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Appendix A Manual of Destruction Technologies for Chlorofluorocarbons Dr. Koichi Mizuno
Manual of Destruction Technologies for Chlorofluorocarbons
1.
Background In Japan, the production of chlorofluorocarbons (CFCs) for domestic uses had been phased-out by the end of 1995. From now on, it is important for all countries to promote the development and utilization of technologies for the recovery and destruction of CFCs, which have been used until now, to prevent global warming and protect the ozone layer. As an international activity, the Technical Assessment Committee (TAC) was set up under the United Nations Environment Programme (UNEP). TAC evaluated the technologies for the destruction of ozone depleting substances (ODS).
As a result, TAC set the criteria for ODS destruction, i.e. the destruction
efficiency (DE). In Japan, more than 30 commercial facilities are currently destroying fluorocarbons, and number is expected to increase with the further promotion of ozone layer protection and global warming prevention. In view of the above international and domestic situation, it is important to establish a framework for appropriate disposal of fluorocarbons in accordance with UNEP TAC DE and domestic laws. Based on UNEP TAC DE and domestic laws, this manual quantitatively and qualitatively sets forth the adequate management of fluorocarbon destruction in the facilities, and serves as a guide for existing and newly constructed facilities in Japan.
1
2. Procedures in preparation of this manual 2.1 Explanation of Procedures This manual outlines destruction technologies for fluorocarbons based on a survey of them. The survey was conducted to analyze the technical factors governing a wide variety of destruction technologies, ranging from those already commercialized to the fundamental types now under R&D. Besides examining technologies, the survey also viewed existing successful destruction facilities that were in operation in 1999. The term "successful destruction facility" refers to a facility that is capable of destroying the fluorocarbons while taking appropriate measures in technology, structure and operational management for emissions. As a result, both [Technologies for Fluorocarbon Destruction] and [Facilities of Fluorocarbon Destruction] were systematically classified. [Technologies for Fluorocarbon Destruction]: The technologies are classified on the basis of available technical reports and articles. The primary classification of technologies is based on the technical method of the destruction.
Technical method is
divided into seven categories: [destruction by thermal energy in incineration], [destruction by catalysis], [destruction by supercritical water], [destruction by reactions with chemical substances], [destruction by microbes], [destruction by photoreaction], and [destruction by ultrasonic irradiation ]. These seven categories are further classified from the viewpoint of practical uses.
[Facilities of Fluorocarbon Destruction]: Based on the destruction technologies that were established as of August 1999, the facilities are classified in two large categories: [multi-purpose equipment] and [exclusive equipment].
[Multi-purpose
equipment] is defined as the facilities that conduct the destruction of fluorocarbons while also performing other purposes such as disposing waste and manufacturing products.
On the other hand, [exclusive
equipment] is defined as the facilities that conduct only fluorocarbon destruction. [Multi-purpose equipment] is
further classified, based on the kind of waste or products mixed with fluorocarbons in the equipment. Similarly, [exclusive equipment] is also classified from the technical viewpoint. In this manual, the management indexes were made from technical point of view for the existing facilities of fluorocarbon destruction. Therefore, different facilities with the same technical requisites are categorized into the same group, as far as possible. Accordingly, in this manual, the management indexes are made for respective groups, and the technical requisites unable to be classified into the same group are indicated for each facility. In addition, this manual also describes the management indexes of the equipment and processing of the exhaust gases and wastewater, and the code of good practice (good house keeping) in the facilities.
2
2.2 Technologies for Fluorocarbon Destruction Table 1 presents a classification and outline of the technologies for fluorocarbon destruction. Table 1. Classification and Outline of Technologies for Fluorocarbon Destruction (as of August 1999) Type of Technology
Outline
Incineration / Pyrolysis Destroy instantaneously at a high temperature and a high pressure induced by a shock wave of the gas detonation. Destroy at a temperature of 2000~2200°C by oxygenhydrogen flame Destroy in a reaction with superheated vapor
Gas Detonation Reactor Cracking Superheated Vapor Reaction
Destroy with industrial waste in a high-temperature electric furnace Incinerate in a rotating cylindrical kiln with waste Incinerate in a rotating cylindrical kiln with clinker production. Acid gases produced are neutralized with alkaline component in cement. Destroy in a lime calcinations furnace. Acid gases produced are neutralized with lime. Destroy at high temperature in a secondary combustion kiln connected behind gas incinerator. Destroy at a high temperature (more than 1,700°C) with waste. The fluorocarbons in insulators are destroyed in a secondary combustion kiln
Electric Furnace Rotary Kiln Rotary Kiln
Staticflooring Slagging type Incinerator Stoker Furnace Submerged Combustion
Plasma
Cement Kiln Lime Calcinations Furnace Waste Tires Incineration Plants Two-staged Burning System Gasifying Melting System Municipal Waste Incinerator
Destroy in a stoker type incinerator with municipal waste Destroy by injecting fluid waste, air, and fluorocarbons into a furnace with LPG. Destroy by supplying steam, air, and fluorocarbons into a furnace with LPG. The amount of steam is larger than the normal liquid injection incinerator. Destroy at an ultra-high temperature in plasma induced by high-frequency current. Destroy at an ultra-high temperature in plasma induced by arc discharge. Destroy at an ultra-high temperature in plasma induced by microwave discharge.
Destroy in exceeded critical water at a high temperature and a high pressure
Chemical Destruction
Molten metal
Destroy in a reaction with silicon-compounds at a high temperature by electric heating. Destroy in a reaction with Na-naphthalenide in liquid phase at a low temperature of 25-150°C. Destroy in a reaction with Na dissolved in ammonia. The NaNH2 produced is reused by the reduction to ammonia. Destroy in molten sodium.
Sodium oxalate
Destroy in a reactor containing sodium oxalate at 270°C
Pyrolysis using chemical substances Na-naphthalenide Na-ammonia (SET)
Destroy using microbe Ultra-violet Ray Near ultra-violet Ray
Destroy under ultra-violet irradiation Destroy under 254-nm ultraviolet irradiation assisted by a catalyst. It is effective for dilute fluorocarbons . Destroy under ultrasonic irradiation, probably due to a cavitation phenomenon.
$ The terms for destruction technology in this manual are based on those used by the manufacturer of the technology.
3
2.3 Facilities of Fluorocarbon Destruction Table 2 presents practical facilities of fluorocarbon destruction and the name of organization that owns them. Table 2. Fluorocarbon Destruction Facilities and Organizations (as of August 1999) Type of Facility
Organization Owning the Facility
Stoker Furnace Incinerate with general waste
Multipurpose equipment
Incinerate with waste
Gasifying Melting System
Incinerate with Rotary Kiln industrial waste
Waste Tires Incineration Plants Two-staged Burning System Destroy in a Manufacturing Process
Cement Kiln Lime Calcinations Furnace
Gaseous/Fume Oxidation Incinerate Assisted by Fuels (fuels; LPG, waste oils, Liquid Injection Incinerator etc.) Inductively-coupled Radio-frequency Plasma Destroy Using Plasma
Arc Plasma
Exclusive Microwave Plasma equipment Destroy Using Chemical Pyrolysis Using Substance under a High Substances Temperature Destroy by Superheated Vapor
Chemical Gunma Prefecture, fluorocarbon Disposal Center
Superheated Vapor Reaction
TiO2 catalysts
Kyoto City, Department of Environment, South Clean Center Kamaishi City, Cleansing office, Cleansing plant Ibaraki City, Environmental Health Center Sanyuu Plant Service. Co., Ltd., Yokohama and Sapporo Plants Dowa Clean Technical Service Co., Ltd., Kureha environment. Co. Ltd. Nichizou metal chemistry. Ltd., Aizu Plant, EcoPark-Izumozaki, Kiraku Mining Co., Ltd. Mie Central Development Co., Ltd., Mie Plant Okinawa Prefecture, Medical Waste Cooperative Association
Create Chemical Co., Ltd. Asahikiki Engineering Co., Ltd. EGS Ltd. Fuji Sangyo Co., Ltd. Toguchi Co., Ltd. Term Co., Ltd. Wakayama City, Li ving Environment Section Ibara Jihan Recycling Center [OITA University]
$ Names in parentheses, indicates facility manufacturers, not facilities. $$ The terms for destruction technology in this manual are based on those used by the manufacturer of the technology 2.4 Grouping of Destruction Facility of Fluorocarbons from the Technical Viewpoint This manual presents management indexes for each group of facilities for fluorocarbon destruction. As mentioned above, the reasons for the classification are; (1) there are cases in which the technologies are similar even though they have different names, and (2) the performances of the different destruction technologies can be compared in scale. A variety of data in basic experiments and practical operations were collected from technical articles and other such sources, to list up the management indexes quantitatively wherever possible. This grouping also serves as a bridge between the type of technology and the type of facility. Based on these considerations, the grouping system is shown in Table 3. 4
Table 3. Grouping of Destruction Facility of Fluorocarbons from the Technical Viewpoint Type of Technology
Molten metal Sodium oxalate Microbial Destruction Photoreaction
Microbial Destruction Ultraviolet ray Near ray
ultraviolet
Ultrasonic Irradiation
Photoreaction Ultrasonic Irradiation
$ The terms for destruction technology and facilities in this manual are based on those used by the manufacturer of the technology and facility. $$ The groups in shaded boxes
, are the technologies that are covered in this manual.
In this manual, the groups indicated by circled numbers in the above shaded boxes are regarded as [established technology], and the management indexes are considered for respective groups. The indexes are based on datasheets for respective facilities.
5
Based on the above system, Table 4 outlines each group.
850°C
> 1,500°C at the bottom of furnace
1,050°C
of
fluorocarbon
Feed of fuel Excess air (oxygen) ratio Temperature in main furnace Pressure in main furnace Residence time of gas in main furnace Oxygen concentration in main furnace Feed rate of waste
Gauge pressure$6
—0.001~—0.00031 kgf/cm2
4 seconds (including the secondary chamber) 9~10% at the secondary chamber exit Industrial waste : 2,083 kg/h
Around atmospheric pressure
Gauge pressure
—0.0014 kgf/cm2
8 seconds
> 2 seconds
14.1% at tuyere (low concentration of O2 at part of fusion)
9%
Municipal waste : 2,700 kg/h
$6
Waste tires : 625 kg/h
$5 percent by weight of fluorocarbon in combustible waste $6 gauge pressure : pressure difference between the atmospheric pressure and the pressure in the furnace. Minus signs indicate a pressure lower than atmospheric pressure.
18
( 2 ) Group of Incineration in Manufacturing Processes Facilities in this group
Cement kiln
¡ Cement kiln
¡
¡
¡
¡ ¡
¡
¡
¡
¡
$ confirm whether the facility meets the “destruction conditions” as stated below when conducting the destruction.
Destruction conditions
1. Achieve a fluorocarbon destruction efficiency of more than 99.99% at the exit of the facility 2. Ensure the safety and stability of the destruction facilities by prevention of equipment degradation, etc.
n [in case of CFC-12] Management Conditions
The following indexes for each item are measures to operate the equipment for fluorocarbon destruction. “Main furnace" means the part in which the destruction of fluorocarbons actually occurs. Management item
Index
3. Take measures
to minimize the environmental emissions from the destruction of
fluorocarbons.
n Management at the Start-up Stage of the Operation
Because the operation conditions such as furnace temperature are unstable at the start-up, perform the fluorocarbon destruction after all conditions of equipment have become stable. n Management of Emissions (gas, drainage, residue)
Cement kiln :
Feed of fuels
¡
Lime calcination furance
¡ Lime calcination furance
Feed of fluorocarbons
Reported Fluorocarbons Destroyed in the Facilities at DE > 99.99% (¡ : destroyed fluorocarbons reported by Dec,1999) CFC HCFC HFC Facilities in this group 11 12 113 114 115 R-502 22 134a
The feed rate must be set so that the increase of chlorine concentration in final product falls within the allowable range of the quality specification$1. Lime calcination furance : About 1.3% of weight of raw material disposed per unit of time The purpose is manufacture of products. Use amounts enough to maintain the temperature set in the index for [temperature in main furnace].
Feed of water
Emissions from Fluorocarbon $2 Destruction
None
Feed of air
None
Temperature in main furnace
More than 1,000°C in case of cement kiln, more than 1,400°C at the burner
Pressure in main furnace
Around atmospheric pressure
Residence time of gas in main furnace
More than 6 seconds
Oxygen concentration in main furnace
None
$1 Standard are prescribed by JIS(Japanese Industrial Standards) for portland cement (JIS-R5210), blast furnace cement (JIS-R5211), fly ash cement (JIS-R5213), etc. In case of portland cement, chlorine concentration is must be below 200ppm.
19
Gas (see P.40) ¡
Drainage (see P.47)
Residue (see P.48)
—
—
¡
¡
—
(Carbon dioxide(CO2))
¡
—
—
Chlorine (Cl2 )
¡
—
—
Dioxin (DXN)
¡
¡
—
Nitrogen oxide (NO X)
¡
—
—
Particulate matter
¡
—
—
Carbon monoxide (CO)
¡
—
—
Chlorobenzene (C6 H5Cl)
¡
¡
—
Chlorophenol (C6 H5ClO)
¡
¡
—
Waste
—
—
¡
Emissions
Emissions Entailed $3 by Management
Others
Hydrogen chloride (HCl) Hydrogen fluoride (HF) $4
$2 Emissions from Fluorocarbon Destruction: This manual focuses on fluorocarbons which do not contain chlorine (Cl). However, most facilities destroy chlorofluorocarbons such as CFC-12 (CCl 2F2). Therefore, hydrogen chloride (HCl) is also included in the emissions from fluorocarbon destruction. $3 Emissions Entailed by Management: Although, ideally, these emissions should be zero, there exist some, however small in amount. Thus, these emissions are added to this management indexes. $4 Management indexes for carbon dioxide (CO2) are excluded from this manual.
20
Schematic Diagrams of Typical Destruction Facilities ¡ Cement kiln
[Resource]
Tokyo Metropolitan Government Bureau of environmental conservation, Tokyo Metropolitan Institute of Environmental Sciences, Chichibu Onoda Cement Corporation final report of experimental study [cement kiln method], 1996
¡ Lime calcination furance
[Resource] Ueda lime Co. Ltd., guidance material of fluorocarbon destruction system
21
[Reference]
Empirical Values for Management Items in the Group of Incineration in Manufacturing Processes (CFC-12 Destruction ) Examples of empirical values
Management items
Feed rate of fluorocarbon Percent of fluorocarbon fed Feed of fuel Temperature in main furnace Pressure in main furnace Residence time of gas in main furnace
$5
Cement kiln
Lime calcination furance
5kg/h ∼
27kg/h
0.0017% ∼
1.28%
Feed coal
Feed coke
> 1,400°C at the burner > 1,000°C at the part in the back of kiln. $6 Gauge pressure 2 —0.062kgf/cm 8 seconds
> 1,000 Around atmospheric pressure
About 7 seconds
$5 percent by weight of fluorocarbon in combustible waste $6 gauge pressure pressure difference between the atmospheric pressure and the pressure in the furnace. Minus signs indicate a pressure lower than atmospheric pressure.
(¡: destroyed fluorocarbons reported by Dec,1999) CFC HCFC HFC 11
12
113
TiO2–series catalytic reactor
¡
¡
¡
114
115
R-502
22 ¡
AlPO4–series catalytic reactor
¡
¡
¡
¡
134a ¡
$ confirm whether the facility meets the “destruction conditions” as stated below when conducting the destruction.
Destruction conditions
1. Achieve a fluorocarbon destruction efficiency of 2.. Ensure
more than 99.99% at the exit of the facility
the safety and stability of the destruction facilities by prevention of equipment
degradation, etc.
3. Take measures
to minimize the environmental emissions from the destruction of
fluorocarbons.
n [in case of CFC-12] Management Conditions
The following indexes for each item are measures to operate the equipment for fluorocarbon destruction. “Main reactor" means the part in which the destruction of fluorocarbons actually occurs. Management item
Feed of fluorocarbons
index ¡ Fluorocarbon must be fed within the capacity of exhaust gas treatment equipment installed after the reactor for fluorocarbon destruction ¡ The mixed rate (volume fraction) of fluorocarbon in mixed gas, which is fed into catalyst packed bed, must be kept under 3%. ¡ (The rate of feed must follow the index for [Feed of water])
Feed of fuels
—
Feed of water
The ratio of water feed to fluorocarbon weight, which is fed per unit of time, must be more than 75%
Feed of air
Feed in order to control the concentration of fluorocarbon in catalyst packed bed
Temperature in main reactor
Follow the indexes noted below to obtain ample efficiency in fluorocarbon destruction, and curtail catalyst degradation TiO2–series catalytic reactor About 440°C About 500°C AlPO4–series catalytic reactor
Pressure in main reactor Residence time of gas in main reactor
n Management at the Start-up Stage of the Operation
Because the operation conditions such as furnace temperature are unstable at the start-up, perform the fluorocarbon destruction after all conditions of equipment have become stable. n Management of Emissions (gas, drainage, residue)
Emissions from Fluorocarbon $2 Destruction
Emissions Entailed $3 by Management
Around atmospheric pressure Follow the index for [Space velocity in catalyst packed bed]
Oxygen concentration in main reactor In this group, also note the following items.
index
Space velocity in catalyst $1 packed bed
Less than 1,500h
Residue (see P.48)
—
—
Hydrogen fluoride (HF)
¡
¡
—
(Carbon dioxide(CO2))
¡
—
—
Chlorine (Cl2 )
¡
—
—
Dioxin (DXN)
¡
¡
—
Nitrogen oxide (NO X)
¡
—
—
Particulate matter
¡
—
—
Carbon monoxide (CO)
¡
—
—
Chlorobenzene (C6 H5Cl)
¡
¡
—
Chlorophenol (C6 H5ClO)
¡
¡
—
Others
Waste
—
—
¡
$4
$2 Emissions from Fluorocarbon Destruction: This manual focuses on fluorocarbons which do not contain chlorine (Cl). However, most facilities destroy chlorofluorocarbons such as CFC-12 (CCl 2F2). Therefore, hydrogen chloride (HCl) is also included in the emissions from fluorocarbon destruction. $3 Emissions Entailed by Management: Although, ideally, these emissions should be zero, there exist some, however small in amount. Thus, these emissions are added to this management indexes. $4 Management indexes for carbon dioxide (CO2) are excluded from this manual.
None
Management items
Drainage (see P.47)
Hydrogen chloride (HCl)
Gas (see P.40) ¡
Emissions
-1
$1 Space velocity [h-1] = gas volume disposed per hour [L/h] ÷ fill of catalyst [L]
31
32
Schematic Diagrams of Typical Destruction Facilities ¡ TiO2–series catalytic reactor
[Resource] Hitachi, Ltd., Material concerning the collecting and the destruction system about fluorocarbon
¡ AlPO4–series catalytic reactor
[Resource] OITA University, Outline figure of destruction system of fluorocarbon
33
[Reference]
Empirical Values for Management Items in the Group of Catalytic Destruction (CFC-12 Destruction ) Examples of empirical values
Management items
Feed rate of fluorocarbon Percent of fluorocarbon fed
TiO2–series catalytic reactor
AlPO4–series catalytic reactor
1kg/h
5kg/h
Follow [feed ratio of water]
Follow [feed ratio of water]
3%
1%
75%
About 600%
Concentration of fluorocarbon Feed ratio of water
$5
Feed of air Temperature in main reactor Pressure in main reactor Space velocity in catalyst packed bed
3
3
5.5m /h
39m /h
About 440°C
500°C
Gauge pressure∗ 2 —0.03kgf/cm -1
1,500h
6
Around atmospheric pressure About 250h
-1
$5 Feed ratio of water to weight of fluorocarbon fed per hour $6 gauge pressure : pressure difference between the atmospheric pressure and the pressure in the reactor. Minus signs indicate a pressure lower than atmospheric pressure.
34
Reported Fluorocarbons Destroyed in the Facilities at DE > 99.99%
$ confirm whether the facility meets the “destruction conditions” as stated below when conducting the destruction.
Destruction conditions 1. Achieve a fluorocarbon destruction efficiency of 2. Ensure
more than 99.99% at the exit of the facility
the safety and stability of the destruction facilities by prevention of equipment
3. Take measures
to minimize the environmental emissions from the destruction of
fluorocarbons.
degradation, etc.
n [in case of CFC-12] Management Conditions
The following indexes for each item are measures to operate the equipment for fluorocarbon destruction. “Main reactor" means the part in which the destruction of fluorocarbons actually occurs. Management item Feed of fluorocarbons
index ¡ Fluorocarbon must be fed within the capacity of exhaust gas treatment equipment installed after the reactor for fluorocarbon destruction ¡ (Rate of feed must follow the index for [Feed of water])
Feed of fuels
—
Feed of water
Ratio of water feed to fluorocarbon weight, which is fed per unit of time, must be 100%
Feed of air
In the case of disposing mixed gas containing HCFC, HFC, the theoretical air ratio must be over 120% to incinerate carbon monoxide and hydrogen, which are generated with the destruction of fluorocarbon.
