Contribution

Contribution of Japanese Cement Industry towards Addressing Environmental Issues
Rokuro TOMITA
Executive Officer General manager, R&D Center
copyright TCC
Taiheiyo Cement Corporation

2006.11.17 KCI Symposium
Contents of Todays Presentation

1. Current data on the Japanese cement industry 2. Status of recycling in Japan 3. Recycling technologies of Taiheiyo cement corp. 4. Turning municipal incinerator ash into a resource 5. Chlorine by-pass technology 6. Conclusions
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Cement production of Japan
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Kiln Type
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Heat consumption (Coal equivalent)

kg/t-cement 140 131.7 130
Electric power consumption
kwh/t-cement 120 116.7 115 110
120
105 100
101.6
110
107.6 103.3 95 90 80
94.4
100 80
85
90 Year
95
00
05
85
90 Year
95
00
05
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Types and Sales of Cement
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Waste Material Used in Cement Industry

Item Blast furnace slag Coal ash Gypsum by-product Dirt, Sludge Soil from construction Non-ferrous slag Unburned ash, soot, dust Molding sand Steel manufacture slag Wood chips Waste plastic Coal tailing Recycled oil Waste oil Used tire Used clay Bone-meal feed Others Total Rate of consumption cement) 2001 11,915 5,822 2,568 2,235 1,236 943 492 935 20 171 574 204 149 284 82 2 428 28,061 (kg/t355 2002 10,474 6,320 2,556 2,286 269 1,039 874 507 803 149 211 522 252 100 253 97 91 435 27,238 361 fiscal year 2003 10,173 6,429 2,530 2,413 629 1,143 953 565 577 271 255 390 238 173 230 97 122 378 27,566 375 2004 9,231 6,937 2,572 2,649 1,692 1,305 1,110 607 465 305 283 297 236 214 221 116 90 452 28,782 401 2005 9,214 7,185 2,707 2,526 2,097 1,318 1,189 601 467 340 302 280 228 219 194 173 85 468 29,593 400
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Recycling in the Japanese Cement Industry

Cement production and volume of waste used; changes in consumption 100,000
82,407 79,045 75,451 73,504 71,771 73,931 80,000
600 500 k g /t-ce m e n t Cement production Waste consumption Vol. of waste used
1 ,0 0 0 t
60,000 40,000 20,000 0 2000 2001 332 355 361
375
401
400 400
300 28,061 27,238 27,564 28,780 29,593 27,359 200 100 2002 2003 Fiscal year 2004 2005
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Advantages of Waste Recycling at Cement Plants

1. 2. 3. 4. 5. No generation of waste by-products Detoxification of waste material Reduced natural raw-material consumption Reduced production of greenhouse gases Contribution to creation of a local recycling society (->Disposal site life extension)
2006.11.17 KCI Symposium 10
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Cement Materials and Chemical Composition

Cement materials and chemical composition
Component Limestone Portland cement Recy cled r esour ces Ash
Water purifier sludge
Sewage
Waste tires
CaO
64-65%
23.0%
13.9%
10.1%
0.1%
SiO2
Clay (Silica)
20-21%
27.3%
33.0%
30.7%
---
Al2O3
5%
14.3%
16.2%
19.5%
0.05%
Iron
Fe2O3
3%
6.2%
4.8%
5.2%
5-20 95-80
(Combustible materials)
(Natural materials, for reference)

CaO Limestone Clay Silica Iron material 47-55% < 5% < 2% SiO2 < 4% 45-78% 77-96% Al2O3 < 2% 10-26% 2-10% Fe2O3 < 2% 3-9% < 5% 40-90%
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Treatment of Pollutants
Complete decomposition at high temperature
Dioxin decomposition temp.: 800C or higher for 2 sec. or more Temp. in kiln: over 1,450C
Dioxins Pollutants in waste materials

Heavy metals
Detoxification
Included as ferrous material in cement

Solidified in ferrous material during cement clinker sintering process
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Cement Industry Recycling of Waste and By-products Extends the Life of Disposal Sites (estimated)
(A) Remaining volume of industrial waste disposal sites (B) Volume transported to disposal site per year (C) Remaining disposal site volume times no. of years (C=A/B) (D) Volume of cement recycled per year (E) No. of years remaining for disposal site if cement were not recycled (E=A/(B+D) (F) Length of extension of life of disposal site resulting from cement plant recycling (F=C-E) 179,410,000m3 40,000,000m3 4.5 Years 19,500,000m3 3.0 Years +1.5 Years
Note: Japan Cement Association estimate


