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Clean Coal Technologies in Japan

Toward the Technology Innovation in the Field of Coal Utilization

New Energy and Industrial Technology Development Organization

Center for Coal Utilization, Japan


Clean Coal Technologies in Japan
Toward the Technology Innovation in the Field of Coal Utilization

Preface ---------------------------------------------------------------------------2 B. Pyrolysis Technologies

3B1. Multi-Purpose Coal Conversion Technology (CPX)-----------51

Part1 Classification of CCT -----------------------------------------------3 3B2. Coal Flash Partial Hydropyrolysis Technology ----------------53

(1)Classification of CCT in Coal Flow -------------------------------------3 C. Powdering, Flowing, and Co-utilization Technologies

(2)Clean Coal Technology System ----------------------------------------5 3C1. Coal Cartridge System (CCS) ---------------------------------------55

(3)Appreciation of CCT in Markets -----------------------------------------6 3C2. Coal Slurry Production Technology ------------------------------56

(4)CCT in Japanese Industries ---------------------------------------------7 3C3. Briquette Production Technology --------------------------------57

(5)Environmental Technologies --------------------------------------------11 3C4. Coal and Woody Biomass Co-firing Technology -------------59

(6)International Cooperation -----------------------------------------------12 D. De-ashing and Reforming Technologies

3D1. Hyper-Coal based High Efficiency Combustion Technology(Hyper Coal) ---61

Part2 Outline of CCT -------------------------------------------------------13 3D2. Low-Rank Coal Upgrading Technology (UBC Process) ----63

(1) Coal Fired Power Generation Technologies (4) Environmental Protection Technologies

A. Combustion Technologies A. Coal Ash Effective Use Technologies

1A1. Pulverized Coal Fired Power Generation Technology(Ultra Super Critical Steam) ----3 4A1. Coal Ash Generation Process and Application Fields -------65

1A2. Circulating Fluidized Bed Combustion Technology (CFBC) ----15 4A2. Effective use for Cement/Concrete ------------------------------67

1A3. Internal Circulating Fluidize Bed Combustion Technology (ICFBC) ----16 4A3. Effective use for Civil Engineering/Construction and Others --69

1A4. Pressurized Internal Circulating Fluidized Bed Combustion Technology (PICFBC) ---17 4A4. Valuable Resources Recovery Technologies for Coal Ash --------71

1A5. Coal Partial Combustor Technology (CPC) ---------------------19 B. Flue Gas Treatment and Gas Cleaning Technologies

1A6. Pressurized Fluidized Bed Combustion Technology (PFBC) ---------------21 4B1. SOx Reduction Technology ----------------------------------------73

1A7. Advanced Pressurized Fluidized Bed Combustion Technology (A-PFBC) ---23 4B2. NOx Reduction Technology ----------------------------------------75

B. Gasification Technologies 4B3. De-SOx and De-NOx Technology --------------------------------77

1B1. Hydrogen-from-Coal Process (HYCOL) -------------------------25 4B4. Soot/dust Treatment Technology and Trace Elements Removal Technology ----79

1B2. Integrated Coal Gasification Combined Cycle (IGCC) -------27 4B5. Gas Cleaning Technology ------------------------------------------81

1B3. Coal Energy Application for Gas, Liquid and Electricity (EAGLE) ------29 C. CO2 Recovery Technologies

(2) Iron Making and General Industry Technologies 4C1. Hydrogen Production by Reaction Integrated Novel Gasification Process (HyPr-RING) --83

A. Iron Making Technologies 4C2. CO2 Recovery and Sequestration Technology ----------------85

2A1. The Formed-Coke making Process (FCP) ----------------------31 4C3. CO2 Conversion Technology -------------------------------------86

2A2. Pulverized Coal Injection for Blast Furnace (PCI) -------------33 4C4. Oxy-fuel Combustion (Oxygen-firing of conventional PCF System) --87

2A3. Direct Iron Ore Smelting Reduction Process (DIOS) ---------35 (5) Basic Technologies for Advanced Coal Utilization

2A4. Super Coke Oven for Productivity and Environment Enhancement toward the 21st Century (SCOPE21) --37 5A1. Modelling and Simulation Technologies for Coal Gasification -----89

B. General Industry Technologies (6) Coproduction System

2B1. Fluidized Bed Advanced Cement Kiln System (FAKS) ------41 6A1. Co-generation System ----------------------------------------------93

2B2. New Scrap Recycling Process (NSR) ---------------------------39 6A2. Coproduction System ------------------------------------------------95

(3) Multi-Purpose Coal Utilization Technologies

A.Liquefaction Technologies Part3 Future Outlook for CCT ------------------------------------------97

3A1. Coal Liquefaction Technology Development in Japan --------43

3A2. Bituminous Coal Liquefaction Technology (NEDOL) ----------45 Mathematical Table ------------------------------------------------------100

3A3. Brown Coal Liquefaction Technology (BCL) --------------------47

3A4. Dimethylether Production Technology (DME) -------------------49

1
Preface
New Energy and Industrial Technology Development Organization (NEDO) and
Center for Coal Utilization, Japan (CCUJ) have jointly prepared this brochure to
review the history of "Clean Coal Technology (CCT)" in Japan, to systematically
describe the present state of CCT to the extent possible, and to enhance the
activities toward novel technology innovation on the firm recognition of the
present state.
NEDO and CCUJ expect that the brochure will be helpful in understanding the
CCT of Japan as an attractive technology in the current state of ever-increasing
complexity of coal utilization owing to global warming and other environmental
issues, and also expect that the brochure will become a starting point of the
approaching rapid progress of CCT and the foundation of a coal utilization
system.

As described herein, CCT progress in Japan has reached the world’s highest
level of technological superiority, and consequently, the technology is
exceptionally attractive for Asian countries which depend on coal as an energy
source. In Japan, coal consumption has rapidly increased since 1998 with thermal
power generation efficiency increasing from approximately 38% to 41% over the
past decade. In addition, emissions of SOx and NOx per generated power unit
from thermal power plants are far below the level of other industrialized
countries. In this regard, CCT is expected to establish a worldwide system
satisfying both economic and environmental conditions through the efforts of
reducing CO2 emissions while maintaining economic growth.

Technological innovation has no boundaries, and unlimited progress is attained


by sustainable and progressive efforts and by patient and continuous activities
to accumulate the effects of technological development and to support an ever-
advancing society. NEDO and CCUJ are confident that this brochure will be
effective in CCT development and anticipate the emergence of epoch-making
technological innovations in the coal utilization field.
1.40

Increase in coal consumption and trend of economy, environment, and energy in Japan (1990-2002)
1.35

1.30
Coal consumption Electric power
generation
1.25

1.20

1.15

GDP
1.10 Total primary energy supply
CO2 emissions
1.05
Thermal power
generation efficiency
1.00
CO2 emissions/GDP
0.95

0.90
1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002
Fiscal year

2
Part1 Classification of CCT
Classification of CCT in Coal Flow

Carbonization
Coal tanker

Pulverizing/Briquetting

Slurry preparation

Liquefaction

Gasification
Coal mine

Coal train DME/GTL


CWM

Mining, Processing,
crushing Transportation reforming
and pulverizing and storage and converting

Coal physical properties Multi-purpose utilization


Bituminous technology Hydrogen Production Technology
Anthracite Brown coal 4C1
coal in Coal Utilization
Specific Gravity 1.5~1.8 1.2~1.7 0.8~1.5
Gasification 1B1-3
High Calorific Value Gas
Apparent Specific Gravity - 0.75~0.80 0.55~0.75 technology Production Technology

Specific heat 0.22~0.24 0.24~0.26 0.26~0.28


Liquefaction Coal Liquefaction Technology
3A1
Thermal conductivity(W/m K) - 1.26~1.65 - technology Development in Japan

Ignition point( ) 400~450 300~400 250~300


Bituminous Coal Liquefaction
3A2
Technology (NEDOL)
Heating value(Kcal/kg (on dry basis)) 8,200~8,500 7,500~8,800 5,500~7,500

3A3
Brown Coal Liquefaction
Classification of coal depending on the degree of carbonization Technology (BCL)

Classification Heating value (Kcal/kg(on dry basis)) Fuel ratio Caking property Dimethylether Production
3A4
Anthracite - 4.0 or more Non-caking Technology (DME)
1.5 or more
8,400 or more Strong-caking
Bituminous 1.5 or less
Multi-purpose Coal Conversion
coal 1.0 or more Caking Pyrolysis 3B1
8,100 or more Technology (CPX)
1.0 or less Weak-caking
1.0 or more Weak-caking Coal Flash Partial
3B2
Subbituminous 7,800 or more Hydropyrolysis Technology
1.0 or less Non-caking
coal
7,300 or more - Non-caking
6,800 or more -
Brown coal Non-caking Pulvelization, fluidization 3C1 Coal Cartridge System (CCS)
5,800 or more and co-utilization
technology
Coal classification depending on the utilizations (expressed as coal)
3C2 Coal Slurry Production Technology
Indication in TEXT report Coal in the Trade Statistics

Anthracite Anthracite 3C3 Briquette Production Technology

coking coal A Ash content of 8% or less


Strong-caking Coal and Woody Biomass
coking coal

3C4
coal for coke Co-firing Technology
coking coal B Ash content of more than 8%

coking coal C Bituminous Other coal Ash content of 8% or less


coal for coke Deashing and reforming Hyper-Coal based High Efficiency
3D1
coking coal D Ash content of more than 8% technology Combustion Technology(Hyper Coal)

steam coal A Other Ash content of more than 8%


steam coal

Low-Rank Coal Upgrading Technology


3D2
(UBC Process)
steam coal B Ash content of 8% or less
Other coal
steam coal C Ash content of more than 8% Basic technology
for advanced coal utilization 5A1 Modelling and Simulation Technologies
for Coal Gasification

3
Clean Coal Technologies in Japan

CO2
Flue gas treatment reduction

Power plant

Electric
precipitator EOR by CO2

Coal ash
Coal Center effective use
Cement plant
Flue gas desulfurization unit

Iron works Chemical plant Flue gas denitration unit Yokohama Landmark

Environmental
Utilization
countermeasures

Coal fired power generation Flue gas treatment


technology technology
Pulverized Coal Fired Power Generation 4B1 SOx Reduction Technology
1A1 Technology(Ultra Super Critical Steam)

Circulating Fluidized Bed Combustion 4B2 NOx Reduction Technology


Combustion technology 1A2
Technology (CFBC)
Combustion Technology Internal Circulating Fluidize Bed 4B2
Intra-furnace Dinitrogen Monoxide
1A3 Removal Technology
Combustion Technology (ICFBC)
Pressurized Internal Circulating Fluidized 4B3
De-SOx and De-NOx
1A4
Bed Combustion Technology (PICFBC) Technology

Soot/dust Treatment Technology and


1A5 Coal Partial Combustor Technology (CPC) 4B4
Trace Elements Removal Technology

Pressurized Fluidized Bed Combustion 4B5 Gas Cleaning Technology


1A6
Technology (PFBC)
Advanced Pressurized Fluidized Bed
1A7 Combustion Technology (A-PFBC) Hydrogen Production by Reaction Integrated
4C1
Novel Gasification Process (HyPr-RING)
Hyper-Coal utilization High Efficiency CO2 reduction
3D1 CO2 Recovery and Sequestration
Combustion Technology (Hyper Coal) technology 4C2
Technology

Gasification technology 1B1 Hydrogen-from-Coal Process (HYCOL) 4C3 CO2 Conversion Technology

Integrated Coal Gasification Oxy-fuel Combustion


1B2 4C4
Combined Cycle (IGCC) (Oxygen-firing of conventional PCF System)
Coal Energy Application for Gas,
1B3 Coal ash utilization
Liquid and Electricity (EAGLE) Coal Ash Generation Process
4A1
technology and Application Fields

2A1
The Formed-Coke making 4A2 Effective use for Cement/Concrete
Iron making technology Process (FCP)

Pulverized Coal Injection for Civil field 4A3 Soil Improvement Method (FGC)
2A2
Blast Furnace (PCI)

Direct Iron Ore Smelting Reduction 4A3 Base Materials Production Technology
2A3
Process (DIOS)

Super Coke Oven for Productivity and Environment High Strength Artificial Aggregate
2A4
Enhancement toward the 21st Century (SCOPE21) Architecture field 4A3
Production Technology

4A3 Agriculture and Fishery Field


Fluidized Bed Advanced Cement
2B1
Kiln System (FAKS) New use development Valuable Resources Recovery
4A4
Technologies for Coal Ash
Technology for general
2B2 New Scrap Recycling Process (NSR)
industries 4A4
Dry Desulfurization Technology
which used Coal Ash
6A1 Co-generation System

6A2 Coproduction System 1A1 Classification No. according to the technology overview
1A1 Classification No. according to the related technology overview

4
Part1 Classification of CCT
Clean Coal Technology System Clean Coal Technologies in Japan

(Coal flow) (Target)


Advanced coal Conventional coal preparation techniques
cleaning technology (jig, floatation, heavy media separation)
Coal preparation
Technology for low emission
Preparation coal utilization Preparation process control technology
Diversification of energy
Sources/expansion of
Bio-briquetting
Briquetting application fields
Carbonization briquetting

Processing
Coal Cartridge System (CCS)
Handling Coal liquid mixture (CWM,COM)
Desulfurized CWM
Ease of handling
Bituminous coal liquefaction technology (NEDOL)
Liquefaction Brown coal liquefaction technology (BCL)
Upgrading of Coal-Derived Liquids

Conversion Integrated coal gasification combined cycle power generation


technology (IGCC)
More efficient use of energy/
Gasification Coal-based hydrogen production technology (HYCOL)
CO2 reduction
(as a measure against the
Coal Energy Application for Gas,Liqud and Electricity (EAGLE)
greenhouse effect)

Multi-purpose coal conversion (CPX)


Pyrolysis Coal Flash Partial hydropyrolysis technology

Topping cycle. Pressurized fluidized Fluidized bed boiler


bed combustion (PFBC) Reduction in SOx, NOx,
O2/CO2 and waste (as a measure
Combustion High-efficiency
combustion Fluidized bed Advanced cement Kilm System(FAKS)
combustion against acid rain)
Direct Iron-Ore Smelting (as a global environmental
reduction process(DIOS) measure)

Advanced flue-gas Dry desulfurization/ Wet desulfurization


treatment denitration
Flue gas Denitration
treatment Hot gas clean up technology
Removal of dust
Alkaline, etc. removal technology
Pollutant reduction

Ash utilization Coal Ash Utilization Technologies

(Degree of technology maturity)

Proved reserves and R/P (ratio of reserves to production) World reserves of coal, oil, and natural gas resources
of major energy resources (Unit: 100 million tons oil equivalent) (Saurce: BP 2003)
1,667
Coal Natural gas Oil Uranium 1,260
687
World reserves 9,845 billion ton 156 trillion m3 1,480 billion barrel 393 million ton 1,220
437

North America 26.1% 4.4% 3.6% 17.9% 82 1,606


561 5,012
Local reserves

S.& Cent. America 2.3% 4.7% 10.6% 6.5%


934 Russia 589
Europe 13.2% 3.8% 1.8% 3.5% 133 64 66
Former Soviet Union 22.9% 35.4% 7.5% 30.6% 515 North America 3848
Europe, FSU 556 2514
Middle East 0.2% 36.0% 65.4% 0.0% 1,427
11 U.S.A.
Africa 5.6% 7.6% 7.4% 17.8% China 1,430
368
109 7 7 116
Asia Pacific 29.7% 8.1% 3.7% 23.8% 52
103 Middle East
India 141
Asia and Oceania
Annual production 27 billion barrel Africa 98 65
rate 4.83 billion ton 2.5 trillion m3 (73.9 million BD) 0.037 million ton 415
330
South and Central America
R/P 204 years 60.7 years 40.6 years 61.1 years 4 23
0 0
Prepared from Oil, natural gas, and coal: BP Statistics 2003 South Africa Australia
Natural gas

Uranium: OECD/NEA,IAEA URANIUM2001


Coal
Oil

Worldwide
5
Appreciation of CCT in Markets Clean Coal Technologies in Japan

Technological difficulty
Domestic coal conversion and reforming technology Domestic coal utilization technology
HyPr-RING

P-CPC Hyper Coal Power Generation

Technical scope in which Technological IGFC


and economical difficultes remain SCOPE21
EAGLE
HYCOL Hyper Coal DIOS
Gasification furnace (fluidized bed, spouted bed) A-PFBC Formed-coke
PFBC IGCC
Technology at a practical use level NSR CPX
Advanced flue
USC PICFB
PCI
FAKS
gas treatment
FBC I C F B Coal Ash utilization
Economic difficulty

Economic difficulty
DME Commercialization
Cement raw material P C F B C Flue gas Melting and fiber-forming
technology
Ash-removed CWM Gypsum board CFBC treatment FGC melting and mixing treatment
CWM CCS Fluidized bed solidification material
COM Pneumatic transfer Artificial aggregate
CC
NEDOL Briquette Simplified dry desulfurization Tt
ran
sfe
BCL Bio-coal r
Wet coal preparation
Brown coal dewatering

Cost reduction technology development


DME GTL
Dry coal preparation

Hyper Coal

Overseas demonstration
(International demonstration cooperated jointly)
Conventional technology
development region

Overseas coal conversion and reforming technology Overseas coal utilization technology

Technological difficulty
Coal production and consumption by country in 2002 (Total coal production in the world: 3,837 billion ton. Total coal consumption in the world: 3,853 billion ton.)
and Coal import to Japan (Total coal import to Japan: 168.5 million ton)

Source: 3,837 3,853


IEA COAL INFORMATION 2003
Coal Yearbook 2003
1,326
1,252
917
896
164140
30 20
103 81 ex-USSR Canada
30 58
U.K. Poland ) (production) (consumption)
(5.7%
29 60 9.6
33.5(19.9%)
Germany
America
334 357
163 0.4(0.2%) World
China 0
16,317
Japan
15,236 15,457 Others 276

India Cement/
Trend of coal demand in Japan ceramics 1,296
(Unit: 10 thousand tons)
)

13,057
.6%

) (Source : Coal Note 2003) Chemicals 575


3%
11

0 . 91.8(54.5%) 11,548
4(
.6(

11,145
0.
19

101 Electric power 6,186


9,079 9,394
28
223 276
156 8,225
Steam coal

Indonesia
78
Pulp / paper 491
Australia
Gas / coke 412
Coking coal

Iron making 6,221

FY1970 ’75 ’80 ’85 ’90 ’95 ’00 ’01 ’02

6
Part1 Classification of CCT
CCT in Japanese Industries Clean Coal Technologies in Japan

Power generation field Iron making field

Location of coal fired power plants Location of iron works


Numerals in parentheses designate power generate capacity Numerals in parentheses designate produced crude steel
(10 thousand kW) at the end of FY2001. (MT) as of FY2002.

Sunagawa(25)
Naie(35)
Tomatou Atsuma
Nanao Ota(120) (103.5)
Toyama Shinko Kyodo(50)
Noshiro(120)
Tsuruga(120) Kobe Steel (Kobe)(1,062,063)
Maizuru (under construction) Sakata(70) Sendai(52.5) Kobe Steel (Kakogawa)(5,397,267)
Takasago(50) Shinchi(200)
Mizushima(28.1) Haramachi(200) Sumitomo Metal
JFE Steel (Mizushima)(8,423,478) (Kashima)(6,820,450)
Osaki(25) Hirono (under construction)
Takehara(130) Nakoso(145) JFE Steel (Fukuyama)(9,885,534) JFE Steel (Chiba)(4,186,020)
Hitachi Naka (100) Nippon Steel (Kimitsu)
Misumi(100) 180 180
180 1800 (9,195,689)
Shin-onoda(100) Isogo (120) Nippon Steel (Yawata)
160

Crude steel production (million ton)


160
Shimonoseki(17.5) (3,514,941)
Domestic total coal consumption

Coal consumption (million ton)


160 1600
Domestic total coal consumption Kanda(36) 140 140 JFE Steel (Keihin)(3,472,723)
Coal consumption (million ton)

140 1400 Minato(15.6)


Hekinan(310) 120 120 Nippon Steel (Nagoya)(5,651,300)
Generated power (GkWh)

Matsuura(270)
120 1200 Crude steel production
Omura(15.6)
Generated power 100 100 Sumitomo Metal (Wakayama)(3,412,887)
Matsushima(100) Tachibanawan(210+70)
100 1000
Reihoku(70) 80 Coal consumption 80 Nippon Steel (Oita)(8,012,585)
Saijo(40.6) Kin(22)
80 800
Ishikawa(31.2) 60 60
60 Coal consumption 600 Gushikawa(31.2)
40 40
40 400
20 20
20 200
0 0
0 0 1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02
1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02
Coal consumption in power generation sector and generated power Coal consumption in iron making sector and crude steel production

Coal fired power generation technology 1A1


Pulverized Coal Fired Power Generation 1A4
Pressurized Internal Circulating Fluidized Iron making technology
Technology(Ultra Super Critical Steam) Bed Combustion Technology (PICFBC)
Pulverized Coal Injection
Circulating Fluidized Bed Combustion 2A2
for Blast Furnace (PCI)
2A1 The Formed-Coke making Process (FCP)
1A2 1A5 Coal Partial Combustor Technology (CPC)
Technology (CFBC)

Internal Circulating Fluidize Bed Pressurized Fluidized Bed Combustion Blast furnace
1A3 1A6
Combustion Technology (ICFBC) Technology (PFBC)
Advanced Pressurized Fluidized Bed Coking
1A7 Combustion Technology (A-PFBC) Pig iron
coal Formed-coke
Converter
furnace
Steam Combustion
coal furnace
boiler
PCI
Coal Electric
furnace
Gas
cleaning
Stack
Iron and steel

Coal Coal
Gas Steam
Pulverized gasification Generator SCOPE21
turbine turbine
coal furnace Slag
Steam
coal
Electric
4B5 Gas Cleaning Technology power
DIOS
Wastewater NSR
Coal Energy Application for Gas,
1B1 Hydrogen-from-Coal Process (HYCOL) 1B3
Liquid and Electricity (EAGLE)
2A4
Super Coke Oven for Productivity and Environment Direct Iron Ore Smelting
2A3
Enhancement toward the 21st Century (SCOPE21) Reduction Process (DIOS)
Hyper-Coal based High Efficiency
1B2 Integrated Coal Gasification Combined Cycle (IGCC) 3D1
Combustion Technology (Hyper Coal)
2B2 New Scrap Recycling Process (NSR)

7 8
Part1 Classification of CCT
CCT in Japanese Industries Clean Coal Technologies in Japan

Power generation field Iron making field

Location of coal fired power plants Location of iron works


Numerals in parentheses designate power generate capacity Numerals in parentheses designate produced crude steel
(10 thousand kW) at the end of FY2001. (MT) as of FY2002.

Sunagawa(25)
Naie(35)
Tomatou Atsuma
Nanao Ota(120) (103.5)
Toyama Shinko Kyodo(50)
Noshiro(120)
Tsuruga(120) Kobe Steel (Kobe)(1,062,063)
Maizuru (under construction) Sakata(70) Sendai(52.5) Kobe Steel (Kakogawa)(5,397,267)
Takasago(50) Shinchi(200)
Mizushima(28.1) Haramachi(200) Sumitomo Metal
JFE Steel (Mizushima)(8,423,478) (Kashima)(6,820,450)
Osaki(25) Hirono (under construction)
Takehara(130) Nakoso(145) JFE Steel (Fukuyama)(9,885,534) JFE Steel (Chiba)(4,186,020)
Hitachi Naka (100) Nippon Steel (Kimitsu)
Misumi(100) 180 180
180 1800 (9,195,689)
Shin-onoda(100) Isogo (120) Nippon Steel (Yawata)
160

Crude steel production (million ton)


160
Shimonoseki(17.5) (3,514,941)
Domestic total coal consumption

Coal consumption (million ton)


160 1600
Domestic total coal consumption Kanda(36) 140 140 JFE Steel (Keihin)(3,472,723)
Coal consumption (million ton)

140 1400 Minato(15.6)


Hekinan(310) 120 120 Nippon Steel (Nagoya)(5,651,300)
Generated power (GkWh)

Matsuura(270)
120 1200 Crude steel production
Omura(15.6)
Generated power 100 100 Sumitomo Metal (Wakayama)(3,412,887)
Matsushima(100) Tachibanawan(210+70)
100 1000
Reihoku(70) 80 Coal consumption 80 Nippon Steel (Oita)(8,012,585)
Saijo(40.6) Kin(22)
80 800
Ishikawa(31.2) 60 60
60 Coal consumption 600 Gushikawa(31.2)
40 40
40 400
20 20
20 200
0 0
0 0 1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02
1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02
Coal consumption in power generation sector and generated power Coal consumption in iron making sector and crude steel production

Coal fired power generation technology 1A1


Pulverized Coal Fired Power Generation 1A4
Pressurized Internal Circulating Fluidized Iron making technology
Technology(Ultra Super Critical Steam) Bed Combustion Technology (PICFBC)
Pulverized Coal Injection
Circulating Fluidized Bed Combustion 2A2
for Blast Furnace (PCI)
2A1 The Formed-Coke making Process (FCP)
1A2 1A5 Coal Partial Combustor Technology (CPC)
Technology (CFBC)

Internal Circulating Fluidize Bed Pressurized Fluidized Bed Combustion Blast furnace
1A3 1A6
Combustion Technology (ICFBC) Technology (PFBC)
Advanced Pressurized Fluidized Bed Coking
1A7 Combustion Technology (A-PFBC) Pig iron
coal Formed-coke
Converter
furnace
Steam Combustion
coal furnace
boiler
PCI
Coal Electric
furnace
Gas
cleaning
Stack
Iron and steel

Coal Coal
Gas Steam
Pulverized gasification Generator SCOPE21
turbine turbine
coal furnace Slag
Steam
coal
Electric
4B5 Gas Cleaning Technology power
DIOS
Wastewater NSR
Coal Energy Application for Gas,
1B1 Hydrogen-from-Coal Process (HYCOL) 1B3
Liquid and Electricity (EAGLE)
2A4
Super Coke Oven for Productivity and Environment Direct Iron Ore Smelting
2A3
Enhancement toward the 21st Century (SCOPE21) Reduction Process (DIOS)
Hyper-Coal based High Efficiency
1B2 Integrated Coal Gasification Combined Cycle (IGCC) 3D1
Combustion Technology (Hyper Coal)
2B2 New Scrap Recycling Process (NSR)

7 8
Part1 Classification of CCT
CCT in Japanese Industries Clean Coal Technologies in Japan

Cement production field Coal chemicals and other fields

Location of cement plants Location of chemicals complexes


Numerals in parentheses designate clinker production capacity Numerals in parentheses designate ethylene production capacity
(1000 t/y) as of April 1, 2003. (1000 t/y) at the end of FY2002.

Nittetsu Cement (Muroran)(968)


Myojo Cement (Itoigawa)(2,108)
Denki Kagaku Kogyo (Omi)(2,703) Taiheiyo Cement (Kamiiso)(3,944)
Mitsubishi Material (Aomori)(1,516)
Sumitomo Osaka Cement (Gifu)(1,592) Hachinohe Cement (Hachinohe)(1,457)
Tsuruga Cement (Tsuruga)(816) Taiheiyo Cement (Ofunato)(2,680)
Mitsubishi Chemical (Mizushima)(450)
Asahi Kasei (Mizushima) Mitsubishi Chemical (Kashima)(828)
Tokuyama (Nanyo)(5,497) Mitsubishi Material (Iwate)(670) Sanyo Petrochemical (443) Maruzen Petrochemical (Goi)(480)
Tosoh (2,606) Hitachi Cement (Hitachi)(848) Keihin Ethylene(690)
Mitsui Chemicals
Ube Industries (1,612) Sumitomo Osaka Cement (Tochigi)(1,489) (Iwakuni-otake)(623) Mitsui Chemicals (Ichihara)(553)
Ube Industries (4,872) Chichibu Taiheiyo Cement (Chichibu)(800) 4,600 Idemitsu Petrochemical Idemitsu Petrochemical (Chiba)(374)
540
180 180 Taiheiyo Cement (Kumagaya)(2,267) (Suo)(623) Sumitomo Chemical
4,400 (19.5)
Mitsubishi Material (Yokoze)(1,213) 520 (Anegasaki, Sodegaura)(380)
160 160 GDP
Domestic total coal consumption Taiheiyo Cement (Saitama)(1,655)
Cement production (million ton)
Coal consumption (million ton)

4,200 (19.0) 500 Nippon Petrochemicals (Kawasaki)(404)


140 140 DC (Kawasaki)(1,108)

Coal energy supply (PJ)


(17.8)
(17.8)
Taiheiyo Cement (Fujiwara)(2,407) 4,000 480 Tonen Chemical (Kawasaki)(478)
120 120

GDP (trillion yen)


Cement production Taiheiyo Cement (Tosa)(1,165) Coal energy supply Mitsubishi Chemical (Yokkaichi)
3,800 460
100 100 Taiheiyo Cement (Kochi)(4,335) (16.7) (16.3) (17.2) Tosoh (Yokkaichi)(493)
(16.5) (16.4)
3,600 440
80 80 Taiheiyo Cement (Tsukumi)(4,598) (16.3)
Mitsui Chemicals (Osaka)
Taiheiyo Cement (Saeki)(1,426) 3,400 318.6 317.3 316.7 420
316.0 Osaka Petrochemical (455)
60 60 (16.9)
(16.1) (16.0) 311.4
(16.5) 309.1 307.4
3,200 307.1 303.3 400
40 40 Showa Denko (Oita)(581)
Nippon Steel Blast Furnace Cement (Tobata)(808) CO2 emissions (Mt-C)
Coal consumption Mitsubishi Materials (Kyushu)(8,039) 3,000 294.5 291.0 380
20 20 291.4 286.1
Ube Industries (Kanda)(3,447) 2,800 360
0 0 Kanda Cement (Kanda)(1,085) 1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 Ryukyu Cement (Yabu)(722)
1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 Kawara Taiheiyo Cement (Kawara)(800)
Mitsui Mining (Tagawa)(1,977) Ryukyu Cement Coal energy supply, GDP, and CO2 emissions in Japan
Coal consumption in cement production sector and cement production
Aso Cement (Tagawa)(1,412) (Yabu)(722)
Numerals in parentheses designate the percentage of coal in primary energy.

Coal Liquefaction Technology Dimethylether Production


Coal chemicals process 3A1
Development in Japan
3A4
Technology (DME)
Bituminous Coal Liquefaction Hydrogen Production by Reaction Integrated
Cement production technology 3A2
Technology (NEDOL)
4C1
Novel Gasification Process (HyPr-RING)
Coal
3A3
Brown Coal Liquefaction
2B1 Fluidized Bed Advanced Cement Kiln System (FAKS) Technology (BCL) Vent
Coal
<Technology for Effective Utilization of Coal Ash> (Fractionation process)
Electric precipitator 4A2
Effective use for Cement/Concrete (Raw material charge process)

Electric precipitator
Track (Coal conversion process) Medium distillate
Gypsum
Heavy distillate
Limestone Cement Water
Cement (Separation, purification process)
Clay Coal mill silo
cooler
Iron raw
material
Drier

Recycle raw material Heavy oil tank


Air
separator
Silo Air High value-added product

BTX and mono- and di-cyclic components


Tanker
Air Residue coal
Raw material mill separator (Recycle)
Preheater
Rotary Wastewater
kiln Clinker
cooler Hyper-Coal based High Efficiency
3B1
Multi-Purpose Coal Conversion 3D1
Clinker Pre-pulverizing Technology (CPX) Combustion Technology(Hyper Coal)
silo mill
3B2 Coal Flash Partial Hydropyrolysis
Low-Rank Coal Upgrading Technology
3D2
Technology (UBC Process)

9 10
Part1 Classification of CCT
CCT in Japanese Industries Clean Coal Technologies in Japan

Cement production field Coal chemicals and other fields

Location of cement plants Location of chemicals complexes


Numerals in parentheses designate clinker production capacity Numerals in parentheses designate ethylene production capacity
(1000 t/y) as of April 1, 2003. (1000 t/y) at the end of FY2002.

Nittetsu Cement (Muroran)(968)


Myojo Cement (Itoigawa)(2,108)
Denki Kagaku Kogyo (Omi)(2,703) Taiheiyo Cement (Kamiiso)(3,944)
Mitsubishi Material (Aomori)(1,516)
Sumitomo Osaka Cement (Gifu)(1,592) Hachinohe Cement (Hachinohe)(1,457)
Tsuruga Cement (Tsuruga)(816) Taiheiyo Cement (Ofunato)(2,680)
Mitsubishi Chemical (Mizushima)(450)
Asahi Kasei (Mizushima) Mitsubishi Chemical (Kashima)(828)
Tokuyama (Nanyo)(5,497) Mitsubishi Material (Iwate)(670) Sanyo Petrochemical (443) Maruzen Petrochemical (Goi)(480)
Tosoh (2,606) Hitachi Cement (Hitachi)(848) Keihin Ethylene(690)
Mitsui Chemicals
Ube Industries (1,612) Sumitomo Osaka Cement (Tochigi)(1,489) (Iwakuni-otake)(623) Mitsui Chemicals (Ichihara)(553)
Ube Industries (4,872) Chichibu Taiheiyo Cement (Chichibu)(800) 4,600 Idemitsu Petrochemical Idemitsu Petrochemical (Chiba)(374)
540
180 180 Taiheiyo Cement (Kumagaya)(2,267) (Suo)(623) Sumitomo Chemical
4,400 (19.5)
Mitsubishi Material (Yokoze)(1,213) 520 (Anegasaki, Sodegaura)(380)
160 160 GDP
Domestic total coal consumption Taiheiyo Cement (Saitama)(1,655)
Cement production (million ton)
Coal consumption (million ton)

4,200 (19.0) 500 Nippon Petrochemicals (Kawasaki)(404)


140 140 DC (Kawasaki)(1,108)

Coal energy supply (PJ)


(17.8)
(17.8)
Taiheiyo Cement (Fujiwara)(2,407) 4,000 480 Tonen Chemical (Kawasaki)(478)
120 120

GDP (trillion yen)


Cement production Taiheiyo Cement (Tosa)(1,165) Coal energy supply Mitsubishi Chemical (Yokkaichi)
3,800 460
100 100 Taiheiyo Cement (Kochi)(4,335) (16.7) (16.3) (17.2) Tosoh (Yokkaichi)(493)
(16.5) (16.4)
3,600 440
80 80 Taiheiyo Cement (Tsukumi)(4,598) (16.3)
Mitsui Chemicals (Osaka)
Taiheiyo Cement (Saeki)(1,426) 3,400 318.6 317.3 316.7 420
316.0 Osaka Petrochemical (455)
60 60 (16.9)
(16.1) (16.0) 311.4
(16.5) 309.1 307.4
3,200 307.1 303.3 400
40 40 Showa Denko (Oita)(581)
Nippon Steel Blast Furnace Cement (Tobata)(808) CO2 emissions (Mt-C)
Coal consumption Mitsubishi Materials (Kyushu)(8,039) 3,000 294.5 291.0 380
20 20 291.4 286.1
Ube Industries (Kanda)(3,447) 2,800 360
0 0 Kanda Cement (Kanda)(1,085) 1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 Ryukyu Cement (Yabu)(722)
1990 ’91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 Kawara Taiheiyo Cement (Kawara)(800)
Mitsui Mining (Tagawa)(1,977) Ryukyu Cement Coal energy supply, GDP, and CO2 emissions in Japan
Coal consumption in cement production sector and cement production
Aso Cement (Tagawa)(1,412) (Yabu)(722)
Numerals in parentheses designate the percentage of coal in primary energy.

Coal Liquefaction Technology Dimethylether Production


Coal chemicals process 3A1
Development in Japan
3A4
Technology (DME)
Bituminous Coal Liquefaction Hydrogen Production by Reaction Integrated
Cement production technology 3A2
Technology (NEDOL)
4C1
Novel Gasification Process (HyPr-RING)
Coal
3A3
Brown Coal Liquefaction
2B1 Fluidized Bed Advanced Cement Kiln System (FAKS) Technology (BCL) Vent
Coal
<Technology for Effective Utilization of Coal Ash> (Fractionation process)
Electric precipitator 4A2
Effective use for Cement/Concrete (Raw material charge process)

Electric precipitator
Track (Coal conversion process) Medium distillate
Gypsum
Heavy distillate
Limestone Cement Water
Cement (Separation, purification process)
Clay Coal mill silo
cooler
Iron raw
material
Drier

Recycle raw material Heavy oil tank


Air
separator
Silo Air High value-added product

BTX and mono- and di-cyclic components


Tanker
Air Residue coal
Raw material mill separator (Recycle)
Preheater
Rotary Wastewater
kiln Clinker
cooler Hyper-Coal based High Efficiency
3B1
Multi-Purpose Coal Conversion 3D1
Clinker Pre-pulverizing Technology (CPX) Combustion Technology(Hyper Coal)
silo mill
3B2 Coal Flash Partial Hydropyrolysis
Low-Rank Coal Upgrading Technology
3D2
Technology (UBC Process)

9 10
Part1 Classification of CCT
Environmental Technologies Clean Coal Technologies in Japan

1)Flue gas treatment technology 2)Coal ash effective use technology

3)Global warming countermeasures technology 4)Environmental Protection


(Technology to reduce CO2 emissions) and fuel conversion technology
(DME, GTL)

Flue gas treatment technology Effective coal ash utilization in Japan


Emission reduction technology to remove dust, sulfur oxides, Ash generated during coal combustion is effectively
and nitrogen oxides is developed by treating and combusting used as raw material for cement and other applications.
flue gas from coal combustion through superior process design. Power in Japan: Effective use of coal ash generated from general industries, (FY2002)
(Source: Center for Coal Utilization, Japan)
Mechanism of Mechanism of flue Mechanism of flue
electrostatic precipitator gas denitration unit gas desulfurization unit Agriculture, forestry,
NH3 and fishery fields 1.8% Cement raw material
(Ammonia) Fertilizer, soil improving
Clean gas 5,694 73.7%
NO X
NH 3
NO X (to stack) material, etc. 139 1.8% Other
DC high voltage NO X NO X
NO X
NH 3
NO X
NH 3
NH 3
Other building 446 5.8%
Electrode NO X
NO X
Pump materials
29 0.4% Other
Discharge
Catalyst 5.8%
electrode Mixed liquor of Building material
Collected
limestone and water
board 347 4.5%
Total 7,724
coal ash N2 H 2O
Flue gas Architecture
Collecting
N2 H 2O (thousand ton)
electrode
H 2O
N2
Civil work field 4.9%
H 2O
N2
Cement field
Gypsum Pump material, etc. Civil field 8.8% 78.7%
Gypsum
134 1.7%
Flue gas (from boiler)
Road and base Cement admixture 239 3.1%
materials
Electrostatic Precipitator 115 1.5%
Concrete admixture 147 1.9%

Flue gas passes between two electrodes that are charged by a


Coal mine filler
high voltage current. The ash and dust are negatively charged, 188 2.4% Ground improving material 246 3.2%
and are attracted toward and deposit on the cathode. The ash
and dust deposited on the cathode where periodical hammering
occurs are collected in the lower section of the electrostatic
CO2 emissions in Japan
precipitator and subsequently removed. The principle is the
same with the phenomenon that paper and dust adhere to a CO 2 emissions in Japan for individual sectors
celluloid board electrostatically charged by friction. (Source: Headquarters of Countermeasures to Global Warming (FY2000))

Flue Gas Desulfurizer Other (non-fuel sector, etc.)