Temperature in main reactor
n Management at the Start-up Stage of the Operation
Because the operation conditions such as furnace temperature are unstable at the start-up, perform the fluorocarbon destruction after all conditions of equipment have become stable. n Management of Emissions (gas, drainage, residue)
Emissions from Fluorocarbon $1 Destruction
Emissions Entailed $2 by Management
More than 850°C at the reactor entrance More than 900°C at the reactor exit
Pressure in main reactor
Around atmospheric pressure
Residence time of gas in main reactor
More than 1.8 second
Oxygen concentration in main reactor
none
35
Drainage (see P.47)
Residue (see P.48)
Hydrogen chloride (HCl)
Gas (see P.40) ¡
—
—
Hydrogen fluoride (HF)
¡
¡
—
(Carbon dioxide(CO2))
¡
—
—
Chlorine (Cl2 )
¡
—
—
Dioxin (DXN)
¡
¡
—
Nitrogen oxide (NO X)
¡
—
—
Particulate matter
¡
—
—
Carbon monoxide (CO)
¡
—
—
Chlorobenzene (C6 H5Cl)
¡
¡
—
Chlorophenol (C6 H5ClO)
¡
¡
—
Waste
—
—
¡
Emissions
Others
$3
$1 Emissions from Fluorocarbon Destruction: This manual focuses on fluorocarbons which do not contain chlorine (Cl). However, most facilities destroy chlorofluorocarbons such as CFC-12 (CCl 2F2). Therefore, hydrogen chloride (HCl) is also included in the emissions from fluorocarbon destruction. $2 Emissions Entailed by Management: Although, ideally, these emissions should be zero, there exist some, however small in amount. Thus, these emissions are added to this management indexes. $3 Management indexes for carbon dioxide (CO2) are excluded from this manual.
36
Schematic Diagrams of Typical Destruction Facilities ¡ Superheated Vapor Reactor
[Resource] TADANO LTD. , outline figure of system for destruction of fluorocarbon
37
[Reference]
Empirical Values for Management Items in the Group of Other Systems (CFC-12 Destruction ) Examples of empirical values
Management items Superheated Vapor Reactor
Feed rate of fluorocarbon
10kg/h Follow [Feed ratio of water]
Percent of fluorocarbon fed Feed ratio of water
$4
Feed of air Temperature in main reactor Pressure in main reactor Residence time of gas in main reactor Oxygen concentration in main reactor
100% No feed if only CFC-12 is destroyed But in case of disposing mixed gas containing HFC or HCFC, 130∼300L/min of air is fed. > 850°C > 900°C Around atmospheric pressure 1.8 second
$4 Feed ratio of water to weight of fluorocarbon fed per hour
38
3.2.3 Management Indexes for Emissions from Installations due to Fluorocarbon Destruction It is necessary to manage emissions of the following substances caused by the fluorocarbon destruction in the installations. In the Groups of Incineration with Waste and Incineration in Manufacture Processes, some of the emissions can be governed by the standards specified by the Air Pollution Control Law, the Water Pollution Control Law, and other relevant laws/regulations. In such cases, the emission standards of the corresponding laws and regulations are adopted. However, in cases where there are no applicable laws, ordinances, and other regulations, the criteria or targets to be achieved are set for the facilities for fluorocarbon destruction with reference to the emission standards for similar facilities that are regulated by concerned laws and ordinances. If lower emission standards are set by ordinances of the local entity in which the facility is located, these ordinances take precedence. (1) Emissions (gas, drainage, and residue) Entailed by Management Classification Emissions from $1 Destruction
Fluorocarbon
Emissions Entailed by $2 Management
Others
Name of substances
Gas
Drainage
Residue
Hydrogen chloride (HCl)
¡
—
—
Hydrogen fluoride (HF)
¡
¡
—
Carbon dioxide (CO2)
¡
—
—
Chlorine (Cl2 )
¡
—
—
Dioxins (DXN)
¡
¡
—
Nitrogen oxides (NOX)
¡
—
—
Particulate matter
¡
—
—
Carbon monoxide (CO)
¡
—
—
Chlorobenzene (C6 H5Cl)
¡
¡
—
Chlorophenol (C6 H5ClO)
¡
¡
—
Residue
—
—
¡
$1 Emissions from Fluorocarbon Destruction: This manual focuses on the fluorocarbons which does not contain chlorine (Cl), However, most facilities destroy the chlorofluorocarbon such as CFC-12 (CCl2F2). Therefore, hydrogen chloride (HCl) is also included in the emissions from fluorocarbons. $2 Emissions Entailed by Management: Although, ideally, these emissions should be zero, there exist some, however small in amount..
The Air Pollution Control Law and other laws specify the standards for atmospheric emissions of HCI, HF, -
DXN, NOX, and CO. The Water Pollution Control Law specifies the standards for effluents of pH, F (fluorine) ion, biological oxygen demand (BOD), chemical oxygen demand (COD), and suspended solids (SS) in drainage. The Law Concerning Special Measures against Dioxins has recently specified emission standards for dioxins at some incineration sources. The disposal of solid residue produced from fluorocarbon destruction is regulated by the Waste Disposal and Public Cleansing Law.
39
(2) Frequency of Measurements of Pollutants The frequency of measurement is regulated for some pollutants by related laws and ordinances. The pollutants that are not regulated by laws and ordinances are must be measured at least once a year. (3) Emission Standards for Each Pollutant (3-1) Exhaust Gases
! Hydrogen chloride (HCI) The first clause of Article 17 of the Air Pollution Control Law specially regulates hydrogen chloride (HCl), and emission standards for two kinds of facilities. HCl is also regulated by ordinances in local entities such as Kanagawa prefecture. In the Group of Incineration with Waste, it is required to adopt the emission standards contained in the Air Pollution Control Law and ordinances. The other groups are required to set original emission criteria or targets with reference to the emission standards recommended by UNEP and the emission standards for the specific facilities, such as those for chlorine quenching in the chlorinated ethylene manufacturing governed by the Air Pollution Control Law. If lower emission standards are set by ordinances of the local entity, in which the facility is located, these ordinances take precedence.
!
Emission Standards for Compliance by the Group of Incineration with Waste
Substance
HCI
Related laws and regulations Standards Recommended by UNEP The Air Pollution Control Law Example of Local Entity $4 Kanagawa Prefecture
Related facilities Facilities for Destruction of Fluorocarbon Waste Incinerator
$3
Waste Incinerator Facilities other than Waste Incinerator
(as of February 2000) Emission standards 100 mg/Nm
3
700 mg/Nm
3
700 mg/Nm
3
8 mg/Nm
3
$3 Waste Incinerator: Ii the 13th clause of the first schedule form of the Law $4 ”Enforcement Regulations of the Ordinance Concerning Life Environment Preservation by Kanagawa Prefecture (amended of September 24, 1999),” the 6th schedule form
" Emission Standards for Compliance or Reference by the Groups Other Than the Group of Incineration with Waste (as of February 2000) Related laws and Emission Substance Related facilities regulations standards Standards Recommended Facilities for Destruction of 3 100 mg/Nm by UNEP Fluorocarbon HCI Facilities for Chlorine Quenching The Air Pollution Control 3 for Chlorinated Ethylene 80 mg/Nm Law $5 Manufacturing $5 : The facilities designed in the 16th~19th clause of the first schedule form of the Law: facility for chllorine quenching for chlorinated ethylene manufacturing, welding bath used for production of ferric chloride, reactor used for production of activated carbon, facility for chlorine reaction used for production of chemical products, facility for hydrogen chloride reaction, and facility of hydrogen chloride absorption (partially amended in November 1990)
40
‚Chlorine (Cl2) For chlorine (Cl2), all groups must set original emission criteria or targets with reference to the following emission standards. If lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. ¨ Emission Standards for Compliance or Reference by All Groups Substance
Chlorine
Related laws and regulations
(as of February, 2000)
Related facilities
Emission standards
The Air Pollution Control Law
Facilities for Chlorine Quenching for Chlorinated Ethylene $5 Manufacturing
Example of Local Entity (1) $6 Kanagawa Prefecture
Plants or Business Establishments
3.17 mg/Nm
Example of Local Entity (2) $7 Metropolis of Tokyo
Reaction Facilities and Absorption Facilities used for Production of $8 Chemical Products
10 mg/Nm
30 mg/Nm
3
3
3
$5 The facilities designed in the 16~19th clause of the first schedule form of the Law: facility for quenching chlorine for chlorinated ethylene manufacturing, welding bath used for production of ferric chloride, reactor used for production of activated carbon, facility for reaction of chlorine used for production of chemical products, facility for hydrogen chloride reaction, and facility of hydrogen chloride absorption (partially amended in November 1990) $6 ”Enforcement Regulations of the Ordinance Concerning Life Environment Preservation by Kanagawa Prefecture (amended of September 24, 1999),” the 6th schedule form $7 ”Pollution Control Ordinance by Metropolis of Tokyo,” the 4th schedule form (harmful gas ) $8 Welding bath used for ferric chloride production and reaction facility and absorption facility used for chemical products manufacture
41
ƒHydrogen fluoride (HF) For hydrogen fluoride (HF), all groups must set original emission criteria or targets with reference to the following emission standards. If lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. ¨ Emission Standards for Compliance or Reference by All Groups Substance
Related laws and regulations Standards Recommended by UNEP
(as of February, 2000)
Related facilities Facilities for Destruction of fluorocarbon Reaction Facilities Used for Production of Glass or Glass $5 Products $9
The Air Pollution Control Law
Electrolysis Furnace
Electric Furnace, etc.
HF
Example of Local Entity (2) $7 the Metropolis of Tokyo
5 mg/Nm
3
10 mg/Nm
3
1.0 mg/Nm
3
$10
15 mg/Nm
3
$11
20 mg/Nm
3
Open Hearth Furnace Example of Local Entity (1) $6 Kanagawa Prefecture
Emission standards
Plants or Business Establishment [emission standards as for HF] Calcination Furnace Used for Production of Glass or Glass $12 Products
2.5 mg/Nm 10 mg/Nm
3
3
$5 In the first schedule form of the Ordinance, the facilities used for production of glass or glass products in the 9th clause, reaction facility, facility for condensation and melting furnace, in the 21st clause, and the facilities in the 22nd, 23rd clauses $6 “Enforcement Regulations of the Ordinance Concerning Life Environment Preservation by Kanagawa Prefecture (amended of September 24, 1999),” the 6th schedule form $7 ”Pollution Control Ordinance by Metropolis of Tokyo,” the 4th schedule form (harmful gas) $9 Electrolysis furnace in the 20th clause of the first schedule form of the Law $10 Electric furnace for reaction facilities and melting furnace in 21st clause the first schedule form of the Law $11 an Open hearth furnace of calcination furnace and melting furnace in the 21st clause of the first schedule form of the Law (the 3rd schedule form of enforcement regulation, amended in June 1977) $12 Calcination furnace and melting furnace used for production of glass or glass products , and other facilities which generate fluorine or fluorine compound, other than the soot facilities
42
„ Dioxins (DXN) As of February 2000, dioxins are regulated as the specific substances under the 9th clause of the supplementary regulations of the Air Pollution Control Law, and criteria concerning emissions restriction have been set. In addition, criteria concerning operation and maintenance have been set by the enforcement order and regulation, which are based on the Waste Disposal and Public Cleansing Law. (However, based on the arrangement of the related laws involved in the enforcement of the Law Concerning Special Measures against Dioxins, partial amendments were made in the 9th clause of the supplementary regulations of the Air Pollution Control Law. In the amendments, dioxins were taken off from the list of specific substances that are controlled under the criteria of emission restrictions, and the facilities concerning dioxins were also taken off from list of the specific facilities (to be enforced on January 15, 2001).) As for the Group of Incineration with Waste, in Article 8 of the Law Concerning Special Measures against Dioxins, which was enforced on January 15, 2000, contains emission standards for exhaust gases and drainage. The other groups are required to refer to the following emission standards in setting original emission criteria or targets. If lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. n Emission Standards for Compliance by the Group of Incineration with Waste
Substance
Dioxins
Related laws and regulations The Law Concerning Special Measures against Dioxins
Related facilities and disposal capacity of combustion chamber
Waste $13
Incinerator
(as of Feb. 2000) Emission standards as new furnace
> 4 t/h
0.1ng-TEQ/Nm
3
2∼4 t/h
1 ng-TEQ/Nm
3
< 2 t/h
5 ng-TEQ/Nm
3
$13 Waste incinerator in No.5 of the first schedule form of the Law
¨ Emission Standards for Compliance or Reference by the Groups Other Than the Group of Incineration with Waste (as of February, 2000) Substance Dioxins
Related laws and regulations The Law concerning Special Measures against Dioxins
Related facilities and disposal capacity of combustion chamber
Emission standards (for new furnaces)
$14
0.5 ng-TEQ/Nm
Electric Furnace
$14 Electric furnace in No.2 of the first schedule form of the Law
43
3
…Particulate matter As for particulate matter, in the Group of Incineration with Waste and the Group of Incineration in Manufacturing Processes, the emission standards are set by Article 4 of the enforcement regulation of the Air Pollution Control Law. Other groups are must set the original emission criteria or targets with reference to the following emission standards. If lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. n Emission Standards for Compliance by the Group of Incineration with Waste
Substance
Particulate matter
Related facilities and disposal capacity of combustion chamber
Related laws and regulations
The Air Pollution Control Law
Waste Incinerator $16
(as of Feb. 2000) Emission standards Normal
Special
$15
> 4 t/h
0.04 g/Nm
3
2∼4 t/h
0.08 g/Nm
3
< 2 t/h
0.15 g/Nm
3
n Emission Standards for Compliance by the Group of Incineration in Manufacturing Processes
(as of Feb. 2000)
Substance
Particulate matter
Related laws and regulations
Emission standards
Related facilities
The Air Pollution Control Law
Lime calcination furnace
Normal
Undersurface 17 furnace Other than undersurface 18 furnace
Cement production facility
19
Special
15
0.40g/Nm
3
0.20g/Nm
3
0.30g/Nm
3
0.15g/Nm
3
0.10g/Nm
3
0.05g/Nm
3
¨ Emission Standards for Compliance or Reference by the Groups Other Than the Above-Mentioned (as of Feb.2000) Substance
Related laws and regulations
Emission standards
Related facilities and Amount of exhaust gas
Normal 3
Particulate matter
The Air Pollution Control Law
200,000 Nm /h and over 40,000 ∼ 200,000 3 Nm /h 10,000 ∼ 40,000 3 Nm /h Under 3 10,000Nm /h
exclusive incinerator of oil fuel and the boiler incinerating both gas and liquid
Special
15
0.05g/Nm
3
0.04g/Nm
3
0.15g/Nm
3
0.05g/Nm
3
0.25g/Nm
3
0.15g/Nm
3
0.30g/Nm
3
0.15g/Nm
3
$15 Area in which many facilities, which discharging soot related particulate matter and specific harmful substance are established $16 As for waste incinerators in the 13th clause of the first schedule form of the Law (amended of November, 1990) $17 Undersurface types of calcination furnace in 9th clause of the first schedule form of the Law (amended in November 1990). $18 Facilities other than the above-mentioned ($1) of calcination furance in the 9th clause of the first schedule form of the Law (amended in November 1990) $19 Facilities used for cement production in the category of calcination furance in the 9th clause of the first schedule form (amended in November 1990)
44
†Nitrogen Oxides (NO X) The emission standards for Nitrogen Oxides (NO X), in the Group of Incineration with Waste and the Group of Incineration in Manufacturing Processes, are specified in the 2nd clause of Article 5 of the enforcement regulation of the Air Pollution Control Law. The other groups must set the original criteria or targets with reference to the following emission standards. If lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. n Emission Standards Required to be Complied by the Group of Incineration with Waste (as of Feb. 2000)
Related laws and regulations
Substance
Nitrogen Oxides (NO X)
The Air Pollution $20 Control Law
Related facilities
Waste Incinerator $21
Emission standards
Suspension Rotary Firing-type
450 ppm
(continuous $22 incinerator)
Other than the $23 above-mentioned
250 ppm
n Emission Standards for Compliance by the Group of Incineration in Manufacturing Processes
(as of Feb. 2000) Substance
Related laws and regulations
Related facilities and amount of exhaust gas Lime Calcination Furnace (only the gas incineration rotary $24 kiln)
Emission standards Facilities whose construction began on or after June 18, 1977
250 ppm
Facilities whose construction began on or before June 17, 1977
480 ppm
3
Nitrogen Oxides (NO X)
The Air Pollution Control 20 Law
Exhaust gas: 100,000m /h and over (other than the facilities covered below) 3
Cement Calcination $25 Furnace
Exhaust gas: under 100,000m /h (other than the facilities covered below) Facilities whose construction began from December 10, 1975 to June 17, 1977. (Only facilities whose exhaust gas is 3 more than 100,000m /h) Facilities whose construction began on or before June 17, 1977 (other than wet systems)
45
250 ppm 350 ppm 250 ppm 480 ppm
¨ Emission Standards for Compliance or Reference by the Groups Other Than the Above-Mentioned (as of Feb.2000) Substance
Nitrogen Oxides(NO X)
Related laws and regulations
The Air Pollution $20 Control Law
Related facilities and Amount of exhaust gas exclusive incinerator of oil fuel and the boiler incinerating both gas and liquid
Emission standards 3
> 200,000 Nm /h
130∼150 ppm
40,000 ∼ 200,000 3 Nm /h
150 ppm
10,000 ∼ 40,000 3 Nm /h
150 ppm
3
< 10,000 Nm /h
180 ppm
$20 The 2nd clause of the 3rd schedule form in enforcement regulation (partially amended in March, 1996) $21 As waste incinerators in 13th clause of the first schedule form of the Law (partially amended in November, 1990) $22 For Suspension rotary firing type (continuous incinerator only), in the category of waste Incinerator in the 13th clause of the first schedule form of the Law (partially amended in November, 1990) $23 The facilities of $22, and waste incinerators which incinerate the waste discharged from a process in which nitrocompound, amino-compounds or cyano-compounds or their derivatives are produced or used, or a process in which drainage is disposed using ammonia, in the category of waste incinerator in the 9th clause of the first schedule form of the Law (partially amended in November, 1990) (only facilities whose amount of exhaust gas is more than 40,000 m 3, if they are not continuous incinerators) $24 Lime calcination furnace (only the rotary kiln type which incinerate gas , in the category of calcination furnace in the 9th clause of the first schedule form of the Law (partially amended in November, 1990) $25 The facilities used for cement production of calcination furnace in the 9th clause of the first schedule form of the Law (partially amended in November, 1990)
‡ Carbon monoxide (CO) For the Carbon Monoxide, the Ministry of Health and Welfare notifi ed the standards for operation and maintenance in the Guideline for Prevention of Dioxins Generation as the following table. In all groups, however, if lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. ¨ Emission Standards for Compliance or Reference by All Groups Substance
Related laws and regulations
Carbon Monoxide
standards for operation and maintenance contained in the Guideline for Prevention of Dioxins Generation by the Ministry of Health and Welfare
46
(as of Feb. 2000) Standards for operation and maintenance 100ppm
(3-2) Drainage The Water Pollution Control Law (the 2nd schedule form of enforcement order partially amended in August 1993) specifies the emission standards for Content of fluorine (F), pH (hydrogen ion concentration), BOD (biochemical oxygen demand), COD (chemical oxygen demand), and SS (suspended solids) for drainage. These standards apply to the effluents from the destruction of fluorocarbons. There are cases where more stringent effluent standards are set by ordinance of the local authority, based on Article 3 of the Water Pollution Control Law. The emission standards fot dioxins at some sources were set by the Law Concerning Special Measures for Dioxins enforced on Jan 15, 2000. In all groups, if lower emission standards are set by ordinances of the local entity, in which the facilities are located, these ordinances take precedence. n National Standards
Substance
(as of February, 2000) Related laws and regulations
Content of fluorine (F)
pH (hydrogen ion concentration)
Emission standards
Applying to drainage discharged by plants or business establishments where the average daily volume of 3. drainage is more than 50 m
Under 15 mg/L as contents of fluorine ion
The drainage discharged into public areas other than the sea The Water Pollution Control Law
BOD COD SS Dioxins (DXN)
Related area
The Law Concerning Special Measures against Dioxins
The drainage discharged into the sea Average daily volume of drainage is 120mg/l or less Average daily volume of drainage is 120mg/l or less Average daily volume of drainage is 120mg/l or less The facilities listed from No.1 to No.7 of the 2nd schedule form of the Law (for new facilities)
n Example of Standards by Local Authority (Kanagawa Prefecture)
Substance Content of fluorine (F) BOD COD SS
Related laws and regulations
More than 5.8 and under 8.6 as hydrogen ion concentration More than 5.0 and under 9.0 as hydrogen ion concentration 160 mg/L or less 160 mg/L or less 200 mg/L or less 10 pg/L or less
(as of February, 2000)
Related area
Emission standards
The drainage discharged by
0.8 mg/L or less (as HF) 15 mg/L or less (under 10 mg) 15 mg/L or less (On or under 10 mg) 35 mg/L or less (20 mg or less)
More stringent effluent general business establishments standards were set by the into water other than lakes for Ordinance of Kanagawa conservation of water quality $1 (for new facilities ) Prefecture based on the 3rd clause of Article 3 of the Water Pollution The values in ( ) on the right indicate the standards for average Control Law daily volume.
