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P 1
Development of High Throughput and Energy Efficient Technologies for Carbon Capture in the Integrated
Steelmaking Process
NEDO PROJECT COURSE 50
Masao Osame
Sub-Project Leader of COURSE50 (JFE Steel Corporation)
CCS Workshop
Düsseldorf, Germany
November 8-9, 2011
P 2
Introduction of COURSE50 Project
NEDO PROJECT COURSE 50
P 3
Member of COURSE50* Project
*CO2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50
New Energy and Industrial Technology Development Organization
P 4
Cool Earth Innovative Energy Technology Program
P 5
Time Table of Technology Development
Phase 1 Step 1
(2008～12）
Phase 1 Step 2
(2013-17）
Phase 2 Industrialization & Transfer
2008 2009 2010 2011 2012
2010 2020 2030 2040 2050
Phase 1 Step 1
(2008～12）
(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.
NEDO Project
0.6 2 – 3 2 – 3 2 – 3 2 – 3 (billion yen)
Project Targets
P 6
COURSE50 ／ CO2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50
(1) Technologies to reduce CO2 emissions from blast furnace (2) Technologies for CO2 capture
・Chemical absorption Reduction of coke Iron ore
H2 amplification
H2
BOF
Electricity
High strength & high reactivity coke
Coking plant
Coke BFG
BF
Shaft furnace
・Physical adsorption
CO-rich gas
Regeneration Tower
Reboiler
Absorption Tower
Steam
Hot metal
Cold air
Hot air Sensible heat recovery from slag (example) Waste heat recovery boiler
CO2 storage
technology
Kalina cycle
Power generation
Slag
Iron ore pre-reduction
technology Coke substitution
reducing agent production technology CO2 capture technology
Coke production technology for BF hydrogen reduction
for BF hydrogen reduction Reaction control technology
Technology for utilization of unused waste heat
Other project
COG reformer
Project Outline
P 7
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.
NEDO
Kobe Steel, Ltd. JFE Steel Corporation Nippon Steel Corporation Nippon Steel Engineering Co., Ltd. Sumitomo Metal Industries, Ltd. Nisshin Steel Co., Ltd.
Contract research
* COURSE 50 Committee at the Japan Iron and Steel Federation (JISF) supports the 6 companies’ R&D activities.
COURSE 50 Committee
Sub Projects
R&D Organization
Research and Development Organization
P 8
Study of Carbon Capture Technology
NEDO PROJECT COURSE 50
P 9
BF
Coke Oven
Carbon Flow in Integrated Steelmaking Process
Gas CO2
Emission (1000t/Year)※
Major Composition（％ Vol.） Heat Capacity (kcal/Nm3) H2 CO CO2 N2 CH4
Coke Oven Gas 40 56 6 3 3 30 4,800
Blast Furnace Gas 2,000 4 23 22 51 - 800
LD(BOF) Gas 120 1 65 14 15 - 2,000
Hot Stove Gas 1,000 - - 25 69 - - ※Average annual emission from a middle sized blast furnace
Coke 5
Coke 66
COG 8
Tar 3
Coal 77
Input C 100 PC 18
Coke 62
Sinter etc 9
By-product Gas 87• Furnace, Power Plant etc
Dust 1
Pig Iron 9
BFG 70
BOF
LDG 8
Waste 1
Air 96
Chemical Prduct 3
Carbon Flow
P 10
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+• 1.0+•
Temperature (℃ ) 144 (Outlet) ⇒ Room temp. 50～110
Compo- sition
CO２ (%) 22 (±2) 13 (Coal)､3～9 (LNG)
CO (%) 23 (±2) 0
H2 (%) 4 (-1～+2) 0
Heat Cap. (kcal/m3 Approx. 800 0
<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 11
Example of Existing CO2 Capture Technologies
Chemical Absorption Physical Adsorption Membrane Separation Pure Oxygen Combustion
Process Outline
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
Off-gas CO2
Re-boiler Feed Gas
Regenerator Absorber
Off-gas
Feed Gas
Vacuum Pump
Gas Holder
Boiler
Rich CO2,H2O,O2 etc
Water
Pure O2
Fuel SOx,NOx etc
CO2
Cooling Treat-ment
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 12
Chemical Absorption Technology
NEDO PROJECT COURSE 50
P 13
Features ・CO2 recovery rate: 90% or more ・CO2 purity: 99% or more ・Issue: A large amount of heat is required. 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.
