173KkJ,= the kJ/mol
absorption heat of chemical
3 × （ CH
reaction in the+ production of 1+mol
4 COof2 = 2H 2 + 2CO）
Fe with H2 is 31.747ΔkJ, 
H1173
and =261.004
K kJ/mol
the absorption heat of chemical
(34)
reaction in the production of 1 mol of Fe with CH4 is 373.061 kJ.
Fe 2O3 + 3CH 4 =2Fe + 6H 2 + 3CO ΔH1173

K =746.121 kJ/mol
Fe2 O3 + 3CO = 2Fe + 3CO2 ∆H1173K

= −36.890 kJ/mol
Fe
+ 3 × (CH4 + O + 3H
3 2 = 2H
2 CO = 2Fe + 3H O Δ H 
2 2 + 2CO) 2 ∆H1173K1173K =63.495kJ/mol
= 261.004 kJ/mol (34)
CO） ∆HΔ

+3Fe×2 O3 （ CH4 +=H2Fe
+ 3CH
4 O+= 6H
3H2 ++ 3CO
2 2 H = 746.121
1173K =227.542 kJ/mol
kJ/mol
1173 K (35)

3 +3H 2Fe++3H 2 O2 + 3CO ΔH


FeFe2 O
2O3+ 3CH
2 =4 =2Fe 6H ∆H1173K

=K
1173 =746.121
63.495 kJ/mol kJ/mol
+3 × (CH4 + H2 O = 3H2 + CO) ∆H1173K

= 227.542 kJ/mol (35)
When the initial CH4 concentration is set to be 10% at most, the amount of CO2 and H2O in the
Fe2 O3 + 3CH4 = 2Fe + 6H2 + 3CO ∆H1173K
= 746.121 kJ/mol
system are excessive relative to that of CH4; that is, the conversion reaction of CH4 is relatively
When as
sufficient, theshown
initial in
CH 4 concentration
Figure 2d. When isthe setinitial
to be concentration
10% at most, the amount
of CO and H of2 CO 2 and
in the gasHphase
2 O in
changes,
the system the
areconcentration
excessive relativeof COto 2 and
thatHof2O CHgenerated
4 ; that is,by
thethe reduction
conversion reaction
reaction also
of CH changes
4 is along
relatively
with it, thus
sufficient, making
as shown the reaction
in Figure 2d. Whenenthalpy of CH
the initial 4 conversion
concentration of different.
CO and H2The reduction
in the gas phase utilization
changes,
rateconcentration
the of H2 is higherofthan CO2that andofHCO2 O at 900
generated°C. Increasing
by the the
reductioninitial H
reaction
2 concentration
also changes can increase
along withtheit,
overall gas utilization rate and the concentration
thus making the reaction enthalpy of CH 4 conversionof H2O in the gas phase. In addition, the reaction
different. The reduction utilization rate of H 2
enthalpy
is of Hthat
higher than 2O +of CH CO 4 is 900 ◦ C.than
at lower that of the
Increasing COinitial
2 + CH H4,2 which reducescan
concentration theincrease
increasedthereaction
overall
enthalpy of the system.
The transformation reaction of CH4 are reactions in which the amount of substance increases.
Increasing the gas pressure can decrease the amount of forwarding reaction and the gas utilization
rate, which lowers the increased reaction enthalpy of the system.
Energies 2020, 13, 5053 15 of 18

gas utilization rate and the concentration of H2 O in the gas phase. In addition, the reaction enthalpy
of H2 O + CH4 is lower than that of CO2 + CH4 , which reduces the increased reaction enthalpy of
the system.
The transformation reaction of CH4 are reactions in which the amount of substance increases.
Increasing the gas pressure can decrease the amount of forwarding reaction and the gas utilization rate,
which lowers the increased reaction enthalpy of the system.

