Professional Documents
Culture Documents
Swerea MEFOS AB
Box 812, SE- 971 25 Lule, Sweden
+46 920 20 19 00
lena.sundqvist@swerea.se
maria.lundgren@swerea.se
2
Luossavaara-Kiirunavaara AB (LKAB)
Box 952, SE-971 28 Lule, Sweden
+46 920 38 000
carina.brandell@lkab.com
INTRODUCTION
When the temperature in the thermal reserve zone is reduced, the equilibrium between CO/CO2 and Fe/FeO is shifted towards metallic
Fe at a specific reducing power of the gas as can be seen in Figure 1. The use of highly reactive nut coke mixed ferrous materials is
one possible method for reducing the temperature.
Figure 1 Fe-O-C equilibrium diagram including the Boudouard curve as well as the degree of reduction in the presence of CO and
CO21
In studies conducted by Nomura et al. 2, 3 it has been shown that the reactivity of coke can be increased either by adding a catalyst to
the coal blend prior coking or to treat the produced coke. Reactive coke was successfully produced by using a coal type with Ca rich
ash in the coal blend for coke making2. In laboratory testing the coke showed high chemical reaction rate with CO 2 at 950 C, but the
reactivity index (CRI) increased less and the strength after reaction (CSR) could be more or less kept unchanged if the addition of the
Ca-rich coal was less than 10%. In full scale coke production 5-7% of the Ca rich coal was added. Adiabatic BF simulator trials with
sinter showed decreased thermal reserve zone temperature and higher reduction degree of sinter for the Ca-rich coke compared to
ordinary coke. The total reductant rate of the operational BF decreased when changing from ordinary coke to the Ca-rich coke. Results
were also reported from the addition of iron ore or iron oxide prior to the production of a reactive coke 4. The iron oxide caused
decreased strength after reaction and increased reactivity of the coke but the strength measured as drum index was proper. The iron
oxide has a tendency to react with the silica brick in the coke oven at temperatures of 1200C but not at a temperature of 1100C.
A catalyst can be added post coke making and deteriorating effects on strength can be avoided 3. In laboratory testing it was estimated
that 70% of the addition made as a solution or slurry with a desirable composition should sustain raw material handling. The reaction
rate and the weight loss are increased with the addition of Fe and Ca containing compounds and the results indicate that the thermal
reserve zone temperature may decrease and improved reduction of ferrous material possibly be achieved. The authors think that more
studies are needed to explore and confirm the effect further.
By using a high ratio of nut coke mixed with the ferrous material the high temperature properties of the iron ore in terms of reduction
degree was improved up to 10% addition5. Improved shaft efficiency decreased reductant rate and the permeability of the cohesive
zone were stated in industrial trials charging approximately 100 kg nut coke/tHM. The reactivity of the coke is not stated but the coke
has a CaO content of 0.25 wt%.
Aiming for reduced consumption of reducing agents in the BF, the most appropriate method for activation of nut coke were analyzed
in the laboratory and later up-scaled for use in pilot scale treatment at LKAB in Malmberget. To explore the effect on the process
conditions and the energy efficiency operational trials in the LKAB experimental BF in Lule were planned and conducted. The
results from the trials are presented and discussed.
EXPERIMENTAL
The LKAB Experimental Blast Furnace (Experimental BF)
The first campaign in the Experimental BF was conducted in 1997 and these trials were conducted as one part of the 29th campaign. It
is usually operated twice every year and the length of each campaign is approximately 6 to 8 weeks. The operation and control of the
Experimental BF are comparable with the industrial BF but the response time is shorter.
Position on radius
Upper skinflow
-0.44
-0.90
Lower skinflow
-1.05
-3.46
-4.21
From 210 to 0
Tuyeres
-5.7
30 , 150 , 270
The Experimental BF is also well-equipped for measuring of temperature and pressures. The shaft has no water cooling,
thermocouples are installed inside the refractory and pressure measurements over the height of the shaft. In order to study the
atmosphere inside the shaft and collect material samples during operation, material and gas/temperature probes are fitted to the blast
furnace, as shown in Figure 3.