Heat Exchanger
Absorbent
Absorber Stripper
Steam Feed Gas
Pump
Pump
① ② ③
Reaction in absorbent
Absorption and desorption of CO2
120℃ Ambient temperature Desorption
area
Absorption area
CO2 loading on absorbent
CO
2 pa
rtia
l pre
ssur
e in
gas
Outline of system
Gas other than CO2
CO2 loaded
absorbent
What is the chemical absorption process ?
P 14
1.Development of chemical absorbent to reduce energy consumption for CO2 capture
① Identification of reaction mechanisms of chemical absorbents using quantum chemistry and molecular dynamics, as well as component designing.
② Designing of high-performance amine compounds by chemoinformatics (analysis by multivariable regression model) with the existing amine database.
③ Examination of synthesis technologies for mass production of high-performance amines.
④ Exploration of absorbents other than amines. ⑤ 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.
Development of Chemical Absorbents (Collaborative Research with RITE)
P 15
Development of new chemical absorbents (NSC + RITE + Univ. of Tokyo)
Quantum chemical calculations
Design new amine Compounds.
Synthesize new amines Design absorbents Evaluate the performance
Suggest new amine compounds
Experiment Chemoinformatics
Evaluation with test plants (NSEC)
CAT1 (1t-CO2/d）
CAT30 (30t-CO2/d）
Industrial application
Stripper Absorber
Reboiler
Collaboration Scheme to Develop New Chemical Absorbents
P 16
RN-1
RN-2
RN-3 ｽﾙﾎﾗﾝ
結合が弱化
RITE-5C * COCS
（2004-2008）
COURSE50
(2008 – 2012)
Projects
Absorbents Development Status
（NO.１）
（NO.２）
* Cost-saving CO2 Capture System
2-component absorbent
Under plant test at CAT1
Single-component absorbent
Results evaluation of plant tests at CAT1 & CAT30
2-component absorbent
Under investigation for practical use
Under exploration
Development of New Absorbents
P 17
Designing of absorbents incorporating newly found tertiary amines
【Objective】 Development of new amines / absorbents with the aid of quantum chemical calculations
RN-3 family absorbent
● Experimental confirmation of high performance
high absorption rate without
increasing heat of reaction
●Prediction of absorption rate and heat of reaction Structural transformation of DMAE
R
CO2 HCO3-
- 10
- 5
0
5
10
Ener
gy (k
cal/
mol
)
DMAE New Amine
Reactant Transition State Product
activation energy
heat of reaction
Development of Technologies for Chemical Absorbents for CO2 Capture from BFG
P 18 2010 ,17 June
Nippon Steel Kimitsu Works No. 4BF CO2
Off gas
Rebolier
Absorber Regenerator
Test Equipment： Process Evaluation Plant（30t/D）
Bench Plant（1t/D）
Regenerator
Absorber
Development of the chemical absorption process
P 19
6000
5000
4000
3000
CO2 Separation
Cost（JP￥/t-CO2）
2.5 2.0 Heat Unit Consumption （GJ/t-CO2）
2000
Waste heat recovery
Optimization of the entire system (with the improvement of steel-making process)
Strategy for Cost Reduction
Optimization of the chemical absorption process
Development of the chemical
absorbent
2004Fy
Present
Goal 3.0
Development of the chemical absorption process
P 20 Plant scale (ton/day)
0.1 1 10 100 1,000 10,000
Hea
t en
erg
y co
nsu
mp
tio
n (
GJ/
ｔ-
CO
2)
CAT - 1
NO. 1 (estimated value)
NO. 2 (estimated value) 2.5
Literature values
CAT - 30 CCS commercial plant
NO. 2
5.0
4.0
3.0
2.0
1.0
NO. 1
MEA(conventional absorbent) Absorbent developed by competitors
Project Target
Performance Evaluation (Energy Consumption)
P 21
Operation time （hours）
0 500 1,000 1,500 2,000 2,500
Am
ine
loss
(Wｔ％)
15
10
0
5
No.1
MEA （Literature value ※）
※：CO2 collection from combustion exhaust gas
No.2
Evaluation of Chemical Absorbent Degradation
P 22
1.5
1.0
0.5
0
SS
400
CO
RT
EN
SU
S30
4
SS
400
CO
RT
EN
SU
S30
4
SS
400
CO
RT
EN
SU
S30
4
SS
400
CO
RT
EN
SU
S30
4
①Feed gas ②Off Gas ③Stripper inlet ④Stripper outlet
Co
rro
sio
n l
evel
（
mm
/yea
r）
MEA (general absorbent) No.1
Ste
el q
ual
ity
g
rad
e
①
② ③
④
(off gas)
Absorbent
Gas after removal of CO2
Feed Gas
Absorber
Product gas CO2
Stripper
Pretreat - ment Steam
Absorbent
Containing CO2
Corrosion Test Results
P 23
Physical Adsorption Technology
NEDO PROJECT COURSE 50
P 24
Conceptual diagram of 2-staged PSA for BF gas
Selection of adsorbent
PSA lab. tests
Adsorption simulation
Bench scale PSA operation
・Operating conditions
・Design bench scale test equipment
・Cost reduction
・Establish adsorption model
・Compare with lab. tests
Utilities simulation
Concretize industrial process Clarify & reduce recovery cost
Data accumulation for Scaling up
・Data matching
incorporation
Gas flow simulation
Outline of technology development Non combustible gases
Combustible gases
Outline of Physical Adsorption Technology
P 25
Recovery cost has come down to near the target level.