2.0% (direct incineration: 2.0%)
Limestone is powdered to prepare a water-based mixture Waste (plastics and waste oil incineration)
(limestone slurry). The mixture is sprayed into the flue gas to 2.0% (direct incineration: 2.0%)
Energy conversion sector (power plant, etc.)
induce a reaction between the limestone and the sulfur oxides Industrial process 6.9% (direct incineration: 30.9%)
(limestone consumption)
in the flue gas to form calcium sulfite, which is further reacted 4.3% (direct incineration: 4.3%)

with oxygen to form gypsum. The gypsum is then separated as


a product. 3 Transportation sector (automobile, Energy-related
ship, and aircraft) sectors
Flue Gas Denitrizer 20.7% (direct incineration: 20.2%)
Industry sector
(93.7%) 40.0% (direct incineration: 31.0%)
Ammonia is added to the flue gas containing nitrogen oxides.
The mixture gas is introduced to a metallic catalyst (a
substance to induce chemical reactions). The nitrogen oxides
in the flue gas undergo catalyst-induced chemical reactions to Commercial sector (Business)
Commercial sector (Household)
13.5% (direct incineration: 6.0%)
decompose into nitrogen and water. 12.3% (direct incineration: 5.2%)

Reaction formulae
4NO + 4NH3 + O2 4N2 + 6H2O CO2 emissions in major countries (million ton as carbon)
(Nitrogen (Source: IEO 2004)
(Ammonia) (Nitrogen gas)
monoxide)
Unit 1990 2000 2001 2005 2010 2020
6NO2 + 8NH3 7N2 + 12H2O USA Mt-C 1,352 1,578 1,559 1,624 1,800 2,082
(Nitrogen dioxide) (Nitrogen gas)
% 23.0 26.9 26.5 27.7 30.7 35.5
Canada Mt-C 129 158 155 172 186 196
Emissions of SOx and NOx per generated power in major countries UK Mt-C 164 151 153 155 163 176
Source; The Federation of Electric Power Companies of Japan
France Mt-C 102 109 108 106 108 122
(g/kWh) (Thermal power plant)
9 Germany Mt-C 271 226 223 224 232 241
7.1 SOx
8 Italy Mt-C 113 121 121 124 129 140
NOx
7 Mt-C 1,036 638 654 780 825 939
ex-USSR
6
% 17.6 10.9 11.1 13.3 14.0 16.0
4.8
5
4.0 China Mt-C 617 780 832 888 1,109 1,574
4
3.2
3.0 2.7 % 10.5 13.3 14.2 15.1 18.9 26.8
3
2.1
2
2.0 India Mt-C 153 249 250 272 321 435
1.4 1.2
0.9 0.7 Mt-C 269 310 316 319 334 365
1 Japan
0.20 0.26
0 % 4.6 4.8 4.8 4.6 4.3 3.9
France UK America Italy Canada Germany Japan
(1998) (1999) (1999) (1999) (1999) (2002) Mt-C 5,872 6,417 6,522 6,908 7,685 9,372
World total

11
Part1 Classification of CCT
International Cooperation Clean Coal Technologies in Japan

1)Pollution countermeasures technology 2)High efficiency power generation technology


(SOx, NOx, and dust/soot reduction technology) (IGCC, IGFC)

3)CO2 emissions reduction technology


(CDM, JI countermeasures technology)

Current state of international cooperation From GAP to CDM


Concomitant with the progress of industrialization and In recent years, the global warming issue has attracted intense
urbanization, developing countries face serious air and water international concern. Global warming is a serious problem for
pollution issues. Particularly in Asia and Oceania, the percentage the future of the earth and humankind, and is closely related to
of coal in the energy mix is large and sustainable economic human economic activity and the accompanying energy
development further emphasizes the importance of the consumption. Thus, satisfying both "economic development" and
development and widespread dissemination of coal utilization "the environment" becomes an important issue.
technology with full-scale environmental conservation measures. The Kyoto Protocol, adopted at Kyoto in December 1997 and
Since developing countries do not have sufficient capital, ratified by Japan in June 2002, includes the "Kyoto Mechanisms",
technology, and human resources for such technology, self-help an important instrument of international cooperation. In particular,
efforts are limited, and the assistance of developed countries the Kyoto Mechanisms include a market mechanism called the
including Japan and of international organizations is requested. Clean Development Mechanism (CDM), which is a forthcoming
Japan has promoted international cooperation in terms of system that aims to reduce greenhouse gases through
"pollution countermeasure technology" to reduce emissions of cooperation between developed and developing countries.
SOx, NOx, and dust, and of "high efficiency power generation From the viewpoint of overcoming global environmental issues
technology" to improve energy use efficiency with a focus on the that continue to spread worldwide, developing countries are
Green Aid Plan (GAP) counterpart countries of China, Indonesia, requested to maximize their self-help efforts toward improvement
Thailand, Malaysia, the Philippines, India, and Vietnam. of the environment in order to prevent ever-increasing pollution
and global warming.
Japan is requested to contribute to the economic growth and
environmental improvement of developing countries through the
active introduction of Japanese Clean Coal Technology (CCT)
into Asian countries such as China, which are expected to show
continued increases in coal consumption.

List of clean coal technologies and model projects relating to GAP

Project name Project period Target country Site Counterpart

Cleaning after combustion

Simplified FY1993-FY1995 People’s Republic of China


desulfurization unit

FY1995-FY1997 Thailand

FY1998-FY2001 People’s Republic of China

Coke oven gas desulfurization unit FY1999-FY2002 People’s Republic of China

Cleaning during combustion, improvement of combustion efficiency

Circulating fluidized FY1993-FY1995 People’s Republic of China


bed boiler

Philippines

FY1995-FY1997 People’s Republic of China

Indonesia

FY1996-FY1998 People’s Republic of China

FY1996-FY1999 People’s Republic of China

FY1997-FY1999 Thailand

FY1997-FY2001 People’s Republic of China

Cleaning before combustion

Briquette production FY1993-FY1995 People’s Republic of China


unit
Indonesia

FY1996-FY1998 Indonesia

Electricity Generating Authority of


FY1997-FY1999 Thailand Thailand (Lampang)
FY1998-FY2002 Philippines

Water-saving coal FY1994-FY1997 People’s Republic of China


preparation system

Desulfurization type CWM unit FY1995-FY1998 People’s Republic of China

12
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Combustion Technologies)

1A1. Pulverized Coal Fired Power Generation Technology (Ultra Super Critical Steam)
Outline of technology

1.Efficiency increase
Increase in the thermal efficiency of power generation plant is an
important issue in terms not only of economy to decrease the 600OC 610OC
power generation cost but also of suppression of CO2 emissions. 566OC 593OC
538OC
In particular, coal fired power plants which are the main stream of 600

current large thermal power plants increase their steam 31.0MPa


24.5MPa
Steam temperature
temperature level. The right figure summarizes the trend of steam 500 30

Steam temperature OC
(Left scale)

Steam pressure MPa


24.1MPa
conditions in recent years.
16.6MPa
400 20
In 1989, Kawagoe No.1 plant (700 MW) of Chubu Electric Power
Co., Inc. adopted steam condition of 316 kg/cm2G (31.0 MPa) x Steam pressure
300 (Right scale) 10
566 C/566 C/566 C. In 1993, Hekinan No.3 plant (700 MW) of
O O O

the company adopted the steam condition of 246 kg/cm2G (24.1


200
MPa) x 538OC/593OC, which 593OC was the first highest 0

temperature of reheated steam in Japan. After that, Misumi No.1 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000

plant (1000 MW) of The Chugoku Electric Power Co., Inc. and Fig. 1 Changes in steam condition with time
Haramachi No.2 plant (1000 MW) of Tohoku Electric Power Co.,
Inc. adopted the steam condition of 24.5 MPa x 600OC/600OC in
1998. Furthermore, Tachinbanawan No.1 and No.2 plant (1050
MW) of Electric Power Development Co., Ltd. adopted the steam
condition of 25.0 MPa x 600OC/610OC in 2000. The figure below
5
shows an example of relation between the steam condition and
Efficiency increase rate (%)

the increase in efficiency at a supercritical pressure plant. 4

3
Responding to the movement of increase in the steam
temperature, power companies, steel manufacturers, and boiler 2

manufacturers promote the development and practical


1
application of high strength materials having superior high
temperature corrosion resistance, steam-oxidation resistance, 0
and workability. The high-temperature materials for 650OC level Temperature of main steam (OC) 538 538 566 600 625
Temperature of reheated steam (OC) 566 593 593 600 625
use have already been in the practical application stage, and the
(Base)
study proceeds to satisfy 700OC level use aiming at further high
efficiency of the thermal plants. The figure below shows the Fig. 2 Relation between the steam condition and the
efficiency improvement at supercritical pressure plants
steam conditions and the high temperature materials for the
respective steam conditions.

Fig. 3 Steam conditions and high temperature materials

Steam temperature (OC) 538 566 593 621 649

Main steam pipe 2.25Cr 1Mo 9 Cr 12 Cr 18 Cr

Superheater tube 18 Cr 20-25 Cr

Hot reheat pipe 2.25Cr 1Mo 9 Cr 12 Cr 18 Cr

Reheater tube 9 Cr 18 Cr 20-25 Cr

: Ferritic Material : Austenitic Material

13
Clean Coal Technologies in Japan

2.Combustion technology
Various combustion technologies have been developed and intrafurnace denitration using the whole zones in the furnace.
practically applied responding to the need to satisfy current (1) Low NOx combustion at coal burner
severe environmental regulations and to respond to the high Although the structure of burner differs between large-boiler
efficiency combustion. The emission level of NOx and dust manufacturers, the most advanced burners basically adopt the
generated during the combustion of coal is the world’s lowest separation of dense and lean pulverized coal streams and the
level even at boiler exit, though the ultimate emission level owes multilayer charge of combustion air aiming to attain the ignitability
the flue gas treatment given at downstream side of the boiler. increase and to conduct the intraflame denitration. Figures 4 to 7
Since emission of NOx and that of dust are very closely related to show the burner structure of several manufacturers.
each other, this paper focuses on the low NOx combustion
technology. The low NOx combustion technology is roughly
grouped to the suppression of NOx generation at burner and the

Dense
Enhancing intraflame denitration combustion by the outer periphery stable ignition
flame
Secondary air Tertiary air
Tertiary air
Tertiary air swirling vane
Secondary air
Lean
Distributor vane
flame
Oil burner
Reducing flame

Dense flame
Lean flame Primary air + Pulverized coal

Dense flame Primary throat Primary flame holding plate


Secondary throat Rib Secondary flame holding plate

Dense flame
Fig.5 CC type pulverized coal fired burner: Kawasaki Heavy Industries, Ltd.
Lean flame
Dense flame
Fig.4 Pulverized coal fired A-PM burner: Mitsubishi Heavy Industries, Ltd.

Burner inner cylinder Secondary air inner vane


Burner outer cylinder Secondary air vane
Primary air + Pulverized coal Flow detector
Throat ring

Tertiary air damper

Oil burner Primary air Inner periphery Outer periphery


Primary air + Pulverized coal (Pulverized coal + Air) secondary air secondary air
Tertiary air
Volatile matter combustion zone NOx decomposition zone
Reducing agent generation zone Char combustion enhancing zone

Furnace wall
Oil burner support tube Fig.7 Pulverized coal fired NR burner: Babcock-Hitachi K.K.
Outer secondary air
Secondary air vane driver Inner secondary air
Secondary air
Secondary air inner vane driver

Fig.6 DF intervene pulverized coal fired burner: Ishikawajima-Harima Heavy Industries Co., Ltd.

Furnace exit

(2) Intrafurnace denitration Combustion completion zone

Intrafurnace denitration is conducted by reducing the NOX


Aditional Air
generated in the main burner zone using the residual
NOx reducing zone
hydrocarbons or the hydrocarbons generated from small amount containing unburned fuel

of fuel oil charged from the top of the main burner. The
Over Fire Air
intrafurnace denitration is performed in two stages. Figure 3 is Main burner
combustion zone
the conceptual drawing of the intrafurnace denitration. Main burner

In the first stage, hydrocarbons reduce NOx. In the second


stage, the unburned matter is completely combusted by the
additionally charged air.
Fig.8 Conceptual drawing of intrafurnace denitration

14
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Combustion Technologies)

1A2. Circulating Fluidized Bed Combustion Technology (CFBC)


Outline of technology

1.Features
The features of circulating fluidized bed boiler are described NOx depending on temperature) are suppressed. In addition, the
below. operation of circulating fluidized bed boiler is conducted by two-
1)Wide range of fuel adaptability stage combustion: the reducing combustion at the fluidized bed
Conventional boilers for power generation can use only fossil fuel section; and the oxidizing combustion at the freeboard section.
such as high grade coal, oil, and gas. The CFBC also uses low Then, the unburnt carbon is collected by a high temperature
grade coal, biomass, sludge, waste plastics, and waste tire as fuel. cyclone located at exit of the boiler to recycle to the boiler, thus
2)Low pollution increasing the denitration efficiency.
Emissions of pollutants such as NOx and SOx are significantly 3)High combustion efficiency
decreased without adding special environment measures. For High combustion efficiency is attained by excellent combustion
the case of fluidized bed boiler, the desulfurization is intrafurnace mechanism of circulating fluidization mode.
desulfurization using mainly limestone as the fluidizing material. 4)Space saving and high maintenance ability
For the denitration, ordinary boilers operate at combustion Space saving is attained because there is no need of separate
temperatures from 1,400 C to 1,500 C, and the circulating
O O
desulfurization unit, denitration unit, and fuel finely crashing unit.
fluidized bed boiler operates at lower temperatures ranging from Accordingly, sections of trouble occurrence become few, and
850 C to 900 C so that the thermal NOx emissions (generated
O O
maintenance becomes easy.

2.Outline of technology
Figure 1 shows a typical process flow of CFBC Hot cyclone CFBC boiler body

Generated steam

Coal Limestone
Flue gas

Boiler feed water Boiler feed water heater

Secondary air
Cyclone Primary air
Circulating Air preheater
fluidized Electric
bed furnace precipitator
Heat ID fan
recovery Stack
section

Ash storage tank

Fig.1 Process flow of circulating fluidized bed boiler

Figure 2 shows rough structure of CFBC. Generally CFBC is


Fig.2 Schematic drawing of CFBC structure
structured by the boiler and the high temperature cyclone. The
intrafurnace gas velocity is as high as 4 to 8 m/s. Coarse fluidizing increase the thermal efficiency, a preheater for fluidizing air and
medium and char in the flue gas are collected by the high combustion air, and a boiler feed water heater are installed. Most of
temperature cyclone, and are recycled to the boiler. The recycle the boiler technologies are introduced from abroad: mainly from
maintains the bed height and increases the denitration efficiency. To Foster Wheeler, Lurgi, Steinmuller, ALSTOM, and Babcock & Wilcox.

3.Study site and application field


Photograph 1 shows overview of the CFBC boiler facilities. The CFBC Co., Ltd., and Isa plant (210 t/h) of Ube
became popular mainly as coal fired boilers. Recently, however, CFBC Industries, Ltd. Example of RDF fired boiler is
using RDF and wood-base biomass as the fuel has drawn attention. Tomakomai plant of Sanix Inc. As for the
Typical applications of coal fired biogas are Tamashima plant (70 t/h) of biomass fuel, mixed combustion with coal is
Kuraray Co., Ltd, Chiba worksoil refinery (300 t/h) of Idemitsu Kosan adopted for decrease of CO2 emission.

4.Study period
Most of the technologies of circulating normal pressure fluidized
bed boiler (CFBC) are introduced into Japan from abroad
beginning from around 1986. Photo 1 CFBC appearance
5.Progress and result of the development
The CFBC was introduced from abroad as the coal fired boiler, of CFBC include further investigations of and efforts for initial cost
and is used in power companies, iron making companies, paper and power generation efficiency in the boilers using fuel such as
making companies, and other sectors. The CFBC is planned to RDF, industrial waste, and wood-base biomass.
distribute in China under the Green Aid Plan (GAP). The issues
15
Clean Coal Technologies in Japan

1A3. Internal Circulating Fluidize Bed Combustion Technology (ICFBC)


In charge of research and development: Center for Coal Utilization, Japan; Ebara Corporation;
Idemitsu Kosan Co., Ltd.
Project type: Coal Production and Utilization Technology Promotion Grant
Period: 1987-1993

Outline of technology

1.Features
The ICFBC has basic functions described below. 3)Low pollution
I.Uniform temperature in fluidize bed owing to the swirling flow of The emissions of pollutants such as NOx and SOx are
sand. significantly reduced without adding special environmental
II.Easy discharge of noncombustible owing to vigorous material. For the fluidizing bed boiler, the desulfurization
movement of sand. proceeds mainly in the furnace. However, ICFBC does not have
III.Available in controlling the temperature of fluidized bed by heat transfer tube in the fluidizing section so that the boiler raises
adjusting the heat recovery from fluidized bed. no wear problem on the heat transfer tube in bed. Thus, the
Based on the basic functions, ICFBC has features described fluidizing material of ICFBC does not need to use soft limestone,
below. and it can use silica sand. As a result, ICFBC needs minimum
1)Adoption of various fuels quantity of limestone as the intrafurnace desulfurization agent.
Similar with CFBC described before, the applicable fuel for The desulfurization efficiency of ICFBC becomes close to 90% at
ICFBC includes not only fossil fuel such as high grade coal, oil, Ca/S molar ratio of around 2, though the efficiency depends on
and gas, but also low grade coal, biomass, sludge, waste the coal grade, applied limestone, and temperature of fluidized
plastics, and waste tire. bed. The denitration is conducted by two-stage combustion: the
2)Control of bed temperature reducing combustion at the fluidized bed section; and the
Since the overall heat transfer coefficient varies almost linearly oxidizing combustion at the freeboard section. The unburnt
with the variations in air flow rate in the heat recovery chamber, carbon coming from the boiler is collected by the high
the quantity of recovering heat is easily controlled through the temperature cyclone installed at exit of the boiler, which collected
control of air flow rate. In addition, control of the quantity of unburnt carbon is recycled to the boiler to increase the
recovering heat controls the temperature of fluidized bed. Since denitration efficiency.
the control of recovering heat is performed solely by varying the 4)Space saving and maintenance ability
air flow rate, the load control is very simple, which is a Similar with the above-described CFBC, the ICFBC does not
strongpoint of ICFBC. need separate units for desulfurization, denitration, and fuel finely
crushing, therefore, the ICFBC facilities are space saving one
and have high maintenance ability owing to the fewer sections of
trouble-occurrence.

2.Outline of technology
Figure 1 shows outline of ICFBC. The technology uses silica
sand as the fluidizing material. The fluidized bed is divided into Freeboard
the main combustion chamber and the heat recovery chamber by
Primary
a tilted partition to create swirling flow inside the main combustion
chamber
combustion chamber and the circulation flow between the main
combustion chamber and the heat recovery chamber. A
circulation flow is created to return the unburnt char and
unreacted limestone coming from the cyclone at exit of the boiler Heat
recovery
to the boiler. chamber
1)The swirling flow in the main combustion chamber is created by
dividing the window box in the main combustion chamber to three
sections, and by forming a weak fluidized bed (moving bed) at
the center section introducing small amount of air, while forming
rigorous fluidized bed at both end-sections introducing large
amount of air. As a result, the center section of the main
combustion chamber forms a slow downward moving bed, and
the fluidizing material which is vigorously blown up from both
ends sediments at the center section, and then ascends at both
Fig. 1 Outline of ICFBC
end-sections, thus creating the swirling flow.
16
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Combustion Technologies)

2)The circulation flow between the main combustion chamber 3.Study site and use field
and the heat recovery chamber is created by the movement Examples of coal fired ICFBC include: Chingtao, EBARA CORP.
described below. A portion of the fluidizing material which is (10 t/h); Jiangsan in China (35 t/h); and Nakoso, Nippon Paper
vigorously blown up at both end-sections in the main combustion Industries Co. (104 t/h). Examples of ICFBC using industrial
chamber turns the flow direction toward the heat recovery waste as the fuel include: Motomachi, Toyota Motor Corp. (70
chamber at above the tilted partition. The heat recovery chamber t/h); Tochigi, Bridgestone Corp. (27 t/h); Fuji, Daishowa Paper
forms mild fluidized bed (downward moving bed) by the Mfg. Co., Ltd. (62 t/h); Amaki, Bridgestone Corp. (7.2 t/h); and
circulation bed air injected from under the chamber. Accordingly, Akita, Tohoku Paper Mfg. Co., Ltd. (61.6 t/h). An example of RDF
the fluidizing material circulates from the main combustion fuel ICFBC is Shizuoka, Chugai Pharmaceutical Co., Ltd. (3.7
chamber to the heat recovery chamber, and again to the main t/h).
combustion chamber from the lower part of the heat recovery
chamber. Since the heat recovery chamber is equipped with heat
transfer tubes, the circulation flow recovers the thermal energy in
the main combustion chamber. 4.Development period
3)The circulation flow coming from the cyclone at exit of the boiler The ICFBC was developed in 1987, and was further
passes through the cyclone or other means to collect unburnt developed and validated as the low pollution, small scale, and
char, emitted fluidizing material, and unreacted limestone, and high efficiency fluidized bed boiler for multiple coal grades in
then returns to the main combustion chamber or the heat the "Study of Fluidized Bed Combustion Technology" of the
recovery chamber using screw conveyer, pneumatic conveyer, or Coal Utilization Technology Promotion Grant project of the
other means. The circulation flow is extremely effective to Ministry of the International Trade and Industry over six years
increase combustion efficiency, to decrease NOx generation, and from 1988 to 1993.
to increase desulfurization efficiency.

5.Progress and result of the development


Although ICFBC was developed initially to use industrial waste
giving high calorific value, it was improved to use solid fuel with a
high calorlfic value and has been developed as a coal-fired boiler.
For China having abundant coal reserves, a boiler plant was
constructed at Chingtao as the production base in China.
Recently in Japan, wood-base biomass is used as the fuel in
some cases. However, further reduction in investment is
required to propagate the technology to Southeast Asia and other
areas rich in the biomass resource and low grade coal.

Photo 1 Overview of ICFBC

Steam
Dry Coal Boiler
Drum
Stack
Dry
Feed
Hot gas Air
Coal System
Filter Heater
Bunker IDF
Steam
Depressurizing
Unit
Crusher
PICFB

Bag
Limestone Filter
CWP
Pulverized Coal Mixing
System
Slurry Waste Heat
Feed Boiler
System (Gas Cooier)
CWP Pump Ash Cooling Ash
Pipe
Air Compressor Pressure Vessel Deashing
Boiler Water System
Circulation
Pump
Hot Blast Generator Pneumatic Ash Transport System

Fig. 2 Flowchart of PICFBC hot model test plant

17
Clean Coal Technologies in Japan

1A4. Pressurized Internal Circulating Fluidized Bed Combustion Technology (PICFBC)


In charge of research and development: Center for Coal Utilization, Japan; Ebara Corporation
Project type: Coal Production and Utilization Technology Promotion Grant
Period: 1992-1998

Outline of technology

1.Outline
The basic technology is the technology of internal circulating PICFBC mounts ICFBC in a pressure vessel.
fluidized bed boiler (ICFBC) described in preceding section. The
2.Features
The pressurized internal circulating fluidized bed boiler (PICFBC) heat transfer tube in bed is decreased, silica sand can be used
is structured applying the circulation flow technology of above- as fluidizing material, and the amount of limestone can be
described ICFBC. Accordingly, the load control is available minimized to a necessary level for the intrafurnace desulfurization,
without varying the height of fluidized bed. In addition, cooling of thus suppressing the generation of ash. Furthermore, the main
combustion gas is avoided because the intrabed heat transfer combustion chamber has no intrabed heat transfer tube so that
tubes do not expose on the bed during load controlling action, the problem of interference of intrabed heat transfer tube against
which minimizes the generation of CO2 and eases the maintaining the particle movement does not occur, which prevents the
temperature at inlet of gas turbine. Since the wear problem of generation of agglomeration.(the solidification of melted medium)

3.Outline of technology
Figure 1 shows schematic drawing of chamber and the heat recovery chamber.
PICFBC. The cylindrical pressure vessel Figure 2 (P.17) shows the rough flowchart of the hot model test plant
contains the cylindrical ICFBC. Similar at Sodegaura. The coal feed unit has two lines: the lock hopper
with ICFBC, silica sand is used as the system which feeds lump coal ; and the CWP(Coal Water Pellet)
fluidizing material. The fluidized bed is mixing system which feeds coal as slurry mixed with water. The
divided into the main combustion dust of combustion gas is removed by the high temperature bag
chamber and the heat recovery chamber filter structured by ceramics filter. The lock hopper system
by the tilted partition. The swirling flow technology is applied to develop the pressurized two-stage
is created in the main combustion gasification technology.
Fig. 1 chamber, and the circulation flow is
Schematic drawing of PICFBC
created between the main combustion

4.Study site and use field


The PICFBC hot model test was carried out at a site next to the generation. The pressurized two-stage gasification technology is in
Coal Research Laboratory (Nakasode, Sodegaura City, Chiba) of operation as a commercial plant (195 t/d of waste plastics
Idemitsu Kosan Co., Ltd. Applicable fields include the steam throughput) at Kawasaki of Showa Denko K.K. since 2003.
turbine generator using the generated steam and the gas turbine
generator using the combustion flue gas. Therefore, IGCC at coal
fired thermal power plant is a candidate. Photograph 1 shows the
installed hot model of PICFB 4 MWth. Photograph 2 shows the
overview of the pressurized two-stage gasification plant (30 t/d of
waste plastics throughput) in a demonstration test at a site next
to the Ube Ammonia plant. The pressurized two-stage
gasification technology has a use field of production of hydrogen
Photo 1 Photo 2
which is used for ammonia synthesis and fuel cell power Overview of pressurized
Overview of PICFBC
two-stage gasification plant

5.Period of development
The PICFBC hot model test was carried out from 1992 to 1997. The hot 1996. The pressurized two-stage gasification technology was developed
model test was conducted jointly with The Center for Coal Utilization,Japan, jointly with Ube Industries, Ltd. The demonstration operation of the plant
as the Coal Utilization Technology Promotion Grant project of the Ministry of (30 t/d of waste plastics throughput) began from January 2000, and the
International Trade and Industry. The test operation began from December commercial operation began from January 2001.
6.Progress and issue of the study
As the coal fired PICFBC, the study proceeded up to the hot pressurized fluidized bed are applied.
model test at Sodegaura. The technology, however, has The issues of pressurized system include the improvement in the
developed to the pressurized two-stage gasification technology in reliability of lock hopper system in the fuel charge line and the
which the thermal load and the lock hopper system in the measures to low temperature corrosion.
18
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Combustion Technologies)

1A5. Coal Partial Combustor Technology (CPC)


In charge of research and development: Center for Coal Utilization, Japan; Kawasaki Heavy Industries, Ltd.;
Kawasaki Steel Corp.; Chubu Electric Power Co., Inc.; and Electric Power Development Co., Ltd.
Project type: Coal Production and Utilization Technology Promotion Grant
Period: 1978-1986 (9 years)

Outline of technology

1.Background and outline of technology


Owing to the abundant reserves and wide distribution of Coal Partial Combustor (CPC) is a furnace where coal and air are
production countries, coal has high supply stability, and is injected at high speed into a swirling melting furnace in tangential
positioned as an important energy source in the future. direction, thus conducting partial combustion (gasification) of coal
Compared with other fuels such as oil and gas, however, coal under the condition of high temperature, heavy load, and strong
contains large amount of ash and nitrogen, thus has many issues reducing atmosphere, and after most of ash in coal is melted and
in use, including facility trouble caused by ash and significant separated to remove, the produced fuel gas is subjected to
increase in NOx emissions. Furthermore, global warming issue secondary combustion. That is, CPC is a technology of coal
has become international concern in recent years, which raises gasification combustion in boiler or gas turbine to utilize coal at
an urgent requirement of development of technology to reduce high efficiency and environmentally compatible state. The CPC
emissions of CO2 which is one of the main cause materials of has the normal pressure CPC technology and pressurized CPC
global warming. In this respect, the world waits for the technology. The former conducts very low NOx combustion
development of technology of high efficient and environmentally through the gasification in boiler, or generates low calorific gas at
compatible utilization of coal which generates large amount of normal pressure. The latter achieves high efficiency power
CO2 per calorific value. generation by pressuring the gas on the basis of the developed
technology of the former, and by combining it with gas turbine.

2.Normal pressure coal partial combustor technology


Boilers of fusion and combustion type aiming at volume-reduction
and detoxication of ash discharged from boiler and at use of Preheating burner
difficult-to-combust coal were constructed and are operating in Preliminary
Baffle Secondary
large number centering on Western countries. The conventional combustor
combustor
melting and combustion method has advantages of high
combustion efficiency and recovery of ash as nontoxic molten High temperature
Combustion combustion gas
slag. However, the method has drawback of large NOx
air
emissions caused by high temperature combustion.

Responding to the issue, our technology development focused Pulverized


coal
on the development of coal partial combustor system aiming to
simultaneously achieve the fusion to remove ash from coal and
the low NOx combustion. The system adopted direct mount of
CPC to the side wall of boiler, and the combustible gas generated
in CPC is directly charged to the boiler furnace, where the gas is
completely combusted with charged air.
Molten slag

As medium to small coal fired boilers, CPC can significantly


reduce NOx emissions while maintaining the compactness of Fig.1 Schematic drawing of normal pressure coal partial
boiler similar with the scale of oil fired boiler, and can recover all combustor (CPC) boiler

the coal ash as molten slag.

The right figure shows schematic drawing of the normal pressure


CPC boiler.

19
Clean Coal Technologies in Japan

3.Pressurized coal partial combustor technology


On the basis of the result of normal pressure CPC development, The figure below shows rough flow chart of the pressurized CPC
the development of pressurized CPC technology began aiming at pilot plant having 25 t/d of coal gasification capacity (operating at
the development of high efficiency power generation system by oxygen 21%). The pilot plant ran the coal gas generation test
pressurizing CPC and combining it with gas turbine. using CPC under pressure of 20 ata which can be applied to gas
turbine. The test proved the effectiveness of the pressurized PCP.

Pressurized pulverized coal feeder Kerosene tank

Gas cooler Ceramic filter

Gas incinerator

Pulverized coal
production unit

Denitration unit

Flux feeder Char hopper


Cooler

Liquid oxygen tank Primary air compressor

Slag tank

Char feeder
Air compressor
Desulfurization unit
Liquid nitrogen tank
Fig.2 Rough flow chart of pressurized CPC pilot plant

4.Issue and feasibility of practical application


The normal pressure CPC technology has already been brought
into practical applications as low NOx emission technology in
swirling melting furnaces of municipal waste gasification melting
furnaces and in very low NOx boiler for heavy oil combustion.
Also the normal CPC technology is in the development stage of
coal ash melting type low NOx boiler. The pressurized CPC
technology is in the stage of completion of pilot plant test, and is
in the research and development stage in private sector aiming at
practical use of the technology. These basic technologies have
also been integrated with the development of biomass
gasification gas turbine power generation technology.

Photo 1 Total view of pilot plant

20
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Combustion Technologies)

1A6. Pressurized Fluidized Bed Combustion Technology (PFBC)


In charge of research and development: Center for Coal Utilization, Japan; and Electric Power Development Co., Ltd.
Project type: Coal Production and Utilization Technology Promotion Grant
Period: 1989-1999 (11 years)

Outline of technology

1.Background and process outline


(1)The research and development of pressurized fluidized bed (2)Outline of facilities
combined power generation technology was conducted at Plant output 71.0 MWe
Wakamatsu Coal Utilization Research Center (present Pressurized fluidized bed combustion once-through boiler (ABB-
Wakamatsu Research Institute) of Electric Power Development IHI production)
Co., Ltd. using the 71 MWePFBC Plant, which was the first PFBC Bubbling type pressurized fluidized bed, Coal water paste
plant in Japan. The test plant was the first plant in the world in (70-75%) injection type
terms of full-scale adoption of ceramic tube filter (CTF) which is Combustion temperature 860 C O

able to collect dust from high temperature and high pressure gas Combustion air pressure 1 MPa
at high performance. Outline of the process is shown in Fig. 1.

Ammonia water injection


(Non-catalytic denitration)

Main steam / Reheated steam


Ash recirculation 593 C/593 C
O O

Ceramic tube filter cyclone


Steam turbine
(CTF)

Air

Gas turbine

CTF ash

Fuel
nozzle Condenser
Intercooler
Coal,
limestone,
water Pressure Deaerator
vessel

Denitration Bottom ash (BM)


unit Water
supply
pump
Fuel slurry pump

Water
Economizer supply
heater

Fig. 1 Outline of PFBC process

21
Clean Coal Technologies in Japan

2.Development object and technology to be developed


Object of PFBC technology development desulfurization unit.
(1) Increase in efficiency through the combined power generation Result of PFBC technology development
utilizing the pressurized fluidized bed combustion conditions: (1) Gross efficiency of 43% level was achieved by increased
(gross efficiency of 43%) efficiency through the combined power generation utilizing the
(2) Providing advanced environmental characteristics including: pressurized fluidized bed combustion conditions.(2) SOx level of
SOx reduction through the in-bed desulfurization; NOx reduction about 5 ppm through the in-bed desulfurization, NOx level of
through the low temperature combustion (about 860 C); Dust O
about 100 ppm through the low temperature combustion (about
reduction by CTF; and CO2 reduction by increased efficiency. 860 C), and the dust level of less than 1 mg/Nm3 or less by CTF
O

(3) Space saving of plant through the compact design of boiler was achieved.
adopting pressurized condition and the elimination of

3.Progress and result of the development


Detail design of the facilities began in FY1990, construction modified to adopt the ash-recycle system. Phase 2
began in April 1992, and facilities installation began in October demonstration operation was conducted from August 1998 to
1992. Test operation began in April 1993, coal combustion December 1999. The cumulative operating time of PFBC was
began in September 1993, and 100% load was achieved in 16,137 hours including 10,981 hours in Phase 1 and 5,156 hours
January 1994. The two-stage cyclone system passed the in Phase 2. In particular, Phase 2 achieved continuous operation
examination before entering operation in September 1994, and of 1,508 hours. Through the operation, valuable data and
the CTF system passed the examination before operation in findings were acquired in terms of performance and reliability.
December 1994. Phase 1 demonstration operation was These results have already been applied to the construction of
conducted until December 1997. After that, the plant was commercial facilities of the three electric power companies.

PFBC development schedule


Fiscal year
FY1989 FY1990 FY1991 FY1992 FY1993 FY1994 FY1995 FY1996 FY1997 FY1998 FY1999
Item

Final assessment
Interim assessment
Basic and detail design
Construction start Integration
Construction of demonstration plant

Test operation and adjustment

Demonstration operation Phase 1 Test operation

Modification Modification

Demonstration operation Phase 2 Test operation

4.Issue and feasibility of practical application


The feature of PFBC is adaptability to urban-operation owing to materials and waste, utilizing the superior combustion
the excellent environment-compatible characteristics including 10 performance; the in-bed desulfurization; the combination with
ppm or lower SOx emissions, 10 ppm of NOx emissions, and 1 catalytic or non-catalytic denitration; and the high temperature
mg/Nm3 or lower dust concentration, and to the reduced space and high performance dust collection by CTF. The issue is to
of plant owing to the elimination of desulfurization unit. These improve economy by fully utilizing these characteristics of the
advantageous characteristics are obtained by: the diversification system and by selecting adequate location.
of applicable fuels such as difficult-to-combust or low grade

Reference
Yamada et al.: "Coal Combustion Power Generation Technology", Bulletin of the Japan Institute of Energy, Vol.82, No.11, November, pp822-829, (2003)

22
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Combustion Technologies)

1A7. Advanced Pressurized Fluidized Bed Combustion Technology (A-PFBC)


In charge of research and development: Center for Coal Utilization, Japan; Electric Power Development Co., Ltd.;
Chubu Electric Power Co., Inc.; and Mitsubishi Heavy Industries, Ltd.
Project type: Coal Production and Utilization Technology Promotion Grant
Period: 1996-2002

Outline of technology

1.Outline
The development of coal utilization high efficiency power about 850 C to about 1,350 C), and to recover high temperature
O O

generation technology is an urgent issue from the viewpoints of steam, thus to attain higher efficiency of power generation (about
reduction in greenhouse gases and of resource saving. 46% of net efficiency; about 40% for the current coal fired power
Technology A-PFBC is a further advanced technology of PFBC plants) by the combination of PFBC with the fluidized bed
(pressurized fluidized bed combustion). That is, the development gasification technology.
aimed to increase the temperature at inlet of gas turbine, (from

Synthesis gas cooler


Limestone

Desulfurizer Ceramic Filer


Cyclone

Partial
Gasifier
Combustor

Ash

Gas turbine
Air
Char

Coal

Gas Flow Flue gas


Air

Steam Flow Ash Steam turbine


Oxdizer (PFBC)

Fig. 1 Flowchart of A-PFBC combined power generation system

2.Development object and technology to be developed


(1) High efficiency power generation [Net efficiency: about 46%] (2) Mild gasification condition [Carbon conversion: about 85%]
- Increase of gas turbine inlet temperature - 100% gasification in the partial gasifier by the combination with
(from about 850 C to about 1,350 C)
O O
the oxdizer (perfect oxidizing atmosphere)
- Recovery of high temperature steam (3) Utilization of results of related technologies
(High temperature steam recovery at the synthesis gas cooler - PFBC technology
applying the high temperature desulfurizer) - Various coal gasification technologies

23
Clean Coal Technologies in Japan

3.Progress and result of the development


Aiming at the practical application of the above-described
system, the study team installed a small scale process
development unit (refer to the photograph of total view of PDU)
at Wakamatsu Research Inditnte (Kita Kyushu City) of Electric
Power Development Co., Ltd. The PDU test operation began in
July 2001. By the end of FY2002, the cumulative gasification
operation time reached 1,200 hours, and the continuous
gasification operation reached 190 hours. The PDU test Desulfurizer

confirmed the three-reactors link operation, which is an


objective of the system validation, and acquired characteristics
Partial gasifier
of each reactors, thus confirmed the data necessary for scale up.
Oxidizer
The development has an issue of validation of total system
combined with gas turbine at larger scale, or pilot plant scale.

