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 absorptionReduction of cokeIron 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 CorporationNippon Steel CorporationNippon 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

GasCO2

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 C100 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/cm ２ ) 2.4 (Outlet) ⇒ 1.0+α 1.0+α

Temperature ( )℃ 144 (Outlet) Room temp.⇒ 50 ～ 110

Compo-

sition

CO ２ (%) 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-boilerFeed Gas

RegeneratorAbsorber

Off-gas

Feed Gas

Vacuum Pump

Gas Holder

Boiler

Rich CO2,H2O,O2 etc

Water

Pure O2

Fuel SOx,NOx etc

CO2

CoolingTreat-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

SteamFeed Gas

Pump 　

Pump 　

①②③

Reaction in absorbent

Absorption and desorption of CO2

120℃Ambient temperatureDesorption

area

Absorption area

CO2 loading on absorbent

CO

2 p

artia

l pre

ssu

re in

ga

s

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 aminesDesign absorbentsEvaluate the performance

Suggest new amine compounds

ExperimentChemoinformatics

Evaluation with test plants (NSEC)

CAT1 (1t-CO2/d ）

CAT30 (30t-CO2/d ）

Industrial application

StripperAbsorber

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 confirmationof high performance

high absorption rate without

increasing heat of reaction

●Prediction of absorption rate and heat of reactionStructural transformation of DMAE

R

CO2HCO3-

N CH2 CH2 OH

N CH2 Rn

- 10

- 5

0

5

10

Energ

y (k

cal

/m

ol)

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. 4BFCO2

Off　gas

Rebolier

AbsorberRegenerator

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 20Plant scale (ton/day)

0.1 　　　 　　　 1 　　 　　　 10 　　 　　　　 100 　　　　　 1,000 　　　 　 10,000 　

Hea

t en

erg

y co

nsu

mp

tio

n(G

J/ｔ

-C

O2)

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

lo

ss

(W ｔ％ )

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

①Feed gas ② Off Gas ③ Stripper inlet ④Stripper outlet

MEA (general absorbent) No.1

①

② ③

④

(off gas)

Absorbent

Gas after removal of CO2

Feed Gas

Absorber

Product gas CO2

Stripper

Pretreat- ment Steam

Absorbent

ContainingCO2

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 PSAoperation

・ Operating conditions・ Design bench scale

test equipment

・ Cost reduction

・ Establish adsorption model

・ Compare with lab. tests

Utilitiessimulation

Concretize industrial processClarify & reduce recovery cost

Data accumulation for Scaling up

・ Data matching

incorporation

Gas flowsimulation

Outline of technology developmentNon 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

ConventionalLaboratoryEstimation

Target

Index o

f R

eco

very

Cost

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

ＢＦＧ

Compressor

Gas cooler

Dehumidifier SulferAdsorber

CO2-PSACO2 tank

BufferTank

VaccumPump

CO-PSA

Mixing Tank

ＢＦＧBlower

Blower

Blower

CO tankVaccumPump

*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.

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.03/

8

3/11

3/11

3/14

3/15

3/16

3/17

3/18

3/22

3/23

3/24

CO

2 Rec

over

y(t/

day)

0

10

20

30

40

50

60

70

80

90

100

CO

2 Pur

ity, R

ecov

ery

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 waterCOG ammonia water

HDG NOF

HDG RF

CAPL NOF

Plate Mill RF

HRM RFMain exhaust gas after heat recovery

Main exhaust gasCooler exhaust gas

0

200

400

600

800

1000

1200

1400

1600

1800

Te

mp

era

ture

[]

℃

Sintering process Coking plant BF Steelmaking Rolling exhaust gas

３０００２０００

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℃ steamfor 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

【 ２ nd 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

ＡＢ

Ｃ

Ｄ

140℃ steamfor 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)

Th

ickn

ess

of

sla

g

(mm

) 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-axisTop

Slag

bottom

Slag Air

Air

Heat-transfer calculationin 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

fro

m

top

of

tow

er (

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

Φ1.6 ｍ copper twin water cooling roll

Target production rate ： 1ton/min

Direct pouring from slag ladle

heat-resistant conveyorLadle tilt machineLadle tilt machine

ConveyerConveyerCooling rollCooling roll

TroughTrough

Slag ladleSlag ladle

（（ 60t/ch60t/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 machineLadle tilt machine

ConveyerConveyer

Cooling rollCooling roll

TroughTrough

Slag ladleSlag ladle

ROCSS Operating Status

Target ( after roll forming)

Thickness of slag : 5mm≦

Slag temperature : 1000≧ ℃

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 - COURSE50Post - 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

Partial substitution of carbon by hydrogen

CO2 capturefrom BFG

CO2 capturefrom BFG

Hydrogen

Steelmaking

Intern’l collaboration

Development of fundamental technologies Establishment of infrastructure

PhaseⅠPhaseⅠ （ Step 1 ）

Industrialization

PhaseⅠPhaseⅠ（ Step 2 ）

PhaseⅡPhaseⅡ

Mini

exp. BF

Exp. BF+PartiallyIndustrial

Matching between capture equipment and mini exp. BF

Integrated operation of semi-industrial capture equipment (several hundred t-CO2/D) with exp. BFULCOS (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 fundamentalsOptimized gas injectionBench-scale H2 enrichment

Process evaluation plantTotal evaluation

incorporating mid - low temperature waste heat recovery

Timetable for Industrialization