NEDO PROJECT COURSE 50
Development of High Throughput and
Energy Efficient Technologies for
Carbon Capture in the Integrated
Steelmaking Process
CCS Workshop
Düsseldorf, Germany
November 8-9, 2011
Masao Osame
Sub-Project Leader of COURSE50 (JFE Steel Corporation)
P1
NEDO PROJECT COURSE 50
Introduction of COURSE50 Project
P2
Member of COURSE50* Project
*CO2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50
New Energy and Industrial Technology Development Organization
P3
Cool Earth Innovative Energy Technology Program
P4
Project Targets
(1) Development of technologies to reduce CO2 emissions from blast furnace
・ Develop technologies to control reactions for reducing iron ore with reducing agents such as
hydrogen with a view to decreasing coke consumption in blast furnaces.
・ Develop technologies to reform coke oven gas aiming at amplifying its hydrogen content by
utilizing unused waste heat with the temperature of 800℃ generated at coke ovens.
・ Develop technologies to produce high-strength & high reactivity coke for reduction with
hydrogen.
(2) Development of technologies to capture - separate and recover - CO2 from blast furnace gas
(BFG)
・ Develop techniques for chemical absorption and physical adsorption to capture - separate
and recover - CO2 from blast furnace gas (BFG).
・ Develop technologies contributing to reduction in energy for capture - separation and
recovery - of CO2 through enhanced utilization of unused waste heat from steel plants.
Time Table of Technology Development
2010
2020
Phase 1
Phase 1
Step 1
Step 2
(2008～12） (2013-17）
NEDO Project
Phase 1
Step 1
(2008～12）
2030
Phase 2
2040
2050
Industrialization & Transfer
2008
2009
2010
2011
2012
0.6
2–3
2–3
2–3
2 – 3 (billion yen)
P5
Project Outline
(1) Technologies to reduce CO2 emissions from blast furnace
(2) Technologies for CO2 capture
Reduction of coke
Iron ore
H2 amplification
Coke production technology
for BF hydrogen reduction
Coke
・Chemical absorption
・Physical adsorption
BFG
CO-rich gas
CO2 storage
Shaft furnace
technology
COG reformer
Coking plant
Regeneration
Tower
BF
Reboiler
High strength & high reactivity coke
H2
Iron ore
pre-reduction
technology
Other project
Absorption
Tower
Coke substitution
reducing agent production technology
Reaction control technology
for BF hydrogen reduction
Sensible heat recovery from slag (example) Waste heat recovery boiler
Hot air
Slag
Cold air
Kalina
cycle
Power generation
Technology for utilization of unused waste heat
CO2 capture
technology
Steam
Electricity
Hot metal
BOF
COURSE50 ／ CO2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50
P6
Research and Development Organization
R&D Organization
Contract research
NEDO
COURSE 50 Committee
*
Kobe Steel, Ltd.
JFE Steel Corporation
Nippon Steel Corporation
Nippon Steel Engineering Co., Ltd.
Sumitomo Metal Industries, Ltd.
Nisshin Steel Co., Ltd.
COURSE 50 Committee at the Japan Iron and Steel Federation (JISF) supports the 6 companies’ R&D activities.
Sub Projects
1. Development of technologies to utilize hydrogen for iron ore reduction.
2. Development of technologies to reform COG through the amplification
of hydrogen.
3. Development of technologies to produce optimum coke for hydrogen
reduction of iron ore.
4. Development of technologies to capture – separate and recover – CO2
from BFG.
5. Development of technologies to recover unused sensible heat.
6. Holistic evaluation of the total process.
P7
NEDO PROJECT COURSE 50
Study of Carbon Capture Technology
P8
Carbon Flow in Integrated Steelmaking Process
Carbon Flow
BF
Waste 1
Dust 1
Input C
100
Coke 5
PC 18
Pig Iron 9
Coke Oven
Coke 62
BFG 70
Coal 77
Coke 66
COG 8
BOF
LDG 8
Sinter etc 9
Air 96
By-product Gas 87→Furnace, Power Plant etc
Tar 3
Gas
Chemical Prduct 3
CO2
Emission
Major Composition（％ Vol.）
Heat
Capacity
(1000t/Year)※
H2
CO
CO2
N2
CH4
(kcal/Nm3)
40
56
6
3
3
30
4,800
2,000
4
23
22
51
-
800
LD(BOF) Gas
120
1
65
14
15
-
2,000
Hot Stove Gas
1,000
-
-
25
69
-
-
Coke Oven Gas
Blast Furnace Gas
P9
※Average annual emission from a middle sized blast furnace
Property of Blast Furnace Gas (BFG)
Blast Furnace gas
(BFG)
Flue Gas of
Thermal Power Plant
Operating Ratio (%)
97 (-3～+1)
40 (Average)
Load Factor (%)
Approx. 100
30～100
Pressure(kg/cm２)
2.4 (Outlet) ⇒ 1.0+α
1.0+α
Temperature (℃ )
144 (Outlet) ⇒ Room temp.
