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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 (1)Classification of CCT in Coal Flow -------------------------------------3 (2)Clean Coal Technology System ----------------------------------------5 (3)Appreciation of CCT in Markets -----------------------------------------6 (4)CCT in Japanese Industries ---------------------------------------------7 (5)Environmental Technologies --------------------------------------------11 (6)International Cooperation -----------------------------------------------12

3B2. Coal Flash Partial Hydropyrolysis Technology ----------------53 C. Powdering, Flowing, and Co-utilization Technologies 3C1. Coal Cartridge System (CCS) ---------------------------------------55 3C2. Coal Slurry Production Technology ------------------------------56 3C3. Briquette Production Technology --------------------------------57 3C4. Coal and Woody Biomass Co-firing Technology -------------59 D. De-ashing and Reforming Technologies 3D1. Hyper-Coal based High Efficiency Combustion Technology(Hyper Coal) ---61

Part2 Outline of CCT -------------------------------------------------------13 (1) Coal Fired Power Generation Technologies A. Combustion Technologies 1A1. Pulverized Coal Fired Power Generation Technology(Ultra Super Critical Steam) ----3 1A2. Circulating Fluidized Bed Combustion Technology (CFBC) ----15 1A3. Internal Circulating Fluidize Bed Combustion Technology (ICFBC) ----16 1A4. Pressurized Internal Circulating Fluidized Bed Combustion Technology (PICFBC) ---17 1A5. Coal Partial Combustor Technology (CPC) ---------------------19 1A6. Pressurized Fluidized Bed Combustion Technology (PFBC) ---------------21 1A7. Advanced Pressurized Fluidized Bed Combustion Technology (A-PFBC) ---23 B. Gasification Technologies 1B1. Hydrogen-from-Coal Process (HYCOL) -------------------------25 1B2. Integrated Coal Gasification Combined Cycle (IGCC) -------27 1B3. Coal Energy Application for Gas, Liquid and Electricity (EAGLE) ------29 (2) Iron Making and General Industry Technologies A. Iron Making Technologies 2A1. The Formed-Coke making Process (FCP) ----------------------31 2A2. Pulverized Coal Injection for Blast Furnace (PCI) -------------33 2A3. Direct Iron Ore Smelting Reduction Process (DIOS) ---------35 2A4. Super Coke Oven for Productivity and Environment Enhancement toward the 21st Century (SCOPE21) --37 B. General Industry Technologies 2B1. Fluidized Bed Advanced Cement Kiln System (FAKS) ------41 2B2. New Scrap Recycling Process (NSR) ---------------------------39 (3) Multi-Purpose Coal Utilization Technologies A.Liquefaction Technologies 3A1. Coal Liquefaction Technology Development in Japan --------43 3A2. Bituminous Coal Liquefaction Technology (NEDOL) ----------45 3A3. Brown Coal Liquefaction Technology (BCL) --------------------47 3A4. Dimethylether Production Technology (DME) -------------------49

3D2. Low-Rank Coal Upgrading Technology (UBC Process) ----63 (4) Environmental Protection Technologies A. Coal Ash Effective Use Technologies 4A1. Coal Ash Generation Process and Application Fields -------65 4A2. Effective use for Cement/Concrete ------------------------------67 4A3. Effective use for Civil Engineering/Construction and Others --69 4A4. Valuable Resources Recovery Technologies for Coal Ash --------71 B. Flue Gas Treatment and Gas Cleaning Technologies 4B1. SOx Reduction Technology ----------------------------------------73 4B2. NOx Reduction Technology ----------------------------------------75 4B3. De-SOx and De-NOx Technology --------------------------------77 4B4. Soot/dust Treatment Technology and Trace Elements Removal Technology ----79 4B5. Gas Cleaning Technology ------------------------------------------81 C. CO2 Recovery Technologies 4C1. Hydrogen Production by Reaction Integrated Novel Gasification Process (HyPr-RING) --83 4C2. CO2 Recovery and Sequestration Technology ----------------85 4C3. CO2 Conversion Technology -------------------------------------86 4C4. Oxy-fuel Combustion (Oxygen-firing of conventional PCF System) --87 (5) Basic Technologies for Advanced Coal Utilization 5A1. Modelling and Simulation Technologies for Coal Gasification -----89 (6) Coproduction System 6A1. Co-generation System ----------------------------------------------93 6A2. Coproduction System ------------------------------------------------95

Part3 Future Outlook for CCT ------------------------------------------97

Mathematical Table ------------------------------------------------------100

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 worlds 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 everadvancing 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

1.10

Total primary energy supply CO2 emissions

GDP

1.05

1.00

Thermal power generation efficiency CO2 emissions/GDP

0.95

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

Part1 Classification of CCT


Classification of CCT in Coal Flow

Carbonization
Coal tanker

Pulverizing/Briquetting

Slurry preparation Liquefaction

Coal mine

Gasification

Coal train CWM

DME/GTL

Mining, crushing and pulverizing


Coal physical properties Anthracite Specific Gravity Apparent Specific Gravity Specific heat Thermal conductivity(W/m K) Ignition point( ) 1.5~1.8 0.22~0.24 400~450 Bituminous coal 1.2~1.7 0.75~0.80 0.24~0.26 1.26~1.65 300~400

Transportation and storage

Processing, reforming and converting

Brown coal 0.8~1.5 0.55~0.75 0.26~0.28 250~300

Multi-purpose utilization technology


4C1

Hydrogen Production Technology in Coal Utilization High Calorific Value Gas Production Technology

Gasification technology

1B1-3

Liquefaction technology

3A1

Coal Liquefaction Technology Development in Japan Bituminous Coal Liquefaction Technology (NEDOL) Brown Coal Liquefaction Technology (BCL) Dimethylether Production Technology (DME)

3A2

Heating value(Kcal/kg (on dry basis)) 8,200~8,500 7,500~8,800 5,500~7,500


3A3

Classification of coal depending on the degree of carbonization Classification Heating value (Kcal/kg(on dry basis)) Anthracite Bituminous coal 8,400 or more 8,100 or more 7,800 or more 7,300 or more 6,800 or more 5,800 or more Fuel ratio 4.0 or more 1.5 or more 1.5 or less 1.0 or more 1.0 or less 1.0 or more 1.0 or less Caking property Non-caking Strong-caking Caking Weak-caking Weak-caking Non-caking Non-caking Non-caking Pulvelization, fluidization and co-utilization technology
3B2 3A4

Pyrolysis

3B1

Multi-purpose Coal Conversion Technology (CPX) Coal Flash Partial Hydropyrolysis Technology

Subbituminous coal Brown coal

3C1 Coal Cartridge System (CCS)

Coal classification depending on the utilizations (expressed as coal) Indication in TEXT report Anthracite coking coal A coking coal coking coal B coking coal C coking coal D steam coal steam coal A steam coal B Other coal steam coal C Ash content of more than 8% Basic technology for advanced coal utilization Coal in the Trade Statistics Anthracite Strong-caking coal for coke Bituminous Other coal coal for coke Other Ash content of 8% or less

3C2 Coal Slurry Production Technology

3C3 Briquette Production Technology

3C4

Ash content of more than 8% Ash content of 8% or less Ash content of more than 8% Ash content of more than 8%
3D2

Coal and Woody Biomass Co-firing Technology

Deashing and reforming technology

3D1

Hyper-Coal based High Efficiency Combustion Technology(Hyper Coal) Low-Rank Coal Upgrading Technology (UBC Process)

Ash content of 8% or less


5A1 Modelling and Simulation Technologies

for Coal Gasification

Clean Coal Technologies in Japan CO2 reduction

Flue gas treatment

Power plant Electric precipitator Coal Center Cement plant Flue gas desulfurization unit

EOR by CO2

Coal ash effective use

Iron works

Chemical plant

Flue gas denitration unit

Yokohama Landmark

Utilization

Environmental countermeasures

Coal fired power generation technology


1A1

Flue gas treatment technology Pulverized Coal Fired Power Generation Technology(Ultra Super Critical Steam) Circulating Fluidized Bed Combustion Technology (CFBC) Internal Circulating Fluidize Bed Combustion Technology (ICFBC) Pressurized Internal Circulating Fluidized Bed Combustion Technology (PICFBC) Coal Partial Combustor Technology (CPC) Pressurized Fluidized Bed Combustion Technology (PFBC) Advanced Pressurized Fluidized Bed Combustion Technology (A-PFBC) Hyper-Coal utilization High Efficiency Combustion Technology (Hyper Coal) CO2 reduction technology
4B1

SOx Reduction Technology NOx Reduction Technology Intra-furnace Dinitrogen Monoxide Removal Technology De-SOx and De-NOx Technology Soot/dust Treatment Technology and Trace Elements Removal Technology Gas Cleaning Technology Hydrogen Production by Reaction Integrated Novel Gasification Process (HyPr-RING) CO2 Recovery and Sequestration Technology CO2 Conversion Technology Oxy-fuel Combustion (Oxygen-firing of conventional PCF System) Coal Ash Generation Process and Application Fields Effective use for Cement/Concrete Soil Improvement Method (FGC) Base Materials Production Technology High Strength Artificial Aggregate Production Technology Agriculture and Fishery Field Valuable Resources Recovery Technologies for Coal Ash Dry Desulfurization Technology which used Coal Ash

Combustion technology Combustion Technology

1A2

4B2

1A3

4B2

1A4

4B3

1A5

4B4

1A6

4B5

1A7

4C1

3D1

4C2

Gasification technology

1B1

Hydrogen-from-Coal Process (HYCOL) Integrated Coal Gasification Combined Cycle (IGCC) Coal Energy Application for Gas, Liquid and Electricity (EAGLE) Coal ash utilization technology

4C3

1B2

4C4

1B3

4A1

Iron making technology

2A1

The Formed-Coke making Process (FCP) Pulverized Coal Injection for Blast Furnace (PCI) Direct Iron Ore Smelting Reduction Process (DIOS) Super Coke Oven for Productivity and Environment Enhancement toward the 21st Century (SCOPE21) Architecture field Civil field

4A2

2A2

4A3

2A3

4A3

2A4

4A3

4A3

Fluidized Bed Advanced Cement 2B1 Kiln System (FAKS) Technology for general industries
2B2

New use development

4A4

New Scrap Recycling Process (NSR)


4A4

6A1

Co-generation System Coproduction System


1A1 1A1

6A2

Classification No. according to the technology overview Classification No. according to the related technology overview

Part1 Classification of CCT


Clean Coal Technology System Clean Coal Technologies in Japan

(Coal flow)
Coal preparation Preparation

Advanced coal cleaning technology Technology for low emission coal utilization

Conventional coal preparation techniques (jig, floatation, heavy media separation)

(Target)

Preparation process control technology Bio-briquetting

Diversification of energy Sources/expansion of application fields

Briquetting
Carbonization briquetting

Processing Handling

Coal Cartridge System (CCS) 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 Gasification

Integrated coal gasification combined cycle power generation technology (IGCC) Coal-based hydrogen production technology (HYCOL)

More efficient use of energy/ CO2 reduction (as a measure against the greenhouse effect)

Coal Energy Application for Gas,Liqud and Electricity (EAGLE) Multi-purpose coal conversion (CPX) Coal Flash Partial hydropyrolysis technology

Pyrolysis

Topping cycle.

Pressurized fluidized Fluidized bed boiler bed combustion (PFBC) Fluidized bed Advanced cement Kilm System(FAKS) Direct Iron-Ore Smelting reduction process(DIOS)

Reduction in SOx, NOx, and waste (as a measure against acid rain) (as a global environmental measure)

Combustion

High-efficiency combustion

O2/CO2 combustion

Advanced flue-gas treatment

Dry desulfurization/ denitration

Wet desulfurization Denitration

Flue gas treatment Pollutant reduction Ash utilization

Hot gas clean up technology Removal of dust Alkaline, etc. removal technology

Coal Ash Utilization Technologies

(Degree of technology maturity)

Proved reserves and R/P (ratio of reserves to production) of major energy resources
Coal World reserves North America S.& Cent. America Europe Former Soviet Union Middle East Africa Asia Pacific Natural gas Oil Uranium

World reserves of coal, oil, and natural gas resources (Saurce: BP 2003) (Unit: 100 million tons oil equivalent)
1,667 687 437 561 934 133 Europe, FSU 368 11 7 7 India 515 556 2514 China 116 52 Asia and Oceania 415 4 23 Australia Coal Oil Natural gas 141 98 65 South and Central America 1,427 1,430 82 Russia 589 1,606 5,012 64 66 North America 3848 U.S.A. 1,260 1,220

9,845 billion ton 156 trillion m3 1,480 billion barrel 393 million ton 26.1% 2.3% 13.2% 22.9% 0.2% 5.6% 29.7% 4.83 billion ton 204 years 4.4% 4.7% 3.8% 35.4% 36.0% 7.6% 8.1% 2.5 trillion m3 60.7 years 3.6% 10.6% 1.8% 7.5% 65.4% 7.4% 3.7% 17.9% 6.5% 3.5% 30.6% 0.0% 17.8% 23.8%

Local reserves

109 103 Middle East

Annual production rate R/P

27 billion barrel (73.9 million BD) 0.037 million ton 40.6 years 61.1 years

Africa 330 0 0 South Africa

Prepared from Oil, natural gas, and coal: BP Statistics 2003 Uranium: OECD/NEA,IAEA URANIUM2001

Worldwide

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 Technical scope in which Technological and economical difficultes remain HYCOL

Hyper Coal Power Generation IGFC EAGLE Hyper Coal A-PFBC IGCC PCI Advanced flue gas treatment

Gasification furnace (fluidized bed, spouted bed) PFBC Technology at a practical use level PICFB I C F B Cement raw material P C F B C Gypsum board CFBC USC FBC

SCOPE21 DIOS Formed-coke NSR FAKS CPX

Economic difficulty

DME Ash-removed CWM CWM COM NEDOL BCL Brown coal dewatering DME GTL

Commercialization technology CCS Pneumatic transfer Briquette Bio-coal Wet coal preparation

Flue gas treatment

FGC melting and mixing treatment Fluidized bed solidification material Artificial aggregate

Simplified dry desulfurization

CC

Tt

ran

sfe

Cost reduction technology development

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: IEA COAL INFORMATION 2003 Coal Yearbook 2003

3,837 3,853

1,326 1,252 164140 30 58 U.K. 29 60 Germany 334 357 China 163 0 Japan India
11 .6% )

917 896 30 20 Canada


(5 9.6 .7% )
(production) (consumption)

103 81 Poland

ex-USSR

33.5(19.9%)

0.4(0.2%)

America World
16,317 15,236 15,457 Others 276 Cement/ ceramics 1,296 Chemicals 575

Trend of coal demand in Japan


(Unit: 10 thousand tons)

13,057 11,548

19 .6(

0.

0 4(

3%

(Source : Coal Note 2003)

91.8(54.5%)

11,145

Indonesia

78 Australia

Steam coal

223 156

101 28

9,079

9,394 8,225

Electric power 6,186

276

Pulp / paper 491 Gas / coke 412

Coking coal

Iron making 6,221

FY1970

75

80

85

90

95

00

01

02

Economic difficulty

Coal Ash utilization Melting and fiber-forming

Part1 Classification of CCT


CCT in Japanese Industries

Power generation field Location of coal fired power plants


Numerals in parentheses designate power generate capacity (10 thousand kW) at the end of FY2001.

Nanao Ota(120) Toyama Shinko Kyodo(50) Noshiro(120) Tsuruga(120) Maizuru (under construction) Takasago(50) Mizushima(28.1) Osaki(25) Takehara(130) Misumi(100) Sakata(70)

Sunagawa(25) Naie(35) Tomatou Atsuma (103.5)

Sendai(52.5) Shinchi(200) Haramachi(200) Hirono (under construction) Nakoso(145) Hitachi Naka (100) Isogo (120)

180 160 Coal consumption (million ton) 140 120

1800

Domestic total coal consumption

1600 1400 1200 Generated power (GkWh)

Generated power
100 80 60 40 20 0 1990 91 92 93 94 95 96 97 98 99 00 01 02 1000 800

Shin-onoda(100) Shimonoseki(17.5) Kanda(36) Minato(15.6) Matsuura(270) Omura(15.6) Matsushima(100) Reihoku(70)

Hekinan(310) Tachibanawan(210+70) Saijo(40.6) Kin(22) Ishikawa(31.2) Gushikawa(31.2)

Coal consumption

600 400 200 0

Coal consumption in power generation sector and generated power

Coal fired power generation technology

1A1

Pulverized Coal Fired Power Generation Technology(Ultra Super Critical Steam) Circulating Fluidized Bed Combustion Technology (CFBC) Internal Circulating Fluidize Bed Combustion Technology (ICFBC)

1A4

Pressurized Internal Circulating Fluidized Bed Combustion Technology (PICFBC) Coal Partial Combustor Technology (CPC) Pressurized Fluidized Bed Combustion Technology (PFBC) Advanced Pressurized Fluidized Bed Combustion Technology (A-PFBC)

1A2

1A5

1A3

1A6

1A7

Steam coal

Combustion furnace boiler

Coal Gas cleaning

Stack

Coal Pulverized coal gasification furnace

Gas turbine

Steam turbine

Generator

4B5

Gas Cleaning Technology

Electric power Wastewater

1B1

Hydrogen-from-Coal Process (HYCOL) Integrated Coal Gasification Combined Cycle (IGCC)

1B3

Coal Energy Application for Gas, Liquid and Electricity (EAGLE) Hyper-Coal based High Efficiency Combustion Technology (Hyper Coal)

1B2

3D1

Clean Coal Technologies in Japan

Iron making field Location of iron works


Numerals in parentheses designate produced crude steel (MT) as of FY2002.

Kobe Steel (Kobe)(1,062,063) Kobe Steel (Kakogawa)(5,397,267) JFE Steel (Mizushima)(8,423,478) JFE Steel (Fukuyama)(9,885,534) Sumitomo Metal (Kashima)(6,820,450) JFE Steel (Chiba)(4,186,020) Nippon Steel (Kimitsu) (9,195,689)

180 160 Coal consumption (million ton) 140 120 100 80 60 40 20 0 1990 91 92 93 94 95 96 97 98 99 00 01 02

180

Domestic total coal consumption Crude steel production Coal consumption

140 120 100 80 60 40 20 0

Crude steel production (million ton)

160

Nippon Steel (Yawata) (3,514,941)

JFE Steel (Keihin)(3,472,723) Nippon Steel (Nagoya)(5,651,300) Sumitomo Metal (Wakayama)(3,412,887) Nippon Steel (Oita)(8,012,585)

Coal consumption in iron making sector and crude steel production

Iron making technology


2A2

Pulverized Coal Injection for Blast Furnace (PCI)

2A1

The Formed-Coke making Process (FCP)

Blast furnace Coking coal Pig iron Converter

Formed-coke furnace

PCI Electric furnace

Iron and steel Coal SCOPE21 Steam coal Slag

DIOS NSR
2A4

Super Coke Oven for Productivity and Environment Enhancement toward the 21st Century (SCOPE21)

2A3

Direct Iron Ore Smelting Reduction Process (DIOS)


2B2

New Scrap Recycling Process (NSR)

Part1 Classification of CCT


CCT in Japanese Industries

Cement production field Location of cement plants


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

Myojo Cement (Itoigawa)(2,108) Denki Kagaku Kogyo (Omi)(2,703) Sumitomo Osaka Cement (Gifu)(1,592) Tsuruga Cement (Tsuruga)(816)

Nittetsu Cement (Muroran)(968) Taiheiyo Cement (Kamiiso)(3,944) Mitsubishi Material (Aomori)(1,516) Hachinohe Cement (Hachinohe)(1,457) Taiheiyo Cement (Ofunato)(2,680) Mitsubishi Material (Iwate)(670) Hitachi Cement (Hitachi)(848) Sumitomo Osaka Cement (Tochigi)(1,489) Chichibu Taiheiyo Cement (Chichibu)(800) Taiheiyo Cement (Kumagaya)(2,267) Mitsubishi Material (Yokoze)(1,213) Taiheiyo Cement (Saitama)(1,655) DC (Kawasaki)(1,108) Taiheiyo Cement (Fujiwara)(2,407) Taiheiyo Cement (Tosa)(1,165) Taiheiyo Cement (Kochi)(4,335) Taiheiyo Cement (Tsukumi)(4,598) Taiheiyo Cement (Saeki)(1,426)

Tokuyama (Nanyo)(5,497) Tosoh (2,606) Ube Industries (1,612) Ube Industries (4,872)

180 160 Coal consumption (million ton) 140 120 100 80 60 40 20 0

180 Cement production (million ton)

Domestic total coal consumption

160 140 120

Cement production
100 80 60 40

Coal consumption
1990 91 92 93 94 95 96 97 98 99 00 01 02

20 0

Coal consumption in cement production sector and cement production

Nippon Steel Blast Furnace Cement (Tobata)(808) Mitsubishi Materials (Kyushu)(8,039) Ube Industries (Kanda)(3,447) Kanda Cement (Kanda)(1,085) Kawara Taiheiyo Cement (Kawara)(800) Mitsui Mining (Tagawa)(1,977) Aso Cement (Tagawa)(1,412)

Ryukyu Cement (Yabu)(722)

Cement production technology


2B1

Fluidized Bed Advanced Cement Kiln System (FAKS)


Coal

Electric precipitator

4A2

<Technology for Effective Utilization of Coal Ash> Effective use for Cement/Concrete

Electric precipitator Gypsum

Track

Limestone Clay Iron raw material


Drier

Coal mill

Cement cooler

Cement silo

Recycle raw material


Air separator Silo

Heavy oil tank

Tanker Raw material mill Air separator Rotary kiln Clinker cooler Clinker silo Pre-pulverizing mill

Preheater

Clean Coal Technologies in Japan

Coal chemicals and other fields Location of chemicals complexes


Numerals in parentheses designate ethylene production capacity (1000 t/y) at the end of FY2002.

Mitsubishi Chemical (Mizushima)(450) Asahi Kasei (Mizushima) Sanyo Petrochemical (443) Mitsui Chemicals (Iwakuni-otake)(623) Idemitsu Petrochemical (Suo)(623)

Mitsubishi Chemical (Kashima)(828) Maruzen Petrochemical (Goi)(480) Keihin Ethylene(690) Mitsui Chemicals (Ichihara)(553) Idemitsu Petrochemical (Chiba)(374) Sumitomo Chemical (Anegasaki, Sodegaura)(380) Nippon Petrochemicals (Kawasaki)(404)

4,600 4,400 4,200 Coal energy supply (PJ) 4,000 3,800 3,600 3,400 3,200 3,000 2,800
291.4 286.1 (16.5) (16.9) (16.1) (16.0) 307.1 294.5 291.0 (19.5)

540

GDP
(19.0) (17.8) (17.8)

520 500 GDP (trillion yen) 480 460 440

Tonen Chemical (Kawasaki)(478) Mitsubishi Chemical (Yokkaichi) Tosoh (Yokkaichi)(493) Mitsui Chemicals (Osaka) Osaka Petrochemical (455) Showa Denko (Oita)(581)

Coal energy supply


(16.7) (16.3) (17.2) (16.5) (16.4) (16.3) 318.6 316.0 309.1 303.3 317.3 311.4 307.4 316.7

420 400 380 360

CO2 emissions (Mt-C)


1990 91 92 93 94 95 96 97 98 99 00 01 02

Ryukyu Cement (Yabu)(722)

Coal energy supply, GDP, and CO2 emissions in Japan


Numerals in parentheses designate the percentage of coal in primary energy.