(1) Outline of the test of the process development unit (PDU)


[Object of the test]
For the system of three-reactors combination (oxidizer, partial
gasifier, and desulfurizer), (refer to Fig. 2), the acquisition of Fig. 2 PDU: LAyout of three reactors
reaction characteristics and operation characteristics, and the
validation of the process are conducted to acquire the scale up
data.
- Validation of the three-reactor link process
- Confirmation of performance of individual facilities (oxidation,
gasification, desulfurization, etc.)
- Confirmation of basic operability
- Acquisition of various characteristics, acquisition of scale up
data, etc.
[Outline of facilities]
With the main object of validation of the system, the plant
contains limited range of facilities including the main three
reactors, (coal treated scale: 15 t/d). Gas turbine system and
steam turbine system are not installed in PDU because their
performance is available from similar systems.
Fig.3 PDU: Total view

A-PFBC development schedule

Fiscal year
FY1996 FY1997 FY1998 FY1999 FY2000 FY2001 FY2002
Item

(1) Research plan, technology study

(2) Elementary test and F/S


Installation completion

(3) PDU test (15 t/d) Design, manufacturing, and installation Test operation

(4) Process evaluation

Reference
Preprint for the 13th Coal Utilization Technology Congress, "A-PFBC"; sponsored by Center for Coal Utilization

24
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Gasification Technologies)

1B1. Hydrogen-from-Coal Process (HYCOL)


In charge of research and development: HYCOL Association [Idemitsu Kosan Co., Ltd.; Osaka Gas Co., Ltd.;
Electric Power Development Co., Ltd.; Tokyo Gas Co., Ltd.; Toho Gas Co., Ltd.; Nikko Kyoseki Co., Ltd.; The Japan Steel Works, Ltd.;
Hitachi Ltd.; and Mitsui Coal Liquefaction Co., Ltd.]
Contract project of NEDO
Project type: Contract project of NEDO

Outline of technology

1. Background and process outline


The technology is a gasification technology utilizing spouted bed efficiency is attained, and heavy load gasification is performed.
in which pulverized coal with oxygen under high temperature and (2)The slag self-coating technology for the water cooled tubes
high pressure condition. Trough the gasifier, we can obtain the was developed. By the technology it is realized to prolong the life
medium calorific value gas that is rich in hydrogen and carbon of the tubes and to have reliability for the gasifier.
monoxide. The technology is called the "HYCOL process". (3)The swirling gas flow distributor was developed and adopted
Through the shift reaction, the gas yields carbon monoxide and as the technology to easily and uniformly distribute coal to many burners.
changes steam to carbon dioxide and hydrogen. After separating (4)Ash in coal is melted in the gasification furnace. The melting
the carbon monoxide and carbon dioxide, the gas is purified to become ash is discharged through the slug hole located on the hearth at
high purity hydrogen. the furnece. As the result of the swirling gas flow, the high
Hydrogen is used in oil refinery and chemical industry, further in temperature of the slag hole is maintained, and the smooth
coal liquefaction process. On the other hand, the obtained gas flowdown of the slag is secured.
containing carbon monoxide is expected to be used widely as a (5)The unreacted char discharged from the gasification furnace
raw material of chemical synthetic products, fuel for fuel cell, and accompanied with gas is separated by cyclone or other device to
fuel in various industries. recycle to the gasification furnace in high temperature and high
The HYCOL process has the features described below. pressure state, thus ensuring complete reaction.
(1)The process uses a dry-feed type one-chamber and two-stage (6)Ash in coal is recovered as slag which does no elute toxic
swirling spouted bed gasification furnace. Pulverized coal which ingredients. Together with the advantage of ready recovery of
is pressurized in a lock hopper is fed, in dry state, to the sulfur-components and nitrogen components in a form of H2S
gasification furnace via burners in swirling mode. The burners and NH3, respectively, the ash recovery significantly reduces the
are arranged by four of them in each stage. The oxygen feed environmental loads.
and the coalification rate at upper stage and lower stage are Coal to have lower melting point of ash or to have smaller fuel
separately controlled. Through the operation, high thermal ratio (fixed carbon to volatile matter) is more easily gasified.

2. Progress and result of the development 3.Issue and feasibility of practical application
HYCOL association (structured by above-listed nine private The development of coal gasification fuel cell system (IGFC) for
companies) contracted the research and development agreement power generation utilizing HYCOL technology has begun from
on the pilot plant under supported by NEDO. On the other hand, 1995, (EAGLE Project).
five private companies (Hitachi Ltd., Babcock-Hitachi K.K., Asahi
Glass Co., Ltd., Shinagawa Refractories Co., Ltd., and NGK
Spark Plug Co., Ltd.) contracted the basic study on the structure
of the furnace and on the materials with NEDO.
For establishing the process, the pilot plant was constructed at
Sodegaura, Chiba. The operational study of the pilot plant was
conducted from 1991 to 1994. The performance target was
achieved, and the world’s top gasification furnace technology was
established.

25
Clean Coal Technologies in Japan

Pretreatment process Gasification process Water-washing process Product gas firing process

Boiler
Gasification
furnace
Lock Water-washing
column
Coal hopper

Incineration
furnace Waste
Pulverized heat boiler
coal Distributor
apparatus Desulfurization unit
Lock
hopper

Air heater

Recycle gas
compressor

Ash treatment process

Fig.1 Flowchart of pilot plant

Specification and target performance of pilot plant

Coal throughput max. 50 ton/day

Gasification agent Oxygen

Gasification pressure 30 kg/cm2(G)

Gasification temperature 1,500-1,800 C O

O2/Coal 0.8-0.9 (weight ratio)

Product gas volume about 91 kNm3/day

Gas composition CO 61%

(design) H2 31%

CO2 3%

Carbon conversion 98% or more

Cool gas efficiency 78 % or more

26
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Gasification Technologies)

1B2. Integrated Coal Gasification Combined Cycle (IGCC)


In charge of research and development: Clean Coal Power R&D Co., Ltd.
(Until 2000, the study has been conducted as a joint activity of power companies led by The Tokyo Electric Power Co., Inc.)
Project type: Grant for "Demonstration of Integrated Coal Gasification Combined Cycle Power Generation "/ the Agency
of Natural Resources and Energy of the Ministry of Economy, Trade and Industry
Period: 1999-2009

Outline of technology

1. Outline and object of IGCC demonstration test


Integrated Coal Gasification Syngas 1. Increase in thermal efficiency---Compared with conventional
Combined Cycle (IGCC) is a Unreacted pulverized coal fired power plants, IGCC can increase net
coal (char)
high efficiency power thermal efficiency by about 20% for commercial plant.
Char
generation technology which recovery 2. Better environmental characteristics---Owing to the increase in
unit
gasifies coal to be used as the thermal efficiency, the emissions of SOx, NOx, and dust per
Reductor Char
fuel for gas turbine. Japanese (gasification generated power are reduced. In addition, amount of CO2
chamber)
power companies promoted emissions is reduced to the level of heavy oil fired power
research and development of Coal generation process.
IGCC technology applying the 3. Increase in applicable grades of coal---IGCC can use coal,
Coal Combustor
Nakoso pilot plant (PP) type (combustion having low ash melting points, which are difficult to be used in
Air chamber) Air
gasifier 1,2) as the core conventional pulverized coal fired power plants. As a result,
Molten slag
technology3). The PP type IGCC widens the variety of coal grades applicable in coal fired
gasifier applies dry coal fed, Water power plant.
Slag hopper
oxygen-enriched air blown, 4. Increase in applicable fields of ash---Since IGCC discharges
pressurized two stage coal ash in a form of glassy molten slag, the ash is expected to
Molten slag
entrained beds, as shown in be effectively used as materials for civil works.
Fig. 1 Nakoso PP type gasifier
Figure 1, which is expected to 5. Reduction of water consumption---Owing to the direct
give higher efficiency than preceding gasifiers in abroad. desulfurization of generated gas, IGCC does not need the flue
On the basis of the study results, the IGCC demonstration test gas desulfurization unit which consumes large amount of water.
project was started with the aims to validate the reliability, Accordingly, IGCC significantly reduces the water consumption
operability, maintenance ability, and profitability of IGCC, and to compared with conventional pulverized coal fired power plant.
confirm the feasibility of coal fired IGCC commercial plant.
Compared with conventional pulverized coal fired power plants ,
IGCC has many advantages as described below.

2.Specification and object of IGCC demonstration plant


Figure 2 shows the flow diagram of the IGCC demonstration MW, 1700 t/d of coal feed) is about a half of commercial plant.
plant. Table 1 shows main specifications and target values of the The gasifier is of the Nakoso PP type. Wet type gas clean up
plant. Figure 3 shows conceptional drawing of IGCC system with MDEA is adopted . The gas turbine is the 1200OC-
demonstration plant. The scale of IGCC demonstration plant(250 class gas turbine corresponding to the output of 250 MW.

Coal
Gas cleanup
Gasifier Heat
exchanger Char
recovery unit Table 1 Main specifications and target values of IGCC demonstration plant
Combustor Air
Output 250 MW class
Gas turbine Steam turbine Coal feed rate about 1,700 t/d
Dry coal fed, air blown,
Gasifier pressurized two stage spouting beds
Type
Gas cleanup Wet gas cleanup (MDEA) + Gypsum recovery
Gas turbine 1200 OC - class
Waste heat
recovery boiler Target thermal Gross efficiency 48%
Stack
efficiency (LHV) net efficiency 42%

Nitrogen
Oxygen Gasifier Environmental SOx emission concentration 8 ppm (O2 16% conversion)
Heat exchanger
Air separator characteristic NOx emission concentration 5 ppm (O2 16% conversion)
(target value) Dust emission concentration 4 mg/Nm3 (O2 16% conversion)
Fig.2 Flow diagram of IGCC demonstration plant

27
Clean Coal Technologies in Japan

3.Organization for executing the IGCC demonstration test


The IGCC demonstration test is conducted by Clean Coal Power
R&D Co., Ltd. (CCP R&D Co., Ltd.) which was established by Gasification
train
nine power companies and Electric Power Development Co., Ltd. Combined cycle
block
As for the project cost, 30% of the cost is national aid (Ministry of
Economy, Trade and Industry), and 70% is shared by total eleven
corporations: nine power companies, Electric Power
Development Co., Ltd., and Central Research Institute of Electric
Power Industry. (Refer to Fig. 4.)

METI

30% subsidy
Joint project agreement
Gas cleanup train
Nine power companies
70% contribution
Electric Power Development Co., Ltd.
CCP R&D Co., Ltd.
Central Research Institute of Electric
Personnel Power Industry

Fig. 4 Schem of demonstration project Fig. 3 Conceptional drawing of IGCC demonstration plant

4.Schedule and progress


Table 2 shows the schedule of demonstration project. As of test are scheduled to start from second half period of FY2007 for
January 2004, the detail design and the environmental about three years.
assessment are in progress. Plant operation and demonstration

Fiscal year 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Preliminary validation test


Establishment of
Design of demonstration plant CCP R&D Co., Ltd

Environmental assessment

Construction of demonstration plant

Plant operation and demonstration test

Table 2 Schedule of IGCC demonstration project

5.Activities until now


The pilot plant test (200 t/d of coal feed) which is the preliminary
Nakoso Power Plant of Executed site of pilot plant test;
stage of the demonstration test was carried out through a period Joban Joint Power Co., Ltd. Planned site for demonstration test
from 1986 to 1996 at Nakoso Power Plant of Joban Joint Power
Co., Ltd. in Iwaki City, Fukushima, (Fig. 5). The pilot plant test
was conducted jointly by nine power companies, Electric Power
Development Co., Ltd., and Central Research Institute of Electric
Power Industry, as a contracted project of NEDO. The pilot plant
test of 4,770 hours including 789 hours of continuous operation
test proved the practical applicability of the IGCC technology3).
Based on the success of the pilot plant test, the demonstration
test reflected the optimum system which was selected by
feasibility study given by NEDO. Through various investigations,
the demonstration test will be conducted at the site of pilot plant
in Nakoso Power Plant of Joban Joint Power Co., Ltd. again. Fig. 5 Planned site for demonstration test.
(Iwaki City, Fukushima, site for pilot scale test)

References
1) Shozo Kaneko,et.al., "250MW AIR BLOWN IGCC DEMONSTRATION PLANT PROJECT",
Proceeding of the ICOPE-03(2003),3-pp163~167
2) Christopher Higman,Maarten van der Burgt,"Gasifaication"(2003), pp126-128
3) Narimitsu Araki and Yoshiharu Hanai: Bulletin of Japan Energy, 75-9, (1996) pp839-850

28
Part2 Outline of CCT
Coal Fired Power Generation Technologies (Gasification Technologies)

1B3. Coal Energy Application for Gas, Liquid and Electricity (EAGLE)
In charge of research and development: New Energy and Industrial Technology Development Organization;
Electric Power Development Co.,Ltd.; The Center for Coal Utilization, Japan; and Babcock Hitachi K.K.
Project type: Coal Production and Utilization Technology Promotion Grant; and Grant for the Development of
Advanced Technology for Generation of Fuel Gas for Fuel Cell Development
Period: 1995-2006 (12 years)

Outline of technology

1.1. Summary of technology


The multi-purpose coal gas production technology development blown, single-chamber, two-stage swirling flow gasifier that permits
(EAGLE) mentioned here aims, in an attempt to reduce the high-efficiency production of synthetic gas (CO+H2). The
environmental load, (particularly, to decrease the amount of application of this gasifier and its combination with gas turbines,
greenhouse gas generated) at establishing a coal gasification steam turbines, and fuel cells further permit high-efficiency power
technology which is widely applicable to chemical materials, generation [Integrated Coal Gasification Fuel Cell Combined Cycle
hydrogen production, synthetic liquid fuel, electric power, and other (IGFC)], which will optimistically generate 30% less CO2 emissions
purposes through the development of the most advanced oxygen- than that of existing thermal power plants.

2.Development targets and technology to be developed


When applying coal gasification gas for IGFC and synthetic
Target item Target of development
fuel/hydrogen/chemical fertilizer production, it is necessary to set
Gas calorific value: 10,000 kJ/Nm3 or more
targets to meet the refinement level required by fuel cells as well Coal gasification Carbon conversionrate: 98% or more
performance Cold gas efficiency: 78% or more
as the catalyst since impurities contained in the gas such as Gasification pressure: 2.5 Mpa
sulfur compounds may poison fuel cells and the reactor catalyst, Continuous
1,000 hours or more
operation performance
thereby weakening their performance. Although not so much has
Adaptability to Acquisition of gasification data for 5 or more grades
been reported, even globally, about the effects of fuel cell- various grades coal coal having different properties from each other
poisoning materials (including halogen) in particular, the EAGLE Acquisition of data for scale up aiming at about
Capability to scale up
10 fold of scale up
Project has established development targets as listed in the table Sulfur compounds: 1 ppm or less
on the right with reference to DOE, MCFC Association, and other (precise desulfurizer outlet)
Halogens: 1 ppm or less
reports. Gas purification (precise desulfurizer outlet)
performance Ammonia: 1 ppm or less
(precise desulfurizer outlet)
Dust: 1 mg/Nm3 or less
(precise desulfurizer outlet)

Coal Gasification Facilities Gas Clean-up Facilities

Precise desulfurizer
Gasifier SGC
MDEA
Regenerator
Pulverized coal
COS converter Acid Gas
Furnace

Filter

Limestone
Primary Seconday MDEA Absorber
Scrubber Scrubber Absorber
Char
Slag

Incinerator HRSG

Compressor Air
Rectifier

Air separator Stack


Gas turbine facility

Fig.1 Flowchart of EAGLE 150 t/d pilot plant

29
Clean Coal Technologies in Japan

3.The Process and its Prograss


A joint team from New Energy and Industrial Technology the Technology Development Center of Electric Power
Development Organization and Electric Power Development Co., Development Co., Ltd., (refer to photograph). The plant is
Ltd. among others promotes the project. The pilot plant (150 t/d) undergoing test operations.
was constructed on the grounds of the Wakamatsu Laboratory at

EAGLE development schedule


Fiscal year
1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
Item

F/S

Final assessment
Primary test Test

Design of pilot plant Design

Construction of pilot plant Construction

Test operation Test operation

Analysis

4.Future issues and the feasibility of practical application


Through the acquisition of basic characteristics and performance, analysis of issues related to improved gasification performance
research and development is scheduled to acquire and to long-term operation.
characteristics of various grade coal, to acquire, analyze, and With respect to practical application and commercialization,
evaluate data, and to establish operational control technology active promotion will be enhanced based on the results of the
with stepwise confirmation of reliability and identification and testing, research, and development.

Gasifier Syngascooler Gas clean-up

Filter
Coal
Air Nitrogen
Oxygen

HRSG
Expansion turbine
Compressor
Steam turbine
Heat
recovery
boiler Gas turbine
Air
Circulation Circulation
blower blower

Catalyst burner

Photo 1 Total view of the pilot test facilities Fig.2 IGFC system

Reference
1) Masao Sotooka: Coal Gasification Technology (II) - Coal Energy Application for Gas, Liquid and Electricity (EAGLE),
The Japan Institute of Energy, Vol.82, No.11, November, pp836-840, (2003)

30
Part2 Outline of CCT
Iron Making and General Industry Technologies (Iron Making Technologies)

2A1. The Formed-Coke making Process (FCP)


InMembers in research
charge of charge of research and development
and development: Center for Coal Utilization, Japan; and Japan Iron and Steel Federation
Period: 1978-1986 (9 years)

Outline of technology

1.Outline 3.Result of study


The formed-coke process (FCP) starts from noncaking coal as 1. Production of formed coke from 100% noncaking coal
the main raw material, prepares formed coal using a binder, and Pilot plant operation was given normally with 70% noncaking coal
then carbonizes the coal in as-formed shape in a vertical furnace and 30% caking coal. The operation with 100% noncaking coal
to obtain coke. was also attained.
2.Establishing stable operation technology and engineering
technology
2.Features Long period of operation at the facility capacity of 200 t/d was
The FCP has a series of steps including raw material processing, carried out. Production of 300 t/d (1.5 times the design capacity)
forming, carbonizing the formed coal, and cooling the carbonized was achieved. Regarding the unit requirement of heat, 320
coke. In particular, carbonizing and cooling steps are conducted Mcal/t-formed coal was achieved.
in a vertical furnace with closed system, providing many superior 3. Long period and continuous use of 20% formed coke in large
features in terms of work environment, work productivity, blast furnace
easiness of stop and start up, and narrow installation space to In an actual large blast furnace, long period and continuous
those of conventional chamber oven process. operation test was carried out for 74 days with normal 20% and
maximum 30% mixing rate of formed coke to confirm that the
formed coke is applicable similar to the chamber oven coke.

4.Progress of research and development

Table 1 Progress of research and development

Fiscal year 1978 79 80 81 82 83 84 85 86

Core

Construction

Pilot plant test


Test operation

31
Clean Coal Technologies in Japan

Flow chart of continuous formed-coke production

Noncaking coal Caking coal


Carbonizing stage
The formed coal is charged to the carbonization
furnace (v), where the coal passes through the low
temperature carbonizing zone, and then the coal is
1.Drying heated to 1000 C in the high temperature carbonizing
O

zone (vii) to undergo carbonization. The heat-up rate


is controlled so as the coal not to generate collapse
2.Pulverizing and break caused by bulging and shrinking. The
carbonized coal (coke), is cooled to 100 C or lower O

Binder temperature in the cooling zone (viii) by a normal


temperature gas injected from the bottom of the
Forming stage furnace before discharged from the furnace.

Noncaking coal is the main 3.Kneading


raw material (60-80%). The
coal is dried to 2-3% of water
content: (i). The dried coal is Generated gas
pulverized: (ii). A binder is The coke oven gas (300-350 C) leaving the top of the furnace
O

added to the pulverized coal, 4.Forming is cooled by the precooler (ix) and the primary cooler (x).
which mixture is then After removing tar mist in (xi), most of the gas is recycled to
kneaded: (iii), and formed: the furnace. The surplus portion of the gas is withdrawn from
(iv), thus obtaining the the system, which is then subjected to rectification and
Formed coal
formed coal. desulfurization to become a clean fuel having high calorific
value, (3800kcal/Nm3).

10.Primary
9.Precooler cooler
5.Carbonization furnace 11.Electric precipitator
(Generated gas)

Main blower

6.Low temperature carbonizing zone


Ammonia water

12.Decanter

Tar

7.High temperature carbonizing zone

Byproducts
8.Cooling zone 13.High temperature The liquid in the gas is
gas heating furnace
introduced to the decanter
15.Ejector (xii) to separate ammonia
water and tar by decantation
and precipitation. Each of
14.Low temperature these byproducts is sent to
gas heating furnace respective existing plants for
further treatment. After
treated, tar is reused as the
binder for the formed coke.
Gas recycle
Formed coke The gas after separating tar mist in the electric precipitator is heated to
about 1000 C in the high temperature gas heating furnace (xiii), and then
O

is injected to the high temperature carbonizing zone (vii). The gas heated
to 450 C in the low temperature gas heating furnace (xiv) drives the
O

ejector (xv). The ejector (xv) sucks the high temperature gas which was
used to cool the coke to feed to the low temperature carbonizing zone
(vi) at a gas temperature of about 600 C. O

32
Part2 Outline of CCT
Iron Making and General Industry Technologies (Iron Making Technologies)

2A2. Pulverized Coal Injection for Blast Furnace (PCI)


In charge of research and development: Nippon Steel Corp. and other blast furnace steel making companies
Period: Introducing the technology successively to domestic blast furnaces starting from 1981

Outline of technology

1.Background and process outline


Injection of pulverized coal to blast furnace in Japan began at 4. Drying, pulverizing, and collecting coal are conducted in two
Oita No.1 blast furnace of Nippon Steel Corp. in 19811). parallel lines to assure stable blast furnace operation.
Although the main reducing material in blast furnace is coke, the 5. Flow velocity of carrier air and pressure resistance of facilities are
blast furnace operation during and after the 1960s adopted heavy determined with full consideration of preventing fire and explosion.
oil as an assistant fuel injecting from tuyere to enhance the Bag Filter
productivity, efficiency, and scale up. After the two times of oil
Cyclone
crisis, however, the high price of heavy oil forced the producers
Raw coal bunker
to switch the blast furnace operation to all-coke operation, or the
Receiving
reducing material had to fully depend on coke. Nevertheless, hopper

introduction of inexpensive assistant fuel instead of heavy oil was


wanted to reduce the cost of blast furnace operation and to Reservoir
tank
secure stable operation of the blast furnace.
P.A.fan Feeder Distributor
In this regard, Oita No.1 blast furnace introduced the ARMCO
type pulverized coal injection system first in Japan, (Fig.1). The
Air heater Pulverizer

Transport line
features of the system are the following.
1. High pressure transportation and injection lines have no 1 2 3
Feed tank furnace
mechanical rotation part, which avoids troubles of wear and

Disperser
damage.
2. Applied gas is not recycled to assure reliability of operation. O.T.
N2 compressor
3. Distribution of pulverized coal charged to individual tuyeres
ensures uniform distribution utilizing the geometrically symmetric Air compressor
flow characteristic of fluid. Fig.1 Pulverized coal injection facility at Oita No.1 blast furnace

2.Development object and technology to be developed


The introduced technology has field results in abroad. 2. Model plant test (1 t/h scale) for coal treatment, transportation,
Considering the differences in facility configuration and scale, and control.
and in operating conditions between abroad and Japan, the study 3. Test on actual furnace injecting coal through a single tuyere:
team conducted tests and investigations focusing on the Combustibility evaluation at the tuyere of actual furnace;
following-listed items, and reflected the result on the design. sampling and evaluation of coke inside the furnace.
1. Pulverized coal combustion test: Evaluation of influence of 4. Distribution of pulverized coal along circumference: With a
grade and size of pulverized coal; temperature, pressure, and model of actual furnace size, grasping powder flow characteristic
oxygen rich condition of air feed; and other variables. and determining distribution accuracy.

3.Progress and result of the development


Considering the heavy oil injection level during increased 1982. Following the domestic technology, Kobe Steel, Ltd.
production rate period and the experienced long time result, the introduced the U.S. Petrocarb technology and constructed
capacity of Oita No.1 blast furnace was designed to 80 kg/t. Two Kakogawa No.2 blast furnace and Kobe No.3 blast furnace in
lines of mill each having 25 t/h capacity were installed. After the 1983 as the Kobelco system. After that, Nippon Steel Nagoya
start of the plant, facility operation and injection operation No.1 blast furnace of ARMCO type and Nisshin Steel Kure No.2
proceeded smoothly to establish the stable production system. blast furnace of ARMCO type entered commercial operation in
After the success of Oita No.1 blast furnace, Godo Steel, Ltd. 1984. In 1986, the pulverized coal injection facility for blast
started the operation of the exclusively-developed system in furnace was adopted by 16 blast furnaces in Japan, accounting

33
Clean Coal Technologies in Japan

200 550
for 50% of the total. The number increased to 25 blast furnaces
in 1996. In 1998, all the operating domestic blast furnaces had
the pulverized coal injection facility, which increased the domestic

PC rate(kg/t-pig),Number of PCIBF
150 500
average pulverized coal ratio to 130 kg/t level, (Fig. 2). Table 1 coke rate(mean) PC rate(mean)
shows the various types of injection for the blast furnace

Coke Rate(kg/t-pig)
pulverized coal facilities. Table 2 shows the highest level in
Japan of a typical operational index of blast furnace during the 100 450

operation with pulverized coal injection.

50 400

number of BF equiped PCI


0 350
1980 1990 2000
year
Fig. 2
Increase in applications of pulverized coal injection for blast furnace in Japan
Table 1 Various facility types of pulverized coal injection to blast furnace

Type of distribution Pneumatic Control of flow rate


Name of type conveying Velocity Use Investment
/transportation concentration in branched pipe

Carrier gas pressure National Steel,


Petrocarb Low High Kobe Steel, Medium
and flow rate (Downtake)
JFE (NKK)
DENKA Pneumatic conveying Low High ditto (Uptake) JFE (Kawasaki Steel) Medium
from feed tank directly
Kuettner High Low ditto + Flow meter Thyssen Large
to each tuyere
ex-PW Medium Low Rotary Valve Dunkerque Medium
Simon Macawber Low High Coal Pump Scunthorpe Large
Uniformly distributing to give Nippon Steel Corp.,
ARMCO Low High uniform pressure drop across Small
Hoogovens
in individual pipes
Feed tank Uniformly distribution
new PW Main pipe High Low Sidmar, Solac Fod Small
by throttled pipes
Distributor
Klockner Tuyere High Low ditto Dunkerque, Taranto Small
Rotary Feeder+Uniform
Sumitomo Low Low pressure drop (one way) Sumitomo Medium
Metal Mining. Co., Ltd. distribution Metal Mining. Co., Ltd.

Table 2 Domestic highest level operation indexes for blast furnace operation with pulverized coal injection
Year Coal dust ratio Coke ratio Reducing material ratio Tapping ratio
and Steel works, blast furnace
Month kg/t kg/t kg/t t/d/m3

Maximum pulverized coal ratio (PCR) 98.6 Fukuyama No.3 blast furnace 266 289 555 1.84
Minimum coke ratio (CR) 99.3 Kobe No.3 blast furnace 214 288 502 2.06
Minimum reducing material ratio (RAR) 94.3 Oita No.1 blast furnace 122 342 464 1.95
Maximum tapping ratio 97.1 Nagoya No.1 blast furnace 137 350 487 2.63

4.Issues and feasibility of practical application


Average operating years of domestic coke ovens have reached possibility of innovation of blast furnace toward a combined
around 30 years, and the importance of the technology of smelting furnace through the combined injection via tuyeres of
injection of pulverized coal as an assistant fuel for blast furnace blast furnace together with reducing materials such as waste
increases year after year. Compared with coke which depends on plastics and biomass, and further with reducing ores. Thus, the
caking coal, pulverized coal increases the expectation for the technology is expected to develop as a core technology of blast
injection material owing to the flexible adaptability to the coal furnace solving the issues of resources, energy, and carbon
resources. The technology of pulverized coal injection has a dioxide.

Reference
Shinjiro Waguri: Ferram vol.8, p371 (2003)

34
Part2 Outline of CCT
Iron Making and General Industry Technologies (Iron Making Technologies)

2A3. Direct Iron Ore Smelting Reduction Process (DIOS)


In charge of research and development: Center for Coal Utilization, Japan; and Japan Iron and Steel Federation
Period:1988-1995 (8 years)

Outline of technology

1.Outline 3.Result of study


The DIOS directly uses noncaking coal in powder or granular Feasibility study was given to new installation of commercial
shape and iron ore without using coke process and sintering plant of blast furnace process and of DIOS at seaside green field.
process which are required in blast furnace process. The Considering its superiority to blast furnace process as described
noncaking coal is directly charged to a smelting reduction below, the feasibility of DIOS can be demonstrated for the model
furnace, while the iron ore is preliminarily reduced before of 6,000 tons of molten iron production (annual production of 2
charged to the furnace, thus the molten iron is produced. million tons).
1. Investment cost is decreased by 35%.
2.Features 2. Molten iron production cost is decreased by 19%.
1. Applicable of inexpensive raw material and fuel, (noncaking 3. Coal consumption per 1 ton of molten iron production is the
coal, in-house dust, etc.) same level with that of the blast furnace process, 730-750 kg.
2. Low operation cost 4. Net energy consumption is decreased by 3 to 4%.
3.Responding flexibly to variations of production rate 5. CO2 emissions in the iron making process is decreased by 4 to 5%.
4. Compact facilities, and low additional investment
5. Available in stable supply of high quality iron source
6. Effective use of coal energy
7. Easy coproduction of energy (cogeneration)
8. Low environmental load, (low SOx, NOx, CO2, dust
generation, no coke oven gas leak)

4.Progress of research and development


Table 1 Progress of research and development

Fiscal year 1988 89 90 91 92 93 94 95

Core

Construction
Pilot plant test Test operation

1) Core technology study (FY1988-FY1990) 2. With various raw materials, the conditions of facilities and of
Core technologies necessary for the construction of pilot plant operation to achieve high thermal efficiency to substitute the blast
were established. These core technologies include the increase furnace were determined.
in thermal efficiency of smelting reduction furnace (SRF), the 3. Technology for water cooling of furnace body was established.
connection with preliminary reduction furnace (PRF), the molten Conceptual design and economy evaluation (FS) for commercial
slag discharge technology, and the SRF scale up. facilities were conducted. The conditions of facilities and of
2) Pilot plant test (FY1993-FY1995) operation to prove the superiority to the blast furnace as shown in
1. Applicability of direct use of powder and granular ore and coal the results of the research was clarified.
was confirmed, and necessary facility conditions were
determined.

35
Clean Coal Technologies in Japan

Plant size 500 t-molten iron/day

Height 9.3m.
Smelting reduction Inner diameter 3.7m.
furnace Pressure less than 2.0kg/cm2 - G(300kPa)

Prereduction Height 8.0m.


furnace Inner diameter 2.7m.

Coal Flux Iron ore


952kg 80kg 1450kg
Preheating
furnace

RD 8.7%
2,326Nm3
2,789Mcal(11.7GJ)
RD 8.6%
600 C O

Prereduction
furnace
Venturi scrubber

RD 27.0%
779 C
O

O2 Pressure control value


RD 27.1%
608Nm3
OD 31.6%

Off-gas

Tapping device
Smelting reduction
furnace
1.9kg/cm2 - G(290kPa)
24.7t/h
Molten iron 1,540OC
1,000kg
Legend
N2 70Nm3 OD : Oxidation degree

RD : Reduction degree

Fig.1 An example of the DIOS pilot plant operation (per 1,000kg of molten iron)

36
Part2 Outline of CCT
Iron Making and General Industry Technologies (Iron Making Technologies)

Super Coke Oven for Productivity and Environment Enhancement


2A4. toward the 21st Century (SCOPE21)
In charge of research and development: Center for Coal Utilization, Japan; and Japan Iron and Steel Federation
Project type: Coal Production and Utilization Technology Promotion Grant
Period:1994-2003 (10 years)

Outline of technology

1.Background and process outline


The existing coke production process,which rapidly heats the coal The SCOPE21 process aims to develop an innovative process
at 350 C(low temperature carbonization),as opposed to the old
O
responding to the need in 21st century in terms of effective use of
method of a 1200OC coke furnace, has many problems such as coal resource, improvement in productivity, and environmental
unavoidable coal grade limitation of using mainly strong caking and energy technologies. As shown in the figure, the existing
coke owing to the limitation of coke strength, large energy coke production process is divided into three stages along the
consumption owing to the process characteristic, and process flow, namely the coal rapid heating, the rapid carbonization,
environmental issues. Coke ovens in Japan have reached their and the medium-to-low temperature coke reforming. Development
average life of 30 years, and enter their replacement time. In this was carried out of a revolutionary process with overall balance
occasion of requirement for replacement, there is a need to that pursued the functions of each stage the utmost.
develop an innovative next-generation coke production technology
that has flexibility to handle coal resource and that has excellent Currently the SCOPE21 is only one large development project for
environmental measures, energy saving, and productivity. new coke process in the world, and it is hoped that it can be put
Responding to the need, the team develops a new coke process. to practicul use.

Hot briquetting machine


Plug flow conveying system

Stationary charge unit

Highly sealed oven door


Pneumatic Emission free
preheater Coke upgrading
coke pushing

Carbonizing chamber
High heat conductivity brick
Pressure control Power plant
Smokeless
Coarse (750-850OC) Steam
Fine coal discharge
coal
Fluidized
bed dryer Regenerator
Stack
Coal
Coke (150-200OC)
Foundation
Coke sealed transportation
(750-850OC)
Blast furnace
Hot blast
Fuel stove Flue gas

Fig.1 Outline of the next-generation coke oven process

2.Development object and technology to be developed


(1)Increasing the use ratio of noncaking coal to 50% current level, the study significantly reduces the carbonizing time
With the aim of increasing the use ratio of noncaking coal to by increasing the thermal conductivity of wall of the carbonizing
50%, which noncaking coal is not suitable for coke production chamber and by discharging the material at temperatures lower
and the current use ratio is only about 20%, the study develops than normal carbonization point, (medium-to-low temperature
the technology to increase the bulk density of charging coal carbonization). The resulting insufficient carbonization
through the improvement of caking property utilizing the coal temperature is compensated by reheating in the coke dry
rapid heating technology and through the forming treatment of quenching unit (CDQ) to secure the product quality.
fine coal powder. (3)Reducing NOx generation by 30% and achieving smokeless,
(2)Increasing the productivity by three times odorless, and dustless operation
Aiming at the increase in the productivity by three times that of Full scale prevention of generation of smoke, odor, and dust
37
Clean Coal Technologies in Japan

during coke production is attained by the sealed transportation of 20% through the increase in the temperature to start the
coal using the plug transportation, the sealed transportation of carbonization by preheating the charging coal to high
coke, and the prevention of gas leak from coke oven applying temperature, the reduction in the carbonization heat by reducing
intrafurnace pressure control. Furthermore, improved combustor the discharging temperature applying medium-to-low temperature
structure of the coke oven reduces NOx generation. carbonization, and the easy recovery of sensible heat of
(4)Saving energy by 20% generated gas and of combustion flue gas owing to the scale-
The energy necessary to produce coke is aimed to reduce by reduction of facilities resulted by the increased productivity.

3.Progress and result of the development


The project proceeds under the joint work of Center for Coal
Utilization, Japan and Japan Iron and Steel Federation. The pilot
plant (6 t/h) was constructed in Nagoya Works of Nippon Steel
Corp., (refer to photograph), and the test operation was conducted.

Energy saving and Economical Evaluation


The SCOPE21 process is composed of innovative
technologies, enabling effective use of coal resources, energy
saving, and environment enhancement. As a result, it has a
great economical advantage over the conventional process.
[Reduction of construction costs]
Coal Common
Coke over Preliminary equipment Total

Conventional 89 --- 11 100

SCOPE21 40 25 19 84 Photo 1 Total view of pilot plant

Energy saving [Evaluation consumption] [Reduction of coke production costs]


Reduction of total energy use by 21% due to 800 100
adopting a pretreatment process with direct heating Power
Fuel gas
of coal and a high effciency coke oven with a heat
Energy consumption (Mcal/t-coal)

70 80 Variable
Coke Production cost (%)

recovery system. 600 CDO 47


Recovered Variable
Construction costs 271
133 CDO
60 38
recovered
Reduction by 16% by greatly reducing the number of 277
400
coke ovens even while expanding the coal
600 40
pretreatment plants and environmental protection.
Total 460 Fixed
Coke production cost 200 Total
53 Fixed
399 20
316 44
Reduction by 18% by increasing the poor coking
coal ratio and decreasing construction costs even
while increasing electricity and fuel gas in the coal 0 0
Conventional SCOPE21 Conventional SCOPE21
pretreatment plant.

SCOPE21 Development schedule

1994 95 96 97 98 99 2000 01 02 03

Survey and study

Core technology development Core technology


combination test

Construction Disassembly and


investigation
Pilot plant study
Test operation

(4)Issue and feasibility of practical application


The aging of coke ovens in Japan proceeds, though there are changed. The developed technology will be introduced to these
progresses of furnace repair technology. Thus coke ovens still aged coke ovens, though it is influenced by the economic
need replacement and the replacement schedule has not been conditions.

Reference
1) Kunihiko Nishioka et al.: Lecture papers at the 12th Coal Utilization Technology Congress, Tokyo, p.1-2.1, November (2002)

38
Part2 Outline of CCT
Iron Making and General Industry Technologies (General Industry Technologies)

2B1. Fluidized Bed Advanced Cement Kiln System (FAKS)


Outline of technology

1.Features
The objectives of development of fluidized bed advanced cement
kiln system (FAKS) are the efficient combustion of low grade
coal, the significant reduction of NOx emissions, and increase in
the heat recovery efficiency between solids and gases
discharged from the process by utilizing the inherent
characteristics of fluidized bed process, including combustion
performance, heat transfer performance, particle diffusion and
granulation properties. Thus, the ultimate object of the
development is to contribute to the global environment
conservation, the energy saving, and the fulfillment of demand of
various kind and/or special grade cement.

Cement clinker

Photo 1 Clinker produced from fluidized bed kiln Photo 2 Total view of 200 t/d plant

2.Outline of technology
The FAKS is configurated by a granulation sintering kiln and two-
stage coolers. The granulation sintering kiln granulates the raw
material to a specific size for melting to high quality cement, and
then sinters thus granulated raw material at high temperatures.
The two-stage coolers combine a fluidized bed cooler and a
packed bed slow-cooling cooler to increase the heat recovery
efficiency.
The most important technology in the system is the granulation
control technology. Compared with the other development which
needed "charge of the seed-core clinker as the core of the
granule from outer side for controlling the granulation process,
thus allowing high temperature raw material to adhere and grow
on the seed-core clinker", the FAKS process applies "hot self-
granulation" for the first time in the world. The "hot self-
granulation" is "the process where a nucleus of granule is
generated by agglomerating the small particle of raw material,
and to allow other raw material to adhere and grow on the
nucleus, thus to conduct the granulation control."
The granulation sintering kiln furnace integrates two major
technologies for performing the granulation control: a raw
material injection unit, and a bottom classification and discharge
unit.