0.0
0.2
0.4
0.6
0.8
1.0
Conventional Laboratory Estimation
Target
Inde
x of
Rec
over
y C
ost
0.55～0.63
0.50
Operational studies will be made with the bench-scale plant to achieve the target.
Cost Reduction Target
P 26 *ASCOA: Advanced Separation system by Carbon Oxides Adsorption
Flow Diagram of Bench-scale Plant (ASCOA-3* )
P 27
Bird’s-eye View of ASCOA-3
P 28
Maximum CO2 recovery of 4.3tons/day was reached! (Target:3tons/day)
All 3 targets were achieved at the same time.
0.00.51.01.52.02.53.03.54.04.55.0
3/8
3/11
3/11
3/14
3/15
3/16
3/17
3/18
3/22
3/23
3/24
CO2 Re
cove
ry(t/
day)
0102030405060708090100
CO2 Pu
rity,
Reco
very
Rat
io(%
)
Recover target:3t/ day
Purity target:90%
Recovery ratio target 80%
Recovery Ratio
Purity
Achieve 3 targets
Max. Recovery:4.3t/ day
Max. Purity:99.5%
Recovery
3 targets achieved
Results of the First Run at ASCOA-3
P 29
Utilization of Unused Waste Heat for Energy Supply for CO2 Capture
NEDO PROJECT COURSE 50
P 30
COG sensible heat
Hot stove gas
BOF gas sensible heat
BF slag sensible heat Steelmaking slag sensible heat
Slag granulation tank water COG ammonia water
HDG NOF
HDG RF
CAPL NOF
Plate Mill RF
HRM RF Main exhaust gas after heat recovery
Main exhaust gas Cooler exhaust gas
0
200
400
600
800
1000
1200
1400
1600
1800
Tem
per
atu
re [℃
]
Sintering process Coking plant BF Steelmaking Rolling exhaust gas
３０００ ２０００
Calorie (TJ/year) ４０００
Unstable generation rate
Coke oven flue gas after heat recovery
CAPL RF
Model steelworks 8 million ton – crude steel per annum
Waste heat at medium to low temperatures / molten materials at high temperatures difficult to recover economically currently unused
Unused Thermal Energy in Various Process
P 31
Exhaust gas from processes
【 1st stage】
Generation of saturated steam at 140℃ to the lower temperature limit
375℃
140℃ steam for chemical absorption
T G
133℃
133℃
T G
Organic Rankine Cycle
Kalina Cycle
Power for physical adsorption
PCM heat accumulation
Transport
100℃
75℃
Thermal catalyst for chemical absorption
Heat pump
Direct use of sensible heat
Fuel reforming
Heat pump for high temperature
105℃
Rankine cycle for medium temperature
【 ２nd stage】
Recovery of waste gas after steam generation by new technologies
・Heat accumulation with PCM (Phase Change Material)
・Heat pump ・Power generation with low
boiling point. medium
Ａ Ｂ
Ｃ
Ｄ
140℃ steam for chemical absorption
Cascade Use of Unused Thermal Energy
P 32
Common issues Specific issues
Boiler
Heat pump Enhancement of chemical heat pump
reaction
・ Development of catalysts
・ Improvement of reactors
PCM Development of PCM
・ Extension of temperature range
・ Improvement of heat accumulation density
・ Control of expansion
・ Improvement of corrosivity
Power generation
with low boiling
point medium
Improvement of system efficiency
Technology to prevent thermal
decomposition of working medium
Technology to prevent leakage
Direct use of heat
Fuel reforming
Improvement of heat
exchanger
・Increased heat transfer rate
・Compactification
・Prevention of corrosion &
clogging
Thermal insulation
technology
Reduction in equipment
cost
Optimization of recovery
technologies for various
waste heat (including
combination with heat
accumulation)
Development of catalysts
Optimal reaction conditions (steam ratio, etc)
・Scaling up
・Increase in
rate of heat
absorption
& release
Issues of Unused Thermal Energy Usage
P 33
100mm
Slag A CaO/SiO2＝3.8
1.46mm
2.17mm
4.55mm
0
1
2
3
4
5
6
7
8
0 2 4 6 8 10 12 14 16
Rotating rate of cooling roll (rpm)
Thi
ckne
ss o
f sla
g (m
m) Obs.