Coal chemicals process


Coal

3A1

Coal Liquefaction Technology Development in Japan Bituminous Coal Liquefaction Technology (NEDOL) Brown Coal Liquefaction Technology (BCL)

3A4

Dimethylether Production Technology (DME) Hydrogen Production by Reaction Integrated Novel Gasification Process (HyPr-RING)

3A2

4C1

3A3

Vent

(Fractionation process) (Raw material charge process) Medium distillate Heavy distillate Water (Separation, purification process)

(Coal conversion process)

Air

High value-added product BTX and mono- and di-cyclic components Residue coal (Recycle) Wastewater
3B1

Multi-Purpose Coal Conversion Technology (CPX) Technology

3D1

Hyper-Coal based High Efficiency Combustion Technology(Hyper Coal) Low-Rank Coal Upgrading Technology (UBC Process)

3B2 Coal Flash Partial Hydropyrolysis

3D2

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 (Technology to reduce CO2 emissions)

4)Environmental Protection and fuel conversion technology (DME, GTL)

Flue gas treatment technology


Emission reduction technology to remove dust, sulfur oxides, and nitrogen oxides is developed by treating and combusting flue gas from coal combustion through superior process design.
Mechanism of electrostatic precipitator Mechanism of flue gas denitration unit Mechanism of flue gas desulfurization unit
Clean gas (to stack)

Effective coal ash utilization in Japan


Ash generated during coal combustion is effectively used as raw material for cement and other applications.
Power in Japan: Effective use of coal ash generated from general industries, (FY2002) (Source: Center for Coal Utilization, Japan)
Agriculture, forestry, and fishery fields 1.8% Fertilizer, soil improving material, etc. 139 1.8% Other building materials 29 0.4% Building material board 347 4.5% Civil work material, etc. 134 1.7% Road and base materials 115 1.5% Coal mine filler 188 2.4% Other 446 5.8% Other 5.8% Architecture field 4.9% Civil field 8.8%

NH3 (Ammonia)
NO X NH 3 NO X NO X NH 3 NO X NO X NO X NH 3 NH 3 NO X

Cement raw material 5,694 73.7%

DC high voltage Electrode

NO X

Pump

Discharge electrode Collected coal ash Collecting electrode

Catalyst Mixed liquor of limestone and water


N2 N2 H 2O H 2O N2 H 2O N2 H 2O

Total 7,724
(thousand ton)

Flue gas

Gypsum

Gypsum

Pump

Cement field 78.7%

Flue gas (from boiler)

Electrostatic Precipitator Flue gas passes between two electrodes that are charged by a high voltage current. The ash and dust are negatively charged, 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 precipitator and subsequently removed. The principle is the same with the phenomenon that paper and dust adhere to a celluloid board electrostatically charged by friction. Flue Gas Desulfurizer Limestone is powdered to prepare a water-based mixture (limestone slurry). The mixture is sprayed into the flue gas to induce a reaction between the limestone and the sulfur oxides in the flue gas to form calcium sulfite, which is further reacted with oxygen to form gypsum. The gypsum is then separated as a product. Flue Gas Denitrizer 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 decompose into nitrogen and water.

Cement admixture 239 3.1% Concrete admixture 147 1.9%

Ground improving material 246 3.2%

CO2 emissions in Japan


CO 2 emissions in Japan for individual sectors
(Source: Headquarters of Countermeasures to Global Warming (FY2000))

Other (non-fuel sector, etc.) 2.0% (direct incineration: 2.0%) Waste (plastics and waste oil incineration) 2.0% (direct incineration: 2.0%) Industrial process (limestone consumption) 4.3% (direct incineration: 4.3%) Energy conversion sector (power plant, etc.) 6.9% (direct incineration: 30.9%)

3 Transportation sector (automobile, Energy-related ship, and aircraft) sectors 20.7% (direct incineration: 20.2%)

(93.7%)

Industry sector 40.0% (direct incineration: 31.0%)

Commercial sector (Business) 12.3% (direct incineration: 5.2%)

Commercial sector (Household) 13.5% (direct incineration: 6.0%)

Reaction formulae
(Nitrogen (Ammonia) monoxide) (Nitrogen dioxide)

4NO + 4NH3 + O2 6NO2 + 8NH3

4N2 + 6H2O
(Nitrogen gas)

CO2 emissions in major countries (million ton as carbon)


Unit 1990 1,352 23.0 129 164 102 271 113 1,036 17.6 617 10.5 153 269 4.6 5,872 2000 1,578 26.9 158 151 109 226 121 638 10.9 780 13.3 249 310 4.8 6,417 2001 1,559 26.5 155 153 108 223 121 654 11.1 832 14.2 250 316 4.8 6,522 2005 1,624 27.7 172 155 106 224 124 780 13.3 888 15.1 272 319 4.6 6,908

(Source: IEO 2004)

2010

2020

7N2 + 12H2O
(Nitrogen gas)

USA

Mt-C %

1,800 2,082 30.7 186 163 108 232 129 825 14.0 35.5 196 176 122 241 140 939 16.0

Canada

Mt-C Mt-C Mt-C Mt-C Mt-C Mt-C %

Emissions of SOx and NOx per generated power in major countries


Source; The Federation of Electric Power Companies of Japan

UK France Germany Italy ex-USSR

(g/kWh) 9 8 7 6 5 4 3 2 1 0

(Thermal power plant) SOx NOx

7.1

4.8 4.0 3.0 3.2 2.1 1.4 0.9 2.7 2.0 1.2 0.7 0.20 0.26 France (1998) UK America Italy Canada Germany Japan (1999) (1999) (1999) (1999) (2002)

China

Mt-C %

1,109 1,574 18.9 321 334 4.3 26.8 435 365 3.9

India Japan

Mt-C Mt-C %

World total

Mt-C

7,685 9,372

11

Part1 Classification of CCT


International Cooperation
1)Pollution countermeasures technology (SOx, NOx, and dust/soot reduction technology) 3)CO2 emissions reduction technology (CDM, JI countermeasures technology)

Clean Coal Technologies in Japan


2)High efficiency power generation technology (IGCC, IGFC)

Current state of international cooperation Concomitant with the progress of industrialization and urbanization, developing countries face serious air and water pollution issues. Particularly in Asia and Oceania, the percentage of coal in the energy mix is large and sustainable economic development further emphasizes the importance of the development and widespread dissemination of coal utilization technology with full-scale environmental conservation measures. Since developing countries do not have sufficient capital, technology, and human resources for such technology, self-help efforts are limited, and the assistance of developed countries including Japan and of international organizations is requested. Japan has promoted international cooperation in terms of "pollution countermeasure technology" to reduce emissions of SOx, NOx, and dust, and of "high efficiency power generation technology" to improve energy use efficiency with a focus on the Green Aid Plan (GAP) counterpart countries of China, Indonesia, Thailand, Malaysia, the Philippines, India, and Vietnam.

From GAP to CDM In recent years, the global warming issue has attracted intense international concern. Global warming is a serious problem for the future of the earth and humankind, and is closely related to human economic activity and the accompanying energy consumption. Thus, satisfying both "economic development" and "the environment" becomes an important issue. The Kyoto Protocol, adopted at Kyoto in December 1997 and ratified by Japan in June 2002, includes the "Kyoto Mechanisms", an important instrument of international cooperation. In particular, the Kyoto Mechanisms include a market mechanism called the Clean Development Mechanism (CDM), which is a forthcoming system that aims to reduce greenhouse gases through cooperation between developed and developing countries. From the viewpoint of overcoming global environmental issues that continue to spread worldwide, developing countries are requested to maximize their self-help efforts toward improvement 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 desulfurization unit FY1993-FY1995 Peoples Republic of China

FY1995-FY1997 FY1998-FY2001 Coke oven gas desulfurization unit FY1999-FY2002

Thailand Peoples Republic of China Peoples Republic of China

Cleaning during combustion, improvement of combustion efficiency Circulating fluidized bed boiler FY1993-FY1995 Peoples Republic of China

Philippines FY1995-FY1997 Peoples Republic of China Indonesia FY1996-FY1998 FY1996-FY1999 FY1997-FY1999 FY1997-FY2001 Cleaning before combustion Briquette production unit FY1993-FY1995 Peoples Republic of China Indonesia FY1996-FY1998 Indonesia Electricity Generating Authority of Thailand (Lampang) Peoples Republic of China Peoples Republic of China Thailand Peoples Republic of China

FY1997-FY1999 FY1998-FY2002 Water-saving coal preparation system Desulfurization type CWM unit FY1994-FY1997

Thailand Philippines Peoples Republic of China

FY1995-FY1998

Peoples 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 power generation cost but also of suppression of CO2 emissions. In particular, coal fired power plants which are the main stream of current large thermal power plants increase their steam
Steam temperature OC 600 24.5MPa 24.1MPa 16.6MPa 400 20 31.0MPa Steam pressure MPa 30 538OC 566OC 600OC 593OC 610OC

temperature level. The right figure summarizes the trend of steam conditions in recent years. 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 566 C/566 C/566 C. In 1993, Hekinan No.3 plant (700 MW) of
O O O

Steam temperature 500 (Left scale)

300

Steam pressure (Right scale)

10

the company adopted the steam condition of 246

kg/cm2G

(24.1
200 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 0

MPa) x 538OC/593OC, which 593OC was the first highest temperature of reheated steam in Japan. After that, Misumi No.1 plant (1000 MW) of The Chugoku Electric Power Co., Inc. and 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 shows an example of relation between the steam condition and the increase in efficiency at a supercritical pressure plant. Responding to the movement of increase in the steam temperature, power companies, steel manufacturers, and boiler manufacturers promote the development and practical application of high strength materials having superior high temperature corrosion resistance, steam-oxidation resistance, and workability. The high-temperature materials for 650OC level use have already been in the practical application stage, and the study proceeds to satisfy 700OC level use aiming at further high efficiency of the thermal plants. respective steam conditions.
Fig. 3 Steam conditions and high temperature materials
Steam temperature (OC) 538
Efficiency increase rate (%)

Fig. 1 Changes in steam condition with time

5 4 3 2 1 0 Temperature of main steam (OC) 538 (Base) 538 593 566 593 600 600 625 625

Temperature of reheated steam (OC) 566

The figure below shows the

steam conditions and the high temperature materials for the

Fig. 2 Relation between the steam condition and the efficiency improvement at supercritical pressure plants

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 practically applied responding to the need to satisfy current severe environmental regulations and to respond to the high efficiency combustion. The emission level of NOx and dust generated during the combustion of coal is the worlds lowest level even at boiler exit, though the ultimate emission level owes the flue gas treatment given at downstream side of the boiler. Since emission of NOx and that of dust are very closely related to 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 intrafurnace denitration using the whole zones in the furnace. (1) Low NOx combustion at coal burner Although the structure of burner differs between large-boiler manufacturers, the most advanced burners basically adopt the separation of dense and lean pulverized coal streams and the multilayer charge of combustion air aiming to attain the ignitability increase and to conduct the intraflame denitration. Figures 4 to 7 show the burner structure of several manufacturers.

Dense flame
Secondary air Tertiary air Tertiary air swirling vane

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

Lean flame

Dense flame Lean flame Dense flame

Primary air + Pulverized coal Primary throat Secondary throat Rib Primary flame holding plate Secondary flame holding plate

Dense flame Lean flame Dense flame Fig.4 Pulverized coal fired A-PM burner: Mitsubishi Heavy Industries, Ltd.
Burner inner cylinder Primary air + Pulverized coal Burner outer cylinder Secondary air inner vane Secondary air vane Flow detector Throat ring

Fig.5 CC type pulverized coal fired burner: Kawasaki Heavy Industries, Ltd.

Tertiary air damper Oil burner Primary air + Pulverized coal Tertiary air Primary air (Pulverized coal + Air) Inner periphery Outer periphery secondary air secondary air Volatile matter combustion zone Reducing agent generation zone NOx decomposition zone Char combustion enhancing zone

Oil burner support Secondary air vane driver Secondary air inner vane driver

Furnace wall tube Outer secondary air Secondary air Inner secondary air

Fig.7 Pulverized coal fired NR burner: Babcock-Hitachi K.K.

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

(2) Intrafurnace denitration Intrafurnace denitration is conducted by reducing the NOX generated in the main burner zone using the residual hydrocarbons or the hydrocarbons generated from small amount of fuel oil charged from the top of the main burner. the conceptual drawing of the intrafurnace denitration. In the first stage, hydrocarbons reduce NOx. additionally charged air. In the second The
Over Fire Air Aditional Air

Combustion completion zone

NOx reducing zone containing unburned fuel

intrafurnace denitration is performed in two stages. Figure 3 is

Main burner combustion zone Main burner

stage, the unburned matter is completely combusted by the


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 below. 1)Wide range of fuel adaptability Conventional boilers for power generation can use only fossil fuel such as high grade coal, oil, and gas. The CFBC also uses low grade coal, biomass, sludge, waste plastics, and waste tire as fuel. 2)Low pollution Emissions of pollutants such as NOx and SOx are significantly decreased without adding special environment measures. For the case of fluidized bed boiler, the desulfurization is intrafurnace desulfurization using mainly limestone as the fluidizing material. For the denitration, ordinary boilers operate at combustion temperatures from 1,400 C to 1,500 C, and the circulating
O O

NOx depending on temperature) are suppressed. In addition, the operation of circulating fluidized bed boiler is conducted by twostage combustion: the reducing combustion at the fluidized bed section; and the oxidizing combustion at the freeboard section. Then, the unburnt carbon is collected by a high temperature cyclone located at exit of the boiler to recycle to the boiler, thus increasing the denitration efficiency. 3)High combustion efficiency High combustion efficiency is attained by excellent combustion mechanism of circulating fluidization mode. 4)Space saving and high maintenance ability Space saving is attained because there is no need of separate desulfurization unit, denitration unit, and fuel finely crashing unit. Accordingly, sections of trouble occurrence become few, and maintenance becomes easy.

fluidized bed boiler operates at lower temperatures ranging from 850 C to 900 C so that the thermal NOx emissions (generated
O O

2.Outline of technology Figure 1 shows a typical process flow of CFBC


Generated steam Coal Limestone Flue gas Boiler feed water Secondary air Primary air Electric precipitator Heat recovery section ID fan Stack
Air preheater Boiler feed water heater Hot cyclone CFBC boiler body

Circulating fluidized bed furnace

Cyclone

Ash storage tank

Fig.1 Process flow of circulating fluidized bed boiler

Figure 2 shows rough structure of CFBC.

Generally CFBC is The

structured by the boiler and the high temperature cyclone.

Fig.2 Schematic drawing of CFBC structure

intrafurnace gas velocity is as high as 4 to 8 m/s. Coarse fluidizing medium and char in the flue gas are collected by the high temperature cyclone, and are recycled to the boiler. The recycle maintains the bed height and increases the denitration efficiency. To 3.Study site and application field Photograph 1 shows overview of the CFBC boiler facilities. The CFBC became popular mainly as coal fired boilers. Recently, however, CFBC using RDF and wood-base biomass as the fuel has drawn attention. Typical applications of coal fired biogas are Tamashima plant (70 t/h) of Kuraray Co., Ltd, Chiba worksoil refinery (300 t/h) of Idemitsu Kosan 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. 5.Progress and result of the development The CFBC was introduced from abroad as the coal fired boiler, and is used in power companies, iron making companies, paper making companies, and other sectors. The CFBC is planned to distribute in China under the Green Aid Plan (GAP). The issues
15

increase the thermal efficiency, a preheater for fluidizing air and combustion air, and a boiler feed water heater are installed. Most of the boiler technologies are introduced from abroad: mainly from Foster Wheeler, Lurgi, Steinmuller, ALSTOM, and Babcock & Wilcox.

Co., Ltd., and Isa plant (210 t/h) of Ube Industries, Ltd. Example of RDF fired boiler is Tomakomai plant of Sanix Inc. As for the biomass fuel, mixed combustion with coal is adopted for decrease of CO2 emission.

Photo 1 CFBC appearance

of CFBC include further investigations of and efforts for initial cost and power generation efficiency in the boilers using fuel such as RDF, industrial waste, and wood-base biomass.

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

circulation flow is created to return the unburnt char and unreacted limestone coming from the cyclone at exit of the boiler to the boiler. 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 end-sections, thus creating the swirling flow.
16 Fig. 1 Outline of ICFBC

Part2 Outline of CCT


Coal Fired Power Generation Technologies (Combustion Technologies)

2)The circulation flow between the main combustion chamber and the heat recovery chamber is created by the movement described below. A portion of the fluidizing material which is vigorously blown up at both end-sections in the main combustion chamber turns the flow direction toward the heat recovery chamber at above the tilted partition. The heat recovery chamber forms mild fluidized bed (downward moving bed) by the circulation bed air injected from under the chamber. Accordingly, the fluidizing material circulates from the main combustion chamber to the heat recovery chamber, and again to the main 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. 3)The circulation flow coming from the cyclone at exit of the boiler passes through the cyclone or other means to collect unburnt char, emitted fluidizing material, and unreacted limestone, and then returns to the main combustion chamber or the heat recovery chamber using screw conveyer, pneumatic conveyer, or other means. The circulation flow is extremely effective to increase combustion efficiency, to decrease NOx generation, and to increase desulfurization efficiency.

3.Study site and use field Examples of coal fired ICFBC include: Chingtao, EBARA CORP. (10 t/h); Jiangsan in China (35 t/h); and Nakoso, Nippon Paper Industries Co. (104 t/h). Examples of ICFBC using industrial waste as the fuel include: Motomachi, Toyota Motor Corp. (70 t/h); Tochigi, Bridgestone Corp. (27 t/h); Fuji, Daishowa Paper Mfg. Co., Ltd. (62 t/h); Amaki, Bridgestone Corp. (7.2 t/h); and Akita, Tohoku Paper Mfg. Co., Ltd. (61.6 t/h). An example of RDF fuel ICFBC is Shizuoka, Chugai Pharmaceutical Co., Ltd. (3.7 t/h).

4.Development period The ICFBC was developed in 1987, and was further developed and validated as the low pollution, small scale, and high efficiency fluidized bed boiler for multiple coal grades in the "Study of Fluidized Bed Combustion Technology" of the Coal Utilization Technology Promotion Grant project of the Ministry of the International Trade and Industry over six years from 1988 to 1993.

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

Dry Coal

Steam Boiler Drum Stack

Coal Bunker Crusher Limestone Pulverized Coal Slurry Feed System Air Compressor

Dry Feed System

Hot gas Filter

Air Heater Depressurizing Unit Steam

IDF

PICFB

CWP Mixing System

Bag Filter

CWP Pump Pressure Vessel

Waste Heat Boiler (Gas Cooier) Ash Cooling Pipe Boiler Water Circulation Pump Deashing System

Ash

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 fluidized bed boiler (ICFBC) described in preceding section. The 2.Features The pressurized internal circulating fluidized bed boiler (PICFBC) is structured applying the circulation flow technology of abovedescribed ICFBC. Accordingly, the load control is available without varying the height of fluidized bed. In addition, cooling of combustion gas is avoided because the intrabed heat transfer tubes do not expose on the bed during load controlling action, which minimizes the generation of CO2 and eases the maintaining temperature at inlet of gas turbine. Since the wear problem of 3.Outline of technology Figure 1 shows schematic drawing of PICFBC. The cylindrical pressure vessel contains the cylindrical ICFBC. Similar with ICFBC, silica sand is used as the fluidizing material. The fluidized bed is divided into the main combustion chamber and the heat recovery chamber by the tilted partition. The swirling flow is created in the main combustion chamber, and the circulation flow is created between the main combustion

PICFBC mounts ICFBC in a pressure vessel.

heat transfer tube in bed is decreased, silica sand can be used as fluidizing material, and the amount of limestone can be minimized to a necessary level for the intrafurnace desulfurization, thus suppressing the generation of ash. Furthermore, the main combustion chamber has no intrabed heat transfer tube so that the problem of interference of intrabed heat transfer tube against the particle movement does not occur, which prevents the generation of agglomeration.(the solidification of melted medium)

chamber and the heat recovery chamber. Figure 2 (P.17) shows the rough flowchart of the hot model test plant at Sodegaura. The coal feed unit has two lines: the lock hopper system which feeds lump coal ; and the CWP(Coal Water Pellet) mixing system which feeds coal as slurry mixed with water. The dust of combustion gas is removed by the high temperature bag filter structured by ceramics filter. The lock hopper system technology is applied to develop the pressurized two-stage gasification technology.

Fig. 1 Schematic drawing of PICFBC

4.Study site and use field The PICFBC hot model test was carried out at a site next to the Coal Research Laboratory (Nakasode, Sodegaura City, Chiba) of Idemitsu Kosan Co., Ltd. Applicable fields include the steam 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 which is used for ammonia synthesis and fuel cell power 5.Period of development The PICFBC hot model test was carried out from 1992 to 1997. The hot model test was conducted jointly with The Center for Coal Utilization,Japan, as the Coal Utilization Technology Promotion Grant project of the Ministry of International Trade and Industry. The test operation began from December 6.Progress and issue of the study As the coal fired PICFBC, the study proceeded up to the hot model test at Sodegaura. The technology, however, has developed to the pressurized two-stage gasification technology in which the thermal load and the lock hopper system in the
18

generation. The pressurized two-stage gasification technology is in operation as a commercial plant (195 t/d of waste plastics throughput) at Kawasaki of Showa Denko K.K. since 2003.

Photo 1 Overview of PICFBC

Photo 2 Overview of pressurized two-stage gasification plant

1996. The pressurized two-stage gasification technology was developed jointly with Ube Industries, Ltd. The demonstration operation of the plant (30 t/d of waste plastics throughput) began from January 2000, and the commercial operation began from January 2001. pressurized fluidized bed are applied. The issues of pressurized system include the improvement in the reliability of lock hopper system in the fuel charge line and the measures to low temperature corrosion.

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 production countries, coal has high supply stability, and is positioned as an important energy source in the future. Compared with other fuels such as oil and gas, however, coal contains large amount of ash and nitrogen, thus has many issues in use, including facility trouble caused by ash and significant increase in NOx emissions. Furthermore, global warming issue has become international concern in recent years, which raises an urgent requirement of development of technology to reduce emissions of CO2 which is one of the main cause materials of global warming. In this respect, the world waits for the development of technology of high efficient and environmentally compatible utilization of coal which generates large amount of CO2 per calorific value. Coal Partial Combustor (CPC) is a furnace where coal and air are injected at high speed into a swirling melting furnace in tangential direction, thus conducting partial combustion (gasification) of coal under the condition of high temperature, heavy load, and strong reducing atmosphere, and after most of ash in coal is melted and separated to remove, the produced fuel gas is subjected to secondary combustion. That is, CPC is a technology of coal gasification combustion in boiler or gas turbine to utilize coal at high efficiency and environmentally compatible state. The CPC has the normal pressure CPC technology and pressurized CPC technology. The former conducts very low NOx combustion The latter achieves high efficiency power through the gasification in boiler, or generates low calorific gas at normal pressure. 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 difficult-to-combust coal were constructed and are operating in large number centering on Western countries. The conventional melting and combustion method has advantages of high combustion efficiency and recovery of ash as nontoxic molten slag. However, the method has drawback of large NOx emissions caused by high temperature combustion. Responding to the issue, our technology development focused 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 Combustion air High temperature combustion gas Preliminary combustor Preheating burner Baffle Secondary combustor

Pulverized coal

As medium to small coal fired boilers, CPC can significantly reduce NOx emissions while maintaining the compactness of boiler similar with the scale of oil fired boiler, and can recover all the coal ash as molten slag. The right figure shows schematic drawing of the normal pressure CPC boiler.
Fig.1 Schematic drawing of normal pressure coal partial combustor (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 development of pressurized CPC technology began aiming at the development of high efficiency power generation system by pressurizing CPC and combining it with gas turbine. The figure below shows rough flow chart of the pressurized CPC pilot plant having 25 t/d of coal gasification capacity (operating at oxygen 21%). The pilot plant ran the coal gas generation test 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 Air compressor Char feeder 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 combined power generation technology was conducted at Wakamatsu Coal Utilization Research Center (present Wakamatsu Research Institute) of Electric Power Development Co., Ltd. using the 71 MWePFBC Plant, which was the first PFBC plant in Japan. The test plant was the first plant in the world in terms of full-scale adoption of ceramic tube filter (CTF) which is able to collect dust from high temperature and high pressure gas at high performance. Outline of the process is shown in Fig. 1. (2)Outline of facilities Plant output 71.0 MWe Pressurized fluidized bed combustion once-through boiler (ABBIHI production) Bubbling type pressurized fluidized bed, Coal water paste (70-75%) injection type Combustion temperature 860 C
O

Combustion air pressure 1 MPa

Ammonia water injection (Non-catalytic denitration) Ash recirculation cyclone Main steam / Reheated steam 593 C/593 C Steam turbine
O O

Ceramic tube filter (CTF) Air Gas turbine

CTF ash Intercooler Coal, limestone, water Fuel nozzle Condenser

Pressure vessel Bottom ash (BM)

Deaerator

Denitration unit

Water supply pump

Fuel slurry pump Water supply heater

Economizer

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 (1) Increase in efficiency through the combined power generation utilizing the pressurized fluidized bed combustion conditions: (gross efficiency of 43%) (2) Providing advanced environmental characteristics including: SOx reduction through the in-bed desulfurization; NOx reduction through the low temperature combustion (about 860 C); Dust
O

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

reduction by CTF; and CO2 reduction by increased efficiency. (3) Space saving of plant through the compact design of boiler adopting pressurized condition and the elimination of

was achieved.

