Development of Ferro-Coke Process for Mitigating CO2 ... and Steel 2 Secured... · Kanji Takeda...
Transcript of Development of Ferro-Coke Process for Mitigating CO2 ... and Steel 2 Secured... · Kanji Takeda...
1 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Development of Ferro-Coke Process for Mitigating CO2 Emissions in Ironmaking
IEAGHG/IETS Iron & Steel Industry CCUS & Process Integration Workshop
November 2013 Tokyo Tech Front, Tokyo Institute of Technology, Japan
Kanji TakedaKanji Takeda(Project Leader) (Project Leader)
JFE Steel Corp.JFE Steel Corp.Nippon Steel & Sumitomo Metal Corp.Nippon Steel & Sumitomo Metal Corp.
Kobe Steel, Ltd.Kobe Steel, Ltd.
2 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
CO2 mitigation and usage of low grade resources in ironmaking process
Forming
Coking coal
Coke ovens
Innovative Ironmaking process
BF
Coke
Shaftfurnace
PJPJ
Conventional Conventional ironmakingironmaking processprocess
Low grade
Lowgrade
Ore fine
Sintering machine SinterHigh grade
Burden 1
Burden 2
Burden 3
Coke reduction
Utilization of low grade ore/coal
Innovative binder
Non-coking coal
Ore fine
InnovativeBF operation
Ferro-coke
Low environmental
risk
Energy savings(CO2 mitigation)
Partial replace
NEDO/METI grant project : Period: FY2009/10 , FY2011/12 :Grant ratio : 1/2
Participants: JFE Steel, Nippon Steel, Sumitomo Metals, Kobe Steel, Major Japanese Universities
Concept of Innovative ironmaking process
3 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Development of innovative ironmaking process
Ferro-coke
Direct heating
Innovative binder
Metallic iron Carbon(coke)Binder
Ore particle
Coal particle
Fe
Fe
Fe
Briquette
Coke layer
Sintered ore layer
Blast furnace(Coke mixed charging)
Structure and compositions of agglomerates
Carbonization and reduction
Blast furnace operation using Ferro-
coke
Three key technologies
Low gradeOre and coke
Ferro-coke
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
4 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Coal Properties
Ore Properties
Coal Ro(%) VM(%) MF(ddpm) Ash(%)
A 0.72 36.1 307 8.4
B 1.80 11.2 0 8.6
T.Fe FeO SiO2 Al2O3 SPCaO MgO Na K
A 67.5 0.21 0.01 0.49 0.73 0.01 0.033 <0.01 <0.01 <0.01
Coal A :Slightly caking coalCoal B :Non caking coal
(VM,Ash:dry base)
(mass%)
Properties of coal and ore
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
5 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Briquette conditionsTotal roll power 30~50tonBriquetting pressure 3~5 t/cm
6 rpm
100~120℃
Cup volume 6cc
Roll speedBriquetting temp.
Coal/ore = 7/3Coal/ore(mass%)
20kg-dry/batchTotal sample weight
Roll diameter 650mm
Binder(mass%) SOP+ASP=5-9%Particle size Coal; -3mm,
Ore A; -250μm B; -1mm
Size:30x25x15mm
Hot briquetting test in bench plant
Briquette machine
Coal Hopper Ore Hopper
Mixer
MixerDischarge
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
6 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Carbonization test conditionsCarbonization temp (at wall) ;1000℃
Carbonization time ;6h
Packing ;with/without coke breeze
Carbonization temperature
885℃
0
200
400
600
800
1000
0 60 120 180 240 300 360Time (min)
Car
boni
zatio
n te
mp
at c
ente
r(C
)
Briquette
Heater
Schematics of carbonization furnace
T/C
Without coke fine Embedded to coke fine
Packing conditions
Carbonization tests in batch furnace
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
7 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Adhesion ratio of the ferro-coke at the blending ratio of 30% and 70%
Effect of coal and ore ratio on adhesion and swelling
Coal : A/B = 70/30(mass%)
Ore; 0mass% Ore; 10mass% Ore; 30mass%
Coal A70%
+Coal B
30%
Coal A100%
Carbonized in coke fine
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
8 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Hypercoal
Residue Coal
coal
Solvent recoverySlurry make up Extraction Solid-Liquidseparation
Pre-heater
ExtractorSettler
Recycle-solvent
DryerFlasher
FlasherEvaporator
Mixer
Hypercoal
Residue Coal
coal
Solvent recoverySlurry make up Extraction Solid-Liquidseparation
Pre-heater
ExtractorSettler
Recycle-solvent
DryerFlasher
FlasherEvaporator
Mixer
Innovative binder
ObjectivesObjectivesTo develop a innovative binder for Ferro-coke by utilizing the KSL’s proprietary coal solvent extraction technology (Hyper-coal)TargetsTargets
Higher Ferro-coke strength compared to a conventional asphalt pitch binder (ASP) Features of the innovative binder processFeatures of the innovative binder process1. No hydrogenation, mild reaction conditions (ca. 400oC, 2MPa)2. Product separation by gravity settling3. Recycled use of naphthalene-based solvent
Photo Test production facility for the innovative binderCapacity: 0.1 ton-coal/day
Development of an innovative binder for Ferro-coke
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9 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
- Softening temperature of the binder can be controlled by the extraction conditions. - The innovative binder prepared by extracting a bituminous coal at 410 oC exhibitedlower softening temperature and superior fluidity than the ASP binder.