$1 "New facilities" means the specific business establishments those are established after November 11, 1971. If they are the specific establishments newly regulated by amendment of Article 1 of the enforcement order of the Water Pollution Control Law, "November 11, 1971" is replaced by the day when the specific establishments were established. Here, the facilities which were under construction before November 11, 1971, are not included in " specific establishments "
47
(3-3) Residue (emission as solid) l Disposal of Particulate Matter, Cinders and Sludge In the Group of Incineration with Waste and the Group of Incineration in Manufacturing Processes, particulate matter collected with dust collector equipment and cinders as ash remaining in incinerators are the object of disposal as waste. In other groups, in addition to particulate matter collected with dust collector equipment, sludge emitted from exhaust gas treatment facilities is also the object of disposal. The particulate matter collected with dust collector equipment is regulated as the “Special Controlled Municipal Waste” by the Waste Disposal and Public Cleansing Law. Cinders and sludge are also regulated as “Industrial Waste” and must be disposed of in the controlled landfill sites. l Recycling of Calcium Fluoride Calcium fluoride is generated as solid discharge in the destruction of fluorocarbons. As for the disposal of calcium fluoride, calcium fluoride should be purified and reused as a resources, However, most of it is disposed of as waste because of mixture with ash and sludge. For the futures, it should be recycled into raw materials for products.
48
Appendix B List of Attendees
3/11/01
Page 1 of 5
Geneva ODS Workshop Participants List
Title Co-chair, Aerosols Technical Options Committee Senior Policy Officer Waste Management Policy Director Ozone Protection Operations Manger
Undersecretary Office of the Prime Minister Environment Officer (Chemicals & Ozone) Expert, Ozone Layer Protection
Dr.
Melanie
Miller
Mr.
Peter
Horrocks
Mr. Ms.
Ronald Terezhina Bassani
Marijnissen Campos
Ms. Mr.
Lidia Gabriel
Assenova Hakizimana
Mr. Mr. Mr. Mr.
Vic Alain Alex Philippe
Buxton Carriere Cavadias Chemouny
Mr.
Abe
Finkelstein
Mr. Mr.
Ian Tony
Glew Hetherington
Mr. Mr. Mr. Mr. Mr.
John Ian Dan Adrian Don
Hilborn McGregor Nolan Steenkamer Thomson
Ms.
Anna-Marie
Muise
Dr.
First Name Helen
Last Name Tope
Mr. Mr.
Milton Garry
Catelin Cranny
Mr. Ms.
Robert Tamara
Hawkes Curll
Dr.
Tamas
Dr.
Geneva Wshop 001010.xls
Methyl Bromide Technical Options Committee Head of Sector Directorate General ENV/D.3 First Secretary, Environment Division Department of Special Affairs Ministry of Foreign Relations Senior Expert Coordonnateur du Bureau Ozone
351 St. Joseph Blvd., 18th Floor 2233 Argentia Road, Suite 308 351 St. Joseph Blvd., 12th Floor 351 St. Joseph Blvd., 18th Floor
Hull Mississauga Hull Hull
Quebec Ontario Quebec Quebec
Canada Canada Canada Canada
Chief, Clean Processes and Technologies Process Engineer Deputy Chief Officer
Environment Canada
351 St. Joseph Blvd., 19th Floor
Hull
Quebec
Bovar Waste Management Multilateral Fund Secretariat
Swan Hills, Montreal
Manager, Stratospheric Ozone President
Environment Canada Fielding Chemical Technologies Inc. Cantox Environmental Inc. Environment Canada Manitoba Ozone Protection Industry Association (MOPIA) Environment Canada
Mail Bag 180 Montreal Trust Bldg. 1800 McGill College Avenue, 27 Floor 351 St. Joseph Blvd., 11th Floor 3549 Mavis Road P.O. Box 846 351 St. Joseph Blvd., 19th Floor 2141 B Henderson Highway 351 St. Joseph Blvd., 11th Floor
Engineering and Metallurgical Industries P.O. Box 300 Branch United Nations Industrial Development Organization Federal Ministry for the Agriculture, Forestry, Stubenbastei 5 Environment and Water Management UNIDO Vienna International Centre P.O. Box 300, A-1400 Federal Ministry for the Agriculture, Forestry, Stebenbastei 5 Environment and Water Management Environment Science & Technology P.O. Box cb-19048 Commissioin Ministry of Environment, Energy & Natural SirFrank Walcott Building, 4th Floor Resources Culloden Road Commission Européenne Boulevard du Triomphe, 174 Direction-Générale Environnement D3, TRMF 1/72 Av. Etang Decellier 19
Ministry of Environment and Water Ministere de l'Amenagement du Territoire et de l'Environnement Director, Technology & Industry Branch Environment Canada Scientist Cantox Environmental Inc. A/Head, Ozone Protection Program Environment Canada International Technology Transfer Office Environment Canada
Organization Manitoba Ozone Protection Industry Association (MOPIA) Friends of the Earth Environmental Division Ministry of Foreign Affairs State Environmental Protection Administration State Environmental Protection Administration Ministry of Environment
Past President
Ms. Mr.
Beatrice Javier E.
Olivastri Matta
Chief Executive Officer Second Secretary
Mr.
Yi
Liu
Ms.
Qing
Wang
Mr.
Marco
Pinzon
Mr.
Alfonso Liao
Lee
Deputy Director General Foreign Economic Cooperation Office Project Officer Foreign Economic Cooperation Office National Coordinator Ozone Unit Ozone Technical Unit National Corodinator
Dr.
L. Nelson
Dr.
Fabio
Mr.
Hong Song
Comisión Gubernamental del Ozono Ministerio del Ambiente y Energia Espinosa Peña Director de la Oficina Técnica del Ozono Ministerio de Ciencia Tecnologia y Medio Ambiente Fajardo-Moros Vice-Minister Ministerio de Ciencia Tecnologia y Medio Ambiente Bok Deputy Chief Engineer Vinalon Factory
Mr.
Yon Chan
Ju
Senior Officer Department of External Cooperation
Mr.
Rafael
Veloz
Mr.
Francisco Enrique
Guevara
Ministry of Chemical Industry
Mrs. Else Maarit
Peuranen
Ms.
Eliisa
Irpola
Coordinador, Comité Gubernamental de Ozono Subsecretaria de Recursos Naturales Secretaria de Extado de Agricultura Coordinator Ministerio de Medio Ambiente y Recursos Oficina de Protectión del Ozono Naturales Convenios Ambentales Multilaterales Senior Advisor Environment Protection Department Ministry of the Environment Senior Advisor, Chemicals Division Finnish Environment Institute
Mr. Mr.
Nick Geoffrey
Campbell Tierney
Environment Manager Network Manager
Mrs. Laurence
Musset
Ms.
Claude
Putavy
Dr.
Wolfgang R.
Hartmann
Fluorinated Products United Nations Environment Programme Energy and Ozon Action Unit Division of Technology, Industry and Chef de Bureau DPPR/SDPD/BSPC Ministère de Bureau des Substances et Préparations l'Aménagement du Territoire et de Chimiques l'Environnement DPPR/SDPD/BSPC Ministère de Exotoxicologue Bureau des Substances et Préparations l'Aménagement du Territoire et de l'Environnement Chimiques Engineering Consultant SRL Plasma Ltd
Dr. Dr.
Siegismut Heinrich W.
Hug Kraus
President Deputy Director General
Dr. Mr. Mr. Mrs.
Stefanie Dirk Setphan Elpida
Pfahl Legatis Sicars Politi
Ecologic GTZ Proklima
Mr.
Francisco J.
Argeñal
Geneva Wshop 001010.xls
International Relations and European Union Affairs Coordinator de la Unidad Técnica del Ozono
Province/ State Country Manitoba Canada
Postal/ Zip Code Telephone # R2G 1P8 (204) 474-4806
Hug-Engineering Protection oof the Ozone Layer Federal Ministry for the Environment GTZ Proklima
Forstmeisterstrasse 3
3/11/01
Mr. Mr.
First Name Laszlo Atul
Last Name Dobo Bagai
Mr.
Winston J.
Samuel
Mr.
Viswanath
Chiravuri
Director
Mr.
Herru
Manager of Laboratory
Mr.
Rajiman
Soetomo Prawoto Wilman
Mr.
Antonio
Lumicisi
Ms.
Federica
Fricano
Dr.
Koichi
Mizuno
Mr.
Yuichi
Fujimoto
Mr.
Haruhiko
Kono
Director, Ozone Layer Protection Office
Mr.
Akira
Okawa
Deputy Secretary General
Mr.
Shizuko
OTA
Deputy Director
Mr.
Ghazi Faleh
Odat
Deputy Director General
Dr.
Madhava
Sarma
Mr.
Gerald
Mutisya
Executive Secretary Ozone Secretariat Programme Officer / IT
Mr.
David
Okioga
Ms.
Jayne
Toroitich
Dr. Mr. Mr.
Saud A. Aziz Mazen K. Yahyah
Al-Rashied Hussein Pathel
Mr.
Francesco
Castronovo
Mr.
Jorge
Corona
Mr. Mr.
Sergio Jacinto
Lozano Martinez
Dr.
Klaus Peter
Störmer
Mrs. Petra Karin
Page 3 of 5
Geneva ODS Workshop Participants List
Laaser
Geneva Wshop 001010.xls
Organization Hungarian Ministry of Environment Ozone Cell Ministry of Environment and Forests Refrigerant Gas Manufacturer's Association (REGMA) Ministry of Envrionment and Forests India Habitat Centre Garuda Maintenance Facility National Halon Bank Garuda Maintenace Facility National Halon Bank Ministry of the Environment
Dir. of Quality Contraol / Halon Bank Project Coordinator Directorate General for Global Atmosphere, Air and Noise Pollution International Activities Ministry of the Environment Director General for Global Atmosphere, Air, Noise Pollution and Industrial Risk
Soekarno-Hatta Airport
Director, Environmental Assessment Ministry of International Trade and Industry Department, National Institute for Resources and Environment, Agency of Industrial Science and Technology Senior Expert Member Japan Industrial Conference for Ozone Layer Protection
16-3 Onogawa, Tsukuba Ibaraki 305
Ozone Secretariat, UNEP
National Ozone Unit Ministry of Environment and Natural Desk Officer Ozone Matters Kenya Mission to UNEP Ministry of Foreign Affairs and International Cooperation Director Environment Public Authority Noise & Air Pollution Monitoring Dept. State of Kuwait Project Manager - Ozone Office Ministry of Envrironment Environment Officer Ministry of Environment Urban and Rural Development Coordinador de la Unidad de Proteccion Instituto Nacional de Ecologia al Ozono Secretaria de Medio Ambiente Co-chair, Solvent Technical Options CANACINTRA Environmental Commission Committee General Manager, Chemical Division Quinobasicos S.A. de C.V. Asesor Presidencia Association Comité Regional de Sanidad Vegetal Costa Agricultores Sur Head Proklima International GTZ 4454 GTZ Proklima Executive Assistant GTZ Proklima
Postal/ Zip Code
Fax # 36-1-204-3056 91-11-436-1712
City 1011 Budapest New Delhi 110003 New Delhi 110067 New Delhi 110003 19110 Jakarta
Basic Industries Bureau Ministry of International Trade and Industry Japan Industrial Conference for Ozone Layer Protection Wide Area Atmospheric Protection Office Air Quality Bureau Environment Agency General Corporation for Environmental Protection United Nations Environment Programme
Province/ State
Telephone # 36-1-457-3565 91-11-464-2176
Mailing Address Fo Utca 44 -50 Core 4B, India Habitat Centre Lodhi Road A-16, Aruna Asaf Ali Marg Qutub Institutional Area Core IV B Lodhi Road Soekarno-Hatta Airport
P.O. Box 24395 Antelias P.O. Box 10-7091 2nd Floor Ken Lee Tower, Barracks Street Av. Revolucion No. 1425, Nivel 30 Col. Tlacopac Cto. Misioneros G-8, Dep. 501, cd Satelite Ave. Ruiz Cortines No. 2333 Poniente Baja California Norte
National Ozone Office Department of Pollution Control and Environmental Health Directora de Asuntos Normativos y Jefa Ministerio de Industria, Turismo, Integración de la Oficina Técnica del Ozono y Negociaciones Comerciales Director's Plenipotentiary on Ozone Institute of Industrial Chemistry Layer Protection Head of Ozone Protection Unit Senior Advisor General Directorate of Environment-Minstry of Environment Portugal Senior Advisor General Directorate of Environment Ministry of Environment Assistant Manager Korea Specialty Chemical Industry Fund Administration Department Association Managing Director Korea Specialty Chemical Industry Association Deputy General Director Centre for Preparation and Implementation Executive Director of ODS Production of International Projects on Technical and Consumption Phase-Out Projects Assistance Deputy Director Ministry of the Environment Office of Global Environmental Issues Head of Air Protection Group Ministry of the Environment Air Protection Department B.Sc. Chemical Engineer Nature Protection Authority Swedish Environmental Protection Agency
Senior Administrative Officer, Section for Chemicals Control Co-chair, Halons Technical Options Committee Senior Scientific Officer Office Fédéral de l'Environnement, des Forêts et du Paysage Third Secretary CIJ, Environment, Météorologie et Union interparlementaire
Title Directorate General for Environmental Protection Directora Control Ambiental/Ozone Office Direccion General Calidad Ambiental Chef de Service de Lutte Contre les Pollutions et Nuisances Deputy Director Pollution Control and Environmental Health Department Principal Environmental Scientist
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John Y.
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A-2.0Description of emerging technologies ............................................................................................................ 54 A-2.1 INCINERATION TECHNOLOGIES ................................................................................................................. 54 A-2.1.1 Waste Gasification .............................................................................................................................. 54 A-2.1.2 Gas Injection Oxidation/Hydrolysis.................................................................................................... 54 A-2.2 PLASMA TECHNOLOGIES ........................................................................................................................... 55 A-2.2.1 Plasma Conversion of CFCs into Harmless Polymer Using Ethylene or Ethane as Co-monomer .... 55 A-2.2.2 Destruction of ODS in Dilute Exhaust Stream Using Energetic Electron Induced Plasma - Adsorbent Filter Hybrid System.......................................................................................................................................... 55 A-2.2.3 High Voltage Gliding Arc Plasma Discharge Reactor for CFC Destruction ..................................... 55 A-2.2.4 Freon 113 Destruction in Air Under the Effect of Nanosecond Corona and Microwave Discharge . 55 A-2.3 CHEMICAL DESTRUCTION TECHNOLOGIES ................................................................................................ 56 A-2.3.1 Chemical Reduction of ODS Using Metallic Sodium on a Solid Substrate ........................................ 56 A-2.3.2 Chemical-Thermal Destruction of Halogenated Hydrocarbon with Calcium Silicate or Oxide ........ 56 A-2.3.3 Mineralization of CFCs with Sodium Oxalate .................................................................................... 56 A-2.3.4 Aerosol Mineralisation of CFCs by Sodium Vapour Reduction ......................................................... 56 A-2.3.5 Molten Metal Technology (MMT) ....................................................................................................... 57 A-2.3.6 Pressurized Coal Iron Gasification (P-CIG) ...................................................................................... 57 A-2.3.7 Dormier Incineration Process in Steel Smelter................................................................................... 57 A-2.3.8 Destruction of CFCs During Chemchar Gasification......................................................................... 57 A-2.4 PHOTOCHEMICAL TECHNOLOGIES ............................................................................................................. 57 A-2.4.1 UV Laser Photolysis for the Destruction or Transformation of Halon 1301 into CF3I ...................... 57 A-2.4.2 Photochemical Degradation of Organic Wastes with a TiO2 Catalyst ............................................... 58 A-2.4.3 UV Laser Controlled Decomposition of CFCs.................................................................................... 58 A-2.5 CATALYTIC TECHNOLOGIES ...................................................................................................................... 58 A-2.5.1 Dry Distillation Disposal System for Waste Foam and Refrigerators ................................................ 58 A-2.5.2 Halohydrocarbon Destruction Catalyst .............................................................................................. 58 A-2.5.3 Catalytic Oxidation of CFCs with a Pt/ZrO2-PO4 Based Catalyst...................................................... 58 A-2.5.4 CFC Oxidation in a Catalyst-Sorbents Packed Bed ........................................................................... 59 A-2.5.5 Transformation of CFCs to HFCs Using Dehalogenation Catalysts in a H2 Environment ................ 59 A-2.6 OTHER TECHNOLOGIES ............................................................................................................................. 59 A-2.6.1 Use of Waste CFC in an Antimony Process ........................................................................................ 59 A-2.6.2 CFC Destruction into Biocatalytic System [Ref 20, 29c] ................................................................... 59 A-2.6.3 Supercritical Water Oxidation (SCWO).............................................................................................. 59 A-2.6.4 Electrohalogenation of CFC-113 on Pb/Pd Cathodes Combined with H2 Diffusion Anode .............. 60 APPENDIX B: EXPERT REVIEW COMMITTEE............................................................................................. 61 APPENDIX C: STAKEHOLDER WORKING GROUP ...................................................................................... 63 APPENDIX D: SUMMARY OF LITERATURE SEARCH ................................................................................ 71 Keywords Used in Search Strategy ......................................................................................................................... 71 Overall Search Strategy ........................................................................................................................................... 72 APPENDIX E: STAKEHOLDER WORKING GROUP MEETING SUMMARY ........................................... 73 Discussion .................................................................................................................................................................. 74 Path Forward ............................................................................................................................................................ 76
EXECUTIVE SUMMARY In September 1999, CANTOX ENVIRONMENTAL INC., (CEI) in partnership with the Pioneer Technology Centre, (PTC) was contracted by Environment Canada to develop a Guidance Document for the disposal of surplus CFCs and halons in Canada, in consultation with appropriate experts and stakeholders, as described in the revised CCME National Action Plan. The objective of this Guidance Document is to provide Canadian stakeholders with up-to-date information on technologies available for the disposal of surplus quantities of ODS. This Guidance Document aims to provide clear guidance on the latest mechanisms, technologies, and procedures for ensuring the safe and effective destruction, transformation, and/or permanent stabilization of ODS stockpiles. In all, 42 ODS disposal technologies were identified and described, then evaluated on the basis of mandatory environmental criteria and commercial availability. As a result, the 42 identified technologies were categorized into two main groups: 1. Commercially available and environmentally acceptable technologies. 2. Emerging technologies. ODS disposal technologies were included in the first group only if they met mandatory environmental criteria. The first group of technologies were then further evaluated in two separate ways, based on two different sets of criteria:
environmental and technical criteria; and commercial and economic criteria.
The environmental/technical evaluation is intended to provide guidance as to which technologies are considered to provide the best technical solutions to the disposal of ODS in terms of avoiding adverse environmental and/or human health impacts. These issues include the prevention of the ultimate release of ODS and the depletion of the ozone layer, the prevention of the release of Global Warming Gases (GWGs, or “greenhouse gases”) that contribute to global warming, as well as avoiding the production and release of byproducts of destruction that may themselves have adverse health or environmental effects. The commercial/economic evaluation addresses different issues, and is meant to provide some guidance as to the current and future availability of technologies and facilities for the disposal of anticipated Canadian surpluses of ODS, as well as an assessment as to what the costs of destruction for the various identified technologies may be. Although a detailed and precise cost analysis for each technology was well beyond the scope of this project, some attempt was made to characterize the absolute and relative costs for the various technologies, based on reported information and upon the engineering expertise of the project team.
In addition to the identification and evaluation of ODS disposal technologies, the Guidance Document provides information regarding the handling of ODS surplus quantities, including applicable regulations relating to transportation, storage and reporting requirements. Finally, a number of valuable comments related to the implementation of an ODS disposal strategy in Canada were expressed by stakeholders during a Stakeholder Workshop held in Ottawa on March 9, 2000. Many of these remarks address potential barriers and disincentives to the implementation of such a program. A significant comment was made regarding handling procedures for surplus ODS. Stakeholders indicated that if ODS is considered as a hazardous waste, the required handling and manifesting procedures would create a significant barrier to the collection and destruction of surplus ODS in Canada. Unless some exemption mechanism is provided to allow stakeholders to store and ship ODS to collection facilities without having to satisfy requirements normally applicable to the handling of hazardous waste, a collection program may not work in practice. Another important conclusion that came out of the Stakeholder Workshop was that there may be a business opportunity to develop a multi-purpose waste disposal facility in Canada that could handle surplus ODS as well as other types of specialized wastes, and that Environment Canada would be interested in receiving such a proposal and potentially supporting its development. The comments offered during the Stakeholder Workshop are captured in detail in a meeting summary provided in Appendix E.