3.Progress and result of the development Detail design of the facilities began in FY1990, construction began in April 1992, and facilities installation began in October 1992. Test operation began in April 1993, coal combustion The two-stage cyclone system passed the began in September 1993, and 100% load was achieved in January 1994. examination before entering operation in September 1994, and the CTF system passed the examination before operation in December 1994. Phase 1 demonstration operation was After that, the plant was conducted until December 1997.
PFBC development schedule
Fiscal year Item FY1989 FY1990 FY1991 FY1992 FY1993 FY1994 FY1995 FY1996 FY1997 FY1998 FY1999

modified to adopt the ash-recycle system.

Phase 2

demonstration operation was conducted from August 1998 to December 1999. The cumulative operating time of PFBC was 16,137 hours including 10,981 hours in Phase 1 and 5,156 hours in Phase 2. In particular, Phase 2 achieved continuous operation of 1,508 hours. Through the operation, valuable data and findings were acquired in terms of performance and reliability. These results have already been applied to the construction of commercial facilities of the three electric power companies.

Basic and detail design Construction start Construction of demonstration plant Test operation and adjustment Demonstration operation Phase 1 Modification Test operation Integration

Modification

Demonstration operation Phase 2

Interim assessment

Test operation

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

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

Final assessment

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 generation technology is an urgent issue from the viewpoints of reduction in greenhouse gases and of resource saving. Technology A-PFBC is a further advanced technology of PFBC (pressurized fluidized bed combustion). That is, the development aimed to increase the temperature at inlet of gas turbine, (from about 850 C to about 1,350 C), and to recover high temperature
O O

steam, thus to attain higher efficiency of power generation (about 46% of net efficiency; about 40% for the current coal fired power plants) by the combination of PFBC with the fluidized bed gasification technology.

Synthesis gas cooler Limestone

Desulfurizer

Cyclone

Ceramic Filer

Partial Gasifier Combustor Ash

Gas turbine Air Char Coal Flue gas Air Steam Flow Ash Oxdizer (PFBC) Steam turbine

Gas Flow

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%] - Increase of gas turbine inlet temperature (from about 850 C to about 1,350 C)
O O

(2) Mild gasification condition [Carbon conversion: about 85%] - 100% gasification in the partial gasifier by the combination with the oxdizer (perfect oxidizing atmosphere) (3) Utilization of results of related technologies - PFBC technology - Various coal gasification technologies

- Recovery of high temperature steam (High temperature steam recovery at the synthesis gas cooler applying the high temperature desulfurizer)

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 of each reactors, thus confirmed the data necessary for scale up. 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 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 Fig. 2 PDU: LAyout of three reactors
Partial gasifier Oxidizer

A-PFBC development schedule Fiscal year Item FY1996 FY1997 FY1998 FY1999 FY2000 FY2001 FY2002

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

2. Progress and result of the development HYCOL association (structured by above-listed nine private companies) contracted the research and development agreement on the pilot plant under supported by NEDO. On the other hand, 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

3.Issue and feasibility of practical application The development of coal gasification fuel cell system (IGFC) for power generation utilizing HYCOL technology has begun from 1995, (EAGLE Project).

achieved, and the worlds top gasification furnace technology was established.

25

Clean Coal Technologies in Japan

Pretreatment process

Gasification process

Water-washing process

Product gas firing process

Gasification furnace Coal Lock hopper

Boiler

Water-washing column

Pulverized coal apparatus

Incineration Waste furnace heat boiler Distributor Lock hopper Desulfurization unit

Air heater

Recycle gas compressor Ash treatment process

Fig.1 Flowchart of pilot plant

Specification and target performance of pilot plant Coal throughput Gasification agent Gasification pressure Gasification temperature O2/Coal Product gas volume Gas composition (design) max. 50 ton/day Oxygen 30 kg/cm2(G) 1,500-1,800 C
O

0.8-0.9 (weight ratio) about 91 kNm3/day CO H2 CO2 61% 31% 3%

Carbon conversion Cool gas efficiency

98% or more 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 Combined Cycle (IGCC) is a high efficiency power
Char recovery unit Reductor (gasification chamber) Char Unreacted coal (char) Syngas

1. Increase in thermal efficiency---Compared with conventional pulverized coal fired power plants, IGCC can increase net thermal efficiency by about 20% for commercial plant. 2. Better environmental characteristics---Owing to the increase in thermal efficiency, the emissions of SOx, NOx, and dust per generated power are reduced. In addition, amount of CO2 emissions is reduced generation process. 3. Increase in applicable grades of coal---IGCC can use coal, to the level of heavy oil fired power

generation technology which gasifies coal to be used as the fuel for gas turbine. Japanese power companies promoted research and development of IGCC technology applying the Nakoso pilot plant (PP) type gasifier 1,2) technology3). as the core The PP type
Water Coal Air Combustor (combustion chamber) Coal

Air Molten slag

having low ash melting points, which are difficult to be used in conventional pulverized coal fired power plants. power plant. 4. Increase in applicable fields of ash---Since IGCC discharges coal ash in a form of glassy molten slag, the ash is expected to As a result, IGCC widens the variety of coal grades applicable in coal fired

gasifier applies dry coal fed, oxygen-enriched air blown, pressurized two stage entrained beds, as shown in Figure 1, which is expected to

Slag hopper

Molten slag

be effectively used as materials for civil works. 5. Reduction of water consumption---Owing to the direct desulfurization of generated gas, IGCC does not need the flue gas desulfurization unit which consumes large amount of water. Accordingly, IGCC significantly reduces the water consumption compared with conventional pulverized coal fired power plant.

Fig. 1 Nakoso PP type gasifier

give higher efficiency than preceding gasifiers in abroad. On the basis of the study results, the IGCC demonstration test project was started with the aims to validate the reliability, operability, maintenance ability, and profitability of IGCC, and to 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 plant. Table 1 shows main specifications and target values of the plant. Figure 3 shows conceptional drawing of IGCC demonstration plant. The scale of IGCC demonstration plant(250
Coal Gasifier Heat exchanger Gas cleanup Char recovery unit Combustor Gas turbine

MW, 1700 t/d of coal feed) is about a half of commercial plant. The gasifier is of the Nakoso PP type. Wet type gas clean up system with MDEA is adopted . The gas turbine is the 1200OCclass gas turbine corresponding to the output of 250 MW.

Table 1 Main specifications and target values of IGCC demonstration plant


Air Steam turbine

Output Coal feed rate Gasifier

250 MW class about 1,700 t/d


Dry coal fed, air blown, pressurized two stage spouting beds

Waste heat recovery boiler Oxygen Air separator Gasifier Heat exchanger

Stack

Nitrogen

Fig.2 Flow diagram of IGCC demonstration plant

Gas cleanup Gas turbine Target thermal Gross efficiency efficiency (LHV) net efficiency Environmental SOx emission concentration characteristic NOx emission concentration (target value) Dust emission concentration

Type

Wet gas cleanup (MDEA) + Gypsum recovery 1200 OC - class 48% 42% 8 ppm (O2 16% conversion) 5 ppm (O2 16% conversion) 4 mg/Nm3 (O2 16% conversion)

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 nine power companies and Electric Power Development Co., Ltd. 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 70% contribution CCP R&D Co., Ltd. Personnel Nine power companies Electric Power Development Co., Ltd. Central Research Institute of Electric Power Industry Gas cleanup train Combined cycle block Gasification train

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 about three years. January 2004, the detail design and the environmental assessment are in progress. Plant operation and demonstration
Fiscal year Preliminary validation test Design of demonstration plant Environmental assessment Construction of demonstration plant Plant operation and demonstration test Table 2 Schedule of IGCC demonstration project 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Establishment of CCP R&D Co., Ltd

5.Activities until now The pilot plant test (200 t/d of coal feed) which is the preliminary stage of the demonstration test was carried out through a period 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)

Nakoso Power Plant of Joban Joint Power Co., Ltd.

Executed site of pilot plant test; Planned site for demonstration 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 (EAGLE) mentioned here aims, in an attempt to reduce environmental load, (particularly, to decrease the amount of greenhouse gas generated) at establishing a coal gasification technology which is widely applicable to chemical materials, hydrogen production, synthetic liquid fuel, electric power, and other purposes through the development of the most advanced oxygen2.Development targets and technology to be developed When applying coal gasification gas for IGFC and synthetic fuel/hydrogen/chemical fertilizer production, it is necessary to set targets to meet the refinement level required by fuel cells as well as the catalyst since impurities contained in the gas such as sulfur compounds may poison fuel cells and the reactor catalyst, thereby weakening their performance. Although not so much has been reported, even globally, about the effects of fuel cellpoisoning materials (including halogen) in particular, the EAGLE Project has established development targets as listed in the table on the right with reference to DOE, MCFC Association, and other reports.
Gas purification performance Coal gasification performance Continuous operation performance Adaptability to various grades coal Capability to scale up Target item Target of development Gas calorific value: 10,000 kJ/Nm3 or more Carbon conversionrate: 98% or more Cold gas efficiency: 78% or more Gasification pressure: 2.5 Mpa 1,000 hours or more Acquisition of gasification data for 5 or more grades coal having different properties from each other Acquisition of data for scale up aiming at about 10 fold of scale up Sulfur compounds: 1 ppm or less (precise desulfurizer outlet) Halogens: 1 ppm or less (precise desulfurizer outlet) Ammonia: 1 ppm or less (precise desulfurizer outlet) Dust: 1 mg/Nm3 or less (precise desulfurizer outlet)

blown, single-chamber, two-stage swirling flow gasifier that permits the high-efficiency production of synthetic gas (CO+H2). The application of this gasifier and its combination with gas turbines, steam turbines, and fuel cells further permit high-efficiency power generation [Integrated Coal Gasification Fuel Cell Combined Cycle (IGFC)], which will optimistically generate 30% less CO2 emissions than that of existing thermal power plants.

Coal Gasification Facilities

Gas Clean-up Facilities

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

Filter

Primary Scrubber Char Slag

Seconday Scrubber

MDEA Absorber

Limestone Absorber

Incinerator

HRSG

Compressor

Rectifier Air separator

Air 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 Development Organization and Electric Power Development Co., Ltd. among others promotes the project. The pilot plant (150 t/d) was constructed on the grounds of the Wakamatsu Laboratory at
EAGLE development schedule Fiscal year Item F/S Primary test Design of pilot plant Construction of pilot plant Test Design Construction Final assessment Test operation Analysis 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

the Technology Development Center of Electric Power Development Co., Ltd., (refer to photograph). undergoing test operations. The plant is

Test operation

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

Gasifier

Syngascooler

Gas clean-up

Filter Coal Air Nitrogen Oxygen

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

Gas turbine

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)


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

Outline of technology

1.Outline The formed-coke process (FCP) starts from noncaking coal as the main raw material, prepares formed coal using a binder, and then carbonizes the coal in as-formed shape in a vertical furnace to obtain coke.

3.Result of study 1. Production of formed coke from 100% noncaking coal Pilot plant operation was given normally with 70% noncaking coal and 30% caking coal. The operation with 100% noncaking coal was also attained. 2.Establishing stable operation technology and engineering technology

2.Features The FCP has a series of steps including raw material processing, forming, carbonizing the formed coal, and cooling the carbonized coke. In particular, carbonizing and cooling steps are conducted in a vertical furnace with closed system, providing many superior features in terms of work environment, work productivity, easiness of stop and start up, and narrow installation space to those of conventional chamber oven process.

Long period of operation at the facility capacity of 200 t/d was carried out. Production of 300 t/d (1.5 times the design capacity) was achieved. Regarding the unit requirement of heat, 320 Mcal/t-formed coal was achieved. 3. Long period and continuous use of 20% formed coke in large blast furnace In an actual large blast furnace, long period and continuous 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 heated to 1000 C in the high temperature carbonizing zone (vii) to undergo carbonization. The heat-up rate is controlled so as the coal not to generate collapse and break caused by bulging and shrinking. The carbonized coal (coke), is cooled to 100 C or lower temperature in the cooling zone (viii) by a normal temperature gas injected from the bottom of the furnace before discharged from the furnace.
O O

1.Drying

2.Pulverizing Binder

Forming stage
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 pulverized: (ii). A binder is added to the pulverized coal, 4.Forming which mixture is then kneaded: (iii), and formed: (iv), thus obtaining the Formed coal formed coal.

Generated gas
The coke oven gas (300-350 C) leaving the top of the furnace is cooled by the precooler (ix) and the primary cooler (x). After removing tar mist in (xi), most of the gas is recycled to the furnace. The surplus portion of the gas is withdrawn from the system, which is then subjected to rectification and desulfurization to become a clean fuel having high calorific value, (3800kcal/Nm3).
O

10.Primary 9.Precooler cooler 5.Carbonization furnace

11.Electric precipitator (Generated gas)

Main blower 6.Low temperature carbonizing zone 12.Decanter Tar 7.High temperature carbonizing zone

Ammonia water

Byproducts
8.Cooling zone 13.High temperature gas heating furnace 15.Ejector The liquid in the gas is introduced to the decanter (xii) to separate ammonia water and tar by decantation and precipitation. Each of these byproducts is sent to respective existing plants for further treatment. After treated, tar is reused as the binder for the formed coke.

14.Low temperature gas heating furnace

Gas recycle
Formed coke
O

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 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 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 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 Oita No.1 blast furnace of Nippon Steel Corp. in 19811). Although the main reducing material in blast furnace is coke, the blast furnace operation during and after the 1960s adopted heavy oil as an assistant fuel injecting from tuyere to enhance the productivity, efficiency, and scale up. After the two times of oil crisis, however, the high price of heavy oil forced the producers to switch the blast furnace operation to all-coke operation, or the reducing material had to fully depend on coke. Nevertheless, introduction of inexpensive assistant fuel instead of heavy oil was wanted to reduce the cost of blast furnace operation and to secure stable operation of the blast furnace. In this regard, Oita No.1 blast furnace introduced the ARMCO type pulverized coal injection system first in Japan, (Fig.1). The features of the system are the following. 1. High pressure transportation and injection lines have no mechanical rotation part, which avoids troubles of wear and damage. 2. Applied gas is not recycled to assure reliability of operation. 3. Distribution of pulverized coal charged to individual tuyeres ensures uniform distribution utilizing the geometrically symmetric flow characteristic of fluid.
N2 compressor Feed tank P.A.fan Feeder Reservoir tank Distributor Receiving hopper Cyclone Raw coal bunker

4. Drying, pulverizing, and collecting coal are conducted in two parallel lines to assure stable blast furnace operation. 5. Flow velocity of carrier air and pressure resistance of facilities are determined with full consideration of preventing fire and explosion.
Bag Filter

Transport line

Air heater

Pulverizer

furnace Disperser

O.T.

Air compressor

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

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

the pulverized coal injection facility, which increased the domestic average pulverized coal ratio to 130 kg/t level, (Fig. 2). Table 1 shows the various types of injection for the blast furnace pulverized coal facilities. Table 2 shows the highest level in Japan of a typical operational index of blast furnace during the operation with pulverized coal injection.

150 coke rate(mean) PC rate(mean)

500 Coke Rate(kg/t-pig)

100

450

50

400

number of BF equiped PCI 0 1980 1990 year 2000 350

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 Name of type Type of distribution /transportation Pneumatic conveying concentration Low Pneumatic conveying from feed tank directly to each tuyere Low High Medium Low Low Feed tank Main pipe Distributor Tuyere Velocity Control of flow rate in branched pipe Carrier gas pressure and flow rate (Downtake) ditto (Uptake) ditto + Flow meter Rotary Valve Coal Pump Uniformly distributing to give uniform pressure drop across in individual pipes Uniformly distribution by throttled pipes ditto Rotary Feeder+Uniform pressure drop (one way) distribution Use National Steel, Kobe Steel, JFE (NKK) JFE (Kawasaki Steel) Thyssen Dunkerque Scunthorpe Nippon Steel Corp., Hoogovens Investment

Petrocarb DENKA Kuettner ex-PW Simon Macawber ARMCO

High High Low Low High High

Medium Medium Large Medium Large Small

new PW Klockner Sumitomo Metal Mining. Co., Ltd.

High High Low

Low Low Low

Sidmar, Solac Fod Dunkerque, Taranto

Small Small

Sumitomo Medium Metal Mining. Co., Ltd.

Table 2 Domestic highest level operation indexes for blast furnace operation with pulverized coal injection Year and Month Maximum pulverized coal ratio (PCR) Minimum coke ratio (CR) Minimum reducing material ratio (RAR) Maximum tapping ratio 98.6 99.3 94.3 97.1 Steel works, blast furnace Fukuyama No.3 blast furnace Kobe No.3 blast furnace Oita No.1 blast furnace Nagoya No.1 blast furnace Coal dust ratio kg/t 266 214 122 137 Coke ratio kg/t 289 288 342 350 Reducing material ratio kg/t 555 502 464 487 Tapping ratio t/d/m3 1.84 2.06 1.95 2.63

4.Issues and feasibility of practical application Average operating years of domestic coke ovens have reached around 30 years, and the importance of the technology of injection of pulverized coal as an assistant fuel for blast furnace increases year after year. Compared with coke which depends on caking coal, pulverized coal increases the expectation for the injection material owing to the flexible adaptability to the coal resources.
Reference

possibility of innovation of blast furnace toward a combined smelting furnace through the combined injection via tuyeres of blast furnace together with reducing materials such as waste plastics and biomass, and further with reducing ores. Thus, the technology is expected to develop as a core technology of blast furnace solving the issues of resources, energy, and carbon dioxide.

The technology of pulverized coal injection has a

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 The DIOS directly uses noncaking coal in powder or granular shape and iron ore without using coke process and sintering process which are required in blast furnace process. The noncaking coal is directly charged to a smelting reduction furnace, while the iron ore is preliminarily reduced before charged to the furnace, thus the molten iron is produced. 2.Features 1. Applicable of inexpensive raw material and fuel, (noncaking coal, in-house dust, etc.) 2. Low operation cost 3.Responding flexibly to variations of production rate 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)

3.Result of study Feasibility study was given to new installation of commercial plant of blast furnace process and of DIOS at seaside green field. Considering its superiority to blast furnace process as described below, the feasibility of DIOS can be demonstrated for the model of 6,000 tons of molten iron production (annual production of 2 million tons). 1. Investment cost is decreased by 35%. 2. Molten iron production cost is decreased by 19%. 3. Coal consumption per 1 ton of molten iron production is the same level with that of the blast furnace process, 730-750 kg. 4. Net energy consumption is decreased by 3 to 4%. 5. CO2 emissions in the iron making process is decreased by 4 to 5%.

4.Progress of research and development


Table 1 Progress of research and development Fiscal year Core 1988 89 90 91 92 93 94 95

Construction Pilot plant test Test operation

1) Core technology study (FY1988-FY1990) Core technologies necessary for the construction of pilot plant were established. These core technologies include the increase in thermal efficiency of smelting reduction furnace (SRF), the connection with preliminary reduction furnace (PRF), the molten slag discharge technology, and the SRF scale up. 2) Pilot plant test (FY1993-FY1995) 1. Applicability of direct use of powder and granular ore and coal was confirmed, and necessary facility conditions were determined.

2. With various raw materials, the conditions of facilities and of operation to achieve high thermal efficiency to substitute the blast furnace were determined. 3. Technology for water cooling of furnace body was established. Conceptual design and economy evaluation (FS) for commercial facilities were conducted. The conditions of facilities and of operation to prove the superiority to the blast furnace as shown in the results of the research was clarified.

35

Clean Coal Technologies in Japan

Plant size Smelting reduction furnace Prereduction furnace

500 t-molten iron/day Height 9.3m. Inner diameter 3.7m. Pressure less than 2.0kg/cm2 - G(300kPa) Height 8.0m. Inner diameter 2.7m.

Coal 952kg

Flux 80kg

Iron ore 1450kg Preheating furnace

RD 8.7% RD 8.6% 600 C


O

2,326Nm3 2,789Mcal(11.7GJ)

Prereduction furnace Venturi scrubber RD 27.0% 779 C


O

O2 608Nm3 OD 31.6%

RD 27.1%

Pressure control value

Off-gas

Tapping device Smelting reduction furnace 1.9kg/cm2 - G(290kPa)


Molten iron 24.7t/h 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)

2A4. toward the 21st Century (SCOPE21)

Super Coke Oven for Productivity and Environment Enhancement

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 at 350 C(low temperature carbonization),as opposed to the old
O

The SCOPE21 process aims to develop an innovative process responding to the need in 21st century in terms of effective use of coal resource, improvement in productivity, and environmental and energy technologies. As shown in the figure, the existing coke production process is divided into three stages along the process flow, namely the coal rapid heating, the rapid carbonization, and the medium-to-low temperature coke reforming. Development was carried out of a revolutionary process with overall balance that pursued the functions of each stage the utmost. Currently the SCOPE21 is only one large development project for new coke process in the world, and it is hoped that it can be put to practicul use.

method of a 1200OC coke furnace, has many problems such as unavoidable coal grade limitation of using mainly strong caking coke owing to the limitation of coke strength, large energy consumption owing to the process characteristic, and environmental issues. Coke ovens in Japan have reached their average life of 30 years, and enter their replacement time. In this occasion of requirement for replacement, there is a need to develop an innovative next-generation coke production technology that has flexibility to handle coal resource and that has excellent environmental measures, energy saving, and productivity. Responding to the need, the team develops a new coke process.

Hot briquetting machine Plug flow conveying system

Stationary charge unit

Highly sealed oven door Pneumatic preheater Emission free coke pushing Carbonizing chamber High heat conductivity brick Pressure control (750-850OC) Smokeless discharge Power plant Steam Coke upgrading

Fine coal Stack

Coarse coal Fluidized bed dryer

Regenerator Foundation Coke (150-200OC) Coke sealed transportation (750-850OC) Blast furnace

Coal

Fuel

Hot blast 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% With the aim of increasing the use ratio of noncaking coal to 50%, which noncaking coal is not suitable for coke production and the current use ratio is only about 20%, the study develops the technology to increase the bulk density of charging coal through the improvement of caking property utilizing the coal rapid heating technology and through the forming treatment of fine coal powder. (2)Increasing the productivity by three times Aiming at the increase in the productivity by three times that of
37

current level, the study significantly reduces the carbonizing time by increasing the thermal conductivity of wall of the carbonizing chamber and by discharging the material at temperatures lower than normal carbonization point, (medium-to-low temperature carbonization). The resulting insufficient carbonization temperature is compensated by reheating in the coke dry quenching unit (CDQ) to secure the product quality. (3)Reducing NOx generation by 30% and achieving smokeless, odorless, and dustless operation Full scale prevention of generation of smoke, odor, and dust

Clean Coal Technologies in Japan


during coke production is attained by the sealed transportation of coal using the plug transportation, the sealed transportation of coke, and the prevention of gas leak from coke oven applying intrafurnace pressure control. Furthermore, improved combustor structure of the coke oven reduces NOx generation. (4)Saving energy by 20% The energy necessary to produce coke is aimed to reduce by 20% through the increase in the temperature to start the carbonization by preheating the charging coal to high temperature, the reduction in the carbonization heat by reducing the discharging temperature applying medium-to-low temperature carbonization, and the easy recovery of sensible heat of generated gas and of combustion flue gas owing to the scalereduction 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]
Coke over Conventional SCOPE21 89 40 Coal Preliminary --25 Common equipment 11 19 Total 100 84

Photo 1 Total view of pilot plant

Energy consumption (Mcal/t-coal)

600

Construction costs Reduction by 16% by greatly reducing the number of coke ovens even while expanding the coal pretreatment plants and environmental protection. Coke production cost Reduction by 18% by increasing the poor coking coal ratio and decreasing construction costs even while increasing electricity and fuel gas in the coal pretreatment plant.

CDO Recovered 271

Coke Production cost (%)

Energy saving Reduction of total energy use by 21% due to adopting a pretreatment process with direct heating of coal and a high effciency coke oven with a heat recovery system.