3.6. The Heat Needed per Ton Fe

The total heat needed of reduction of iron oxide by gas at 900 ◦ C consists of three parts: reaction
heat, the sensible heat of solid Fe2 O3 from 25 ◦ C to 900 ◦ C, and sensible heat of gas mixture from 25 ◦ C
to 900 ◦ C. MJ/tFe represents heat unit per ton Fe.
Figure
Energies 11x FOR
2020, 13, showsPEERthe relationship between reduced sensible heat of reduction gas and15CH
REVIEW of 184
concentration, gas pressure, and H2 concentration, which is compared with the reduction without CH4 .
CH 4. As
As can becan
seenbefrom
seen Figure
from Figure 11a,
11a, the the reduced
reduced sensiblesensible
heat of heat of reduction
reduction gas increases
gas increases with thewith the
increase
increase of CH 4 concentration and has little been influenced by the gas pressure in the range of 1–9
of CH4 concentration and has little been influenced by the gas pressure in the range of 1–9 atm. As can
atm.
be seenAs from
can be seen11b,
Figure from Figure
under the 11b,
sameunder the same
gas pressure andgas
CHpressure and CH4 concentration, the
4 concentration, the reduced sensible
reduced sensible heat
heat of reduction of reduction
gas decreases gas
with thedecreases
increase with
of H2the increase of H2 concentration.
concentration.

(a) (b)
Figure 11. The
Figure 11. Therelationship
relationshipbetween
between thethe reduced
reduced sensible
sensible heatheat of gas
of total totaland
gastheand theCH
initial initial CH4
4 volume
volume at 900 ◦ C.
fraction fraction at 900 °C.
(a) H 2 % =
(a) H
45,
2 % =
CO%45,=CO%
45, = 45,
total total pressure
pressure is 1–9 is 1–9
atm; atm;
(b) H 2(b)
% +H %
CO%
2 + =
CO%90, = 90,
total
total pressure
pressure is 4 atm.
is 4 atm.

In addition, according
according to tothe
thesensible
sensibleheat
heatcalculation
calculationFormula
Formula(24) and
(24) andgas composition,
gas composition, it can be
it can
obtained that that
the saved sensible heat of gas 3
be obtained the saved sensible heatper ofmgas CHper
4 is 7.338–8.952
m CH4 is MJ.
3 The former
7.338–8.952 MJ. corresponds
The former to
gas mixture Hto2 %gas
corresponds = 90, CO% =
mixture H200,
% =CH 4 %CO%
90, + N2=%00,= 10,
CHand
4% gas
+ Npressure = 9atm.
2% = 10, and gas The latter =corresponds
pressure 9atm. The
latter mixture H2 %to=gas
to gascorresponds 0, CO% = 90,
mixture H2CH
% =40, + N2 %
% CO% = 10,
= 90, CH and
4% gas
+ N2pressure = 1atm.
% = 10, and gas pressure = 1atm.
Figure 12
Figure 12 shows
showsthe therelationship
relationshipbetween
between increased
increased reaction
reaction heat
heat andand
CH4CH 4 concentration,
concentration, gas
gas pressure,
pressure, andand H2 concentration,
H2 concentration, which
which is compared
is compared with
with thereduction
the reductionwithout
withoutCHCH44. .As
Ascan
canbebe seen
seen
from Figure 12a, the increased reaction heat goes up with the increase of CH4 concentration concentration andand has
been little
little influenced
influencedby bythe
thegas
gaspressure
pressure in the range
in the of 1–9atm.
range As can
of 1–9atm. As be
canseen
be from
seen Figure 12b, under
from Figure 12b,
the same gas pressure and
under the same gas pressure and CH 4 concentration, the increased reaction heat decreases with
CH4 concentration, the increased reaction heat decreases with the the increase
of H2 concentration.
increase of H2 concentration.
 Figure 12 shows the relationship between increased reaction heat and CH4 concentration, gas
pressure, and H2 concentration, which is compared with the reduction without CH4. As can be seen
from Figure 12a, the increased reaction heat goes up with the increase of CH4 concentration and has
been little influenced by the gas pressure in the range of 1–9atm. As can be seen from Figure 12b,
under
Energies the
2020,same gas pressure and CH4 concentration, the increased reaction heat decreases with
13, 5053 the
16 of 18
increase of H2 concentration.