Cement Production Process and Resource Recycling
Cement production process
Raw meal process

Raw mill
Sintering process
Finish process
Shipping
Preheater Pre-grinding mill Bagging
Electrostatic precipitator Limestone Clay Silica Iron Raw meal silo Coal storage
Cement mill Cooler
Bulk truck Cement silo Bulk car
Gypsum storage Coal mill
Recycled materials
Resource recycling
Coal ash Sludge Sewage incinerator
ash
Non-ferrous slag Molding sand
Thermal recycling Recycled oil Waste tires Waste plastics Used pachinko machines Wood waste Other
Recycled materials Municipal trash
Recycled materials

incinerator ash
(dust, ash) Soil from
Blast furnace slag By-product gypsum
Coal ash
construction Sewage
(dewatered cake)
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Changes in Consumption of Waste Materials and Household Waste by Taiheiyo Cement

Waste & by-product consumption Raw-material-related 400 25.6 26.3
(kg/t-cement) 10 0.4 0.3 8.3 5.8 0 12.8 10.0 12.9 0.7 Household waste consumption Raw-material-related 15 1.1 1.1 Fuel-related
Fuel-related
300 (kg/t-cement) 13.9 200 253.4 100 265.7 14.3
20.7
274.9
295.8
319.4
0 2000 2001 2002 2003 Fiscal year 2004
2000
2001
2002 2003 Fiscal year
2004
16
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Background of Development on AK System

-The recycle process of urban waste as a raw material of cement Hidaka City, Saitama prefecture, operates a MSW incinerator since more than 30 years and was forced to build a new incinerator to replace worn out one until December 2002. For a long time (from 1993) , Taiheiyo Cement Corporation had been asked by Hidaka city to co-operate to solve the citys MSW issue. Taiheiyo Cement Corporation and Hidaka city had continued the discuss about a new MSW treatment technology. In 1999, Taiheiyo Cement Corporation proposed our AK System to Hidaka City and Hidaka City decided to apply AK System to solve the citys MSW issue in June 2000. The idle kiln in our Saitama factory was converted to a Digester (one of the main facility in AK system) and the demonstration test was carried out from March of 2001 to October 2002.
AK System
AK System
Operation started at Saitama Plant in February 2002 15,000t/y of Hidaka Citys trash turned into resources
Overview of the AK system

Three days of aerobic digestion turns organic contents of waste into soil-like cement raw material. Day 3 Breakdown of waste into finer pieces accelerates aerobic digestion. Day 2 Mechanical breakdown process begins immediately as tons of MSW are tumbled onto itself, breaking open bags, and pulping the waste. Day 1 MS W
Three-day processing Digester5.0m62.1m
Digeste d MSW
Crushing, Sieving, Separating

Cement raw material
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Municipal solid waste (MSW) of Hidaka city
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Freon Breakdown
Freon gas charging facility
Flow adjustment valve
Developed jointly with Metropolitan Tokyo Breakdown efficiency: 99.99 Completely broken down by incineration Acidic gas absorbed by raw material after breakdown Commercialized at Chichibu Plant Cement kiln Emergency cut-off valve Burner
Manifold
Freon tanks
Pressure adjustment valve
Liquid Freon charger
Central control room
Low-temperature storage room Compressed air
Ejector
Clinker cooler
Changeover valve
Receiving pump
Flow adjustment valve Receiving tank
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Treatment of Used Pachinko Machines

Receiving of used pachinko machines

Secondary crusher
Forklift Primary crusher Crusher
Crusher
Magnetic sorter
Metal scrap
Metal scrap storage
Compaction, solidification
Screw
Screw
Rotary kiln
1,450C Cement raw meal
Double-shaft screw-type compactor-solidifier Compacted, solidified material
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Treatment of Waste Plastics

1. Outline of treatment facilities
Secondary crusher 2.8t 2.5t/h Hoist 3 Container 1.5m Primary crusher 2.5t/h Multi feeder 1.5t/h
Primary storage tank 97.8m3

SC
Secondary tank 15m3
Circle feeder 2/5t/h To Weigh kiln feeder 1.2t/h RF
2. Types of waste plastics expected to be treated

Source Sekisui Chemical Musashino Plant Composition PE foam Bridge PE Compacted products Shape Volume (t/y) 210t 1,440t 720t 2,640 t 1,380 t
Remarks
Rolled sheets Rolled sheets Block Rolled film Rolled film, etc.
Hitachi Chemical PET, PE, phenol Yamazaki Plant, Mie Structural Products Other PET, PE
Planned volume of waste plastics treated 6,500t/y Start of operation Dec. 1998
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6,390t 2006.11.17 KCI Symposium 23