[Evaluation consumption]
800
Power Fuel gas

[Reduction of coke production costs]


100

70 133
CDO recovered 277

80

Variable 47 Variable 38

60

400 600 200


Total 399

40 Fixed 53

460
Total 316

20

Fixed 44

0 Conventional SCOPE21

Conventional

SCOPE21

SCOPE21 Development schedule 1994 Survey and study 95 96 97 98 99 2000 01 02 03

Core technology development

Core technology combination test Construction Disassembly and investigation Test operation

Pilot plant study

(4)Issue and feasibility of practical application The aging of coke ovens in Japan proceeds, though there are progresses of furnace repair technology. Thus coke ovens still need replacement and the replacement schedule has not been changed. The developed technology will be introduced to these aged coke ovens, though it is influenced by the economic 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 twostage 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 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 selfgranulation" for the first time in the world. The "hot selfgranulation" 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. cooler and a packed bed slow-cooling cooler to increase the heat recovery

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 Kawasaki Heavy Industries, Ltd. and Sumitomo Osaka Cement Co., Ltd., the technology development proceeded beginning from 1986 as the Coal Production and Utilization Technology Promotion Grant project which is a project of Agency of Natural Resources and Energy of the Ministry of International Trade and Industry. A 20 t/d pilot plant was constructed in June 1989 jointly by Center for Coal Utilization, Japan, Kawasaki Heavy Industries, 5.Issues The performance comparison between the conventional technology and FAKS for a 1,000 t/d commercial plant is shown 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 NO2 as N content in coal is 1% and NOx convert in 10% O2 CO2 *1 depends on electric power and fuel consumption Basis of calculation Production capacity Annual operating time Heat consumption Power consumption Exhaust gas specific quantity Lower calorific value of coal ton-clinker/day ton-cement/day Day/year kJ/ton-clinker KWh/ton-clinker Nm3/kg-clinker kJ/kg-coal 1,000 1,050 330 3,411x103 27 1.46 25,116 1,000 1,050 330 2,993x103 36 1.49 25,116 Discharge quantity (mg/Nm3) Annual discharge quantity (ton-NO2/year) Discharge quantity(g/Nm3) Annual discharge quantity (ton-CO2/year) Rotary Kiln & AQC 708 341 245 118x103 FAKS 476 233 220 108x103

Ltd., and Sumitomo Osaka Cement Co., Ltd. Then the pilot plant operation test began. From April 1993, the basic plan and design started for a 200 t/d plant jointly by Center for Coal Utilization, Japan, and Japan Cement Association. Through the operation test toward the practical application begun from February 1996, the system was validated, and the development work completed at the end of December 1997.

adopted as an innovative substitute cement production technology.

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

2.Development schedule The development was promoted by a joint team of Center for Coal Utilization, Japan, Nippon Sanso Corp., and NKK Corp. (present JFE Steel Corporation). The main subject of development was the furnace structure and the burner arrangement to attain high
Table 1 Development schedule 1992 Survey Batch-furnace Bench scale (1 t/batch) Pilot plant scale (5 t/batch) Continuous furnace (pilot plant scale: 6 t/h) 1993 1994 1995 1996 1997

efficiency melting. The study began from a batchwise melting furnace. With the result of the batch-furnace operation, the continuous melting furnace was developed aiming at higher energy efficiency.

3.Outline of process and result of study Figure 1 shows the process outline of the continuous melting furnace. The melting furnace has a melting section, basin section, and holding section, each of which is separately functioned. Each section has pulverized coal - oxygen burner. The oxygen supplied to the burner is preheated to high temperatures (400-600 C) by an oxygen preheater to combust
O

the pulverized coal. With the above-described system, even pulverized coal normally giving slow combustion rate can be combusted at high rate and high efficiency similar with those of liquid fuel such as heavy oil. The melting section is in shaft shape, where the raw material charged from top of the furnace is directly melted by the burner

Bag filter Flue gas

Blower Raw material Oxygen generator Burner controller Oxygen preheater Pulverized coal charge unit Tuyere Nitrogen generator Open/close damper Slide gate

Pulverized coal oxygen burner

Pulverized coal tank

Molten steel

Fig. 1 NSR process flow 41

Fig. 2 Pilot plant (6t/h)

Clean Coal Technologies in Japan

flame at lower section of the furnace. The melted raw material flows through the basin section and enters the holding section. The basin section soaks the molten steel. The carbon content of the molten steel in the basin section can be controlled by injecting powder coke into the furnace.
O

transmission. Compared with normal arc furnace, the melting energy was reduced by 40%, achieving high energy efficiency. Furthermore, the process achieved highly superior result to the conventional process in terms of environmental measures such as the significant suppression of generation of dust (excluding ash in pulverized coal) and of dioxins owing to the control of intrafurnace atmosphere.
1600 Coke 1400 Melting energy(Mcal/T) 1200 1000 800 600 400 200 0 EAF (380Wh/T) NSR Pulverized coal Electric power Oxygen

The holding section

stores the molten steel for a specified period, and rapidly heats the molten steel to about 1,600 C, and then taps the molten steel by the EBT system. To the basin section and the holding section, molten steel agitation gas is injected from bottom of the respective furnaces to enhance the heat transfer from flame to molten steel and the slag-metal reaction. All the combustion gas coming from individual sections passes through the melting section, and is vented from the furnace top after being used to preheat the raw material in the melting section. The raw material is continuously charged from the furnace top and melted in the furnace. The tapping from the holding section is conducted intermittently. The process effectively utilizes the heat transfer characteristics of oxygen burner, and achieves high efficiency melting. Figure 3 shows the result of comparison of melting energy between the process and the arc furnace. The electric power (oxygen is also added because it is produced by electricity) is counted to the primary energy including loss of power generation and of power

Fig. 3 Comparison of melting energy

4.Toward practical application The study team has already completed the design for actual scale facilities. With the influence of current poor economy in the electric furnace industry, however, the process has not been brought into practical application. Nevertheless, since the process is a non-power melting technology which is few in the world, and has a strong advantage of not influenced by electric power infrastructure, the study team continues to make efforts 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 important source of energy by humankind. Coal consumption surpassed that of firewood and charcoal for the first time in the latter half of the nineteenth century, making coal the worlds major source of energy. In Japan, coal also became the In the predominant energy source in the twentieth century.
1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998
Operation Recommendations to the 48th Subcommittee Meeting for Coal Conversion (March, 1995) The period of research extended for completion (March 31, 1999) -The Research Center inaugurated (June 24, 1995) -The ground-breaking ceremony for a pilot plant held (July 10,1996) -Coal-in trial run (Nov. 26-29, 1996, Feb. 25-27, 1997) -Coal-in RUN-1 (March 26, 1997-) -Coal-in RUN-7 (-Sept. 9, 1998) Cleaning, etc. Research on dismantlement Removal Total coal-in time of 6,062 hours or 262 days (excluding that for trial runs) The longest coal-in continuous run time of 1,921 hours -Operation completion ceremony held on Sept. 29, 1998. -Pilot plant operation completion report meeting held (Dec. 1, 1998) at a Gakushi Kaikan hall. -Pilot plant operation research completed (March 31, 2000). Construction Review of total project costs toward reduction (April, 1991, agreed upon at the operation meeting.) -Kashima Establishment opened (Oct. 1, 1991). -The ground-breaking ceremony for a pilot plant held (Nov. 25, 1991)Construction , NEDO s Coal Technology Development Office reorganized into CCTC (Oct., 1992). Total project costs reconsidered to be clearly defined in value (Nov., 1992). Set at 68.8 billion yen. The New Sunshine Project costs (1993) 150 t/d design Conceptual design of 250 t/d 250 t/d design 1st interim report (the same as the Joint Council report mentioned below) (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) Unification of three processes/development of NEDOL Process -NCOL established (Oct. 1, 1984)

Development History of NEDOL Process


Year
Three liquefaction processes

Articles and others

The Sunshine Project started (July, 1974) Research on three liquefaction processes started. (1) Solvent Extraction Process (2) Direct Hydrogenation Process (3) Solvolysis Process NEDO established (Oct. 1, 1980), succeeding three liquefaction processes of Coal Technology Development Office.

1960s, however, the presence of coal gradually faded as it was replaced by easier-to-use oil. It was after the oil crises of 1973 and 1978 that coal was thought highly of once again. With the oil crises as a turning point, the development of oil-alternative energy, particularly coal utilization technology, came under the spotlight amid calls for the diversification of energy sources. During that time, liquefaction of coal, which had been positioned as the strongest oil-alternative energy contender because of its huge reserves, was undergoing development in many countries. Research in Germany and the United States involved pilot plants with the capacity to treat hundreds of tons of coal per day. In Japan as well, development of coal liquefaction technology was being promoted under the Sunshine Project mainly by the New Energy and Industrial Technology Development Organization (NEDO). Despite the lag of a decade or so behind Germany and the United States, slow but steady development progress led to the successful completion of operations of a 150 t/d-scale pilot plant for the liquefaction of bituminous coal in 1998 with substantial results, thereby drawing equal with Germany and the United States as well as establishing state-of-the-art coal liquefaction technology. Coal-producing countries such as China and Indonesia are also strongly interested in the commercialization of coal liquefaction technology, with high expectations for its future development.
1999 2000 2001

Basic concept Conceptual design preparation

PDU (1 t/d of Sumitomo Metals-Hasaki)-based PSU (1 t/d of Nippon Steel-Kimitsu)-based research (design) started (around 1985). PSU operation research started (1987).

A 150 t/d pilot plant started.

(Downscaled from 250 t/d to 150 t/d.)

2.History of Coal Liquefaction Technology Development in Japan 2.1 Dawning of coal liquefaction technology development Between around 1920 and 1930, South Manchurian Railway Co., Ltd. started basic research on coal liquefaction using the Bergius Process and, around 1935, initiated operation of a bench-scale PDU (process development unit) plant. Based on this research, a plant annually producing twenty thousand tons of coal oil was built at Wushun Coal Mine, China, and operated until 1943. In the meantime, Korean Artificial Petroleum Co., Ltd. succeeded between 1938 and 1943 at its Agochi factory in the continuous operation of a direct coal liquefaction plant capable of treating 100 t/d of coal. Production of coal oil at both of the above plants was suspended at the request of the military to use the plants for hydrogenation of heavy oil or to produce methanol. At around 1930, besides the direct coal liquefaction method (Fischer Process), the Bergius Process was used as an indirect coal liquefaction method to study coal liquefaction technology and to produce synthetic oil. The Fischer Process was introduced into Japan upon its announcement in Germany in 1935 and, in 1937, plant construction started in Miike, winding up
43

in 1940 with the completion of an oil synthesis plant annually producing thirty thousand tons of coal oil. Under the background of a wartime situation, production of synthetic oil was continued until the end of World War II. 2.2 Post-war research on coal liquefaction Immediately after the war, the U.S. Armed Forces Headquarters banned research into coal liquefaction, alleging that it was military research. In 1955, coal liquefaction research was resumed at national laboratories and universities. This was not, however, research on coal oil production but the production of chemicals from high-pressure hydrocracking of coal, which was continued until around 1975. The Sunshine Project was inaugurated in 1974 on the heels of the first oil crisis, encouraging efforts to devise liquefaction technology unique to Japan as part of an oil-alternative energy development program. Under the Sunshine Project, technological development has been undertaken for the three coal liquefaction processes of Solvolysis, Solvent Extraction, and Direct Hydrogenation to liquefy bituminous coal. R&D of brown coal

Clean Coal Technologies in Japan

liquefaction processes has also taken place since the end of 1980. 2.3 Amalgamation of three coal liquefaction processes With the oil crises as an impetus, the practice of coal liquefaction technology development was incorporated for further promotion into the Sunshine Project based on Japans international obligations and the need for a large, constant supply of liquid fuel; diversification of energy sources and development of oil-alternative energy held great significance. In 1983, NEDO (the New Energy Development Organization, the
Coal Solvent Coal Coal

Solvent Extraction System (PDU) (Catalyst) Liquefaction reaction Solvent 450OC,150atm Hydrogen Solvent hydrogen Ni-Mo catalyst (Medium to a little heavy) Separation Coal oil Solvent

Solvent hydrogenation technology high-performance catalyst technology

NEDOL Process
High-performance catalyst (Fe)

Coal Liquefaction reaction Solvent


450 C,170atm Hydrogen Ni-Mo catalyst
O

Separation

Coal oil Solvent

Direct Hydrogenation System (PDU) High-performance catalyst (Fe) Liquefaction reaction Solvent 450OC,250atm Hydrogen Separation

Solvent hydrogen (Heavy)


Hydrogen

Coal oil Solvent

[Referential] EOS Process (U.S.) 450OC,140atm Liquefaction reaction Solvent Hydrogen Bottom recycle Hydrogen Separation Ni-Mo catalyst Solvent,hydrogen Coal oil Solvent

Solvent hardening technology

Solvolysis System (PDU) Ni-Mo catalyst Degree of dissolution SRC Deashing Liquefaction reaction Separation Coal oil Solvent

Coal

(Ultra-heavy oil) 450OC150atm

Ash Hydrogen 400OC,150atm

Fig. 1 Basic Philosophy of NEDOL Process

present New Energy and Industrial Technology Development Organization) assembled the R&D results thus far obtained from the three bituminous coal liquefaction processes as follows: (1) Result from Direct Hydrogenation Process: Under any of certain reaction conditions, the better the catalyst function, the higher the liquid yield rate becomes. (2) Result from Solvent Extraction Process: Hydrogen offers liquefaction under mild conditions.

(3) Result from Solvolysis Liquefaction Process: For priority acquisition of light oil, it is effective to thicken the circulation solvent. These three processes were amalgamated on the strength of their features into the NEDOL Process. 2.4 Bituminous coal liquefaction technology development (NEDOL Process) Bituminous coal liquefaction technology development is described in [3A-2]. 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 sometime in the future, takes an active stance toward the development/adoption of coal liquefaction technology. NEDO, as part of its international cooperation program, installed 0.1 t/d liquefaction equipment in China in 1982 for subsequent utilization such as in liquefaction tests of Chinese coal, exploration of catalysts for liquefaction, and human capacity building. Since 1997, at the request of China, cooperation has been offered for the implementation of feasibility studies on the location of a coal liquefaction plant using Yilan coal of Heilongjiang Province. Furthermore, a survey entrusted by China estimates Shenhua coal reserves in Shenxi Province/Inner Mongolia Autonomous Region at as much as 200 billion tons, justifying high expectations for coal as an inexpensive source of energy. It is further considered certain that Indonesia will become a net oilimporting country in the near future. Indonesian brown coal. In 1992, the Indonesian
QINGHAI GANSU NINGXIA HUIZU SHAANXI MONGOLIA JILIN NEIMONGGOL HEBEI Beijing LIAONING

operation concluded in a shift from the research stage to the commercialization stage. It seems that commercialization will be enhanced particularly through international cooperation with coalproducing countries such as China and Indonesia. In China, not only Japan but also the United States and Germany have embarked on feasibility studies of location with commercialization in mind.
Yilan coal Japan (CCUJ-JICA)

Shenhua coal U.S. (HTI-USDOE) Japan (NEDO)

HEILONGJIANG Harbin

SHANXI SHANDONG JIANGSU HENAN ANHUI HUBEI ZHEJIANG HUNAN GUIZHOU JIANGXI FUJIAN TAIWAN

government requested cooperation in coal liquefaction research on In response, NEDO signed in 1994 a memorandum on cooperative coal liquefaction research with the Agency for the Assessment and Application of Technology of Indonesia (BPPT) and began a new round of brown coal liquefaction technology development that aimed at the realization of commercial plants for Indonesian brown coal. Coal liquefaction technology development that has continued since the Sunshine Project was inaugurated in 1974 has now seen plant

SICHUAN

Kunming YUNNAN GUANGDONG GUANGXI ZHUANGZU

Xianfeng coal Germany(Ruhr Kohle-Nordrhein Westfalen State)

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 The conceptual design of a 250 t/d pilot plant (PP) began in FY1984. Owing to changes in economic conditions, however, the design of a 150 t/d PP began in FY1988. As a support study to the pilot plant, the operational study of a 1 t/d process support unit (PSU) was carried out. The 1 t/d PSU, constructed in FY1988 at Kimitsu Ironworks of Nippon Steel Corp., consists of four stages: coal storage and pretreatment, liquefaction reaction, coal liquefied oil distillation, and solvent hydrogenation. Over the ten-year period from FY1989 to FY1998, the joint study team of Nippon Steel Corp., Mitsui Coal Liquefaction Co., Ltd., and Nippon Coal Oil Co., Ltd. conducted operational studies on 9 coal grades under 72 sets of conditions. Through the 26,949 hours of cumulative coal slurry operations, the stability and the overall operability of the NEDOL Process were confirmed, and optimization of the process was established. Finally, the necessary design data was acquired. Construction of the 150 t/d PP was launched in 1991 at Kashima Steelworks of Sumitomo Metal Industries, Ltd. (Kashima City, Ibaraki), requiring nearly five years for completion. The PP consists of five main facilities: the coal preliminary treatment unit, the liquefaction reaction unit, the coal-liquefied oil distillation unit, the solvent hydrogenation unit, and the hydrogen production unit.

2. Evaluation of NEDOL Process Figure 1 shows the progress of coal liquefaction technology since before World War II, expressed by the relation between the severity of liquefaction reaction and the yield of coal-liquefied oil in individual generations. As seen in the figure, the NEDOL Process is competitive with the processes in Europe and the United States in terms of technology, economics, and operational stability, and thus the NEDOL Process is one of the most advanced processes in the field, reaching a position to shift to commercialization in the shortest amount of time.
Large

Yield of coal-liquefied oil

Third generation
NEDOL Process CC-ITSL Process (U.S.A.) IGOR+ Process (Germany)

First generation
Processes in the 40s

Second generation
Processes after the Oil Crisis

Small Severe

Severity of reaction

Mild

Fig. 1 Relation between the severity of liquefaction reaction and the yield of coal-liquefied oil
Coal liquefied oil distillation unit
Gas
Separator Atmospheric pressure distillation column

Coal preliminary treatment technology


Coal
Slurry mixer

Liquefaction/reaction unit
Iron-base catalyst Circulation gas compressor Hydrogen Hydrogen compressor Preheating furnace

170kg/cm2G (16.7MPa) 450@C

Naphtha

Coal bin

Slurry tank

High temperature separator Vacuum distillation column Let-down valve Heating furnace

Kerosene/ gas oil distillate

Slurry heat exchanger

Liquefaction reactor (3 units) Fuel

High pressure slurry pump

Separator
110kg/cm2G (10.8MPa) 320@C

Hydrogen Preheating furnace

Fuel

Drying/ pulverizing unit (Hydrogen-donor solvent)

Residue Solvent booster pump (Heavy distillate)

Stripper

Solvent 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 exclusively in Japan. The process has integrated the advantages of three bituminous liquefaction processes (Direct Hydrogenation Process, Solvent Extraction Process, and Solvolysis process), thus providing superiority in both technology and economics. The advantages of the NEDOL Process include: (1) attaining high liquid yield under mild liquefaction reaction conditions owing to the iron-based fine powder catalyst and to the hydrogen-donating solvent; (2) producing coal-liquefied oil rich in light distillate; (3) assuring high process stability because of the highly reliable 4.Typical reaction conditions of the NEDOL Process
Liquefaction reaction Temperature Pressure Kind of catalyst Solvent hydrogenation reaction Temperature Pressure Kind of catalyst LHSV Liquefaction catalyst Catalyst composition Fe (wt%) S(wt%) Catalyst Hydrogenation catalyst

core process stages; and (4) applicable to a wide range of coal grades, covering from subbituminous coal to low coalification grade bituminous coal.

48.2 51.0 0.8 Other(wt%) Specific surface area (m2/g) 6.1 0.7~0.8 Size of pulverized catalyst [D50]( m)

Ni-Mo/ Al2O3 190 0.7 Micropore volume (ml/g) 14.5 Mean micropore size (nm)
Catalyst composition Fe (wt%) Specific surface area (m2/g)

450 C 170kg/cm2 G
O

Slurry concentration 40wt%(dry coal basis) Slurry retention time 60min Gas/slurry ratio

Iron-base fine powder catalyst Added amount of catalyst 3wt%(dry coal basis)

700Nm3/t

Hydrogen concentration in recycle gas 85vol%

320 C 110kg/cm2 G Ni-Mo-Al2O3 1 hr(-1)


O

Gas/solvent ratio Hydrogen concentration in recycle gas

500Nm3/t 90vol%

5. Objectives and current progress of the pilot plant


Objective of the development 1. Yield of coal-liquefied oil 2. Slurry concentration 3. Added amount of catalyst 4. Continuous operation time 5. Range of applicable coal grades Target For the operation standard coal, 50 wt% or higher yield of light to medium oils, and 54 wt% of higher total yield. 40-50 wt% of coal concentration in slurry. Achieved result With the operation standard coal, there were attained 51 wt% yield of light to medium oils, and 58 wt% of total yield. Stable operation was achieved at 50 wt% of coal concentration in slurry.

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. 1,000 hours or more for the operation standard coal. Three coal grades or more. Continuous operation of 80 days (1,920 hours) was achieved with the operation standard coal. 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, and the support study data were summarized in a technology package preparing for practical application. At the Development and Assessment Committee meeting for Bituminous Coal Liquefaction Technology in the Assessment Work Group of the Industrial
Fuel unit Liquefaction reaction unit Central control building Solvent hydrogenation unit

developed materials and new processes are expected to significantly influence development in other industries.

Technology Council, held on December 22, 1999, the NEDOL Process was highly evaluated: "The NEDOL Process is at the highest technology level in the world, and has reached the stage where worldwide diffusion is expected." Thus, the development of coal liquefaction technology in Japan has already exited the research and development stage and entered the practical application stage. Furthermore, the

Coal-liquefied oil distillation unit

Coal preliminary treatment unit

Hydrogen production unit Storage unit

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 about one trillion tons, about half of which is comprised of lowgrade coal such as sub-bituminous coal and brown coal. Coal has a larger ratio of reserves to production (R/P) than that of oil and natural gas. For full-scale effective utilization of coal, Lowhowever, the effective use of low-grade coal is critical. As shown in the figure, the BCL process has four stages: the slurry dewatering stage where the water is efficiently removed from lowgrade coal; the liquefaction stage where liquefied oil production yield is increased by using a highly active limonite catalyst and the bottoms recycling technology; the simultaneous hydrogenation stage where the heteroatoms (sulfur-laden compounds, nitrogenladen compounds, etc.) in the coal-liquefied oil are removed to obtain high quality gasoline, kerosene, and other light fractions; and the solvent deashing stage where the ash in coal and the added catalysts are efficiently discharged from the process system. In Asian countries, economic growth steadily increases energy demand, and countries possessing low-grade coal resources, such as Indonesia, anticipate commercialization of the technology.

grade coal contains a large amount of water but has an autoignition property in a dry state compared with bituminous coal and other higher grade coals. Consequently, brown coal liquefaction technology development progressed aiming to contribute to a stable supply of energy in Japan by converting the difficult-to-use low-grade coal into an easy-handling and useful product, or by producing clean transportation fuels such as gasoline and kerosene from the low-grade coal.

Liquefaction stage
Hydrogen Recycle gas

In-line hydrotreatment stage


Sulfur recovery unit Sulfur

Slurry dewatering stage

Recycle gas

Off gas purification unit

Product gas (Fuel gas) Hydrogenated light oil

Coal (Raw brown coal) Water Evaporator

Reactor

Fixed bed hydrogenation reactor

Distillation column

Hydrogenated medium oil Preheater Slurry charge pump

Solvent deashing stage


Settler CLB (heavy oil) separator Sludge CLB (Boiler fuel)

Catalyst supply unit CLB recycle 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 (19871990), 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. During the study period, (the 1990s), however, a state of low oil prices and stable oil supplies existed worldwide owing to a stable international oil supply and demand situation. Thus, further improvements in the economics of the coal liquefaction process were requested, while cleaner liquefied oil was demanded owing to increased environmental concerns. Accordingly, the study team constructed a bench-scale plant (0.1 t/d) in the Takasago Works of Kobe Steel, Ltd. to conduct a study for improving the process. The study developed: a limonite catalyst which has extremely high activity compared with existing liquefaction catalysts, and which has superior handling properties such as crushing property; a method to maintain catalytic activity through the bottoms recycling technology; a simultaneous hydrogenation technology which significantly improves the quality of coal-liquefied oil; and various improvements for increasing operational reliability. Through the development work, the study established the improved BCL process (Improved Brown Coal Liquefaction Process, refer to the flowchart on the preceding page) that significantly improves the economics, reliability, and environmental compatibility of the brown coal liquefaction process.
Fig.2 50t/d Pilot plant (Australia)

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

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

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 environmental load, generating no sulfur oxide or soot during combustion. Owing to the non-toxicity and easy liquefaction properties, DME is easy in handling, thus it can be used as domestic-sector fuel (substitute for LPG), transportation fuel (diesel vehicle, fuel cell automobile), power plant fuel(thermal 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), (reaction (1)). The DME production through the dehydration of methanol, (reaction (3)), is the existing technology. The plant scale under actual operation, however, is rather small, and the scale up is an issue to produce DME commercially for fuel service. In addition, (1) 3CO+3H2 CH3OCH3+CO2 (2) CO+2H2 CH3OH (3) 2CH3OH CH3OCH3+H2O Currently DME is produced by dehydration of methanol at amount of about 10 thousand tons a year in Japan, and 150 thousand tons a year in the world. The main use of DME is spray propellant. If the supply of DME is available in large amount at low price, DME is expected to be used as fuel in wide fields owing to the above-described superior properties.