Figure 3 The Experimental BF including shaft probes, inclined probe and vertical probe
The vertical temperature profile of the Experimental BF can be measured by inserting a thermocouple from the top allowing it to
descend with the burden. This measurement normally withstands temperatures up to approximately 1250C before the thermocouple is
damaged. The levels where thermocouples and other important blast furnace equipment have been installed are listed in Table I and
the radial sampling and measurements with probes are shown in Figure 4.
Raw Materials
The ferrous burden for all periods was LKAB olivine pellets from Malmberget. Quartzite was added to reach the desired slag volume
and a limestone and BOF slag was used for basicity adjustment of the final slag. The chemical compositions of raw materials,
including the activated coke, are given in Table II.
Nut coke and coke used in the coke layers were crushed and screened into the fraction 15-30 mm. Three types of treatments were used
for nut coke to be added to ferrous layers; a solution with Zr-tracer, a slurry of magnetite with Zr-tracer and a slurry of burnt lime with
Zr-tracer. The solutions and slurries were sprayed on the coke under rotation in a drum (left photo in Figure 5) and finally the coke
was dried (right photo in Figure 5) and samples for analyses taken before transportation to the Experimental BF plant.
Figure 5 Processes of preparation of activated nut coke by coating and drying of coated coke afterwards
The original nut coke used as well as the Zr-traced one has similar chemical composition as the coke used in the coke layers. As the
activated coke was coated with slurries of magnetite or hydrated lime the chemical composition was changed somewhat. The content
of C was lowered at the same time as either the content of Fe or CaO increased. The slurries also contained zirconium sulphate for
tracing the activated nut coke in samples collected during the trials.
14
12
% moisture
10
Large sample
Zr Large
Lime large
Magnetite large
Small sample
Zr small
Lime small
Magnetite small
8
6
4
2
0
13-05-01 00:00
13-05-06 00:00
13-05-11 00:00
13-05-16 00:00
13-05-21 00:00
13-05-26 00:00
Figure 6 Moisture content in coke and nut coke used during the Experimental BF tests
Samples of raw materials were collected every time the raw material bins were filled up. Moisture content of coke and ferrous material
as well as the particle size distribution of pellets were analyzed for each sample. In case of changed moisture content to a new stable
level the new values were introduced in the system and used in the recipe calculations. The variation in measured moisture content of
pellets was minor and the variation in coke moisture is shown in Figure 6. To minimize the variations in coke moisture one single
delivery of coke was used during the trial and in general the moisture was in the range of 4-6%. However, a few significant changes in
moisture was experienced although this precaution. The lime coated coke had lower moisture content compared to the other coke
types due to longer time for drying after coating.
Table II Raw materials used during the trial and their composition, given in wt.-%
Nut coke
BOF
Lime
Magnetite
MPBO Limestone Quartzite
slag
activated activated
CaO
0.43
58.0
0.199
40.5
1.30
0.03
MgO
1.31
0.93
0.23
11.8
0.09
0.09
SiO2
1.76
1.06
97.9
8.75
7.03
6.49
Al2O3
0.35
0.48
0.75
1.71
3.12
3.03
TiO2
0.30
0.02
0.03
1.49
0.16
0.18
V 2O 5
0.21
0.01
0.004
4.57
0.00
0.19
Na2O
0.07
0.13
0.061
0.022
K 2O
0.01
0.09
0.247
0.02
0.098
0.069
S
0
0.069
0.029
0.063
0.57
0.55
P
0.01
0.002
0.005
0.29
0.020
0.007
Mn
0.04
0.01
0.01
3.13
0.00
0.00
Fe
66.8
0.058
0.149
19.067
0.41
2.02
C
85.4
85.4
H2
0.087
0.087
O2
0.20
0.20
N2
1.16
1.16
Original &
Zr-traced
0.03
0.09
6.62
3.09
0.18
0.00
0.022
0.07
0.55
0.007
0.00
0.53
87.1
0.089
0.20
1.188
Coke
0.03
0.09
6.62
3.09
0.18
0.00
0.022
0.07
0.55
0.007
0.00
0.53
87.1
0.089
0.20
1.19
PC
0.37
0.16
3.24
1.80
0.06
0.00
0.04
0.1
0.340
0.017
0.02
0.609
82.9
4.10
3.77
2.18
Test Conditions
The test periods operated and evaluated consisted of four main parts
Reference period without nut coke in ferrous layers
Reference periods with 150 kg/tHM of original or Zr-traced nut coke charged in ferrous layers
Test period with 150 kg/tHM of Zr-traced, magnetite activated nut coke charged in ferrous layers
Test period with 150 kg/tHM of Zr-traced, lime activated nut coke charged in ferrous layers
From the operational tests, stable data periods stated in Table III were selected for the evaluation of in-furnace conditions, operational
conditions as well as energy efficiency of the set-ups. The two periods for lime coated nut coke has the same start but the long period
extends longer in time including some slightly more varied conditions.