Development of Technology for Turning Municipal Trash Incinerator Ash into a Resource
Local government Trash treatment plant
Collection
General household Municipal trash
Conventional
Incineration in a stoker type furnace, etc.
Municipal trash incinerator ash

Technology development
Disposal site Land fill
Cement resource
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Concept for Development of Creating Resource for Cement from Municipal Trash Incinerator Ash
Air preheater
QuickQuick-cooling reaction tower
Trash
Dust collector
Stack
Fly ash (dust)

Washing removes chlorine Treatment of washing drainage Detoxification of dioxins
Washing dechlorination Becomes a cement resource
Air Stoker furnace Water seal device

copyright TCC Bottom ash
Removal of impurities (iron lumps) Detoxification of dioxins
Impurities removed Becomes a cement resource 26
Bottom ash Treatment Technology Ash properties Moisture 25-30% Contains calcium component Problems Adheres to transporter; clogs chute Solidifies during storage
Fly ash De-chlorination Technology Technical problems High chlorine content (10-20%) -> De-chlorination technology Heavy metals in drainage water -> Proper treatment Dioxin content (fixed within the cement,breakdown)
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Sample Treatment Water Composition After Each Operation

Concentrate
Treatment water composition for all processes Carbonation Chemical treatment 0.01 N.D. N.D. N.D. N.D. 0.04 0.1 N.D. 17 0.46 Filter
Unit
composition
Permissib le sewage discharge value
Pollutants Cadmium Lead Total mercury Alkyl mercury Hexavalent chrome Environmental items Copper Zinc Chrome Suspended matter DXN copyright TCC mg/L mg/L mg/L mg/L Ng-TEQ/L 0.09 7.1 0.02 450 1,200 0.4 0.5 0.012 42 7.9 0.04 0.05 N.D. 4 0.09 3 5 2 600 10 29 mg/L mg/L mg/L mg/L mg/L 0.69 250 0.001 N.D. N.D. 0.01 0.4 0.001 N.D. N.D. N.D. N.D. N.D. N.D. N.D. 0.1 0.1 0.005 N.D. 0.5
Results of Breakdown of Dioxins in Exhaust Gas

Dioxins in fly ash are not dissolved out on the water side; they remain in the washing cake and/or caked precipitate from the drainage water treatment process. The cake is charged directly into the kiln where it is broken down and rendered harmless by high-temperature (1,450C) sintering.
Density of dioxins in exhaust gas 0.0000074 - 0.0025 (ng-TEQ/m3N)

Development of Ash Treatment System

March 1995 1996-1997 April 1998 Kumagaya City sounded out on effective use of incinerator ash Saitama Prefecture double-plant planned; ash washing and de-chlorination technology adopted for zero-emission promotion and demonstration business Experimental plant built (treatment capacity, 8,000t/y); demonstration tests of use of municipal trash incinerator ash in cement production begun (joint research by Saitama Prefecture and Kumagaya City) Calcining method approved as one of the dust treatment regulations set by Minister of Health and Welfare Establishment of ash washing system technology recognized by Technical Committee Approval for construction of facilities for treatment of general waste received Agreement reached with Saitama prefectural wide-area waste treatment measures conference on basic items for consignment of wide-area treatment Industrialization plant operation begun; treatment capacity 63,000t/y
Jan. 2000 March Nov. Feb. 2001 July
Incinerator ash collected from areas around northern Saitama; business for use of waste as a resource for cement begun
What is Ecocement
siliceous sand iron material limestone
Coinage; Ecology and Cement Comparison of raw materials for Ordinary Portland Cement and Ecocement
others limestone
clay
incineration ash etc.
Ordinary Portland Cement
Ecocement
Ecocement process replaces large quantity of natural resources (limestone and clay etc.) with incineration ash etc.
Incineration ash Limestone

Other wastes
Flush Blenders
(after crushing)
Production process of Ecocement

(Na2CO3)
To atmosphere from stack (after severe gas treatment)
Bag filter
Raw meal
E Powder
Mainly chlorinated dust containing NaCl, KCl plus
Cooling Tower Rotary kiln (1350-1400C)
PbCl2, ZnCl2, CuCl2 , CdCl2, CaCl2, etc.
Water
Heavy Metal Refining Process

(next slide)
33
Ecocement
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Heavy Metal Refining Process