100 H2+CO conversion [%] (1) 3CO + 3H2 80 60 40 20 (2) CO + 2H2 CH3OH CH3OCH3 + CO2

the equilibrium conversion of the methanol synthesis reaction (2) 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 avoidable the conversion is higher than that of methanol synthesis. The reaction formulae relating to the direct DME synthesis are given below. The equilibrium conversion of methanol synthesis 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 the syngas produced from coal gasification (H2/CO=0.5-1). The targets of the development study include the following. <1.DME production rate: 100 ton/d or more, Syngas total 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 >

0.0

0.5

1.0

1.5

2.0

2.5

3.0

H2/CO ratio [-]


Fig. 1 Equilibrium conversion (280 C, 5Mpa)
O

49

Clean Coal Technologies in Japan

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

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

Purge gas

CO2 Natural gas Coal mine methane Coal Oxygen Steam

CO2

Non-reacted gas DME

Liquid/gas separator

Reaction condition 250~280OC 3~7Mpa CO,CO2,H2 Synthesis gas generation furnace Gas purification column DME synthesis reactor CO2 separation column Methanol 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 project is intended to develop a multi-purpose coal conversion technology excellent in efficiency, economy, and environmentfriendliness, mainly for the purpose of manufacturing mediumcalorie gas as industrial fuel and liquid products as raw materials for chemicals. The features of this process are as follows: 1. Moderate operational conditions - The pyrolysis reactor works at a temperature of as low as 600950 C.
O

4. Efficient separation of coal ash - Coal ash is discharged from the gasifier as molten slag and then granulated with water. 5. Diversified utilization of products available - Among products, gas can be used as industrial fuel, liquid (light oil/tar), as raw materials for chemicals, solid char, as fuel or a reducer, and slag, as an ingredient of cement. - The heating value of gas produced from the process is as high as about 3,500kcal/Nm3. - The yield of gas and liquid (light oil/tar) combined is 70% or more of coal input. 6. Controllable yield of products - A change in pyrolysis temperature (600-950 C) or coal kind
O

- The reaction pressure of lower than 1Mpa is much lower than several to tens of Mpa at which the coal liquefaction and hydrogasification processes operate. 2. High overall thermal efficiency - 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 subbituminous to highly volatile bituminous coal for the main material enables gas/tar to be obtained in large quantities.

allows product yields to be correspondingly changed.

Heat recovery Cyclone Tar cooler Scrubber Coal Pyrolysis reactor Crushing/drying Char heat recovery Char gasifier Decanter Char hopper Gas purification Gas

Steam

Separator

Tar

Slag Fig.1 Process Flow Sheet 51

Char

Clean Coal Technologies in Japan

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

exchange with thermal oil while tar passes the venture scrubber/tar cooler to be recovered. Pyrolysis gas is made

heating/pyrolysis reaction of pulverized coal (Fig.1).

entrained-bed coal flash pyrolysis has been developed as a process which not only produces more high value-added gas and liquid (tar and oil) possessing a coke oven gas (COG)-equivalent heating value but also supplies heat necessary for pyrolysis. Pulverized and dried coal (of about 50 m in grain size) is blown into the pyrolysis reactor and mixed with hot gas at 600-950 C
O

available for use as industrial-purpose fuel gas after purification such as through light oil (BTX) recovery and desulfurization. At the pilot plant (Photo 1) built within Yawata Works of Nippon Steel Corp., tests were conducted mainly with a view to the evaluation/verification of process component/total system technologies to establish the technological basis for

and several atm, with 2 seconds as its reaction time, to be flashheated/pyrolyzed. In terms of heat necessary for pyrolysis

commercialization as well as obtain data which would help design an actual plant (1,000t/d) and evaluate its economy. In two years from 1999, it was test-run 10 times in all, achieving a maximum 210-hour stable continuous operation. During the

reaction, part of pyrolysis product solid char is recycled to the hot gas generation section (char gasifier) to be partially oxidized by oxygen and steam, thus allowing an about 1,500-1,600 C stream
O

time, the aforementioned features were verified, assuring the controllability of products at a pyrolysis temperature (Fig.2) before the completion of process data taking.

of gas mainly composed of CO and H2 to generate so that sensible heat of the gas is used for the supply of such heat. The 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 reactors 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 Intl 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 perspective of a single industry in pursuit of a single product is reaching its limits in terms of efficiency and economy, calling the necessity to develop such innovative technologies as could completely change what energy and material production should be. Coal Flash Partial Hydopyrolysis Technology is a technology 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 oxidation section of a coal flash partial hydropyrolsyis reactor, pulverized coal and recycled char are gasified with oxygen and steam at a pressure of 2-3MPa and at a temperature of 1,5001,600 C to give hot gas mainly composed of CO and H2. At the
O

be evolved such as into Integrated Gasification Combined-Cycle (IGCC) power generation, indirect liquefaction (GTL), and chemicals while co-producing light oil as chemicals and fuel. The realization of a coal-based cross-industrial composite project (led by electric power/chemistry/steel) with this technology as its core will hopefully bring a dramatic improvement to total energy utilization efficiency.

concentration (H2 in hot gas and recycle H2 combined). At that time, hot gas from the partial oxidation section also functions as a source of the reaction heat required at the reforming section. At the reforming section, a hydrogenation reaction adds H2 to primary pyrolysis, such as tar released from pulverized coal, changing heavy tar-like matter to light oil. The gas, light oil, and char produced at the partial hydropyrolysis reactor follow a process where, after char separation at the cyclone and subsequent sensible heat recovery, synthetic gas (syngas) should be formed by way of oil recovery, desulfurization, and other gas purification processes. Part of syngas is converted into

reforming section directly connected through a throat to the partial oxidation section, pulverized coal is injected together with recycled H2 into the hot gas stream from the partial oxidation section to complete the reforming reaction (partial hydropyrolysis) in a moment under the condition of 2-3MPa in pressure, 700900 C in temperature, and about 30-50% in hydrogen
O

Decarboxylation

Shift conversion to H2 Heat recovery Gas purification

Syngas

Chemicals

IGCC fuel

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

Coal

Partial hydropyrolysis reactor Hot gas Partial oxidation section

Char

Heat

Coal
Light oil

Light oil

Chemicals

Fuel for 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 (CO2 recovery) and, after pre-heated via heat exchange, recycled to the partial hydropyrolysis reactors reforming section. A final syngas product is characterized by its main composition of H2, CO, and CH4 as well as high hydrogen contents at H2/CO 1 and used as source gas of IGCC, GTL, and chemicals. Light oil is mainly composed of aromatic compounds with 1-2 rings such as benzene and naphthalene, finding its application as chemicals or fuel for power generation. 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

required at the reforming section, providing high energy conversion efficiency. 2. Flexible productivity: The reforming section temperature as well as the amount of hydrogen injected can be controlled so as to freely change the gas/oil composition and output ratio, thereby flexibly responding to consumers needs. 3. Economy: For the purpose of syngas production, gas production cost may be reduced through its deduction by coproduced high value-added oil.

3.Progress status of development 1) Basic partial hydropyrolysis test (1996 through 1999, 1kg/day) Using a small-scale test unit, the pyrolysis behavior of coal under target conditions of this technology was reviewed, confirming that the hydropyrolysis of primary tar released from flash heating/pyrolysis reaction of coal successfully proceeded. 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. 3) Pilot plant test (2003 through 2008, 20t/day) Tests are conducted, using a pilot plant having its thermally selfsupportable reactor together with other ancillary process units, to have forecasts for a demonstration unit (up to 1,000t/day) as the next step.

Table 1 Development Subjects for Pilot Plant Tests Technology to be developed R&D items

Verification of the reaction in the partial hydropyrolysis reactor/ establishment of reactor control technology

- Quantification of partial hydropyrolysis reactor reaction - Establishment of reactor conditions for optimum transition zone formation - Establishment of high-efficiency gasification (partial oxidation section) operational conditions - Establishment of technology to separate/recover char from gas - Establishment of technology to recover heat from gas co-existent with oil - Establishment of long-hour continuous operation technology - Establishment of a scale-up approach for demonstration unit design

Development of process/factor technologies

Total system evaluation, etc.

Table 2 Development Schedule 2003 Pilot plant test Design/production/construction works Studies by testing Studies by disassembly Assistant studies 2004 2005 2006 2007 2008

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

2.Characteristics of system Common systems of pulverized coal firing, before burning the coal stored at its stockyard, pulverize it with a mill for the supply to a boiler, but in CCS, after coal is pulverized at a production/supply facility, all processes are to be completed within a closed system of gaseous-phase carriage, from loading onto tank lorries to deacquisition to consumers coal silos and then supply to boilers. This not only eliminates the problem of coal dust scattering, thereby keeping the environment clean, but also enables smooth operation to be realized through easier control of powder flows and, therefore, fluctuations in boiler loads. In behalf of consumers, this also advantageously requires no mill installation, dispenses with a coal yard since coal can be stored in a silo, and lessens equipment investment due to the compact equipment configuration, thus leading to labor saving and the better environment. CCS is, as mentioned above, a coal utilization system of improved coal handling with a closed powder carriage system of pulverized coal.

3.Technical data Attributes of CCS coal in general are shown in (Table 1)


(Table 1) Attributes of CCS Coal in General Brand Referential control Raw coal for mixture Total moisture Wt% AR Heating value kcal/kg * Moisture Wt% dry Ash Wt% dry Volatiles Wt% dry dry Fixed carbon Wt% Fuel ratio daf Carbon Wt% daf Hydrogen Wt% daf Nitrogen Wt% daf Oxygen Wt% daf Sulfur Wt% dry Total sulfur Wt% dry Grain size -200mest
Proximate analysis Ultimate analysis

A 3 kinds 2.9 6490 0.0 12.1 39.6 48.3 1.22 80.30 5.80 1.60 11.80 0.48 0.45 84.5

B 3 kinds 2.8 6480 0.0 12.4 39.5 48.1 1.22 80.00 5.80 1.50 12.40 0.47 0.43 78.9

C 2 kinds 2.7 6490 0.0 12.1 35.6 50.3 1.41 82.00 5.90 1.50 10.50 0.45 0.41 83.50

4.Process flow (Fig.1) shows a flow sheet and system outline of the CCS coal production/supply facility.
Screw conveyor Pulverized coal collection bag filter

Raw coal bunker Product silo Conveyor Mill supply hopper Table feeder Chain conveyor Product silo Product silo Product silo

Raw coal hopper

Magnetic separator

Volumetric coal feeder

Pulverizer Fuel gas Kerosene Gas cooler Fuel air blower Cooling tower Industrial water Air heater Seal gas blower

Truck scale

Recycle gas blower

Recycle gas line

Nitrogen generator tank tank

Outline of equipment
1 Raw coal hopper 20m3x1 unit 2 Raw coal bunker 400m3/Hx2 units 3 Pulverizer 25t/Hx2 units

4 Bag filter 67,500Nm3/Hx1 unit 5 Product silo 680m3x4 units 6 Truck scale 4 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 complex handling than a fluid does, environmental measures against dust, and spacious land for a coal yard, its slurry form has been noted as a means to make heavy oil-comparative, clean use of coal. Coal slurry fuel is found as COM (coal oil mixture) prepared by adding heavy oil to coal to give slurry, aside from CWM (coal water mixture), a mixture of coal and water. COM, a combination of coal and heavy oil convenient for burning, was earlier than CWM to be technically reviewed but failed to prevail after all, rather bottlenecked by the necessity of heavy oil. CWM is a mixture of water and coal, raising no problem of 2.Characteristics of high-concentration CWM Typical characteristics of high-concentration CWM (Chinese coal CWM) are shown in (Table1) below.
(Table 1) Characteristics of High-Concentration CWM Coal concentration (wt%) Higher heating value (kcal/kg) Lower heating value (kcal/kg) Apparent consistency (mPa-s) Specific gravity(-) Ash content (wt%) Sulfur content (wt%) Grains of 200 mesh or less (%) 68~70 5,000~5,200 4,600~4,800 1,000 1.25 6.0 0.2 80~85

spontaneous firing or dust scattering and can advantageously be handled as an easy-to-treat liquid. Conventional coal slurry using no additive can be piped but, due to its water contents of about 50%, is poor in long-run stability, requiring dehydration before firing. High-concentration CWM can now, as a result of studies on the particle size distribution of coal and a dispersant and other additives development, be kept fluid as well as stable even if less water is added and, therefore, directly burnt without being de-watered. Only a slight amount of additives added realize stable coal-water slurry in which coal particle of a certain size distribution are uniformly dispersed with their weight concentration of about 70%.

3) Particle size distribution For higher concentration/stability of CWM, pulverized coal sizes should preferably be distributed over a wide range rather than sharply distributed. Ordinary particle sizes used are roughly as shown in (Table 2).
(Table 2) Grain Size Distribution of High-Concentration CWM Maximum grain size Average grain size Grains of 74 m or less Fine grains of several micrometers or less 150~500 m 10~20 m 80% or more Around 10%

1) Coal type As a general trend, high-carbonization, low-inherent moisture (about 5% or less in approximate analysis), and less-oxygen content (about 8% or less in ultimate analysis) coal is suitable for high-concentration CWM. 2) Additives Additives consist of dispersants and stabilizers. A dispersant functions to disperse coal particles into slurry, using electrostatic repulsion effects or steric repulsion effects and sodium sulfonate of naphthalene, polystyrene, polymethacrylate, polyolefine, and the like 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 CWM size can be achieved suitable by for
Cold wet smashing De-watering Smashed coal/water/additives mixing

4) Rheological characteristics CWMs fluidity has characteristics of a non-Newtonian fluid but can be construed as a near-Bingham fluids. kind, concentration, additive, and flow state. speed of 100/s). 5) Heating value The heating value depends upon that of coal used. An average lower heating value is 4,600-4,800kcal/kg. The fluidity The apparent characteristics also changes, depending upon, such as the coal viscosity is roughly 1,000mPa-s (at room temperature and shear

Reception/storage of feed coal Smashing

pulverizng coal into a particle distribution


Hot wet smashing Coal smashing and mixing with water/additives to be done within a pulverizer Dry smashing

CWM, selecting correct additives (a dispersant and stabilizer), and appropriately water, and blending additives coal, to

Smashed coal/water/additives mixing

manufacture high-concentration, low-viscosity, high-stability, and good-quality CWM. A block flow of CWM manufacturing process is shown in Fig.1.
Enhancement of mixing CWM storage CWM shipment

(Fig.1) CWM Manufacturing Process 56

Coal Water Mixture (CWM)

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

2.Carbonized briquettes (1)Process outline Process for producing briquettes by coal carbonization has the carbonization stage and the forming stage. Figure 1 shows the basic process flow. The carbonization stage has the internal heating low temperature fluidized bed carbonization furnace (about 450 C of carbonization
O

(2)Carbonization stage The raw material coal (10% or lower surface water content, 5-50 mm of particle size) is preliminarily dried in the rotary drier. The gas leaving the drier passes through multi-cyclone to remove dust before venting to atmosphere. Figure 2 shows the cross sectional view of the internal heating low temperature fluidized bed carbonization furnace which performs most efficient carbonization of semicoke while retaining about 20% of volatile matter in the semicoke. The preliminarily dried raw material coal is charged to the middle section of the furnace, and is subjected to fluidization carbonization. The product semicoke is taken out from top of the furnace together with the carbonization gas. The semicoke is separated from the carbonization gas by the primary cyclone and the secondary cyclone. After cooled, the semicoke is
Drying Coalite Crushing Cyclon

temperature) to produce smokeless semicoke containing about 20% of volatile matter. The carbonization furnace has a simple structure having no perforated plate and agitator so that the operation and the maintenance of the furnace are easy. In the forming stage, the smokeless semicoke and auxiliary raw materials (hydrated lime and clay) are thoroughly mixed at a predetermined mixing ratio. After pulverizing, the mixture is blended with a caking additive while adding water to adjust the water content of the mixture. The mixture is kneaded to uniformize the distribution of caking additive, and to increase the viscosity to attain an easy-forming condition. Then the mixture is introduced to the molding machine to prepare briquettes. The briquettes are dried and cooled.

Raw Coal

Fig. 2 Cross sectional view of carbonization furnace

transferred

to

the

stockyard, and the carbonization gas is supplied to the combustion furnace lined with refractory, where the carbonization gas is mixed with air to combust. The generated hot gas is introduced to the raw material coal drier and to the succeeding briquette drier to use as the drying heat source of preliminary
Desulfurizer Binder Water Kneading Mixing

Carbonizing

heating of the raw material coal and the drying heat source of the formed oval briquettes. (3)Forming stage The semicoke (Coalite) produced in the carbonization stage is the briquette raw material containing adequate amount of volatile matter, small amount of ash and sulfur, and emitting no smoke and no odor. The semicoke as the main raw material is mixed with hydrated lime (sulfur fixing agent), clay (assistant for forming), and a caking additive.

Briquette

Briquetting

Drying

Fig. 1 Process flow of briquette production

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 with 10-25% of vegetable matter (biomass) such as wood bagasse (strained lees of sugar cane), straws, and haulms of corn, further with desulfurizing agent (Ca(OH)2) by an amount corresponding to the sulfur content in the coal. Owing to the high pressure briquetting (1-3 t/cm2), the coal particles and the fibrous vegetable matter in the bio-briquette strongly interwind and adhere to each other. As a result, they do not separate from each other during combustion, thus attaining combined combustion of the vegetable matter having low ignition temperature and the coal. The combined combustion gives favorable ignition and fuel properties, emits very small amount of dust and soot, and generates sandy combustion ash to leave no clinker. Furthermore, since the desulfurizing agent also adheres to the coal particles, the agent effectively reacts with the sulfur in the coal to fix about 60-80% of the sulfur into the ash. Applicable coal grades are many, including bituminous coal, subbituminous coal, and brown coal. In particular, the bio-briquettes utilizing low grade coal containing large amount of ash and having low calorific value gives large effect of coal-cleaning, thus the biobriquette technology is an effective technology to produce clean fuel for household heaters and industrial small boilers. (1)Production flow of bio-briquettes Figure 3 shows the basic flow of bio-briquette production. The coal and the biomass as the raw materials are pulverized to about 3 mm or smaller size, which are then dried. The dried mixture is further mixed with a desulfurizing agent (Ca(OH)2). The mixture is formed by compression molding in the high pressure briquetting machine. be added to some coal grades. The production process does not contain high temperature operation, and has a structure centering on the dry high pressure briquetting machine. The process is simple facility flow which is safe and which does not require skilled operational technique. Owing to the high pressure briquetting method, the coal particles and the biomass strongly interwind and adhere to each other, thus the process produces rigid formed coal which does not separate their components during combustion. (2)Bio-briquette characteristics 1. Compared with the coal direct combustion, the bio-briquette combustion decreases the generation of dust and soot by one fifth to one tenth. The coal direct combustion gives increased
Fig. 3 Basic flow of bio-briquette production 58
Bio-briquette High pressure briquetting Deodorant Caking additive Caking additive may be required depending on the coal grade. Mixing Pulverization Drying Pulverizing

the low temperature region (200-400 C) does not completely


O

combust. To the contrary, bio-briquettes combust simultaneously the low ignition point biomass which entered between coal particles with the coal, which assures the combustion of volatile matter released in the low temperature coal combustion region. As a result, the amount of generated dust and soot significantly reduces. 2. The bio-briquettes prepared by adding 15-20% of biomass to coal gives significantly short ignition time to improve the ignition property. In addition, the bio-briquettes have low expansion caking property so that the aeration between briquettes is secured during continuous combustion in a fireplace, giving favorable combustion characteristic. Consequently, the bio-briquettes have superior combustionsustaining property, and do not die out in a fireplace or other heater even when air rate is decreased to slow down the combustion rate, which makes the adjustment of combustion rate easy. 3. Since fibrous biomass enters between coal particles, there is no fear of clinker-lump formation during combustion caused by adhesion of fused ash in coal, thus the ash falls in sandy form through grate. Therefore, aeration is secured to stabilize the combustion state. Furthermore, since no clinker is formed, ash contains very small amount of unburnt coal. 4. The bio-briquettes are formed under high compressive force. Accordingly, the desulfurizing agent and the coal particles strongly adhere to each other, and they effectively react during combustion. With the addition of desulfurizing agent at about 1.2-2 of Ca/S ratio, 60-80% of the sulfur in coal is fixed in the ash.
Coal Biomass

Powder coal may be applied

without subjected to pulverization. A small amount of binder may


Drying

generation of dust and soot because the volatile matter released in

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 advanced countries are practicing mechanisms to promote the adoption of power generation using renewable energy. One of them is the RPS (Renewable Portfolio Standard) System. Since April 2003, the "Special Measures Law concerning the Use of New Energy by Electric Utilities (RPS Law)" has bee enacted, obligating electric utilities to use a certain amount of new energy for power generation. The normal usage (obligation amount) of new energy for electricity is assumed to increase from 3.3GkWh in 2003 to 12.2GkWh in 2010. What is defined as new energy includes biomass fuel. Co-firing of coal and woody biomass in the power generation sector, though already under way in U.S. and European countries, is a novel trial facing a variety of technological problems. For pulverized coal-fired boilers, there are roughly two methods of co-firing. One is to simply input woody biomass into an existing mill (pulverizer) and grind it for the combustion of pulverized coal-biomass mixture fuel in a boiler, using the existing burner. This method requires less adaptation of equipment and, therefore, less cost while there is a problem that a mixture of more than several % biomass causes the mills power consumption to sharply increase due to the difficulty in grinding woody biomass with ordinary pulverizers. method is to establish a biomass-dedicated mill. The other Despite the

equipment cost higher than the former, this method is advantageous not only because the ratio of mixture may be made higher but also because the amount of NOx generated can be reduced. Here, the latter method for which technology development is under way, commissioned by the New Energy and Industrial Technology Development Organization (NEDO), is introduced.

Combustion test/evaluation

Woody biomass technology investigation


Boiler Mill Coal Burner Woody biomass Separation Storage Drying Grinding Exhaust gas treatment

Pre-treatment technology development

FS for commercialization

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

59

Clean Coal Technologies in Japan

2.Development target (1)Co-firing ratio of woody biomass: 5-10% (2)Clearance of current regulatory environmental limits (3)Existing coal thermal power plants-comparable power 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).

3.Technologies to be developed (1)Woody biomass pre-treatment technology mainly of grinding (2)Woody biomass combustion technology (co-firing burner/biomass-dedicated burner)

Bag filter Burner To stacks Biomass Hopper Feeder Hopper Cyclone Heater Feeder Drier Blower

Mill [1]
Bin Furnace

Crusher

Mill [2]

Fig.2 Pilot Scale Test Equipments

4.Development in progress and results This project, under way jointly at the Chugoku Electric Power Co., Inc., Hitachi, Ltd., and Babcook Hitachi K.K., commissioned by NEDO, is now at the stage of FS for the evaluation of pilot 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) Development of component technologies for processes from reception to storage, crushing, dry boiler combustion, and then flue gas/ash disposal 1.Woody biomass technology investigation 2.Pre-treatment technology development 3.Combustion test and evaluation 4.FS for commercialization [Review of forest biomass utilization by local governments] Utilization planning and system design/verification Planning

Demonstration test Component technology development results-based deployment toward demonstration tests

Installation works Demonstration test

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 reserves, the expectation of stable supply, and the low price, though the influence of CO2 and other substances on the environment is relatively large compared with other fossil fuels. In the situation, to decrease the emissions of CO2 from coal fired power plants which account for large percentage in the coal utilization field, it is important to develop a power generation technology of higher thermal efficiency than ever, and to bring the technology widespread use over the world. If coal is utilized as a gas turbine fuel, the adoption of combined 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

steam turbine) realizes higher efficient power generation than that of existing pulverized coal fired power generation. To this point, if coal can remove impurities such as ash and alkali metals, the resulting clean coal can be used as fuel to directly combust in gas turbine. Regarding the issue, NEDO conducts development of technology of combined power generation system, where the coal is treated by solvent extraction and ion exchange to remove ash and alkali metals to obtain clean coal (Hyper-Coal), which is then directly combusted in gas turbines.