The enhanced fluidity of the binder may improve the inter-particle adhesion between ore and coal particles under the Ferro-coke carbonization conditions
0
1
2
3
4
5
6
150 200 250 300 350 400 450 500 550
Temperature [℃]
Gie
sela
r flu
idity
, log
ddp
m
380℃ Extaction 410℃ ExtractionRef.(Asphalt pitch)
Effects of the extraction conditions on the binder properties
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10 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Briquette ejector Mixer
Mixer
Double roll press
Coal hopper Ore hopperTable Compositions for the feed [wt%]
Table Briquetting conditions
HPC: 23.02.028.539.926.65
HPC: 23.02.028.539.926.64
ASP/HPC: 13.01.01.028.539.926.63
ASP/HPC: 13.01.01.028.539.926.62
Ref.3.02.028.539.926.61
RemarksSOPHPC2HPC1ASPOre ACoal BCoal ANo.
Extraction temperature for the innovative binders: HPC1, 380oC; HPC2, 410oC
20 kg/batchFeed rate
Coal, <2mm; Ore, <250mParticle size
SOP, 3%; ASP (or HPC), 2%Binder content
7/3 (by weight)Coal/ore ratio
6 cc (30x25x15 mm)Pocket volume
170 oCMaterial temperature
6 rpmRotation speed
650 mmRoll diameter
3-5 ton/cmPressure
Experiments for evaluating the innovative binders
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11 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Strength of Ferro-coke prepared by the innovative binders
Fig. Drum indices of the Ferro-coke
60
65
70
75
No.1 No.2 No.3 No.4 No.5ID
I(60
0/10
)[-
]
Briquettes
Heater
Fig. A schematic for 3kg-scalecarbonization apparatus
Thermo couple
410oC extractionbinder (HPC2)
ASP380oC (HPC1)
Wall temperature: 1000oCMaterial temperature: 900oCDuration: 6 hour
Table Carbonization conditions
It was demonstrated that the innovative binder prepared by solvent extractionof coal at 410oC improves the Ferro-coke strength compared to the ASP binder
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12 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Effect of coking temperature and holding time
Carbonized particle
6cc
Discharge
Gas pre-heater
Charging BC
Bench scale plant 0.5t/d
Shaft furnaceElectricheater
Coke
Cross section
Metallic iron
0.2mm
Effect of coking temperature on the reduction ratio
Bench scale plant of 0.5 t/d and products.
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13 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
DEM model development of Ferro-coke plant
1.25m
0.96m
12m
2m
1.25m
1.33m
Width : 1.25mLength : 1.33mHeight : 14.0m
Discrete Element Method
Inter particle
Voigt model
14 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
3D images of tracer particle flow
14
Initial charging
15 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Process flow of a pilot plant of 30t/d
Forming
Gas heating
Gas cooler
Iron ore30%
Non-coking coke70%
DryerPre-heater
Mixer/kneader
Crusher
Oven coke
Blast furnaceFerro-cokeBriquette
Shaft furnace
EPPlant
Carbonization/Reduction
Furnace type : Shaft Capacity : 30t/dLocation : JFE Steel Corp.,East Work (Keihin)
Sintered ore
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16 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Overview of the 30t/d ferro-coke pilot plant
Briquetting Carbonization
Stockyard
Gas recycle
Crushing and heating
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17 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
0
50
100
150
200
11:00 12:00 13:00 14:00 15:00 16:00 17:00Tem
p. o
f mix
er [℃
]
0
50
100
150
200
11:00 12:00 13:00 14:00 15:00 16:00 17:00
BQ
forc
e [t]
84
88
92
96
100
① ② ③ ④
Stre
ngth
ID30
/16[
-]
Target
Target DI>88
Start briquetting
Charging start
Continuous operation for 5hr
Briquette for carbonization tests
10mm
Target range of BQ force
Time
Typical continuous briquetting operation
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
18 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Development of innovative ironmaking process
Ferro-coke
Direct heating
Innovative binder
Metallic iron Carbon(coke)Binder
Ore particle
Coal particle
Fe
Fe
Fe
Briquette
Coke layer
Sintered ore layer
Blast furnace(Coke mixed charging)
Structure and compositions of agglomerates
Carbonization and reduction
Blast furnace operation using Ferro-
coke
Three key technologies
Low gradeOre and coke
Ferro-coke
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.
