Technology Presentations

6. Technology Presentations

6.1 Destruction Technologies for ODSin Japan

Dr. Koichi Mizuno, Japan

Destruction Technologies for Ozone Depleting Substances in Japan

Koichi Mizuno

National Institute for Resources and Environment

1. Guidelines and Management Manual for CFC Destruction

Because of the importance of the destruction of ozone depleting substances, the Government ofJapan has issued both the Guidelines and the Management Manual for CFC destructiontechnologies.

The first set of Guidelines was issued in May 1996 and they were amended in March 1999. Theamended Guidelines include:

• Confirmation of Destruction: Coinjection of ODS into the destruction equipment, destructionefficiency, frequency of check up

• Hazardous Emissions: national and local emission standards, measurement methods (JapanIndustrial Standards; JIS), frequency of monitoring

• Operational Stability: monitoring of temperature and exhaust gas, frequency of check up

The Management Manual for CFC destruction facilities has also been issued by the Government ofJapan in May 2000. The Manual aims at the safe and environmentally sound management in view ofmore than 30 current facilities and an expected increase of the facilities. Up to now, more than 800copies of the Manual have been distributed.

The Manual includes:

1) Overviews of Destruction

2) Management of Handling of CFCs in the Facilities

− acceptance of CFCs to the facilities

− recovery of CFCs in the facilities

− transfer of CFCs contained in cylinder to the storage tank

− storage of CFCs

− charge of CFCs into the destruction equipment

3) Management of Destruction Technologies in Six Categories

− waste incineration: rotary kiln, municipal waste direct melting furnace,fixed-bed two-stage combustion

− destruction by manufacturingplant:

cement kiln, lime rotary kiln

− incineration in water: liquid injection (submerged combustion), gaseous/fume oxidation (high-temperature steam decomposition)

− plasma: r.f. plasma, microwave plasma, arc plasma− catalytic process: TiO2-type catalyst, AlPO4-type catalyst

− others: thermal vaporization

4) Targets of management

− destruction efficiency: equal to or more than 99.99%

− safe operation: corrosion prevention and so forth

− minimum emission standards: PCDD/PCDF and other pollutants in airemissions, water effluents, and solid residue

2. Commercial Destruction Technologies in Practice

The locations of destruction facilities in Japan are shown in Figure 1. More than 30 facilities with awide variety of destruction technologies and capacities are being operated.

Figure 1. Locations of CFC Destruction Facilities in Japan

Rotary kilnCement kilnLime rotary kilnMunicipal waste direct melting furnaceCatalytic processHigh-temperature steam decompositionr.f. Plasma

Submerged combustionChemical thermal decomposition

arc Plasma

Thermal vaporizationFixed-bed two-stage combustion

Hokkaido

Honshu

Shikoku

KyushuOkinawa

3. Brief Description of Typical Destruction Technologies in Japan

3.1 IncinerationThere are many test data of CFC destruction by incineration available in Japan. An example amongthem is the gaseous/fume oxidation method owned by the ICI-Teijin Fluorochemicals Co., Ltd.(ITF) in Mihara City, Hiroshima Prefecture (see Figure 2). This destruction technology is also calledthe high-temperature steam decomposition, since a large amount of steam is fed into the furnace.Injection of fuel, steam, and air into the furnace gave rise to such a high temperature, approximately1,200-1,250oC, that the destruction efficiency achieved was more than 99.999%. The ratedthroughput of CFCs ranged from 15 to 165 kg/hr. In a destruction test using a mixture of CFC-12and HCFC-22, the emissions of HCl, HF, CO, particulates, SO2, and NOx met the standards, andthe PCDD/PCDF emissions to the atmosphere were below 0.03 ng-TEQ/Nm3.