Hyper-Coal

Solvent

Coal

Solvent penetrates into coal

Cohesion of coal becomes weak, and soluble portions of coal dissolve.

Insoluble portions and ash are 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 Coal is extracted by a solvent, and then is treated by rapid filtration to remove residue, thus Hyper-Coal is produced. (Design temperature: 500 C, design pressure: 3MPa)
O

(2)Sedimentation-separation unit The unit is a sedimentation tank having coal extraction performance, (design temperature: 500 C, design pressure: 5 MPa).
O

Vertically to

arranged

five

valves

collect

samples

The unit produces various grades of Hyper-Coal samples.

determine the sedimenting condition of nondissolved 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 metals (Na, K) are decreased to 0.5 ppm or lower level by ion 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

excellent gasification raw material, and it is expected to increase high efficiency of gasification.

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


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

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

Raw coal

Asphalt

Slurry dewatering

Solid-liquid separation Decanter

Evaporator (140 C/350kPa)


O

Slurry preparation Solvent recovery

Waste water

Recycle solvent

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 high moisture low-rank coal is mixed with recycled oil (normally petroleum light oil), then laced with heavy oil (such as asphalt), and heated in a shell & tube-type evaporator, moisture is 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 the moisture within them is removed in the course of evaporation. During that time, laced heavy oil is effectively adsorbed onto pore surfaces, thus preventing spontaneous combustion. Moreover, the heavy oil expresses its nature to water repellency, functioning to prevent the re-adsorption of

moisture and accumulation of heat of wetting. The right figure shows this phenomenon conceptually.

Befor dewatering

After dewatering

Capillary water Surface water

Selective adsorption of asphalt onto pore surfaces

Asphalt

Fig.2 Fundamentals of Low-Rank Coal Upgrading

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

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
Photo 2 Low-Rank Coal Upgrading Demonstration Plant

upgraded-coal is similar to normal bituminous coal in easiness of handling and re-crushing. 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 in the first half of the 1950s, been widely used in applications such as for cement raw material, cement mixture, roadbed material, backfilling material, and piling-up material, finding its way mostly in the cement sector, particularly, as cement raw material (clay-alternative). 2.Generation rate According to a questionnaire survey conducted by the Center for Coal Utilization, Japan in 2001, the coal ash generation rate in Japan is 8,810 thousand tons a year, up 5% in ratio or 380 thousand tons in quantity from the preceding year. Most coalfiring boilers for the electric utility industry are those burning pulverized coal. On the other hand, in general industries, 132 coal-firing boilers are in operation with an installed power generation capacity of 1,000kW or more and, by burning methods, the majority is accounted for by pulverized coal burning (72 boilers). In terms of boiler capacity (steam generation rate), boilers of 50t/h or less are mostly of a stoker burning type while many of 100t/h or more burn pulverized coal. Fig. 2 shows changes in the rate of coal ash utilization as well as generation from electric power utilities and 1,000kW or moreinstalled power generation capacity establishments in general industries from 1993 through 2001.
Bottom ash (5~15%) Breaker Fly ash (85~95%) Clinker hopper Economizer Air pre-heater Electrostatic precipitator Boiler Coal-fired power plant Steam Household/factory Steam turbine Generator Transformer Chimney stack Power transmission

Coal burning methods are roughly divided as follows: (1) Pulverized coal burning (dry-type) (2) Stoker firing (3) Fluidized-bed burning (4) Circulating fluidized-bed burning

Rate of Utilization Rate of generation

Grader

Coal ash (thousand tons)

De-watering tank

Silo

Silo

Silo

Bagger

Humidifier

Humidifier

Dump truck

Ship

Truck

Jet vac truck Dump truck

Jet vac truck Dump truck

Year

Fig. 2. Changes in Coal Ash Generation and Utilization Rates

Fig. 1. Process Example of Coal Ash Generation from a Pulverized Coal-Firing Boiler Source: Data from the Japan Fly Ash Association

3.Physicality of coal ash In Japan, 90% or more of coal ash generated from pulverized coal burning, dwarfing 7% or so from fluidized-bed and some 12% from stoker burning. The generation ratio of fly ash and clinker ash (bottom ash) is 90:10. As for the shape of coal ash particle, low-melting point ash is often globular while much of high-melting point ash is indeterminate in shape. The average grain size of fly ash from pulverized coal burning is about 25 m, similar to silt in fineness between finer clay and coarser fine-grained sand for the use as ground material. The chemical composition abounds in silica (SiO2) and alumina (Al2O3), resembling mountain soil, and these two inorganic components alone account for 70-80% of total. Other than these, ferric oxide (Fe2O3), magnesium oxide (MgO), and calcium oxide (CaO) are also contained in slight amounts. In Japan, the physicality of coal wide varies since coal of 100 brands or more is imported from all over the world.

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Clean Coal Technologies in Japan

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

Table 1 Breakdown of Fields for Effective Coal Ash Utilization (2001) Item Sector Cement Description Cement raw material Cement mixture Cement admixture Sub-total Civil engineering Foundation improving material Civil work-purpose Power supply construction-purpose Roadbed material Asphalt/filler material Coal mine filling material Sub-total Construction Boards as construction material Artificial light-weight aggregate Secondary concrete product Sub-total Agriculture /forestry/fisheries Fertilizer (including snow melting agent) Soil conditioner Sub-total Others Sewage treatment agent Steel making-purpose Others Sub-total Total of effective utilization Electric utilities Rate of utilization 3,608 140 87 3,835 271 67 20 47 3 320 728 191 24 35 250 42 10 52 3 1 402 406 5,271 Composition ratio(%) 68.45 2.66 1.65 72.76 5.14 1.27 0.38 0.89 0.06 6.07 13.81 3.62 0.46 0.66 4.74 0.80 0.19 0.99 0.06 0.02 7.63 7.70 100.00 General industry Rate of utilization 1,307 154 47 1,508 94 22 0 54 0 0 170 118 0 3 121 12 80 92 1 1 9 11 1,902 Composition ratio(%) 68.72 8.10 2.47 79.28 4.94 1.16 0.00 2.84 0.00 0.00 8.94 6.20 0.00 0.16 6.36 0.63 4.21 4.84 0.05 0.05 0.47 0.58 100.00

[unit : thousand tons] Total Rate of utilization 4,915 294 134 5,343 365 89 20 101 3 320 898 309 24 38 371 54 90 144 4 2 411 417 7,173 Composition ratio(%) 68.52 4.10 1.87 74.49 5.09 1.24 0.28 1.41 0.04 4.46 12.52 4.31 0.33 0.53 5.17 0.75 1.25 2.01 0.06 0.03 5.73 5.81 100.00

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)

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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 challenged through investigations into pozzolana. Enhanced 1950s, standards were established for fly ash in 1958 and then for fly ash cement in 1960, encouraging wide applications for general concrete structures. In the meantime, fly ash came to be used as a clay-alternative in cement raw material in 1978 and, as of 2001, 68.5% of the total rate of effective utilization is accounted for by such applications.

research on the use of fly ash as a good-quality alternative to pozzolana brought its first late-1940s application to concrete admixture of structures like a dam in the United States for subsequent further dissemination into other countries. In Japan, 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 Cement raw material is composed of lime stone, clay, silica, and silver oxide, with clay accounting for 15% of total composition. Coal ash containing silica (SiO2) and alumina (Al2O3) is also used as an alternative to such clay. But it contains less SiO2 and more Al2O3 than clay to require more silica as a source of SiO2 which becomes short if coal ash is used in large quantities, thereby limiting the substitutability of coal ash for clay. At present, about 5% of cement raw material is substituted by coal ash but its alternative use is said theoretically possible to around 10%. 2) Utilization as cement mixture JIS specifies standards for fly ash cement2), allowing fly ash to be mixed by 5-30%. In general, fly ash can also be used as Portland cement mixture by 5% or less.

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

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Clean Coal Technologies in Japan

breaker superstructure works and foot protection/anti-turbulence blocks which are not required to be so strong. 4. Industrial standards for concrete-purpose fly ash Following the evaluation of fly ash as concrete admixture of excellent performance due to its high fineness and few unburnt carbon contents, high-fineness items were commercialized by means of an advanced grader and higher-performance qualities

or qualities likely to prove effective as admixture despite their sub-standard state were added to JIS Standards3) as 4th-grade items, thereby facilitating the selection of a quality suitable for the purpose of utilization. Class-1 fine fly ash is used as admixture such as for concrete products that must cut off water, be durable, etc. including ocean concrete and long haul- and pressuretransported special back-filling material.

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

Class Item Silica dioxide (%) Moisture content (%) Ignition loss *1(%) Density (g/cm3) Fineness*2 Residue on 45 m sieve (screen sieve method) *3(%) Specific surface area (Blaine method) (cm2/g) Flow value ratio (%) Activity index (%) Material age: 28 days Material age: 91 days

Class I fly ash

Class II fly ash 45.0 or more 1.0 or less

Class III fly ash

Class IV fly ash

3.0 or less

5.0 or less 1.95 or more

8.0 or less

5.0 or less

10 or less 5000 or more 105 or more 90 or more 100 or more

40 or less 2500 or more 95 or more 80 or more 90 or more

40 or less 2500 or more 85 or more 80 or more 90 or more

70 or less 1500 or more 75 or more 60 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)

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

2.Utilization in the civil engineering 1. Road construction material The "Outline of Asphalt Pavement" 1) allows fly ash to be used as asphalt filler material and clinker ash, as lower subbase material, frost heave depressant, and cutoff layer material. Fly ash can be used for the upper/lower subbase and road bed. A cement stabilization treatment construction method adds fly ash to cement to be treated under moderate moisture contents for application. This construction method realizes early manifestation of strength and achieves long-run stability. Another technology2,3,4,5) has also been developed to process coal ash for the use as road construction material. 2. Earthwork material Fly ash can be effectively used as piling-up or back-filling material since it is lighter than common earthwork material. In recent years, therefore, various technology development efforts6,7,8) have been made, coming up with a number of applications including a usage in the original powder state with cement added as a solidifier to coal ash, utilization as stabilizing treatment material, hardening for application, and granulation or other processing to use it. Review is also under way for intended commercialization of fly ash as soft ground improving material or a construction sludge conditioner due to its high activity of pozzolana as well as property of self-hardening9). Meanwhile, basic research of coal ashs 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

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Clean Coal Technologies in Japan

3.Utilization in the construction sector 1. Artificial light-weight aggregate Development efforts11,12) have successfully come up with technology to palletize/calcine coal ash and cement or the like into artificial light-weight aggregate. Demand for it is expected to grow such as due to the progress of urban development and high rising of buildings, making it important to further technology development of artificial light-weight aggregate as well as to reduce its production cost. 2. Others The resemblance of its components to the chemical composition of existing construction materials also allows coal ash to be used as clay-alternative raw material for ceramic products such as clay roofings, bricks, and tiles or a cement mixture for boards (interior/exterior wall material for construction) on the strength of such characteristics.

4.Utilization in the agriculture/forestry/fisheries sector 1. FertilizerCoal ash was designated in the capacity of pulverized coal-burning ash as a special fertilizer in 1960 for fly ash and in 1992 for bottom ash. A potassium silicate fertilizer making effective use of hard-to-solve silicic acid contained in coal ash is also produced about thousands of tons a year. 2. Soil conditioner Clinker ash whose chief ingredients are almost the same as those of ordinary soil, mostly composed of SiO2 and Al2O3, is suitable for the growth of vegetables. Moreover, it is used as sod for golf courses or to improve soil of poor-drainage places or arable land since its numberless spores hold water well for longer duration of fertilizer effects and, at the same time, its similarity to sand in shape provides comparable waterpermeability. 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 Example of Artificial Aggregate Fabricated from Coal Ash (Toughlite)

Photo 3 Application as fertilizer

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 Centers 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)

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

2.Valuable resources recovery Coal ash contains valuable substances including cenosphere (hollow ash), Magnetite silica, alumina, iron oxide, and titanium oxide, other than which valuable metals are also present though in trace amounts. 1) Recovery of valuable resources through physical treatment (1)Magnetite recovery through magnetic separation The recovery of magnetite (Fe3O4) from fly ash is also positioned at the pre-process of the chemical treatment method to recover valuable elements such as Si, Al, Ti, and Fe. Magnetite can be used, e.g., an alternative to heavy separation medium recovered by magnetic separation. 2) Recovery of valuable resources through chemical treatment (1)Direct hydrofluoric acid extraction method As a method of recovering valuable resources from fly ash through chemical treatment, the acid extraction method which uses an acid mixture of hydrofluoric acid and hydrochloric acid has been developed. The SiO2 recovered here is characteristically of high purity (99.9% or more) and fine particles (1 m or less). (2)Calcination method This method burns fly ash with a source of calcium to change 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 and, as part of its features, has a porous structure and, therefore, a large specific surface area as well as contains ionexchangeable cations and crystallization water that can be adsorbed/desorbed. On the strength of its such characteristics, Zeolite is used, e.g., as an adsorbent, catalyst, and disiccant1). It is known that hydrothermal treatment of a coal ash-alkaline aqueous solution mixture2) gives various kinds of zeolite, depending upon conditions for reaction. The Clean Japan Center3) now conducts demonstration tests at a coal ash zeolite production demo-plant of a level of 10 thousandton/year in 1990. At this coal ash zeolite production process, coal ash zeolite is obtained if coal ash is boiled with sodium hydroxide P type. Meanwhile, coal ash zeolite production processes so far commercialized are batch-wise like those for other than coal ash while flow-through continuous synthesis processes have also been developed4). In addition, review is now made on the exploitation of applications where large-quantity utilization is wellexpected, reduction of production costs, and technology to synthesize zeolite of a kind suitable for each application. while stirring and then solid contents are separated/washed/de-watered. The zeolite given here is of a Na-

Coal ash Caustic soda Boiling /stirring Buffer tank Drainage Water washing De-watering

Primary products storage

Drying

Bagging

NaOH drainage pit

Water drainage pit Water treatment station

Fig. 1. Coal Ash Zeolite Production Process

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Clean Coal Technologies in Japan

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

Structure

Molecular formula

Pore size (A)

Pore volume CEC (cc/g) (meq/100g)

Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] 27H 2 O

Na type: 4 Ca type: 5

Na type: 0.3

548

SiO4

Na 6 [(AlO 2 ) 6 (SiO 2 ) 10 ] 15H 2 O

Na type: 2.6 Na type: 0.36

514
*The figure is small but the exchange rate is small.

X
AlO4

Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] 264H 2 O

Na type: 7.4 Na type: 0.24

473

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)

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

2.Technology (1)Wet lime stone-gypsum method stone slurry is reacted on SO2 within exhaust gas for the recovery of sulfur contents as gypsum (CaSO4-2H2O). The overall reaction is as follows: CaCO3+SO2+0.5H2O CaSO3-0.5H2O+CO2 CaSO4-2H2O CaSO3-0.5H2O+0.5O2+1.5H2O

Members in charge of research and development: Mitsubishi Heavy Industries, Ltd.; Babcook Hitachi K.K.; Ishikawajima-Harima Heavy Industries Co., Ltd.; CHIYODA Corporation; Kawasaki Heavy Industries, Ltd.; others
Outline The lime stone-gypsum method is found in a soot-separation type which installs in its upstream a dedusting (cooling) tower for dust collection, HCl/HF removal, and cooling or in a sootmixed type having no such tower. Soot-separation types are used when high-purity gypsum containing no soot/dust is desired. At present, however, more and more soot-mixed types, less-expensive-to-install, are adopted since a high-performance dust collection system like the advanced low-temperature electrostatic precipitator has been developed, lowering soot/dust concentrations. In the absorption tower, on the other hand, water-mixed lime

There are two types of absorption tower as shown in Fig. 1; CaSO3-0.5H2O oxidation tower-separated types and all-in-one internal oxidation types. after-year increase. At present, the utilization of lessexpensive-to-install/operate internal oxidation types is on a yearMethods for causing recycled absorption liquid to contact SO2 in the absorption tower section include Spray Method to spray absorption liquid, Grid Method to shed absorption liquid on the surface of a grid-like pad, Jet-Bubbling Method to blow exhaust gas into absorption liquid, and WaterColumn Method to shed a fountain flow of absorption liquid in the absorption tower. 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 Sulfuric acid Oxidation tower

Absorption tower

Basic flow
Gypsum Gas Lime stone Absorption tank Air Gas Air Lime stone Absorption tower tank

Gypsum

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

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Clean Coal Technologies in Japan

(2)Coal ash-based dry desulfurization method

20% and dust collection efficiency of 96% or more. By 2003, it had been installed at No. 1 unit (350 KkW) of Hokkaido Electric Powers Tomato-Atsuma Thermal Power Plant as a facility currently in operation to treat half of its flue gas in amount.

Members in charge of research and development: Hokkaido Electric Power Co., Inc.; Hitachi, Ltd.; Babcook Hitachi K.K. Kind of project: Subsidized development of oil-alternative energy-related technology for commercialization Development period: 1986-1989
Outline It is one of technologies developed to make effective use of coal ash. This method is to fabricate a new absorption spent from lime stone, calcium hydroxide (Ca(OH)2), and spent absorption agent and then, using the absorption agent, remove SOx from flue gas. Fig.2 shows an outline of its process. This process also includes the stage to manufacture the absorption agent. Desulfurization reaction here is a reaction which allows Ca(OH)2 to remove SO2. Temperature is conditioned at 100200 C, where an SOx removal efficiency of 90% or more can be
O

Coal ash

Slack lime

Used desulfurization agent Water Kneader Drier Hot air

Boiler Exhaust gas

Conveyor Blender

Extruder Conveyor Steam

Pre-absorption agent

Primary absorption agent

Desulfurization silo

Clean gas Desulfurization fan

Weighing machine Steam generator

Screen

Weighing machine Used desulfurization agent Breaker


O

obtained. The process is also capable of dust collection and De-NOx, having achieved a NOx removal efficiency of about (3)Spray Drier Method

Fig. 2 Coal Ash-Based Dry Desulfurization Method Proces

giving a particle mixture of gypsum (CaSO4-H2O) and calcium sulfite (CaSO3-0.5H2O). These particles are recovered at a down-stream precipitator. Since this method is not enough for good-quality gypsum to be obtained and, moreover, ash remains mixed in, desulfurized particles are disposed of as waste. Electric Power Development Company, as part of the "Green Aid Plan," installed a spray drier desulfurizer with an exhaust gas treatment capacity of 300Km3N/h (half of total exhaust), which is currently in operation, at Huangdao Power Plant No. 4 Unit (210KkW) in Qingdao, China, for 70% desulfurization rate verification tests (Oct., 1994 through Oct., 1997). SO2 at a furnace temperature of 760-860 C: CaCO3 CaO+CO2 CaO+SO2 CaSO3 At present, this method is in practice at normal-pressure fluidized-bed boilers of J-POWERs Takehara Thermal Power Plant No. 2 Unit as well as pressurized fluidized-bed boilers of Hokkaido Electric Powers Tomato-Atsuma Thermal Power Plant, Kyushu Electric Powers New Kanda Thermal Power Plant, and Chugoku Electric Powers Osaki Thermal Power Plant. At pressurized fluidized-bed boilers, lime stone does not break down into CaO due to the high partial pressure of CO2 but SO2 is removed in accordance with the following reaction: CaCO3+SO2 CaSO3+CO2

Members in charge of research and development: Electric Power Development Company; Mitsubishi Heavy Industries, Ltd.; Hokkaido Electric Power Co., Inc. Kind of project: Voluntary under the Green Aid Plan
Outline It is a so-called semi-dry method, where water is added to burnt lime (CaO) to make slack lime (Ca(OH)2) slurry, which is sprayed into a spray drier, causing SO2 in exhaust gas to react on Ca(OH)2 to be removed. Within the drier, desulfurization reaction and lime stone drying take place at the same time, (4)Furnace desulfurization method

Members in charge of research and development: Hokkaido Electric Power Co., Inc.; Kyushu Electric Power Co., Inc.; Electric Power Development Company; Chugoku Electric Power Co., Inc.; Mitsubishi Heavy Industries, Ltd.; Ishikawajima-Harima Heavy Industries Co., Ltd.; Kawasaki Heavy Industries, Ltd. Kind of project: Voluntary project
Outline It is a desulfurization method used for fluidized-bed boilers. Lime stone for desulfurization is mixed with coal to be fed together with coal, causing the following reaction to remove

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

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

2.Technology (1)Selective contact reduction method

Members in charge of research and development: Mitsubishi Heavy Industries, Ltd.; Ishikawajima-Harima Heavy Industries Co., Ltd.; Babcook Hitachi K.K.
Outline In this method, ammonia (NH3) is blown into exhaust gas, allowing ammonia (NH3) to selectively react on nitrogen oxides NOx(NO, NO2), and decomposed them into water (H2O) and Nitrogen (N2). In the De-NOx reactor, since exhaust gas entails soot and dust, a grid- or plate-like catalyst is mainly used, as shown in Fig. 1. The catalyst is filled in the reactor, as shown in Photo 1/Photo 2, to react on the NH3 blown into the catalyst layer 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 added as active ingredients. 4NO + 4NH3 +O2 4N2 + 6H2O
O

process is also so designed that NH3 leaked from the reactor should amount to 5ppm or less and if much NH3 leaks, it will react on SO3 in exhaust gas, giving NH4HSO4, which is separated out in the air pre-heater to clog the piping. NOx removal efficiency is around 80-90% for pulverized coalfired thermal power plants. On the other hand, measures for equal dispersion/mixture of NH3 in exhaust gas as well as greater uniformity of exhaust gas flows to cope with growing boiler sizes are contrived such as by placing a current plate called Guide Vane at the gas inlet or dividing the gas inlet into grids to be each equipped with an NH3 injection nozzle.

Smokestack

The temperature range is 350 C, at which the catalyst can demonstrate its performance. At a lower temperature than this, 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

Catalyst layer

performance, regardless of SO3 concentrations.