19 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Tw control
Pre-reduction
O/Fe
Highly reactive composite forTw decrease
FeO
Fe
Temp CO2/(CO+CO2)
W point at800℃
Catalytic effect
RAR reduction
10001000℃℃
800800℃℃
W point W point at 1000at 1000℃℃
Base
②
③
④
①→② RAR reduction in short term・Improve sinter reducibility・Burden distribution control
②→③ Thermal reserve temp. Tw・Highly reactive coke・Carbon contained agglomerates
②→④ Innovative agglomerates③→④
Catalytic effect for high reactivity
①
Basic concept of low carbon technologies
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20 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Gas flow
Solid flow
Experimental conditions with BIS and large thickness
Sinter
Coke
Sinter
330mm
330mm
φ65mm
Reducing gas
Ferro-coke
Coke
Blast furnace Inner reaction simulator
30% of conventional coke was replaced with Ferro-coke.
Different mixing conditions with Ferro-coke were tested.
Condition with large layer thickness as plant, 330 mm, was tested.
コークス層
焼結鉱層
フェロコークス
70mm
ベース 焼結層に均一混合
焼結層上層に混合
コークス層に均一混合
Ferro-coke
Sinter
Coke
Base Homogeneously mixed
Upper layer
Mixed in coke
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21 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
850
900
950
1000
1050
1100
ベース 鉱石層
均一混合
鉱石層
上層混合
コークス層
均一混合
熱保
存帯
温度
(℃)
コークス層
焼結鉱層
BIS testsTemperature of thermal reserve zone was lowered by 100℃ with using Ferro-coke. Proper arrangement of Ferro-coke was homogeneously mixed or segregated in upper layer.
Both reactivity of sinter and Ferro-coke were large in homogeneously mixed.
Evaluation with a large layer thickness as plant, 330 mm
Sinter
Coke
Base Homogeneously mixed
Upper layer
Mixed in coke
Tem
pera
ture
of t
herm
al
rese
rve
zone
(℃)
30
40
50
60
70
80
30
40
50
60
70
80
1 2 3 4
Carbo
n con
sump
tion r
atio
of fer
ro-co
ke (%
)
Redu
ction
degre
e of s
inter
(%)
26
28
32
34
36
30
□ Average of reduction degree of sinter- Minimum and maximum of reduction degree
of sinter● Carbon consumption ratio of ferro-coke
Base Homogeneouslymixed
Upperlayer
Lower layer
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22 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Concept of Mathematical Blast Furnace Model
Fe2O3,Fe3O4, FeO,Ganuge
FeO, Fe,Gangue
Fe2O3→Fe3O4→FeO→Fe
FeO(l), Fe(l),Gangue(l)
CO
CO2 CO
Ore Coke
COCO COCO22
C, Fe, Gangue
CC↓↓, Fe, Gangue
CC→→00, Fe, Gangue
Fe(l), Gangue(l)
Ferro-coke
This mathematical blast furnace model can estimate inner furnacereactions when Ferro-coke is charged into blast furnaces.
This mathematical blast furnace model can estimate inner furnacereactions when Ferro-coke is charged into blast furnaces.
Gasification model of Ferro-coke is required to evaluate the effect of Ferro-coke on blast furnace operation.Gasification model of Ferro-coke is required to evaluate the effect of Ferro-coke on blast furnace operation.