Figure 2. Flow Diagram of the Gaseous/Fume Oxidation Method

(High-temperature Steam Decomposition)

3.2 Cement KilnThe destruction experiments using a cement kiln were carried out at the Chichibu Plant No.2 inSaitama Prefecture, which is owned by the Taiheiyo Cement Corporation. The kiln was a dry rotarytype equipped with a new suspension preheater (NSP), with a diameter of 5.5 m and a length of 83m. The plant produces clinker for ordinary Portland cement with a manufacturing capacity of 5,000tonnes per day. CFC-11, CFC-12, and CFC-113 were fed through an auxiliary fuel injection portat the rates ranging from 2.7 kg/h to 3.72 kg/h, depending on the type of CFCs fed (see Figure 3).Since the furnace temperature was as high as 1,450 oC and the gas residence time was 6-7 sec, thedestruction of CFCs achieved was more than 99.99% (see Table 1). The emissions of HCl, HF,PCDD/PCDF, and other twelve halogenated organic compounds were measured. The total

Steam ?120kgs/h

LPG ?45kg/h

CFC or HCFC Gas ?165kgs/h

Cylinder

Gas CollectionTank

Air ?700kgs/h

TICChamber

?1250oC

Air BlowerCooling

Tank

CW

Cooling Air

1250kgs/h

O

2

AR

Sampling PointScrubber

Basic Water

Waste AcidHold Tank Neutralisation

Tank

Ca(OH)2 Slurry

CaCl2 aq.

ClarifierSludgeMixingTank

Filtre PressFiltrate

Sampling Point

Water

Basic Water Tank

By-Produced CaF2

emissions of PCDD/PCDF were below 0.08 ng-TEQ/Nm3. The cement kiln eliminates the need totreat HCl and HF. No significant change in the cement quality was observed.

Figure 3. Schematic Diagram of Cement Kiln.

Table 1. CFC destruction efficiency by cement kiln.

CFC FeedRate

Exhaust GasFlow Rate

Average Emission Rate ofCFCs (g/min)

DestructionEfficiency

(g/min) (m3/min) Blank run CFC feed (%)

CFC-12 58.7 5,750 0.007 0.011 99.99CFC-11 44.3 5,750 0.015 0.020 99.99CFC-113 66.5 5,750 0.17 0.13 -

3.3 r.f. PlasmaA plant using an inductively-coupled radio-frequency plasma, so-called r.f. plasma, has beenoperated at Ichikawa City, Chiba Prefecture. A mixture of CFCs and steam was fed continuouslyinto a cylindrical plasma torch with an inner diameter of 6.1 cm and a length of approximately 30 cm.The torch has a nominal output power of 100 kW. Reacted gases were quenched in a cooling tankbeneath the torch, where products of HF and HCl were dissolved. The exhaust gas was furtherwashed in a scrubber. The aqueous acid solutions were pumped to a neutralization tank to beneutralized by Ca(OH)2 (see Figure 4). The throughput capacity was more than 50 kg/h, and the

Rotary Kiln

CFC Injection

Clinker cooler

Kiln burner

Chlorine

Crashed raw

secondary productsNe

Waste heatboiler

Raw

Raw material

Raw material

ESP

Sampling

IDF

IDF

IDF

Heat flux

Material flux

mill

dryer

hopper

suspensionpreheater

By-pass

(i.d.5.5 lengt 83

material

hopper

Dusttoport

energy consumption of the plasma was 1.28 kWh/kg-CFC-12. The total emissions ofPCDD/PCDF were below 0.03 ng/Nm3, and the emissions of CO, HCl, HF, and particulates andthose of F- ion, biological oxygen demand (BOD), chemical oxygen demand (COD), and suspendedsolids (SS) in wastewater were below the standards.

Figure 4. Schematic Diagram of r.f. Plasma Reaction System.

4. Destruction of Halons

The destruction of halons was tested or is planned to be tested in three commercial-scale plants.

One of the tests is the destruction using an r.f. plasma reactor with an output power of 35 kW, whichis almost similar to that of the 100 kW plasma as shown in Figure 4. The plant is designed to have acapacity of 30 kg-halons/h. The r.f. plasma was proven to destroy halons by a fundamental researchconducted in 1990. The commercial-scale facility supported by the Government of Japan isscheduled to be constructed in the Asahi Glass Co. Ltd. in Chiba Prefecture. The experiments willbe carried out by the end of March 2001.