Fig.1 FAKS-I System structure

39
Clean Coal Technologies in Japan

3.Demonstration site and use field


1)Demonstration site : Tochigi plant of Sumitomo Osaka Cement
Co., Ltd.
2)Use field : Cement production
3)Development period : 1996-1998

Fig.2 Key Technology

4.Progress of development
On the result of basic study begun from 1984 by the joint team of Ltd., and Sumitomo Osaka Cement Co., Ltd. Then the pilot plant
Kawasaki Heavy Industries, Ltd. and Sumitomo Osaka Cement operation test began. From April 1993, the basic plan and design
Co., Ltd., the technology development proceeded beginning from started for a 200 t/d plant jointly by Center for Coal Utilization,
1986 as the Coal Production and Utilization Technology Japan, and Japan Cement Association. Through the operation
Promotion Grant project which is a project of Agency of Natural test toward the practical application begun from February 1996,
Resources and Energy of the Ministry of International Trade and the system was validated, and the development work completed
Industry. A 20 t/d pilot plant was constructed in June 1989 jointly at the end of December 1997.
by Center for Coal Utilization, Japan, Kawasaki Heavy Industries,

5.Issues
The performance comparison between the conventional adopted as an innovative substitute cement production
technology and FAKS for a 1,000 t/d commercial plant is shown technology.
in the table below. The FAKS is expected to be commercially

Comparison of rotary kiln type process and FAKS at a 1,000 t/d plant in terms of environmental improvement effect
Discharge quantity Rotary Kiln & AQC FAKS
Discharge quantity (mg/Nm3) 708 476
NO2
as N content in coal is 1% and Annual discharge quantity
NOx convert in 10% O2 341 233
(ton-NO2/year)

Discharge quantity(g/Nm3) 245 220


CO2 *1
depends on electric power Annual discharge quantity
and fuel consumption 118x103 108x103
(ton-CO2/year)

Basis of calculation
ton-clinker/day 1,000 1,000
Production capacity
ton-cement/day 1,050 1,050
Annual operating time Day/year 330 330
Heat consumption kJ/ton-clinker 3,411x103 2,993x103
Power consumption KWh/ton-clinker 27 36
Exhaust gas specific quantity Nm3/kg-clinker 1.46 1.49
Lower calorific value of coal kJ/kg-coal 25,116 25,116
*1 Based on IPCC : Guideline for National Greenhouse Gas Inventories, Reference Manual Carbon Emission Coefficient
/ Basic Calculation ; Carbon Emission Factor = 26.8 tC/TJ , Fraction of Carbon oxidized = 0.98

Reference
1) Isao Hashimoto, Tatsuya Watanabe, et al.: Development of Fluidized Bed Advanced Cement Kiln Process Technology (Part 9),
The 8th Coal Utilization Technology Congress, Japan, September (1998)

40
Part2 Outline of CCT
Iron Making and General Industry Technologies (General Industry Technologies)

2B2. New Scrap Recycling Process (NSR)


In charge of research and development: Center for Coal Utilization, Japan; Nippon Sanso Corp.;
and NKK Corp. (present JFE Steel Corporation)
Project type: Coal Production and Utilization Technology Promotion Grant
Period:1992-1997 (6 years)

Outline of technology

1.Background
In Japan, currently about 30 million tons of iron scrap is recycled energy efficiency is wanted. To this point, the NSR process is a
every year, and most of them are melted in arc furnaces non-power melting technology that melts metals such as iron
consuming large amount of electric power. The energy efficiency scrap utilizing high temperature energy obtained from direct
of arc furnace is as low as about 25% (converted to primary combustion of pulverized coal by oxygen. The NSR process has
energy taking into account of efficiency of power generation and been developed aiming to significantly increase the energy
of power transmission). Thus a melting process having higher efficiency compared with that of conventional technology.

2.Development schedule
The development was promoted by a joint team of Center for efficiency melting. The study began from a batchwise melting
Coal Utilization, Japan, Nippon Sanso Corp., and NKK Corp. furnace. With the result of the batch-furnace operation, the
(present JFE Steel Corporation). The main subject of development continuous melting furnace was developed aiming at higher
was the furnace structure and the burner arrangement to attain high energy efficiency.

Table 1 Development schedule


1992 1993 1994 1995 1996 1997
Survey
Bench scale (1 t/batch)
Batch-furnace
Pilot plant scale (5 t/batch)
Continuous furnace (pilot plant scale: 6 t/h)

3.Outline of process and result of study


Figure 1 shows the process outline of the continuous melting the pulverized coal.
furnace. The melting furnace has a melting section, basin With the above-described system, even pulverized coal normally
section, and holding section, each of which is separately giving slow combustion rate can be combusted at high rate and
functioned. Each section has pulverized coal - oxygen burner. high efficiency similar with those of liquid fuel such as heavy oil.
The oxygen supplied to the burner is preheated to high The melting section is in shaft shape, where the raw material
temperatures (400-600 C) by an oxygen preheater to combust
O
charged from top of the furnace is directly melted by the burner

Bag filter
Flue gas

Blower
Raw material

Oxygen Burner Open/close damper


generator controller Slide gate

Oxygen preheater Pulverized coal


oxygen burner
Pulverized
coal charge
Pulverized unit
coal tank Tuyere

Nitrogen
generator
Molten steel

Fig. 1 NSR process flow Fig. 2 Pilot plant (6t/h)

41
Clean Coal Technologies in Japan

flame at lower section of the furnace. The melted raw material transmission. Compared with normal arc furnace, the melting
flows through the basin section and enters the holding section. energy was reduced by 40%, achieving high energy efficiency.
The basin section soaks the molten steel. The carbon content of Furthermore, the process achieved highly superior result to the
the molten steel in the basin section can be controlled by conventional process in terms of environmental measures such
injecting powder coke into the furnace. The holding section as the significant suppression of generation of dust (excluding
stores the molten steel for a specified period, and rapidly heats ash in pulverized coal) and of dioxins owing to the control of
the molten steel to about 1,600 C, and then taps the molten steel
O
intrafurnace atmosphere.
by the EBT system. To the basin section and the holding section,
molten steel agitation gas is injected from bottom of the 1600
respective furnaces to enhance the heat transfer from flame to Coke
1400 Oxygen
molten steel and the slag-metal reaction. All the combustion gas
coming from individual sections passes through the melting 1200

Melting energy(Mcal/T)
section, and is vented from the furnace top after being used to
1000
preheat the raw material in the melting section. The raw material
is continuously charged from the furnace top and melted in the 800
Electric power
furnace. The tapping from the holding section is conducted
600
intermittently.
400
The process effectively utilizes the heat transfer characteristics of Pulverized coal
200
oxygen burner, and achieves high efficiency melting. Figure 3
shows the result of comparison of melting energy between the 0
EAF NSR
process and the arc furnace. The electric power (oxygen is also (380Wh/T)
added because it is produced by electricity) is counted to the Fig. 3 Comparison of melting energy
primary energy including loss of power generation and of power

4.Toward practical application


The study team has already completed the design for actual process is a non-power melting technology which is few in the
scale facilities. With the influence of current poor economy in the world, and has a strong advantage of not influenced by electric
electric furnace industry, however, the process has not been power infrastructure, the study team continues to make efforts
brought into practical application. Nevertheless, since the toward the practical applications also in abroad.

Fig. 4 Commercial scale plant (50 t/h)

References
1) Hiroshi Igarashi, Toshio Suwa, Yukinori Ariga, and Nobuaki Kobayashi: ZAIRYO TO PROCESS (Materials and Processes), Vo.12, No.1, p135 (1999)
2) Hiroshi Igarashi, Nobuaki Kobayashi, and Hiroyuki Nakabayashi: Technical Bulletin of Nippon Sanso Corp., (19) pp30-37 (2000)

42
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Liquefaction Technologies)

3A1. Coal Liquefaction Technology Development in Japan


Outline of technology

1.Background of Coal Liquefaction Technology Development


Since the Industrial Revolution, coal has been used as an Development History of NEDOL Process

important source of energy by humankind. Coal consumption Year Articles and others
Three liquefaction
surpassed that of firewood and charcoal for the first time in the processes

latter half of the nineteenth century, making coal the world’s 1979 The Sunshine Project started (July, 1974)
Research on three liquefaction processes started.
major source of energy. In Japan, coal also became the 1980 (1) Solvent Extraction Process (2) Direct Hydrogenation Process (3) Solvolysis Process

predominant energy source in the twentieth century. In the NEDO established (Oct. 1, 1980), succeeding
1981 three liquefaction processes of Coal Technology Development Office.
1960s, however, the presence of coal gradually faded as it was
1982
replaced by easier-to-use oil. It was after the oil crises of 1973
1983 1st interim report (the same as the Joint Council report mentioned below)
and 1978 that coal was thought highly of once again. With the oil (Aug., 1983) The unification of three liquefaction processes recommended.
NEDO set out for conceptual pilot plant planning (three processes and a proposal for their unification)
1984
crises as a turning point, the development of oil-alternative Conceptual design Unification of three processes/development of NEDOL Process Basic concept
of 250 t/d Conceptual design
1985
energy, particularly coal utilization technology, came under the 250 t/d design
-NCOL established (Oct. 1, 1984) preparation

1986 PDU (1 t/d of Sumitomo Metals-Hasaki)-based


spotlight amid calls for the diversification of energy sources. PSU (1 t/d of Nippon Steel-Kimitsu)-based research (design)
started (around 1985).
During that time, liquefaction of coal, which had been positioned 1987 PSU operation research started (1987).

as the strongest oil-alternative energy contender because of its 1988


A 150 t/d pilot plant started. (Downscaled from 250 t/d to 150 t/d.)

huge reserves, was undergoing development in many countries. 1989


150 t/d design

Research in Germany and the United States involved pilot plants 1990
with the capacity to treat hundreds of tons of coal per day. 1991
Review of total project costs toward reduction
(April, 1991, agreed upon at the operation meeting.)
In Japan as well, development of coal liquefaction technology -Kashima Establishment opened (Oct. 1, 1991).
-The ground-breaking ceremony for a pilot plant held (Nov. 25, 1991)Construction
1992 Construction ,
NEDO s Coal Technology Development Office reorganized into CCTC (Oct., 1992).
was being promoted under the Sunshine Project mainly by the Total project costs reconsidered to be clearly defined in value
1993 (Nov., 1992). Set at 68.8 billion yen.
New Energy and Industrial Technology Development The New Sunshine Project costs (1993)
1994
Organization (NEDO). Despite the lag of a decade or so behind
1995
Germany and the United States, slow but steady development Recommendations to the 48th Subcommittee Meeting for Coal Conversion (March, 1995)
1996 The period of research extended for completion (March 31, 1999)
progress led to the successful completion of operations of a 150 -The Research Center inaugurated (June 24, 1995)
-The ground-breaking ceremony for a pilot plant held (July 10,1996)
1997
t/d-scale pilot plant for the liquefaction of bituminous coal in 1998 Operation -Coal-in trial run (Nov. 26-29, 1996, Feb. 25-27, 1997)

with substantial results, thereby drawing equal with Germany and 1998 -Coal-in RUN-1 (March 26, 1997-)

-Coal-in RUN-7 (-Sept. 9, 1998)


the United States as well as establishing state-of-the-art coal
Cleaning,
Total coal-in time of 6,062 hours or 262 days (excluding that for trial runs)
liquefaction technology. Coal-producing countries such as China 1999
etc.
The longest coal-in continuous run time of 1,921 hours

Research on dismantlement
and Indonesia are also strongly interested in the 2000 -Operation completion ceremony held on Sept. 29, 1998.
Removal -Pilot plant operation completion report meeting held
commercialization of coal liquefaction technology, with high 2001
(Dec. 1, 1998) at a Gakushi Kaikan hall.
-Pilot plant operation research completed (March 31, 2000).

expectations for its future development.

2.History of Coal Liquefaction Technology Development in Japan


2.1 Dawning of coal liquefaction technology development in 1940 with the completion of an oil synthesis plant annually
Between around 1920 and 1930, South Manchurian Railway Co., producing thirty thousand tons of coal oil.
Ltd. started basic research on coal liquefaction using the Bergius Under the background of a wartime situation, production of
Process and, around 1935, initiated operation of a bench-scale synthetic oil was continued until the end of World War II.
PDU (process development unit) plant. Based on this research, 2.2 Post-war research on coal liquefaction
a plant annually producing twenty thousand tons of coal oil was Immediately after the war, the U.S. Armed Forces Headquarters
built at Wushun Coal Mine, China, and operated until 1943. In banned research into coal liquefaction, alleging that it was
the meantime, Korean Artificial Petroleum Co., Ltd. succeeded military research. In 1955, coal liquefaction research was
between 1938 and 1943 at its Agochi factory in the continuous resumed at national laboratories and universities. This was not,
operation of a direct coal liquefaction plant capable of treating however, research on coal oil production but the production of
100 t/d of coal. Production of coal oil at both of the above plants chemicals from high-pressure hydrocracking of coal, which was
was suspended at the request of the military to use the plants for continued until around 1975.
hydrogenation of heavy oil or to produce methanol. The Sunshine Project was inaugurated in 1974 on the heels of
At around 1930, besides the direct coal liquefaction method the first oil crisis, encouraging efforts to devise liquefaction
(Fischer Process), the Bergius Process was used as an indirect technology unique to Japan as part of an oil-alternative energy
coal liquefaction method to study coal liquefaction technology development program. Under the Sunshine Project, technological
and to produce synthetic oil. The Fischer Process was development has been undertaken for the three coal liquefaction
introduced into Japan upon its announcement in Germany in processes of Solvolysis, Solvent Extraction, and Direct
1935 and, in 1937, plant construction started in Miike, winding up Hydrogenation to liquefy bituminous coal. R&D of brown coal
43
Clean Coal Technologies in Japan

liquefaction processes has also Solvent Extraction System (PDU)

Solvent hydrogenation technology


NEDOL Process
taken place since the end of 1980. Coal
(Catalyst)

Liquefaction reaction Separation Coal oil


2.3 Amalgamation of three coal Solvent
Solvent
High-performance catalyst (Fe)
450OC,150atm
Hydrogen
liquefaction processes Coal
Solvent hydrogen Liquefaction reaction Separation Coal oil
With the oil crises as an impetus, the Ni-Mo catalyst
(Medium to a little heavy)
Solvent
450 C,170atm O Solvent
practice of coal liquefaction technology Hydrogen

high-performance catalyst technology


Direct Hydrogenation System (PDU)
development was incorporated for Ni-Mo catalyst
High-performance catalyst (Fe)
Solvent hydrogen
further promotion into the Sunshine Coal
Liquefaction reaction Separation Coal oil
(Heavy)
Project based on Japan’s international Solvent
450OC,250atm Solvent Hydrogen
Hydrogen
obligations and the need for a large,
constant supply of liquid fuel; [Referential] EOS Process (U.S.)

Solvent hardening technology


Solvolysis System (PDU)
diversification of energy sources and Ni-Mo catalyst Coal
450OC,140atm Ni-Mo catalyst
Coal Liquefaction reaction Separation Solvent,hydrogen Coal oil
Degree of
development of oil-alternative energy Solvent
dissolution SRC Deashing
Liquefaction
reaction
Separation Coal oil Solvent
Solvent
Solvent Bottom recycle
(Ultra-heavy oil) Hydrogen Hydrogen
held great significance. 450OC150atm
Ash Hydrogen
400OC,150atm
In 1983, NEDO (the New Energy
Development Organization, the Fig. 1 Basic Philosophy of NEDOL Process
present New Energy and Industrial Technology Development (3) Result from Solvolysis Liquefaction Process: For priority acquisition
Organization) assembled the R&D results thus far obtained from the of light oil, it is effective to thicken the circulation solvent.
three bituminous coal liquefaction processes as follows: These three processes were amalgamated on the strength of their
(1) Result from Direct Hydrogenation Process: Under any of certain features into the NEDOL Process.
reaction conditions, the better the catalyst function, the higher the liquid 2.4 Bituminous coal liquefaction technology development (NEDOL Process)
yield rate becomes. Bituminous coal liquefaction technology development is described in
(2) Result from Solvent Extraction Process: Hydrogen offers liquefaction [3A-2].
under mild conditions. 2.5 Brown coal liquefaction technology development (BCL Process)
Brown coal liquefaction technology development is described in [3A-3].

3. Coal Liquefaction in the Future


China, expecting stringency in its oil supply-demand situation for operation concluded in a shift from the research stage to the
sometime in the future, takes an active stance toward the commercialization stage. It seems that commercialization will be
development/adoption of coal liquefaction technology. NEDO, as enhanced particularly through international cooperation with coal-
part of its international cooperation program, installed 0.1 t/d producing countries such as China and Indonesia. In China, not
liquefaction equipment in China in 1982 for subsequent utilization only Japan but also the United States and Germany have embarked
such as in liquefaction tests of Chinese coal, exploration of catalysts on feasibility studies of location with commercialization in mind.
for liquefaction, and human capacity building. Since 1997, at the
Yilan coal
request of China, cooperation has been offered for the Japan (CCUJ-JICA)
implementation of feasibility studies on the location of a coal
liquefaction plant using Yilan coal of Heilongjiang Province. Shenhua coal
U.S. (HTI-USDOE)
Furthermore, a survey entrusted by China estimates Shenhua coal Japan (NEDO) HEILONGJIANG
Harbin
reserves in Shenxi Province/Inner Mongolia Autonomous Region at
MONGOLIA JILIN
as much as 200 billion tons, justifying high expectations for coal as
NEIMONGGOL LIAONING
an inexpensive source of energy. HEBEI
Beijing
It is further considered certain that Indonesia will become a net oil-
importing country in the near future. In 1992, the Indonesian GANSU SHANXI
SHANDONG
QINGHAI NINGXIA HUIZU
government requested cooperation in coal liquefaction research on JIANGSU
SHAANXI HENAN
Indonesian brown coal. In response, NEDO signed in 1994 a ANHUI
HUBEI
memorandum on cooperative coal liquefaction research with the SICHUAN
ZHEJIANG

Agency for the Assessment and Application of Technology of HUNAN


JIANGXI
FUJIAN
Indonesia (BPPT) and began a new round of brown coal liquefaction Kunming
GUIZHOU
TAIWAN
YUNNAN GUANGDONG
technology development that aimed at the realization of commercial GUANGXI ZHUANGZU

plants for Indonesian brown coal.


Coal liquefaction technology development that has continued since Xianfeng coal
Germany(Ruhr Kohle-Nordrhein Westfalen State)
the Sunshine Project was inaugurated in 1974 has now seen plant
Fig. 2 Review of Coal Liquefaction for Commercialization in China

References
1) Sadao Wasaka: "Bulletin of The Japan Institute of Energy", 78 (798), 1999
2) "Development of Coal Liquefaction Technology - A Bridge for Commercialization", Nippon Coal Oil Co., Ltd.
3) Haruhiko Yoshida: "Coal Liquefaction Pilot Plant", New Energy and Industrial Technology Development Organization

44
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Liquefaction Technologies)

3A2. Bituminous Coal Liquefaction Technology (NEDOL)


In charge of research and development: New Energy and Industrial Technology Development Organization; Nippon Coal Oil Co., Ltd.
[Sumitomo Metal Industries, Ltd.; Idemitsu Kosan Co., Ltd.; Nippon Steel Corp.; Chiyoda Corp.; NKK Corp.; Hitachi Ltd.; Mitsui Coal Liquefaction Co., Ltd.;
Mitsui Engineering & Shipbuilding Co., Ltd.; Mitsubishi Heavy Industries, Ltd.; Kobe Steel, Ltd.; Japan Energy Co., Ltd.; Sumitomo Metal Mining Co., Ltd.;
Asahi Chemical Industry, Co., Ltd.; Toyota Motor Corp.; Sumitomo Coal Mining Co., Ltd.; Nissan Motor Co., Ltd.; The Japan Steel Works, Ltd.; Yokogawa
Electric Corp.; and The Industrial Bank of Japan, Ltd.]
Project type: Development of bituminous coal liquefaction technology, and development of NEDOL Process
Period: 1983-2000 (18 years)

Outline of technology

1. Outline of NEDOL Process development 2. Evaluation of NEDOL Process


The conceptual design of a 250 t/d pilot plant (PP) began in Figure 1 shows the progress of coal liquefaction technology since
FY1984. Owing to changes in economic conditions, however, the before World War II, expressed by the relation between the
design of a 150 t/d PP began in FY1988. As a support study to severity of liquefaction reaction and the yield of coal-liquefied oil
the pilot plant, the operational study of a 1 t/d process support in individual generations. As seen in the figure, the NEDOL
unit (PSU) was carried out. Process is competitive with the processes in Europe and the
The 1 t/d PSU, constructed in FY1988 at Kimitsu Ironworks of United States in terms of technology, economics, and operational
Nippon Steel Corp., consists of four stages: coal storage and stability, and thus the NEDOL Process is one of the most
pretreatment, liquefaction reaction, coal liquefied oil distillation, advanced processes in the field, reaching a position to shift to
and solvent hydrogenation. Over the ten-year period from commercialization in the shortest amount of time.
FY1989 to FY1998, the joint study team of Nippon Steel Corp.,
Large

Mitsui Coal Liquefaction Co., Ltd., and Nippon Coal Oil Co., Ltd.
conducted operational studies on 9 coal grades under 72 sets of Third generation
Yield of coal-liquefied oil

conditions. Through the 26,949 hours of cumulative coal slurry


operations, the stability and the overall operability of the NEDOL NEDOL Process
CC-ITSL Process (U.S.A.)
Process were confirmed, and optimization of the process was IGOR+ Process (Germany)
established. Finally, the necessary design data was acquired.
Construction of the 150 t/d PP was launched in 1991 at Kashima First generation Second generation
Steelworks of Sumitomo Metal Industries, Ltd. (Kashima City,
Ibaraki), requiring nearly five years for completion. The PP Processes in the ’40s Processes after the Oil Crisis
Small

consists of five main facilities: the coal preliminary treatment unit,


the liquefaction reaction unit, the coal-liquefied oil distillation unit,
Severe Severity of reaction Mild
the solvent hydrogenation unit, and the hydrogen production unit. Fig. 1 Relation between the severity of liquefaction
reaction and the yield of coal-liquefied oil

Coal preliminary Liquefaction/reaction unit Coal liquefied oil distillation unit


treatment technology Iron-base
catalyst Gas
Separator
Circulation gas compressor Atmospheric
Coal pressure
distillation column
Hydrogen Naphtha
Slurry mixer 170kg/cm2G
(16.7MPa)
Hydrogen Preheating 450@C
compressor furnace High
temperature Kerosene/
Slurry tank separator gas oil distillate
Coal bin

Slurry heat Vacuum


exchanger Liquefaction
reactor distillation
(3 units) column
Heating
furnace
Let-down valve
High pressure Fuel
slurry pump

Separator Hydrogen
Fuel
Preheating
110kg/cm2G furnace
Drying/
pulverizing (10.8MPa)
unit 320@C Residue
Solvent booster
pump
(Hydrogen-donor solvent) Stripper Solvent (Heavy distillate)
hydrogenation
reactor
Fuel
Solvent hydrogenation unit

Fig. 1 Relation between the severity of liquefaction reaction and the yield of coal-liquefied oil
45
Clean Coal Technologies in Japan

3.Features of NEDOL Process


The NEDOL Process is a coal liquefaction process developed core process stages; and
exclusively in Japan. The process has integrated the advantages (4) applicable to a wide range of coal grades, covering from sub-
of three bituminous liquefaction processes (Direct Hydrogenation bituminous coal to low coalification grade bituminous coal.
Process, Solvent Extraction Process, and Solvolysis process),
thus providing superiority in both technology and economics. Catalyst

The advantages of the NEDOL Process include: Liquefaction catalyst Hydrogenation catalyst

(1) attaining high liquid yield under mild liquefaction reaction Catalyst composition Fe (wt%) 48.2 Ni-Mo/ Al2O3
Catalyst composition Fe (wt%)
conditions owing to the iron-based fine powder catalyst and to S(wt%) 51.0 190
Specific surface area (m2/g)

the hydrogen-donating solvent; Other(wt%) 0.8 Micropore volume (ml/g) 0.7


Specific surface area (m2/g) 6.1 Mean micropore size (nm) 14.5
(2) producing coal-liquefied oil rich in light distillate;
Size of pulverized catalyst [D50]( m) 0.7~0.8
(3) assuring high process stability because of the highly reliable

4.Typical reaction conditions of the NEDOL Process


Liquefaction reaction Solvent hydrogenation reaction
Temperature 450 C O
Slurry concentration 40wt%(dry coal basis) Temperature 320 C O
Gas/solvent ratio 500Nm3/t
Pressure 170kg/cm2 G Slurry retention time 60min Pressure 110kg/cm2 G Hydrogen concentration in recycle gas 90vol%
Kind of catalyst Iron-base fine powder catalyst Gas/slurry ratio 700Nm3/t Kind of catalyst Ni-Mo-Al2O3
Added amount of catalyst 3wt%(dry coal basis) Hydrogen concentration in recycle gas 85vol% LHSV 1 hr(-1)

5. Objectives and current progress of the pilot plant

Objective of the development Target Achieved result

For the operation standard coal, 50 wt% or higher With the operation standard coal, there were attained 51 wt%
1. Yield of coal-liquefied oil
yield of light to medium oils, and 54 wt% of higher total yield. yield of light to medium oils, and 58 wt% of total yield.

2. Slurry concentration 40-50 wt% of coal concentration in slurry. Stable operation was achieved at 50 wt% of coal concentration in slurry.
3. Added amount of catalyst 2-3 wt% (dry-coal basis) of added amount of iron sulfide-base catalyst. Operation was conducted in a range from 1.5 to 3 wt% of added amount of iron sulfide-base catalyst.
4. Continuous operation time 1,000 hours or more for the operation standard coal. Continuous operation of 80 days (1,920 hours) was achieved with the operation standard coal.
5. Range of applicable coal grades Three coal grades or more. Operation was conducted with wide range of degree of coalification: namely, Adaro coal, Tanitohalm coal, and Ikejima coal.

6. Research and development schedule of the NEDOL Process pilot plants


(Fiscal year)
~1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998

250 t/d PP design 150 t/d PP design Construction Operation

Core technology research and support study

7. Result of the research and development


All the acquired data including the PP data, the basic research data, developed materials and new processes are expected to
and the support study data were summarized in a technology significantly influence development in other industries.
package preparing for practical application. At the
Development and Assessment Committee meeting Central control building
Solvent hydrogenation unit
for Bituminous Coal Liquefaction Technology in the
Assessment Work Group of the Industrial
Technology Council, held on December 22, 1999, the Fuel unit Liquefaction reaction unit

NEDOL Process was highly evaluated: "The NEDOL


Coal-liquefied oil distillation unit
Process is at the highest technology level in the Coal preliminary treatment unit

world, and has reached the stage where worldwide


Hydrogen production unit
diffusion is expected." Thus, the development of coal
Storage unit
liquefaction technology in Japan has already exited
the research and development stage and entered the
practical application stage. Furthermore, the Fig. 3 Total view of NEDOL Process pilot plant (150 t/d)

References
1) Sadao Wasaka: "Bulletin of The Japan Institute of Energy", 78 (798), 1999
2) "Development of Coal Liquefaction Technology - A Bridge for Commercialization", Nippon Coal Oil Co., Ltd.
3) Haruhiko Yoshida: "Coal Liquefaction Pilot Plant", New Energy and Industrial Technology Development Organization

46
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Liquefaction Technologies)

3A3. Brown Coal Liquefaction Technology (BCL)


In charge of research and development: New Energy and Industrial Technology Development Organization;
Kobe Steel, Ltd.; Nissho Iwai Corp.; Mitsubishi Chemical Corp.; Cosmo Oil Co., Ltd.; Idemitsu Kosan Co., Ltd.;
and Nippon Brown Coal Liquefaction Co., Ltd.
Project type: Development of Brown Coal Liquefaction Technology; Development of Liquefaction Basic Technology;
Coal Liquefaction International Cooperation Project; and other projects
Period: 1981-2002 (21 years)

Outline of technology

1.Background and process outline


Economically viable global coal reserves are expected to total As shown in the figure, the BCL process has four stages: the slurry
about one trillion tons, about half of which is comprised of low- dewatering stage where the water is efficiently removed from low-
grade coal such as sub-bituminous coal and brown coal. Coal grade coal; the liquefaction stage where liquefied oil production
has a larger ratio of reserves to production (R/P) than that of oil yield is increased by using a highly active limonite catalyst and the
and natural gas. For full-scale effective utilization of coal, bottoms recycling technology; the simultaneous hydrogenation
however, the effective use of low-grade coal is critical. Low- stage where the heteroatoms (sulfur-laden compounds, nitrogen-
grade coal contains a large amount of water but has an laden compounds, etc.) in the coal-liquefied oil are removed to
autoignition property in a dry state compared with bituminous obtain high quality gasoline, kerosene, and other light fractions;
coal and other higher grade coals. Consequently, brown coal and the solvent deashing stage where the ash in coal and the
liquefaction technology development progressed aiming to added catalysts are efficiently discharged from the process
contribute to a stable supply of energy in Japan by converting the system.
difficult-to-use low-grade coal into an easy-handling and useful In Asian countries, economic growth steadily increases energy
product, or by producing clean transportation fuels such as demand, and countries possessing low-grade coal resources, such
gasoline and kerosene from the low-grade coal. as Indonesia, anticipate commercialization of the technology.

Liquefaction stage In-line hydrotreatment stage


Sulfur
Hydrogen Sulfur
recovery unit
Recycle gas

Slurry dewatering stage Recycle gas Off gas


purification unit Product gas
(Fuel gas)

Coal Reactor
(Raw brown coal) Hydrogenated
Water light oil

Evaporator
Fixed bed
hydrogenation Distillation column
reactor

Hydrogenated
medium oil
Preheater Solvent deashing stage
Slurry charge pump
Settler

Catalyst supply unit CLB (heavy oil)


separator

CLB recycle Sludge


(Boiler fuel)
CLB
Solvent recycle
DAO (deashed heavy oil) recycle

Fig.1 Flowchart of BCL

47
Clean Coal Technologies in Japan

2.Development objectives and technology to be developed


A pilot plant (refer to the photograph) study
conducted under the governmental cooperation of
Japan and Australia investigated the subjects
listed below.
(1) Achieving high liquefied oil production yield:
50% or more
(2) Achieving long-term continuous operation:
1,000 hours or more
(3) Achieving high deashing performance: 1,000
ppm or less
(4) Establishing a new slurry dewatering process
Through four years of operation and study (1987-
1990), all of the above targets were achieved.
Furthermore, scale-up data necessary to
construct commercial liquefaction plants and
expertise on plant operation was obtained
through pilot plant operation.
Fig.2 50t/d Pilot plant (Australia)
During the study period, (the 1990s), however, a
state of low oil prices and stable oil supplies existed worldwide such as crushing property; a method to maintain catalytic activity
owing to a stable international oil supply and demand situation. through the bottoms recycling technology; a simultaneous
Thus, further improvements in the economics of the coal hydrogenation technology which significantly improves the quality
liquefaction process were requested, while cleaner liquefied oil of coal-liquefied oil; and various improvements for increasing
was demanded owing to increased environmental concerns. operational reliability. Through the development work, the study
Accordingly, the study team constructed a bench-scale plant (0.1 established the improved BCL process (Improved Brown Coal
t/d) in the Takasago Works of Kobe Steel, Ltd. to conduct a study Liquefaction Process, refer to the flowchart on the preceding
for improving the process. The study developed: a limonite page) that significantly improves the economics, reliability, and
catalyst which has extremely high activity compared with existing environmental compatibility of the brown coal liquefaction
liquefaction catalysts, and which has superior handling properties process.

3.Progress and result of the development


On the basis of a memorandum on cooperative coal liquefaction engineers through instruction and supply of liquefaction testing
research between the Agency for the Assessment and equipment.
Application of Technology of Indonesia and New Energy and In 1999, the study team selected three candidate sites for the
Industrial Technology Development Organization, the study team liquefaction plant in Indonesia, and carried out a feasibility study
carried out surveys and liquefaction tests of the low-grade coal in on coal liquefaction, including an economic evaluation. The
Indonesia beginning in 1994, in addition to screening of feasibility study revealed that coal liquefaction would be
candidate coals for liquefaction. Furthermore, the team economically feasible only if the price of oil did not decrease.
endeavored to increase the technical abilities of the Indonesian

4.Issue and feasibility of practical application


Supported by steady economy growth, Asian countries exhibit the energy security of Japan, expectations are high for the
rapidly increasing energy demand. Although currently a net oil- practical application of brown coal liquefaction technology
exporting country, Indonesia is expected to become a net oil- utilizing unexploited low-grade coal. From a medium-term
importing country by around 2010. Since the stable supply of viewpoint, the possibility of practical application of the technology
energy from Asian countries to Japan significantly contributes to is large.

References
1) Shunichi Yanai and Takuo Shigehisa: CCT Journal, vol.7, p 29 (2003)
2) Report of the Result of the International Coal Liquefaction Cooperation Project
(Cooperative Study of Development of Low Grade Coal Liquefaction Technology) (2003)

48
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Liquefaction Technologies)

3A4. Dimethylether Production Technology (DME)


In charge of research and development:DME Development Co., Ltd. (The company was established in 2001 in collaboration of following-listed
ten companies aiming to establish the technology of direct synthesis of DME.), JFE Holdings Co., Ltd.; Nippon Sanso Corp.;
Toyota Tsusho Corp.; Hitachi Ltd.; Marubeni Corp.; Idemitsu Kosan Co., Ltd.; INPEX Corporation; TOTAL S.A.(France);
LNG Japan Co., Ltd.; and Japan Petroleum Exploration Co., Ltd.(JAPEX)
Project type: National Grant project of "Development of Technology for Environmental Load Reducing Fuel Conversion" of the
Agency of Natural Resources and Energy of the Ministry of Economy, Trade and Industry
Period: 2002-2006 (5 years)

Outline of technology

1.Background and process outline


Dimethylether (DME) is a clean energy source of low Currently DME is produced by dehydration of methanol at
environmental load, generating no sulfur oxide or soot during amount of about 10 thousand tons a year in Japan, and 150
combustion. Owing to the non-toxicity and easy liquefaction thousand tons a year in the world. The main use of DME is spray
properties, DME is easy in handling, thus it can be used as propellant. If the supply of DME is available in large amount at
domestic-sector fuel (substitute for LPG), transportation fuel low price, DME is expected to be used as fuel in wide fields
(diesel vehicle, fuel cell automobile), power plant fuel(thermal owing to the above-described superior properties.
plant, cogeneration plant, fuel cell), and raw material for chemical
products.

2.Development object and technology to be developed


The object of the study is the development of direct synthesis
process of DME from syngas (mixed gas of H2 and CO), (1) 3CO+3H2 CH3OCH3+CO2
(reaction (1)). (2) CO+2H2 CH3OH
The DME production through the dehydration of methanol, (3) 2CH3OH CH3OCH3+H2O
(reaction (3)), is the existing technology. The plant scale under
actual operation, however, is rather small, and the scale up is an
100
issue to produce DME commercially for fuel service. In addition,
H2+CO conversion [%]

the equilibrium conversion of the methanol synthesis reaction (2) (1) 3CO + 3H2 CH3OCH3 + CO2
80
is relatively small as show in Fig.1.
On the other hand, in the direct DME synthesis reaction (1)
because the limitation of equilibrium of methanol synthesis is 60
avoidable the conversion is higher than that of methanol
synthesis. 40
The reaction formulae relating to the direct DME synthesis are
given below. The equilibrium conversion of methanol synthesis (2) CO + 2H2 CH3OH
20
and of direct DME synthesis is given in Fig. 1.
Since the direct synthesis gives maximum conversion at
H2/CO=1 of the syngas composition, the process is suitable for 0.0 0.5 1.0 1.5 2.0 2.5 3.0
the syngas produced from coal gasification (H2/CO=0.5-1). The
H2/CO ratio [-]
targets of the development study include the following.
<1.DME production rate: 100 ton/d or more, Syngas total Fig. 1 Equilibrium conversion (280 C, 5Mpa)
O

conversion: 95% or more, DME selectivity: 90% or more, DME


purity: 99% or more
2. Establishing scale up technology
3. Optimization of total system
4. Establishing stable plant operation >

49
Clean Coal Technologies in Japan

3.Progress and result of the development


The development of direct synthesis process has been led by with the aid of the Ministry of Economy, Trade and Industry. The
JFE (ex-NKK). The first step is the search of direct synthesis construction of demonstration plant finished in November 2003,
catalyst. The second step is the small bench plant (5 kg/d). The and the operation is scheduled to start at the end of 2003 to
third step is the pilot plant (5 ton/d) 1)2) constructed with the aid of conduct five runs of long period continuous operations (2 to 3
the Ministry of Economy, Trade and Industry. The fourth step is months) until 20063).
the demonstration plant (as large as 100 ton/d) constructed also

Photo 1 5 ton/d pilot plant Photo 2 100 ton/d demonstration plant

4.Issue and feasibility of practical application


DME is already utilized as a fuel at inland area of China in small the future, however, they are supposed to switch the raw material
scale. In Japan, activities toward the practical application of DME to coal which is larger in reserves quantity than natural gas.
as fuel are in progress at: DME International Co., Ltd. which was In natural gas case, the CO2 obtained from CO2 separation
established by the same ten companies of DME Development column is returned to syngas generation furnace, but the same is
Co., Ltd. aiming at the study for Commercialization of DME; released to atmosphere in coal case. When the CO2 storage
Japan DME Co., Ltd. which was established by four companies, technology in long term is established in future, the coal based
namely, Mitsubishi Gas Chemical Co., Inc., Mitsubishi Heavy process can provide purified CO2 without any additional facilities.
Industries, Ltd., JGC, and Itochu Corp.; Mitsui & Co., Ltd. and Also in western world, DME draws attention in wide fields as a
Toyo Engineering Corp.; (the last two adopted the methanol new fuel. They however, expect mainly to use in diesel vehicles
dehydration process). These activities aim to supply DME to fully utilize the advantageous characteristic of no-generation of
product in 2006. All of them plan to use natural gas as the raw soot.
material, because natural gas requires small initial investment. In

Purge gas

CO2 CO2 Non-reacted gas

Natural gas
DME
Coal mine methane

Coal

Oxygen

Steam

Liquid/gas separator

Reaction condition
250~280OC
3~7Mpa

CO,CO2,H2
Methanol
Synthesis gas generation furnace Gas purification column DME synthesis reactor CO2 separation column DME purification column

Fig. 2 Typical process flow diagram of DME direct synthesis plant from coal or natural gas

References
1) Tsunao Kamijo et al.: Lecture papers of The 8th Coal Utilization Technology Congress, Tokyo 1998, pp.194-205
2) Yotaro Ono et al.: Preprint for the lectures of the 30th Petroleum and Petrochemical Discussion Meeting, Tokyo 2000, pp.26-29
3) Yotaro Ono: Japan DME Forum Workshop 2002, Tokyo, pp.113-122

50
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Pyrolysis Technologies)

3B1. Multi-Purpose Coal Conversion Technology (CPX)


In charge of research and development: Center for Coal Utilization, Japan; Nippon Steel Corporation;
NKK Corporation; Kawasaki Steel Corporation; Sumitomo Metal Industries, Ltd.; Kobe Steel Ltd.; Ube Industries, Ltd.;
Idemitsu Kosan Co., Ltd.; Nippon Steel Chemical Co., Ltd.
Project type: Subsidized coal production/utilization technology promotion
Period: 1996-2000 (5 years)

*Coal Flash Pyrolysis Process: CPX stands for Coal Pyrolysis suffixed with X meaning diversified products.