O

At a high The

Exhaust gas

Reactor

temperature above 400 C, NH3 is oxidized to decrease in amount, thereby reducing the De-NOx performance.
Fig. 1 Selective Contact Reduction Method Denitration Process

Photo 1 Grid-like catalyst

Photo 2 Plate-like catalyst

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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

down NOx into H2 and H2O without any catalyst. Despite its method achieving NOx removal efficiency of as low as some 40% at the NH3/NOx molar ratio of 1.5 is used in 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 precipitation in the case of high-SO3 concentration exhaust gas. This technology is mainly used such as at small commercial boilers and refuse incinerators. With respects to thermal power plant applications, it was installed only at Chubu Electric Powers Chita Thermal Power Plant No. 2 Unit (375kw) in 1977.
Brine water for nozzle-cooling

Injection nozzle

merits of requiring no catalyst and lower installation costs, this

AH

Ammonia Mixer Air for dilution

SAH

FDF

Booster fan

Fig. 2 Selective Non-Catalytic Denitration Methods 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. target performance. At present, basic research is under way at the Center for Coal Utilization, Japan, toward expected commercialization around 2010. It is a technology aimed at NOx concentration of 10ppm or less for its

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 technology but requires a variety of feed water as well as advanced waste water treatment measures. Meanwhile, an already commercialized ammonia selective reduction (SCR) method needs not only life control of expensive De-NOx catalysts but also measures against leaked ammonia. Development efforts are, therefore, under way for a dry combined desulfurization De-NOx method to remove NOx and SOx at the same time without any feed/waste water treatment or De-NOx 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 between SO2 in exhaust gas and blown-in NH3 on active carbon at 120-150 C, thereby converting SO2 into such form as
O

first stage, with De-NOx performance also achieving 80% NOx removal efficiency. This technology, verified after upscaled to a capacity to treat gas of a 150Km3N/h level in amount, was adopted in 1995 for the De-NOx unit of Takehara Coal Thermal Power Plant No. 2 Units normal-pressure fluidized-bed boiler (350KkW) and is currently in operation. It was further installed in 2002 at J-Powers Isogo Thermal Power Plant No. 1 New Unit (600KkW) as its desulfurizer (Photo 1) currently in operation but none is operated as combined desulfurization-denitration equipment.
Active carbon

ammonium hydrogen sulfate (NH4HSO4) and ammonium sulfate ((NH4)2SO4) for adsorption/removal while decomposing NOx into nitrogen and water as SCR Method does. process. Fig.1 shows the The moving-bed adsorption tower (desulfurization This method first

tower) at the first-stage removes SO2 and, at the second stage (denitration tower), NOx is decomposed. removes SOx and then NOx since, as shown in the figure, the presence of high-concentration SO2 tends to lower NOx removal efficiency. Active carbon that has absorbed NH4HSO4 is heated to 350 C or
O

above in the desorption tower to desorb NH4HSO4 after decomposing it into NH3 and SO2 while active carbon is regenerated. In the desulfurization tower, SO2 can be adsorbed and removed in the form of sulfuric acid (H2SO4) even if NH3 is not blown in but since, at the time of this desorption, the following reaction with carbon contents occurs, consuming active carbon, NH3 is added at the time of desulfurization for the purpose of preventing this. H2SO4 SO3+H2O SO2+CO2
O

Desulfurization tower

Hot air

Denitration tower

Desorption tower

Exhaust gas

Desorbed gas

Hot air

Fig.1 Active Carbon-Method Desulfurization Process

SO3+0.5C

Desorbed SO2 is reduced into elemental sulfur by coal at 900 C 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 JPowers 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. improvement in De-NOx performance, a For further combined SOx was
Photo 1 Active Carbon-Method Desulfurizer

desulfurization De-NOx pilot plant that can treat 3,000m3N/h of gas with two tower units was tested (1984-1986). almost completely removed by the desulfurization tower at the

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 This method, as shown in Fig.2, injects an electron beam on SOx/NOx in exhaust gas and blown-in NH3 to cause a reaction for their recovery as ammonium sulfate ((NH4)2SO4) or ammonium nitrate (NH4NO3) in the downstream precipitator. Byproducts; ammonium sulfate and ammonium nitrate are used as fertilizers. The performance of 98% or more SOx and 80% NOx removal efficiencies for the NH3/NO molar ratio of 1 is obtained at 70-120 C.
O

For this method, technology development was undertaken by Ebara Corporation and U.S. partners including DOE through their joint contributions (1981-1987). In Japan, based on development results, a pilot plant (that can treat gas of 12,000m3N/h) was built at Chubu Electric Powers Shin-Nagoya Power Plant, where the technology has been verified (1991-1994). Regarding this technology, a plant that can treat gas of 300Km3N/h (90KkW) (Photo 2) was installed at Chengdu HeatElectricity Factory (co-generation power plant) in Sichuan province, China, and currently in operation for demonstration under 80% NOx removal efficiency conditions.

NOx removal efficiency also characteristically

increases with increasing SO2 concentration, though SOx removal efficiency does not affect the inlet concentration of SO2.
Existing boiler Air pre- Dry electrostatic heater precipitator

Air

Smokestack

Cooling water

Electron beam generator Dry electrostatic precipitator

Reactor Cooling tower Ammonia equipment Granulator Nitrogen fertilizer (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 by-fuel kind/-boiler size concentrations. At present, however, there are some regions subject to the total amount control which limits the overall emissions from each region as in the case of sulfur and nitrogen oxides. In coping with such regulations, an electrostatic precipitator was employed in Yokosuka Thermal Power Plant for the first time in the world in 1966 for mainly other thermal power plants to follow suit. Development of pressurizedbed combustion and coal gasification combined-cycle technologies is also under way for high-efficiency power generation, using cyclones and ceramics/metal precision-removal filters. On the other hand, trace materials-related control is now being intensified such as through the addition of boron (B) and selenium (Se) to waste water materials to be regulated and U.S. 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 soot/dust in exhaust gas in accordance with the theory that any 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. The dust collection performance depends upon the electrical resistance of soot/dust, preferring particles of 104-1011 -cm in the apparent electrical resistivity range. In the case of pulverized 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 collection are adjusted. Electrical resistance changes as shown in Fig.2. Those successfully developed/commercialized from the use of such characteristics are a high-temperature electrostatic precipitator run at 350 C, a higher temperature than that of
O

DC high voltage Power supply

Discharge electrode Collected soot/dust Dust collecting electrode

Flue gas (from boiler)

Fig. 1 Theory of Electrostatic Precipitator

conventional low-temperature electrostatic precipitators (130temperature electrostatic precipitator run, with its electrical resistance lowered by operating it at a dew point-or-lower temperature (90-100 C).
O

Low-alkali /low-sulfur coal

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 electrostatic precipitator where a film of liquid is shed to wash away dust. Another measure has also been taken with electric discharge methods commercialized, including an intermittent charge method to supply a pulsed voltage on the order of several milliseconds and a pulse charge method for tens of microseconds-order energization. At present, leading pulverized coal-firing plants built in and after 1990 are provided with very low-temperature electrostatic dustcollection means that can treat different properties as well as shapes of soot/dust.
79

Advanced Low-temperature ESP Conventional low-temperature ESP

High-alkali /high-sulfur coal High-alkali /low-sulfur coal

Temperature(OC)

Fig. 2 Temperature Effects on Electrical Resistance of Coal Ash

High-temperature ESP

150 C) to lower electrical resistance and an advanced lowO

Low-alkali /high-sulfur coal

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 from hot gas for pressurized-bed combustion and integrated gasification combined-cycle (IGCC) power generation processes. This technology utilizes a multi-cyclone, ceramics- or metalbased 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). Schumacher. Such filters used here were developed by Nihon Garasu Kogyo or overseas by Paul Such technologies, now under durability are used for pressurized-bed evaluation/demonstration, Plant but also under the EAGLE Project. It is also expected to be used at an IGCC demonstration unit (250KkW) slated for initial operation in 2007.

combustion power generation at Hokkaido Electric Powers 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 released into the atmosphere at the highest rate, with about 30 percent of the failure to be removed at precipitators/desulfurizers proved to be released. However, bivalent mercury (Hg2+) is nearly all removed, leaving nonvalent one (Hg) as discharge matter. A method to remove this nonvalent mercury is under active review. The Center for Coal Utilization, Japan, though still in the process of basic research, selected active carbon, natural inorganic minerals, and lime stone as materials which absorb mercury and is now evaluating their absorption characteristics. The research results prove that, if the method to inject active carbon or an FCC ash catalyst into the flue for the removal of metal mercury is combined with removal at the flue gas desulfurizer, 90% or more mercury can be removed easily.

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)

4B5. Gas Cleaning Technology


Outline of technology

1.Background For the development of coal gasification gas-based power generation and fuel synthesis technologies, it is necessary to remove sulfur compounds (H2S, COS), halides (HCl, HF), and other gas contents. As shown in Fig.1 a main application of this technology is found in the wet gas purification method which, after removing water-soluble halides and other contents by a water scrubber, desulfurizes the gas with a methyldiethylamine (MDEA) or other amine-based liquid absorbent for gas purification. This method, however, requires the gas to be cooled down to around room temperature, thus losing much heat. Furthermore, the
H 2S absorption tower Renewal tower Reboiler Sulfur recovery equipment Coal gasifier Ceramic filter

For solution of problems with such a wet gas purification method, efforts are now exercised to develop dry gas purification
COS conversion catalyst Scrubber (dehalogenation, deammonification)

process becomes complex since it requires not only a heat exchanger but also a catalyst which changes hard-to-remove COS into H2S. It is also difficult to precisely reduce sulfur compounds to a 1-ppm level.

Fig. 1 Wet Gas Purification Process

2.Technology (1)Dry desulfurization method

Members in charge of research and development: Center for Coal Utilization, Japan; IGCC Research Association; Technology Research Association for Molten Carbonate Fuel Cell Power Generation System; Central Research Institute of Electric Power Industry; Electric Power Development Company; Ishikawajima-Harima Heavy Industries Co., Ltd.; Mitsubishi Heavy Industries, Ltd.; Kawasaki Heavy Industries, Ltd. Kind of project: Voluntary project /NEDO-commissioned business Development period: 1986-1998
Outline It is a method in which, as shown in Fig. 2, metal oxides are reduced by coal gasification gas, and reduced metal oxides remove sulfur compounds from gas, then are converted to sulfides. This method can be used more than once by letting sulfides react with oxygen for the release of sulfur contents as SO2 to bring back metal oxides. The development of this method as a technology for integrated gasification combined-cycle power generation (IGCC) was promoted, targeting to reduce sulfur oxides to 100ppm or less in the temperature range of 400-500 C where economical carbon
O

Nakoso IGCC Pilot Plant Project (for coal gas production of 43,600m3N/h in amount), a pilot plant that can treat the amount of coal gas produced by a tenth and is under verification of performance. Meanwhile, Kawasaki Heavy Industries, Ltd. has developed an iron oxide-based highly wear-resistant granular desulfurization agent for use in a moving-bed combineddesulfurization/dust collection system (Fig.5) and evaluated its performance at the pilot plant capable of treating the 1/40 amount of coal gas produced, which was buiilt under the 200-Ton/Day

steel can be used for piping. As the metal oxide to be used, iron oxide was selected and Ishikawajima-Harima Heavy Industries Co., Ltd. built a fluidized-bed desulfurization pilot plant (Fig.3) that can treat the total amount of coal gas, using 100-200- m iron ore particles, and is now under verification for performance, under the 200-Ton/Day Nakoso IGCC Pilot Plant Project (19911995). On the other hand, the Central Research Institute of Electric Power Industry and Mitsubishi Heavy Industries, Ltd. , assuming its use in fixed-bed desulfurization systems (Fig.4), have jointly developed an iron oxide-based honeycomb desulfurization agent. They also built, under the 200-Ton/Day
Reproduction

Reduction
Mt: Elementary metal

Desulfurization

Fig. 2 Desulfurization Reaction Cycle

81

Clean Coal Technologies in Japan

To dust collector Dust filter Cyclone Desulfurization agent


Desulfurization tower

Coal gas (from dust collector)

Gas for sulfur reduction Heat exchanger Air Sulfur recovery equipment

Anthracite Reproduction tower SOx reduction tower Sulfur condenser


Desulfurization process Reduction process Reduction process

Sulfur

Air Carrier Coal gas Ash Sulfur

To gas turbine

Gas in excess

Fig.4 Fixed-Bed Desulfurization Process

Separator

Soot/dust filter

Fig.3 Fluidized-Bed Desulfurization Process


Distributor

Nakoso Pilot Plant Project. stage.

This fact indicates that IGCC-

Soot/dust To sulfur recovery system Air Reduction gas (coal gas) To sulfur recovery system

dedicated technologies have already reached their validation At present, a desulfurization agent that can reduce sulfur compounds to a 1ppm level is under development for use in such applications as molten carbonate fuel cells, solid oxide fuel cells, and fuel synthesis. At the Central Research Institute of Electric Power Industry (CRIEPI), a desulfurization agent using zinc ferrite (ZnFe2O4), a double oxide of iron and zinc, has been developed and found capable of reduction to 1ppm or less, now being at the stage of real-gas validation. Efforts to cope with airblown entrained-bed gasification gas have so far been the main theme of review while another important problem is adaptation to high-carbon monoxide concentration gas like oxygen-blown gasification gas which degrades the desulfurication agent by allowing carbon to be separated out in it.
1. Regeneration tower 2. Reduction tower 3. Desulfurization tower
Coal gas

To gas turbine

Desulfurization agent carrier

Fig.5 Moving-Bed Combined Dust Collection-Desulfurization Process

(2)Dry dehalogenation method

Members in charge of research and development: Central Research Institute of Electric Power Industry Kind of project: Voluntary project
Outline For the use of coal gasification gas in molten carbonate/solid oxide fuel cells and fuel synthesis, it is necessary to remove not only soot/dust and sulfur compounds but also halogen compounds. For the adaptation to these technologies, efforts are under way to develop a halide absorption agent capable of reduction to 1ppm or less. At present, a method to remove HCl/HF contents of gas as NaCl/NaF, using a sodic compound is under development. CRIEPI test-made a sodium aluminate (NaAlO2)based absorbent, confirming possible reduction to 1ppm or less, but such efforts still remain on a laboratory scale as well as developing stage. This method faces an important problem of how the absorbent should be reproduced or recycled.

References

1) Nakayama et al, "Development State of 3 Dry Gas Cleanup Methods in Dry Gas Cleanup Technology Development for Integrated Gasification Combined-Cycle Power Generation", the Japan Institute of Energy Journal, Vol. 75, No. 5, 1996 2) Shirai et al, "Coal Gasification Gas-Based Fixed-Bed Dry Desulfurization Technology Development", the Society of Powder Technology, Japans journal, Vol. 40, No. 8, 2003 3) M. Nunokawa et al, "Developments of Hot Coal Gas Desulfurization and Dehalide Technologies for IG-MCFC Power Generation System", CEPSI proceedings 2002 Fukuoka

82

Part2 Outline of CCT


Environmental Protection Technologies (CO2 Recovery Technologies)

4C1. Hydrogen Production by Reaction Integrated Novel Gasification Process (Hypr-RING)


In charge of research and development: Center for Coal Utilization, Japan; National Institute of Advanced Industrial Science and Technology; Ishikawajima-Harima Heavy Industries Co., Ltd.; Babcook Hitachi K.K.; Mitsubishi Materials Corporation; JGC Corporation Project type: Subsidized by the Ministry of Economy, Trade and Industry Period: 2000-2010

Outline of Technology

1.Background Coal, the worlds most abundantly reserved energy resources, is used as important primary energy due to its excellence in economic terms as well. Its consumption is expected to increase with the growth of economy as well as increasing population in the future. Meanwhile, solution of global environment problems, to begin with the global warming due to CO2, has become a task assigned to human beings, earnestly claiming a technology to use coal clean and more efficiently, particularly, a technology contributing to CO2 reduction. HyPr-RING Process is now under development for commercialization as a technology which, in an attempt to answer such a claim, enables hydrogen necessary for future hydrogenenergy communities to be produced from coal and supplied.

2.Theory of HyPr-RING Process HyPr-RING Process is a process in which a CO2-absorbent CaO is directly added into the coal gasifier and the CO2 thus produced is fixed as CaCO3 to finish preparing hydrogen within a furnace. The reaction between CaO and H2O causes heat so that the heat necessary for reaction is internally supplied in the furnace as a great merit from a thermal point of view. Within the furnace, a series of reactions from Equation (1) to Equation (4) and the overall reaction of Equation (5) take place. One mole of input coal carbon gives about 1 mole of hydrogen (including that producible from CO). For this, however, gasification gas must be sent through a low-temperature shifter and then exposed to a low-temperature absorbent such as amine for CO2 separation. At that time, the amount of CO2 gas separated is 1 mole per mole of hydrogen. On the other hand, HyPr-RING Process uses dry CaO to absorb CO2 in the furnace (650 C, 30atm). In this case, heat is released
O

What is difference from Conventional gasification? Conventional gasification secures the heat necessary for gasification by partial combustion of coal, with a reaction expressed by the following equation taking place in the gasifier:

with CO2 absorption and made available for maintaining high This overall reaction is an exothermic reaction with C, H2O, and CaO as starting reactants. This means there is no need of external heat in theory. It is also found that CO2 fixation shifts the reactions (2) and (3) to H2 generation. Fig. 1 shows the process concept of HyPr-RING. Product CaCO3 is reproduced by calcining into CaO for its recycle as an absorbent. Most of the heat energy required for calcining is carried as chemical energy of CaO and made available for the reaction to give H2 in the furnace. temperature in the gasifier . Here, post-CO2 absorption CaCO3 is returned to CaO by calcination (reproduction) and, at that time, 50-80% of thermal energy required changes into chemical energy of CaO for reuse in the gasifier (Fig. 2). As seen from Equation (5), 2-mol hydrogen production from 1 mol of carbon is another important feature.

Fig. 1 Concept of HyPr-RING process 83

Fig. 2 Hydrogen production using HyPr-RING process.

Clean Coal Technologies in Japan

3.Characteristics of HyPr-RING Process Cold gas efficiency HyPr-RING Process gasifies an easy-to-gasify portion under low-temperature (600-700 C) conditions into hydrogen and
O

Ca(OH)2 in the furnace is employed. Gasification at a temperature as low as possible is also employed to prevent eutectic melting of calcium minerals. In such cases, unreacted product carbon can be used as a heat source for CaO reproduction.
Coal 1,000t/d Mixing Heat exchange Cyclone Methane reforming Calcining

uses the remaining hard-to-react char as fuel for CaCO3 calcination. In such cases, recovery of pure CO2 requires its burning with oxygen. Fig. 3 shows an example of process configuration with a fluidized bed gasifier and an internal combustion-type calcining furnace. For product gas composition of 95% H2 and 5% CH4, the cold gas efficiency proved about 0.76.

Rock hopper

Heat exchange

Absorbent CaO At the gasifier inlet, where temperature is low, CaO first reacts with H2O to produce Ca(OH)2, providing heat to coal pyrolysis. Then, at a high-CO2 partial pressure region, Ca(OH)2 absorbs CO2 to produce CaCO3, releasing heat. This heat is used for the gasification of char. To prevent CaO from becoming less active due to hightemperature sintering, a method of absorbing CO2 by way of
Coal supply 1,000t/d Heating value 6,690kcal/kg Cold gas efficiency 0.76

Gasifier

Water vapor

O2 separation

Steam turbine

Fig. 3 Analysis of HyPr-RING process

4.Outline of project Under this project that started in 2000, process configuration identification and FS through testing with batch/semi-continuous equipment were paralleled with a variety of factor tests required. In and after 2003, it is expected that 50-kg/d (coal base) continuous test equipment will be fabricated for continuous testing and then, based on the results, running tests and FS of a 0.5-1t/d-scale bench plant are to be carried out in and after 2006 for its established commercialization process. Table 1 shows development targets of the project and Table 2 shows, the scheduleof the project.
Table 1 Targets Item 1. Gasification efficiency 2. Product gas purity 3. CO2 recovery Target 1. Cold gas efficiency: 75% or more 2. Sulfur contents of product gas: 1ppm or less 3. High-purity CO2 recovery rate: 40% or more of input coal carbon to be recovered (per-unit of energy CO2 exhaust to be less than that from natural gas)

Table 2 Development Schedule Item (1)Fundamental test 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Mid-term evaluation

Pre-final evaluation

(2)Acquisition of design data (3)50-kg/d test facility (4) 500-kg/d PDU (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 84

Final evaluation

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 exhaust gas) CO2 separation/recovery widely prevails in natural gas and syngas sectors and already has a decades-long history. CO2 contents of natural gas are not only useless themselves because of making natural gas less caloric but also trouble LNG/ethane recovery plants by solidifying CO2 into dry ice. CO2 is hence removed to prevent such troubles. In a plant where natural gas or naphtha is reformed to manufacture H2, CO2 is separated after converted from the CO produced with hydrogen as syngas. In an ammonia/urea plant, CO2 is separated from the gas mixture of H2, N2, and CO2 to produce urea, using H2/N2-derived synthetic ammonia and separated CO2. Previously, however, CO2 separation/recovery from exhaust gas was not in so large demand, finding limited applications only in food/dry ice production. In case that CO2 is separated from natural gas or syngas, the separation is relatively easy because of a high gas pressure while CO2 separation/recovery from exhaust gas is difficult in many technological respects due to a very low level of exhaust gas pressure as well as oxygen, SOx, NOx, and soot/dust that are contained in exhaust gas. (2) Necessity to recover CO2 from fixed sources Most of fossil fuel (oil, natural gas, and coal) in the world is used as fuel of boilers, gas turbines, and internal combustion engines, releasing CO2 into the atmosphere as exhaust gas. As a result, it is alleged that the atmospheric concentration of CO2 has increased to cause the 2.CO2 sequestration technology As for methods of CO2 sequestration, geological sequestration and ocean sequestration are widely studied and a commercial project of the former has already started. Geological sequestration of CO2 is practiced, using the Enhanced Oil Recovery (EOR) method or the coal seam sequestration-accompanied Coal Bed Methane Recovery method but, if intended only for CO2 sequestration, methods of aquifer sequestration and sequestration into closed oil/gas fields may also be used. Fig. 1 shows a conceptual view of CO2 recovery - EOR combination. CO2-EOR commercialization started in the 1970s 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

global warming, which can never be prevented unless CO2 release into air is mitigated. There are, however, many difficulties in recovering and sequestrating CO2 from movable bodies such as automobiles and vessels, naturally rendering it easier to recover CO2 from boilers, gas turbines, and other fixed sources. (3) Characteristics and superiority of technology to recover CO2 from exhaust gas The Kansai Electric Power Co., Inc. and Mitsubishi Heavy Industries, Ltd. started in 1999 a joint R&D program to recover CO2 from exhaust gas of power plants and other facilities as a measure against the global warming. First, they assessed the conventional "monoethanolamine (MEA) liquid absorbent-based technology considered at that time a CO2 recovery process that could save the largest amount of energy. It is a process developed by former Dow Chemical Co. and later assigned to Fluor Daniel, Inc. This MEA-based technology was found disadvantageous for use in large plants as a measure against the global warming because of such problems as a large amount of energy required for CO2 recovery and a great loss in the liquid absorbent due to its rapid deterioration. Kansai Electric Power and Mitsubishi Heavy Industries started with basic research to explore a new liquid absorbent, resulting in successful development of a novel energy-saving and uneasier-to-be-deteriorated/-lost liquid absorbent, which has already been put into practice for urea manufacture in Malaysia.

in these cavities, which indigenously contains water (mainly salt water), by pressing in it there to replace water. This has already started in Norway. For Japan, Norway-like CO2 sequestration into aquifers distributed over continental shelves is considered the most realistic. Other than into aquifers, CO2 can also be sequestrated into closed oil/gas fields where production had already terminated. Closed oil/gas fields may, since their ceilings are so geologically structured from ancient times as not to permit any oil/gas leaks for possible formation of oil/gas wells, be CO2 containment-secured locations for pressing in CO2

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 raw material. If H2 and CO are synthesized by steam-reforming 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 steam reformer exhaust gas to add a worthwhile amount of CO2 in carbon contents within the process. capacity of Saudi Arabian methanol plants. Fig. 1 shows a system where, in the process to produce methanol with natural gas as raw material, CO2 is recovered from At present, active planning for CO2 addition is under way to improve the production
CO2 CO2 recovery Methanol synthesis Methanol

steam reformer exhaust gas to optimize the H2:CO ratio for methanol synthesis, thereby enhancing methanol production.

Exhaust gas Natural gas Syngas Steam reformer compressor Steam Fuel

Fig. 1 System to recover CO2 from exhaust gas for enhanced methano 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 production.
CO2 CO2 recovery Methanol synthesis DME DME synthesis

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

Fig. 3 CO2 recovery from exhaust gas-integrated liquid fuel production system

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

combustion stage is a hopeful technology of direct CO2 recovery

Ordinary recovery process Stack Coal Air


Compressor

Recovery process using oxygen combustion Coal Air


Air separator Boiler Dust removal Compressor

Boiler

Dust removal

Desulfurization

CO2 separation and recovery

O2/CO2

Flue gas recycle

Recovered CO2 Fig. 1 Comparison of CO2 recovery between oxygen combustion process and ordinary air combustion process

Recovered CO2

2.Result of the development Efforts of reduction in CO2 emissions have been promoted over the world responding to the issues of global warming in recent years. Specifically, coal is known as a source of heavy emissions of environmental loading substances (SOx, NOx, CO2, etc.), though the coal is expected as a sustainable energy resource also in the future. Since coal generates large quantity of CO2 per unit calorific value, research and development of the CO2 recovery and CO2 separation technologies are in progress on various points of views. With the background, the study team focused on the development of technology to recover CO2 from coal-fired power plants utilizing oxygen (O2/CO2) combustion, and has promoted the research of CO2 recovery technology. The CO2 recovery in the oxygen

combustion stage is a hopeful technology of direct CO2 recovery from large scale coal-fired power plants. Ordinary coal-fired power plants combust coal by air. Since air contains N2 by 79%, all of the N2 is emitted to atmosphere during the combustion process, thus the CO2 concentration in the combustion flue gas is only 13-15% level. The oxygen combustion

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Clean Coal Technologies in Japan

technology is a process to separate oxygen from the combustion 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 efficiency.