The other two tests have been performed by the gaseous/fume oxidation method and the rotary kilnmethod, the latter being supported by the government. The facility using the gaseous/fume oxidationowned by ITF in Hiroshima Prefecture is described previously. The rotary kiln facility is owned bythe Dowa Clean Technological Service in Akita Prefecture. The destruction of halon-1211 by usingthe rotary kiln was carried out at a feed rate of 38.3 kg/h, which corresponds to approximately3wt% of sludge. The results indicated a slight decrease in the temperature, leading to a lower

Plasmatorch

Radio-frequencyoscillator

Reactionchamber

Cooling tank

Activatedcarbontower

Exhaustgasscrubber

Circulation pump

Neutralizationtank

CFCs

steam

water

Ca(OH)2

CaCl2CaF2

destruction efficiency of 99.753% and slight increases of PCDD/PCDF emissions. However, asmaller feed rate of halons (the rotary kiln) or a higher temperature (the gaseous/fume oxidation)gave the destruction efficiency of more than 99.99% and the reduction of air pollutants emissionsincluding dioxins.

Destruction Technologies for Ozone DepletingSubstances in Japan

Koichi MizunoNational Institute for Resources and Environment

Agency of Industrial Science and TechnologyMinistry of International Trade and Industry of Japan

! Guidelines for CFC Destruction: issued in May 1996, amended in March 1999

" Confirmation of Destruction: 　　　 　injection of ODS into the equipment,destruction efficiency, frequency of check up

" Hazardous Emissions: national and local emission standards,measurement methods (Japan Industrial Standards; JIS), frequency of monitoring

" Operational Stability: monitoring of temperature and exhaust gas,frequency of check up

! Manual for Destruction of Chlorofluorocarbons: issued May 2000• Background• Procedures in Preparation of this Manual• Management of Facilities Concerning Fluorocarbon Destruction3.1 Explanation

3.2 Management of Technology and Facilities for Fluorocarbon Destruction 3.2.1 Management of the Storage of Fluorocarbon Recovered 3.2.2 Management Index of Fluorocarbon Destruction Facilities (equipment)

Incineration with Waste / Incineration in Manufacturing Processes / SubmergedCombustion / Plasma / Catalytic Destruction / Other Systems

3.2.3 Management Indexes for Emissions from Installations due to FluorocarbonDestruction

[Reference] Items Related to Achievement Record of Fluorocarbon Destruction

Guidelines and Manual for Destruction

Figure. Flow Diagram of Gaseous/Fume Oxidation (High-temperature Steam Decomposition)

ICI-Teijin Fluorochemicals Co., Ltd.

Steam　～　～　～　～120kgs/h

ＬＰＧ　～ＬＰＧ　～ＬＰＧ　～ＬＰＧ　～45kg/h

CFC or HCFC Gas ～～～～165 kgs/h

Cylinder

Gas CollectionTank

Air ～～～～700kgs/h

TICChamber～～～～1250oC

Air Blower CoolingTank

CW

Cooling Air

1250 kgs/h

O2AR Sampling PointScrubber

Basic Water

Waste AcidHold Tank Neutralisation

Tank

Ca(OH)2 SlurryCaCl2 aq.

ClarifierSludgeMixingTank

Filtre Press Filtrate Sampling Point

Water

Basic Water Tank

By-Produced CaF2

ICI-Teijin

scrubber

chamber

Entry ofwasteCFCs,fuels, air

ICI-Teijin

Injection ports of waste CFCs, fuels, and air

ICI-Teijin

T em perature of chamber ca. 1200oCPressure ca. 10 kPaResidence tim e 1 - 2 secT hroughput 15 - 165 kg/h

(0 .4 - 4.0 tes/d)Destruction effic iency > 99.999%

CFC-12 < 10 ppbHCFC-22 < 10 ppbHCl < 3.0 mg/Nm3

HF < 0.5 mg/Nm3

CO < 34 ppmParticulates < 30 mg/Nm3

PCDD/PCDF < 0.03 ng-T EQ /Nm3

*Data w ere obta ined at a feed rate of 165 kg/h for a m ixture of CFC-12and HCFC-22.