The Montreal Protocol and Ozone-Depleting Substances
The 1987 Montreal Protocol on Substances That Deplete the Ozone Layer (the “Montreal Protocol”) was originally signed by 24 countries including Canada in September 1987 and had been ratified by 169 countries as of July 1999. The Montreal Protocol resulted in a series of legally binding measures to control or eliminate the production and consumption of OzoneDepleting Substances (ODS) in various countries. The Montreal Protocol is a living treaty with built-in provisions for making changes on the basis of new scientific information and technological developments (UNEP 1997). The depletion of the ozone layer in the Earth’s stratosphere reduces the atmosphere’s ability to provide protection from UV radiation from the sun, which results in serious risks to human health, including increased risk of cancer and the weakening of immune system functions. Increased UV radiation due to ozone layer depletion has also been associated with adverse environmental impacts such as reduced vegetation production on land and reduced plankton production in oceans. The Montreal Protocol is widely regarded to be one of the most important and effective international environmental agreements ever signed. Since 1994, atmospheric concentrations of ODS have declined about 3%, largely due to declines in methyl chloroform concentrations. Emissions of most ODS have diminished substantially from peak levels in the late 1980s. Despite this progress, atmospheric concentrations of some ODS continue to increase. Continued releases contribute to existing atmospheric concentrations, which exhibit significant environmental persistence. Once concentrations of methyl chloroform stabilize over the next 10 to15 years, the rate of decrease in total atmospheric ODS is likely to diminish. The restrictions put into place following the Montreal Protocol have resulted in a growing surplus of unused CFCs and halons due to their replacement with more environmentally friendly substances. The surplus consists of unused ODS, ODS in use in older equipment, and ODS either recycled, reclaimed, or stockpiled after removal from such equipment. Surplus quantities of ODS are expected to continue to grow as a result of management initiatives related to the Montreal Protocol. In Canada, with the exception of mobile air conditioning sources, current uses of ODS based on stockpiled quantities have the potential to continue for many years. In several sectors, given the status quo, significant environmental releases of ODS from current uses are expected over the next ten to twenty years. It is generally assumed that all of the current inventory of ODS will eventually be emitted to the atmosphere unless some kind of management program involving destruction technologies is put into place (Environment Canada 1998). The above considerations highlight the importance of making progress in reducing or eliminating further ODS emissions. While restrictions on the production, importation, and consumption of ODS resulting from the Montreal Protocol are necessary steps for managing ODS currently in use or stockpiled, a critical challenge facing world governments lies in disposing of the growing
surplus of ODS in such a way as to avoid further atmospheric emissions. To this end, an up-to-date evaluation of existing and emerging ODS disposal technologies is required. In this context it is relevant to note that two decisions were recently taken under the Montreal Protocol to require Parties to develop management strategies, in which disposal issues are addressed, for both CFCs and halons (decisions XI/16 and X/7, respectively). 1.2
Regulation of ODS in Canada
The production and importation of chlorofluorocarbons (CFCs) and halons were banned in Canada in 1994-95 under the Ozone-depleting Substances Regulations and the Ozone-depleting Substances Products Regulations (Canada Gazette 1995a, 1995b). The goal of these restrictions is to diminish the threat posed by ODS and allow a return to former stratospheric ozone levels.1 By 1999, the import and export of recycled and reclaimed CFCs and halons had also been banned in Canada. Hydrochlorofluorocarbons (HCFCs), which are CFC replacements with much less Ozone Depletion Potential (ODP) than CFCs, are also being controlled. The current Canadian regulations already limit and control the production, import and export of HCFCs, and prescribe a gradual phase-out of these substances to be completed in 2030. Environment Canada has recently developed a strategy to accelerate the phase-out of the use of CFCs and halons in Canada and has completed a series of public consultations on this strategy, which consists primarily of proposed bans on the refilling of equipment with CFCs and/or halons (Environment Canada 1999). These restrictions, as currently proposed, would prescribe a ban on the refilling of all equipment with CFCs and/or halons, with the exception of residential white goods. The proposed refill bans would take effect between the years 2000 and 2008 and would represent, if implemented, a significant step towards the elimination of the use of CFCs and halons in Canada. The proposed refill bans, in combination with regulatory restrictions already in place and the general trend towards the use of alternatives to CFCs and halons, are intended to accelerate the accumulation of surplus quantities of ODS in Canada. The current total inventory of CFCs and halons in Canada (including quantities charged to existing equipment and stockpiled quantities) is estimated to be about 23 000 tonnes of CFCs and 3100 tonnes of halons (Environment Canada 1999). Thus, regulatory initiatives in Canada pursuant to the Montreal Protocol will likely result in the creation of a significant quantity of surplus ODS that will have to be disposed of in order to avoid ultimate release to the atmosphere and further degradation of the ozone layer. 1.3
Previous Reviews Of ODS Disposal Technologies
In order to address the issue of surplus ODS, an ad hoc Technical Advisory Committee (TAC) was established in 1990 under the auspices of the United Nations Environmental Programme (UNEP) to review ODS disposal technologies. The 1992 TAC Report recommended six destruction technologies, all of which fell within the category of thermal oxidation (UNEP 1992).
1 “It is anticipated that, as a result of the measures adopted by the Parties to the Montreal Protocol at the meeting held in Copenhagen in 1992, the ozone layer will have fully recovered by 2080.” (Canada Gazette 1995)
The TAC Report also recommended that an Advisory Panel be established to re-assess these ODS destruction technologies periodically, and to assess emerging technologies. In 1993 a Technology and Economic Assessment Panel (TEAP) was formed to update the 1992 TAC Report. In 1994, the TEAP recommended that the TAC meet again with a group of industry, technology and regulatory stakeholders to update the 1992 TAC Report. Following this recommendation, a special UNEP-sponsored workshop was held in Montreal in May 1995. The resulting report, indicated a number of existing technologies commercially available at that time, including several emerging ODS destruction and chemical transformation technologies (UNEP 1995). The 1995 UNEP Report indicated that existing ODS destruction facilities in developed countries were sufficient to dispose of the current and projected ODS wastes until the year 2000. Existing and emerging technologies were said to be able to handle ODS surpluses after 2000, although destruction of ODS would likely depend not only on availability of technologies but also on available capacity, as well as the effectiveness of economic and regulatory incentives. The current Guideline Document focusses on the issue of the disposal of anticipated surplus quantities of ODS in Canada, and extends the work described in the 1992 and 1995 UNEP reports in the following ways:
1.4
by providing an updated report on emerging and commercially available ODS disposal technologies; by providing a technical/environmental assessment of commercially available technologies that meet minimum environmental criteria; and, by providing an updated report on commercial availability and cost issues associated with those technologies that are the most likely candidates for disposing of Canadian ODS surplus quantities in the near future. The Canadian National Action Plan on Ods
The 1997 Report of the Auditor General of Canada described a need for Environment Canada to articulate clearly a strategy for the management and disposal of surplus ODS (OAG 1997). The 1998 Canadian Council of Ministers of the Environment (CCME) revised National Action Plan for the Environmental Control of Ozone-Depleting Substances (ODS) and their Halocarbon Alternatives (the “revised NAP”) contained an initiative to develop a plan for the disposal of surplus CFCs and halons (CCME 1998). It was proposed that the plan should involve an assessment of available ODS disposal technologies and the development of guidelines for disposing of ODS surplus in Canada. The current Guidance Document is a direct result of this proposal.
The process for developing this Guidance Document relied on a combination of literature research, personal communications with various experts and stakeholders, and consultation with government representatives, technology experts, and Canadian stakeholders. A thorough literature search was conducted to identify newly emerging ODS disposal technologies and to update information on previously-identified technologies (see Appendix D). A large number of representatives of government, academia, waste disposal facilities, and technology development companies were identified and contacted individually to obtain up-to-date information (see Appendices B and C). The project team included four process engineers, two from CEI and two from the Pioneer Technology Centre. These team members were responsible for communications with those providing information on specific technologies, and for the development of the individual descriptions of identified disposal technologies (see Appendix A). An Expert Review Committee (ERC) was formed in consultation with Environment Canada (Appendix B). The ERC included 14 representatives from government, academia and industry from around the world, covering all of the categories of disposal technology identified. An initial draft of the Review of Technologies was reviewed by individual ERC members, and was further discussed in a teleconference on February 11, 2000. A Stakeholder Working Group (SWG) was also formed, consisting primarily of Canadian stakeholders such as government representatives, technology developers, ODS recyclers and reclaimers, waste disposal facility representatives, Environmental Non-Governmental Organization (ENGO) representatives, industry representatives, and representatives of organizations that have or anticipate having surplus stocks of ODS in the future. The SWG consisted of 34 participating and 20 corresponding members (Appendix C). Participating stakeholders attended a workshop in Ottawa on March 9, 2000, to discuss issues related to the development of the Guidance Document (see meeting summary in Appendix E). Corresponding stakeholders were given a one-month period to provide written comments after receiving a copy of the draft document. A screening analysis was performed on all 42 identified technologies in order to create a sub-set of environmentally acceptable and commercially available technologies for the disposal of Canadian ODS surplus. ODS disposal technologies that passed the screening evaluation were then assessed according to environmental and technical criteria on the one hand, and on the basis of commercial and economic criteria on the other. The technical/environmental evaluation of those technologies selected by the screening analysis was provided in order to give all stakeholders additional information with which to determine the appropriateness of the available technologies for use in disposing of current and future surplus ODS in Canada. The commercial/economic assessment provides stakeholders with up-to-date information regarding the state of commercial development and availability, and the estimated average disposal costs for the technologies already identified as being environmentally acceptable. Thus, the screening
assessment identifies commercially available and environmentally acceptable ODS disposal technologies; the further analysis provides more detailed information on technical, environmental, commercial and economic issues. In considering the issues likely to be important to Environment Canada and to a wide variety of Canadian stakeholders, it was felt that the most meaningful evaluation procedure would involve separate consideration of the environmental/technical issues and the commercial/economic issues. The environmental and technical issues are important in addressing the question: which technologies are acceptable? As for the commercial and economic questions, they will ultimately be decided by market forces; the reason for providing this evaluation is to give regulators as well as stakeholders up-to-date information regarding the practicality and potential financial implications of decisions regarding the choice of disposal technologies. 2.2
Objectives And Scope
The objective of this Guidance Document is to provide Canadian stakeholders with up-to-date information on technologies available for the disposal of surplus quantities of ODS. Specific objectives include the following:
identification of commercially available and emerging technologies for the disposal of ODS; gathering of up-to-date information on these technologies, including technical information, state of development, commercial availability, and estimated costs; identification of technologies that meet minimum technical and environmental standards developed in consultation with Environment Canada; identification of technologies that meet minimum criteria of commercial availability from the point of view of Canadian stakeholders; a technical/environmental evaluation of available ODS technologies; an assessment of commercial and cost issues for available technologies; a summary description of regulatory issues associated with the handling of surplus ODS in Canada, including applicable federal and provincial regulations and transportation, storage, and reporting requirements; and, a discussion of barriers to the disposal of ODS surplus in Canada, based on stakeholder input.
Disposal refers to the destruction of ODS, transformation to another non-hazardous material, or stabilization in such as way that potential hazard to the environment is permanently eliminated. In practice, ODS disposal technologies are limited to the first two of these three possibilities. Management initiatives including recycling, re-use, or involving atmospheric release, are not considered here, only those activities leading to the permanent removal of ODS from surplus inventories in Canada. The scope of this Guidance Document is limited to the determination of ODS disposal technologies that are appropriate to consider for the disposal of current and future ODS surplus in Canada. Although further information is provided in two separate evaluations of the technologies in this group that involve the ranking of available technologies, no attempt has been made to indicate which individual technologies within this group should be given preference for the disposal of ODS surplus in Canada.
Rather, the currently available information on each of these technologies is placed at the disposal of the reader in order to assist with this task, which remains outside the scope of this Guidance Document. In other words, this Guidance Document aims to provide a framework for the anticipated discussion as to which technologies should be considered for the disposal of surplus ODS in Canada. Technologies discussed in the 1992 and 1995 UNEP documents on ODS disposal, generally involved destruction by thermal oxidation. In can be said that there is great interest on the part of the international community to use non-incineration technologies for the disposal of ODS that do not generate greenhouse gases and that do not have the potential for releases of dioxins and furans. As part of the scope of this document, non-incineration and chemical transformation technologies are identified and described that could provide alternative choices to incineration for the disposal of surplus ODS. Although it is not the objective of this Guidance Document to determine the current capacity for ODS disposal available to Canadian stakeholders, some general comments on this subject are in order. At present there is only one Canadian facility permitted to dispose of ODS, a rotary kiln incinerator operated by Bovar Waste Management in Swan Hills, Alberta. This facility is limited in terms of its capacity, and significant upgrades would be required to handle the quantities of ODS expected to be disposed of in Canada in the future. Current capacity is said to be of the order of 40 tonnes/year. The required upgrade would take about 6 months and would result in a capacity of about 3000 tonnes/year (Ian Glew, Bovar Waste Management, personal communication). In the U.S., several incineration facilities exist that can accept significant quantities of ODS. Various ODS disposal facilities with commercial-scale capacity also exist in Europe, and Australia has a facility using plasma arc technology that has already been used to destroy a significant quantity of ODS. As surplus quantities of ODS grow, there will be both more stakeholders in search of alternatives to dispose of their surplus and more incentive for developers of technologies to provide these alternatives on a commercial scale. Ultimately, regulatory initiatives will create a market for the disposal of surplus ODS, and assuming significant stockpiles remain at that point, the current review of ODS disposal technologies suggests that a number of technologies are available or could become available to address the issue of disposing of surplus quantities of ODS in Canada.
Efforts to phase-out the production and use of ODS around the world, largely as a result of initiatives related to the Montreal Protocol, have driven the development of technologies to dispose of these substances permanently. In some European countries, stringent restrictions on the use of CFCs and halons have resulted in the rapid accumulation of surplus ODS and the development of programs for the ultimate disposal of these substances. In Sweden in particular, much of the surplus inventory of CFCs and halons has already been destroyed. The technologies used for ODS disposal in Europe to date have been largely incineration technologies (such as reactor cracking). The same is true of most of the ODS that has been destroyed to date elsewhere in the world, including the U.S. and Japan. A notable exception is Australia, where a significant amount of that country’s inventory of surplus halons has been destroyed using an argon plasma technology. In anticipation of the need to provide Canadian stakeholders who are or who will be in possession of surplus ODS with an appropriate choice among disposal technologies, Environment Canada commissioned this review of ODS disposal technologies. The following provides a framework for evaluating and ranking ODS disposal technologies that have been developed to date in order to provide stakeholders with guidance on technology availability and information related to technical, environmental, commercial, and economic issues. Appendix A contains a comprehensive description of ODS disposal technologies that have been identified. The description of technologies in Appendix A expands upon the information assembled in the 1992 and 1995 UNEP documents through information obtained from the most recent literature and from many personal communications with representatives of chemical waste disposal facilities, with developers of ODS disposal technologies, as well as with academics experts and government representatives from various countries. A number of new technologies not mentioned in the previous UNEP reports have been identified and are discussed. In the case of technologies previously identified the information has been updated, particularly regarding issues of technology development status, commercial availability and cost. Forty-two ODS disposal technologies are identified and discussed in this Guidance Document. All ODS disposal technologies identified were initially assessed against a set of mandatory criteria to determine whether they were environmentally acceptable and commercially available. Of the 42 identified disposal technologies, 26 failed to meet the mandatory criteria. The reason these technologies did not pass the initial screen was typically because they were not considered to be commercially available. For this reason, this group of 26 technologies has been designated as “emerging technologies.”
The 16 technologies that satisfied the mandatory requirements were then considered in two separate further evaluations, one involving a set of environmental/technical criteria (Section 3.3), and another addressing commercial/economic issues (Section 3.4). In this document, these 16 technologies are referred to as “commercially available” technologies, however a qualification should be noted: these technologies are not only commercially available, they also meet mandatory environmental and technical criteria. Thus they are more accurately referred to as commercially available and environmentally acceptable technologies. For purposes of convenience, ODS disposal technologies have been grouped according to three general categories: incineration technologies, plasma technologies, and other non-incineration technologies. As noted in greater detail below, plasma technologies are not considered to be incineration technologies, despite the fact that they involve the thermal destruction of ODS, because they employ inert gas environments and avoid oxidation reactions. 3.2
Screening Of ODS Disposal Technologies
The screening assessment of 42 ODS technologies identified in this Guidance Document consisted of determining and applying mandatory criteria for the selection of commercially available and environmentally acceptable technologies. These criteria were established in consultation with Environment Canada and with members of an Expert Review Committee and a Stakeholder Working Group. Only technologies satisfying the mandatory screening criteria were further evaluated and ranked in the technical/environmental and commercial/economic assessments. The screening assessment mandatory requirements are as follows: 1. Total polychlorinated dibenzo-paradioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emissions are not to exceed 0.1 ng/m3 toxic equivalence (TEQ) using the international method (NATO 1988; Van de Berg 1998). 2. Destruction or conversion efficiency is not to be less than 90%. 3. The disposal technology must be commercially available by January 1st, 2003. Given the ultimate goal of minimizing ODS emissions, a mandatory minimal standard for destruction efficiency of not less than 90% was established. A destruction efficiency of not less than 99.99% had been suggested as a minimal standard in the past (UNEP 1992). There are other issues to be considered, however, such as environmental impacts, commercial availability, cost and practicality. In practice, a technology with significantly lower destruction efficiency but that performs very well in terms of limiting the production of greenhouse gases, provides a low-cost solution that is widely available commercially, and that is convenient to holders of ODS surplus may be more effective in reducing overall emissions of ODS than an expensive, inconvenient, but highly efficient technology. Consequently, it was felt that technologies with a destruction efficiency as low as 90% should be given consideration. The destruction efficiency criterion was given very high weighting in the subsequent technical/environmental evaluation, however, as it was thought to be a critical determinant of an environmentally acceptable technology.
For the mandatory screening criterion for dioxin/furan emissions, a very stringent emission level of 0.1 ng/m3 (TEQ) was established. Although a previous standard of 1.0 ng/m3 (TEQ) had been suggested, (UNEP 1992), advances in technology in recent years justified a significantly more stringent level. This was also in accordance with the level suggested for the Canada-Wide Standard for dioxins/furans. The dioxin/furan criterion was also given high weighting in the subsequent technical/environmental evaluation due to concerns for adverse health effects associated with these substances. Dioxins and furans have been categorized among the group of Canada’s most toxic substances, and under the new CEPA legislation they may be targeted for virtual elimination. It was therefore considered important to favour disposal technologies that minimize or eliminate dioxin/furan emissions. The third mandatory criterion was commercial availability, and in practice this turned out to be the most stringent of the mandatory criteria for the evaluation of the identified disposal technologies. Where technologies failed to meet the mandatory criteria, this was inevitably because they were judged not to be commercially available. All technologies reviewed passed the destruction efficiency criterion, particularly given the fact that multi-stage units could theoretically ensure any desired level of destruction efficiency (although this strategy would naturally result in elevated costs). Similarly, none of the technologies identified failed the dioxin/furan criterion. The intent was avoid disqualifying any technology, including the various incineration technologies, if it was reasonable to assume that proper operating conditions and emission control systems would result in the mandatory technical and environmental criteria being satisfied. Some mechanism would clearly need to be in place to deal with the issue of exceptions for individual facilities or in particular cases where the technical/environmental criteria may not be satisfied, however this would not necessarily disqualify the disposal technology itself. Defining exactly what “commercially available” means required some clarification and exercise of judgement. The working definition used for a “commercially available” technology was a technology that is commercially viable, available on an industrial scale, and not significantly limited in capacity by any factor or combination of factors. It was assumed that any process that had been demonstrated on a commercial scale anywhere in the world was commercially available for the disposal of Canadian ODS surplus. Where a process was based on proprietary technology it was assumed that it could be licensed for use in Canada. In cases where a commercial-scale facility existed and had been tested on PCBs or other (non-ODS) chlorinated organics, it was usually assumed that the technology could be applied to ODS, although professional judgement was brought to bear on a case-by-case basis. As a minimum, pilot-scale testing had to have been performed in order for a technology to be considered commercially available. Bench-scale testing, no matter how promising, was not felt to be enough to indicate the availability of a technology in such a short time frame. In general, this mandatory criterion was interpreted conservatively in the sense that no technology would be excluded unless it was felt quite unlikely that the technology would be available on a commercial scale by the year 2003. Where there was some doubt, the technology was included and assessed, keeping in mind that commercial availability was also a ranking criterion in the further commercial/economic evaluation.
The technologies that passed the mandatory screening criteria for technical performance, environmental protection, and commercial availability are listed below. Technologies were grouped into three categories: Plasma, Incineration, and Other technologies: It is important to note that plasma technologies typically involve inert atmospheres such as argon, thus, although they involve thermal destruction, they do not result in oxidation, which limits the potential production of dioxins and furans. Plasma technologies are therefore not considered to be incineration technologies. Plasma Technologies (non-incineration) •
Inductively Coupled Radio Frequency (ICRF) Argon Alternating Current (AC)
Incineration Technologies •
High Performance Liquid Injection Rotary Kiln Gas/Fume Internally Circulated Fluidized Bed (ICFB) Cement Kiln Reactor Cracking
Other Non-Incineration Technologies •
Solvated Electron UV Photolysis Gas Phase Chemical Reduction Catalytic Dehalogenation Liquid Phase Chemical Conversion Vitrification
As a result of this screening process 16 technologies out of the 42 technologies considered were found to satisfy the minimum requirements of technical performance and commercial availability. These included 7 established incineration technologies and 9 non-incineration technologies: 3 plasma technologies and 6 other non-incineration technologies. These 16 commercially available technologies were further evaluated on the basis of technical/environmental criteria, and economic/commercial criteria (Sections 3.3 and 3.4). 3.3
Technical/Environmental Evaluation
A Kepner-Tregoe decision matrix was applied to the evaluation and ranking of commercially available technologies using a number of technical and environmental criteria and associated ranking values to assign total numerical scores to each technology. The set of criteria used to evaluate the qualifying destruction technologies with respect to their environmental/technical concerns are listed in Table 1 along with the weighting factors used in the technology
evaluations. Also included in Table 1 are the guidelines used to generate numerical scores for each criterion. The criteria and the ranking values were developed in consultation with Environment Canada as well as with members of the Expert Review Committee and the Stakeholder Working Group. The purpose of the selected ranking process is to provide a framework for evaluating and prioritizing commercially available ODS disposal technologies in the context of the disposal of surplus ODS in Canada on the basis of environmental and technical criteria. The focus of the evaluation is on the avoidance or minimization of environmental impacts. Although the intent is to provide a quantitative tool that would allow any objective and well-informed party to apply the tool and result in the same outcomes, some degree of subjective interpretation in the application of the tool is inevitable. Throughout the evaluation, where data were estimated, the applicable assumptions and lines of reasoning are clearly stated.