Outline of technology

1.Technological features
In an attempt to further expand versatile utilization of coal, this 4. Efficient separation of coal ash
project is intended to develop a multi-purpose coal conversion - Coal ash is discharged from the gasifier as molten slag and
technology excellent in efficiency, economy, and environment- then granulated with water.
friendliness, mainly for the purpose of manufacturing medium- 5. Diversified utilization of products available
calorie gas as industrial fuel and liquid products as raw materials - Among products, gas can be used as industrial fuel, liquid (light
for chemicals. oil/tar), as raw materials for chemicals, solid char, as fuel or a
The features of this process are as follows: reducer, and slag, as an ingredient of cement.
1. Moderate operational conditions - The heating value of gas produced from the process is as high
- The pyrolysis reactor works at a temperature of as low as 600- as about 3,500kcal/Nm3.
950 C.
O
- The yield of gas and liquid (light oil/tar) combined is 70% or
- The reaction pressure of lower than 1Mpa is much lower than more of coal input.
several to tens of Mpa at which the coal liquefaction and hydro- 6. Controllable yield of products
gasification processes operate. - A change in pyrolysis temperature (600-950 C) or coal kind
O

2. High overall thermal efficiency allows product yields to be correspondingly changed.


- Flash pyrolysis of coal is combined with partial recycle of
generated char to gasify more char, thereby improving the
thermal efficiency of the process.
3. Workable with multiple kinds of coal
- The dependence on cheaper classes of coal from sub-
bituminous to highly volatile bituminous coal for the main material
enables gas/tar to be obtained in large quantities.

Heat recovery

Cyclone
Tar cooler

Scrubber Gas purification Gas

Coal Pyrolysis
Char
reactor hopper

Crushing/drying
Char heat Decanter
recovery

Char gasifier Separator Tar


Steam

Char
Slag

Fig.1 Process Flow Sheet

51
Clean Coal Technologies in Japan

2.Summary of technology
This process is characterized by higher overall thermal efficiency
solid product (char) separated at the cyclone is recycled to the
achieved with a compact low-pressure char/oxygen gasification
char gasifier and the remaining is offered as a product after heat
system, which combines flash pyrolysis of coal and partial
recovery. Heat is recovered from the gas containing pyrolysis
recycle of pyrolysis product char to use sensible heat of char
products until it cools down to about 350 C through indirect heat
O

gasification product gas as a heat source for flash


exchange with thermal oil while tar passes the venture
heating/pyrolysis reaction of pulverized coal (Fig.1). The
scrubber/tar cooler to be recovered. Pyrolysis gas is made
entrained-bed coal flash pyrolysis has been developed as a
available for use as industrial-purpose fuel gas after purification
process which not only produces more high value-added gas and
such as through light oil (BTX) recovery and desulfurization.
liquid (tar and oil) possessing a coke oven gas (COG)-equivalent
At the pilot plant (Photo 1) built within Yawata Works of Nippon
heating value but also supplies heat necessary for pyrolysis.
Steel Corp., tests were conducted mainly with a view to the
Pulverized and dried coal (of about 50 m in grain size) is blown
evaluation/verification of process component/total system
into the pyrolysis reactor and mixed with hot gas at 600-950 C O

technologies to establish the technological basis for


and several atm, with 2 seconds as its reaction time, to be flash-
commercialization as well as obtain data which would help
heated/pyrolyzed. In terms of heat necessary for pyrolysis
design an actual plant (1,000t/d) and evaluate its economy. In
reaction, part of pyrolysis product solid char is recycled to the hot
two years from 1999, it was test-run 10 times in all, achieving a
gas generation section (char gasifier) to be partially oxidized by
maximum 210-hour stable continuous operation. During the
oxygen and steam, thus allowing an about 1,500-1,600 C stream
O

time, the aforementioned features were verified, assuring the


of gas mainly composed of CO and H2 to generate so that
controllability of products at a pyrolysis temperature (Fig.2)
sensible heat of the gas is used for the supply of such heat. The
before the completion of process data taking.
pyrolysis reactor employs an up-flow system where the hot gas
generated at this gasifier is fed from the lower part of the reactor
and, after pyrolysis coal is mixed, leaves the system at the
reactor’s upper part together with pyrolysis products. Part of a

Photo 1 Full View of Pilot Plant


Fig. 2 Relationship between Pyrolysis Product Yield and Pyrolysis Temperature
PDU:7t/d test equipment

References

1) Hiroyuki Kozuru et al.: Advanced Clean Coal Technology Int’l Symposium (2001)
2) Masami Onoda et al.: 10th Annual Conference on Clean Coal Technology abstracts (2000)
3) Shigeru Hashimoto et al.: Pittsburgh Coal Conference (2000)

52
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Pyrolysis Technologies)

3B2. Coal Flash Partial Hydropyrolysis Technology


In charge of research and development: The Center for Coal Utilization, Japan; the New Energy and Industrial
Technology Development Organization; the National Institute of Advanced Industrial Science and Technology;
Nippon Steel Corporation; Babcook Hitachi K.K.; Mitsubishi Chemical Corporation
Project type: Subsidized coal production/utilization technology promotion project
Period:1. Coal utilization next-generation technology development survey/1996 through1999 (4 years)
2. Coal utilization commercialization technology development/2003 through 2008 (6 years)

Outline of technology

1.Objective of technology
Clean Coal Technology-related technology development having a be evolved such as into Integrated Gasification Combined-Cycle
perspective of a single industry in pursuit of a single product is (IGCC) power generation, indirect liquefaction (GTL), and
reaching its limits in terms of efficiency and economy, calling the chemicals while co-producing light oil as chemicals and fuel.
necessity to develop such innovative technologies as could The realization of a coal-based cross-industrial composite project
completely change what energy and material production should (led by electric power/chemistry/steel) with this technology as its
be. core will hopefully bring a dramatic improvement to total energy
Coal Flash Partial Hydopyrolysis Technology is a technology utilization efficiency.
which causes rapid reaction to pulverized coal under high
pressure (2-3Mpa) and in a moderate hydrogen atmosphere to
highly efficiently obtain, from one reactor, synthetic gas easy to

2.Outline of technology
Fig. 1 shows a total process flow of this technology. At the partial concentration (H2 in hot gas and recycle H2 combined). At that
oxidation section of a coal flash partial hydropyrolsyis reactor, time, hot gas from the partial oxidation section also functions as a
pulverized coal and recycled char are gasified with oxygen and source of the reaction heat required at the reforming section. At
steam at a pressure of 2-3MPa and at a temperature of 1,500- the reforming section, a hydrogenation reaction adds H2 to
1,600 C to give hot gas mainly composed of CO and H2. At the
O
primary pyrolysis, such as tar released from pulverized coal,
reforming section directly connected through a throat to the changing heavy tar-like matter to light oil. The gas, light oil, and
partial oxidation section, pulverized coal is injected together with char produced at the partial hydropyrolysis reactor follow a
recycled H2 into the hot gas stream from the partial oxidation process where, after char separation at the cyclone and
section to complete the reforming reaction (partial hydropyrolysis) subsequent sensible heat recovery, synthetic gas (syngas)
in a moment under the condition of 2-3MPa in pressure, 700- should be formed by way of oil recovery, desulfurization, and
900 C in temperature, and about 30-50% in hydrogen
O
other gas purification processes. Part of syngas is converted into

Decarboxylation Shift conversion to H2

Heat Gas
Syngas Chemicals IGCC fuel
recovery purification

Reforming section
Coal reforming reaction
GTL fuel City gas
Heat Gas
H2 concentration 30-50%

Heat Coal
Coal Partial Char Light oil
hydropyrolysis reactor

Hot gas
Partial oxidation section Light oil Fuel for
Chemicals power generation

Steam

Slag

Fig. 1 Process Flow

53
Clean Coal Technologies in Japan

H2-rich gas in the course of shift reaction and decarboxylation required at the reforming section, providing high energy
(CO2 recovery) and, after pre-heated via heat exchange, recycled conversion efficiency.
to the partial hydropyrolysis reactor’s reforming section. A final 2. Flexible productivity: The reforming section temperature as
syngas product is characterized by its main composition of H2, well as the amount of hydrogen injected can be controlled so as
CO, and CH4 as well as high hydrogen contents at H2/CO 1 and to freely change the gas/oil composition and output ratio, thereby
used as source gas of IGCC, GTL, and chemicals. Light oil is flexibly responding to consumers’ needs.
mainly composed of aromatic compounds with 1-2 rings such as 3. Economy: For the purpose of syngas production, gas
benzene and naphthalene, finding its application as chemicals or production cost may be reduced through its deduction by co-
fuel for power generation. produced high value-added oil.
This technology is roughly featured as follow:
1. High-efficiency: The sensible heat of hot gas generated at the
partial oxidation section is effectively used as a source of heat

3.Progress status of development


1) Basic partial hydropyrolysis test (1996 through 1999, 1kg/day) 3) Pilot plant test (2003 through 2008, 20t/day)
Using a small-scale test unit, the pyrolysis behavior of coal under Tests are conducted, using a pilot plant having its thermally self-
target conditions of this technology was reviewed, confirming that supportable reactor together with other ancillary process units, to
the hydropyrolysis of primary tar released from flash have forecasts for a demonstration unit (up to 1,000t/day) as the
heating/pyrolysis reaction of coal successfully proceeded. next step.
2) Process development unit (PDU) test (2000 through 2003,
1t/day *NSC in-house research)
Using a reforming/partial oxidation-integrated PDU test unit, the
basic performance of a partial hydropyrolysis reactor as the core
of this technology was evaluated, clarifying the reaction in the reactor.

Table 1 Development Subjects for Pilot Plant Tests

Technology to be developed R&D items

Verification of the reaction - Quantification of partial hydropyrolysis reactor reaction


in the partial hydropyrolysis reactor/ - Establishment of reactor conditions for optimum transition zone formation
establishment of reactor control technology - Establishment of high-efficiency gasification (partial oxidation section) operational conditions

- Establishment of technology to separate/recover char from gas


Development of process/factor technologies
- Establishment of technology to recover heat from gas co-existent with oil

- Establishment of long-hour continuous operation technology


Total system evaluation, etc.
- Establishment of a scale-up approach for demonstration unit design

Table 2 Development Schedule

2003 2004 2005 2006 2007 2008

Pilot plant test

Design/production/construction works

Studies by testing

Studies by disassembly

Assistant studies

References
1) H. Shimoda et al, 10th Annual Conference on Clean Coal Technology lecture collection, p296, 2000
2) H. Yabe et al, 2nd Japan-Australia Coal Research Workshop Proceedings, p257, 2002

54
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Powdering, Liquefaction, and Common Use Technologies)

3C1. Coal Cartridge System (CCS)


Outline of technology

1.Outline of system
The CCS (Coal Cartridge System) is a system where, on behalf from 1985, to demonstration tests at manufacture/supply and
of medium-/small-lot consumers using several thousands of tons combustion bases, in an attempt to establish the reliability of
of coal a year, for whom it is difficult to import overseas coal CCS as well as coal blending and suitable quality requirements
constantly for themselves, overseas coal is collectively imported for CCS standard coal production. As a result, the first Japanese
and blended into qualities suitable for each such consumer to be CCS center (with a capacity to produce 200 thousand tons a
supplied as pulverized coal. year) was built in 1991 and then 2 CCS coal-dedicated boilers
This technology was subjected, under a 3-year program starting started operation.

2.Characteristics of system 3.Technical data


Common systems of pulverized coal firing, before burning the coal Attributes of CCS coal in general are shown in (Table 1)
stored at its stockyard, pulverize it with a mill for the supply to a (Table 1) Attributes of CCS Coal in General
boiler, but in CCS, after coal is pulverized at a production/supply Brand Referential control A B C
facility, all processes are to be completed within a closed system Raw coal for mixture 3 kinds 3 kinds 2 kinds
of gaseous-phase carriage, from loading onto tank lorries to Total moisture Wt% AR 2.9 2.8 2.7
Heating value kcal/kg * 6490 6480 6490
deacquisition to consumers’ coal silos and then supply to boilers.
Moisture Wt% dry 0.0 0.0 0.0
This not only eliminates the problem of coal dust scattering,
Ultimate
analysis

Ash Wt% dry 12.1 12.4 12.1


thereby keeping the environment clean, but also enables smooth Volatiles Wt% dry 39.6 39.5 35.6
operation to be realized through easier control of powder flows Fixed carbon Wt% dry 48.3 48.1 50.3
and, therefore, fluctuations in boiler loads. Fuel ratio 1.22 1.22 1.41
Carbon Wt% daf 80.30 80.00 82.00
In behalf of consumers, this also advantageously requires no mill
Proximate

Hydrogen Wt% daf 5.80 5.80 5.90


analysis

installation, dispenses with a coal yard since coal can be stored in a Nitrogen Wt% daf 1.60 1.50 1.50
silo, and lessens equipment investment due to the compact equipment Oxygen Wt% daf 11.80 12.40 10.50
configuration, thus leading to labor saving and the better environment. Sulfur Wt% daf 0.48 0.47 0.45
CCS is, as mentioned above, a coal utilization system of improved Total sulfur Wt% dry 0.45 0.43 0.41
Grain size -200mest dry 84.5 78.9 83.50
coal handling with a closed powder carriage system of pulverized coal.

4.Process flow
(Fig.1) shows a flow sheet and system outline of the CCS coal Pulverized coal collection bag filter

production/supply facility.
Screw conveyor

Raw coal bunker

Product Product Product Product


silo silo silo silo
Conveyor

Mill supply
hopper

Raw coal hopper Magnetic Table feeder


separator
Volumetric Chain conveyor
coal feeder

Pulverizer Truck scale

Fuel gas Air heater Seal gas


Kerosene blower
Gas cooler
Recycle gas blower
Recycle gas line
Fuel air blower
Cooling tower
Industrial water
Nitrogen generator
tank
tank

Outline of equipment 4 Bag filter 67,500Nm3/Hx1 unit


1 Raw coal hopper 20m3x1 unit 5 Product silo 680m3x4 units
2 Raw coal bunker 400m3/Hx2 units 6 Truck scale 4 units
3 Pulverizer 25t/Hx2 units 7 Nitrogen generator 350Nm3x1 unit

(Fig.1) CCS Coal Production/Supply Facility


55
Clean Coal Technologies in Japan

3C2. Coal Slurry Production Technology


Outline of technology

1.Outline of coal slurry


Since coal is a solid material with some problem, requiring more spontaneous firing or dust scattering and can advantageously be
complex handling than a fluid does, environmental measures handled as an easy-to-treat liquid. Conventional coal slurry using
against dust, and spacious land for a coal yard, its slurry form no additive can be piped but, due to its water contents of about
has been noted as a means to make heavy oil-comparative, 50%, is poor in long-run stability, requiring dehydration before firing.
clean use of coal. Coal slurry fuel is found as COM (coal oil High-concentration CWM can now, as a result of studies on the
mixture) prepared by adding heavy oil to coal to give slurry, aside particle size distribution of coal and a dispersant and other additives
from CWM (coal water mixture), a mixture of coal and water. development, be kept fluid as well as stable even if less water is
COM, a combination of coal and heavy oil convenient for burning, added and, therefore, directly burnt without being de-watered. Only
was earlier than CWM to be technically reviewed but failed to a slight amount of additives added realize stable coal-water slurry in
prevail after all, rather bottlenecked by the necessity of heavy oil. which coal particle of a certain size distribution are uniformly
CWM is a mixture of water and coal, raising no problem of dispersed with their weight concentration of about 70%.

2.Characteristics of high-concentration CWM


Typical characteristics of high-concentration CWM (Chinese coal 3) Particle size distribution
CWM) are shown in (Table1) below. For higher concentration/stability of CWM, pulverized coal sizes
should preferably be distributed over a wide range rather than
(Table 1) Characteristics of High-Concentration CWM
sharply distributed. Ordinary particle sizes used are roughly as
Coal concentration (wt%) 68~70
Higher heating value (kcal/kg) 5,000~5,200 shown in (Table 2).
Lower heating value (kcal/kg) 4,600~4,800
(Table 2) Grain Size Distribution of High-Concentration CWM
Apparent consistency (mPa-s) 1,000
Specific gravity(-) 1.25 Maximum grain size 150~500 m
Ash content (wt%) 6.0 Average grain size 10~20 m
Sulfur content (wt%) 0.2 Grains of 74 m or less 80% or more
Grains of 200 mesh or less (%) 80~85 Fine grains of several micrometers or less Around 10%

1) Coal type 4) Rheological characteristics


As a general trend, high-carbonization, low-inherent moisture CWM’s fluidity has characteristics of a non-Newtonian fluid but
(about 5% or less in approximate analysis), and less-oxygen can be construed as a near-Bingham fluid’s. The fluidity
content (about 8% or less in ultimate analysis) coal is suitable for characteristics also changes, depending upon, such as the coal
high-concentration CWM. kind, concentration, additive, and flow state. The apparent
2) Additives viscosity is roughly 1,000mPa-s (at room temperature and shear
Additives consist of dispersants and stabilizers. A dispersant speed of 100/s).
functions to disperse coal particles into slurry, using electrostatic 5) Heating value
repulsion effects or steric repulsion effects and sodium sulfonate of The heating value depends upon that of coal used. An average
naphthalene, polystyrene, polymethacrylate, polyolefine, and the like lower heating value is 4,600-4,800kcal/kg.
is used here. Additives including CMC and xanthan gum are used to
prevent coal particles in slurry from settling for stabilization.

3.Manufacturing process of high-concentration CWM


Production of high-concentration Reception/storage of feed coal
CWM can be achieved by Smashing
pulverizng coal into a particle
size distribution suitable for Hot wet smashing
CWM, selecting correct additives Cold wet smashing Coal smashing and mixing Dry smashing
with water/additives to be
(a dispersant and stabilizer), and done within a pulverizer
De-watering
appropriately blending coal,
Smashed coal/water/additives mixing Smashed coal/water/additives mixing
water, and additives to
manufacture high-concentration,
Enhancement of mixing
low-viscosity, high-stability, and
CWM storage
good-quality CWM. A block flow
CWM shipment
of CWM manufacturing process
is shown in Fig.1. (Fig.1) CWM Manufacturing Process Coal Water Mixture (CWM)
56
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Powdering, Liquefaction, and Common Use Technologies)

3C3. Briquette Production Technology


Outline of the technology

1.Background
The global warming issue caused by CO2 and other substances To this point, the briquette production technology is an
has become world concern in recent years. To protect forestry environmental countermeasure technology, or a clean coal
resource as a major absorbent of CO2, control of ever-increasing technology, providing the stable supply of briquettes to contribute
deforestation along with the increase in consumption of wood fuel to the prevention of flood damage and the conservation of
such as firewood and charcoal is an urgent issue. Thus, the forestry resource.
development of substitute fuel for charcoal is emphasized.

2.Carbonized briquettes
(1)Process outline (2)Carbonization stage
Process for producing briquettes by coal carbonization has the The raw material coal (10% or lower surface water content, 5-50
carbonization stage and the forming stage. Figure 1 shows the mm of particle size) is preliminarily dried in the rotary drier. The
basic process flow. gas leaving the drier passes through multi-cyclone to remove
The carbonization stage has the internal heating low temperature dust before venting to atmosphere. Figure 2 shows the cross
fluidized bed carbonization furnace (about 450 C of carbonization
O
sectional view of the internal heating low temperature fluidized
temperature) to produce smokeless semicoke containing about bed carbonization furnace which performs most efficient
20% of volatile matter. The carbonization furnace has a simple carbonization of semicoke while retaining about 20% of volatile
structure having no perforated plate and agitator so that the matter in the semicoke.
operation and the maintenance of the furnace are easy. The preliminarily dried
In the forming stage, the smokeless semicoke and auxiliary raw raw material coal is
materials (hydrated lime and clay) are thoroughly mixed at a charged to the middle
predetermined mixing ratio. After pulverizing, the mixture is section of the furnace,
blended with a caking additive while adding water to adjust the and is subjected to
water content of the mixture. The mixture is kneaded to fluidization carbonization.
uniformize the distribution of caking additive, and to increase the The product semicoke is
viscosity to attain an easy-forming condition. Then the mixture is taken out from top of the
introduced to the molding machine to prepare briquettes. The furnace together with the
briquettes are dried and cooled. carbonization gas. The
semicoke is separated
from the carbonization
gas by the primary cyclone
and the secondary cyclone.
After cooled, the semicoke
Raw Coal Fig. 2 Cross sectional view of carbonization furnace
is transferred to the
stockyard, and the carbonization gas is supplied to the
Drying
combustion furnace lined with refractory, where the carbonization
Coalite
gas is mixed with air to combust. The generated hot gas is
Crushing Cyclon
introduced to the raw material coal drier and to the succeeding
Carbonizing briquette drier to use as the drying heat source of preliminary
Desulfurizer
Binder
heating of the raw material coal and the drying heat source of the
Water formed oval briquettes.
Kneading
Mixing (3)Forming stage
The semicoke (Coalite) produced in the carbonization stage is
Briquetting
the briquette raw material containing adequate amount of volatile
Briquette
matter, small amount of ash and sulfur, and emitting no smoke
Drying and no odor. The semicoke as the main raw material is mixed
with hydrated lime (sulfur fixing agent), clay (assistant for
Fig. 1 Process flow of briquette production forming), and a caking additive.

57
Clean Coal Technologies in Japan

To attain uniform composition and improved formability, the mixed


raw material is fully kneaded. Forming of the mixture is carried
out using the roll molding machine at normal temperature and
under about 1,000 kg/cm (300-500 kg/cm2) of line pressure.
Photograph 1 shows the forming state.
The formed briquettes are dried in the continuous drier to become
the product. Since the semicoke as the raw material of briquettes
has strong ignition property and readily ignites in the furnace, the
drier is requested to operate at low temperature level. The drier
is designed considering the temperature-sensitive operation.

Photo 1 Formed briquettes


3.Bio-briquettes
Bio-briquettes are a kind of solid fuels, prepared by blending coal the low temperature region (200-400 C) does not completely
O

with 10-25% of vegetable matter (biomass) such as wood combust. To the contrary, bio-briquettes combust simultaneously
bagasse (strained lees of sugar cane), straws, and haulms of the low ignition point biomass which entered between coal particles
corn, further with desulfurizing agent (Ca(OH)2) by an amount with the coal, which assures the combustion of volatile matter
corresponding to the sulfur content in the coal. Owing to the high released in the low temperature coal combustion region. As a
pressure briquetting (1-3 t/cm2), the coal particles and the fibrous result, the amount of generated dust and soot significantly reduces.
vegetable matter in the bio-briquette strongly interwind and 2. The bio-briquettes prepared by adding 15-20% of biomass to
adhere to each other. As a result, they do not separate from coal gives significantly short ignition time to improve the ignition
each other during combustion, thus attaining combined property. In addition, the bio-briquettes have low expansion
combustion of the vegetable matter having low ignition caking property so that the aeration between briquettes is
temperature and the coal. The combined combustion gives secured during continuous combustion in a fireplace, giving
favorable ignition and fuel properties, emits very small amount of favorable combustion characteristic.
dust and soot, and generates sandy combustion ash to leave no Consequently, the bio-briquettes have superior combustion-
clinker. Furthermore, since the desulfurizing agent also adheres sustaining property, and do not die out in a fireplace or other heater
to the coal particles, the agent effectively reacts with the sulfur in even when air rate is decreased to slow down the combustion rate,
the coal to fix about 60-80% of the sulfur into the ash. which makes the adjustment of combustion rate easy.
Applicable coal grades are many, including bituminous coal, 3. Since fibrous biomass enters between coal particles, there is
subbituminous coal, and brown coal. In particular, the bio-briquettes no fear of clinker-lump formation during combustion caused by
utilizing low grade coal containing large amount of ash and having adhesion of fused ash in coal, thus the ash falls in sandy form
low calorific value gives large effect of coal-cleaning, thus the bio- through grate. Therefore, aeration is secured to stabilize the
briquette technology is an effective technology to produce clean fuel combustion state. Furthermore, since no clinker is formed, ash
for household heaters and industrial small boilers. contains very small amount of unburnt coal.
(1)Production flow of bio-briquettes 4. The bio-briquettes are formed under high compressive force.
Figure 3 shows the basic flow of bio-briquette production. The Accordingly, the desulfurizing agent and the coal particles strongly
coal and the biomass as the raw materials are pulverized to adhere to each other, and they effectively react during combustion.
about 3 mm or smaller size, which are then dried. The dried With the addition of desulfurizing agent at about 1.2-2 of Ca/S
mixture is further mixed with a desulfurizing agent (Ca(OH)2). ratio, 60-80% of the sulfur in coal is fixed in the ash.
The mixture is formed by compression molding in the high
Coal Biomass
pressure briquetting machine. Powder coal may be applied
without subjected to pulverization. A small amount of binder may
be added to some coal grades.
Pulverization Drying
The production process does not contain high temperature
operation, and has a structure centering on the dry high pressure Drying
briquetting machine. The process is simple facility flow which is Pulverizing
Deodorant
safe and which does not require skilled operational technique.
Caking additive
Owing to the high pressure briquetting method, the coal particles
Caking additive may be
and the biomass strongly interwind and adhere to each other, required depending on the Mixing
coal grade.
thus the process produces rigid formed coal which does not
separate their components during combustion.
(2)Bio-briquette characteristics High pressure briquetting

1. Compared with the coal direct combustion, the bio-briquette


combustion decreases the generation of dust and soot by one fifth Bio-briquette
to one tenth. The coal direct combustion gives increased
generation of dust and soot because the volatile matter released in Fig. 3 Basic flow of bio-briquette production

58
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Powdering, Liquefaction, and Common Use Technologies)

3C4. Coal and Woody Biomass Co-firing Technology


In charge of research and development: New Energy and Industrial Technology Development Organization;
the Chugoku Electric Power Co., Inc.; Hitachi, Ltd.; Babcook-Hitachi K.K.
Project type: High-efficiency biomass energy conversion technology development
Period: 2001-2003 (3 years)

Outline of technology

1.Background
As part of measures to arrest global warming, industrially an existing mill (pulverizer) and grind it for the combustion of
advanced countries are practicing mechanisms to promote the pulverized coal-biomass mixture fuel in a boiler, using the
adoption of power generation using renewable energy. One of existing burner. This method requires less adaptation of
them is the RPS (Renewable Portfolio Standard) System. Since equipment and, therefore, less cost while there is a problem that
April 2003, the "Special Measures Law concerning the Use of a mixture of more than several % biomass causes the mill’s
New Energy by Electric Utilities (RPS Law)" has bee enacted, power consumption to sharply increase due to the difficulty in
obligating electric utilities to use a certain amount of new energy grinding woody biomass with ordinary pulverizers. The other
for power generation. The normal usage (obligation amount) of method is to establish a biomass-dedicated mill. Despite the
new energy for electricity is assumed to increase from 3.3GkWh equipment cost higher than the former, this method is
in 2003 to 12.2GkWh in 2010. What is defined as new energy advantageous not only because the ratio of mixture may be
includes biomass fuel. made higher but also because the amount of NOx generated can
Co-firing of coal and woody biomass in the power generation be reduced.
sector, though already under way in U.S. and European Here, the latter method for which technology development is
countries, is a novel trial facing a variety of technological under way, commissioned by the New Energy and Industrial
problems. For pulverized coal-fired boilers, there are roughly two Technology Development Organization (NEDO), is introduced.
methods of co-firing. One is to simply input woody biomass into

Combustion test/evaluation

Woody biomass
technology investigation
Boiler Exhaust
gas
Mill treatment
Coal
Burner

Woody biomass Separation Storage Drying Grinding

Pre-treatment technology FS for commercialization


development

Fig.1 Coal/Woody Biomass Co-Firing System and Practiced Items

59
Clean Coal Technologies in Japan

2.Development target 3.Technologies to be developed

(1)Co-firing ratio of woody biomass: 5-10% (1)Woody biomass pre-treatment technology mainly of grinding
(2)Clearance of current regulatory environmental limits (2)Woody biomass combustion technology (co-firing
(3)Existing coal thermal power plants-comparable power burner/biomass-dedicated burner)
generation efficiency: A decrease in net thermal efficiency to be
made 0.5% or less with the woody biomass co-firing ratio of 5%
(on a calorific base).
Bag
filter
Burner

To stacks Mill [1]

Biomass Bin
Hopper Furnace
Feeder

Hopper
Cyclone

Heater Feeder

Crusher Drier Blower

Mill [2]

Fig.2 Pilot Scale Test Equipments

4.Development in progress and results


This project, under way jointly at the Chugoku Electric Power by NEDO, is now at the stage of FS for the evaluation of pilot
Co., Inc., Hitachi, Ltd., and Babcook Hitachi K.K., commissioned plant test combustion results toward commercialization.

R&D Schedules

2001 2002 2003 2004 2005

Coal/woody biomass co-firing technology R&D (a business commissioned by NEDO) Demonstration test

Development of component technologies for processes from reception to storage, Component technology development results-based
crushing, dry boiler combustion, and then flue gas/ash disposal deployment toward demonstration tests

1.Woody biomass technology investigation

2.Pre-treatment technology development Planning

3.Combustion test and evaluation Installation works

4.FS for commercialization Demonstration test

[Review of forest biomass utilization by local governments]


Utilization planning and system design/verification Supply system and other improvement/development

References
1) Kazuhiro Mae: Coal Utilization Technology Information Journal No. 253 pp. 3~5 (Feb., 2002)
2) Hiroshi Yuasa: A collection of lectures from Oct. 2003 Thermal/Nuclear Power Generation Convention in Fukuoka, pp102/103

60
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (De-ashing and Reforming Technologies)

3D1. Hyper-Coal based High Efficiency Combustion Technology(Hyper Coal)


In charge of research and development: Center for Coal Utilization, Japan; National Institute of Advanced
Industrial Science and Technology; and Kobe Steel, Ltd.
Project type: Development and Survey of Next Generation Technology for Coal Utilization, promoted by New Energy
and Industrial Technology Development Organization (NEDO)
Period: 2002-2007 (6 years)

Outline of the technology

1.Background and object


Coal is expected to increase the demand owing to the abundant steam turbine) realizes higher efficient power generation than
reserves, the expectation of stable supply, and the low price, that of existing pulverized coal fired power generation. To this
though the influence of CO2 and other substances on the point, if coal can remove impurities such as ash and alkali
environment is relatively large compared with other fossil fuels. metals, the resulting clean coal can be used as fuel to directly
In the situation, to decrease the emissions of CO2 from coal fired combust in gas turbine.
power plants which account for large percentage in the coal Regarding the issue, NEDO conducts development of technology
utilization field, it is important to develop a power generation of combined power generation system, where the coal is treated
technology of higher thermal efficiency than ever, and to bring the by solvent extraction and ion exchange to remove ash and alkali
technology widespread use over the world. metals to obtain clean coal (Hyper-Coal), which is then directly
If coal is utilized as a gas turbine fuel, the adoption of combined combusted in gas turbines.
cycle power generation system (combination of gas turbine and

2.What is Hyper-Coal?
A solvent having strong affinity with coal is applied to the coal
extraction, and then unnecessary ash is sedimented to remove
from the coal to obtain very low ash coal (Hyper-Coal).

Charcoal
Hyper-Coal

Solvent Coal Cohesion of coal becomes weak, Insoluble portions and ash are
Solvent penetrates into coal and soluble portions of coal dissolve. sedimented to remove. Extract residue
charcoal
Fig. 1 Conceptual drawing of Hyper coal manufacturing from coal

3.Hyper-Coal production facilities


(1)Preheating-extraction unit (2)Sedimentation-separation unit
Coal is extracted by a solvent, and then is The unit is a sedimentation tank having coal
treated by rapid filtration to remove residue, thus extraction performance, (design temperature:
Hyper-Coal is produced. (Design temperature: 500 C, design pressure: 5 MPa).
O
Vertically
500 C, design pressure: 3MPa)
O
arranged five valves collect samples to
The unit produces various grades of Hyper-Coal determine the sedimenting condition of non-
samples. dissolved ingredients under pressurized and
heated conditions.

Photo 1 Preheating-extraction unit Photo 2 Sedimentation separation unit

61
Clean Coal Technologies in Japan

4.Features of Hyper-Coal
- Ash content is decreased to 200 ppm or lower level. Alkali excellent gasification raw material, and it is expected to increase
metals (Na, K) are decreased to 0.5 ppm or lower level by ion high efficiency of gasification.
exchange.
- Calorific value increases by about 10-20% from that of original
coal.
- Inorganic sulfur is completely removed.
- Content of solid state trace amount of heavy metals is
significantly decreased, (to 1/100 or smaller).
- The residue generated by 30-40% to the original coal during
the production stage can be used as general coal.
- The production cost is low, about 950-1,200 yen/ton-HPC.
- The HPC has excellent ignitability and burn-off property.
- The HPC shows high flowability, and is a good carbon material
for direct reduction iron and for smelting nonferrous metals.
- Since HPC is rich in volatile matter and is free from ash, it is
Photo 3 Test apparatus for manufacturing Hyper coal continuously

5.Configuration of Hyper-Coal based high efficiency power generation system


Overseas mining site Ion exchange vessels The material is flash-sprayed The gas turbine combined cycle power generation system is a power generation
(coal mine) remove alkali metals into the drying tower to system which combines gas turbine with steam turbine. When a gas turbine of 1350oC
which cause high separate the solvent. The level of combustion gas temperature is used, about 20% of CO2 emission reduction is
Roughly deashed coal
(ash content: 5% or less) temperature corrosion. solvent is recovered to reuse. attained compared with the pulverized coal fired power generation system.

Coal is charged into the solvent,


and the system is pressurized
and heated to let the coal
portions disperse into the
solvent. Insoluble ash is treated
by the settler to sediment by
gravity to remove as the residue
coal. The solvent containing
dispersed coal portions is sent Conventional power generation system. Power is
to the ion exchange vessels. generated by combusting the residue coal.

6.Concept of Hyper-Coal based power generation system 7.Schedule of research and development
Interim evaluation

Post-evaluation

62
Part2 Outline of CCT
Multi-Purpose Coal Utilization Technologies (Deashing and Reforming Technologies)

3D2. Low-Rank Coal Upgrading Technology (UBC Process)


In charge of research and development: Japan Coal Energy Center; the Institute of Applied
Energy; Kobe Steel, Ltd.; Nissho Iwai Corp.
Project type:1. Low-rank coal upgrading technology-related investigation
2. Joint research of technologies applicable to coal producing countries
Period: 1. 1995-1998(4 years) 2. 1999-2004(6 years)

Outline of technology

1.Background and process outline


Brown and sub-bituminous coal resources accounting for about also greatly to environmental problems. The low-rank coal
50% of coal reserves are called low-rank coal whose applications upgrading technology (UBC Process) is under development as a
are limited due to its low heating value and spontaneous technology to make effective use of such low-rank coal.
combustion property. Many of these low-rank coals, however, This process, an adaptation of slurry dewatering technology of
are featured such as by low sulfur/ash contents, unlike the brown coal liquefaction process, consists of 3 stages; 1)
bituminous coal. So if they could be efficiently upgraded and slurry preparation/dewatering, 2) solid-liquid separation/solvent
converted into high-grade high-heating value coal, it will then recovery, and 3) briquetting.
contribute not only to the security of stable energy supply but

Asphalt
Raw coal Slurry dewatering Solid-liquid separation

Decanter

Evaporator
(140 C/350kPa)
O

Slurry preparation

Solvent recovery

Recycle solvent
Waste water Upgraded brown coal (UBC) Upgraded brown coal briquette

Fig.1 Low-Rank Coal Upgrading Process (UBC Process) Scheme

At the stage of slurry preparation/dewatering, after pulvelized moisture and accumulation of heat of wetting. The right figure
high moisture low-rank coal is mixed with recycled oil (normally shows this phenomenon conceptually.
petroleum light oil), then laced with heavy oil (such as asphalt),
and heated in a shell & tube-type evaporator, moisture is
Befor dewatering After dewatering
recovered as water vapor. This water vapor is sent to the shell
side of the evaporator after pressurized by a compressor to use
the waste-heat as a heating source, thereby having so far
substantially saving energy consumption at the stage of
dewatering. Low-rank coal also contains numerous pores and
Selective adsorption of asphalt
the moisture within them is removed in the course of onto pore surfaces
Capillary water
evaporation. During that time, laced heavy oil is effectively Asphalt
Surface water
adsorbed onto pore surfaces, thus preventing spontaneous
combustion. Moreover, the heavy oil expresses its nature to Fig.2 Fundamentals of Low-Rank Coal Upgrading
water repellency, functioning to prevent the re-adsorption of

63
Clean Coal Technologies in Japan

At the stage of solid-liquid separation/solvent recovery, after


recycled solvent is recovered from the dewatered slurry by the
decanter, the recycled solvent remaining in the pores of upgraded
coal is also recovered by the steam tubular drier.
Upgraded coal obtained from UBC Process is still in a powdery
state, requiring to be briquetted due to the necessity of
transportation except when consumers are located nearby. The
upgraded coal, normally binder-less briquettable, can be easily
briquetted, using a double roll briquetter. The right figure shows a
photo of briquetted upgraded-coal.

Photo 1 Briquetted UBC

2.Development target
1)Upgrading cost 4.Future assignments and prospective commercialization
If bituminous coal with a heating value of 6,500kcal/kg is A demonstration-plant of 5 tons/day (raw coal-base) built in
assumed 20 dollars/ton in FOB price, the FOB price of 4,500- Cirebon of the Java Barat province, Indonesia, is now in
kcal/kg sub-bituminous coal is supposed some 13 dollars/ton in operation, where the Ministry of Energy and Mineral Resources’
calorific equivalent. If it is assumed that, from this, upgraded coal Research and Development Agency, Indonesia and the Japan
of 6,500kcal/kg should be obtained, the guideline for treatment Coal Energy Center are main promoters.
cost will be set around 7 dollars/ton. Even with advantages of In Asia-Oceania region, there are a lot of low-rank coal
low-rank coal such as its low ash contents and other features resources. The coal mining companies, which have low-rank
borne in mind, it is necessary to target about 7 to 9 dollars/ton for coal, are highly interested in UBC process, hoping its earlier
treatment costs. commercialization.
2)Thermal efficiency for upgrading
Thermal efficiency in the upgrading process needs to be 90% or
more so that higher thermal efficiency than at direct low-rank coal
firing power plants may be achieved in terms of overall
comparison from UBC firing power generation.