50～110
CO２ (%)
22 (±2)
13 (Coal)､3～9 (LNG)
CO (%)
23 (±2)
0
H2 (%)
4 (-1～+2)
0
Approx. 800
0
Composition
Heat Cap. (kcal/m3
<Key Issues>
1. Small fluctuation of BFG generation and its composition among blast furnaces
=>Experimental results of one blast furnace can be applied to other furnaces.
2. Composition difference between BFG and power plant flue gas
=>Evaluation of CO2 capture performance for various technology is necessary.
P 10
Example of Existing CO2 Capture Technologies
Chemical Absorption
Off-gas
Process
Outline
Physical Adsorption
CO2
Pure Oxygen
Combustion
Membrane Separation
Off-gas
Rich
CO2,H2O,O2 etc
Water
Feed Gas
Boiler
Treatment
Cooling
Vacuum Pump
Re-boiler
Feed Gas
Absorber
Regenerator
SOx,NOx
etc
Fuel
CO2
Pure O2
Gas Holder
Feature
*Well established
and commodity
technology
*Suitable for scale-up
*Large energy
consumption
*Simple structure
*Well established
technology
*Large power
consumption required
for vacuum pump
*Simple structure
*Low CO2 collection
efficiency and
expensive membrane
*Suitable for high
pressure gas
*Lower CO2
separation cost
*Large energy
consumption for O2
production
Further
R&D
Status
*Lower energy
consumption
*Combination of
other tecnologies
*Lower energy cost
through performance
improvement of
adsorptive material
*Early development
stage
*Commercial test
stage
Considering from BFG property and required performance, high throughput and
energy efficient technologies will be developed based on the existing “chemical
absorption” and “physical adsorption” practice.
P 11
NEDO PROJECT COURSE 50
Chemical Absorption Technology
P 12
What is the chemical absorption process ?
 Features
・CO2 recovery rate: 90% or more
・CO2 purity: 99% or more
・Issue: A large amount of heat is required.
Outline of system
Gas other than CO2
Absorbent
Absorber
Feed Gas
③Heat Exchanger
①
②
Stripper
Steam
Pump
CO2 loaded
Pump
absorbent
CO2 partial pressure in gas
Reaction in absorbent
Desorption
area
120℃
Ambient temperature
Absorption area
 Outline of process
① In the absorber, the absorbent is in
contact with the gas containing CO2.
CO2 is selectively absorbed.
② The absorbent is sent to the stripper
and is heated to about 120℃ to release
CO2.
③ The absorbent is cooled to ambient
temperature and is fed to the top of the
absorber to absorb CO2 again.
Absorption and desorption of
CO2
CO2 loading on absorbent
P 13
Development of Chemical Absorbents
(Collaborative Research with RITE)
1.Development of chemical absorbent to reduce energy
consumption for CO2 capture
①
②
③
④
⑤
Identification of reaction mechanisms of chemical absorbents using
quantum chemistry and molecular dynamics, as well as component
designing.
Designing of high-performance amine compounds by
chemoinformatics (analysis by multivariable regression model) with
the existing amine database.
Examination of synthesis technologies for mass production of highperformance amines.
Exploration of absorbents other than amines.
Evaluation of chemical absorbents by laboratory experiments and
process models.
2.Testing of new chemical absorbents for industrial application
① Evaluation of new absorbents in terms of corrosivity and long-term
stability.
② Support for experiments with real gas by model simulations.
P 14
Collaboration Scheme to Develop New
Chemical Absorbents
Development of new chemical absorbents (NSC + RITE + Univ. of Tokyo)
Quantum chemical
calculations
Design new amine
Compounds.