CO2 recovery type oxygen pulverized coal combustion power plant

CO2 underground disposal Oxygen production facility CO2 tank

Boiler

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 generation system and the CO2 recovery type IGCC, the study team conducted research and development and has proposed a power generation system which has superiority in terms of performance and economy as a CO2 recovery technology. In the global warming and for reducing the CO2 emissions, though there are technologically validating issues such as the safety of power generation system with the oxygen combustion and the operability of CO2 recovery type IGCC. As for the practical

application of the system, positive study should be conducted on the basis of the obtained results, while studying the application of the CO2 recovery type oxygen pulverized coal combustion system and of the CO2 recovery type IGCC, respectively, for the cases of application of CO2 recovery to an existing plant and of new plant.

addition, in the basic combustion test, the study team has acquired academically valuable results (including the effect of reduction in NOx emissions). It should be emphasized to further promote the study for controlling

Recovered CO2
CO2 compression

CO2 CO2 H 2O H2 N2 HRSG

Coal Gasification

CO CO2 H2 H 2O

Gas purification

CO-shift reaction

H2

CO2 removal

Steam

Air Air separation

Air
N2
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 variety of manners. Coal also influences the nature in each of its production, transportation, and utilization processes. In the process of its utilization in particular, coal dust, ash dust, acid gas (NOx, SOx), and carbon dioxide are discharged, suggesting that unregulated guzzling of coal may possibly have a great impact on the environment. On the other hand, technologies to limit the impacts derived from coal utilization on the environment to the minimum, as measures to cope with the above-mentioned situations, were collectively called Clean Coal Technology (CCT), for which advanced R&D is in wide practice in major advanced countries including Japan. With such circumstances , the "Basic Technology Development Program for Advanced Coal Utilization (BRAIN-C)," mainly targeting at the coal gasification technology and to realize early commercialization of new high-efficiency and clean coal utilization technologies such as coal gasification and pressurized fluidized-bed processes, has sought and accumulated basic data on coal from different angles. In the meantime, numerical simulation is a very effective tool to predict characteristics of a pilot or actual production unit from the above-mentioned basic data or, in reverse, to evaluate and select useful basic data. With this taken into consideration as well, technology development under the BRAIN-C is proceeded with from both aspects of useful basic data retrieval/storage and high-precision numerical simulation. Fig.1 shows "BRAIN-C Technology Map." Products from this project are roughly grouped into the following three categories: (1) Entrained flow gasification simulator (2) Predicted model/parameter correlative equation (3) Coal database Each category is explained below. Every categories, as integral part of products from this project, is indispensable for their actual use in a variety of situations, and ingenious utilization of each in accordance with the situation where it is used allows such products to be given full play.

Volatilization model Volatile contents release data Volatile contents database Char reaction data Reaction database
Reaction temperature constant Typical temperature history Volatile contents composition in quantity al data pic Ty ature r pe tem

Trace element data CPC actual measurement data Basic database

Trace element distribution model Program Equilibrium model

Coal Physicality Physicality database (coal and char) +General analysis +Particle size-surface area +Special analysis CCSEM, XRD, EDS

Parameter correlative equation

Gasification simulation code + RESORT + FLUENT


temTypic pe al da ratur ta e

Rad

ia

p tion

ara

me

ter

Growth flowage judgment model

Heat transmission coefficient Heat transmission test data Particle radiation data

Particle size density fluctuation model

Adhesion judgment equation Adhesion data

Fig. 1 BRAIN-C Technology Map

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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 temperature distribution, ash adhesion locations, gas coal composition, etc. within a gasifier if given as input data such parameters as reactor shapes, operation conditions, 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 BRAIN-C, developing a coal gasification reaction model shown in Fig. 3 and a particle adhesion model shown in Fig. 4 in basic CFD, has compared their calculation results with gasifier operation data in coal-based hydrogen production technology
Fig. 2 Functions of Entrained-Flow Gasification Simulator
Simulation program (For entrained-flow gasification)

Design: Furnace shape Operation: Operational conditions Coal: Property

Pre-test judgment of operational validity


Ash adhesion position Temperature distribution CO concentration

(HYCOL) to verify the adequacy.

Gas-phase reaction

Volatile contents release speed


Oxidizing agent Volatile contents

Product gas

Fixed carbon Ash

Fixed carbon

Ash

Gasification speed 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

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Part2 Outline of CCT


Basic Technologies for Advanced Coal Utilization

Fig. 5 shows an example of results from comparison between the formation position of fused ash layer and the internal condition of gasifier after operations. This found the formation position of fused ash layer calculated with this simulator wellcorresponding to the position where the fused ash layer actually existed, endorsing the adequacy of calculation with actual data. Fig. 6 shows the result of case studies on HYCOL using gasification simulation. The near-wall temperature and ash viscosity on the wall shown on the left side of Fig. 6 are those reproduced by calculation under the condition after 1,000-hour operation . The temperature of the furnace bottom area (in red color) onto which slag flows down is found high against the low ash viscosity in the region (in blue). The temperature of the upper furnace part proves low (in green), giving conditions where particles can hardly adhere. On the other hand, the wall-near

temperature and ash viscosity on the wall shown on the right side of Fig. 6 are from the result of calculation under operational conditions changed intentionally. For this case, the oxygen ratio of the chart top is higher and that of the bottom is lower than shown on the right side of the figure. In such cases, it was found that the temperature of the furnace bottom area goes down (in orange color) and the low-ash-viscosity region (in blue) narrows while the upper furnace part becomes hot (the region in red increases) to form a region where ash is easier to adhere, probably spoiling the operating conditions. In this way, using the gasification simulator, analysis can be easily made even if gasification conditions are altered and, therefore, an expectation is growing on its utilization in future gasification projects.

Case 3 Forecast value Wall-near temperature Temperature: high Growth of slag Throttled section Ash viscosity on the wall The low-viscosity region of the top expands. Amount of adhesion = amount of slag discharged Molten slag A high-viscosity region of the bottom appears. Temperature: low

Pressure detection terminal

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

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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, 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 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 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 Standard Sample Coal Storage Status (AIST)

20-liter container (two-shelf)

50-liter container

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

Reaction Reaction data, data, etc. etc. On-line On-line retrieval retrieval
Fig. 8 Coal Database

Reaction Reaction data, data, etc. etc. Spreadsheet Spreadsheet fileDownload fileDownload
Fig. 9 Basic Data Acquisition

5.Diffusion of basic coal utilization technology products AAn entrained-flow gasification simulator so far developed under the BRAIN-C is capable of making practical predictions through the utilization of various models and basic data. The BRAIN-C Project, soon to meet its final year in 2004, is developing a wellequipped system to make a wide choice of programs and basic data available so that you can use the products developed under this project to your hearts content. We are also preparing detailed service manuals as well as giving workshops for this purpose to encourage your ingenious utilization of these products. Despite the coal gasification technologys predominance in this development project, those outside gasification projects are strongly invited as well to use our simulation code, at least, since 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 secondary energy such as by burning fuel (primary energy) to convert it into electricity and heat is called a co-generation system.

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

Electricity

Electricity Heating Hot water supply Process steam

Jacket cooling water

Hot water

Cooling water heat exchanger Steam

Generator

Diesel or gas engine

Waste heat recovery boiler

Stack

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 power generation plant which takes out only electricity is around 40%. On the other hand, the overall thermal efficiency of a cogeneration system, which combines its power generation efficiency and heat recovery efficiency, depends upon whether it is mainly to supply electricity or mainly to supply heat, with a level of as high as 80% achieved by the co-generation system mainly for heat supply. (1)Co-generation at a large-capacity coal thermal power plant Kobe Steels Kobe Power Plant, a large-scale coal thermal power plant of 1,400MW (700MW x 2 generators) in capacity, has commenced its electricity wholesale/supply activities as an independent power producer (IPP). Electric power products from No. 1 Unit already in operation from April, 2002 and No. 2 whose start of operation is slated for April, 2004 are all to be delivered to the Kansai Electric Power, Inc. (2)Regional supply of heat The steam to be used for power generation is partially taken out for the supply of maximum 40t/h to 4 nearby sake-brewers. This amount, accounting for about 2% of the steam generated at boilers, proves that the share of heat supply is small. The steam 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 No.2 power plant Brewing companies Secondary steam Sawanotsuru Fukumusume Steam generator Drain cooler Industrial water tank Hakutsuru Industrial water Gekkeikan

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. pp15391546 Vol. 54, No. 567, Thermal/Nuclear Power Generation (Dec., 2003) 3) Kida et al: Outline of Power Generation Facilities at Kobe Steels Kobe Power Plant pp2-7, Vol. 53, No. 2, Kobe Steel Technical Report (Sept., 2003) 4) Miyabe et al: Kobe Steels Kobe Power Plant Surplus Steam-Based Heat Supply Facility pp14-18, Vol. 53, No. 2, Kobe Steel Technical Report (Sept., 2003)

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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 single industry faces a limit. To continue further reduction in CO2 emissions, it is necessary to give full scale review of the existing energy and materials production systems and to develop technologies that optimize the individual processes and the interface between processes not only to improve the conversion efficiency and to save energy but also to fundamentally and systematically change the energy and materials production systems. The "fuel coproduction power generation system" which produces power, fuel, and chemicals from coal improves the total energy use efficiency through the unification of industries by structuring a coal industrial complex. In the fields of power, iron and steel, and chemicals where large amount of coal is consumed as the energy source, structuring a core plant which produces energy and chemicals simultaneously,

and assembling peripheral plants to produce various products enhance the unification of industries centering on the core plant, thus forming a coal industrial complex on the new energy and materials production system. As a result, the current industrial style progresses to the next generation hybrid industrial style through the unification of industries. The core technology of that type of fuel coproduction power generation system is the coal gasification technology. By combining the high efficiency power generation system such as IGFC with a process to co-produce storable fuel, the normalization of load to gasification reactor and the significant reduction of CO2 emissions are attained. Furthermore, waste heat source in the coal industrial complex is utilized to recover chemicals from coal while conducting endothermic reactions, thus forming further high energy efficiency and upgraded coal industrial complex.

Existed or new facilities steam boiler

Steam

ST GT Power

Gasification Center Coal + Biomass (Waste, waste plastics, oil-base residue, etc.)
H2,CO

FC

Fluidized bed gasification furnace

Process steam
H2

Non-reacted gas for Fuel cell power generation, for Refinery, for Chemical plant DME market for Petrochemical plant Propylene C2 distillate C4 distillate
H2,CO

fual for heating Coal Spouted bed gasification furnace for Hydrogen production
H2,CO

DME
Coal Thermal decomposition furnace
H2

for Hydrogenation and desulfurization at iron works

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

3. Coproduction system The coproduction system produces both materials and energy to significantly reduce the exergy loss which occurred mainly in combustion stage, and to achieve innovative and effective use of energy. That is, the coproduction system is a new production system which is not only the conventional system which aims to improve the energy conversion efficiency and the cogeneration system which effectively uses the generated thermal energy as far as possible but also the system to produce both energy and materials to significantly reduce the consumption of energy and materials. By making the coproduction system clean, energy Consequently, the coproduction issue and the environmental issue are simultaneously solved and it should activate economy. system that conducts production of energy such as power and fuel while producing materials shall be emphasized from the viewpoint of creation of new energy market and also of creation of new industries. The coal coproduction system centering on the coal gasification is able to solve the environmental issues through the significant reduction in CO2 emissions by realizing high grade and comprehensible coal utilization technology. That type of system technology development triggers the technological innovation in the coal utilization field, and the strong innovation is expected to increase the international competitive power and to encourage the structuring circulation-oriented society. Also in the international society, the development of the coproduction system should be an important technological issue to solve the global environmental issues.
Fuel Power generation in existing steam turbine power generation system Power Fuel for power generation IGCC for industrial complex area Private power generation at iron works GT-CC Co-operative Thermal Power Company GT-CC BTX, etc. Gas Recovered steam Iron works fuel for heating Gas,Power,Steam,BTX, etc.
Fluidized bed gasification reactor

Outside sale Steam

Power Steam

Petroleum industrial complex Process steam fuel for heating Non-reacted gas

Spouted bed gasification reactor Gas Thermal decomposition reactor

Coal yard Waste

Shift reaction H2/CO > 2 H2 separation Hydrogen

Residue oil

DME production Un-recovered gas

Outside sale

for Hydrogenation

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
Planned gross thermal efficiency (HHV % )

60
LNG steam power generation LNG-fueled Combined Cycle (ACC) Coal-fired steam power generation Coal-fired Integrated Gasification Combined Cycle (IGCC) Coal-fired Integrated Gasification Fuel Cell Combined Cycle (IGFC)

may find a technological trend that is, as mentioned below, crucial for society as well as full of diversity. The trend may be separated into three main directions in terms of key technology development systems. The first direction is already seen in two deployment programs now under way which focus on coal gasification technology; one for high-efficiency power generation systems, whose commercialization process is steadily progressing, including "Coal-fired Integrated Gasification Combined Cycle (IGCC)" and "Coal-fired Integrated Gasification Fuel Cell Combined Cycle (IGFC)" and the other for "conversion into liquid fuel and raw material for chemicals" which contains no impurities, such as methanol, DME, or GTL. Moreover, these technologies will give rise to a zero emission-oriented world of "co-production" including co-generation.

55

50

LNG-fueled Gas Turbine Combined Cycle (ACC) (1,700oC-class)

45

Coal-fired Integrated Gasification Combined Cycle (IGCC) (1,500oC-class)

40

35 1960 1970 1980 1990 2000 2010 2020

Start of operation year

Fig.1 Change in LNG and Coal Thermal Power Generation Efficiency


Prepared from High-Efficiency Power Generation Technology Review Meeting Report (Jan., 2003) of the Institute of Applied Energy

Gas oil, naphthalene, etc.

Electric power

IGCC/IGFC

Hybrid gasification of coal, biomass, waste plastics, etc.

Methanol, acetic acid, etc. Boiler Chemicals


Oil

DME,GTL Power plant, automobiles, etc.

Biomass Gasification

Coproduction manufacturing also raw materials for chemicals Synthesis gas (H2, CO) Coproduction manufacturing also reduced iron
Reduced iron Gasification furnace Iron and steel

Coal

Commercial, transportation

Hydrogen station Fuel cell vehicle

Waste plastics

H2 production, CO2 separation and recovery

Blast furnace Slag


Effective use Storage Blast furnace

Stationary fuel cell CO2 H2

Fig. 2 Various CCT developments centering on coal gasification

The second direction is future energy sector advancements to cope with the likely realization of "hydrogen energy communities." According to IIASA 2000 (International Institute for Applied System Analysis 2000), analysis showed that global primary energy consumption was on a near-constant increase between the middle of the 1800s and around 1980 in terms of "H/C (hydrogen/carbon)" ratio. In and after 1980, it remained almost unchanged at around H/C = 2 due to an increase in oil 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 discouraged, even predicting the advent of a situation where coal energy could be used only in the world of HyPr-RING (Hydrogen
97

100.0 Hydrogen economy 10.0 H/C Gas: H/C = 4 Oil: H/C = 2 1.0 Coal: H/C = 1 Methane economy

0.1 1800 1850 1900 1950 2000 2050 2100

Fig. 3 Trend of ratio of hydrogen to carbon (H/C) in the primary energy


Prepared from IIASA 2000

Clean Coal Technologies in Japan

Production by Reaction Integrated Novel Gasification Process, where H/C approximates one) and society will be forced to depend largely upon separating and retrieving CO2 generated by the direct combustion of coal and the technology to separate and sequester CO2. High-efficiency coal utilization technology to

separate/recover and then sequester/store direct combustionderived CO2 or reduce CO2 emissions by using carbon components of coal as fuel or raw material for chemicals by way of coal gasification and reforming/conversion, presents important challenges to Clean Coal Technology.

Separation/recovery

Gas after decarburized CO2 concentration 2%

Sequestration/storage

Separation/recovery Pressure injection from a facility on the sea Pressure injection from a ground facility Tanker transport Discharged CO2 concentration 22% Sources from which CO2 is discharged (including power and steel plants) Separated/recovered CO2 concentration 99%
Cap rock (impervious layer)

Dissolution diffusion Pipeline carriage


CO2 Underground aquifer coal bed

Separation/recovery -Chemical absorption method -Physical absorption method -Membrane separation method

Transportation -Ground: Pipeline after liquefied -Sea: (long-haul) Liquefied CO2 transport vessel

Sequestration/storage -Underground: Aquifer coal bed -Ocean: Dissolution/diffusion or as hydrates (onto the sea bottom)

CO2

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

The third direction is latently potential development of coal utilization technology in conjunction with each of four technology sectors given priority for development in Japan, namely, environmental/energy, bio-, nano-, and information technology 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. Advancements in biotechnology could also unlock methods for the fixation and effective utilization of CO2.

Furthermore, hyper-coal production technology development will lead to processes for the advanced utilization of the carbon within coal. In fact, technological innovation in the nano-technology sector is anticipated to lead to such as nano-carbon fibers.

Steel

Chemicals

Cement

Other by-products

es s

Raw material
ok in g

Steel-making plant
C he pr oc

Fuel (gas/liquid)
al ic pl

Energy and materials linkage between industries Fuel cell vehicle Biomass Coal gasification Coal partial hydrogenation

Light energy

t an

Hydrogen
Gasification/ Conbustion process Dynamic energy Heat energy

Iron and steel Blast furnace

Power plant

Hydrogen station

Chemicals, other Hyper ring

Advanced gasification furnace Electric power

SCOPE21

Coal (solid fuels)

Joul
Environmental facility

Energy conversion system

Electricity

Waste, waste plastics Power plant

Iron and steel works USC CO2 recovery IGCC IGFC

Reformed coal CO2 isolation Coal USB

Air/water

Fig. 5 Future energy-oriented society supported by CCT, (2030)

Exhaust

Drainage

em

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

en tp

Waste heat

la nt

Chemical energy

Electric&magnetic energy

Heat (steam/ hot water)

n/ ss tio ce ac ro ef p qu is Li olys r Py

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 the steelmaking sector, where coal functions not only as an energy source but also as a high-quality reducing agent. A potential task to be assigned to well-established steelmaking processes (e.g. blast-furnace process) is achievement of an innovative level of total coal utilization efficiency, using a coproduction system like DIOS (Direct Iron Ore Smelting reduction process) to simultaneously produce iron and synthetic gas, electric power, hydrogen/thermal energy, raw material for chemicals, etc. from steam coal for steady implementation of improved environmental measures toward zero emissions. As the global leader in coal imports as well as a leader in Clean Coal Technologies, Japan must remain active in international cooperation mainly in Asia for human resources development, technology transfer, and other relevant activities. Such international cooperation may possibly serve not simply those 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

energy while environmental preservation is a problem that should be tackled on a global scale, considering the interdependent relationship between the two. Underlying both, current population growth is both explosive and unprecedented. Efforts toward zero emissions to protect the environment must be assigned top priority in the development of Clean Coal Technologies in Japan. A further obligation, beyond international cooperation activities, is to continuing development of an efficient and advanced coal utilization system to minimize impact on the global environment. It has become necessary for us, presently positioned to undertake technology development in one of the energy-related sectors given top priority, to further concentrate efforts in an attempt to devise innovative Clean Coal Technologies for the establishment of an affluent, clean, and comfortable society where economic growth is compatible with the environment.

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


6 yen/kWh

Unification with CO2 separation and fixation technology


6-7 yen/kWh

Actualization of Zero-emission

Coal gasification technology Fixation technology

Air-blow gasification

Demonstration test
GCC commercial unit 46-48% sending end efficiency GFC commercial unit 55% sending end efficiency

Zero-emission

Oxygen-blow gasification

Research and development

Demonstration test
Industrial gasification furnace A-IGCC /A-IGFC >65% sending end efficiency

Advanced coal gasification CO2 separation and recovery

F/S

Research and development

Demonstration test

Research and development

Demonstration test

Demonstration test of new separation and recovery technology

Research and development

Development toward the full scale storage

CO2 fixation

Demonstration test Timing of commercialization

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

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(1) Main SI units Quantity


Angle Length Area Volume Time Frequency, vibration Mass Density Force Pressure Work, energy Power Thermodynamic temperature Quantity of heat

(2) Prefix of SI system SI unit rad m m2 m3 s (Second ) Hz (Hertz ) kg kg/m2 N (Newton ) Pa (Pascal ) J (Joule ) W (Watt ) K (Kelvin ) J (Joule ) Unit applicable with SI unit (degree ), (minute), (second) (liter) d (day), h (hour), min (minute) t(ton) bar (bar) eV (electron voltage) Multiple to the unit 1018 1015 1012 109 105 103 102 10 10-1 10-2 10-3 10-6 10-9 10-12 Prefix Name Exa Peta Tera Giga Mega kilo hecto deca deci centi milli micro nano pico Symbol E P T G M k h da d c m u n p

(3) Typical conversion factors


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

(4) Coal gasification reactions


(1)
1 2

97.0kcal/mol 29.4kcal/mol 38.2kcal/mol 31.4kcal/mol 18.2kcal/mol 10.0kcal/mol 17.9kcal/mol 49.3kcal/mol

(2) (3) (4) (5) (6) (7) (8) (9)

(5) Standard heating value for each energy source


Energy source
[Coal] Coal Imported coking coal Coking coal for Coke Coking coal for PCI Imported steam coal Domestic steam coal Imported anthracite Coal product Coke Coke oven gas Blast furnace gas Converter gas [Oil] Crude oil Crude oil NGL, Condensate Oil product LPG Naphtha Gasoline Jet fuel Kerosene Gas oil A-heavy oil C-heavy oil Lubrication oil Other heavy oil product Oil coke Refinery gas [Gas] Flammable natural gas Imported natural gas (LNG) Domestic natural gas City gas City gas [Electric power] Generation side Heat supplied to power generator Consumption side Heat produced from electric power [Heat] Consumption side Heat produced from steam

Unit

Standard heating value

Standard heating value (as kcal)

Old standard heating value

Remark
Temporary value

kg kg kg kg kg kg kg Nm3 Nm3 Nm3

28.9 29.1 28.2 26.6 22.5 27.2 30.1 21.1 3.41 8.41

MJ MJ MJ MJ MJ MJ MJ MJ MJ MJ

6904 6952 6737 6354 5375 6498 7191 5041 815 2009

kcal kcal kcal kcal kcal kcal kcal kcal kcal kcal

7600 kcal

6200 kcal 5800 kcal 6500 kcal 7200 4800 800 2000 kcal kcal kcal kcal

38.2 MJ 35.3 MJ kg 50.2 34.1 34.6 36.7 36.7 38.2 39.1 41.7 40.2 42.3 MJ MJ MJ MJ MJ MJ MJ MJ MJ MJ

9126 kcal 8433 kcal 11992 8146 8266 8767 8767 9126 9341 9962 9603 10105 kcal kcal kcal kcal kcal kcal kcal kcal kcal kcal

9250 kcal 8100 kcal 12000 8000 8400 8700 8900 9200 9300 9800 9600 10100 kcal kcal kcal kcal kcal kcal kcal kcal kcal kcal

old NGL

kg kg Nm3

old Other oil product 35.6 MJ 44.9 MJ 8504 kcal 10726 kcal 8500 kcal 9400 kcal

kg Nm3 Nm3

54.5 MJ 40.9 MJ 41.1 MJ

13019 kcal 9771 kcal 9818 kcal

13000 kcal 9800 kcal 10000 kcal

old LNG old Natural gas

kWh kWh

9.00 MJ 3.60 MJ

2150 kcal 860 kcal

2250 kcal 860 kcal

Efficiency 39.98%

kg

2.68 MJ

641 kcal

100oC, 1 atm Saturated steam

Clean Coal Technologies in Japan


March 15, 2004

New Energy and Industrial Technology Development Organization (NEDO)


Muza Kawasaki Central Tower 16F, 1310, Omiya-cho, Saiwai-ku, Kawasaki-shi, Kanagawa 212-8554 Tel. 044-520-5290 Fax. 044-520-5292

Center for Coal Utilization, Japan (CCUJ)


Sumitomogaien Bldg 7F, 24, Daikyocho, Shinjuku-ku, Tokyo 160-0015 Tel. 03-3359-2251 Fax. 03-3359-2280

100

Multi-Purpose Coal Utilization Technology Iron Making and General Industry Technology

Environmental Load Reduction Technology Basic Technology for Advanced Coal Utilization

Coal Fired Power Generation Technology

Co-production System

New Energy and Industrial Technology Development Organization


Muza Kawasaki Central Tower 16F, 1310, Omiya-cho, Saiwai-ku, Kawasaki-shi, Kanagawa 212-8554 TEL.044-520-5290 FAX.044-520-5292 URL: http://www.nedo.go.jp/

Center for Coal Utilization, Japan


Sumitomogaien Bldg 7F, 24, Daikyocho, Shinjuku-ku, Tokyo 160-0015 TEL.03-3359-2251 FAX.03-3359-2280 URL: http://www.ccuj.or.jp/