3.Development in progress and results


The heating value of upgraded coal, though it is varied depending
upon coal properties has been improved to around 6,500kcal/kg,
with its spontaneous combustion problem also successfully
suppressed. It has also been confirmed that briquetted
upgraded-coal is similar to normal bituminous coal in easiness of
Photo 2 Low-Rank Coal
handling and re-crushing. Upgrading Demonstration Plant
Furthermore, upgraded coal, if burnt, quite easily burns itself out
to leave almost no un-burnt portion even under low-NOx
combustion conditions, assuring that it also has excellent
characteristics as fuel.

Reference
1) Toru Sugita et al: UBC(Upgraded Brown Coal) Process Development, Kobe Steel Engineering Reports, 53, 42 (2003)

64
Part2 Outline of CCT
Environmental Protection Technologies (Coal Ash Effective Use Technologies)

4A1. Coal Ash Generation Process and Application Fields


Outline of technology

1.Background and general status of generation process


Coal ash has, since it was commercialized as cement admixture Coal burning methods are roughly divided as follows:
in the first half of the 1950’s, been widely used in applications (1) Pulverized coal burning (dry-type)
such as for cement raw material, cement mixture, roadbed (2) Stoker firing
material, backfilling material, and piling-up material, finding its (3) Fluidized-bed burning
way mostly in the cement sector, particularly, as cement raw (4) Circulating fluidized-bed burning
material (clay-alternative).

2.Generation rate
According to a questionnaire survey conducted by the Center for Power
transmission
Coal Utilization, Japan in 2001, the coal ash generation rate in
Steam
Japan is 8,810 thousand tons a year, up 5% in ratio or 380 Household/factory
thousand tons in quantity from the preceding year. Most coal-
Steam turbine Generator
firing boilers for the electric utility industry are those burning Transformer Chimney stack
pulverized coal. On the other hand, in general industries, 132
Boiler
coal-firing boilers are in operation with an installed power Coal-fired power plant

generation capacity of 1,000kW or more and, by burning


Economizer
methods, the majority is accounted for by pulverized coal burning
Air
pre-heater Electrostatic
(72 boilers). In terms of boiler capacity (steam generation rate), precipitator
boilers of 50t/h or less are mostly of a stoker burning type while
Clinker
many of 100t/h or more burn pulverized coal. hopper
Fig. 2 shows changes in the rate of coal ash utilization as well as
generation from electric power utilities and 1,000kW or more- Breaker Fly ash
(85~95%)
installed power generation capacity establishments in general
industries from 1993 through 2001.

Bottom ash
(5~15%)
Rate of Utilization Grader
Rate of generation
Coal ash (thousand tons)

De-watering Silo Silo Silo


tank

Bagger Humidifier Humidifier

Dump truck Ship Truck Jet vac truck Dump truck Jet vac truck Dump truck

Fig. 1. Process Example of Coal Ash Generation


Year from a Pulverized Coal-Firing Boiler
Fig. 2. Changes in Coal Ash Generation and Utilization Rates Source: Data from the Japan Fly Ash Association

3.Physicality of coal ash


In Japan, 90% or more of coal ash generated from pulverized between finer clay and coarser fine-grained sand for the use as
coal burning, dwarfing 7% or so from fluidized-bed and some 1- ground material.
2% from stoker burning. The generation ratio of fly ash and The chemical composition abounds in silica (SiO2) and alumina (Al2O3),
clinker ash (bottom ash) is 90:10. resembling mountain soil, and these two inorganic components alone
As for the shape of coal ash particle, low-melting point ash is account for 70-80% of total. Other than these, ferric oxide (Fe2O3),
often globular while much of high-melting point ash is magnesium oxide (MgO), and calcium oxide (CaO) are also contained in
indeterminate in shape. The average grain size of fly ash from slight amounts. In Japan, the physicality of coal wide varies since coal
pulverized coal burning is about 25 m, similar to silt in fineness of 100 brands or more is imported from all over the world.

65
Clean Coal Technologies in Japan

4.Application fields
Table 1 shows by-sector rates of effective utilization in 2001. increase can hardly be expected. In coping with a likely increase
The utilization in the cement sector increases year after year, in coal ash in the future, therefore, an important task should be to
reaching 5,343 thousand tons or 74.5% of the 7,173 thousand expand its utilization in other sectors, expecting its application as
tons used in all sectors combined. Recently, however, cement civil engineering material in particular due to its high potential to
production has been on a decrease and its future substantial be used in large quantities.

Table 1 Breakdown of Fields for Effective Coal Ash Utilization (2001) [unit : thousand tons]

Item Electric utilities General industry Total

Sector Description Rate of Composition Rate of Composition Rate of Composition


utilization ratio(%) utilization ratio(%) utilization ratio(%)
Cement Cement raw material 3,608 68.45 1,307 68.72 4,915 68.52

Cement mixture 140 2.66 154 8.10 294 4.10

Cement admixture 87 1.65 47 2.47 134 1.87

Sub-total 3,835 72.76 1,508 79.28 5,343 74.49

Civil engineering Foundation improving material 271 5.14 94 4.94 365 5.09

Civil work-purpose 67 1.27 22 1.16 89 1.24

Power supply construction-purpose 20 0.38 0 0.00 20 0.28

Roadbed material 47 0.89 54 2.84 101 1.41

Asphalt/filler material 3 0.06 0 0.00 3 0.04

Coal mine filling material 320 6.07 0 0.00 320 4.46

Sub-total 728 13.81 170 8.94 898 12.52

Construction Boards as construction material 191 3.62 118 6.20 309 4.31

Artificial light-weight aggregate 24 0.46 0 0.00 24 0.33

Secondary concrete product 35 0.66 3 0.16 38 0.53

Sub-total 250 4.74 121 6.36 371 5.17

Agriculture Fertilizer (including snow melting agent) 42 0.80 12 0.63 54 0.75


/forestry/fisheries
Soil conditioner 10 0.19 80 4.21 90 1.25

Sub-total 52 0.99 92 4.84 144 2.01

Others Sewage treatment agent 3 0.06 1 0.05 4 0.06

Steel making-purpose 1 0.02 1 0.05 2 0.03

Others 402 7.63 9 0.47 411 5.73

Sub-total 406 7.70 11 0.58 417 5.81

Total of effective utilization 5,271 100.00 1,902 100.00 7,173 100.00

References
1) The Center for Coal Utilization, Japan: National Coal Ash Fact-Finding Survey Report (2001 results), (2003)
2) Environmental Technology Association/the Japan Fly Ash Association Coal Ash Handbook 2000 Edition, (2000)
3) Nobumichi Hosoda: CCUJ, Coal Ash Utilization Symposium lecture collection, (1998)
4) Natural Resources and Fuel Department, the Agency for Natural Resources and Energy: Coal Note (2003 edition), (2003)

66
Part2 Outline of CCT
Environmental Protection Technologies (Coal Ash Effective Use Technologies)

4A2. Effective use for Cement/Concrete


Outline of technology

1.Outline of technology
Utilization of fly ash in the cement sector has long been 1950’s, standards were established for fly ash in 1958 and then
challenged through investigations into pozzolana. Enhanced for fly ash cement in 1960, encouraging wide applications for
research on the use of fly ash as a good-quality alternative to general concrete structures.
pozzolana brought its first late-1940’s application to concrete In the meantime, fly ash came to be used as a clay-alternative in
admixture of structures like a dam in the United States for cement raw material in 1978 and, as of 2001, 68.5% of the total
subsequent further dissemination into other countries. In Japan, rate of effective utilization is accounted for by such applications.
following its commercialization as cement admixture early in the

2.Utilization in the cement sector


1) Utilization as a clay-alternative in cement raw material limiting the substitutability of coal ash for clay. At present, about
Cement raw material is composed of lime stone, clay, silica, and 5% of cement raw material is substituted by coal ash but its
silver oxide, with clay accounting for 15% of total composition. alternative use is said theoretically possible to around 10%.
Coal ash containing silica (SiO2) and alumina (Al2O3) is also used 2) Utilization as cement mixture
as an alternative to such clay. But it contains less SiO2 and more JIS specifies standards for fly ash cement2), allowing fly ash to
Al2O3 than clay to require more silica as a source of SiO2 which be mixed by 5-30%. In general, fly ash can also be used as
becomes short if coal ash is used in large quantities, thereby Portland cement mixture by 5% or less.

3.Utilization in the concrete sector


1) Utilization as concrete admixture 2. Pre-packed concrete
1. Dam concrete Pre-packed concrete is a concrete product fabricated by casting coarse
In Japan, research on fly ash as concrete admixture started aggregate of a designated grain size into the mold form or place of
around 1950, demonstrating its favorable performance and application beforehand and injecting mortar into voids there at an
economy through the first commercialization on a dam site in appropriate pressure. The mortar used here must be one of high fluidity,
1953. little material separation, and moderate expansibility and, for this
RCD (roller compacted dam-concrete) is a concrete product purpose, fly ash is generally mixed by 25-50%.
finished by compacting concrete of ultra-thick consistency with a Application fields include underwater concrete, mass concrete, and
vibration roller and the then Ministry of Construction-led repair/reinforcement of existing concrete works. Honshu-Shikoku Bridge
independent technology development tried to rationally embody substructure works also employed this construction method.
this in a concrete dam, successfully systematizing the trial into 3. High-fluidity concrete
the RCD Construction Method to be commercialized for dam FEC (fly ash enriched concrete) is a two components-type high-
construction in 1978. fluidity concrete product using cement and fly ash as powder
Dam concrete is generally required not to become so hot for material. It contains as much as 40% or more of fly ash, giving
prevented cracks. Due to this severe requirement for RCD, only such features as the excellent self-filling capability to need no
part of cement is replaced by fly ash for the purpose of limiting an compaction after cast, scarce cracks due to heat of hydration,
increase in temperature. The replacement ratio used is mostly increasing long-term strength, and higher durability against alkali
20-30%. As many as some 30 dams have so far been built by aggregate reaction and salt/acid damages.
this construction method, justifying its evaluation as a well- FS (fly ash and slag concrete) using steel slag and coal ash as
established engineering method in terms of technology. aggregate is a plain concrete product developed for wave-

67
Clean Coal Technologies in Japan

breaker superstructure works and foot protection/anti-turbulence or qualities likely to prove effective as admixture despite their
blocks which are not required to be so strong. sub-standard state were added to JIS Standards3) as 4th-grade
4. Industrial standards for concrete-purpose fly ash items, thereby facilitating the selection of a quality suitable for the
Following the evaluation of fly ash as concrete admixture of purpose of utilization. Class-1 fine fly ash is used as admixture
excellent performance due to its high fineness and few unburnt such as for concrete products that must cut off water, be durable,
carbon contents, high-fineness items were commercialized by etc. including ocean concrete and long haul- and pressure-
means of an advanced grader and higher-performance qualities transported special back-filling material.

Table 1 Quality of Fly Ash (JIS-A 6201)

Class Class I Class II Class III Class IV


Item fly ash fly ash fly ash fly ash
Silica dioxide (%) 45.0 or more
Moisture content (%) 1.0 or less
Ignition loss *1(%) 3.0 or less 5.0 or less 8.0 or less 5.0 or less

Density (g/cm3) 1.95 or more


Fineness*2 Residue on 45 m sieve (screen sieve method) *3(%) 10 or less 40 or less 40 or less 70 or less
Specific surface area (Blaine method) (cm2/g) 5000 or more 2500 or more 2500 or more 1500 or more

Flow value ratio (%) 105 or more 95 or more 85 or more 75 or more


Activity index (%) Material age: 28 days 90 or more 80 or more 80 or more 60 or more

Material age: 91 days 100 or more 90 or more 90 or more 70 or more


*1 In place of ignition loss, the unburnt carbon content ratio may be measured by the method specified in JIS M 8819 or JIS R 1603 to apply to
the result a stipulated value of ignition loss.
*2 Base fineness on a screen sieve method or Blaine method.
*3 In case of a screen sieve method-based fineness, put down with the result of specific surface area tests by a Blaine method.

Application to dam Application to building

References
1) The Japan Cement Association: Common Practice of Cement, (2000)
2) JIS R 5213-1997, (1997)
3) JIS A 6201-1999, (1999)

68
Part2 Outline of CCT
Environmental Protection Technologies (Coal Ash Effective Use Technologies)

4A3.Effective use for Civil Engineering/Construction and Others


Outline of technology

1.Outline of technology
Coal ash is widely used, other than for concrete, in the civil quantities in the future such as due to further establishment of
engineering sector as road construction, foundation improving, new coal firing power plants, utilization technologies are now
back-filling, or other earthwork material and in the construction under active development out of the necessity to expand its
sector as artificial light-weight aggregate. On the other hand, in utilization in these sectors. Efforts to provide substance to this
the agriculture/forestry/fisheries sector, it is used as a fertilizer or face some problems including diffusion of technology, exploitation
soil conditioner. of demand, and improvement of the distribution mechanism.
In coping with well-expected generation of coal ash in large

2.Utilization in the civil engineering


1. Road construction material 2. Earthwork material
The "Outline of Asphalt Pavement" 1) allows fly ash to be used as Fly ash can be effectively used as piling-up or back-filling
asphalt filler material and clinker ash, as lower subbase material, material since it is lighter than common earthwork material. In
frost heave depressant, and cutoff layer material. recent years, therefore, various technology development
Fly ash can be used for the upper/lower subbase and road bed. efforts6,7,8) have been made, coming up with a number of
A cement stabilization treatment construction method adds fly applications including a usage in the original powder state with
ash to cement to be treated under moderate moisture contents cement added as a solidifier to coal ash, utilization as stabilizing
for application. This construction method realizes early treatment material, hardening for application, and granulation or
manifestation of strength and achieves long-run stability. Another other processing to use it. Review is also under way for intended
technology2,3,4,5) has also been developed to process coal ash for commercialization of fly ash as soft ground improving material or
the use as road construction material. a construction sludge conditioner due to its high activity of
pozzolana as well as property of self-hardening9).
Meanwhile, basic research of coal ash’s trace components
elution10) goes on since fly ash must be used, not raising any
environmental problems, in terms of safety coal-ash utilization as
earthwork material.

Photo 1 Application to road

69
Clean Coal Technologies in Japan

3.Utilization in the construction sector 4.Utilization in the agriculture/forestry/fisheries sector


1. Artificial light-weight aggregate 1. FertilizerCoal ash was designated in the capacity of pulverized
Development efforts11,12) have successfully come up with coal-burning ash as a special fertilizer in 1960 for fly ash and in
technology to palletize/calcine coal ash and cement or the like into 1992 for bottom ash. A potassium silicate fertilizer making
artificial light-weight aggregate. Demand for it is expected to grow effective use of hard-to-solve silicic acid contained in coal ash is
such as due to the progress of urban development and high rising also produced about thousands of tons a year.
of buildings, making it important to further technology development 2. Soil conditioner
of artificial light-weight aggregate as well as to reduce its Clinker ash whose chief ingredients are almost the same as
production cost. those of ordinary soil, mostly composed of SiO2 and Al2O3, is
2. Others suitable for the growth of vegetables. Moreover, it is used as sod
The resemblance of its components to the chemical composition of for golf courses or to improve soil of poor-drainage places or
existing construction materials also allows coal ash to be used as arable land since its numberless spores hold water well for
clay-alternative raw material for ceramic products such as clay longer duration of fertilizer effects and, at the same time, its
roofings, bricks, and tiles or a cement mixture for boards similarity to sand in shape provides comparable water-
(interior/exterior wall material for construction) on the strength of permeability.
such characteristics. 3.Utilization in the fisheries sector
There are long-established cases where coal ash was used for
fish breeding reefs and seaweed beds. A recent attempt aims at
the use of coal ash as mound material for man-made undersea
mountain ranges to cause artificial upwelling currents.13)

Photo 2 Photo 3 Application as fertilizer


Example of Artificial Aggregate Fabricated from Coal Ash (Toughlite)

References

1) The Japan Road Association: Outline of Asphalt Pavement, (1992)


2) Environmental Technology Association/the Japan Fly Ash Association: Coal Ash Handbook 2000 Edition, (2000)
3) Public Works Research Institute: Public Works-Related Material Technology/Technical Review Certification Report "Ash-Roban", (1997)
4) Public Works Research Institute: Public Works-Related Material Technology/Technical Review Certification Report "Pozzotech", (1997)
5) Ohwada et al: 11th Annual Conference on Clean Coal Technology lecture collection, (2001)
6) Shintani et al: CCUJ, Civil Engineering 54th Annual Academic Lecture Meeting, collection of summaries, (1999)
7) Public Works Research Center: Public Works-Related Material Technology/Technical Review Certification Report "Hard Soil-Break Material", (2000)
8) Akira Onaka: The Clean Japan Center’s 11th Resources Recycle Technology Research Presentation Meeting, collection of lecture papers, (2003)
9) Ozasa et al: CCUJ, 11th Annual Conference on Clean Coal Technology lecture collection, (2001)
10) The Japanese Geotechnical Society: Research Committee Report on Utilization of Wastes as Foundations Material, (2000)
11) Ishii et al: The "Bulletin of the Chemical Society of Japan", 5, 431, (1992)
12) Ozasa et al: CCUJ, 10th Annual Conference on Clean Coal Technology lecture collection, (2000)
13) Tatsuo Suzuki: 14th ACAA International Symposium lecture collection, (2001)

70
Part2 Outline of CCT
Environmental Protection Technologies (Coal Ash Effective Use Technologies)

4A4. Valuable Resources Recovery Technologies for Coal Ash


Outline of technology

1.Outline of technology
Coal ash utilization technology is now an R&D subject challenged in as an absorbent, catalyst, ion-exchanger, and desiccant through
diversified manners from an effective-use-of-resources point of view. zeolitization, desulfurization agent, antirust, and application such
Review has been made on the recovery of valuable resources as into admixture and filler of polymeric materials (including
from coal ash by way of physical/chemical treatment, utilization rubber and plastic).

2.Valuable resources recovery


Coal ash contains valuable substances including cenosphere 2) Recovery of valuable resources through chemical treatment
(hollow ash), Magnetite silica, alumina, iron oxide, and titanium (1)Direct hydrofluoric acid extraction method
oxide, other than which valuable metals are also present though As a method of recovering valuable resources from fly ash
in trace amounts. through chemical treatment, the acid extraction method which
1) Recovery of valuable resources through physical treatment uses an acid mixture of hydrofluoric acid and hydrochloric acid
(1)Magnetite recovery through magnetic separation has been developed. The SiO2 recovered here is
The recovery of magnetite (Fe3O4) from fly ash is also positioned characteristically of high purity (99.9% or more) and fine particles
at the pre-process of the chemical treatment method to recover (1 m or less).
valuable elements such as Si, Al, Ti, and Fe. Magnetite can be (2)Calcination method
used, e.g., an alternative to heavy separation medium recovered This method burns fly ash with a source of calcium to change
by magnetic separation. acid-stable mullite in fly ash into acid-soluble anorthite or
gehlenite, characteristically at a high rate of Al recovery.

3.Artificial zeolite
Zeolite is the generic term of hydrated crystalline alumina silicate coal ash zeolite is obtained if coal ash is boiled with sodium
and, as part of its features, has a porous structure and, therefore, hydroxide while stirring and then solid contents are
a large specific surface area as well as contains ion- separated/washed/de-watered. The zeolite given here is of a Na-
exchangeable cations and crystallization water that can be P type.
adsorbed/desorbed. On the strength of its such characteristics, Meanwhile, coal ash zeolite production processes so far
Zeolite is used, e.g., as an adsorbent, catalyst, and disiccant1). commercialized are batch-wise like those for other than coal ash
It is known that hydrothermal treatment of a coal ash-alkaline while flow-through continuous synthesis processes have also
aqueous solution mixture2) gives various kinds of zeolite, been developed4). In addition, review is now made on the
depending upon conditions for reaction. exploitation of applications where large-quantity utilization is well-
The Clean Japan Center3) now conducts demonstration tests at a expected, reduction of production costs, and technology to
coal ash zeolite production demo-plant of a level of 10 thousand- synthesize zeolite of a kind suitable for each application.
ton/year in 1990. At this coal ash zeolite production process,

Coal ash
Primary
Boiling Water
Buffer tank Drainage De-watering products Drying Bagging
/stirring washing
Caustic soda storage

NaOH drainage pit Water drainage pit


Water treatment station

Fig. 1. Coal Ash Zeolite Production Process

71
Clean Coal Technologies in Japan

4.Utilization in other sectors


1) Desulfurization agent alternative to plastic admixtures including calcium carbonate,
Dry desulfurization technology using coal ash has been silica, alumina, wood flour, and pulp.
commercialized because a hardened mixture of coal ash, slack 3) Other
lime, and gypsum has an excellent desulfurization capability. Other than the above, the present technology development also
2) Admixture/filler for polymeric materials (including rubber and envisages coal ash characteristics-based applications such as in
plastic) an agent to prevent rust due to oxidation in steel-making, a water
Fly ash, since it is a gathering of small round glass bead-like fine cleanup agent, or casting sand.
particles, is under review for its use as a rubber filler or as an

Pore size Pore volume CEC


Structure Molecular formula (cc/g)
(A) (meq/100g)

Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] Na type: 4


A Na type: 0.3 548
27H 2 O Ca type: 5

SiO4
Na 6 [(AlO 2 ) 6 (SiO 2 ) 10 ]
P Na type: 2.6 Na type: 0.36 514
15H 2 O *The figure is small
but the exchange rate
is small.

Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ]


X Na type: 7.4 Na type: 0.24 473
AlO4 264H 2 O

Cation-containing aluminosilicate found in different kinds for different structures/compositions,


with each kind having its own performance and application.

References

1) Environmental Technology Association/the Japan Fly Ash Association: Coal Ash Handbook 2000 Edition, (2000)
2) Akio Itsumi: Japan Soil Science and Plant Nutrition, 58 (3), (1987)
3) The Clean Japan Center: Clean Japan, 86, (1991)
4) Masahiko Matsukata: CCUJ, 12th Annual Conference on Clean Coal Technology lecture collection, (2002)

72
Part2 Outline of CCT
Environmental Protection Technologies (Flue Gas Treatment and Gas Cleaning Technologies)

4B1. SOx Reduction Technology


Outline of technology

1.Background
Sulfur oxides (SOx, mainly SO2) is regulated by way of the K- their higher performance and lower costs. At present, most of
value control which uses exhaust heights and regional pulverized coal-fired thermal power plants are equipped with wet
coefficients to limit their emissions as well as the total amount lime stone and gypsum method-based desulfurization means.
control which defines total emissions from the whole of a Furthermore, a wet desulfurization method requiring no waste
region. In coping with these controls, flue gas desulfurizers water treatment is now under development.
were commercialized in 1973, with later continual efforts for

2.Technology
(1)Wet lime stone-gypsum method stone slurry is reacted on SO2 within exhaust gas for the
Members in charge of research and development: Mitsubishi recovery of sulfur contents as gypsum (CaSO4-2H2O).
Heavy Industries, Ltd.; Babcook Hitachi K.K.; Ishikawajima-Harima The overall reaction is as follows:
Heavy Industries Co., Ltd.; CHIYODA Corporation; Kawasaki Heavy CaCO3+SO2+0.5H2O CaSO3-0.5H2O+CO2
Industries, Ltd.; others CaSO3-0.5H2O+0.5O2+1.5H2O CaSO4-2H2O
Outline There are two types of absorption tower as shown in Fig. 1;
The lime stone-gypsum method is found in a soot-separation CaSO3-0.5H2O oxidation tower-separated types and all-in-one
type which installs in its upstream a dedusting (cooling) tower internal oxidation types. At present, the utilization of less-
for dust collection, HCl/HF removal, and cooling or in a soot- expensive-to-install/operate internal oxidation types is on a year-
mixed type having no such tower. Soot-separation types are after-year increase. Methods for causing recycled absorption
used when high-purity gypsum containing no soot/dust is liquid to contact SO2 in the absorption tower section include
desired. At present, however, more and more soot-mixed types, Spray Method to spray absorption liquid, Grid Method to shed
less-expensive-to-install, are adopted since a high-performance absorption liquid on the surface of a grid-like pad, Jet-Bubbling
dust collection system like the advanced low-temperature Method to blow exhaust gas into absorption liquid, and Water-
electrostatic precipitator has been developed, lowering Column Method to shed a fountain flow of absorption liquid in the
soot/dust concentrations. absorption tower.
In the absorption tower, on the other hand, water-mixed lime For developing countries, a simple type installable in the flue gas
duct or at the lower part of a smoke stack has also been
commercialized.

Item Oxidation tower-separated type In-absorption tower oxidation type

Absorption tower Absorption tower

Sulfuric
acid Oxidation
tower

Basic flow
Gypsum
Gas Gas

Lime Air
stone Gypsum
Lime
stone
Absorption tank Air Absorption tower tank

Fig. 1 Outline of Lime Stone-Gypsum Method-Based Desulfurizer

73
Clean Coal Technologies in Japan

(2)Coal ash-based dry desulfurization method 20% and dust collection efficiency of 96% or more. By 2003, it
Members in charge of research and development: Hokkaido had been installed at No. 1 unit (350 KkW) of Hokkaido Electric
Electric Power Co., Inc.; Hitachi, Ltd.; Babcook Hitachi K.K. Power’s Tomato-Atsuma Thermal Power Plant as a facility
Kind of project: Subsidized development of oil-alternative currently in operation to treat half of its flue gas in amount.
energy-related technology for commercialization
Development period: 1986-1989

Coal ash

Slack lime
Outline Used
Boiler Exhaust gas
desulfurization agent
It is one of technologies developed to make effective use of Water
Kneader Drier
coal ash. This method is to fabricate a new absorption spent
Clean

Primary absorption
Desulfurization

Pre-absorption agent
Hot air
from lime stone, calcium hydroxide (Ca(OH)2), and spent Conveyor
Extruder
gas

silo
absorption agent and then, using the absorption agent, remove Blender

agent
Conveyor Desulfurization
SOx from flue gas. Fig.2 shows an outline of its process. This Steam
fan

Weighing
machine
Weighing
process also includes the stage to manufacture the absorption machine Screen
agent. Desulfurization reaction here is a reaction which allows Steam generator

Ca(OH)2 to remove SO2. Temperature is conditioned at 100-


200 C, where an SOx removal efficiency of 90% or more can be
O Used desulfurization agent
Breaker
obtained. The process is also capable of dust collection and
Fig. 2 Coal Ash-Based Dry Desulfurization Method Proces
De-NOx, having achieved a NOx removal efficiency of about

(3)Spray Drier Method giving a particle mixture of gypsum (CaSO4-H2O) and calcium
Members in charge of research and development: Electric Power sulfite (CaSO3-0.5H2O). These particles are recovered at a
Development Company; Mitsubishi Heavy Industries, Ltd.; down-stream precipitator. Since this method is not enough for
Hokkaido Electric Power Co., Inc. good-quality gypsum to be obtained and, moreover, ash remains
Kind of project: Voluntary under the Green Aid Plan mixed in, desulfurized particles are disposed of as waste.
Outline Electric Power Development Company, as part of the "Green Aid
It is a so-called semi-dry method, where water is added to burnt Plan," installed a spray drier desulfurizer with an exhaust gas
lime (CaO) to make slack lime (Ca(OH)2) slurry, which is sprayed treatment capacity of 300Km3N/h (half of total exhaust), which is
into a spray drier, causing SO2 in exhaust gas to react on currently in operation, at Huangdao Power Plant No. 4 Unit
Ca(OH)2 to be removed. Within the drier, desulfurization (210KkW) in Qingdao, China, for 70% desulfurization rate
reaction and lime stone drying take place at the same time, verification tests (Oct., 1994 through Oct., 1997).

(4)Furnace desulfurization method SO2 at a furnace temperature of 760-860 C: O

Members in charge of research and development: Hokkaido CaCO3 CaO+CO2 CaO+SO2 CaSO3
Electric Power Co., Inc.; Kyushu Electric Power Co., Inc.; At present, this method is in practice at normal-pressure
Electric Power Development Company; Chugoku Electric fluidized-bed boilers of J-POWER’s Takehara Thermal Power
Power Co., Inc.; Mitsubishi Heavy Industries, Ltd.; Plant No. 2 Unit as well as pressurized fluidized-bed boilers of
Ishikawajima-Harima Heavy Industries Co., Ltd.; Kawasaki
Hokkaido Electric Power’s Tomato-Atsuma Thermal Power
Heavy Industries, Ltd.
Plant, Kyushu Electric Power’s New Kanda Thermal Power
Kind of project: Voluntary project
Plant, and Chugoku Electric Power’s Osaki Thermal Power
Outline Plant. At pressurized fluidized-bed boilers, lime stone does not
It is a desulfurization method used for fluidized-bed boilers. break down into CaO due to the high partial pressure of CO2
Lime stone for desulfurization is mixed with coal to be fed but SO2 is removed in accordance with the following reaction:
together with coal, causing the following reaction to remove CaCO3+SO2 CaSO3+CO2

References
1) "Introductory Course: Environmental Preservation Technology /Equipment for Thermal Power Plants IV Desulfurization Equipment",
Thermal/Electronic Power Generation Vol. 41 No. 7,911, 1990
2) Kudo et al, "Coal Ash-Based Dry Desulfurizer Development" Thermal/Electronic Power Generation Vol. 41 No. 7,911, 1990
3) "Coal Ash-Based Dry Flue Gas Desulfurizer" pamphlet, Hokkaido Electric Power
4) General View of Thermal Power Generation, Institute of Electric Engineers, 2002

74
Part2 Outline of CCT
Environmental Protection Technologies (Flue Gas Treatment and Gas Cleaning Technologies)

4B2. NOx Reduction Technology


Outline of tecnology

1.Background
Nitrogen oxides are under regulatory control, setting acceptable commercialized in 1977, with later continual efforts to improve
values of their concentrations by fuel kinds and boiler sizes. the durability of De-NOx catalysts as well as reduce costs. The
Currently, however, with regulations further intensified, some De-NOx method used is Selective Catalytic Reduction (SCR)
regions are subject, like sulfur oxides, to the total amount control Method to decompose nitrogen oxides mainly by using
which provides for overall emissions from each region. In coping ammonia.
with these regulations, flue gas denitration equipment was

2.Technology
(1)Selective contact reduction method
Members in charge of research and development: Mitsubishi process is also so designed that NH3 leaked from the reactor
Heavy Industries, Ltd.; Ishikawajima-Harima Heavy Industries should amount to 5ppm or less and if much NH3 leaks, it will
Co., Ltd.; Babcook Hitachi K.K. react on SO3 in exhaust gas, giving NH4HSO4, which is
Outline separated out in the air pre-heater to clog the piping.
In this method, ammonia (NH3) is blown into exhaust gas, NOx removal efficiency is around 80-90% for pulverized coal-
allowing ammonia (NH3) to selectively react on nitrogen oxides fired thermal power plants. On the other hand, measures for
NOx(NO, NO2), and decomposed them into water (H2O) and equal dispersion/mixture of NH3 in exhaust gas as well as
Nitrogen (N2). In the De-NOx reactor, since exhaust gas entails greater uniformity of exhaust gas flows to cope with growing
soot and dust, a grid- or plate-like catalyst is mainly used, as boiler sizes are contrived such as by placing a current plate
shown in Fig. 1. The catalyst is filled in the reactor, as shown in called Guide Vane at the gas inlet or dividing the gas inlet into
Photo 1/Photo 2, to react on the NH3 blown into the catalyst layer grids to be each equipped with an NH3 injection nozzle.
from its inlet, allowing NOx(NO, NO2) to break down into water
vapor (H2O) and nitrogen (N2). The catalyst is mainly composed
of TiO2, to which vanadium (V), tungsten (W), and the like are
Smokestack
added as active ingredients.
4NO + 4NH3 +O2 4N2 + 6H2O
The temperature range is 350 C, at which the catalyst can
O

Catalyst
demonstrate its performance. At a lower temperature than this, layer
SO3 in exhaust gas reacts on NH3, giving ammonium hydrogen
sulfate (NH4HSO4) to cover the catalyst surface, thereby
reducing the De-NOx performance. At a temperature higher than
350 C, the NH4HSO4 decomposes, offering high De-NOx
O

Exhaust Reactor
performance, regardless of SO3 concentrations. At a high gas
temperature above 400 C, NH3 is oxidized to decrease in
O

amount, thereby reducing the De-NOx performance. The Fig. 1 Selective Contact Reduction Method Denitration Process

Photo 1 Grid-like catalyst Photo 2 Plate-like catalyst

75
Clean Coal Technologies in Japan

(2)Selective Non-Catalytic Reduction (SNCR) Method


Members in charge of research and development: Chubu
Electric Power Co., Inc.; Mitsubishi Heavy Industries, Ltd.
Kind of project: Voluntary project
Outline
It is a method to, as shown in Fig.2, blow NH3 into the boiler
section where exhaust gas temperature is 850-950 C and break
O

Injection
down NOx into H2 and H2O without any catalyst. Despite its nozzle
merits of requiring no catalyst and lower installation costs, this

Brine water for nozzle-cooling


method achieving NOx removal efficiency of as low as some
40% at the NH3/NOx molar ratio of 1.5 is used in AH
regions/equipment where there is no need for high NOx removal
efficiency. More NH3 is also leaked than by the selective contact
reduction method, claiming measures to cope with NH4HSO4
Ammonia SAH
precipitation in the case of high-SO3 concentration exhaust gas. FDF
Mixer
This technology is mainly used such as at small commercial
Air for dilution
boilers and refuse incinerators. With respects to thermal power Booster fan
plant applications, it was installed only at Chubu Electric Power’s
Chita Thermal Power Plant No. 2 Unit (375kw) in 1977. Fig. 2 Selective Non-Catalytic Denitration Method’s NOx Removal Process

(3)Radical injection method


Members in charge of research and development: Center for Coal Utilization, Japan
Kind of project: Subsidized coal production/utilization technology promotion
Development period: 1999-2002
Outline
This method, as shown in Fig.3, injects argon plasma into NH3,
generating NH2-, NH2-, and other plasmas, which are then blown
into the boiler to decompose NOx into H2 and H2O. It is a
technology aimed at NOx concentration of 10ppm or less for its
target performance.
At present, basic research is under way at the Center for Coal
Utilization, Japan, toward expected commercialization around
2010.

Fig.3 Outline of Radical Injection Method

References
1) Masahiro Ozawa et al, "Latest Flue Gas Denitrator Technology", Ishikawajima-Harima Technical Journal, Vol. 39 , No. 6, 1999
2) Tadamasa Sengoku et al, "Selective Non-Catalytic Denitration Method for Boilers", Thermal/Nuclear Power Generation,
Vol. 29, No. 5, 1978
3) Coal Utilization Next-Generation Technology Development Survey;
Environment-friendly coal combustion technology field (advanced flue gas treatment technology)/NEDO results report, March 2002
4) Masayuki Hirano, "New Flue Gas Denitrator Technologies for Large Boilers/Gas Turbines", Thermal/Electronic Power Generation,
Vol. 50, No. 8, 1999

76
Part2 Outline of CCT
Environmental Protection Technologies (Flue Gas Treatment and Gas Cleaning Technologies)

4B3. De-SOx and De-NOx Technology


Outline of technology

1.Background
A wet desulfurization method is also matured in terms of but also measures against leaked ammonia. Development
technology but requires a variety of feed water as well as efforts are, therefore, under way for a dry combined
advanced waste water treatment measures. Meanwhile, an desulfurization De-NOx method to remove NOx and SOx at the
already commercialized ammonia selective reduction (SCR) same time without any feed/waste water treatment or De-NOx
method needs not only life control of expensive De-NOx catalysts catalyst.

2.Technology
(1)Active carbon adsorption method
Members in charge of research and development: Electric Power Development Company; Sumitomo Heavy Industries, Ltd.;
Mitsui Mining Co., Ltd.
Kind of project: Voluntary support project for coal utilization promotion
Outline
The active carbon absorption method is to cause a reaction first stage, with De-NOx performance also achieving 80% NOx
between SO2 in exhaust gas and blown-in NH3 on active carbon removal efficiency. This technology, verified after upscaled to a
at 120-150 C, thereby converting SO2 into such form as
O
capacity to treat gas of a 150Km3N/h level in amount, was
ammonium hydrogen sulfate (NH4HSO4) and ammonium sulfate adopted in 1995 for the De-NOx unit of Takehara Coal Thermal
((NH4)2SO4) for adsorption/removal while decomposing NOx into Power Plant No. 2 Unit’s normal-pressure fluidized-bed boiler
nitrogen and water as SCR Method does. Fig.1 shows the (350KkW) and is currently in operation. It was further installed in
process. The moving-bed adsorption tower (desulfurization 2002 at J-Power’s Isogo Thermal Power Plant No. 1 New Unit
tower) at the first-stage removes SO2 and, at the second stage (600KkW) as its desulfurizer (Photo 1) currently in operation but
(denitration tower), NOx is decomposed. This method first none is operated as combined desulfurization-denitration
removes SOx and then NOx since, as shown in the figure, the equipment.
presence of high-concentration SO2 tends to lower NOx removal
efficiency. Active carbon
Active carbon that has absorbed NH4HSO4 is heated to 350 C or O

above in the desorption tower to desorb NH4HSO4 after


Desulfurization tower

Hot
Denitration tower

Desorption tower
air
decomposing it into NH3 and SO2 while active carbon is
regenerated. In the desulfurization tower, SO2 can be adsorbed Exhaust
gas Desorbed gas
and removed in the form of sulfuric acid (H2SO4) even if NH3 is
Hot
not blown in but since, at the time of this desorption, the following air
reaction with carbon contents occurs, consuming active carbon,
NH3 is added at the time of desulfurization for the purpose of
preventing this.
Fig.1 Active Carbon-Method Desulfurization Process
H2SO4 SO3+H2O
SO3+0.5C SO2+CO2
Desorbed SO2 is reduced into elemental sulfur by coal at 900 C O

to be recovered. There is another method which oxidizes SO2


into SO3 to recover it as sulfuric acid.
During the development of this technology carried on at J-
Power’s Matsushima Thermal Power Plant, first, an active carbon
desulfurization method (with an adsorption tower unit) that can
treat gas of a 300Km3N/h (90KkW-equivalent) level in amount
was subjected to verification tests (1983-1986), obtaining 98%
SOx and some 30% NOx removal efficiency. For further
improvement in De-NOx performance, a combined
desulfurization De-NOx pilot plant that can treat 3,000m3N/h of
gas with two tower units was tested (1984-1986). SOx was
almost completely removed by the desulfurization tower at the Photo 1 Active Carbon-Method Desulfurizer

77
Clean Coal Technologies in Japan

(2)Electron beam method


Members in charge of research and development: Ebara
Corporation; Chubu Electric Power Co., Inc.; the Japan
Atomic Energy Research Institute; others
Kind of project: Voluntary project
Outline For this method, technology development was undertaken by
This method, as shown in Fig.2, injects an electron beam on Ebara Corporation and U.S. partners including DOE through their
SOx/NOx in exhaust gas and blown-in NH3 to cause a reaction joint contributions (1981-1987). In Japan, based on development
for their recovery as ammonium sulfate ((NH4)2SO4) or results, a pilot plant (that can treat gas of 12,000m3N/h) was built
ammonium nitrate (NH4NO3) in the downstream precipitator. By- at Chubu Electric Power’s Shin-Nagoya Power Plant, where the
products; ammonium sulfate and ammonium nitrate are used as technology has been verified (1991-1994).
fertilizers. The performance of 98% or more SOx and 80% NOx Regarding this technology, a plant that can treat gas of
removal efficiencies for the NH3/NO molar ratio of 1 is obtained at 300Km3N/h (90KkW) (Photo 2) was installed at Chengdu Heat-
70-120 C.
O
NOx removal efficiency also characteristically Electricity Factory (co-generation power plant) in Sichuan
increases with increasing SO2 concentration, though SOx province, China, and currently in operation for demonstration
removal efficiency does not affect the inlet concentration of SO2. under 80% NOx removal efficiency conditions.