Atmospheric EmissionsDescription and Destruction Efficiency

Performance of Gaseous/Fume Oxidation(ODS Destruction)

ICI-Teijin

Figure. Liquid injection incineratorAsahi Glass

Chamber

Cooling watertank

EvaporatorCylinder

Neutralization tank

Ca(OH)2

Scrubber

to Air

Water

NaOH

Filter press

to Wastewatertreatment

Fuel

Asahi Glass

Liquid injection incinerator

scrubberchamber and cooling tank

Asahi Glass

Cooling Tank

Window on chamber

Asahi Glass

T em perature of cham ber 1,350oCResidence tim e 1.3 secT hroughput ca.11 kg/h

(5 - 10 wt% )Destruction effic iency > 99.99%

CFCs < 1 ppmHCl < 10 mg/Nm3

HF < 1 mg/Nm3

CO < 10 ppmParticulates < 20 mg/Nm3

PCDD/PCDF < 0.52 ng-TEQ/Nm3

F- < 15 mg/LpH -SS < 50 mg/LPCDD/PCDF < 0.062 pg-TEQ/L

Atmospheric Emissions

Effluents water

Description and Destruction Efficiency

Performance of Liquid Injection Incinerator

Rotary kiln(i.d. 5.5 m; length 83 m)

CFC Injection

Clinker cooler

Kiln burner

Chlorineby-pass

Crashed rawmaterial hopper

NewSuspensionpreheater

Waste heat boiler

RawMaterialhopper

Raw materialmill

Raw materialdryer

ESP

Samplingport

IDF

IDF

IDF

Heat flux

Material flux

Dust tosecondary products

Figure Schematic Diagram of Cement KilnTaiheiyo Cement

CFC Fe edRate

ExhaustG aseFlowRate

DestructionEfficie ncy

g/min m3/min Blank CFC fe ed %CFC-12 58.7 5750 0.007 0.011 99.99CFC-11 44.3 5750 0.015 0.020 99.99CFC-113 66.5 5750 0.17 0.13 -

Av erage EmissionRate of CFCs, %

*Destruction efficiencies are on a "net" emission rate, being the dif ference of the C FC emission concentrat ion in the b lank run andthe CFC feed run .

Clinker production 5,000 tons/dayResidence time 6 - 7 secKiln temperature 1450oC

Table. CFC destruction efficiency.

Description of the Cement　　　　Kiln

Taiheiyo Cement

　

n av. min. max. n av. min. max.CFC-12 10 0.8 ƒ 0.1 2.3 10 0.3 ƒ 0.1 1.8CFC-11 2 0.1 ƒ 0.1 0.1 2 ƒ 0.1 ƒ 0.1 ƒ 0.1CFC-113 2 0.1 ƒ 0.1 0.2 2 0.1 ƒ 0.1 0.2

n av. min. max. n av. min. max.CFC-12 10 ƒ 0.2 ƒ 0.2 0.2 10 0.3 ƒ 0.2 0.6CFC-11 2 ƒ 0.2 ƒ 0.2 ƒ 0.2 2 ƒ 0.2 ƒ 0.2 ƒ 0.2CFC-113 2 ƒ 0.2 ƒ 0.2 ƒ 0.2 2 ƒ 0.2 ƒ 0.2 ƒ 0.2

CFC FeedHF Concentrations (ppm)

Blank Run CFC FeedHCI Concentrations (ppm)

Blank Run

Table. HF and HCl concentrations of the exhaust gase.

av . min. max. av . min. max.1,1,1-trichloroe thane (ppb) 1.1 1.0 1.6 1.5 1.1 2.0carbon te trachloride (ppb) < 0.01 < 0.01 < 0.01 < 0.01 <0.01 < 0.01trichloroe thyle ne (ppb) 0.58 0.28 0.83 0.64 0.37 0.93te trachloroe thyle ne (ppb) 0.50 0.14 1.10 0.61 0.21 1.17chlorobe nze ne (ppb) 28 22 36 32 28 38m-dichlorobe nze ne (ppb) 0.9 0.6 1.2 1.0 0.8 1.2p-dichlorobe nze ne (ppb) 0.7 0.5 1.0 0.8 0.6 1.2o-dichlorobe nze ne (ppb) 0.8 0.6 1.0 0.9 0.1 1.11,3,5-trichlorobe nze ne (ppb) < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.21,2,4-trichlorobe nze ne (ppb) < 0.2 < 0.2 0.2 0.2 ƒ 0.2 0.31,2,3-trichlorobe nze ne (ppb) < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2

