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JOURNAL OF IRON AND S T E L RESEARCH, INTERNATIONAL. 2011, 18(3): 01-05
Reduction of 1 -3 mm Iron Ore by CO on Fluidized Bed
PANG Jian-ming, GUO Pei-min, ZHAO Pei
( T h e State Key Laboratory for Advanced Steel Processes and Products, Central Iron and
Steel Research Institute, Beijing 100081, China)
Abstract: The reduction-degree of the sample increases and the utilization ratio of gas decreases when the reaction
lasts longer time, which indicates that the reaction is faster at the beginning of reduction, while it becomes slower in
subsequent process. T h e higher the reaction temperature, the higher the utilization ratio of gas and the reduction-de-
gree are, but the difference of utilization ratio among the different temperatures becomes smaller with time. The uti-
lization ratio of gas can reach about 8% and the reduction-degree is 80% for 20 min reduction at 850 C , indicating
that the reduction reaction by CO is very fast at high temperature. The higher the reaction temperature, the higher
the apparent reaction rate constant is, but the difference of apparent reaction rate constant among the different tem-
peratures becomes bigger. The apparent activation energy is about 59. 11 kJ/mol in the fluidized bed experiment.
T h e increase of reduction-degree with gas velocity shows quite good linearity, indicating that at high temperature even
higher velocity of reducing gas can be used to improve the productivity of reactor when CO is used as reducing gas.
With the increase of charge height, the metallization ratio and the reduction-degree decrease, but the utilization ratio
of gas increases.
Key words: CO; fluidized bed; fine powder; iron ore; reduction-degree
T h e efficiency of production and process energy ity is low, 1-3 mm iron oxide is in a fixed bed.
consumption depended on reduction rate of iron ox- In the present investigation, it is desirable to
ide in the gas-based direct reduced ironmaking study the reduction of 1- 3 mm iron oxide by CO in
process, so researchers at home and abroad are very an attempt to know more about how the reduction of
concerned about the reduction rate of iron oxide. 1-3 mm iron oxide in the fluidized bed. Under the
T h e kinetics of gaseous reduction of iron oxides has sponsoring of the National Science and Technology
been investigated e~tensively"-~'. Most investiga- Support Program for the 11th Five-Year Plan, the
tors direct some interest to the gaseous reduction of technology of CO reduction for fine powder of iron
large particles or lumps of iron oxide, and the gase- ore in the fluidized bed is in d e ~ e l o p m e n t [ ~ - ' ~T' .h e
ous reduction of 1 - 3 mm iron oxide was seldom study was focused on the experimental study of the
studied. It is because the particle size of iron oxide CO reduction for fine powder of iron ore (1- 3 mm
used in the blast furnace ironmaking process is lar- in size) in a lab-fabricated kg-scale high tempera-
ger than 8 m m , therefore, most investigators are ture, which might accumulate the experience on the
not concerned about the reduction kinetics of less fluidized bed processes.
than 8 mm iron oxide.
1 Experimental Materials and Procedure
T h e gaseous reduction of 1 - 3 mm iron oxide
has its particularity in the fluidized bed. According Hematite (Australian iron ore) was used as ex-
to gas consumption of a ton iron, the flowage of 1- perimental material, and its composition is shown in
3 mm iron oxide is in a state between a fixed-bed and Table 1. T h e particle size of the iron ore, obtained
fluidized-bed. 1-3 mm iron oxide is in a fluidization by screening, is around 1-3 mm, and its bulk den-
condition when gas velocity is high, and if gas veloc- sity is 2 020 kg/m3. Additionally, the CO and N2 with
Foundation Item: Item Sponsored by National Natural Science Foundation of China (50474006) ; National Key Technology Research and
Development Program in 11th FiveYear Plan of China (2006BAE03A12, 2006BAE03A05)
Biography:PANG Jian-ming(l980-), Male, Doctor; E-mail: pangjianmingl98012@163. com; Received Date: May 1 0 , 2010
- 2 . Journal of I r o n a n d Steel Research, International Vol. 18
Table 1 ComDosition of hematite (mass oercent, %I the method suggested in Ref. [ 141, and the utiliza-
Burning tion ratio of CO was calculated according to the quantity
TFe SiOz A1203 CaO MgO PZOS S FeO loss
of the ventilated CO and the reduction quantity.