Existing Air pre- Dry electrostatic


boiler heater precipitator

Smokestack
Air

Electron beam generator


Cooling water
Dry electrostatic
precipitator

Reactor
Cooling Ammonia equipment Granulator Nitrogen fertilizer
tower (ammonium sulfate/ammonium nitrate)
Fig.2 Electron Beam-Method Desulfurization Process

Photo 2 Electron Beam Method Desulferizer

References
1) Hanada et al, "Dry Desulfurization-Denitration-Technology Dry Active Carbon-Method Sulfur Recovery Formula at Coal Thermal Power Plant"
Thermal/Electronic Power Generation, Vol. 40, No. 3, 1989
2) "Renewing Isogo Thermal Power Plant" pamphlet, Electric Power Development Company
3) Aoki, "Electronic Beam Flue Gas Treatment Technology", Fuel Association Journal, Vol. 69, No. 3, 1990
4) S. Hirono et al, "Ebara Electro-Beam Simultaneous SOx/NOx Removal", proc 25th Int Tech Conf Util Sys 2000

78
Part2 Outline of CCT
Environmental Protection Technologies (Flue Gas Treatment and Gas Cleaning Technologies)

4B4. Soot/dust Treatment Technology and Trace Elements Removal Technology


Outline of technology

1.Background
Soot and dust are regulated, like NOx, under the provisions for bed combustion and coal gasification combined-cycle
by-fuel kind/-boiler size concentrations. At present, however, technologies is also under way for high-efficiency power
there are some regions subject to the total amount control which generation, using cyclones and ceramics/metal precision-removal
limits the overall emissions from each region as in the case of filters.
sulfur and nitrogen oxides. In coping with such regulations, an On the other hand, trace materials-related control is now being
electrostatic precipitator was employed in Yokosuka Thermal intensified such as through the addition of boron (B) and
Power Plant for the first time in the world in 1966 for mainly other selenium (Se) to waste water materials to be regulated and U.S.
thermal power plants to follow suit. Development of pressurized- regulations on mercury (Hg).

2.Technology
(1)Electrostatic precipitation method
Members in charge of research and development:
Mitsubishi Heavy Industries, Ltd.; Hitachi, Ltd.;
Sumitomo Heavy Industries, Ltd.; others
Outline
The electrostatic precipitation method is a method to remove DC high voltage

soot/dust in exhaust gas in accordance with the theory that any Power supply
dust negatively charged by corona discharge at the discharge
electrode adheres to the positive dust-collecting electrode. The
soot/dust that adhered to the electrode is allowed to come off and
drop by giving a shock to the electrode with a hammering device. Discharge electrode

The dust collection performance depends upon the electrical Collected


resistance of soot/dust, preferring particles of 104-1011 -cm in soot/dust

the apparent electrical resistivity range. In the case of pulverized Dust collecting
electrode
coal thermal, electrical resistance of many particles is high,
urging various measures to be taken against high-electrical
resistance particles.
As one of such measures, temperature conditions for dust
Flue gas
collection are adjusted. Electrical resistance changes as shown (from boiler)
in Fig.2. Those successfully developed/commercialized from the
Fig. 1 Theory of Electrostatic Precipitator
use of such characteristics are a high-temperature electrostatic
precipitator run at 350 C, a higher temperature than that of
O

conventional low-temperature electrostatic precipitators (130-


Low-alkali
150 C) to lower electrical resistance and an advanced low-
O
/high-sulfur coal
High-temperature ESP

temperature electrostatic precipitator run, with its electrical Low-alkali


/low-sulfur coal
resistance lowered by operating it at a dew point-or-lower
temperature (90-100 C). O
Other than these, successful
Electrical resistivity ( -cm)

commercialization is found in the moving electrode method which


brushes off soot/dust by moving the electrode to prevent back
corona due to dust accumulation at the electrode and a semi-wet
Advanced Low-temperature ESP

electrostatic precipitator where a film of liquid is shed to wash


Conventional low-temperature ESP

away dust. Another measure has also been taken with electric
discharge methods commercialized, including an intermittent High-alkali
charge method to supply a pulsed voltage on the order of several /high-sulfur coal

milliseconds and a pulse charge method for tens of High-alkali


/low-sulfur coal
microseconds-order energization.
At present, leading pulverized coal-firing plants built in and after
1990 are provided with very low-temperature electrostatic dust-
collection means that can treat different properties as well as Temperature(OC)
shapes of soot/dust. Fig. 2 Temperature Effects on Electrical Resistance of Coal Ash

79
Clean Coal Technologies in Japan

(2)High-temperature dust collection method


Members in charge of research and development: Mitsubishi Heavy Industries, Ltd.;
Hitachi, Ltd.; Kawasaki Heavy Industries Co., Ltd.; others
Outline
This is under development as a technology to remove soot/dust Plant but also under the EAGLE Project. It is also expected to
from hot gas for pressurized-bed combustion and integrated be used at an IGCC demonstration unit (250KkW) slated for
gasification combined-cycle (IGCC) power generation processes. initial operation in 2007.
This technology utilizes a multi-cyclone, ceramics- or metal-
based filter and the granular-bed method using silica or mullite
material where soot/dust is removed. Multi-cyclones are mainly
used for rough removal. Those used for precision removal
include ceramic or metal filters of a cylindrical porous body into
which SiC and other inorganic materials and iron-aluminum
alloys are formed (Photo 1). Such filters used here were
developed by Nihon Garasu Kogyo or overseas by Paul
Schumacher. Such technologies, now under durability
evaluation/demonstration, are used for pressurized-bed
combustion power generation at Hokkaido Electric Power’s
Tomato-Atsuma Thermal Power Plant, with their verification tests
conducted not only for IGCC at 200-ton/day Nakoso IGCC Pilot Photo 1 SiC Ceramic Filter

(3)Mercury removal method


Members in charge of research and development: Center for Coal Utilization, Japan
Kind of project: Subsidized coal production/utilization technology promotion project
Outline
Among trace contents of coal, mercury is cited as a material inorganic minerals, and lime stone as materials which absorb
released into the atmosphere at the highest rate, with about 30 mercury and is now evaluating their absorption characteristics.
percent of the failure to be removed at precipitators/desulfurizers The research results prove that, if the method to inject active
proved to be released. However, bivalent mercury (Hg2+) is carbon or an FCC ash catalyst into the flue for the removal of
nearly all removed, leaving nonvalent one (Hg) as discharge metal mercury is combined with removal at the flue gas
matter. A method to remove this nonvalent mercury is under desulfurizer, 90% or more mercury can be removed easily.
active review. The Center for Coal Utilization, Japan, though still
in the process of basic research, selected active carbon, natural

References

1) "Thermal/Nuclear Power Generation Companion, 6th edition", Thermal/Nuclear Power Generation Association, 2002
2) Sato, "Design and Actual Operations of High-Temperature Electrostatic Precipitators", Thermal/Nuclear, Vol. 34, No. 4, 1983
3) Tsuchiya et al, "Technology Development of Low Low-Temperature EP in Coal Thermal-Purpose High-Performance Flue Gas Treatment System",
MHI Technical Journal Vol. 34, No. 3, 1997
4) "Toward the Realization of Integrated Gasification Combined-Cycle Power Generation", CRIEPI Review, No. 44, 2001
5) Coal-Based Next-Generation Technology Development Survey
/Environment-Friendly Coal Combustion Technology Field (Trace Element Measurement/Removal Technology), NEDO results report, 2003

80
Part2 Outline of CCT
Environmental Protection Technologies (Flue Gas Treatment and Gas Cleaning Technologies) Clean Coal Technologies in Japan

4B5. Gas Cleaning Technology Dust filter


To dust collector Coal gas (from dust collector)
Gas for sulfur reduction

Heat
Cyclone Anthracite exchanger
Outline of technology SOx Air
Desulfurization Reproduction tower reduction tower Sulfur
agent recovery
1.Background Desulfurization Sulfur
condenser equipment
tower Desulfurization process Reduction process Reduction process
For the development of coal gasification gas-based power For solution of problems with such a wet gas purification method,
generation and fuel synthesis technologies, it is necessary to efforts are now exercised to develop dry gas purification Sulfur
Air
remove sulfur compounds (H2S, COS), halides (HCl, HF), and COS Scrubber (dehalogenation, To gas turbine Gas in excess
Carrier
other gas contents. As shown in Fig.1 a main application of this Ceramic conversion catalyst deammonification) Ash Fig.4 Fixed-Bed Desulfurization Process
filter Sulfur
technology is found in the wet gas purification method which, after Coal gas

removing water-soluble halides and other contents by a water Coal


gasifier Separator Soot/dust filter
scrubber, desulfurizes the gas with a methyldiethylamine (MDEA) Fig.3 Fluidized-Bed Desulfurization Process
or other amine-based liquid absorbent for gas purification. This Distributor
Nakoso Pilot Plant Project. This fact indicates that IGCC- Soot/dust
method, however, requires the gas to be cooled down to around Sulfur recovery
equipment dedicated technologies have already reached their validation To sulfur recovery
room temperature, thus losing much heat. Furthermore, the
stage. system
process becomes complex since it requires not only a heat
At present, a desulfurization agent that can reduce sulfur Air
exchanger but also a catalyst which changes hard-to-remove COS H 2S
absorption Renewal tower
tower compounds to a 1ppm level is under development for use in such To sulfur recovery
into H2S. It is also difficult to precisely reduce sulfur compounds to Reboiler Reduction gas system
applications as molten carbonate fuel cells, solid oxide fuel cells, (coal gas)
a 1-ppm level. Fig. 1 Wet Gas Purification Process
and fuel synthesis. At the Central Research Institute of Electric
Power Industry (CRIEPI), a desulfurization agent using zinc Coal gas To gas turbine
ferrite (ZnFe2O4), a double oxide of iron and zinc, has been
2.Technology
developed and found capable of reduction to 1ppm or less, now
(1)Dry desulfurization method
being at the stage of real-gas validation. Efforts to cope with air-
Members in charge of research and development: Center for Coal Utilization, Japan; IGCC Research Association; 1. Regeneration tower
blown entrained-bed gasification gas have so far been the main 2. Reduction tower Desulfurization
Technology Research Association for Molten Carbonate Fuel Cell Power Generation System; Central Research
theme of review while another important problem is adaptation to 3. Desulfurization tower agent carrier
Institute of Electric Power Industry; Electric Power Development Company; Ishikawajima-Harima Heavy Industries Co., Ltd.;
Mitsubishi Heavy Industries, Ltd.; Kawasaki Heavy Industries, Ltd. high-carbon monoxide concentration gas like oxygen-blown
Kind of project: Voluntary project /NEDO-commissioned business gasification gas which degrades the desulfurication agent by
Fig.5 Moving-Bed Combined Dust Collection-Desulfurization Process
Development period: 1986-1998 allowing carbon to be separated out in it.

Outline Nakoso IGCC Pilot Plant Project (for coal gas production of
It is a method in which, as shown in Fig. 2, metal oxides are 43,600m3N/h in amount), a pilot plant that can treat the amount (2)Dry dehalogenation method
reduced by coal gasification gas, and reduced metal oxides of coal gas produced by a tenth and is under verification of Members in charge of research and development: Central Research Institute of Electric Power Industry
remove sulfur compounds from gas, then are converted to performance. Meanwhile, Kawasaki Heavy Industries, Ltd. has Kind of project: Voluntary project
sulfides. This method can be used more than once by letting developed an iron oxide-based highly wear-resistant granular
sulfides react with oxygen for the release of sulfur contents as desulfurization agent for use in a moving-bed combined- Outline
1ppm or less. At present, a method to remove HCl/HF contents
SO2 to bring back metal oxides. desulfurization/dust collection system (Fig.5) and evaluated its For the use of coal gasification gas in molten carbonate/solid
of gas as NaCl/NaF, using a sodic compound is under
The development of this method as a technology for integrated performance at the pilot plant capable of treating the 1/40 amount oxide fuel cells and fuel synthesis, it is necessary to remove not
development. CRIEPI test-made a sodium aluminate (NaAlO2)-
gasification combined-cycle power generation (IGCC) was of coal gas produced, which was buiilt under the 200-Ton/Day only soot/dust and sulfur compounds but also halogen
based absorbent, confirming possible reduction to 1ppm or less,
promoted, targeting to reduce sulfur oxides to 100ppm or less in compounds.
but such efforts still remain on a laboratory scale as well as
the temperature range of 400-500 C where economical carbon
O For the adaptation to these technologies, efforts are under way
developing stage. This method faces an important problem of
Reduction to develop a halide absorption agent capable of reduction to
steel can be used for piping. As the metal oxide to be used, iron how the absorbent should be reproduced or recycled.
oxide was selected and Ishikawajima-Harima Heavy Industries Mt: Elementary metal
Co., Ltd. built a fluidized-bed desulfurization pilot plant (Fig.3)
that can treat the total amount of coal gas, using 100-200- m References
iron ore particles, and is now under verification for performance, 1) Nakayama et al, "Development State of 3 Dry Gas Cleanup Methods in Dry Gas Cleanup Technology Development for Integrated
under the 200-Ton/Day Nakoso IGCC Pilot Plant Project (1991- Gasification Combined-Cycle Power Generation", the Japan Institute of Energy Journal, Vol. 75, No. 5, 1996
Reproduction Desulfurization
1995). On the other hand, the Central Research Institute of 2) Shirai et al, "Coal Gasification Gas-Based Fixed-Bed Dry Desulfurization Technology Development",
Electric Power Industry and Mitsubishi Heavy Industries, Ltd. , the Society of Powder Technology, Japan’s journal, Vol. 40, No. 8, 2003
assuming its use in fixed-bed desulfurization systems (Fig.4), 3) M. Nunokawa et al, "Developments of Hot Coal Gas Desulfurization and Dehalide Technologies for IG-MCFC Power Generation System",
have jointly developed an iron oxide-based honeycomb CEPSI proceedings 2002 Fukuoka
desulfurization agent. They also built, under the 200-Ton/Day Fig. 2 Desulfurization Reaction Cycle

81 82
Part2 Outline of CCT
Environmental Protection Technologies (Flue Gas Treatment and Gas Cleaning Technologies) Clean Coal Technologies in Japan

4B5. Gas Cleaning Technology Dust filter


To dust collector Coal gas (from dust collector)
Gas for sulfur reduction

Heat
Cyclone Anthracite exchanger
Outline of technology SOx Air
Desulfurization Reproduction tower reduction tower Sulfur
agent recovery
1.Background Desulfurization Sulfur
condenser equipment
tower Desulfurization process Reduction process Reduction process
For the development of coal gasification gas-based power For solution of problems with such a wet gas purification method,
generation and fuel synthesis technologies, it is necessary to efforts are now exercised to develop dry gas purification Sulfur
Air
remove sulfur compounds (H2S, COS), halides (HCl, HF), and COS Scrubber (dehalogenation, To gas turbine Gas in excess
Carrier
other gas contents. As shown in Fig.1 a main application of this Ceramic conversion catalyst deammonification) Ash Fig.4 Fixed-Bed Desulfurization Process
filter Sulfur
technology is found in the wet gas purification method which, after Coal gas

removing water-soluble halides and other contents by a water Coal


gasifier Separator Soot/dust filter
scrubber, desulfurizes the gas with a methyldiethylamine (MDEA) Fig.3 Fluidized-Bed Desulfurization Process
or other amine-based liquid absorbent for gas purification. This Distributor
Nakoso Pilot Plant Project. This fact indicates that IGCC- Soot/dust
method, however, requires the gas to be cooled down to around Sulfur recovery
equipment dedicated technologies have already reached their validation To sulfur recovery
room temperature, thus losing much heat. Furthermore, the
stage. system
process becomes complex since it requires not only a heat
At present, a desulfurization agent that can reduce sulfur Air
exchanger but also a catalyst which changes hard-to-remove COS H 2S
absorption Renewal tower
tower compounds to a 1ppm level is under development for use in such To sulfur recovery
into H2S. It is also difficult to precisely reduce sulfur compounds to Reboiler Reduction gas system
applications as molten carbonate fuel cells, solid oxide fuel cells, (coal gas)
a 1-ppm level. Fig. 1 Wet Gas Purification Process
and fuel synthesis. At the Central Research Institute of Electric
Power Industry (CRIEPI), a desulfurization agent using zinc Coal gas To gas turbine
ferrite (ZnFe2O4), a double oxide of iron and zinc, has been
2.Technology
developed and found capable of reduction to 1ppm or less, now
(1)Dry desulfurization method
being at the stage of real-gas validation. Efforts to cope with air-
Members in charge of research and development: Center for Coal Utilization, Japan; IGCC Research Association; 1. Regeneration tower
blown entrained-bed gasification gas have so far been the main 2. Reduction tower Desulfurization
Technology Research Association for Molten Carbonate Fuel Cell Power Generation System; Central Research
theme of review while another important problem is adaptation to 3. Desulfurization tower agent carrier
Institute of Electric Power Industry; Electric Power Development Company; Ishikawajima-Harima Heavy Industries Co., Ltd.;
Mitsubishi Heavy Industries, Ltd.; Kawasaki Heavy Industries, Ltd. high-carbon monoxide concentration gas like oxygen-blown
Kind of project: Voluntary project /NEDO-commissioned business gasification gas which degrades the desulfurication agent by
Fig.5 Moving-Bed Combined Dust Collection-Desulfurization Process
Development period: 1986-1998 allowing carbon to be separated out in it.

Outline Nakoso IGCC Pilot Plant Project (for coal gas production of
It is a method in which, as shown in Fig. 2, metal oxides are 43,600m3N/h in amount), a pilot plant that can treat the amount (2)Dry dehalogenation method
reduced by coal gasification gas, and reduced metal oxides of coal gas produced by a tenth and is under verification of Members in charge of research and development: Central Research Institute of Electric Power Industry
remove sulfur compounds from gas, then are converted to performance. Meanwhile, Kawasaki Heavy Industries, Ltd. has Kind of project: Voluntary project
sulfides. This method can be used more than once by letting developed an iron oxide-based highly wear-resistant granular
sulfides react with oxygen for the release of sulfur contents as desulfurization agent for use in a moving-bed combined- Outline
1ppm or less. At present, a method to remove HCl/HF contents
SO2 to bring back metal oxides. desulfurization/dust collection system (Fig.5) and evaluated its For the use of coal gasification gas in molten carbonate/solid
of gas as NaCl/NaF, using a sodic compound is under
The development of this method as a technology for integrated performance at the pilot plant capable of treating the 1/40 amount oxide fuel cells and fuel synthesis, it is necessary to remove not
development. CRIEPI test-made a sodium aluminate (NaAlO2)-
gasification combined-cycle power generation (IGCC) was of coal gas produced, which was buiilt under the 200-Ton/Day only soot/dust and sulfur compounds but also halogen
based absorbent, confirming possible reduction to 1ppm or less,
promoted, targeting to reduce sulfur oxides to 100ppm or less in compounds.
but such efforts still remain on a laboratory scale as well as
the temperature range of 400-500 C where economical carbon
O For the adaptation to these technologies, efforts are under way
developing stage. This method faces an important problem of
Reduction to develop a halide absorption agent capable of reduction to
steel can be used for piping. As the metal oxide to be used, iron how the absorbent should be reproduced or recycled.
oxide was selected and Ishikawajima-Harima Heavy Industries Mt: Elementary metal
Co., Ltd. built a fluidized-bed desulfurization pilot plant (Fig.3)
that can treat the total amount of coal gas, using 100-200- m References
iron ore particles, and is now under verification for performance, 1) Nakayama et al, "Development State of 3 Dry Gas Cleanup Methods in Dry Gas Cleanup Technology Development for Integrated
under the 200-Ton/Day Nakoso IGCC Pilot Plant Project (1991- Gasification Combined-Cycle Power Generation", the Japan Institute of Energy Journal, Vol. 75, No. 5, 1996
Reproduction Desulfurization
1995). On the other hand, the Central Research Institute of 2) Shirai et al, "Coal Gasification Gas-Based Fixed-Bed Dry Desulfurization Technology Development",
Electric Power Industry and Mitsubishi Heavy Industries, Ltd. , the Society of Powder Technology, Japan’s journal, Vol. 40, No. 8, 2003
assuming its use in fixed-bed desulfurization systems (Fig.4), 3) M. Nunokawa et al, "Developments of Hot Coal Gas Desulfurization and Dehalide Technologies for IG-MCFC Power Generation System",
have jointly developed an iron oxide-based honeycomb CEPSI proceedings 2002 Fukuoka
desulfurization agent. They also built, under the 200-Ton/Day Fig. 2 Desulfurization Reaction Cycle

81 82
Part2 Outline of CCT
Environmental Protection Technologies (CO2 Recovery Technologies) Clean Coal Technologies in Japan

3.Characteristics of HyPr-RING Process


4C1. Hydrogen Production by Reaction Integrated Novel Gasification Process (Hypr-RING) Cold gas efficiency Ca(OH)2 in the furnace is employed. Gasification at a temperature
HyPr-RING Process gasifies an easy-to-gasify portion under as low as possible is also employed to prevent eutectic melting of
In charge of research and development: Center for Coal Utilization, Japan; National Institute of Advanced
low-temperature (600-700 C) conditions into hydrogen and
O
calcium minerals. In such cases, unreacted product carbon can be
Industrial Science and Technology; Ishikawajima-Harima Heavy Industries Co., Ltd.; Babcook Hitachi K.K.; Mitsubishi
Materials Corporation; JGC Corporation uses the remaining hard-to-react char as fuel for CaCO3 used as a heat source for CaO reproduction.
Project type: Subsidized by the Ministry of Economy, Trade and Industry calcination.

Methane reforming
Coal
1,000t/d Mixing
Period: 2000-2010 In such cases, recovery of pure CO2 requires its burning with Heat
exchange
oxygen. Fig. 3 shows an example of process configuration with Cyclone
Rock hopper
a fluidized bed gasifier and an internal combustion-type
Outline of Technology
calcining furnace. For product gas composition of 95% H2 and
1.Background 5% CH4, the cold gas efficiency proved about 0.76.
Coal, the world’s most abundantly reserved energy resources, is and more efficiently, particularly, a technology contributing to CO2
Heat exchange
used as important primary energy due to its excellence in economic reduction. HyPr-RING Process is now under development for Absorbent CaO Gasifier

terms as well. Its consumption is expected to increase with the commercialization as a technology which, in an attempt to answer At the gasifier inlet, where temperature is low, CaO first reacts

Calcining
growth of economy as well as increasing population in the future. such a claim, enables hydrogen necessary for future hydrogen- with H2O to produce Ca(OH)2, providing heat to coal pyrolysis. Water
energy communities to be produced from coal and supplied. vapor
Meanwhile, solution of global environment problems, to begin with Then, at a high-CO2 partial pressure region, Ca(OH)2 absorbs O2
Coal supply
1,000t/d separation
the global warming due to CO2, has become a task assigned to CO2 to produce CaCO3, releasing heat. This heat is used for
Heating value
the gasification of char. 6,690kcal/kg
human beings, earnestly claiming a technology to use coal clean
Cold gas
To prevent CaO from becoming less active due to high- efficiency
0.76
2.Theory of HyPr-RING Process temperature sintering, a method of absorbing CO2 by way of Steam turbine

HyPr-RING Process is a process in which a CO2-absorbent CaO What is difference from Conventional gasification? Fig. 3 Analysis of HyPr-RING process
is directly added into the coal gasifier and the CO2 thus produced Conventional gasification secures the heat necessary for
is fixed as CaCO3 to finish preparing hydrogen within a furnace. gasification by partial combustion of coal, with a reaction 4.Outline of project
The reaction between CaO and H2O causes heat so that the heat expressed by the following equation taking place in the gasifier: Under this project that started in 2000, process configuration Table 1 Targets
necessary for reaction is internally supplied in the furnace as a identification and FS through testing with batch/semi-continuous Item Target
great merit from a thermal point of view. Within the furnace, a One mole of input coal carbon gives about 1 mole of hydrogen equipment were paralleled with a variety of factor tests required.
1. Gasification efficiency 1. Cold gas efficiency: 75% or more
series of reactions from Equation (1) to Equation (4) and the (including that producible from CO). For this, however, In and after 2003, it is expected that 50-kg/d (coal base) continuous
2. Product gas purity 2. Sulfur contents of product gas: 1ppm or less
overall reaction of Equation (5) take place. gasification gas must be sent through a low-temperature shifter test equipment will be fabricated for continuous testing and then, 3. CO2 recovery 3. High-purity CO2 recovery rate: 40% or more
and then exposed to a low-temperature absorbent such as amine based on the results, running tests and FS of a 0.5-1t/d-scale bench of input coal carbon to be recovered (per-unit
for CO2 separation. At that time, the amount of CO2 gas plant are to be carried out in and after 2006 for its established of energy CO2 exhaust to be less than that
separated is 1 mole per mole of hydrogen. commercialization process. Table 1 shows development targets of from natural gas)

On the other hand, HyPr-RING Process uses dry CaO to absorb the project and Table 2 shows, the scheduleof the project.
CO2 in the furnace (650 C, 30atm). In this case, heat is released
O

with CO2 absorption and made available for maintaining high Table 2 Development Schedule
This overall reaction is an exothermic reaction with C, H2O, and temperature in the gasifier .
Item 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
CaO as starting reactants. This means there is no need of Here, post-CO2 absorption CaCO3 is returned to CaO by
external heat in theory. It is also found that CO2 fixation shifts (1)Fundamental test
calcination (reproduction) and, at that time, 50-80% of thermal

Mid-term evaluation

Pre-final evaluation
the reactions (2) and (3) to H2 generation.

Final evaluation
energy required changes into chemical energy of CaO for reuse (2)Acquisition of design data
Fig. 1 shows the process concept of HyPr-RING. Product CaCO3 in the gasifier (Fig. 2).
is reproduced by calcining into CaO for its recycle as an absorbent. As seen from Equation (5), 2-mol hydrogen production from 1 (3)50-kg/d test facility
Most of the heat energy required for calcining is carried as mol of carbon is another important feature.
(4) 500-kg/d PDU
chemical energy of CaO and made available for the reaction to give
H2 in the furnace. (5)FS

Pilot plant test


(moving to the 2nd phase)

References
1) Shiying Lin, Zenzo Suzuki & Hiroyuki Hatano, Patent No. 29791-49 (1999)
2) Energy Technology and the Environment, Editors: A. Bisio and S. Boots, John Wiley & Sons, New York, 1995
Fig. 1 Concept of HyPr-RING process Fig. 2 Hydrogen production using HyPr-RING process.
83 84
Part2 Outline of CCT
Environmental Protection Technologies (CO2 Recovery Technologies) Clean Coal Technologies in Japan

3.Characteristics of HyPr-RING Process


4C1. Hydrogen Production by Reaction Integrated Novel Gasification Process (Hypr-RING) Cold gas efficiency Ca(OH)2 in the furnace is employed. Gasification at a temperature
HyPr-RING Process gasifies an easy-to-gasify portion under as low as possible is also employed to prevent eutectic melting of
In charge of research and development: Center for Coal Utilization, Japan; National Institute of Advanced
low-temperature (600-700 C) conditions into hydrogen and
O
calcium minerals. In such cases, unreacted product carbon can be
Industrial Science and Technology; Ishikawajima-Harima Heavy Industries Co., Ltd.; Babcook Hitachi K.K.; Mitsubishi
Materials Corporation; JGC Corporation uses the remaining hard-to-react char as fuel for CaCO3 used as a heat source for CaO reproduction.
Project type: Subsidized by the Ministry of Economy, Trade and Industry calcination.

Methane reforming
Coal
1,000t/d Mixing
Period: 2000-2010 In such cases, recovery of pure CO2 requires its burning with Heat
exchange
oxygen. Fig. 3 shows an example of process configuration with Cyclone
Rock hopper
a fluidized bed gasifier and an internal combustion-type
Outline of Technology
calcining furnace. For product gas composition of 95% H2 and
1.Background 5% CH4, the cold gas efficiency proved about 0.76.
Coal, the world’s most abundantly reserved energy resources, is and more efficiently, particularly, a technology contributing to CO2
Heat exchange
used as important primary energy due to its excellence in economic reduction. HyPr-RING Process is now under development for Absorbent CaO Gasifier

terms as well. Its consumption is expected to increase with the commercialization as a technology which, in an attempt to answer At the gasifier inlet, where temperature is low, CaO first reacts

Calcining
growth of economy as well as increasing population in the future. such a claim, enables hydrogen necessary for future hydrogen- with H2O to produce Ca(OH)2, providing heat to coal pyrolysis. Water
energy communities to be produced from coal and supplied. vapor
Meanwhile, solution of global environment problems, to begin with Then, at a high-CO2 partial pressure region, Ca(OH)2 absorbs O2
Coal supply
1,000t/d separation
the global warming due to CO2, has become a task assigned to CO2 to produce CaCO3, releasing heat. This heat is used for
Heating value
the gasification of char. 6,690kcal/kg
human beings, earnestly claiming a technology to use coal clean
Cold gas
To prevent CaO from becoming less active due to high- efficiency
0.76
2.Theory of HyPr-RING Process temperature sintering, a method of absorbing CO2 by way of Steam turbine

HyPr-RING Process is a process in which a CO2-absorbent CaO What is difference from Conventional gasification? Fig. 3 Analysis of HyPr-RING process
is directly added into the coal gasifier and the CO2 thus produced Conventional gasification secures the heat necessary for
is fixed as CaCO3 to finish preparing hydrogen within a furnace. gasification by partial combustion of coal, with a reaction 4.Outline of project
The reaction between CaO and H2O causes heat so that the heat expressed by the following equation taking place in the gasifier: Under this project that started in 2000, process configuration Table 1 Targets
necessary for reaction is internally supplied in the furnace as a identification and FS through testing with batch/semi-continuous Item Target
great merit from a thermal point of view. Within the furnace, a One mole of input coal carbon gives about 1 mole of hydrogen equipment were paralleled with a variety of factor tests required.
1. Gasification efficiency 1. Cold gas efficiency: 75% or more
series of reactions from Equation (1) to Equation (4) and the (including that producible from CO). For this, however, In and after 2003, it is expected that 50-kg/d (coal base) continuous
2. Product gas purity 2. Sulfur contents of product gas: 1ppm or less
overall reaction of Equation (5) take place. gasification gas must be sent through a low-temperature shifter test equipment will be fabricated for continuous testing and then, 3. CO2 recovery 3. High-purity CO2 recovery rate: 40% or more
and then exposed to a low-temperature absorbent such as amine based on the results, running tests and FS of a 0.5-1t/d-scale bench of input coal carbon to be recovered (per-unit
for CO2 separation. At that time, the amount of CO2 gas plant are to be carried out in and after 2006 for its established of energy CO2 exhaust to be less than that
separated is 1 mole per mole of hydrogen. commercialization process. Table 1 shows development targets of from natural gas)

On the other hand, HyPr-RING Process uses dry CaO to absorb the project and Table 2 shows, the scheduleof the project.
CO2 in the furnace (650 C, 30atm). In this case, heat is released
O

with CO2 absorption and made available for maintaining high Table 2 Development Schedule
This overall reaction is an exothermic reaction with C, H2O, and temperature in the gasifier .
Item 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
CaO as starting reactants. This means there is no need of Here, post-CO2 absorption CaCO3 is returned to CaO by
external heat in theory. It is also found that CO2 fixation shifts (1)Fundamental test
calcination (reproduction) and, at that time, 50-80% of thermal

Mid-term evaluation

Pre-final evaluation
the reactions (2) and (3) to H2 generation.

Final evaluation
energy required changes into chemical energy of CaO for reuse (2)Acquisition of design data
Fig. 1 shows the process concept of HyPr-RING. Product CaCO3 in the gasifier (Fig. 2).
is reproduced by calcining into CaO for its recycle as an absorbent. As seen from Equation (5), 2-mol hydrogen production from 1 (3)50-kg/d test facility
Most of the heat energy required for calcining is carried as mol of carbon is another important feature.
(4) 500-kg/d PDU
chemical energy of CaO and made available for the reaction to give
H2 in the furnace. (5)FS

Pilot plant test


(moving to the 2nd phase)

References
1) Shiying Lin, Zenzo Suzuki & Hiroyuki Hatano, Patent No. 29791-49 (1999)
2) Energy Technology and the Environment, Editors: A. Bisio and S. Boots, John Wiley & Sons, New York, 1995
Fig. 1 Concept of HyPr-RING process Fig. 2 Hydrogen production using HyPr-RING process.
83 84
Part2 Outline of CCT
Environmental Protection Technologies (CO2 Recovery Technologies)

4C2. CO2 Recovery and Sequestration Technology


Outline of technology

1.CO2 recovery technology


(1) CO2 recovery technology (for natural gas, syngas, and global warming, which can never be prevented unless CO2 release into
exhaust gas) air is mitigated. There are, however, many difficulties in recovering and
CO2 separation/recovery widely prevails in natural gas and syngas sectors sequestrating CO2 from movable bodies such as automobiles and
and already has a decades-long history. CO2 contents of natural gas are not vessels, naturally rendering it easier to recover CO2 from boilers, gas
only useless themselves because of making natural gas less caloric but also turbines, and other fixed sources.
trouble LNG/ethane recovery plants by solidifying CO2 into dry ice. CO2 is (3) Characteristics and superiority of technology to recover CO2
hence removed to prevent such troubles. from exhaust gas
In a plant where natural gas or naphtha is reformed to manufacture H2, CO2 The Kansai Electric Power Co., Inc. and Mitsubishi Heavy Industries,
is separated after converted from the CO produced with hydrogen as Ltd. started in 1999 a joint R&D program to recover CO2 from exhaust
syngas. In an ammonia/urea plant, CO2 is separated from the gas mixture of gas of power plants and other facilities as a measure against the global
H2, N2, and CO2 to produce urea, using H2/N2-derived synthetic ammonia warming. First, they assessed the conventional "monoethanolamine
and separated CO2. (MEA) liquid absorbent-based technology considered at that time a
Previously, however, CO2 separation/recovery from exhaust gas was not in CO2 recovery process that could save the largest amount of energy. It
so large demand, finding limited applications only in food/dry ice production. is a process developed by former Dow Chemical Co. and later
In case that CO2 is separated from natural gas or syngas, the separation is assigned to Fluor Daniel, Inc. This MEA-based technology was found
relatively easy because of a high gas pressure while CO2 disadvantageous for use in large plants as a measure against the
separation/recovery from exhaust gas is difficult in many technological global warming because of such problems as a large amount of energy
respects due to a very low level of exhaust gas pressure as well as oxygen, required for CO2 recovery and a great loss in the liquid absorbent due
SOx, NOx, and soot/dust that are contained in exhaust gas. to its rapid deterioration. Kansai Electric Power and Mitsubishi Heavy
(2) Necessity to recover CO2 from fixed sources Industries started with basic research to explore a new liquid absorbent,
Most of fossil fuel (oil, natural gas, and coal) in the world is used as fuel resulting in successful development of a novel energy-saving and
of boilers, gas turbines, and internal combustion engines, releasing uneasier-to-be-deteriorated/-lost liquid absorbent, which has already
CO2 into the atmosphere as exhaust gas. As a result, it is alleged that been put into practice for urea manufacture in Malaysia.
the atmospheric concentration of CO2 has increased to cause the

2.CO2 sequestration technology


As for methods of CO2 sequestration, geological sequestration and in these cavities, which indigenously contains water (mainly salt water),
ocean sequestration are widely studied and a commercial project of the by pressing in it there to replace water. This has already started in
former has already started. Norway. For Japan, Norway-like CO2 sequestration into aquifers
Geological sequestration of CO2 is practiced, using the Enhanced Oil distributed over continental shelves is considered the most realistic.
Recovery (EOR) method or the coal seam sequestration-accompanied Other than into aquifers, CO2 can also be sequestrated into closed
Coal Bed Methane Recovery method but, if intended only for CO2 oil/gas fields where production had already terminated. Closed oil/gas
sequestration, methods of aquifer sequestration and sequestration into fields may, since their ceilings are so geologically structured from ancient
closed oil/gas fields may also be used. Fig. 1 shows a conceptual view times as not to permit any oil/gas leaks for possible formation of oil/gas
of CO2 recovery - EOR combination. wells, be CO2 containment-secured locations for pressing in CO2
CO2-EOR commercialization started in the 1970’s mainly in the United
States, realizing the present enhanced oil production of about 200
thousand barrels a day. Outside the United States, such practice is also
witnessed in Canada, Turkey, and Hungary. In terms of by-application
consumption, EOR purposes are the largest in fact.
Underground aquifers are widely distributed wherever on the earth
sedimentary layers are located. Even in Japan, where aquifers are
scarce and, if any, small in structure because it is a volcanic country and,
therefore, a country of earthquakes, surveys are under way, seeking the
possibility of CO2 sequestration.
If a geological underground layer has cavities, CO2 can be sequestrated Photo 1 Conceptual View of Practice to Recover CO2 from
Power Plant Exhaust Gas for EOR

Reference
Masaki Iijima et al, "CO2 Recovery/Effective Utilization/Fixation and Commercialization", MHI Technical Journal, 39(5), 286 (2002)

85
Clean Coal Technologies in Japan

4C3. CO2 Conversion Technology


Outline of technology

1.Urea production
At present, urea is manufactured by synthesizing ammonia with
inexpensive natural gas as its main material to use this ammonia
with the CO2 derived as off-gas at that time for synthesis of urea.
When urea is synthesized with natural gas as raw material,
however, CO2 may sometimes be short in view of the balance
between ammonia and off-gas CO2. In such cases, CO2 is
recovered from exhaust gas of the steam reformer, which
manufactures hydrogen and CO from natural gas, for the supply
to urea synthesis to adjust the ammonia-CO2 balance, thereby
enabling urea to be produced in largest quantities. The plant
Mitsubishi Heavy Industries, Ltd. delivered to Malaysia
PETRONAS Fertilizer Sdn. Bhd. matches this purpose. Photo 1
shows the appearance of this plant.
Photo 1 Total view of Plant
2.Methanol production
Methanol is now also manufactured mainly with natural gas as steam reformer exhaust gas to optimize the H2:CO ratio for
raw material. If H2 and CO are synthesized by steam-reforming methanol synthesis, thereby enhancing methanol production.
natural gas, then the H2:CO ratio is 3:1. On the other hand, for
methanol synthesis, the best H2:CO ratio is 2:1 but the output of
methanol can be maximized through the recovery of CO2 from CO2
CO2 recovery
steam reformer exhaust gas to add a worthwhile amount of CO2
Exhaust gas
in carbon contents within the process. At present, active Natural gas Syngas Methanol Methanol
Steam reformer compressor synthesis
Steam
planning for CO2 addition is under way to improve the production
capacity of Saudi Arabian methanol plants. Fuel
Fig. 1 shows a system where, in the process to produce Fig. 1 System to recover CO2 from exhaust gas for enhanced methano
methanol with natural gas as raw material, CO2 is recovered from production in a methanol plant

3.DME (dimethylether) production


DME is currently synthesized by way of methanol. The process
uses a system similar to that for the above-mentioned methanol CO2
CO2 recovery
production. Exhaust gas
Natural gas Syngas Methanol DME DME
Steam reformer compressor synthesis
Steam synthesis

Fuel
Fig. 2 CO2 recovery from exhaust gas-integrated DME production system

4.GTL production
GTL is the acronym of Gas to Liquid generally referring to a
process to synthesize kerosene and light oil by Fischer-Tropsch
CO2
Method (FT Method). For this GTL synthesis, it is necessary to CO2 recovery

adjust the H2:CO ratio to 2:1 like in the case with methanol and Exhaust gas
Natural gas Syngas FT Liquid fuel
Steam reformer
the same recovery of CO2 from steam reformer exhaust gas for Steam compressor Synthesis
its input within the process system as in methanol production
Fuel
enables the H2:CO ratio to be adjusted.
The method used for the system as a whole, however, recycles Fig. 3 CO2 recovery from exhaust gas-integrated liquid fuel production system
CO2 not contributing to the reaction from FT Synthetic System to
the stream before the steam reformer.