Table III Evaluation periods, 150 kg/tHM of nut coke was used in the ferrous layers in all test periods except for reference
Short name of period
Duration
Start
End
Recipe, type of nut coke
2013-05-02 21:00
2013-05-04 10:00
Ref.
37.0 h
2013-05-15 14:01
2013-05-15 23:54
Orig.
9.9 h
26.0 h
2013-05-15 23:56
2013-05-17 01:53
Zr-traced coke
Zr-traced
2013-05-17 14:00
2013-05-19 12:30
Magnetite
46.5 h
2013-05-20 14:00
2013-05-21 15:00
Lime
25.0 h
2013-05-20 14:00
2013-05-22 03:30
Lime long
37.5 h
Recipe changes were made when starting to use a new type of nut coke, when the moisture content of coke changed, for heat level
control and in order to adjust the slag basicity for sufficient alkali removal. The amount of coke in the ferrous layers was 150 kg/tHM
when nut coke was added, except for during a ramping-up period in the beginning of the reference period with nut coke. As the
efficient C content varied between the nut coke types the amount of coke in the coke layers was influenced correspondingly.
During the all periods the pulverized coal injection (PCI) was kept fairly constant and changes in the amount of reducing agents were
adjusted by changing the coke rate. Also other basic operational parameters were successfully kept more or less constant during the
tests as can be seen in Table IV.
Table IV Indicative and actual operational parameters during trial periods for evaluation
Indicative
Ref.
Orig.
Zr traced Magnetite
Lime
Lime long
Prod. Rate*
1.5
1.50
1.45
1.48
1.53
1.52
1.51
Tot. blast flow
1587
1584
1585
1580
1582
1582
Blast air flow
1500
1500
1500
1500
1500
1500
1500
O2 enrichment
110
111
110
110
110
110
110
O2 in blast
50
50.6
50.3
50.4
50.1
50.2
50.2
O2 to lances
60
60.5
59.3
59.3
59.7
59.4
59.3
Tot. O2 in blast
26.4
26.6
26.6
26.6
26.8
26.7
26.7
PCR
150 (225) 150 (226) 153 (221) 148 (219) 148 (226) 150 (228) 151 (228)
Moisture in blast
20
20
20
20
20
20
20
Blast temp.
1200
1196
1196
1196
1196
1196
1196
Ave. blast temp. at tuyeres**
1120
1117
1114
1114
1114
1113
1113
Flame temp.
~ 2150
2187
2187
2190
2184
2180
2180
* from material balance, **average close to tuyeres
tonne/h
Nm3/h
Nm3/h
Nm3/h
Nm3/h
Nm3/h
Vol%
kg/tHM (kg/h)
g/Nm3
C
C
C
1200
Charged C
480
481
C, kg/tHM
475
600
HM Temp
1470
1000
800
C consumed in process
485
1460
474
1450
471
470
1440
465
400
466
463
1430
460
200
459
457
455
0
Ref.
Orig
Zr
Magnetite
Lime
-200
Lime long
1420
453
450
Ref.
Orig
Zr
Magnetite
459
459
458
Temperature, C
1400
Lime
453
1410
Lime long
Initially the collected Experimental BF data for each period was inserted in the model assuming that data as e.g. weights and analyses
for charged and tapped material and gas analyses are correct. The model iteratively calculates the blast volume and total heat losses.