62.81 3.01 2.18 0.01 0.07 0.202 0.026 0.39 4.85
2 Results and Discussion
2.1 Influence of temperature on reduction degree
high purity were also used. Fig. 2 illustrates the XRD patterns of the sam-
T h e reduction was conducted in a lab-fabricated ples that were reduced at various times at 850 'C.
kg-scale high temperature fluidized bed, which in- T h e reduction degree was calculated by the peak
cluded a distribution chamber, gas pre-heat-er , high heights of related phases.
temperature fluidized bed (100 mm in diameter), cy- Fig. 3 illustrates the influence of reaction tem-
clone scrubber, gas cooling system, bag-type ,dust perature on the metallization ratio and reduction de-
collector, and feeder system. The schematic dia- gree at 750, 800 and 850 'C with the gas velocity of
gram of the fluidized bed system is shown in Fig. l. 0.8 m / s and the still charge height of 6 cm. T h e re-
T h e temperature, pressure and flow velocity of gas duction degree reaches 80% for 20 min reduction
were controlled during the reduction, in which the gas process at 850 "C, and 73.6% at 750 'C for 30 min,
with 50%CG50%N2 was used as the reducing gas. which indicates the reduction reaction of 1 - 3 mm
by CO is quite fast at high temperature.
n 72
I FeO
0
co
1-Nz cylinder; 2-CO cylinder; 3-Mixing vessel;
4-Gas preheater; 5-Alumina balls; 6-Fluidized bed;
7-Feeder system; 8-Cyclone scrubber;
9-Bag-type dust collector. 20 40 60 80
26/(")
Fig. 1 Schematic diagram of the labfabricated
kgscale fluidized bed system Fig. 2 X-ray diffraction patterns of samples
reduced at 850 'c for different time
T h e reduction procedure could be described as
follows: 1) put certain amount of fine powder of iron 5o%N~-so%cO
ore into the fluidized bed by using feeder facility; 2 ) Gas velocity 0.8 m / s
heat the fluidized bed and gas pre-heater to an expec-
ted temperature; 3) after maintaining the system at the
expected temperature for a few hours, keep the pure
N, flowing through the fluidized bed for 20-40 min
to wash the system free from 0, ; 4) switch the pure
N, flow to the flow of the gas mixture of 50%CO- 750°C
50%Nz and keep this reductive atmosphere for 10- 8009:
A 8509:
30 min; 5) switch back to pure N, atmosphere again
and keep this atmosphere until the system was cooled 10 20 ,70
Timdmin
down to room temperature.
The phases of the samples were identified by X-ray Fig. 3 Influence of temperature and reduction
diffraction (XRD, X'Pert Pro, PANalytical, Co target= time on reduction-degree
1. 78897, 20= 20"-80", scanning rate=5 min-I).
Prior to XRD analysis, the sample was mixed uni- 2 . 2 Influence of temperature on the utilization ratio
formly by grindings. T h e metallization ratio and the of gas
reduction degree of samples were calculated by using As shown in Fig. 4, the utilization ratio of gas decr-
Issue 3 Reduction of 1-3 mm Iron Ore by CO on Fluidized Bed - 3 -
E
-
R
, and thus, the apparent activation energy of reac-
5096N2-509M:O
Gas velocity 0.8 m/s tion is calculated.
T h e influence of temperature on reaction rate
constant is shown in Fig. 5. As seen in Fig. 5 , under
the same conditions, the higher the reaction temper-
ature, the higher the apparent reaction rate constant
is, but the difference of apparent reaction rate con-
stant among the different temperatures becomes bigger.
10 20 30
Time/min
Fig. 4 Influence of temperature on gas utilization ratio
eases with reduction time when gas velocity is 0. 8 m/s
and the still charge height is 6 cm, which shows that
the reaction is fast at the beginning of the reduction
process, then it becomes slower in latter period. The 0.4 I I I 1
1 040 1 080 1120
higher the reaction temperature, the higher the utili- TK
zation ratio of gas is, but the difference of utilization
Fig. 5 The influence of temperature on reaction rate constant
ratio among the different temperatures becomes
smaller with time. T h e utilization ratio of gas can
T h e relationship between the logarithm of the
reach 8 % and the metallization ratio 84% for 20 min
reduction rate constant and the reciprocal of absolute
reduction at 850 "C, which shows the reduction re-
temperature is given in Fig. 6. T h e apparent activa-
action by CO is very fast.