E Powder
Leaching Process Plant view
Heavy metal rich filtrate Calcium rich cake
Refining Process
Filtrate (NaCl, KCl) Waste water treatment
Refining Process Enriched Enriched Ca(OH)2 Ca(OH)2

Leaching process
(Pb, Cu, Zn etc.) (Pb, Cu, Zn etc.)
Enriched Enriched heavy metal heavy metal compounds compounds
Drainage Drainage
Raw material for cement Raw materials production for non-ferrous metal industry
Enriched metal compounds

34
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Features of Ecocement Process

Safe destruction of all toxic organic substances such as DXNs in incineration ash, thanks to high temperature in the Ecocement kiln (1350 1400C) Extraction and enrichment of heavy metal compounds, followed by their recycling at non-ferrous metal industry Reduction of CO2 emissions due to less use of limestone No generation of secondary solid waste, contributing to prolonging the life of landfill site (or even landfill-free)
Quality of Ecocement (JIS R 5214)

Quality Density g/cm3 Specific surface area cm2/g Setting time Initial h-m Final h-m Soundness Pat method Le chatelier method mm Compressive strength N/mm2 Chemical composition (%) 1d 3d 7d 28d Magnesium oxide Sulfur trioxide Ignition loss Total alkali Chloride ion
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Type
Normal Ecocement 2500 min 1-00 min 10-00 min Good 10 max 12.5 min 22.5 min 42.5 min 5.0 max 4.5 max 3.0 max 0.75 max 0.1 max
Normal Portland cement 2500 min 1-00 min 10-00 min Good 10 max 12.5 min 22.5 min 42.5 min 5.0 max 3.0 max 3.0 max 0.75 max 0.035 max
36
Ichihara Ecocement Plant

Note) Foundations of the kiln were made using Ecocement
Eco-cement Plant in Tama, Metropolitan Tokyo
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Summary of Volatile Component Circulation and Cyclone Clogging Mechanism

Charging of combustible material at kiln end Facilitation of sulfur volatilization Raw meal CaSO4+2C CaS+2CO2
CaS+3CaSO4 4CaO+4SO2
Bottom cyclone
Calciner
Cyclone clogging
Increased volatile component due to use of waste material Increase of volatile component circulation Generation of Low-melting-point compounds consist of CaO, SiO2 , S and Cl. Ellestadite 3(2CaOSiO2)3CaSO4CaCl2 Sulfate spurrite 2(2CaOSiO2)CaSO4
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Sample Volatile Component Balance

Kiln raw meal
Cl: Na2O: K2O: SO3: Cl: Na2O: K2O: SO3: Cl: Na2O: K2O: SO3: Cl: Na2O: K2O: SO3: 0.022% (3.7x) 0.22% (0.6x) 0.37% (0.8x) 0.2% (0.4x) 0.108% (18x) 0.24% (0.7x) 0.45% (0.9x) 0.6% (1.2x) 0.204% (34x) 0.24% (0.7x) 0.58% (1.2x) 0.5% (1.0x) 0.353% (59x) 0.26% (0.8x) 0.84% (1.8x) 0.8% (1.6x)
EP dust
Cl: Na2O: K2O: SO3: 0.174% (29x) 0.34% (1.0x) 0.78% (1.6x) 0.8% (1.6x)
Chlorine bypass dust
C1 cyclone raw meal
Cl: 21.9% (3,650x))

Na2O: K2O: SO3: 1.96% (5.8x) 29.9% (62x) 10.2% (20x)
C2 cyclone raw meal
Chlorine bypass coarse powder

Cl: Na2O: K2O: SO3: 2.18% (360x) 0.69% (2.0x) 5.06% (11.0x) 8.1% (16x)
C3 cyclone raw meal
Chlorine bypass equipment Bypass ratio: 1.9%
Clinker
Cl: 0.006%
Na2O: K2O: SO3: 0.34% 0.48% 0.5%
C4 cyclone raw meal
Cl: 0.850% (140x)

Na2O: K2O: SO3: 0.42% (1.2x) 2.05% (4.3x) 3.3% (6.6x)
Note: values in parentheses are in relation to clinker 2006.11.17 KCI Symposium 41
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Chlorine Bypass System Flow Chart