Emissions of dioxins and furans [Toxic Equivalent PCDD/PCDF]
15%
Release of other gaseous emissions (NOx, SOx, VOCs, etc.), or generation of liquid wastes and/or solid residues (e.g., salts)
15%
Energy consumption
10%
Chemical recovery
10%
10 = 99.9999% 0 = 99.7% (Interval values calculated on a logarithmic scale) 10 ≤ 0.01 ng/m3 0 = 0.1 ng/m3 (Interval values calculated on a logarithmic scale) 10 = No emissions or waste 8 = Minimal emissions or waste 5 = Minor emissions or waste 3 = Moderate emissions or waste 1 = Significant hazardous emissions or waste 10 = Lowest 0 = Highest (Interval values interpolated linearly) 10 = Chemical recovery 1 = No chemical recovery
Destruction efficiency was an important issue in the examinations of ODS destruction technologies by the UNEP Technical Advisory Committee (UNEP 1992, 1995). Besides the standard established as a mandatory criterion in the screening assessment, the disposal technology destruction efficiency criterion was also given very significant weighting (50%) in this technical/environmental evaluation. The 1992 UNEP report described a destruction efficiency standard of at least 99.99% as “readily achievable in well-designed and operated destruction facilities.” Furthermore, it stated that this standard “strikes a balance between veryhigh efficiency (!99.9999%) destruction facilities available to a limited market, and high efficiency (!99.99%) facilities available to a majority of the potential world market.” (UNEP Environment Canada, Project # K2617-9-0037 Cantox Envronmental Inc Project # 80940
13 March 31, 2000
1992) As discussed above, however, there is also a balance between destruction efficiency and other issues such as environmental impact, commercial availability, cost and practicality. Technologies with less than 99.99% destruction efficiency were therefore also considered.2 Clearly, technologies used to dispose of ODS should have as high a destruction efficiency as is practical in order to minimize ultimate atmospheric emissions of ODS. Ranking scores were established based on the range of destruction efficiencies found for the technologies reviewed. The technology with the lowest destruction efficiency received a scoring value of zero, and the highest a value of ten. Interval scores were assigned according to a logarithmic formula to discriminate between high efficiency and very high efficiency technologies. Destruction efficiency for incineration technologies was assumed to be 99.99% unless specific information indicated otherwise, since it appeared clear that this efficiency level could be obtained as a minimum for well-operated incineration facilities.3 The dioxins/furans criterion was also used both as a mandatory criterion in the screening assessment [≤ 0.1 ng/m3 (TEQ)]. Its inclusion as a criterion in the further environmental/technical ranking allowed for a higher ranking evaluation for disposal technologies that have minimal or no such emissions associated with their operations. A score of ten was assigned to technologies that release no more than 0.01 ng/m3 TEQ PCDD/PCDF, while technologies that just met the mandatory criterion of 0.1 ng/m3 received a value of zero. Interval values were calculated according to a logarithmic formula to further emphasize the weighting towards technologies with near-zero emissions. This criterion was assigned a weighting factor of 15%. Dioxin/furan production for the various incineration technologies was estimated to be 0.1 ng/m3 unless specific test data or a line of reasoning based on a knowledge of the process indicated otherwise.4 The destruction of ODS typically results in a variety of chemical by-products that may themselves become issues of concern if released to the environment. Different ODS disposal technologies produce different by-products, such as acid gases, greenhouse gases (GHGs) and/or halide salts. A criterion was included to favour those technologies that avoid generating emissions or wastes that may be toxic or may present significant issues in terms of atmospheric emissions or of waste management. The scoring for this criterion was based the production of “no emissions or waste” to “significant hazardous emissions or waste.” The criterion necessarily involved subjective interpretation, and was meant to differentiate between technologies on the basis of the production of by-products, rather than to establish a rigorous framework to assign absolute values. This criterion was assigned a weighting factor of 15%.
2 It should be noted that the lowest destruction efficiency for the commercially available technologies identified was 99.7%. Thus, although lower DE would have been considered, it turned out not to be an issue in practice. 3 Destruction efficiencies for PCBs of up to 99.999999% (eight nines) have been reported by Bovar’s Swan Hills facility (Ian Glew, Bovar; personal communication). 4 Two major incineration facilities in Canada have reported minimal (0.01 ng/m3 to non-detection) emissions of dioxins/furans for the incineration of PCBs, and it is reasonable that similar results could be obtained, at least for these types of highly-sophisticated incinerators (Edrienne Turner, Bovar; Jan Sterman, MRR; personal communications). Environment Canada, Project # K2617-9-0037 Cantox Envronmental Inc Project # 80940
14 March 31, 2000
Two final criteria were assigned weighting factors of 10%, as it was felt that some consideration should be given to favouring ODS disposal technologies associated with low energy consumption and with the recovery of useful chemical products. Energy consumption was scored with the lowest energy consuming technology receiving a value of 10 and the lowest receiving a value of 0; the others linearly interpolated between these extremes. The chemical conversion criterion gave full weight to any technology that produced a significant quantity of a useful and marketable by-product as a result of disposing of ODS through chemical conversion. Table 2 summarizes the raw data used to evaluate the technologies according to the environmental and technical criteria, along with notes identifying the source of the data and/or identifying estimates/assumptions that were used to determine individual values. Table 3 summarizes the unweighted evaluation scores for each criteria. Scores were assigned to the data summarized in Table 2 according to the matrix described in Table 1. By reading down along the columns, Table 3 allows the evaluation scores for individual criteria for each technology to be compared. Table 4 lists the overall technology ranking scores resulting from the addition of all weighted evaluation scores for each technical evaluation criterion, with the total then converted in order to be expressed as a value out of 100.
Table 2: Technical Data for the Evaluation of ODS Destruction Technologies Technology
Destruction Efficiency (%)
Dioxins & furans (ng/m3)
Other Effluents
Energy Consumption (KWh/kg CFC)
Chemical Recovery
Incineration Note
Note
2
1
Note
10 High Performance 99.99990 0.100 salt/GHG 1.71 No 1 1 11 Liquid Injection 99.99000 0.100 salt/GHG 1.30 No 1 1 12 Rotary Kiln 99.99000 0.100 salt/GHG 1.54 No 1 1 12 Gas/Fume 99.99000 0.100 salt/GHG 1.30 No 2 1 12 ICFB 99.99900 0.100 salt/GHG 1.30 No 1 1 13 Cement Kiln 99.99000 0.100 GHG 1.86 No 2 2 2 Reactor Cracking 99.99900 0.100 wastewater 1.55 Yes Plasma (non-incineration) 2 2 14 IC RF 99.99000 0.025 salt 3.70 No 2 2 Argon 99.99990 0.025 salt 2.30 No 5 15 AC 99.99000 10 0.025 salt 2.10 No Other (non-incineration) 2 4 16 Solvated Electron 99.99000 0.010 salt 10.00 No 2 4 6 UV Photolysis 99.90000 0.010 spent liners 10.00 No 3 2 7 Gas Phase Chem Red 99.99990 0.060 salt 1.38 No 3 4 8 Catalytic Dehalogenation 99.99900 0.010 salt 0.79 No 2 4 2 Liquid Phase Chem Conv 99.70000 0.010 salt 3.00 No 2 9 2 Vitrification 99.99990 0.100 glass frit 4.88 No Comments: (9) Assumed could limit to acceptable level (1) Typical for conventional incineration (10) Operator reported lower value; adjusted as per (2) Reported data expert comment (3) Data reported for PCB; expect similar for CFC (4) Claimed and expected to be near zero because low (11) Reported by expert for co-incineration (12) Assumed similar to liquid injection process temperature (13) Adjusted for 1400 C operation (5) Assumed similar to IC RF plasma (14) Reported and adjusted per Plascon cooling (6) One expert estimated much higher value (15) Estimated using 90% efficiency (7) Estimated: high temperature but fuel recovered (16) One reported value much higher (8) Estimated: moderate temperature
Argon Plasma Gas Phase Chemical Reduction Catalytic Dehalogenation Vitrification Reactor Cracking High Performance Incineration ICFB Incineration IC RF Plasma Solvated Electron AC Plasma Cement Kiln Incineration Liquid Injection Incineration Gas/Fume Incineration Rotary Kiln Incineration Liquid Phase Chemical Conversion UV Photolysis
Rank
Evaluation Score
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
76 71 69 69 67 65 51 46 45 39 39 36 36 36 31 30
It should be noted that this ranking of destruction technologies is not intended to disqualify or eliminate technologies at the lower end of the list from further consideration. All of these technologies satisfy the minimum performance requirements identified in the screening assessment. The ranking does however identify those technologies which best satisfy the environmental and technical criteria deemed most desirable for ODS destruction technologies. Of the top six technologies it is interesting to note that two represent existing facilities in Canada and four represent technologies available commercially in other countries (two in the U.S., one primarily in Germany, and one in Australia). The foreign technologies could potentially be licensed for construction of facilities in Canada, or alternatively consideration could be given to exporting ODS for destruction. 3.4
Commercial/Economic Evaluation
A Kepner-Tregoe decision matrix was also applied to the evaluation and ranking of commercially available technologies using commercial and economic criteria and associated ranking values to assign total numerical scores to each technology. The set of criteria used to evaluate the qualifying disposal technologies are listed in Table 5 along with the weighting factors used. Also included in Table 5 are guidelines used to generate score values for each criterion. As with the environmental and technical criteria, these criteria and the ranking values were developed in consultation with Environment Canada as well as with members of the Expert
Review Committee and the Stakeholder Working Group. The purpose of the selected ranking process is to provide up-to-date information on ODS disposal technologies with a focus on disposal cost and availability issues. This analysis was based on the available information and the best judgement of the chemical engineers who were members of the project team, in consultation with industry, government and academic experts. It should be emphasized that a detailed and rigorous cost analysis for each technology was well beyond the scope of this project. The information provides an informed estimate of the relative and absolute costs involved in the selected ODS disposal technologies. Although the intent is to provide a quantitative tool that would allow any objective and wellinformed party to apply the tool and result in the same outcomes, some degree of subjective interpretation in the application of the tool is inevitable. As noted earlier, costs are expressed in Canadian dollars (year 2000).
Table 5 Evaluation Criteria, Weighting Factors, and Scoring Criteria
Weight
Scoring
Cost of disposal [Capital, fixed, variable, maintenance costs amortized over 10 years.] Commercial availability
60%
10 = $2.50/kg 1 = $11.00/kg (Interval values calculated on an arithmetic scale)
30%
Geographic availability
10%
10 = Commercial-scale facility available (significant capacity) 7 = Commercial-scale facility available (limited capacity) 5 = Commercial-scale facility available (up-grade required) 3 = Pilot facility in place, commercial facility planned 1 = Commercial-scale facility planned 10 = Available in Canada 5 = Available in U.S. 1 = Not available in North America
Although no minimal mandatory criterion for cost was established in the screening assessment, in practice cost will likely be one of the most important criteria determining whether, how quickly, and how efficiently stakeholders will act to collect and dispose of ODS surplus in Canada. As a result, in the current evaluation cost was given a very significant weighting value of 60%. Ranking scores were established based on the range of costs for the technologies reviewed, with the most expensive receiving a value of 1 and the least expensive a value of 10. Interval values were calculated according to a linear (arithmetic) formula. As with the destruction efficiency and the dioxins/furans criteria, commercial availability was used both as a mandatory criterion in the screening assessment and as a ranking criterion in the further analysis. Given that the technologies considered are expected to be commercially
available for the disposal of Canadian surplus ODS by the year 2003, there remains a good deal of variability in terms of what “commercially available” means. Technologies for which commercial-scale operations exist and are currently in operation were scored higher than technologies that had only been proven to work in pilot-scale tests and where commercial facilities were planned subject to market conditions. Some subjective interpretation was required in order to assess the varying degrees of commercial availability; the process engineering experience of members of the project team from both Cantox Environmental Inc and from the Pioneer Technology Centre was relied upon to make reasonable judgement in the assigning of scores. Scores for this criterion had a 30% weighting factor. The final criterion of geographic availability was assigned a weighting factor of 10% as it was felt that some consideration should be given to favouring ODS disposal technologies associated with convenient geographic availability. Technologies available in Canada received full scores, those available in the U.S. received half scores, and values of zero were assigned to technologies currently located overseas. Table 6 summarizes the raw data used to evaluate the technologies according to the commercial and economic criteria, along with notes identifying the source of the data and/or identifying estimates/assumptions that were used to determine individual values. Table 7 summarizes the unweighted evaluation scores for each criteria. Scores were assigned to the data summarized in Table 6 according to the matrix described in Table 5. Reading down along the columns Table 7 thus allows the evaluation scores for individual criteria for each technology to be compared. Table 8 lists the overall ranking scores resulting from the addition of all weighted evaluation scores for each evaluation criterion, with the total then converted in order to be expressed as a value out of 100. In most cases, direct cost information provided by destruction facility operators or technology suppliers was used, however these data can not be considered to be necessarily precise. Costs provided by destruction facility operators tended to be all inclusive and generally made some allowance for operating overheads, waste disposal and depreciating capital costs. Estimates for new technologies tend to be optimistic, especially where there is limited operating experience, and they often include only direct operating costs. However, the operating costs for most destruction technologies are relatively high compared with the limited capital costs indicated, so the overall destruction cost will be most heavily influenced by operating costs. Based on available cost estimates, destruction costs for incineration were assumed to be of the order of $5/kg on average, i.e., in the medium-to-high range for ODS disposal technologies, unless other specific information suggested otherwise. It should be noted that incineration costs have decreased significantly over the past ten years, and average costs could well be lower than this estimated value. The cost estimate for the Cement Kiln Incinerator process is an approximate assumption of average operating costs given the fairly large range expected from one facility to another. Similarly, the operating cost figure for the Gas Phase Chemical Reduction technology ($10/kg) was a conservatively high estimate based on an understanding of the details of the process. Environment Canada, Project # K2617-9-0037 Cantox Envronmental Inc Project # 80940
20 March 31, 2000
Table 6 Commercial and Economic Data for ODS Disposal Technologies Technology
Destruction Cost Commercial Availability
Incineration High Performance Liquid Injection Rotary Kiln Gas/Fume ICFB Cement Kiln Reactor Cracking Plasma (non-incineration) IC RF Argon AC Other (non-incineration) Solvated Electron UV Photolysis Gas Phase Chem Red Catalytic Dehalogenation Liquid Phase Chemical Conversion Vitrification Comments:
Note
4.00 3.50 3.50 3.50 3.50 3.25 3.75
13
2.50 2.75 2.50
1
11.00 11.00 6.00 3.60 4.00 3.80
1
2 2 2 2 3 1
1 4
1 5 5 14 1
(1) Reported data (2) Typical for incineration (pers communic) (3) Estimated; expected to be lower than other types of incinerators (4) Estimated based on reported Argon costs (5) Estimated based on process temperature and complexity (6) Commercial operation established (7) Demonstrated on ODS in commercial-scale field trial
Canada USA USA USA Japan USA Germany Japan Australia USA USA USA Canada USA/Can? Canada USA
(8) Demonstrated on commercial scale in 35-month field trial (9) Commercial operation but not with ODS; proven with ODS on pilot scale (10) Proven with ODS on pilot scale (11) Commercial operation but not with ODS (12) Commercial operation; readily upgradable to handle ODS (13) Estimated; conventional cost adjusted for high performance (14) Claimed competitive with incineration
Table 8 Commercial/Economic Ranking of ODS Disposal Technologies Technology Cement Kiln Incineration Argon Plasma Rotary Kiln Incineration Liquid Injection Incineration Gas/Fume Incineration High Performance Incineration Catalytic Dehalogenation Liquid Phase Chem Conv Reactor Cracking AC Plasma Vitrification IC RF Plasma Gas Phase Chem Red ICFB Incineration Solvated Electron UV Photolysis
Rank
Evaluation Score
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
90 89 88 88 88 86 84 83 82 80 80 76 69 66 29 14
Unlike the environmental/technical ranking, this commercial ranking is not intended to address issues as to which is a “better” technology. Non-economic issues could suggest that technologies near the bottom of this ranked list might be more appropriate than others that scored higher. Should this be the case, the value of the above exercise would be to identify potential economic barriers to such a technology selection. Again, the purpose of this exercise is to provide regulators and stakeholders with current information regarding the commercial and economic issues associated with available ODS disposal technologies. All of these technologies satisfy the minimum requirements of technical performance and commercial availability. However, a few technologies score very low compared to most others and it is unlikely these would be pursued seriously. The selection of a disposal technology will be made by stakeholders based on criteria judged to be important to them, and such criteria may not align with those used in this evaluation. However, disposal costs will likely dominate any commercial evaluation of technologies, as it does in this evaluation.
In Australia, where a significant amount of surplus halon has already been collected and destroyed over the past few years, all handling, transportation, labelling and container requirements are covered by various national and state Standards. Procedures for handling recovered product are not substantially different than those for virgin material; thus, there are no significant or special barriers to the handling and transportation of ODS for recycling or for destruction. [See Australian contacts in Appendices B & C]. In the U.S., the handling and transport of ODS is controlled by national (as opposed to state) legislation, and requirements are described in Sections 608 and 609 of the U.S. Clean Air Act. [See U.S. contacts in Appendices B & C; helpful U.S. EPA contacts are, for section 608, Julius Banks (202) 564-9870, and for section 609, Lars Wilcut (202) 564-2411.] Regulations applicable to the handling of ODS in Canada depend upon whether or not it is considered surplus, (i.e., whether or not it is considered to be hazardous waste) and whether provincial or national borders are crossed in the case of transportation. The designation as hazardous waste is a critical key issue, since this typically triggers a series of complex handling and manifesting requirements under federal and/or provincial regulations. Although it is important to distinguish between virgin and used material, in practice the key distinction is between ODS that is still a viable product in the commercial market and ODS that is considered surplus. A more precise definition of the former may be found in the Regulations Respecting The Handling, Offering For Transport And Transporting Of Dangerous Goods (the TDGR), where waste specifically does not refer to “a product, substance or organism that is […] returned directly to a manufacturer or supplier of the product, substance or organism for reprocessing, repackaging or resale, including a product, substance or organism that is [either] defective or otherwise not usable for the original purpose, or in surplus quantities but still usable for its original purpose.” (Environment Canada 1992) In general, the ODS that is not considered hazardous waste or that is exempted from hazardous waste regulations may be handled, shipped, and used following typical commercial practices; the only restrictions apply to shipping outside of Canada, in which case the 1998 Ozone-Depleting Substances Regulations and Federal Halocarbon Regulations (as well as the TDGR), would apply. The first two regulations prohibit the export and import of virgin ODS for sale and use, as well as the import of reclaimed/recycled ODS; the latter, however, may be exported for sale and re-use provided the appropriate permit is obtained. Exports of ODS for the purposes of destruction is permitted provided appropriate manifesting and control. There are currently no restrictions in Canada on the refilling of equipment such as refrigeration units, air conditioning units, and fire extinguishing systems with appropriate CFCs or halons, with the exception of the refilling of automotive air conditioning systems, which is restricted under provincial legislation in several provinces. Canada’s Proposed Strategy to Accelerate the
Phasing-Out of Uses of CFCs and Halons and to Dispose of the Surplus Stocks was released by the Federal-Provincial Working Group on Controls Harmonization (Ozone-Depleting Substances) in January, 2000, and national consultations were conducted in February and March. The proposal is to be submitted to the CCME in the summer of 2000. This initiative may lead to provincial legislation restricting the refill of such equipment with CFCs and halons in the near future. Once refill is prohibited, significant quantities of ODS in Canada will become surplus, since it can no longer be used for its intended purpose. Besides virgin material for which there may no longer be a commercial or permitted use, therefore, there are two main categories of ODS waste: •
waste destined for recycling, i.e., ODS that has impurities that, once removed or treated in some way, can be used in the originally intended application, or some other application; and,
•
waste destined for disposal.