tion energy calculated by the following Eqn. ( 2 ) is
T h e utilization ratio of CO is only 34%[15' at
about 59. 11 kJ/mol and the coefficient A calculated
850 "C when the reaction approaches its thermody-
is 0. 78 in the fluidized bed reduction experiment.
namic equilibrium. In the experiments, the still
And the equation of apparent reaction rate constant
charge height is 6 cm and the apparent gas velocity is
is obtained:
3 m/s. In this case, only 20 ms is needed for the gas
to flow through the sample bed. T h e experimental k = O . 78expl -59g;' 6] (3)
result showed that the utilization ratio of gas can
reach 9 % in 20 ms reduction, which means this gas- -6.4 I
solid reaction is quite fast and the utilization ratio of
CO can reach a higher level at high temperature.
2 . 3 Influence of temperature on apparent activation
3 -6.8
energy
According to the Arrhenius the re- -7.2
action rate constant k is expressed as
where, E is the apparent activation energy; T is the Fig. 6 Relationship between Ink and 1 / T
temperature; A is the coefficient; and R is the gas
constant. 2.4 Influence of gas velocity on ore reduction
After the Logarithm transformation for two As shown in Fig. 7 , the increase of metalliza-
sides of Eqn. (1) , the following equation is obtained: tion ratio with gas velocity performs quite good line-
E arity when the reduction is conducted at 850 "C for
Ink =I d - (2)
RT 10 min with the still charge height of 6 cm and CO
~
By I n k - l / T mapping, the straight line slope is as reducing gas, which indicates that the CO reduction
Journal of Iron and Steel Research, International Vol. 18
~
T h e influence of charge height on the ore reduction
70 850 C at 850 'C with gas velocity of 0. 8 m/s and reduction
10 min time of 10 min is represented in Fig. 9. T h e metalli-
Gas velocity 0.8 m/s
50%N2-50%C0 zation ratio and reduction-degree decrease with the
5
c
Q
60
increase of the charge height. However, in the same
case, the gas utilization ratio increases. The above
0 results can be understood by the following idea: when
3 more me powder was put into the bed, the charge height
was increased, if the gas flow rate was kept the same,
the fine powder of iron ore per kilogram would react
50 with less CO, which led to the decline for both the
0.8 1.2 1.6
Gas velocity/(m.s-') metallization ratio and reduction-degree; on the other
hand, if the charge height was increased, the amount of
Fig. 7 Influence of gas velocity on reduction-degree CO would react with more powder, the contact time
between gas and powder was prolonged, therefore,
is quite fast at high temperature. the utilization ratio of gas increases.
Influence of gas velocity on gas utilization de- Fig. 9 shows that the relationship between
gree at 850 "Cis shown in Fig. 8. With the increase charge height and gas utilization ratio deviating from
of gas velocity, the total gas utilization ratio main- the linearity, which is probably due to the COz in
tains at a higher level than the data reported in other the reducing gas. T h e CO, in the gas may reduce re-
~tudies"~'. T h u s , under these circumstances, in- duction ability.
creasing gas velocity can reduce the reduction time.
For example, at 850 "C, when the gas velocity is at Metallization ratio
1. 6 m/s , the metallization ratio can reach 7 0 . 4 % 0 Reduction degree
for only 10 min reduction, but when the gas velocity
is at lower velocity of 0. 8 m/s , it has to spend 20 min
t o approach a similar metallization ratio, which 40
f
c
10 rnin
shows that the productivity of reactor can be im- Gas velocity 0.8 m/s
proved by increasing gas velocity when CO is used as n 50%Nz-50%C0
30.-
reducing gas at high temperature.
850 C
8 10 min
Gas velocity 0.8 m/s
5096Nz-50%CO
/ 850 9:
10 min
Gas velocity 0.8 m/s
0.4 0.8 1.2 1.6 2.0 50%Nz-5O%Co
Gas velocity/(m.s-') 9 , I I
Fig. 8 Influence of gas velocity on gas utilization ratio
2.5 Influence of the charge height on reduction
Since the diameter of the bed is fixed, the charge
height corresponds to the mass of sample. T h e fine 3 Conclusions
powder of iron ore is in the fluidization condition in
the experiment when gas velocity is at 0. 8 m/sC1*'. 1) T h e reduction-degree of the sample increases
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