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23 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Measurement of gasification rate of Ferro-coke
)('2
2 Kppkk CO
CO
Ferro coke Sample ( diameter: 11mm )
(11)(1)
(2)
(3)
(6)
(7)
(10)
(12)
(1)
(2)
(8)(9)
(4)(5)
(11)(1)
(2)
(3)
(6)
(7)
(10)
(12)
(1)
(2)
(8)(9)
(4)(5)
(1) Cooling water Inlet (2) Cooling water outlet(3) Purge gas inlet(4) Strain gauge(5) Copper tube(6) Stainless steel wire(7) Reaction gas outlet(8) Sample(9) Reaction tube(10) Electric Furnace(11) Reaction gas inlet(12) Thermo-couples
Apparent reaction rate constant k’
Reaction rate constant k
)56.174790,170exp(RT
TK
Equilibrium constant
0 600 1200 1800 2400 3000 3600
0
0.1
0.2
0.3
0.4
0.5
1000℃
Frac
tiona
l gas
ifica
tion(
-)
Time(sec)An example of fractional gasification curve.
Gradient of fractional gasification curve
24 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Modeling of gasification rate of Ferro-coke
)RT.exp(.kE f
37 107181102082
・
)RT.exp(.kE f
37 101169100011
・
)RT.exp(.kE f
36 102158108284
・
Ore 0%
Ore 10%
Ore 30%
Where,
Raten = ( C CO2
b - C CO2
e )・s
Bulk ConcentrationEquilibrium Concentration
Volume fraction
ka
f
p
fa kd
kEk 611
Mass transfer coefficient
Over-all reaction rate constant
Particle diameter
Effective reaction rate constant
Gasification model of Ferro-coke was combined into the mathematical blast furnace model
Effective reaction rate constant
Kyushu Univ. NSSMC
Gasification model of Ferro-coke made by Kyushu University was combined into the mathematical blast furnace model developed by NSSMC. The effect of Ferro-coke on blast furnace operation can be evaluated by the model.
Gasification model of Ferro-coke made by Kyushu University was combined into the mathematical blast furnace model developed by NSSMC. The effect of Ferro-coke on blast furnace operation can be evaluated by the model.
Coke D (Ore 30%)Coke E (Ore 30%)Coke F (Normal Coke)
0.6 0.7 0.8 0.9-3
-2
-1
0
1
2
3
1000/T (1/K)
lnE f
・k
(-)
T.Nakamura et.al.: Camp ISIJ, 25(2012),222.
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25 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Effect of Ferro-coke on temperature distribution, gas concentration in blast furnace
Volume fraction of Ferro-coke [%] CO concentration [vol frac.]Solid temperature [℃]
Base 100kg/t Base 100kg/t Base 100kg/t
800
1000
1200
14001600
800
1000
12001400
1600
0.25
0.30
0.35
0.25
0.30
0.35
Variation of inner-furnace state due to the charge of Ferro-coke was estimated.Variation of inner-furnace state due to the charge of Ferro-coke was estimated.
17%
15%
12%10%
JIS-RI=64.1%CRI=30.0%
JIS-RI=64.1%CRI=30.0%
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26 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
21mFerro-coke
54m
Photo ③
Photo ①
Photo ① Photo ②
Photo ③
Photo ②
Stock yard of FerroStock yard of Ferro--coke for blast furnace testcoke for blast furnace test
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27 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
SurgeHopper
Charging BC
Direct charge bin
Ore binNut coke
Stock yard of ferro-coke
Ferro-coke of 2100 ton was transported by truck to the direct charge bin.
Five days charging test was carried out in March 2013.
Feeder gatecontrol
Charging of FerroCharging of Ferro--coke to Chiba No.6 blast furnacecoke to Chiba No.6 blast furnace
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28 IEAGHG/IETS Iron & Steel IndustryCCUS & Process Integration Workshop, November 2013
Concluding Remarks
The innovative inromaking process development was the final year of four years project in FY2012.
1) Optimization of production conditions of an innovative binder from Hyper coal process and evaluation at the pilot plant.
2) Successive operation of briquetting and carbonization was carried in the end of FY2011 and continuous production trials and charging tests to a blast furnace has successfully completed in FY 2012 to findprocess feasibility of the production process and technical subjects of blast furnace charging.
3) Development of charging condition for the optimum layer structure has been established at laboratory scale experiments.
4) Evaluation of blast furnace operation with the Ferro-coke at No.6 blast furnace in Chiba Works.
Copyright © 2013 JFE Steel Corporation. All Rights Reserved.