PC D Ds/PC D Fs (ng-T EQ /Nm3) 0.01 0 0.02 0.04 0 0.08phosge ne (ppb) < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3

B lank Run C FC-12 Fe e d

Table. Analytical results of the exhaust gase (n=10)

Environmental Emissions

Taiheiyo Cement

Rotary kiln

Neutralization

Secondary Chamber(After burner)

Mist Cottrell precipiator

Fuel

Waste CFC

Flow Diagram of Rotary Kiln

cooling fluid

CFC+H2O

inner tube

outer tube

r.f. coil

to reaction chamber

coolingwater

plasma flame

torchhead

Figure. Cross-sectional View ofr.f. Plasma Torch.

Ichikawa Kankyo Eng.

Plasmatorch

Radio-frequencyoscillator

Reactionchamber

Cooling tank

Activatedcarbontower

Exhaustgasscrubber

Circulation pump

Neutralizationtank

CFCs

steam

water

Ca(OH)2

CaCl2

CaF2

Figure. Schematic Diagram of r.f. PlasmaReaction System.

Photo. A Commercial Plant atIchikawa City, Chiba Prefecture

Ichikawa Kankyo Eng.

Exhaus t G asO bs e rve dConce ntration

UN EP S ugge s te dM inimum S tandards

M e tropolitan Tok yoS tandards

D ate o f S ampling M arch 15 ,1995 M arch 16 ,1995

H CI ƒ 10 <100 <41 O bs e rve d TEQ O bs e rve d TEQH F ƒ 5 <5 <9 PC D D sH B r/B r2 ƒ 5 <5 <36 2 ,3 ,7 ,8_T4CD D 0 0Particulate s ƒ 10 ƒ 50 <50* o the r T4CD D s - -CO ƒ 10 ƒ 100 <125 1 ,2 ,3 ,7 ,8_P5CD D 0 0

o the r P5CD D s - - 2 ,3 ,7 ,8_H 6CD D s 0.01 0 .01

O bs e rve d Conce ntration Japane s e S tandards o the r H 6CD D s - -9 15 1 ,2 ,3 ,4 ,6 ,7 ,8_H 7CD D 0 0

84 160 o the r H 7CD D s - -64 160 O 8CD D 0 010 200 S ub Tota l PCD D s 0.01 0 .01

PC D Fs 2 ,3 ,7 ,8_T4CD F 0 0 o the r T4CD Fs - - 1 ,2 ,3 ,7 ,8_P5CD F 0 0 2 ,3 ,4 ,7 ,8_P5CD F 0 0 o the r P5CD Fs - - 2 ,3 ,7 ,8_H 6CD F 0.02 0 .01 o the r H 6CD Fs - - 2 ,3 ,7 ,8_H 7CD F 0 0 o the r H 7CD Fs - - O 8CD F 0 0S ub Tota l PCD Fs 0 .02 0 .01

Tota l PCD D s +PCD Fs 0 .03 0 .02

Table . PCD D s /PC D Fs in r.f. Plas ma D e s truction ofW as te CFC-12 O bta ine d by a D e mons tration Plant Expe rime nts .

Table . Efflue nts W as te wate r mg/L

S S

Table . Exhaus t G as Emis s ions mg/m3

Efflue ntF-B O DCO D

Emissions to the Atmosphere and Wastewater

Ichikawa Kankyo Eng.

0000

10000100001000010000

20000200002000020000

30000300003000030000

40000400004000040000

50000500005000050000

60000600006000060000

70000700007000070000

1994199419941994 1995199519951995 1996199619961996 1997199719971997 1998199819981998 1999199919991999

others

CFC-114

CFC-113

HFC-23

HCFC-141b

R-502

CFC-22

CFC-12

CFC-11

Flu

oro

carb

on

s d

estr

oye

d /

kg

Year

Destruction of Fluorocarbons by r.f. Plasma

Ichikawa Kankyo Eng.