Assuming neither is categorized as a hazardous waste under federal or provincial regulations, the former may be handled and shipped to permitted ODS recyclers, and the latter may be handled and shipped to permitted disposal facilities following appropriate procedures described below [i.e., in the case of compressed gases, the TDGR would apply]. Once ODS is considered surplus, it becomes hazardous waste by definition. That is, once there is no longer a market for a virgin or used CFC or halon material, and no further possibility exists for reclaiming, recycling, or reusing the ODS, and it can not be exported for such purposes or for any other purpose than for destruction, it is automatically considered a controlled substance and a hazardous waste. ODS that is moved from one company to another, or shipped for use in another application, is not considered hazardous waste as long as nothing had to be done to treat it or modify in some way. Once a substance is considered a hazardous waste, either provincial or federal regulations (or both) control its transport and handling, including detailed manifesting provisions. Manifesting and regulations applicable to the transport of hazardous waste differ depending on whether borders are crossed, and depending upon which borders are crossed, i.e., whether they are provincial or national. If the substance is shipped outside Canada, Environment Canada’s Transboundary Movement Division is the regulating authority, and the transport and handling of the substance is regulated by the Export and Import of Hazardous Wastes Regulations under CEPA legislation (Environment Canada 1992). If a provincial boundary is crossed, this activity falls under the interprovincial responsibilities of Transport Canada , i.e., transport and handling would be controlled by the Regulations Respecting The Handling, Offering For Transport And Transporting Of Dangerous Goods (the TDGR). If movement is limited entirely within one province, then the province in question has sole jurisdiction and only provincial regulations apply. All of these regulations describe a complex series of prescriptions for controlling the handling, storage, and transportation of hazardous wastes, including detailed manifesting provisions.
Table 9 lists federal and provincial contact persons who may be of help in determining whether and which hazardous waste regulations apply in individual cases. Another helpful contact in the Transboundary Movement Division of Environment Canada is Suzanne Leppinnen, Program Engineer (819) 953-3378 [[email protected]].
Table 9 Hazardous Waste Task Group Members Name
Phone
Fax
E-Mail
Betty Smith (Chair) Ontario Rob Dalrymple British Columbia John Henderson Nova Scotia Simone Godin New Brunswick Toby Matthews Newfoundland
Marc Pedneault Quebec John Myslicki Canada Joe Wittwer Canada Don Labossière Manitoba Tony Fernandes Alberta Roger Hodges Saskatchewan Bryan Levia Yukon Ken Hall Northwest Territories Robert Eno Nunavut Diane Kunec CCME
It is important to note that a substance may be considered a hazardous waste under provincial regulations even though it is not considered a hazardous waste under national regulations. For example, in Ontario, used R-11 and R-12 are both considered hazardous waste (under Regulation 347) even if they may be reclaimed and recycled for further commercial use. However, if the R-11 or R-12 material is to be 100% recycled, or sent to a wholesaler who intends to collect the ODS and send it to a recycler or to a hazardous waste disposal facility, the material is exempted from hazardous waste regulations and can be transported relatively simply (following basic procedures described in the TDGR, discussed below). This exemption therefore provides an important mechanism allowing stakeholders to handle and transport surplus and reclaimable ODS without having to face burdensome handling and manifesting procedures. Most provincial manifesting follows quite closely the procedures used by Environment Canada’s Transboundary Movement Division, although some provinces have certain specific exemptions or special provisions, as just described. In practice, the environmental aspects of interprovincial movement of dangerous goods is handled by Environment Canada, and the new CEPA will in fact transfer this area of responsibility from Transport Canada to Environment Canada. Transport Canada (i.e., the TDGR) will remain responsible for details such as packaging protocols, labelling, etc. In terms of tracking or maintaining an inventory of hazardous waste movement, provinces are responsible as long as this movement is within Canada, and this information is available on the inter-provincial manifests applicable for each shipment. Information on the ultimate disposal of the material would be obtained from the destruction facility, and this activity falls under provincial jurisdiction. For transportation outside of Canada for the purposes of destruction, as noted, the Transboundary Movement Division of Environment Canada is the regulating authority, and an export permit is required. Environment Canada is responsible for contacting their international counterparts (e.g., in the U.S. EPA) to ensure that there is an ultimate and acceptable destination for the wastes, and will also insist on receiving a certificate of disposal to ensure that the material reached its destination and was destroyed. 4.2
Storage, Handling and Transportation
4.2.1
Overview
This section discusses the requirements applicable to CFCs and halons in Canada for substances that are not considered hazardous wastes, or that are exempt from hazardous waste regulations for the purpose of transport for recycling, reclaiming, or disposal. In general, stakeholder feedback has indicated that if ODS is considered as a hazardous waste, the required handling and manifesting procedures would create a significant barrier to the collection and destruction of surplus ODS in Canada. Unless some exemption mechanism is provided to allow stakeholders to store and ship ODS to collection facilities without having to satisfy requirements normally applicable to the handling of hazardous waste (as is the case in Ontario for R-11 and R-12, for example), a collection program may not work in practice.
As stated above, handling procedures, and in particular manifesting requirements, for ODS that is considered hazardous waste are complex, and these cannot be covered in detail within the scope of this document. The reader is advised to consult Table 9 for a list of provincial and federal contacts for further information regarding regulations and procedures applicable to hazardous wastes. Assuming the ODS is not a hazardous waste and will not cross international borders, handling procedures are relatively straightforward. The key regulations to consider are the Regulations Respecting The Handling, Offering For Transport And Transporting Of Dangerous Goods (the TDGR), which are administered by Transport Canada. For the reader’s convenience, the various regulations and documents most applicable to these issues are listed in Table 10.
Table 10 Regulations & Documents Relevant to the Handling of Surplus ODS Regulation/Document
Reference
Cylinders, Spheres, and Tubes for the Transportation of Dangerous Goods
National Standard of Canada CAN/CSA-B339-88 Environmental Protection Service, Environment Canada. Report EPS 1/RA/2. March 1996.
Environmental Code of Practice for Elimination of Fluorocarbon Emissions from Refrigeration and Air Conditioning Systems Environmental Code of Practice on Halons
Export and Import of Hazardous Wastes Regulations
Federal Halocarbon Regulations Ozone-depleting Substances Products Regulations. Ozone-Depleting Substances Regulations Packing for Transportation of Dangerous Goods in Prescribed Packagings Regulations Respecting The Handling, Offering For Transport And Transporting Of Dangerous Goods
Ozone Protection Programs Section, Commercial Chemicals Evaluation Branch, Environment Canada. www.ec.gc.ca/ozone/firecode.htm Environment Canada, Transboundary Movement Division. SOR/92-637, November 12, 1992. www.ec.gc.ca/tmd/regs.htm Environment Canada www.ec.gc.ca/ozone/fhr-rfh/english/index.htm Canada Gazette Part II, Vol. 129, No. 26 (SOR/95-584). December 13, 1995. Canada Gazette Part II, Vol. 129, No. 26 (SOR/95-576). December 7, 1995. CGSB Provisional Standard 43-GP-152MP. (See Part V of TDGR). Transport Canada 1999 www.tc.gc.ca/Actsregs/TDG/english/part-i.html
The two major categories of ODS in this context are: •
low pressure CFCs that are liquids at room temperature (e.g., R-11, R-113, and R-123); and,
•
high pressure CFCs and halons that are compressed gases at room temperature (e.g., the CFCs R-12, R-22, R-114, R-500, R-502, and the halons 1211 and 1301).
The former category, that is the liquids, are not specifically controlled by the TDGR. Such ODS may therefore be stored and handled in regular drums with adequate labelling as per normal commercial practices (i.e., similar to the containers and labelling procedures used when purchasing the virgin or reclaimed product). They may be transported within Canada without any specific manifesting requirements, although normal record keeping procedures are required by the Ozone-Depleting Substances Regulations and the Federal Halocarbon Regulations. The reader should also be aware of the recommended procedures for ODS handling, reporting, training of personnel, etc., that are contained in the Environmental Code of Practice for Elimination of Fluorocarbon Emissions from Refrigeration and Air Conditioning Systems and the Environmental Code of Practice on Halons, both available from Environment Canada (Environment Canada 1996, 1997). High pressure CFCs and halons are considered “dangerous goods” under the TDGR. Specifically, they are considered either Class 2.2 compressed gases (non-flammable, non-toxic) or Class 6.1 compressed gasses (non-flammable, toxic; e.g., chloroform). Virtually all ODS currently in use are Class 2.2 compressed gases; Schedule II of the TDGR should be consulted to verify the classification in specific cases. The following discussion deals mainly with the storage, handling and transport of Class 2.2 compressed gases. Stakeholders dealing with toxic compressed gases in specific cases (i.e., Class 6.1 gases), should be aware of the existence of considerably more stringent requirements for these substances. 4.2.2
Containers
The TDGR prescribe specific requirements for approved cylinders that may be used to contain the ODS, for labelling and for the training of personnel who will be handling the material. Prior to 1992, cylinders used for compressed gases were considered acceptable if they were approved under either Canadian Transport Commission (CTC) or U.S. Department of Transport (DOT) regulations. After 1992, cylinders for such use had to be approved by Transport Canada (TC). Cylinders to be used to contain, store, and transport CFCs and halons that are compressed gases, therefore, must be TC-approved at the appropriate pressure rating. The pressure rating for most CFCs is typically 260-400 pounds per square inch (psi). In the case of R-13, cylinders must be TC-approved for use at 1800 psi (R-13 is a relatively rare refrigerant used for very low temperature refrigeration in special applications). More specifically, the appropriate cylinders permitted to be used for the collection, storage, and transportation of ODS in Canada must: a) Be in conformance with the National Standard of Canada CAN/CSA-B339-88, Cylinders, Spheres, and Tubes for the Transportation of Dangerous Goods, dated February 1988 and amended January 1992 and February 1993; or, b) Be cylinders where the initial test date of the cylinder or tube is December 31, 1992 or earlier.
Cylinders containing virgin CFCs must be tested and re-certified every 12 years. Used CFCs may be highly corrosive, however, and cylinders containing these materials must be tested and re-certified every 5 years. The key issue for Canadian stakeholders is that cylinders that are already filled with CFCs may be shipped to a recycling facility that is capable of de-gassing and re-certifying the cylinder, even if it is past the 5-year limit (in the case of used product) or 12year limit (in the case of virgin material) for recertification. Cylinders that are out of date, however, may not be re-filled once they are emptied. Stakeholders in Canada should be aware that in 1994, DuPont Canada initiated a successful program to recover a significant portion of existing CFC stock previously sold. A large number of cylinders were approved and made available for this purpose, and many of these are still currently in use among Canadian ODS stakeholders. Technically, the permission of the original owner of the cylinder is required in order for it to be used to collect and store or transport CFCs. However, in order to deal with liability issues, DuPont issued a recall of all of its cylinders; as a result, it is now the responsibility of the company in possession of these cylinders to maintain and re-certify them. In addition to the above, see Part V of the TDGR for various national standards, and particularly the CGSB Provisional Standard 43-GP-152MP, Packing for Transportation of Dangerous Goods in Prescribed Packagings, that apply to the packaging and containers used for the transport of dangerous goods such as compressed gases. Further specifics concerning standards applicable to containers used for Class 2 gases may be found in section 7.32 of the TDGR. Schedule IX of the TDGR contains a list of standards applicable to packaging and containers for dangerous goods. Schedule VIII of the TDGR describes specific standards for the inner and outer packaging of Class 2.2 compressed gases, and CFCs in particular. 4.2.3
Documentation, Labelling, Handling and Personnel Training Requirements
It should be noted that in general, many of the provisions in the TDGR applicable to poisonous gases also apply to corrosive gases such as used ODS. Specific documentation for shipments of ODS that are compressed gases, as prescribed by the TDGR, varies depending on whether the shipment involves interprovincial or international border crossing. The appropriate section describing required documentation may be found in Part IV of the TDGR (see in particular sub-section 4.4, Dangerous Goods Other Than Waste). For ODS that are compressed gases, requirements concerning safety marks, labelling, product identification numbers (PINs) are described in Part V and in Schedule V of the TDGR, in particular those sections applicable to dangerous goods in general and to corrosive gases. See also the CGSB Provisional Standard 43-GP-152MP, Packing for Transportation of Dangerous Goods in Prescribed Packagings referred to in this section.
Detailed descriptions of handling procedures applicable to Class 2.2 compressed gases may be found in Parts VII and VIII of the TDGR, which cover the following items:
Notification; Emergency response assistance planning; Preparation of means of containment; Re-use of drums; Discharge, emission or escape of dangerous goods from packages and small containers; Handling, including loading procedures; and, Standards applicable to containers.
Requirements for training for personnel handling dangerous goods is to be found in Part IX of the TDGR. This part also discusses reporting requirements in the case of accidental releases. It is to be noted that Table 1 of this part of the TDGR indicates that immediate reporting of any accidental release of a Class 2.2 compressed gas is required only if a minimum of 100 L is released.
Bickle, G.M., Suzuki, T., and Mitarai, Y. 1994. Catalytic Destruction of Chlorofluorocarbons and Toxic Chlorinated Hydrocarbons. Applied Catalysis B, Environment 4(2):141-153. April 27, 1994. Brooks, B.R. 1996. Developing a UV Technology Having Multiple Applications Within DOE and DOD. In: American Nuclear Society. Spectrum '96: Proceedings of the 6th International Topical Meeting on Nuclear and Hazardous Waste Management, Seattle, WA. American Nuclear Society, La Grange, Park, IL, Vol. 1:305-310. August 18-23, 1996. Burdeniuc, J., and Crabtree, R.H. 1996. Mineralization of Chlorofluorocarbons and Aromatization of Saturated Fluorocarbons by a Convenient Thermal Process. Science 271(5247):340-341. January 19, 1996 Cabot, P.L., Centelles, M., Segarra, L., and Casado, J. 1997. Palladium-Assisted Electrodehalogenation of 1,1,2-Trichloro-1,2,2- Trifluoroethane on Lead Cathodes Combined With Hydrogen Diffusion Anodes. Journal of the Electrochemical Society 144(11):3749-3757. November 1997. Canada Gazette 1995a. Ozone-depleting Substances Regulations. Canada Gazette Part II, Vol. 129, No. 26 (SOR/95-576). December 7, 1995. Canada Gazette 1995b. Ozone-depleting Substances Products Regulations. Canada Gazette Part II, Vol. 129, No. 26 (SOR/95-584). December 13, 1995. CCME 1998. National Action Plan for the Environmental Control of Ozone-Depleting Substances (ODS) and their Halocarbon Alternatives. Canadian Council of Ministers of the Environment. Prepared by the Federal Provincial Working Group on Controls Harmonization (ODS). CCME PN 1291. January 1998. http://www.ec.gc.ca/ozone/nap-pan/nap_e.htm CCME 1997. National Air Issues Coordinating Committee (NAICC) Meeting, FederalProvincial Working Group on Controls Harmonization (Ozone Depleting Substances). Victoria, BC. February 3-4, 1997. CCME 1995. Strengthening Canada’s Ozone Layer Protection Program: Recommendations to Strengthen Canada’s Ozone Layer Protection Program. Federal-Provincial Working Group on Controls Harmonization (Ozone Depleting Substances). May 1995. Chemical Engineer 1994. Lanstar Cracks CFC Waste Problem. The Chemical Engineer (Bulletin of the Institute of Chemical Engineers, 566:5; no author attributed). 1994. CSA 1988. Cylinders, Spheres, and Tubes for the Transportation of Dangerous Goods. Canadian Standards Association. National Standard of Canada CAN/CSA-B339-88.
Dufaux, D.P., and Zachariah, M.R. 1997. Aerosol Mineralization of Chloroflurocarbons by Sodium Vapor Reduction. Environmental Science & Technology 31(8):2223-2228. August, 1997. Environment Canada 1999. Strategy to Accelerate the Phasing Out of Uses of CFCs and Halons and Dispose of the Surplus Stocks. Federal-Provincial Working Group on Controls Harmonization (ODS). Environment Canada. January 19, 2000. www.ec.gc.ca/ozone/tocnews.htm Environment Canada 1998. Options for the Management of Surplus Ozone-Depleting Substances in Canada. Prepared by Shapiro & Associates (project # K2218-7-0027). June 11, 1998. Environment Canada 1997. Environmental Code of Practice on Halons. Ozone Protection Programs Section, Commercial Chemicals Evaluation Branch. www.ec.gc.ca/ozone/firecode.htm Environment Canada 1996. Environmental Code of Practice for Elimination of Fluorocarbon Emissions from Refrigeration and Air Conditioning Systems. Environmental Protection Service, Environment Canada. Report EPS 1/RA/2. March 1996. Environment Canada 1992. Export and Import of Hazardous Wastes Regulations. Transboundary Movement Division. SOR/92-637, November 12, 1992. www.ec.gc.ca/tmd/regs.htm Farmer, A.J.D. 1998. PLASCON(TM): A Thermal Plasma Process for Destruction of Halon 1211. In: IEEE. 25th Anniversary: IEEE Conference Record--Abstracts: 1998 IEEE International Conference on Plasma Science. (25th IEEE International Conference on Plasma Science, June 1-4, 1998, Raleigh, CA) Institute of Electrical and Electronics Engineers (IEEE), Piscataway, NJ, pp. 290 (Abstract No. 6P65). June, 1998. Friedl, C. 1994. The Disposal of Used FCKW is Unsolved (Entsorgung von alt-FCKW ist ungeloest). VDI-Nachrichten (Verein Deutscher Ingenieure Nachrichten) 6:19-end. 1994. Hug, R.S. 1993. Vernichtung von FCKW unter Rueckgewinnung von Fluss- and Salzsaeure. [Destruction of Fluorochlorohydrocarbons With Recovery of Hydrofluoric Acid and Hydrochloric Acid After Cessation of FCHC Production.] Chemie Ingenieur Technik 65(4):430, 432-433. 1993. Hug, R.S. 1995. Thermisches Spaltverfahren zur Vernichtung von Fluorchlorkohlevwasserstoffen: Konzept einer ruckstandsarmen Kreislaufwirtschaft. [Thermal Splitting Process for the Decomposition of Hydrochlorofluorocarbons: Concept for Low Residue Product Circulation] Pharmazeutische Industrie 57(12):1029-1032. 1995. Ivanov, O.A., Akhmedzhanov, R.A., and Ivanova, L.S. 1999. Evolution of the Products of Destruction of an Admixture of Freon-113 in Air Under the Effect of Nanosecond Corona and Microwave Discharges. High Temperature (Teplofizika Vysokikh Temperatur) 37(5):771-778. 1999. Environment Canada, Project # K2617-9-0037 Cantox Envronmental Inc Project # 80940
33 March 31, 2000
Martin, R.S., Garrison, K.E., Manahan, S.E., Morris, J.S., and Larsen, D.W. 1999. Destruction of Chlorofluorocarbons During Chemchar Gasification. Journal of Environmental Science and Health (Part A - Toxic/Hazardous Substances & Environmental Engineering) A34(4):795-807. 1999. McBrayer, R.N., and Griffith, J.W. Turn Off the Heat: First Commercial Supercritical Water Oxidation System Destroys a Petrochemical Company’s Waste Less Expensively Than Incineration. Industrial Wastewater. July/August 1996. NATO 1988. Scientific Basis for the Development of International Toxicity Equivalency Factor (I-TEF), Method of Risk Assessment for Risk Assessment of Complex Mixtures of Dioxins and Related Compounds. North Atlantic Treaty Organization/Committee on the Challenge of Modern Society. Report No. 176, Washington, D.C. 1988. OAG 1997. 1997 Report of the Auditor General of Canada. Chapter 27, Ozone Layer Protection: The Unfinished Journey. Office of the Auditor General of Canada and the Commissioner of the Environment and Sustainable Development. December, 1997. Process Engineering 1994. Cracking Way to Destroy CFCs. Process Engineering (London) 75:19; December 1994. (No author attribution.) Rehmat, T., Branion, B., Rogak, S., Filopovic, D., Teshima, P., Hauptmann, E., Gairns, S., Lota, J. 1999. Supercritical Water Oxidation for Waste Disposal. Pre-prints of the PACWEST 1999 Conference, Pulp & Paper Technical Association of Canada, Pacific Coast & Western Branches. Chateau Whistler, Whistler, British Columbia. May 19-22, 1999. Russell, S.D., and Sexton, D.A. 1995. Laser Controlled Decomposition of Chlorofluorocarbons. Department of the Navy, Washington, DC, (Patent) Patent 5,362,450. 1995. Russell, S.D., and Sexton, D.A. 1995. Photon Controlled Decomposition of Nonhydrolyzable Ambients. Department of the Navy, Washington, DC, (Patent) Patent 5,451,378. 1995. Samdani, G. 1994a. Plasma Converts Liquid CFCs Into Harmless Polymeric Film or Powder. Chemical Engineering 101(8):17. August 1994. Samdani, G. 1994b. CFCs Find a Home in Environmentally Benign Cement. Chemical Engineering 101(10):19-20. October 1994. Samdani, G. 1995. Incinerators Need Only Minor Changes to Handle CFCs. Chemical Engineering 102(4):19. April 1995. Samdani, G. 1994b. Catalytic System Breaks Down CFC-12 for Disposal. Chemical Engineering 101(7):17. July 1994. Samdani, G. 1997. Destroy CFCs While Making Cement. Chemical Engineering 104(7):21. July 1997.