Experiment
Chemoinformatics
Synthesize new amines
Design absorbents
Evaluate the performance
Industrial
application
Evaluation with test plants CAT1 (1t-CO2/d）
(NSEC)
Suggest new amine
compounds
CAT30 (30t-CO2/d）
Absorber
Stripper
Reboiler
P 15
Development of New Absorbents
Projects
Absorbents
* COCS
RITE-5C
2-component absorbent
（2004-2008）
（NO.１）
Under investigation for practical use
RN-1
COURSE50
（NO.２）
(2008 – 2012)
Development Status
Single-component absorbent
 Results evaluation of plant tests at
CAT1 & CAT30
2-component absorbent
RN-2
RN-3
結合が弱化
Under plant test at CAT1
Under exploration
P 16
ｽﾙﾎﾗﾝ
* Cost-saving CO2 Capture System
Development of Technologies for Chemical
Absorbents for CO2 Capture from BFG
【Objective】
Development of new amines / absorbents with the aid of
quantum chemical calculations
Structural transformation of DMAE
●Prediction of absorption rate and heat of reaction
Energy (kcal/mol)
10
● Experimental confirmation
of high performance
5
activation energy
0
heat of
reaction
-5
DMAE
New Amine
-10
Reactant
Transition State
Product
HCO3-
CO2
R
high absorption rate without
increasing heat of reaction
Designing of absorbents incorporating newly
found tertiary amines
P 17
RN-3 family absorbent
Development of the chemical absorption process
Test Equipment：
Process Evaluation Plant（30t/D）
Off gas
Nippon Steel Kimitsu Works No. 4BF
CO2
Absorber
Bench Plant（1t/D）
Regenerator
Rebolier
Absorber
Regenerator
P 18
2010 ,17 June
Development of the chemical absorption process
Strategy for Cost Reduction
CO2 Separation
Cost（JP￥/t-CO2）
2004Fy
6000
Waste heat recovery
5000
Development of the chemical
absorbent
4000
Present
3000
Optimization of the chemical
absorption process
Optimization of the entire
system (with the improvement
of steel-making process)
Goal
2000
3.0
2.5
P 19
2.0
Heat Unit Consumption
（GJ/t-CO2）
Heat energy consumption (GJ/ｔ-CO2)
Performance Evaluation (Energy Consumption)
MEA(conventional absorbent)
5.0
Absorbent developed by competitors
Literature values
4.0
NO. 1
NO. 1 (estimated value)
3.0
NO. 2 (estimated value)
2.5
NO. 2
2.0
Project Target
1.0
0.1
1
10
CAT - 1
Plant scale
100
CAT - 30
(ton/day)
P 20
1,000
10,000
CCS commercial plant
Evaluation of Chemical Absorbent Degradation
※：CO2 collection from combustion exhaust gas
15
Amine loss
MEA
（Literature value ※）
10
5
No.2
(Wｔ％)
No.1
0
0
500
1,000
1,500
Operation time （hours）
P 21
2,000
2,500
Corrosion Test Results
MEA (general absorbent)
①Feed gas
P 22
②Off Gas
SUS304
CORTEN
SS400
SUS304
CORTEN
0
SS400
0.5
SUS304
Absorbent
Containing
CO2
④
CORTEN
①
Steam
SS400
Pretreat
Feed - ment
Gas
1.0
SUS304
Stripper
CORTEN
Absorber
SS400
③
Absorbent
Steel quality
grade
②
1.5
Product gas
CO2
Corrosion level （mm/year）
Gas after removal of CO2
(off gas)
No.1
③Stripper inlet ④Stripper outlet
NEDO PROJECT COURSE 50
Physical Adsorption Technology
P 23
Outline of Physical Adsorption Technology
Non combustible gases
Outline of technology development
Selection of adsorbent
PSA lab. tests
Adsorption simulation
・Operating conditions
・Establish adsorption model
・Design bench scale
test equipment
・Compare with lab. tests
・Cost reduction
・Data matching
Bench scale PSA
operation
Combustible gases
incorporation
Data accumulation for
Scaling up
Conceptual diagram of 2-staged PSA for BF gas
Utilities
simulation
Gas flow
simulation
Concretize industrial process
Clarify & reduce recovery cost
P 24
Cost Reduction Target
Index of Recovery Cost
 Recovery cost has come down to near the target level.
Operational studies will be made with the bench-scale plant to achieve the
target.