The achieved values for blast volume are compared with the measured ones. Actual heat losses for the Experimental BF are based on
measured heat losses for water cooled part, estimated heat losses based on temperature measurements on the steel shell and calculated
heat losses related to the top gas. A large deviation between totally estimated heat losses based on data and the one calculated in the
model indicate changed amount of coke in the coke reserve. As can be seen in Figure 7, the un-known heat losses varies and e.g
during the period with Zr-traced nut coke the heat losses estimated in the model based on the charged C is much lower than those
stated based on the consumed C. During the first period with original nut coke the starting point was a higher fuel rate in order to
avoid disturbances caused by changed temperature and gas profiles. The coke reserve is accumulated and during the following period
it is then possible to reduce the fuel substantially without coming into low heat level.
To overcome the impact on heat and mass balance from accumulation or consumption of raw materials the amount of consumed C
(coke and coal) is calculated based on the gas analyses and under the use of measured and calculated heat losses. In Figure 8 the
amount of charged and by the process consumed C, respectively, are stated. As can be seen, coke accumulation occurs during the first
period with nut coke when using original coke in the ferrous layers. During the next period when using Zr-traced nut coke the
consumption of some accumulated coke reserve is coke occurs.
The heat level is significantly higher during all test periods compared to during the reference period as shown in Figure 9. This results
in an increased consumption of C for periods when original or Zr-traced nut coke is used. For periods with activated nut coke the C
consumption is lower although higher heat level compared to during the reference. As can be seen the average hot metal temperature
during the reference is ~1429 C compared to 1446-1465 C during trial periods. Additionally, the Si content in hot metal differs as
well, se Figure 9. To be able to compare the C consumption for the different evaluation periods, model calculations for normalized
conditions were conducted. For normalized heat level a hot metal quality with 1.35 wt.-% Si and hot metal temperature of 1430 C
were selected, quite similar as for the reference period. In Figure 10 the difference in estimated C consumption for trial periods
relative reference period is shown for normalized conditions. It can be concluded that the C consumption is reduced with ~ 4-6
kg/tHM (Figure 10) if differences in heat level are not taken into account. For normalized data the reduction in C consumption is ~6-8
kg/tHM (Figure 11).
C (%)
Si (%)
1465
1456
3.5
1450
1448
1446
1440
2.5
1430
1429
1420
1410
Temperature, C
1458
1.69
1.5
1.61
1.43
1.38
1.35
Magn.
Lime
Lime long
1.35
Ref-
Orig.
Zr traced
1470
11.2
10
Wt-% C and Si
1460
HM Temp
12
4.5
1460
8
8.2
1450
4
1440
2
0
0.0
Ref.
1430
Orig
Zr
Magnetite
Lime
Lime long
-4.3
-4.1
-2
-4
Temperature, C
HMT (C)
1470
1420
-5.8
-6
1410
During periods with higher heat level and higher Si content in hot metal the slag basicity is increased and the slag volume reduced.
This results in reduced alkali recovery to the slag. In Figure 12 the average K2O yield to the slag is shown. When the yield is low,
accumulation, recirculation and scaffolding may occur. Recirculation of alkali results in increased C consumption in the lower part of
the furnace due to the reduction and gasification of alkali compounds. In the upper part these are oxidized again. The thermal and
chemical energy returned in the upper part is evened out in the heat and mass balance but in the actual BF it will result in increased
energy consumption. Moreover, during this period the high Si content in hot metal requires an increasing amount to counteract the
accumulation of alkalis.
10
475
470
6
4.9
4
2.1
460
455
2
0
0.0
450
-2
445
-4
440
-6.4
-5.7 -6
-7.8
435
-8
430
-10
Ref.
Orig
Zr
Magnetite
Lime
Slag basicity, B2
160%
1.10
140%
1.05
120%
1.00
100%
80%
0.95
60%
0.90
40%
0.85
20%
0%
0.80
Ref
Orig
Zr traced
Magn.
Lime long
Lime
Lime long
Slag basicity, B2
480
465
K2O yield
K2O yield, %
C consumed in process
Gas efficiency, %
49.2
190
0.7
49.0
185
0.6
49.0
48.5
3
48.0
2
47.7
47.7
47.5
Gasefficiency, %
49.2
47.5
1
0
Ref.
Orig.