Smith, D., Voden, K., Cunningham, R., and Rucker, L. 1997. Socio-Economic Assessment of a Ban on the Use of Existing Products and Equipment Containing CFCs or Halons. Applied Research Consultants (ARC), Ottawa, ON / KPMG. 1997. Soucy, G., Fortin, L., and Boulos, M.I. 1996. Toxic Waste Destruction by Thermal Plasma Technology. In: CEIA: Proceedings of the Evolution of Waste Management to Pollution Prevention and Resource Recovery, Winnipeg, Manitoba. 18th Canadian Waste Management Conference. Canadian Environmental Industry Association (CEIA). October 21-24, 1996. Stenger, H.G., Buzan, G.E., and Berty, J.M. 1993. Chlorine Capture by Catalyst Sorbents for the Oxidation of Air-Pollutants. Applied Catalysis B: Environmental, 2(1):117-130. 1993. Sylvestre, M., Betrand, J.-L., and Viel, G. 1997. Feasibility Study for the Potential Use of Biocatalytic Systems to Destroy Chlorofluorocarbons (CFCs). Critical Review: Environmental Science & Technology 27(2):87-111. 1997. Tezuka, F. 1996. Dry Distrillation Disposal System for Waste Refrigeration. American Chemical Society National Meeting: Abstract Paper (New Orleans) 211(1):I&EC 036. March 24-28, 1996. Transport Canada 1999. Regulations Respecting The Handling, Offering For Transport And Transporting Of Dangerous Goods. www.tc.gc.ca/Actsregs/TDG/english/part-i.html Ueno, H., Iwasaki, Y., Tatsuichi, S., and Soufuki, M. 1997. Destruction Of Chlorofluorocarbons in a Cement Kiln. Journal of the Air Waste Management Association 47(11):1220-1223. 1997. UNEP 1997. Montreal Protocol on Substances That Deplete the Ozone Layer: Technology and Economic Assessment Panel. United Nations Environmental Program (UNEP) Vol. 1. 1997. UNEP 1995. 1995 ODS Disposal Technology Update. United Nations Environmental Program: Report of the Technology and Economic Assessment Panel ODS Disposal Subcommittee Workshop held in Montreal, Canada, May 2-3, 1995. June 1995. UNEP 1994a. 1994 Report of the Solvents, Coatings and Adhesives Technical Options Committee for the 1995 Assessment of the Montreal Protocol on Substances That Deplete the Ozone Layer. United Nations Environmental Program (UNEP). UNEP 1994b. Montreal Protocol on Substances That Deplete the Ozone Layer: 1994 Report of the Flexible and Rigid Foams Technical Options Committee for the 1995 Assessment of the Montreal Protocol on Substances That Deplete the Ozone Layer. United Nations Environmental Program (UNEP). UNEP 1994c. 1994 Report of the Refrigeration, Air Conditioning and Heat Pumps Technical Options Committee. For the 1995 Assessment of the Montreal Protocol on Substances That Deplete the Ozone Layer. United Nations Environment Program. November 1994.
UNEP 1992. Report of the Ad Hoc Technical Advisory Committee on ODS Destruction Technologies. United Nations Environment Program. May 1992. Van den Berg, M., Birnbaum, L., Bowveld, B.T.C., Brunstrom, B., Cook, P., Feeley, M., Giesty, J.P., Hanberg, A., Hasegawa, R., Kennedy, S.W., Kubiak, T., Carsen, J.C., van Leeuwen, F.X.R., Liem, A.K.D., Nolt, C., Peterson, r.E., Poellinger, L., Safe, S., Schrenk, D., Tillitt, D., Tysklind, M., Younes, M., Waern, F., and Zacharewski, T. 1998. Toxic Equivalency Factors (TEFs) for PCBs PCDDs, PCDFs, for Humans and Wildlife. Environ Health Perspect. 106, 775-792. 1998. Wiersma, A., Vandesandt, E., Makkee, M., Vanbekkum, H., and Moulijn, J.A. 1996. Process-Development For The Selective Hydrogenolysis Of CCL2F2 (CFC-12) Into CH2F2 (HFC-32) Studies in Surface Science and Catalysis 101(Part A):369-378. 1996.
CCME Canadian Council of Ministers of the Environment. Each province and territory, and the federal government are represented at the meetings by the respective Minister of the Environment. Wide ranges of environmental issues are discussed at the meetings. Chlorofluorocarbon (CFC) A very stable compound containing chlorine, fluorine, and carbon atoms. Chlorofluorocarbons decompose in the stratosphere and release chlorine, which destroys ozone. Disposable Container A container designed to be used only once for transportation or storage of CFCs or HCFCs; designed in accordance with Transport Canada specification 39 (DOT 39 if made in the USA). Disposal The method used to eliminate a substance that will no longer be used for the original purpose for which it was made. The method may include transformation, destruction, or disposal as a hazardous waste if mixed with other substances. FPWG Federal Provincial Working Group on Controls Harmonization (Ozone-Depleting Substances). The group is responsible for coordinating the development of controls across all jurisdictions for ozone-depleting substances and their alternatives. This group now reports to the National Air Issues Coordinating Committee. GHG Greenhouse gases, such as carbon monoxide and various hydrocarbons. These are widely believed to contribute to global warming and climate change. GWP Global Warming Potential. A relative measure of the warming effect that the emission of a radiative gas might have on the surface troposphere. Usually a factor relative to CO2. Halon A compound containing bromine, chlorine, fluorine, and carbon in its structure. Halons have high ODP. Halocarbon A carbon-based compound that may contain hydrogen, fluorine, chlorine, bromine or iodine in its structure. Hydrochlorofluorocarbon (HCFC) A chemical compound that contains hydrogen, chlorine, fluorine, and carbon atoms. Hydrochlorofluorocarbons are much less stable than CFCs, but small quantities can reach the stratosphere and release chlorine. They are considered acceptable as substitutes for CFCs for a transitional period but because of their low ozone-depletion potential, HCFC production and importation will be phased out by the year 2030. Hydrofluorocarbon (HFC) A chemical compound that contains only hydrogen, fluorine, and carbon. Since no chlorine is present, these compounds have no ozone-depletion potential and are good replacements for CFCs, although they have a global warming effect.
Hydrobromofluorocarbon (HBFC) A compound containing only hydrogen, bromine, fluorine, and carbon atoms in its structure. HBFCs have a higher ODP than CFCs but not as high as halons. Methyl Bromide (MBr) A chemical compound containing bromine, hydrogen and carbon. It is a pesticide used as a fumigant. Montreal Protocol An international agreement titled "The Montreal Protocol on Substances that Deplete the Ozone Layer." The Protocol sets the reduction and phase-out dates for the consumption of ozone-depleting substances. It was developed under the auspices of the United Nations Environmental Programme (UNEP) to provide a coordinated response to the global problem of ozone depletion. More than 160 countries have signed the Protocol. Ozone-Depleting Substance (ODS) A chemical compound that is sufficiently stable to reach the stratosphere and capable of reacting with stratospheric ozone, either directly or through release of a chemical element that reacts after the compound decomposes. Ozone Depletion Potential (ODP) The rated effect of a compound on the ozone layer compared to CFC-11, which is assigned the value of 1.0. Official ODP values is assigned in the Montreal Protocol. Perfluorocarbon (PFC) A chemical compound that contains only fluorine and carbon. PFCs are not ODS. They do however have a high global warming potential. They may be a substitute for CFCs and HCFCs if lower GWP compounds are not available. Recovery Collection of ODS such as CFCs or HCFCs from equipment during servicing or before disposal (as opposed to venting to the atmosphere). Recycling Reuse of recovered ODS by charging back into the equipment after servicing. The ODS goes through some cleanup procedures before return, e.g., filtering, drying. This is usually done at the job site, but may be done off-site, depending on the volume. Reclamation Recovered refrigerants are shipped off-site to a central processing facility and cleaned by filtering, drying, distillation, and chemical treatment to meet or exceed industry accepted reuse standards. Results are verified by laboratory analysis. Refillable Container A container that meets the requirements of Transport Canada and is approved for multiple use.
APPENDIX A: DESCRIPTION OF ODS DISPOSAL TECHNOLOGIES The first section of this Appendix describes Commercially Available technologies that passed the initial screening assessment, i.e., those that met the mandatory requirements of technical performance, environmental emissions, and commercial availability. The second section describes Emerging Technologies that did not meet the mandatory criteria, typically because they failed to meet the criterion for commercial availability. The ODS disposal technologies are described in terms of process type and specific features. Descriptions of commercially available technologies are organized into two parts, a process description and a discussion of the technology’s operating history. The latter part also presents an evaluation of the commercial availability of the technology and most recent cost information. NOTE: All dollar figures in this document are expressed as year 2000 Canadian dollars unless otherwise specified. A-1.0
DESCRIPTION OF COMMERCIALLY AVAILABLE TECHNOLOGIES
A-1.1
Plasma (Non-incineration) Technologies
Introduction: Plasma, which is often described as the fourth stage of matter, is a mixture of electrons, ions and neutral particles at temperatures between 5000°K and 20 000°K. This high temperature, ionized, conductive gas is created by the interaction of a gas with an electric arc or magnetic field. Thermal plasmas are the source of reaction species at high temperatures that favour kinetic reactions. Ionization of gases is not a combustion process. This is a process to convert electrical energy directly to thermal energy at high temperatures. Applying reaction heat with plasma technology renders it possible to control heat and the chemical environment independently. For example, it is possible to heat a reducing gas to a high temperature without the use of oxygen, or to obtain an oxidizing environment without the introduction of any fuel. Thermal plasmas can be generated by passing an electric current through a gas between electrodes, by radio frequency (RF) or AC discharge without electrodes, or by microwaves. The choice of using a direct current (DC) plasma torch is based on its commercial availability at a power range up to 2 megawatts (MW) and at reasonably high energy efficiencies. The efficiency of the transformer and rectifier together is generally 95% to 98%, while the transfer of electrical energy to thermal energy is normally in the range 65% to 85%. Since losses are generally associated with the need to cool the torch with water, the higher efficiencies are achieved at higher gas flow rates and at higher power levels. With a DC plasma torch, plasma gases such as argon, nitrogen, air, argon/hydrogen can be used and plasma volume is relatively small with high energy density.
In RF applications, inductively coupled plasma torches are used, and energy coupling to the plasma is accomplished through the electromagnetic field of the induction coil. The absence of electrodes allows operation with a large range of gases, including inert, reducing or oxidizing atmospheres. In fact, the ability to use steam alone as the gas offers a cost saving compared to the AC plasma torch, which generally requires an inert gas such as argon. This kind of discharge produces a relatively large plasma volume. These plasmas are common at power levels up to 100 kilowatts (kW) and scale-up has been demonstrated up to the 1 MW range. The transfer from line AC to high frequency AC is quite efficient at about 95%. Efficiencies of coupling AC current in the coil to the plasma fireball of 65-75% have been reported with tube-type oscillation power supplies and up to 90% with solid-state power supplies. However, an expert suggested efficiencies up to 50% were more probable for commercial units. More recently, AC plasmas have been reported which are produced from 480V 3-phase power at 60 Hz stepped up through a high voltage transformer. Significantly, there is no need for high frequency AC as in the RF plasma. The equipment required to produce these plasmas is much smaller and less costly than that required for RF plasmas. Electrical efficiencies are higher than for DC plasmas because there is no need for rectification and the electrical to thermal conversion is 85% to 90% efficient. The AC plasma volume produced is also large, comparable to that produced by RF. This technology was developed in Russia and has been further refined by Scientific Utilization International, of Huntsville, AL over the last seven years. There has been very little published about this technology in refereed journals. Operating History: During the past decade plasma technology has evolved as one of the more promising innovative technologies for the thermal destruction of hazardous wastes. The current interest in applying plasmas to the destruction of hazardous wastes is related to the availability of both DC and RF plasma torches in the power range 0.3-1.0 MW. The most notable use of this technology for ODS disposal is in Australia’s halon and CFC destruction program, discussed below. A-1.1.1 Argon Plasma Arc Process Description: PLASCON is an “in flight” plasma process, which means that the waste mixes directly with the argon plasma column. Argon was selected as the plasma gas since it is inert and does not react with the torch components. Waste is rapidly heated (one millisecond, or ms) in the reaction chamber (a flight tube) to about 3000°C, where pyrolysis occurs in about 20 ms. Oxygen is added at the injection manifold to ensure that any carbon formed during pyrolysis is converted to carbon monoxide. Pyrolysis is followed by rapid (2 ms) alkaline quenching from 1500°C to less than 100°C. Such rapid quenching prevents the formation of dioxins and furans. The cool gas from the quench is further scrubbed with alkaline liquor in a counter-current packed column to neutralize HCl and other acid gases. The off-gas from the column, which consists mainly of CO, H2, Ar and some CO2, then passes to a small ground flare that converts CO to CO2 and H2 to H2O.
A destruction efficiency of 99.9999% has been achieved at destruction rates of 150 kg/hr. Onstream factors have run at about 80% due to problems in the flight tube and injection manifold associated with the very hot operating conditions. The halide salt solution from the scrubbing system is stored and discharged on weekends to the Melbourne’s municipal wastewater treatment system during periods of reduced industrial activity. Operating History: PLASCON, an argon plasma arc process, was developed in Australia by SRL Plasma Ltd. in conjunction with the Commonwealth Scientific and Industrial Research Organization (CSIRO). The process was developed over an eight year period and commercialized in 1992. Following extensive pilot studies on various CFCs and halon compounds in 1993, the PLASCON system was provided to the Department of Administrative Services Centre for Environmental Management (DASCEM) for the destruction of Australia’s surplus halons and CFCs. The plant was commissioned in 1996 and since then about 1000 MT of Halon 1011 and about 100 MT of CFCs have been destroyed at destruction rates of 115-120 Kg/hr. Key advantages of this process are the very high destruction efficiencies and negligible dioxins/furans emissions demonstrated on a commercially operating system. Costs are reported to be of the order of $2.75/kg. A-1.1.2 Inductively Coupled Radio Frequency Plasma Process Description: Plasma temperatures of 10 000°C were achieved in the 185 kW torch and destruction efficiencies of at least 99.99% were demonstrated at feed rates of about 50 kg/hr. The equipment for the demonstration plant is essentially the same as that used in the pilot plant except for the electric power supply, which was 132 kW (2.4 MHz, 8.8 kV, 15.0 A). Gaseous CFCs and steam are fed through the plasma torch where they are heated and enter directly into the destruction reactor maintained at about 2000°C for about 2 seconds. Subsequently, the gases are cooled and scrubbed with caustic solution to remove acid gases. At feed rates of at least 50 kg/hr, destruction efficiencies of greater than 99.99% were demonstrated. Testing for trace toxic emissions during the demonstration measured 0.01 ng/m3 total PCDDs and 0.01-0.02 ng/m3 total PCDFs TEQ. Operating History: In 1994, several Japanese researchers from government, academia and industry collaborated in experiments which demonstrated the destruction of CFC-12 and Halon 1301 in a pilot-scale Inductively Coupled Radio Frequency Plasma (ICRFP) reactor. Based on these pilot plant results, a demonstration plant was constructed at the Chiba prefecture by a consortium of industrial concerns under the auspices of the Ministry of International Trade and Industry (MITI). The demonstration plant operated over the period April 1993 to March 1996 by which time 2.443 MT of CFC-12 had been destroyed. A major advantage claimed for the RF plasma over DC plasma is the elimination of electrodes which are known in DC plasmas to be subject to corrosion. The RF plasma also has a slower gas flow rate and a larger plasma flame which results in higher residence time. This process has demonstrated high destruction efficiencies and very low PCDD/PCDF emissions on a scale approaching commercial scale. It is also possible that the RF approach may lead to increased on-stream time over that observed in the PLASCON process described above. No operating costs for a commercial-scale unit are reported but are estimated to be somewhat less than indicated for the Plascon process because argon is not required, that is, costs are expected to be of the order of $2.50/kg.
A-1.1.3 AC Plasma Process Description: Systems incorporating their patented Plasmatron AC plasma are designed by Scientific Utilization International (SUI) for the destruction of hazardous wastes. As discussed above, the AC plasma is produced directly with 60 Hz high voltage power but in other respects is similar to the inductively coupled RF plasma. The system is electrically and mechanically simple and is thus claimed to be very reliable. Also, the Plasmatron process can tolerate a wide variety of working gases, including air, and can tolerate oily gases. While some information is available describing the plasma generator and its associated equipment, no information was provided describing the destruction process, but one could imagine a process very similar to the Plascon process. Operating History: These plasmas have only recently been developed to the stage where they are being applied to hazardous or toxic waste destruction. It has not yet been commercially applied to the destruction of ODS but CFC was destroyed to non-detectable levels in a 500 kW demonstration unit. A 1 MW AC plasma system was shipped in late February 2000 to the U.S. Customs Service in California for destruction of narcotics. The technology satisfies US EPA and State of California environmental requirements. SUI is prepared to offer Plasmatron systems designed for the destruction of ODS. No cost information was provided but destruction costs are estimated to be less than Plascon because of better reliability and its ability to use air as the working gas; that is, $2.50/Kg. A-1.2
Other Non-Incineration Technologies
A-1.2.1 Solvated Electron Technology Process Description: The process is a batch process involving two simple vessels; one a heated reaction vessel and the other a refrigerated ammonia recycle vessel. The ODS compounds are decomposed in the reaction vessel with liquid ammonia and metallic sodium. The process operates at atmospheric pressure. It is expected that no dioxins and furans would be produced by this process since it does not involve oxidation and operates at relatively low temperatures. No atmospheric emissions result from the decomposition of the original ODS material. Only nontoxic waste products are formed: sodium chloride, sodium fluoride, biodegradable organic compounds, and water. Methane and ethane are also produced as by-products. Metallic sodium is consumed in the process and is the major component of operating cost. About 95-98% of the ammonia is recycled and hence does not contribute much to operating cost. The process was demonstrated on a pilot scale to destroy carbon tetrachloride, several CFCs, HFCs, refrigerant blends and halons at greater than 99.99% efficiency. Destruction costs are claimed to range from about $9.00 - $13.75 per kilogram of CFC (an approximate average of $11.00/kg was used for ranking purposes). Operating History: Commodore Advanced Sciences, Inc. of Albuquerque, New Mexico, developed a process for the destruction of ODS in the early 1990s based on solvated electron solutions formed by dissolving metallic sodium in ammonia. A US patent for the process was issued in 1995. While developed specifically for ODS destruction, the process has never been
commercially applied to ODS destruction because of lack of demand. It has been applied successfully to PCB destruction and is currently being applied to the destruction of chemical warfare agents. A major advantage of the process is its simplicity. A disadvantage is the lack of demonstration of ODS destruction on a commercial scale, although there appears to be little doubt that the process could be successfully applied for that purpose. Handling metallic sodium presents safety issues and will require careful attention to operating procedures. Finally, operating cost is heavily dependent on the cost of metallic sodium. A-1.2.2 UV Photolytic Destruction Process description: The process involves mixing the ODS material in the gaseous state with air and leading the mixture into a reactor fitted with low pressure mercury ultraviolet (UV) lamps emitting light with wavelengths in the range 185-254 nm. Photons emitted from these lamps are capable of breaking apart the chemical bonds of the ODS molecule, forming free radicals. PTI affixes a dry, porous reagent liner to the inner surface of the reaction chamber that chemically reacts with the free radicals produced by the photochemical destruction of the ODS molecules. The chemical reaction forms stable, inorganic, solid reaction products within the liner material. The only other by-products from the photochemical destruction of ODS are CO2, water vapour and air. Laboratory bench and pilot-scale tests with a feed rate of 11.4 kg of Halon 1211 per day demonstrated destruction efficiencies of 99.66%. Test results on other ODS demonstrated destruction efficiencies greater than 99.9%. It was believed optimized commercial equipment would achieve greater than 99.99% destruction efficiency. No formation of dioxins and furans is expected due to the low temperature of the entire process. The liner is a PTI proprietary mixture of calcium oxide, calcium hydroxide, magnesium hydroxide and other ingredients. Spent liners are not a hazardous waste as defined by the U.S. Resource Conservation and Reclamation Act (RCRA) and can be disposed of as an ordinary solid waste, or even recycled as a cement ingredient. Operating History: Process Technologies, Inc. (PTI) of Boise, ID developed and patented a proprietary process for the destruction of chlorinated compounds including ODS based on UV photo-dissociation. The process has never been commercialized for ODS destruction due to lack of demand. Advantages of the PTI process are that it is a non-thermal process achieving high destruction efficiencies without dioxin/furan formation, that the liner prevents the formation of HF and HCl in the exhaust, and that the process is simple and modular in design. Costs are reported to be about $11/kg of ODS. It was not possible to obtain further information from PTI; the technology may no longer be actively promoted. A-1.2.3 Gas Phase Chemical Reduction Process Description: The liquid or gas is preheated with boiler steam before injection through atomizing nozzles into the reactor. The gas mixture from the atomizing nozzles swirl around a central stainless steel tube and is heated by vertical radiant tubes with internal electric heating elements to a temperature of about 850°C. The process reactions take place from the bottom of the central tube onwards and take less than one second to complete. Organic compounds are
ultimately reduced to methane, hydrochloric acid, and (reportedly) minor amounts of low molecular weight hydrocarbons. Destruction and removal efficiencies for PCB and DDT wastes were shown to be greater than 99.99999% (seven nines) and 99.9999% (six nines), respectively. Some formation of dioxins and furans at operating temperature is possible, and levels of 40-80 pg/m3 have been reported. The hydrochloric acid is neutralized by addition of caustic soda during initial cooling of the process gas. An attached multi-stage scrubbing system removes inorganics from the reacted gas stream. The product gas, composed primarily of hydrogen and methane, is subsequently used as fuel for system components. Operating History: Eli Eco Logic International Inc. (ECO LOGIC) of Rockwood, Ontario developed and commercialized the ECO LOGIC Gas-Phase Chemical Reduction process. ECO LOGIC applied for a patent for this core technology in 1986. The proprietary process is a nonincineration technology suitable for destroying organic wastes in all matrices including soil, sediment, sludges, high-strength oils, watery wastes and bulk solids such as electrical equipment. ECO LOGIC has destroyed PCB waste and DDT waste on a commercial scale, and has considerable laboratory and field data on many other hazardous wastes including chemical warfare agents. ECO LOGIC supplies fixed systems and provide treatment services with transportable systems. The major advantage of this process is the very high destruction efficiencies achieved. The transportability of the process may also prove beneficial. The major drawback is the lack of experience on any scale in destroying ODS, although the process has been proven on PCBs. Precise cost information is not available, although the process would be expected to be fairly expensive. As an approximate estimate, a high default value of $10/kg was used for ranking purposes. A-1.2.4 Gas Phase Catalytic Dehalogenation Process Description: Hitachi Corp. of Tokyo, Japan has developed a process in which CFCs are destroyed over a proprietary metal oxide catalyst at 400°C at atmospheric pressure. The HCl and HF produced are absorbed in a lime solution. Destruction efficiencies greater than 99.99% were achieved for CFC-12. No dioxin/furan data is available, although formation of these compounds would be expected to be minimal at these operating temperatures. Operating History: Hitachi claims operating costs of about $2.85-4.30/kg CFC. Capital costs were estimated at about $ 430 000 for a 1 kg/hr system and $ 1.43 million for a 10 kg/hr system. A Canadian stakeholder is currently negotiating rights to similar technology from a US licensor. This process has been commercialized for PCB destruction and has been applied to numerous other chlorinated compounds, but has not yet been applied to the destruction of ODS. Laboratory tests are underway and a report on CFC destruction is expected by the end of March 2000. Commercial destruction of PCBs has demonstrated a destruction efficiency of 99.9998%. It is claimed that no dioxins or furans are produced in the process. Destruction costs are anticipated to be consistent with the figures described above. The key advantage of this technology is the expected low destruction cost which results primarily from its low operating temperature relative to incineration technologies. It is also very efficient in destroying CFCs and avoids formation of dioxins and furans.