(a) (b)
Figure
Figure 12.
12. The
The relationship
relationship between
between the the increased
increased reaction
reaction heat
heat and
and the
the initial
initial CH
CH44 volume
volume fraction
fraction at
at
900 ◦
900 °C.
C. (a) H22%%==45,
(a)H CO%==45,
45,CO% 45,total
totalpressure
pressureisis1–9
1–9atm;
atm;(b)
(b)HH
2%%
2 + +
CO%
CO% = =
90, total
90, pressure
total is
pressure 4
isatm.
4 atm.
Energies 2020, 13, x FOR PEER REVIEW 16 of 18
The sensible heat of the solid Fe2 O3 is 1123.381 MJ/tFe, which is a constant under certain
temperature change
The sensible conditions.
heat Therefore,
of the solid Fe2O3 increased total
is 1123.381 heat can
MJ/tFe, be defined
which by the difference
is a constant of gas
under certain
sensible heatchange
temperature and reaction heat, as
conditions. shown inincreased
Therefore, Formula (36).
total heat can be defined by the difference of
gas sensible heat and reaction heat, as shown in Formula (36).
increased total heat = increased reaction heat − reduced gas sensible heat (36)
increased total heat = increased reaction heat - reduced gas sensible heat (36)
The relationship between increased total heat with CH4 concentration, gas pressure, and H2
The relationship between increased total heat with CH4 concentration, gas pressure, and H2
concentration is shown in Figure 13. It can be seen that the increased total heat increases with
concentration is shown in Figure 13. It can be seen that the increased total heat increases with the
the increase of CH4 concentration, and has been little influenced by the gas pressure in the range
increase of CH4 concentration, and has been little influenced by the gas pressure in the range of 1–9
of 1–9 atm. As can be seen from Figure 13b, under the same gas pressure and CH4 concentration,
atm. As can be seen from Figure 13b, under the same gas pressure and CH4 concentration, the
the increased reaction heat increases with the increase of H2 concentration.
increased reaction heat increases with the increase of H2 concentration.

(a) (b)
Figure13.
Figure Therelationship
13.The relationshipbetween
betweenthe
theincreased
increasedtotal
totalheat
heatand
andthe
theinitial
initialCH
CH44volume
volumefraction
fractionat
at900
900
◦ C. (a) H % = 45, CO% = 45, total pressure is 1–9 atm; (b) H % + CO% = 90, total pressure is 4 atm.
°C. (a) H2%2 = 45, CO% = 45, total pressure is 1–9 atm; (b) H2% 2+ CO% = 90, total pressure is 4 atm.

Accordingto
According to Formula
Formula(36),
(36), increasing
increasing11 mm33CH
CH4 4can
canincrease
increasethethetotal
totalheat
heatby
by2.174–3.703
2.174–3.703MJ.
MJ.
The former corresponds to gas mixture H % = 0, CO% = 90, CH % = 1, N % = 9, and gas
The former corresponds to gas mixture H2% = 0, CO% = 90, CH4% = 1, N2% = 9, and gas pressure = 9
2 4 2 pressure = 9 atm.
The latter
atm. corresponds
The latter to gasto
corresponds mixture H2 % =H
gas mixture 90, = 90,=CO%
2%CO% 0, CH=40, = 1,4N
% CH %2=%1,=N 9,2and
% = gas pressure
9, and = 1 atm.
gas pressure
= 1 atm.
Figure 14 shows the relationship between the total heat and CH4 concentration, gas pressure,
and H2 concentration, and its variation trend is the same as that of the increased total heat. Taking
the reduction by H2% = 45, CO% = 45, CH4% = 0, N2% = 10 gas mixture as an example, as shown in
Figure 14a, the total heat needed is 3649.223 MJ/tFe (gas pressure = 1 atm) and 3636.249 MJ/tFe (gas
pressure = 9 atm), and the slight difference is due to the lower reaction heat caused by the increase
Energies 2020, 13, 5053 17 of 18

Figure 14 shows the relationship between the total heat and CH4 concentration, gas pressure,
and H2 concentration, and its variation trend is the same as that of the increased total heat. Taking
the reduction by H2 % = 45, CO% = 45, CH4 % = 0, N2 % = 10 gas mixture as an example, as shown in
Figure 14a, the total heat needed is 3649.223 MJ/tFe (gas pressure = 1 atm) and 3636.249 MJ/tFe (gas
pressure = 9 atm), and the slight difference is due to the lower reaction heat caused by the increase in
pressure. When the gas pressure = 4 atm, as shown in Figure 14b, the total heat needed is 3865.76 MJ/tFe
for the reduction by H2 % = 0, CO% = 90, CH4 % = 0, N2 % = 10 gas mixture and 3390.828 MJ/tFe for
the reduction by H2 % = 90, CO% = 0, CH4 % = 0, N2 % = 10 gas mixture, and the huge difference is due
Energies 2020, 13, x FOR PEER REVIEW 17 of 18
to the exothermic reaction of CO + Fe2 O3 .