1.0
0.8
0.55～0.63
0.6
0.50
0.4
0.2
0.0
Conventional Laboratory
Estimation
P 25
Target
Flow Diagram of Bench-scale Plant (ASCOA3* )
ＢＦＧ
Blower
Compressor
ＢＦＧ
Gas cooler
Dehumidifier
Sulfer
Adsorber
Mixing Tank Blower
Blower
CO2-PSA
Vaccum CO2 tank
Pump
Buffer
Tank
CO-PSA
P 26Oxides Adsorption
*ASCOA: Advanced Separation system by Carbon
Vaccum CO tank
Pump
Bird’s-eye View of ASCOA-3
P 27
Results of the First Run at ASCOA-3
Maximum CO2 recovery of 4.3tons/day was reached! (Target:3tons/day)
All 3 targets were achieved at the same time.
Purity
5.0
100
Purity target:90%
90
Recovery ratio target 80%
80
3.5
70
Recover target:3t/day
3.0
60
Recovery Ratio
2.5
50
2.0
40
3 targets achieved
Achieve
3 targets
1.5
Recovery
30
Max. Recovery:4.3t/day
1.0
0.5
20
10
Max. Purity:99.5%
3/24
3/23
3/22
3/18
P 28
3/17
3/16
3/15
3/14
3/11
0
3/11
0.0
3/8
CO2 Recovery(t/day)
4.0
CO2 Purity, Recovery Ratio(%)
4.5
NEDO PROJECT COURSE 50
Utilization of Unused Waste Heat for
Energy Supply for CO2 Capture
P 29
Unused Thermal Energy in Various Process
Model steelworks 8 million ton – crude steel per annum
1800
Temperature [℃]
Calorie (TJ/year)
1600
1400
1200
Unstable
generation rate
600
Steelmaking slag sensible heat
４０００
３０００
２０００
1000
800
BF slag sensible heat
BOF gas
sensible heat
COG sensible heat
CAPL RF
Coke oven flue gas
after heat recovery
Main exhaust gas
after heat recovery
HDG RF
HRM RF
400
Hot stove gas
200
Plate Mill RF
0
Slag granulation
tank water
Main exhaust gas
COG ammonia water
Cooler exhaust gas
Sintering process
Coking plant
BF
CAPL NOF
Steelmaking
HDG NOF
Rolling exhaust gas
Waste heat at medium to low temperatures / molten materials at high temperatures difficult to
recover economically
currently unused
P 30
Cascade Use of Unused Thermal Energy
【 ２nd stage】
133℃
Exhaust gas from processes
Recovery of waste gas
after steam generation
by new technologies
375℃
Ａ
PCM heat accumulation
Ｂ
Organic Rankine Cycle
Direct use of
sensible heat
Fuel reforming
T
140℃ steam
for chemical
absorption
Power for
physical adsorption
100℃
Kalina Cycle
【 1st stage】
Rankine cycle for
medium
temperature
105℃
75℃
P 31
Thermal catalyst
for chemical
absorption
140℃ steam
for chemical
absorption
Heat pump
T
Generation of saturated
steam at 140℃ to the
lower temperature limit
Transport
Ｃ
G
133℃
Heat pump for
high temperature
・Heat accumulation with PCM
(Phase Change Material)
・Heat pump
・Power generation with low
boiling point. medium
G
Ｄ
Issues of Unused Thermal Energy Usage
Common issues
Boiler
Improvement of heat
Heat pump
exchanger
・ Increased heat transfer rate
・ Compactification
・ Prevention of corrosion &
PCM
clogging
Thermal insulation
Specific issues
・ Scaling up
・ Increase in
rate of heat
absorption
& release
Reduction in equipment
・ Improvement of reactors
Development of PCM
・ Extension of temperature range
・ Improvement of corrosivity
Power generation Optimization of recovery
technologies for various
with low boiling
Improvement of system efficiency
Technology to prevent thermal
waste heat (including
decomposition of working medium
Technology to prevent leakage
combination with heat
Fuel reforming
・ Development of catalysts
・ Control of expansion
cost
Direct use of heat
reaction
・ Improvement of heat accumulation density
technology
point medium
Enhancement of chemical heat pump
accumulation)
Development of catalysts
Optimal reaction conditions (steam ratio, etc)
P 32
Technology Development for Sensible Heat
Recovery from Steelmaking Slag (1)
Development of process for slag product
100mm
Continuous solidification of slag by water cooling roll
（Roll forming process）
⇒ ・Applicable composition : CaO/SiO2=2.2～3.8
・Thickness≦5mm
・Recovery air temperature ≦1000℃
8
trough
Thickness of slag (mm)
Shape controlling
roll
Cooling roll
Conveyor
Slag A CaO/SiO2＝3.8
Obs.