Reference
Masaki Iijima et al, "CO2 Recovery/Effective Utilization/Fixation and Commercialization", MTI Technical Journal, 39(5), 286 (2002)

86
Part2 Outline of CCT
Environmental Protection Technologies (CO2 Recovery Technologies)

4C4. Oxy-fuel Combustion (Oxygen-firing of conventional PCF System)


In charge of research and development: Center for Coal Utilization, Japan; Electric Power Development Co., Ltd.;
Ishikawajima-Harima Heavy Industries, Co., Ltd.; Nippon Sanso Corp.; and Institute of Research and Innovation
Project type: Coal Production and Utilization Technology Promotion Grant
Period: 1992-2000 (8 years)

Outline of technology

1.Background and process outline


Efforts of reduction in CO2 emissions have been promoted over the from large scale coal-fired power plants.
world responding to the issues of global warming in recent years. Ordinary coal-fired power plants combust coal by air. Since air
Specifically, coal is known as a source of heavy emissions of contains N2 by 79%, all of the N2 is emitted to atmosphere during
environmental loading substances (SOx, NOx, CO2, etc.), though the combustion process, thus the CO2 concentration in the
the coal is expected as a sustainable energy resource also in the combustion flue gas is only 13-15% level. The oxygen combustion
future. Since coal generates large quantity of CO2 per unit calorific technology is a process to separate oxygen from the combustion
value, research and development of the CO2 recovery and CO2 air and to directly combust the coal with thus separated oxygen to
separation technologies are in progress on various points of views. increase the CO2 concentration in the flue gas to 90% or more,
With the background, the study team focused on the development then to recover the flue gas in that state (refer to Fig. 1.)
of technology to recover CO2 from coal-fired power plants utilizing Furthermore, the study team investigated a CO2 recovery system
oxygen (O2/CO2) combustion, and has promoted the research of applying oxygen-blow IGCC aiming to further increase the
CO2 recovery technology. The CO2 recovery in the oxygen efficiency.
combustion stage is a hopeful technology of direct CO2 recovery

Ordinary recovery process


Recovery process using oxygen combustion

Stack Coal Compressor


Air Air Boiler Dust removal
Coal CO2 separation
Boiler Dust removal Desulfurization separator
and recovery
Air
Compressor
O2/CO2 Flue gas recycle

Recovered
Recovered
CO2
CO2

Fig. 1 Comparison of CO2 recovery between oxygen combustion


process and ordinary air combustion process

2.Result of the development


Efforts of reduction in CO2 emissions have been promoted over the of technology to recover CO2 from coal-fired power plants utilizing
world responding to the issues of global warming in recent years. oxygen (O2/CO2) combustion, and has promoted the research of
Specifically, coal is known as a source of heavy emissions of CO2 recovery technology. The CO2 recovery in the oxygen
environmental loading substances (SOx, NOx, CO2, etc.), though combustion stage is a hopeful technology of direct CO2 recovery
the coal is expected as a sustainable energy resource also in the from large scale coal-fired power plants.
future. Since coal generates large quantity of CO2 per unit calorific Ordinary coal-fired power plants combust coal by air. Since air
value, research and development of the CO2 recovery and CO2 contains N2 by 79%, all of the N2 is emitted to atmosphere during
separation technologies are in progress on various points of views. the combustion process, thus the CO2 concentration in the
With the background, the study team focused on the development combustion flue gas is only 13-15% level. The oxygen combustion

87
Clean Coal Technologies in Japan

technology is a process to separate oxygen from the combustion


CO2 recovery type oxygen pulverized coal combustion power plant
air and to directly combust the coal with thus separated oxygen to
increase the CO2 concentration in the flue gas to 90% or more,
then to recover the flue gas in that state (refer to Fig. 1.)
Furthermore, the study team investigated a CO2 recovery system
applying oxygen-blow IGCC aiming to further increase the
CO2 underground disposal Boiler
efficiency. Oxygen production facility

CO2 tank

CO2 ocean disposal

Fig. 2 Image-drawing of CO2 recovery type power plant applying


oxygen combust

3.Issues and feasibility to practical application


Regarding the CO2 recovery type oxygen combustion power the global warming and for reducing the CO2 emissions, though

generation system and the CO2 recovery type IGCC, the study there are technologically validating issues such as the safety of

team conducted research and development and has proposed a power generation system with the oxygen combustion and the

power generation system which has superiority in terms of operability of CO2 recovery type IGCC. As for the practical

performance and economy as a CO2 recovery technology. In application of the system, positive study should be conducted on

addition, in the basic combustion test, the study team has acquired the basis of the obtained results, while studying the application of

academically valuable results (including the effect of reduction in the CO2 recovery type oxygen pulverized coal combustion system

NOx emissions). and of the CO2 recovery type IGCC, respectively, for the cases of

It should be emphasized to further promote the study for controlling application of CO2 recovery to an existing plant and of new plant.

Recovered CO2
CO2
compression
CO2

H 2O
CO CO2
Coal N2
CO2 CO-shift H2 H2
Gasification Gas purification reaction CO2 removal HRSG
H2
H 2O
Steam

Air Air
N2
Air separation
Air combustion gas turbine

Bleed

Fig. 3 CO2 recovery type IGCC system

References

1) Hiromi Shimoda: Proceeding of the 10th Coal Utilization Technology Conference, p.211 (2000)
2) S. Amaike: Proceeding of the 5th ASME/JSME Joint Thermal Engineering Conference, "AJTE99-6410" (1999)

88
Part2 Outline of CCT
Basic Technologies for Advanced Coal Utilization

5A1. Modelling and Simulation Technologies for Coal Gasification


In charge of research and development: Center for Coal Utilization, Japan
Project type: NEDO-commissioned project

Outline of technology

1.Outline of basic technology for advanced coal utilization (BRAIN-C)


The consumption of fossil fuel compacts on the environment in a on coal from different angles. In the meantime, numerical
variety of manners. Coal also influences the nature in each of its simulation is a very effective tool to predict characteristics of a
production, transportation, and utilization processes. In the pilot or actual production unit from the above-mentioned basic
process of its utilization in particular, coal dust, ash dust, acid gas data or, in reverse, to evaluate and select useful basic data. With
(NOx, SOx), and carbon dioxide are discharged, suggesting that this taken into consideration as well, technology development
unregulated guzzling of coal may possibly have a great impact on under the BRAIN-C is proceeded with from both aspects of useful
the environment. On the other hand, technologies to limit the basic data retrieval/storage and high-precision numerical
impacts derived from coal utilization on the environment to the simulation.
minimum, as measures to cope with the above-mentioned Fig.1 shows "BRAIN-C Technology Map." Products from this
situations, were collectively called Clean Coal Technology (CCT), project are roughly grouped into the following three categories:
for which advanced R&D is in wide practice in major advanced (1) Entrained flow gasification simulator
countries including Japan. (2) Predicted model/parameter correlative equation
With such circumstances , the "Basic Technology Development (3) Coal database
Program for Advanced Coal Utilization (BRAIN-C)," mainly Each category is explained below. Every categories, as integral
targeting at the coal gasification technology and to realize early part of products from this project, is indispensable for their actual
commercialization of new high-efficiency and clean coal use in a variety of situations, and ingenious utilization of each in
utilization technologies such as coal gasification and pressurized accordance with the situation where it is used allows such
fluidized-bed processes, has sought and accumulated basic data products to be given full play.

Volatilization model Trace element data

Volatile contents release data CPC actual measurement data


Basic database
Volatile contents database
Typical
temperature history
Char reaction data
Reaction database Volatile contents Trace element
composition in quantity al data
pic distribution model
Reaction Ty ature
r
temperature pe Program
constant tem
Coal Physicality Equilibrium model
Physicality database Gasification simulation code
(coal and char) Parameter
+General analysis correlative equation + RESORT
+Particle size-surface area + FLUENT
+Special analysis
ter temTypic Growth flowage
CCSEM, XRD, EDS me pe al
para da ratur judgment model
ia tion ta e
Rad

Heat transmission coefficient Adhesion


Particle size judgment equation
Heat transmission test data -
density fluctuation model Adhesion data
Particle radiation data

Fig. 1 BRAIN-C Technology Map

89
Clean Coal Technologies in Japan

2.Entrained flow gasification simulator


An entrained flow gasification simulator based on the thermal
fluid analysis software (CFD) capable of analyzing flow, reaction,
and heat transmission at the same time can calculate Simulation program
(For entrained-flow gasification)
temperature distribution, ash adhesion locations, gas Design: Furnace shape
composition, etc. within a gasifier if given as input data such Operation: Operational
parameters as reactor shapes, operation conditions, coal
conditions
Coal: Property
property and reaction data. It is imaged in Fig. 2 as "Functions
of an Entrained Flow Gasification Simulator." Highly reliable
prediction results can be used for evaluating operational
condition validity, reactor design, and others in advance. The
Pre-test judgment of
BRAIN-C, developing a coal gasification reaction model shown in
operational validity
Fig. 3 and a particle adhesion model shown in Fig. 4 in basic
Ash adhesion position Temperature distribution CO concentration
CFD, has compared their calculation results with gasifier
operation data in coal-based hydrogen production technology
(HYCOL) to verify the adequacy. Fig. 2 Functions of Entrained-Flow Gasification Simulator

Gas-phase
reaction

Product gas
Volatile contents release speed
Oxidizing agent
Volatile contents

Fixed carbon
Ash

Fixed carbon Gasification speed


Ash Gasification database Ash

Fig. 3 Coal Gasification Process Modeling

Particle viscosity
Particle adhesion judgment conditions

Judgment
value

Reflection

Judgment
value

Adhesion

Wall ash layer viscosity

Fig. 4 Ash viscosity-Based Adhesion Judgment Model

90
Part2 Outline of CCT
Basic Technologies for Advanced Coal Utilization

Fig. 5 shows an example of results from comparison between temperature and ash viscosity on the wall shown on the right side
the formation position of fused ash layer and the internal of Fig. 6 are from the result of calculation under operational
condition of gasifier after operations. This found the formation conditions changed intentionally. For this case, the oxygen ratio
position of fused ash layer calculated with this simulator well- of the chart top is higher and that of the bottom is lower than
corresponding to the position where the fused ash layer actually shown on the right side of the figure. In such cases, it was found
existed, endorsing the adequacy of calculation with actual data. that the temperature of the furnace bottom area goes down (in
Fig. 6 shows the result of case studies on HYCOL using orange color) and the low-ash-viscosity region (in blue) narrows
gasification simulation. The near-wall temperature and ash while the upper furnace part becomes hot (the region in red
viscosity on the wall shown on the left side of Fig. 6 are those increases) to form a region where ash is easier to adhere,
reproduced by calculation under the condition after 1,000-hour probably spoiling the operating conditions.
operation . The temperature of the furnace bottom area (in red In this way, using the gasification simulator, analysis can be
color) onto which slag flows down is found high against the low easily made even if gasification conditions are altered and,
ash viscosity in the region (in blue). The temperature of the upper therefore, an expectation is growing on its utilization in future
furnace part proves low (in green), giving conditions where gasification projects.
particles can hardly adhere. On the other hand, the wall-near

Case 3 Forecast value


Wall-near temperature

Temperature:
high
Growth of slag
Temperature:
low
Throttled section

Ash viscosity on the wall

The low-viscosity
Pressure region of the
detection terminal top expands.
Amount of adhesion
= amount of slag discharged A high-viscosity
Molten slag region of the
bottom appears.
Fig. 5 Ash Adhesion Position Verification Result Fig. 6 Simulator-Based Studies

3. Predicted model/parameter correlative equation


An entrained-flow gasification simulator is generalized against generalized volatilization model and the adhesion judgment
various furnace shapes and operational conditions but not equation are among the tools to prepare parameters. In the
against each coal characteristics. It is, therefore, necessary to meantime, a trace elements distribution model and an adhesion
input such characteristics into the simulator as a parameter by judgment equation model are models making judgments from
types of coal. This parameter generally uses the data obtained simulation results, playing another important role. Under the
from basic test equipment but, in view of quick evaluation, it is BRAIN-C, thus, prediction equations around a gasification
desirable to establish a means to obtain parameters from simulator have also been developed so that the simulator can be
general analysis of coal or structural physicality data (an used effectively and quickly.
advanced model referring as far as to predicted correlative
equations and experiment conditions). More specifically, a

91
Clean Coal Technologies in Japan

4.Coal Database
The development of a correlative equation or a model
indispensably requires physical and basic experiment data,
including general analysis data. There is, however, a big problem
that coal is different in characteristics for different lots arrived
even if its brand (name of the coal mine) is the same. It was, 20-liter container (two-shelf)
therefore, first necessary for each of testing bodies, where
physical and basic data were obtained, to use completely the
same samples of coal. Fig. 7 shows a coal sample bank installed
50-liter container
within the National Institute of Advanced Industrial Science and
Technology. Such unified management of analytical test samples
has materialized the shipment of identical samples to all testing Standard Sample Coal Storage Status (AIST)
research bodies.
As far as these identical sample-based data are concerned, the
measurement of typical data will be completed under this project
on 100 kinds of coal for general/special analysis data and, at
least 10 kinds of coal, depending upon data items, for basic
experiment data. Eventually, all of these measurement data are
to be contained in the Internet-accessible coal database. Some
of the data so far obtained have already been uploaded to the
server of CCUJ for available access or retrieval as shown in Fig.
8. Many of these data are stored in an easy-to-calculate/process
Excel file (see Fig. 9) and can also be downloaded. Standard Sample Coal (for delivery)

Fig. 7 Coal Sample Bank

100
100 kinds
kinds of
of coal
coal
General
General analysis/special
analysis/special analysis
analysis

Reaction
Reaction data,
data, etc.
etc.
Reaction
Reaction data,
data, etc.
etc.
Spreadsheet
Spreadsheet fileDownload
fileDownload
On-line
On-line retrieval
retrieval

Fig. 8 Coal Database Fig. 9 Basic Data Acquisition

5.Diffusion of basic coal utilization technology products


AAn entrained-flow gasification simulator so far developed under detailed service manuals as well as giving workshops for this
the BRAIN-C is capable of making practical predictions through purpose to encourage your ingenious utilization of these
the utilization of various models and basic data. The BRAIN-C products.
Project, soon to meet its final year in 2004, is developing a well- Despite the coal gasification technology’s predominance in this
equipped system to make a wide choice of programs and basic development project, those outside gasification projects are
data available so that you can use the products developed under strongly invited as well to use our simulation code, at least, since
this project to your hearts’ content. We are also preparing it can be widely used in combustion and other sectors.

92
Part2 Outline of CCT
Coproduction System

6A1. Co-generation System


Outline of technology

1.Definition of co-generation
The system which continuously takes out two or more sources of convert it into electricity and heat is called a co-generation
secondary energy such as by burning fuel (primary energy) to system.

2.Co-generation system
Co-generation systems are roughly divided into two types. One The former generally uses liquid or gas fuel and is often found as
is a type which turns a diesel engine, gas engine, gas turbine, or small-scale equipment for hotels, supermarkets, and hospitals.
other motor to generate power while recovering waste heat of the As for the latter, every type of fuel including coal is used as fuel
motor as hot water or steam through the thermal exchange at a for boilers and many are found as relatively large-scale industry-
boiler, etc. and the other generates power by rotating a steam use thermal power plants. Systems are further grouped into ones
turbine with the steam produced at boilers and, if necessary, take mainly to supply electricity (condensing turbines) and the others
out steam of desired pressure as process steam. mainly for steam (heat) supply (back pressure turbines).

Electricity
Electricity

Heating
Jacket cooling water Hot water

Cooling water Hot water supply


heat exchanger
Steam
Process steam

Generator Diesel or Waste heat Stack


gas engine recovery boiler

Fig.1 Typical Outline of a Diesel Engine/Gas Engine Co-generation System1)

3.Efficiency
In general, the power generation efficiency of a coal thermal commenced its electricity wholesale/supply activities as an
power generation plant which takes out only electricity is around independent power producer (IPP). Electric power products from
40%. On the other hand, the overall thermal efficiency of a co- No. 1 Unit already in operation from April, 2002 and No. 2 whose
generation system, which combines its power generation start of operation is slated for April, 2004 are all to be delivered to
efficiency and heat recovery efficiency, depends upon whether it the Kansai Electric Power, Inc.
is mainly to supply electricity or mainly to supply heat, with a level (2)Regional supply of heat
of as high as 80% achieved by the co-generation system mainly The steam to be used for power generation is partially taken out
for heat supply. for the supply of maximum 40t/h to 4 nearby sake-brewers. This
(1)Co-generation at a large-capacity coal thermal power plant amount, accounting for about 2% of the steam generated at
Kobe Steel’s Kobe Power Plant, a large-scale coal thermal power boilers, proves that the share of heat supply is small. The steam
plant of 1,400MW (700MW x 2 generators) in capacity, has generated at multiple boilers of each brewer has so far been put

93
Clean Coal Technologies in Japan

together at the header to be sent to a plant. At present,


however, with the header as a point of competitive taking,
steam extracted after working at turbines is directly supplied to
brewers in an attempt to save energy in the region as a whole.
(3)Heat supply conditions
Turbine extraction steam from a power plant, since it contains
trace amounts of hydrazine as an antirust, cannot be directly
supplied to brewers with a process where steam directly
contacts rice. The steam (secondary steam) produced
indirectly, using a steam generator operated with turbine
extraction steam (primary steam) as the heat source, is supplied
to brewers. The outline of a facility is shown in the right.

Full View of Power Plant3)

No.1 power plant


Steam
Boiler
Turbine Generator

Extracted
Steam

Feed water
Cooling water
(Sea water)

Primary steam

Backup Brewing companies


No.2 power plant
Secondary steam Sawanotsuru

Fukumusume

Steam Hakutsuru
generator Industrial
water
Drain cooler Gekkeikan
Industrial
water tank
Water supply processing

Fig.2 Outline of Heat Supply Facility4)

References
1) Shibamoto et al: Featured Thermal Power Plant Thermal Efficiency Improvement, Article 3 Thermal Efficiency Management Trend;
Thermal Control for a Power Generation System pp1242-1246, Vol. 54, No. 565, Thermal/Nuclear Power Generation (Oct., 2003)
2) The Thermal and Nuclear Power Engineering Society: Introductory Course IV. Industrial-Use Thermal Power Facilities, Etc. pp1539-
1546 Vol. 54, No. 567, Thermal/Nuclear Power Generation (Dec., 2003)
3) Kida et al: Outline of Power Generation Facilities at Kobe Steel’s Kobe Power Plant pp2-7, Vol. 53, No. 2, Kobe Steel Technical Report (Sept., 2003)
4) Miyabe et al: Kobe Steel’s Kobe Power Plant Surplus Steam-Based Heat Supply Facility pp14-18, Vol. 53, No. 2, Kobe Steel Technical Report (Sept., 2003)

94
Part2 Outline of CCT
Coproduction System

6A2. Coproduction System


Outline of technology

1.Feasibility of fuel coproduction power generation system


Conventional work for developing innovative process within a and assembling peripheral plants to produce various products
single industry faces a limit. To continue further reduction in CO2 enhance the unification of industries centering on the core plant,
emissions, it is necessary to give full scale review of the existing thus forming a coal industrial complex on the new energy and
energy and materials production systems and to develop materials production system. As a result, the current industrial
technologies that optimize the individual processes and the style progresses to the next generation hybrid industrial style
interface between processes not only to improve the conversion through the unification of industries.
efficiency and to save energy but also to fundamentally and The core technology of that type of fuel coproduction power
systematically change the energy and materials production generation system is the coal gasification technology. By
systems. combining the high efficiency power generation system such as
The "fuel coproduction power generation system" which IGFC with a process to co-produce storable fuel, the
produces power, fuel, and chemicals from coal improves the total normalization of load to gasification reactor and the significant
energy use efficiency through the unification of industries by reduction of CO2 emissions are attained.
structuring a coal industrial complex. Furthermore, waste heat source in the coal industrial complex is
In the fields of power, iron and steel, and chemicals where large utilized to recover chemicals from coal while conducting
amount of coal is consumed as the energy source, structuring a endothermic reactions, thus forming further high energy
core plant which produces energy and chemicals simultaneously, efficiency and upgraded coal industrial complex.

Existed or new facilities Steam


ST
steam boiler
GT Power
FC
Gasification Center
Coal + Biomass
(Waste, H2,CO
waste plastics, Fluidized bed Process steam Non-reacted
oil-base residue, etc.) gasification furnace H2 gas
for Fuel cell power generation,
fual for heating for Refinery, for Chemical plant

Coal Spouted bed for Hydrogen production DME market


gasification furnace H2,CO

DME for Petrochemical plant


Propylene
H2 for Hydrogenation and C2 distillate
Coal Thermal C4 distillate
decomposition furnace desulfurization at iron
works
H2,CO
for Iron works

BTX, etc.
for Petrochemical plant

CH4
Petrochemical plant, gas company

Fig.1 Energy Flow

95
Clean Coal Technologies in Japan

2. Co-produced fuel and raw materials for chemicals


Regarding the fuel and chemicals produced along with the power the U.S. There are further expectations in producing:
through the coal gasification, there are typical examples of DME which is applicable to the raw material for clean fuel and for
coproduction by coal gasification in abroad, depending on the propylene production;
need of relating companies: the production of synthetic fuel Hydrogen which is expected to increase the demand for the fuel
(GTL) etc. by SASOL group in South Africa; and the production of of fuel cells and for coming hydrogen-oriented society; and
acetyl chemicals by Eastman Chemical Company in USA. Other Clean gas for iron works which responds to the changes in
examples of chemicals synthesis by coal gasification include the energy balance at future iron works.
production of methanol, and of methane, in China, Europe, and

3. Coproduction system
The coproduction system produces both materials and energy to fuel while producing materials shall be emphasized from the
significantly reduce the exergy loss which occurred mainly in viewpoint of creation of new energy market and also of creation
combustion stage, and to achieve innovative and effective use of of new industries.
energy. The coal coproduction system centering on the coal gasification is
That is, the coproduction system is a new production system able to solve the environmental issues through the significant
which is not only the conventional system which aims to improve reduction in CO2 emissions by realizing high grade and
the energy conversion efficiency and the cogeneration system comprehensible coal utilization technology. That type of system
which effectively uses the generated thermal energy as far as technology development triggers the technological innovation in
possible but also the system to produce both energy and the coal utilization field, and the strong innovation is expected to
materials to significantly reduce the consumption of energy and increase the international competitive power and to encourage the
materials. By making the coproduction system clean, energy structuring circulation-oriented society. Also in the international
issue and the environmental issue are simultaneously solved and society, the development of the coproduction system should be an
it should activate economy. Consequently, the coproduction important technological issue to solve the global environmental
system that conducts production of energy such as power and issues.

Fuel
Power generation in existing steam turbine power generation system
Power
IGCC for industrial complex area Outside
Fuel for power Private power generation at iron works GT-CC sale
generation
Co-operative Thermal Power Company GT-CC
Steam

Power Steam BTX, etc. Gas

Recovered steam

Iron works Gas,Power,Steam,BTX, etc. Petroleum industrial complex


Fluidized bed Spouted bed gasification reactor Gas Process steam
fuel for heating gasification fuel for heating
reactor Thermal decomposition reactor
Non-reacted gas

Coal yard Shift reaction Residue oil


Waste H2/CO > 2

H2 separation DME production

Hydrogen Un-recovered gas

for Hydrogenation
Outside sale

Fig.2 Power generation, steam, fuel for process heating, hydrogen, DME, energy supply system in iron works
(The total efficiency of the coproduction system unified with the iron works is estimated to increase from the current level by about 14%,
and the unit requirement of CO2 emissions is expected to decrease by about 17%.)

96
Part3 Future Outlook
Future Outlook for CCT

If we examine the future of Clean Coal Technology from the


viewpoint of technical innovation in the coal utilization sector, we 60
LNG steam power generation
may find a technological trend that is, as mentioned below, Coal-fired Integrated

Planned gross thermal efficiency (HHV % )


LNG-fueled Combined Cycle (ACC) Gasification Fuel Cell
crucial for society as well as full of diversity. 55
Coal-fired steam power generation
Combined Cycle (IGFC)

The trend may be separated into three main directions in terms of Coal-fired Integrated Gasification
Combined Cycle (IGCC) LNG-fueled Gas Turbine
key technology development systems. The first direction is 50 Combined Cycle (ACC)
(1,700oC-class)
already seen in two deployment programs now under way which
focus on coal gasification technology; one for high-efficiency 45 Coal-fired Integrated Gasification
Combined Cycle (IGCC)
(1,500oC-class)
power generation systems, whose commercialization process is
steadily progressing, including "Coal-fired Integrated Gasification 40

Combined Cycle (IGCC)" and "Coal-fired Integrated Gasification


35
Fuel Cell Combined Cycle (IGFC)" and the other for "conversion
1960 1970 1980 1990 2000 2010 2020
into liquid fuel and raw material for chemicals" which contains no
Start of operation year
impurities, such as methanol, DME, or GTL. Moreover, these
technologies will give rise to a zero emission-oriented world of Fig.1 Change in LNG and Coal Thermal Power Generation Efficiency
"co-production" including co-generation. Prepared from High-Efficiency Power Generation Technology
Review Meeting Report (Jan., 2003) of the Institute of Applied Energy

Gas oil, naphthalene, etc. IGCC/IGFC


Electric power
Hybrid gasification of coal, Methanol, acetic acid, etc.
biomass, waste plastics, etc.
Boiler
Chemicals

Oil DME,GTL

Power plant, automobiles, etc.


Coproduction manufacturing also
Biomass raw materials for chemicals

Gasification Synthesis gas (H2, CO)


Coal
Commercial, Hydrogen station
Coproduction manufacturing also transportation
Waste plastics reduced iron Fuel cell vehicle
H2 production, CO2
Reduced iron Iron and steel separation and recovery
Gasification furnace

Blast furnace Stationary fuel cell

Slag
CO2 H2
Effective use
Storage
Blast furnace

Fig. 2 Various CCT developments centering on coal gasification

100.0
The second direction is future energy sector advancements to
cope with the likely realization of "hydrogen energy communities."
Hydrogen
According to IIASA 2000 (International Institute for Applied economy
System Analysis 2000), analysis showed that global primary
10.0
energy consumption was on a near-constant increase between
Gas: H/C = 4
H/C

the middle of the 1800’s and around 1980 in terms of "H/C


Oil: H/C = 2 Methane economy
(hydrogen/carbon)" ratio. In and after 1980, it remained almost
unchanged at around H/C = 2 due to an increase in oil 1.0
Coal: H/C = 1
consumption. As a whole, however, the trend before 1980 is
expected to resume, inviting the situation of H/C = 4 around
2030. In such a society of transition from natural gas to
hydrogen, final energy consumption by carbon combustion will be 0.1
1800 1850 1900 1950 2000 2050 2100
discouraged, even predicting the advent of a situation where coal
Fig. 3 Trend of ratio of hydrogen to carbon (H/C) in the primary energy
energy could be used only in the world of HyPr-RING (Hydrogen Prepared from IIASA 2000

97
Clean Coal Technologies in Japan

Production by Reaction Integrated Novel Gasification Process, separate/recover and then sequester/store direct combustion-
where H/C approximates one) and society will be forced to derived CO2 or reduce CO2 emissions by using carbon
depend largely upon separating and retrieving CO2 generated by components of coal as fuel or raw material for chemicals by way
the direct combustion of coal and the technology to separate and of coal gasification and reforming/conversion, presents important
sequester CO2. High-efficiency coal utilization technology to challenges to Clean Coal Technology.

Separation/recovery Gas after decarburized Sequestration/storage


CO2 concentration 2%

Separation/recovery

Pressure injection from a facility on the sea


Pressure injection from
a ground facility

Tanker transport
Discharged Separated/recovered
CO2 concentration CO2 concentration
22% 99%
Cap rock
Dissolution
Sources from which CO2 is discharged (impervious layer)
diffusion
Pipeline carriage
(including power and steel plants)
CO2
Underground aquifer
coal bed
Separation/recovery Transportation Sequestration/storage CO2
-Ground: Pipeline
-Chemical absorption method -Underground: Aquifer
after liquefied
-Physical absorption method coal bed
-Sea: (long-haul)
-Membrane separation method Liquefied CO2 -Ocean: Dissolution/diffusion or
transport vessel as hydrates (onto the sea bottom)

Fig. 4 CO2 Separation, recovery, isolation, and storage

The third direction is latently potential development of coal Furthermore, hyper-coal production technology development will
utilization technology in conjunction with each of four technology lead to processes for the advanced utilization of the carbon within
sectors given priority for development in Japan, namely, coal. In fact, technological innovation in the nano-technology
environmental/energy, bio-, nano-, and information technology sector is anticipated to lead to such as nano-carbon fibers.
sectors.
Emphasis is placed on environmental/energy technology
development, as mentioned earlier, toward the realization of a
zero-emission society mainly through the implementation of "CO2
countermeasures," and the co-production system is regarded as
being the target such technical innovation must achieve.
Other
Advancements in biotechnology could also unlock methods for Steel Chemicals Cement
by-products
the fixation and effective utilization of CO2.

Raw Steel-making plant


Fuel
material (gas/liquid)
C
s
es

he
oc

m
pr

ic

Light
al
g
in

pl

energy
ok

an
C

Energy and materials linkage between industries


Hydrogen
Fuel cell vehicle
Biomass
Conbustion process

Coal gasification
Iron and steel Dynamic Heat
Gasification/

Power plant

Joul
energy energy
Chemicals, Coal partial hydrogenation Blast furnace
Hydrogen station other SCOPE21 Coal Energy conversion system Electricity
Advanced gasification (solid fuels)
Hyper ring furnace

Waste, waste plastics Power plant Electric power


Iron and steel works
Heat
Chemical Electric&magnetic (steam/
IGCC IGFC energy energy hot water)
USC
Li olys
Py

nt
qu is

la
r

ef p

tp
ac ro

en

CO2 recovery
tio ce

em
n/ ss

Air/water Environmental facility


Reformed coal
Coal
CO2 isolation USB

Exhaust Drainage Waste heat


Fig. 5 Future energy-oriented society supported by CCT, (2030)
Fig.6 co-production system
The ultimate goal of a co-production system lies in zero emissions
(or the state of purified water and steam discharged )

98
Part3 Future Outlook
Future Outlook for CCT Clean Coal Technologies in Japan

CCT has an important role in the power generation as well as in energy while environmental preservation is a problem that
the steelmaking sector, where coal functions not only as an should be tackled on a global scale, considering the
energy source but also as a high-quality reducing agent. A interdependent relationship between the two. Underlying both,
potential task to be assigned to well-established steelmaking current population growth is both explosive and unprecedented.
processes (e.g. blast-furnace process) is achievement of an Efforts toward zero emissions to protect the environment must
innovative level of total coal utilization efficiency, using a co- be assigned top priority in the development of Clean Coal
production system like DIOS (Direct Iron Ore Smelting reduction Technologies in Japan. A further obligation, beyond international
process) to simultaneously produce iron and synthetic gas, cooperation activities, is to continuing development of an efficient
electric power, hydrogen/thermal energy, raw material for and advanced coal utilization system to minimize impact on the
chemicals, etc. from steam coal for steady implementation of global environment.
improved environmental measures toward zero emissions. It has become necessary for us, presently positioned to
As the global leader in coal imports as well as a leader in Clean undertake technology development in one of the energy-related
Coal Technologies, Japan must remain active in international sectors given top priority, to further concentrate efforts in an
cooperation mainly in Asia for human resources development, attempt to devise innovative Clean Coal Technologies for the
technology transfer, and other relevant activities. Such establishment of an affluent, clean, and comfortable society
international cooperation may possibly serve not simply those where economic growth is compatible with the environment.
countries dependent upon coal energy for their economic growth
but as an important measure to address global environment
issues through the extensive influence of the Kyoto Mechanisms,
particularly CDM (Clean Development Mechanism).
Economic growth indispensably requires a stable supply of

Promotion of innovative CCT development toward the actualization of "Zero-emission"

Aiming to position the coal as a source of CO2-free energy by 2030, the project positively promotes the innovative CCT
development including the CO2 fixation technology and the next-generation high efficiency gasification technology toward the
actualization of "Zero-emission", while identifying the position of individual technologies in the total schedule.

Improvement in the thermal efficiency Unification with CO2 separation Actualization of Zero-emission
and fixation technology

6 yen/kWh 6-7 yen/kWh


Coal gasification technology

Air-blow Demonstration test


gasification Zero-emission
GCC commercial
unit GFC commercial
unit
46-48% sending end efficiency
55% sending end efficiency
Oxygen-blow Research and Demonstration test
development
gasification
Industrial gasification A-IGCC
furnace /A-IGFC

>65% sending end efficiency


Advanced coal
gasification F/S Research and development Demonstration test
Fixation technology

CO2 separation Research and development Demonstration test Demonstration test of new separation
and recovery technology
and recovery
Research and development Development toward the full scale storage

CO2 fixation Demonstration test

* Current coal thermal generation unit price is assumed to 5.9 yen/kWh Timing of commercialization
which is estimated by The Federation of Electric Power Companies Japan.

99
(1) Main SI units (2) Prefix of SI system
Quantity SI unit Unit applicable with SI unit Prefix
Multiple to the unit
Angle rad …(degree ), ’(minute), ’’(second) Name Symbol
Length m 1018 Exa E
Area m2 1015 Peta P
Volume m3 (liter) 1012 Tera T
Time s (Second ) d (day), h (hour), min (minute) 109 Giga G
Frequency, vibration Hz (Hertz ) 105 Mega M
Mass kg t(ton) 103 kilo k
Density kg/m2 102 hecto h
Force N (Newton ) 10 deca da
10-1 deci d
Pressure Pa (Pascal ) bar (bar) 10-2 centi c
Work, energy J (Joule ) eV (electron voltage) 10-3 milli m
Power W (Watt ) 10-6 micro u
Thermodynamic temperature K (Kelvin ) 10-9 nano n
Quantity of heat J (Joule ) 10-12 pico p

(3) Typical conversion factors (4) Coal gasification reactions

1. basic Energy Units


1J (joule )=0.2388cal (1)
1cal (calorie )=4.1868J
1Bti (British )=1.055kJ=0.252kcal 97.0kcal/mol (2)
2. standard Energy Units 1
29.4kcal/mol (3)
2
1toe (tonne of oil equivalent )=42GJ=10,034Mcal
1tce (tonne of coal equivalent )=7000Mcal=29.3GJ (4)
38.2kcal/mol
1 barrel=42 US gallons 159l
1m3=35,315 cubic feet=6,2898 barrels
31.4kcal/mol (5)
1kWh=3.6MJ 860kcal
18.2kcal/mol (6)
1,000scm (standerd cubic meters )
of natural gas=36GJ (Net Heat Value ) 10.0kcal/mol (7)
1 tonne of uranium=10,000~16,000toe(Light water reactor, open cycle)
1 tonne of peat=0.2275toe 17.9kcal/mol (8)
1 tonne of fuelwood=0.3215toe 49.3kcal/mol (9)

(5) Standard heating value for each energy source


Energy source Unit Standard heating value Standard heating value (as kcal) Old standard heating value Remark
[Coal]
Coal
Imported coking coal kg 28.9 MJ 6904 kcal 7600 kcal Temporary value
Coking coal for Coke kg 29.1 MJ 6952 kcal
Coking coal for PCI kg 28.2 MJ 6737 kcal
Imported steam coal kg 26.6 MJ 6354 kcal 6200 kcal
Domestic steam coal kg 22.5 MJ 5375 kcal 5800 kcal
Imported anthracite kg 27.2 MJ 6498 kcal 6500 kcal
Coal product
Coke kg 30.1 MJ 7191 kcal 7200 kcal
Coke oven gas Nm3 21.1 MJ 5041 kcal 4800 kcal
Blast furnace gas Nm3 3.41 MJ 815 kcal 800 kcal
Converter gas Nm3 8.41 MJ 2009 kcal 2000 kcal

[Oil]
Crude oil
Crude oil 38.2 MJ 9126 kcal 9250 kcal
NGL, Condensate 35.3 MJ 8433 kcal 8100 kcal old NGL
Oil product
LPG kg 50.2 MJ 11992 kcal 12000 kcal
Naphtha 34.1 MJ 8146 kcal 8000 kcal
Gasoline 34.6 MJ 8266