Fe ed rate Halon-1211 38.3 (av aragekg/hHalon-2402 40 kg/h

De struction Efficiency Halon-1211 99.753 %Halon-2402 99.88% %

Fe ed rate of sludge 1,392 kg/hT e mpe rature in kiln Blank 997 - 1,009oC

Halon-1211 922 - 984oCHalon-2402 921 - 974oC

Rotary Kiln

at Higher Feed Rates of Halons

Blank Hal 1 Hal 2

Nm3/hr(WB) 8,200 8,400 11,800Nm3/hr(DB) 6,000 6,100 8,600

humid % 26.3 27.8 26.3Particulates mg/Nm3 < 1 < 1 <1O2 % 10.9 11.2 10.6CO2 % 8 7.6 8.1CO ppm 11 13 14HCl ppm < 1 10 51Cl2 ppm 2 2 11.4HF ppm < 0.5 < 0.5 < 0.5HBr ppm < 0.5 8.6 39SO2 ppm < 1 <1 < 1NOx ppm 84 63 47halone-1211 ppb - 2,100 -Halon-2402 ppb - - 500CF4 ppb - < 2 8.8C2F6 ppb - < 2 < 2PCDD/PCDF ng-TEQ/Nm3 0.15 2.5 1.4chlorobenzenes ng/Nm3 1,100 1,600 2,200chlorophenols ng/Nm3 210 59 46

Exhaust gas

Fee d rate Halon-1211 20 kg/hHalon-2402 20 kg/h

Destruction Efficiency Halon-1211 99.99 %Halon-2402 99.55% %

Fee d rate of sludge 1,392 kg/hT e mperarue in kiln Halon-1211 992 - 1,057 oC

Halon-2402 989 - 1,045 oC

Halon-1211 Hal 2

Nm3/hr(WB) 39,900 36,300Nm3/hr(DB) 27,800 25,800

humid % 30.4 29Particulates mg/Nm3 1 1O2 % 11.9 12CO2 % 7.2 6.7CO ppm 20 7HCl ppm < 1 < 1HF ppm < 0.5 < 0.5HBr ppm < 1 < 1SO2 ppm 2.9 2.2NOx ppm 78 80halone-1211 ppb < 10 -Halon-2402 ppb - 130CFC-12 ppb 25 < 10PCDD/PCDF ng-TEQ/Nm3 0.35 0.28chlorobenzenes ng/Nm3 7,500 40,000chlorophenols ng/Nm3 1,500 400

Exhaust gas

Rotary Kiln

at Lower Feed Rates Of Halons

•

first run second runFeed@rate of halon-1301

temperature of furnaceFeed rate of steamresidence time

15.2 (avarage) kg/h1,250oC

1 - 2 kg/hca. 2.4 sec

first run second run

Particulates mg/Nm3 < 20 < 20SO2 ppm < 2 < 2NOx ppm 82 83CO ppm 27 33HCl ppm < 1.2 < 1.4

HF mg/Nm3 ƒ 0.3 ƒ 0.3Br2 ppm ƒ 2.0 < 2.0CF4 ppb < 10 ƒ 10

C2F6 ppb < 1 ƒ 1

chlorobenzenes ng/Nm3 420 590

chlorophenols ng/Nm3 60 80

PCDD/PCDF/Co-PCBs ng-TEQ/Nm3 0.0000025 0

brominated dioxins ng-TEQ/Nm3 0 0

Destruction Conditions Atmospheric Emissions

ICI-Teijin

Destruction of Halons by Gaseous/Fume Oxidation

•Feed rate of steam 150 - 350 NL/m inCham ber pressure 200 torrDestruction effic iency > 99.99 %

HCl -HF 34.4 mg/m3

HBr/Br2 2.2 mg/m3

Particulates < 10 mg/m3

CO ND

Atmospheric Emissions

Destruction ConditionsDestruction Halon-1301 by r. f. Plasma

Conclusions

! Guidelines and Manual for CFC Destruction were issued.

! More than 30 facilities are being operated in Japan.

! Destruction efficiencies of CFCs achieved were more than99.99% by incineration such as gaseous/fume oxidation, liquidinjection, cement kiln.

! Environmental emissions met the standards by a normaloperation.

! Destruction of Halons seems technically more difficult.