Zr traced Magnetite
Lime
Water dosage
49.5
0.5
180
0.4
175
0.3
170
47.0
165
46.5
160
0.2
0.1
0.0
Lime long
Ref.
vol%H2
Burden descent
5
Orig.
Zr traced Magnetite
Lime
Lime long
At the upper probe level the gas efficiency is higher during periods with activated coke, see Figure 15. At the lower probe level the gas
efficiency is as seen in Figure 16 highest for periods with magnetite-activated nut coke. In between the tuyeres the gas efficiency is
high also for lime-activated coke. Above the raceway the gas efficiency is quite similar for all periods except for during the magnetiteactivated ones.
Orig.
Zr traced
Magn. 1
Magn. 2
Ref.
60
30
50
25
Gas efficiency, %
Gas efficiency, %
Ref.
40
30
20
10
Orig.
Zr traced
Magn. 1
Magn. 2
20
15
10
5
5
Position
5
Position
water cooled. However, it is indicated that the use of 150 kg/tHM of nut coke results in a flatter temperature profile with less extensive
central gas flow. In the vertical temperature measurement a lowered thermal reserve zone temperature is measured for the period with
lime-activated coke as seen in Figure 19. The period with magnetite-activated nut coke shows similar temperature profile as for nonactivated nut coke.
Ref.
Orig.
Zr traced
Magn. 1
Magn. 2
Orig.
800
Magn. 1
Magn. 2
1050
750
950
Temperature c
700
Temperature c
Zr traced
650
600
850
750
550
650
500
550
450
450
1
5
Position
5
Position
Based on the horizontal and vertical measurements conducted during the evaluation periods but also in connection to them a measured
temperature was deduced and used in the heat and mass balance calculations. If the measured temperature is used in the heat and mass
balance calculations the shaft efficiency reached more than 100% for Zr-traced and magnetite-activated periods. Assuming a similar
shaft efficiency of 99% for all periods, a lower temperature is estimated for all evaluation periods when using activated nut coke,
Figure 20.
200
400
Temperature C
600
800
1000
1200
Approximate measured
1080
1060
500
1040
1000
Temperature, C
1000
2000
2500
3000
4500
5000
1060
1023
1000
980
1000
994
1002
960
965
974
960 961
960
940
3500
4000
1060
1020
1500
Ref.
Magn. 1
Lime and lime long
Zr traced
Magn. 2
920
900
Ref.
Orig
Zr
Magnetite
Lime
Lime long
CONCLUDING REMARKS
During the Experimental BF trials stable operation could be achieved when using 150 kg/tHM of nut coke in the ferrous layers. The
gas efficiency was in general high for all periods and increased from the reference the to the activated nut coke periods.
The charging of high amounts of nut coke is believed to improve the horizontal gas distribution.
High gas efficiency could be achieved although high coke rate during periods with original and Zr-traced nut coke
The horizontal gas profile at upper shaft probe level became flatter with less significant central gas flow
The top gas temperature and water dosage was not significantly increased when high heat levels were reached
Further increase in gas efficiency during periods with activated nut coke is likely caused by lower thermal reserve zone temperature
that improves the indirect reduction of ferrous material and decreases the direct reduction. Lower thermal reserve zone temperatures
were indicated by measured data and heat and mass balance calculation results. Lowering of the thermal reserve zone temperature
moves the equilibrium for Femet/FeO to CO/CO2 towards Femet during the periods with activated nut coke.
The C consumption calculated for all periods using normalized hot metal heat level in terms of Si content and tap temperature states a
reduction of C consumption with 6-8 kg/tHM when activated nut coke is charged. The highest savings are achieved during the period
with magnetite-activated nut coke.
For industrial implementation the method for activation has to be further developed. In the method used the coke reaches a moisture
content corresponding to saturation and cannot be charged without previous drying.
ACKNOWLEDGEMENTS
The research work presented in this paper has been carried out within the project of Innocarb, RFSR-CT-2010-00001, that is cofunded by the Research Fund for Coal and Steel (RFCS). Swedish Energy Agency is greatly acknowledged for additional financial
contribution. The paper is a contribution from CAMM, Centre of Advanced Mining and Metallurgy, at Lule University of
Technology that supported the research scientifically and economically.
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