Ave.
Gap
Conveyor
Shape controlling
roll
Cooling roll
trough
Development of process for slag product
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℃
Technology Development for Sensible Heat Recovery from Steelmaking Slag (1)
P 34
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 air.
Roll forming of slag (thickness≦5mm） = High heat recovery ratio
⇒ Roll forming process of molten slag
& Packed bed heat recovery process with countercurrent flow
z = 0
z = Z
Z-axis Top
Slag
bottom
Slag Air
Air
Heat-transfer calculation in plates
Difference calculus
Surface coefficient of heat transfer
Sphere：Ranz-Marshall`s formula
Plate：Johnson-Rubesin`s formula
Top
Bottom0 200 400 600 800 1,000 1,200
temperature (℃)
0
0.5
1.0
1.5
2.0
2.5
3.0D
ista
nce
from
top
of t
ower
(m
)
Gas temperature
Surface temperature of slag
Average slag temperature
Heat recovery ratio ：49％
797℃
Technology Development for Sensible Heat Recovery from Steelmaking Slag (2)
P 35
• 1.6ｍ copper twin water cooling roll
Target production rate：1ton/min
Direct pouring from slag ladle
heat-resistant conveyor Ladle tilt machine
Conveyer Cooling roll
Trough
Slag ladle
（60t/ch）
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
ROCSS：Roll type Continuous Slag Solidification process
Technology Development for Sensible Heat Recovery from Steelmaking Slag (3)
P 36
Ladle tilt machine
Conveyer
Cooling roll
Trough
Slag ladle
ROCSS Operating Status
Target ( after roll forming)
Thickness of slag : ≦5mm
Slag temperature : ≧1000℃
Technology Development for Sensible Heat Recovery from Steelmaking Slag (4)
P 37
Summary
NEDO PROJECT COURSE 50
P 38
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 39
2000 2002 2004 2006 2008 2010 2012 2015 2020 2030 2050 2100
Post - COURSE50
Green electricity & Green hydrogen production technologies
CO2 Storage & Monitoring
COCS Project ** (2001-2008)
JHFC Project * (2001-)
COG H2 enrichment Project
(2003-2006)
Partial substitution of carbon by hydrogen
CO2 capture from BFG
Hydrogen
Steelmaking
Intern’l collaboration
Development of fundamental technologies Establishment of infrastructure
PhaseⅠ （Step 1）
Industrialization
PhaseⅠ （Step 2）
PhaseⅡ
Mini
exp. BF
Exp. BF + Partially Industrial
Matching between capture equipment and mini exp. BF
Integrated operation of semi-industrial capture equipment (several hundred t-CO2/D) with exp. BF ULCOS (2004-)
1st industrialization by ca. 2030 <Prerequisite> CO2 storage available Economic reasonability
* Japan Hydrogen & Fuel Cell Demo. Project. * *Cost-saving CO2 Capture System
Verification
Hydrogen reduction
CO2 capture
Industrialization
Reduction fundamentals Optimized gas injection Bench-scale H2 enrichment
Process evaluation plant Total evaluation
incorporating mid - low temperature waste heat recovery
Timetable for Industrialization