7
Ave.
6
5
Gap
4.55mm
4
3
2.17mm
2
1.46mm
1
0
0
2
4
6
8
10
12
Rotating rate of cooling roll (rpm)
P 33
14
16
Technology Development for Sensible Heat
Recovery from Steelmaking Slag (2)
Technology for sensible heat recovery
Heat transfer calculation for packed bed with countercurrent flow in consideration
of thermal conductivity of slag
⇒Thin-plate-type slag provides higher heat recovery ratio and higher temperature
797℃
air.
Top
0
Air
Heat-transfer calculation
in plates
Top
Gas temperature
Z-axis
Difference calculus
z=0
Surface coefficient
of heat transfer
Sphere：Ranz-Marshall`s
formula
z=Z
Plate：Johnson-Rubesin`s
formula
Distance from top of tower (m)
Slag
0.5
Average slag temperature
1.0
1.5
Surface temperature of slag
2.0
Heat recovery ratio ：49％
2.5
bottom
Slag
Air
3.0
0
Bottom
1,200
200 400 600 800 1,000
temperature (℃)
Roll forming of slag (thickness≦5mm） = High heat recovery ratio
⇒ Roll forming process of molten slag
P 34
& Packed bed heat recovery process
with countercurrent flow
Technology Development for Sensible Heat
Recovery from Steelmaking Slag (3)
Bench-scale test for sensible heat recovery from slag
・2010：Construction of bench-scale test equipment for roll forming
・2011：Bench-scale test for roll forming
Construction of bench-scale test equipment for sensible heat recovery
・2012：Bench-scale test for sensible heat recovery
 Φ1.6ｍ copper twin water cooling roll
ROCSS：Roll type Continuous Slag Solidification process
 Target production rate：1ton/min
Slag ladle
 Direct pouring from slag ladle
（60t/ch）
 heat-resistant conveyor
Conveyer
Ladle tilt machine
Trough
Cooling roll
P 35
Technology Development for Sensible Heat
Recovery from Steelmaking Slag (4)
ROCSS Operating Status
Cooling roll
Slag ladle
Conveyer
Trough
Target ( after roll forming)
Ladle tilt machine
Thickness of slag : ≦5mm
Slag temperature : ≧1000℃
P 36
NEDO PROJECT COURSE 50
Summary
P 37
Current Status of Technology Development
1. CO2 Capture
(1)30 t-CO2 / day chemical absorption test plant
(CAT30) has been operative since early 2010,
generating a world’s lowest level of heat
consumption.
(2) 3t-CO2 / day physical adsorption test plant
(ASCOA3) has been operative since early 2011,
achieving expected result.
2. Energy Supply for CO2 Capture
(1) Heat recovery from steelmaking slag has been
confirmed through laboratory-scale tests.
*Test plant(ROCSS) has been constructed.
P 38
Timetable for Industrialization
2000 2002
2004
2006
2008
2010
2012
PhaseⅠ
（Step 1）
Hydrogen reduction
Partial
substitution
of carbon
by hydrogen
JHFC Project *
(2001-)
COG H2 enrichment
Project
(2003-2006)
Reduction fundamentals
Optimized gas injection
Bench-scale H2
enrichment
2015
2020
2030
PhaseⅡ
PhaseⅠ
（Step 2）
Exp. BF
+
Partially
Industrial
Mini
exp.
BF
COCS Project **
(2001-2008)
Intern’l collaboration
CO2 capture
from BFG
Process evaluation plant
Total evaluation
incorporating mid - low
temperature waste heat
recovery
2100
Post - COURSE50
Industrialization
Verification
 Development of fundamental Green electricity & Green hydrogen production technologies
technologies
 Establishment of infrastructure
CO2 Storage & Monitoring
CO2 capture
2050
Matching
between
capture
equipment
and mini
exp. BF
ULCOS (2004-)
P 39
Integrated
operation of
semiindustrial
capture
equipment
(several
hundred tCO2/D) with
exp. BF
* Japan Hydrogen & Fuel Cell Demo. Project.
Hydrogen
Steelmaking
1st industrialization by
ca. 2030
<Prerequisite>
 CO2 storage available
 Economic reasonability
Industrialization
* *Cost-saving CO2 Capture System