(a) (b)
Figure
Figure 14.
14. The
Therelationship
relationshipbetween
betweenthethetotal heat
total and
heat thethe
and initial CHCH
initial 4 volume fraction at 900 °C. (a)
◦
4 volume fraction at 900 C.
H 2% = 45, CO% = 45, total pressure is 1–9 atm; (b) H2% + CO% = 90, total pressure is 4 atm.
(a) H % = 45, CO% = 45, total pressure is 1–9 atm; (b) H % + CO% = 90, total pressure is 4 atm.
2 2

The
The maximum
maximum increase
increase rate
rate in total heat caused by the presence of CH CH44 is 10.582% (H22% % == 90,
90,
CH44%% =10, gas pressure= =1 atm)
gaspressure 1 atm) compared
compared to reducing
to the the reducing gas without
gas without CH4 . AnCH 4. An appropriate
appropriate increase
increase in total
in total heat heat is acceptable
is acceptable since itsince
savesit the
savesamount of H2of+ H
the amount CO2 + CO
andand reduces
reduces the the purity
purity limit
limit of
of
H2H +2 CO.
+ CO. However,
However, the the addition
addition of CH of4 CH 4 requires
requires more more heat supply
heat supply for gasfor gas reduction
reduction and mayand may
increase
increase thecontent.
the carbon carbon content.

Conclusions
4. Conclusions
The minimum
The minimum free free energy method
method was used to calculate the equilibrium state composition
composition of
2 %+ + CO%= = %N+2%
N2=%10=at10900
the reduction
reduction of
of iron
iron oxide
oxideby
bygas
gaswith
withHH2% ◦ C under
the CO% 9090 and
and CHCH
4%4+ at 900
°C under 1–9
1–9 atm, and the following conclusions were obtained:
atm, and the following conclusions were obtained:
(1) Increasing
Increasing CHCH44 concentration,
concentration,increasing
increasing
H2 H 2 concentration,
concentration, or reducing
or reducing gas pressure
gas pressure can improvecan
improve the utilization
the utilization rate
rate of total of reduce
gas, total gas,
thereduce
reductionthegas
reduction
demand, gas demand,
and increaseand
theincrease
total heatthe total
needed.
(2) heat
Under the condition of 900 ◦ C and 1–9 atm, increasing 1 m3 CH4 can reduce the gas demand of
needed.
(2) Under the m
6.08–7.29 condition
3 , the gasof 900 °C heat
sensible and 1–9 atm,toincreasing
needed 1 m3 CH
be 7.338–8.952 can the
MJ,4and reduce the gas
increase demand
in the of
reaction
6.08–7.29
heat neededm , to
3 thebegas sensible heat
10.959–11.189 needed to be 7.338–8.952 MJ, and the increase in the reaction
MJ.
(3) heat needed with
Compared to be 3390.828–3865.760
10.959–11.189 MJ. MJ of the total heat of per ton Fe for the reduction by
(3) Compared with 3390.828–3865.760
H2 + CO, increasing MJ of the
1 m3 CH4 can increase thetotal
totalheat
heatofbyper ton Fe forMJ,
2.174–3.703 theand
reduction
increaseby H2 is
ratio +
CO, increasing
0.065–0.096%. 1 m 3 CH4 can increase the total heat by 2.174–3.703 MJ, and increase ratio is

0.065–0.096%.
Author Contributions: Conceptualization, H.G. and J.G.; Methodology, B.L. and W.Y.; Software, B.L. and S.L.;
Author Contributions: Conceptualization, H.G. and J.G.; Methodology, B.L. and W.Y.; Software, B.L. and S.L.;
Data curation, writing—original draft preparation, writing—review and editing, G.S. All authors have read
Data curation,
and agreed writing—original
to the draftofpreparation,
published version writing—review and editing, G.S. All authors have read and
the manuscript.
agreed to the published version of the manuscript.

Funding: This work was supported by the National Natural Science Foundation of China (grant number
51274031) and the National Natural Science Foundation of China (Grant Number U1560203).

Conflicts of Interest: The authors declare no conflict of interest.

Energies 2020, 13, 5053 18 of 18

Funding: This work was supported by the National Natural Science Foundation of China (grant number 51274031)
and the National Natural Science Foundation of China (Grant Number U1560203).
Conflicts of Interest: The authors declare no conflict of interest.

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