Gas extraction
Coarse particle separator cyclone Bag filter Cooler Bypass fan To Kiln
Probe
Coarse dust To kiln K powder (bypass dust) K powder tank K powder tank
Dust additive
Kiln
Feeder
To Finish Process Probe Cooling fan copyright TCC Cooler Cooling fan 2006.11.17 KCI Symposium 42
Volume of Municipal Trash Incinerator Ash That Can Be Used in Cement Kilns
Without chlorine bypass Permissible chlorine input vol. (clinker conversion) Ash chlorine density Fly ash chlorine density Permissible vol. of ash kg/t-clinker Permissible vol. of fly ash kg/t-clinker Permissible vol. of incinerator ash (ash + fly ash ) kg/t-clinker Chlorine bypass type 250 Fly ash washing desalination Chlorine bypass type 250 + Fly ash washing desalination
15ppm
216ppm
1.4%
15ppm
216ppm
15.0% 0.2 0.1 2.4 1.2 0.9 0.5
0.45% 13.3 6.6
0.3
3.6
1.4
19.9
Input chlorine from source fuels other than urban trash incinerator ash is 20ppm (clinker conversion). Ratio of ash to fly ash is 2:1 depending on volume produced; fly ash washing desalination efficiency is 97%.
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KCl Washing process Process of KCl Recovered K Powder Recovery Waste water treatment process

Removal of calcium
Kpowder tank
water
Removal of heavy metals
Kiln
Kiln Crystallization process
Electro
dialysis
KCl
44
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Quality Target and Actual Performance of KCl Recovered K Powder
Target K2O Ca SO4 Heavy metals

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Actual performance 60% 100mg/kg max 100mg/kg max 0.2mg/kg max

45
57% min 1000 mg/kg max 1000 mg/kg max 10 mg/kg max
Conclusions
The contents of this report can be summarized as follows. In Japan, energy saving technologies in the cement production have been developed, and at the same time as many types of advanced recycling technologies of waste materials. The amount of waste materials and by-products utilized in 1 ton of cement produced in the Japanese cement industry has reached an average of 400 kg. By treatment technologies, represented by the chloride bypass process, the incineration ash of municipal waste containing chloride compounds has been utilized increasingly in the cement production process. Three unique methods of utilizing municipal wastes, fly ash washing system, ecocement system, and AK system were in practical use and the method to be selected varied depending on actual conditions in each region.
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We want to contribute to the creation of a recycling society.
Thank you for your attention
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47

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Contribution of Japanese Cement Industry towards Addressing Environmental Issues

Taiheiyo Cement Corporation

Contents of Todays Presentation

Cement production of Japan

2006.11.17 KCI Symposium

2006.11.17 KCI Symposium

Heat consumption (Coal equivalent)

Electric power consumption

kwh/t-cement 120 116.7 115 110

2006.11.17 KCI Symposium

Types and Sales of Cement

2006.11.17 KCI Symposium

Contents of Todays Presentation

Waste Material Used in Cement Industry

2006.11.17 KCI Symposium

Recycling in the Japanese Cement Industry

60,000 40,000 20,000 0 2000 2001 332 355 361

2006.11.17 KCI Symposium

Advantages of Waste Recycling at Cement Plants

Cement Materials and Chemical Composition

(Natural materials, for reference)

2006.11.17 KCI Symposium

Dioxins Pollutants in waste materials

Included as ferrous material in cement

2006.11.17 KCI Symposium

Note: Japan Cement Association estimate

Contents of Todays Presentation

Cement Production Process and Resource Recycling

Cement production process

Raw meal process

Preheater Pre-grinding mill Bagging

Cement mill Cooler

Bulk truck Cement silo Bulk car

Gypsum storage Coal mill

Coal ash Sludge Sewage incinerator

Recycled materials Municipal trash

Blast furnace slag By-product gypsum

2006.11.17 KCI Symposium

Changes in Consumption of Waste Materials and Household Waste by Taiheiyo Cement

300 (kg/t-cement) 13.9 200 253.4 100 265.7 14.3

0 2000 2001 2002 2003 Fiscal year 2004

2002 2003 Fiscal year

2006.11.17 KCI Symposium

Background of Development on AK System

Overview of the AK system

Three-day processing Digester5.0m62.1m

Crushing, Sieving, Separating

Cement raw material

Municipal solid waste (MSW) of Hidaka city

2006.11.17 KCI Symposium

Pressure adjustment valve

Liquid Freon charger

Central control room

Low-temperature storage room Compressed air

Flow adjustment valve Receiving tank

2006.11.17 KCI Symposium

Treatment of Used Pachinko Machines

Forklift Primary crusher Crusher

Metal scrap storage

Double-shaft screw-type compactor-solidifier Compacted, solidified material

2006.11.17 KCI Symposium

Treatment of Waste Plastics

Primary storage tank 97.8m3