A-1.2.5 Liquid-Phase Chemical Conversion Process Description: This technology uses a liquid-phase chemical conversion process operating at between 80-120°C, where ODS is reacted with a blend of potassium hydroxide and polyethylene glycol. Based on lab-scale demonstrations, the destruction efficiency is greater than 99.7% for CFCs and halons. It has been tested on ODS in pilot-scale tests and is used commercially for PCB wastes. The process is claimed to require and low capital investment and to be almost emission free. No dioxins/furans are generated in this relatively low-temperature process. Operating History: This mobile system technology was developed by Ontario Hydro Technologies to destroy a variety of wastes. Two mobile units are currently in operation for PCB destruction. Although commercial destruction of ODS is not currently available using this process, Ontario Hydro has indicated that modifications to existing equipment, demonstration testing, and regulatory approval could be obtained in a relatively short time (3-4 months claimed), should a demand for this service materialize. Costs are estimated to be less expensive than incineration for ODS, based on extrapolation from experience with PCB waste disposal. A-1.2.6 Vitrification Process Description: This process fixes the products of ODS dissociation and hydrolysis into chemically durable glass frit which is capable of being processed into glass product. The first stage involves destruction of organics at high temperature typically with a plasma arc. Once the halogens are separated from the carbon and hydrolyzed in the off-gas treatment system, the glass manufacturing process begins. Naturally, the gas cleaning system would have to include rapid cooling to prevent significant formation of dioxins and furans. A specially formulated mixture of calcium oxide and silica oxide along with other proprietary chemicals are added to the smelter to begin the formation of glass. The additives ensure that the glass frit product can be returned to commerce for additional processing into higher quality glass product. Operating History: The process is offered by Pure Chem, Inc., a specialty refrigerant processor with experience in the conversion of halogenated compounds into a glass matrix using vitrification. The process has not been applied to CFCs but has been applied to carbon tetrachloride achieving 99.9999% destruction. The process has also been used by the U.S. Department of Energy to fix radioactive materials and heavy metals. Operating cost of about $ 3.80/Kg is reported and capital cost, depending on the size of the facility, is reported in the range $1.5 to $3.5 million. Although the byproducts of this process are incorporated in the glass frit, which is then sold, the process was not considered to be a chemical conversion process that results in a directly marketable chemical product. However, it is significant that the profits of the sale of the glass frit can be used to offset the costs of destruction, and that the process avoids the costs of dealing with the disposal of byproducts such as halide salts. These factors may result in significantly lower overall disposal costs, in comparison to some other technologies where the estimated costs of dealing with the disposal of byproducts has not been factored in.
The only technologies recommended in the 1992 UNEP report for the destruction of ODS were thermal oxidation (incineration) processes. Incineration is the use of controlled flame combustion to destroy ODS in an engineered device. Several specific processes were recommended, however not all may be appropriate for all classes of ODS. The technologies are described separately below, but there are a number of characteristics common to all incineration processes. The significance of the production of greenhouse gases (GHGs) from incineration technologies is important to note. This has become a major scientific and political concern in many countries, and as a result there is significant incentive for the consideration of non-incineration technologies for the disposal of ODS. However, incineration technologies do have the general advantage of being fully developed commercially and conveniently located geographically, and thus are given due consideration in terms of finding realistic and timely solutions to the disposal of ODS surplus. All of these factors have been taken into account in the ranking of commerciallyavailable ODS disposal technologies. Process Description: Thermal oxidation processes generally operate at temperatures of 900°C or higher, i.e., temperatures at which organic compounds are destroyed. Destruction efficiencies of 99.99% are readily achieved in well-designed units that are operated properly. High performance incinerators designed specifically to destroy stable organic compounds, such as PCBs and ODS, operate at significantly higher temperatures, generally at 2100°C or higher. Such high performance incinerators generally achieve 99.9999% destruction. Because halogen-containing ODS has a low heat value, the required high operating temperatures can only be achieved by use of a supplementary fuel such as natural gas, fuel oil, or propane. The primary products from the thermal destruction of ODS are carbon dioxide (CO2), water (H2O) and hydrochloric and hydrofluoric acids (HCl and HF). Hydrogen bromide (HBr) and/or bromine (Br2) are produced in the case of the destruction of halons. Products of incomplete combustion (PICs) such as carbon monoxide, hydrocarbons, organic acids and partially degraded products may also be produced, but these PICs are emitted in only small amounts from welldesigned incineration facilities that provide high temperatures, adequate residence times (1 to 2 seconds), excess oxygen and good mixing. A more serious problem is the potential production of toxic polychlorinated dibenzo-paradioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in trace quantities. PCDD/PCDF formation can be minimized in well-designed incinerators. Since these compounds generally form in the temperature range 500 to 900°C, their formation is unavoidable as the hot flue gases from incinerators are cooled in the associated gas cleaning system. It has also been reported that the incineration of halons increases the potential for dioxin formation This is believed to be due
to the free radical scavenging effect of bromine. However, inclusion of a quench cooling operation to rapidly cool the gas to a temperature well below the dioxin/furan formation temperature range usually limits formation of these toxic byproducts to acceptable levels. It should be noted that the formation and control of dioxins and furans is independent of the type of incinerator. Another serious technical problem is the production of the above-mentioned acid gases, which must be removed by inclusion of a gas scrubbing system. This generally involves the use of electrostatic precipitators, baghouses, Venturi scrubbers, packed bed scrubbers or plate scrubbers. The formation of bromine compounds in the case of halon incineration is particularly troublesome. In general this substance is particularly difficult to remove, however several approaches can be taken to minimize the formation of Br2, including the introduction of sulphurcontaining compounds and the minimization of the cooling period. The formation of halide acids also presents some technical difficulties. An HF-resistant refractory lining and binder must be used in the combustion chambers through the quench area. Corrosion resistant fiberglass-reinforced plastic (FRP) is generally required in the scrubbing systems and the presence of fluoride requires special lining of the FRP to avoid attack of the glass fibers. Finally, the acid gases also require upgrading of the bag material in the baghouse. Incineration facilities typically are not fitted with such equipment, however retro-fitting of existing facilities is possible. Cost factors would naturally have to be taken into consideration before performing such a retrofit, and it is not yet clear whether a sufficient market for ODS surplus will become available to warrant this investment in Canadian and U.S. facilities (Sterman, 1999). Operating History: The only incineration facility in Canada currently permitted to dispose of ODS is Bovar’s facility in Swan Hills, Alberta, although at this time there are technical issues that severely limit capacity (see discussion of rotary kilns below). A number of the various types of incineration technologies are available in the U.S. and have been in operation for many years for the destruction of hazardous waste materials, including ODS. Operating costs for the incineration of ODS are expected to be in the medium-to-high range compared with most technologies. Precise cost estimates vary considerably depending upon the type of ODS, quantities to be destroyed, and market conditions. Low pressure ODS such as CFC-11 and CFC113, which are usually mixed with other solvents, are less expensive to incinerate than high pressure ODS such as CFC-12 and CFC-22, while halons are in the high pressure category and also have additional issues because of their bromine content. There are indications that hazardous waste incinerators in the U.S. may be currently running low on supply; prices may therefore fall in the future. Based on information available in the current literature and on several personal communications with incineration facilities, an approximate value of $5 per kilogram of ODS destroyed has been selected as a default value for incineration technologies for which no other specific cost information could be obtained.
A-1.3.1 High Performance Incineration Process Description: The Bovar facility at Swan Hills, Alberta, is a state-of-the-art high performance incineration facility where the company operates two rotary kilns. The smaller of these includes a rapid cooling step and is thus more amenable to modifications that would allow the kiln to be used for ODS destruction. The operating temperature of the secondary combustion chamber is maintained at 1200°C, higher than the 1100°C typical for conventional incinerators. The unit has been specifically designed to ensure adequate residence time (greater than 2 sec) at greater than 1100°C in sufficiently turbulent conditions to ensure destruction of PCB to a DRE of 99.9999%. Furthermore, Bovar submits its unit to a three day compliance test every 6–16 months during which the incinerator is loaded with PCB material and these compliance tests have consistently demonstrated 99.999999% DRE. The incinerator proposed for ODS destruction is expected to achieve 99.9999% destruction because the autodecomposition temperatures of CFCs are comparable to PCBs. Nevertheless, Bovar would propose to run a compliance test prior to processing ODS material. Operating History: Under Alberta regulations, Bovar may destroy ODS at its Swan Hills facility; in fact this is the only facility currently permitted to destroy ODS in Canada. Bovar has indicated an interest in pursuing the necessary modification to its facility to handle significant quantities of ODS should an appropriate market for ODS surplus disposal materialize in Canada. Bovar indicates it would take about six months to implement the necessary modifications. A-1.3.2 Liquid Injection Incineration Process Description: Liquid injection incinerators are usually single-chamber units with one or more waste burners into which the liquid waste is injected, atomized into fine droplets, and burned in suspension. Problems of flame stability may result when large volumes (greater than 40%) of CFCs or other ODS are injected into the burner. These incinerators are able to handle a wide range of liquid or vapour wastes, have high turndown ratios and have no moving parts. Liquid injection incinerators are limited to treating wastes that can be atomized through the burner and are therefore susceptible to plugging, however, the incineration of ODS is not likely to be limited by these constraints to a significant degree. Operating History: The only liquid injection hazardous waste incinerator in Canada is operated by Safety Kleen in Sarnia, Ontario, but it is not presently capable of nor permitted to destroy halogenated wastes. A-1.3.3 Reactor Cracking Process Description: The process uses a cylindrical, water-cooled reactor made of graphite, and an oxygen-hydrogen burner system. The reactor is flanged directly to an absorber. Waste gases typically consisting of CFCs, HCFCs and HFCs are fed into the reaction chamber where the temperature is maintained between 2000-2600°C. The gases are broken down to HF, H2O, HCl, CO2 and Cl2. The cracked products are cooled in the absorber and the acid gases are purified and recovered as 55% HF and 33% HCl, both of technical grade quality. Cracking efficiency exceeds
99.999%. The resulting waste gas essentially only consists of CO2, O2 and water vapour and meets the requirements of the German Clean Air regulations (TA-Luft). The process is fueled with 35-40 Kg of hydrogen per MT CFC and consumes 300 Kwh of electrical energy per MT CFC. Operating History: Reactor cracking is a proprietary process developed by Hoechst AG (Frankfurt, Germany). A European patent (EP 0 212 410 B1) was issued in 1986. Solvay acquired Hoechst’s fluorocarbon business in 1996, and now operates the cracking destruction facility, which is located near Frankfurt. Solvay works in collaboration with Westab, a company that collects and transports waste CFCs. The process has operated since 1983 to treat waste gases from the production of CFCs and, more recently, waste CFCs. Solvay has legal permission to destroy 9700 tonnes of CFC per year. Principal advantages of the process are its use of an oxygen-hydrogen flame which limits formation of NOx, its very high operating temperature and rapid cooling (which prevents the formation of PCDD/PCDF), and the recovery of hydrofluoric and hydrochloric acids. The process is limited to gaseous feeds although commercial destruction of CFCs could involve the inclusion of a vaporization step in the facility. Solvay indicates a cost of about $3.75 for destruction at its Frankfurt facility. Solvay is also prepared to offer its technology under license for construction of a facility in Canada. Solvay estimates a 1600 MT/year CFC cracking unit would cost about $3 million excluding the license fee and engineering. A-1.3.4 Gaseous/Fume Oxidation Process Description: This process uses refractory-lined combustion chambers for the thermal destruction of waste vapour streams, most often VOCs. The fume stream is heated using an auxiliary fuel such as natural gas or fuel oil. A combustion temperature near 1100°C is required for most ODS compounds. Gaseous residence times in fume incinerators is about 1-2 seconds. Some fume incinerators are equipped with heat exchangers in the flue gas outlet to pre-heat the combustion air and/or the waste fume. These recuperative incinerators are capable of recovering up to 70% of the energy in the flue gas. Operating History: Fume incinerators are designed for continuous operation and are a simple, proven technology and, as noted above, can include energy recovery. Some of the ODS (e.g. CFC-12, CFC-114, or CFC-115) are gases at ambient temperature and can be destroyed by feeding directly from their pressurized storage into the incinerator. Fume incinerators are almost always privately operated and are typically found in manufacturing plants . They are seldom used at commercial hazardous waste incineration facilities because of the impracticality of transporting low density fumes and gases. A-1.3.5 Rotary Kiln Incineration Process Description: Rotary kiln incinerators are refractory-lined rotating cylindrical steel shells mounted on a slight incline from horizontal. Capable of handling both liquid and solid wastes, the rotation of the shell enhances mixing and the inclination causes ash or molten slag to fall out.
Most rotary kilns are equipped with an afterburner which ensures complete destruction of exhaust gases. Liquid materials such as CFCs, halons and other ODS can be fed into the rotary kiln or directly into the afterburner. Operating History: Rotary kilns have been used to destroy all forms of hazardous waste (gas, liquid, solids, including sludge). Because of this flexibility, rotary kilns are most frequently incorporated into the design of commercial incinerator facilities. The principal advantage of the rotary kiln is its ability to handle a wide variety of liquid and solid wastes. However, these kilns are very expensive to build and maintenance costs are high. Also, because of the production of acid by-products noted above, there are generally severe restrictions on the amount of ODS in the raw material feed to the kiln. A-1.3.6 Cement Kilns Process Description: Existing cement kilns, when properly operated, can destroy most organic compounds including PCBs because the temperature in the burning zone is over 1500°C and residence times are up to 10 seconds. Tests have demonstrated CFC destruction efficiencies of greater than 99.99%. In general, most cement kilns could tolerate the controlled addition of ODS, but this would have to be evaluated on a case-by-case basis. Fluorine can be beneficial to the cement making process because it allows the cement-producing reactions to occur at a lower temperature, thus offering the opportunity for reduced fuel consumption. However, higher levels of fluorine have negative effects on cement quality. As a broad generalization, the maximum fluorine content is about 0.25% of the raw material feed. Chlorine is generally regarded as an unwanted constituent because it creates operating problems and the newer pre-heater/pre-calciner kilns are expected to have the lowest tolerance for chlorine. The theoretical limit for chlorine is about 0.015% of the raw material feed but the practical tolerance is believed to be much higher. Operating History: The major advantage of this approach is that there are large existing capacities in Canada and the U.S. The disadvantage is that fluorine and chlorine input rates need to be carefully controlled. Furthermore, cement kilns are not currently set up to handle or burn CFCs and halon wastes. Necessary modifications would require equipment for monitoring hazardous emissions. Operation costs per unit of ODS destroyed are estimated to be less than those for most incineration technologies, i.e., about $4/kg as opposed to about $5/kg. A Canadian stakeholder has entered into discussions with an overseas firm that has access to a cement kiln for which addition of appreciable quantities of chloride are beneficial due to the nature of the kiln raw material. Comprehensive testing has reportedly demonstrated that there are no adverse environmental impacts from substitution of up to 500-1,000 MT/year of CFCs in place of addition of chlorine. Due to the limited availability of CFCs locally there may be an opportunity to export CFCs from Canada for destruction to this facility. A-1.3.7 Internally Circulating Fluidised Bed Incineration Process Description: . Internally circulating fluidized bed incinerators can be fired with any solid, liquid or gas fuel. CFCs and air are blown through the incinerator fluidized bed, and CFCs are broken down by the presence of methane and hydrogen in the reducing atmosphere of
the incinerator. Calcium carbonate is also fed into the incinerator to adsorb the corrosive HCl and HF gases formed by the breakdown of the CFCs, although one expert indicated he was unable to substantiate this claim. Operating History: In 1995, a joint effort by Japan’s National Institute of Materials & Chemicals Research (NIMCR) and the incinerator supplier Ebara Corp. of Tokyo demonstrated CFC destruction in an internally circulating fluidized bed (ICFB) incinerator. The incinerator was modified by attachment of a special nozzle at the bottom of the incinerator to blow CFCs and air through the fluidized bed. Tests using a 30 MT/day incinerator at Ebara’s Fujisawa factory have shown that burning with wood chips can destroy more than 99.9998% of CFCs. The main attraction of this approach is its relative simplicity and the large number of wood chip burners in Canada, although it is not necessary to burn wood chips in ICFB incinerators. However, an ABB fluid bed incinerator is known to have been operating on a BC pulp mill since 1997. Nevertheless, such installations would need to install gas cleaning systems incorporating quench cooling.
The following ODS disposal technologies were reviewed and evaluated, and judged not to represent realistic solutions for Canadian stakeholders in possession of surplus ODS within the time frame required. In most cases the main reason for this determination was the lack of evidence of commercial availability. Where other reasons applied, they were included in the brief descriptions below. The decision not to include a particular technology in the previous discussion of commercially available technologies does not necessarily mean that the technology could not become a viable contender for the disposal of ODS surplus stocks in Canada should circumstances change or unforeseen developments ensue. Many of the technologies described certainly have merit from a theoretical point of view, particularly those which involve chemical transformation and the potential recovery of a valuable chemical product. Should a particular technology be promoted actively, and sufficient resources made available, it is conceivable that it could become commercially available in a relatively short time frame, and could then compete favourably with the commercially available technologies discussed previously. In practice, however, the time required to develop a new technology and make it available on a commercial scale would restrict the technologies described below to ODS destruction well after the criterion date of January 1, 2003. The current review presents a picture of the technology situation at this point in time and given the available data; allowance should be made for future reconsideration of the technologies described in this section should circumstances change. A-2.1
Incineration Technologies
A-2.1.1 Waste Gasification Waste is gasified at 1600°C, forming a molten ash bath. The hot gases generated are further treated in a hot coke bed where any unconverted halogenated hydrocarbons are decomposed. The molted ash is dripped into water, where it forms a glass-like agglomerate for disposal. Dioxin and furan formation is unlikely. The system consumes coke, which may introduce additional ash and sulfur. A Dutch facility using this process has an annual capacity of 5000 tons of waste. Originally classified as a commercially available technology in the 1992 UNEP document, this process was not considered to be a likely candidate as a solution for Canadian ODS surplus. Only limited tests were performed with CFCs and halons were not tested, but more importantly, confirmation of destruction efficiency with ODS is lacking. No further information was found to suggest this technology could realistically be applicable to the disposal of ODS in Canada by 2003. A-2.1.2 Gas Injection Oxidation/Hydrolysis Also known as “burn box” technology, this was commercialized as a packaged fume incinerator. It was not specifically tested on ODS, but rather on similar compounds. The 1992 UNEP document reported that two US vendors were beginning a testing project to evaluate destruction efficiency for CFCs. No additional information was found to determine current status.
Essentially, this is simply a smaller version of commercially available incinerators, and it was felt unlikely that someone would buy such an incinerator specifically to destroy CFCs. A-2.2
Plasma Technologies
A-2.2.1 Plasma Conversion of CFCs into Harmless Polymer Using Ethylene or Ethane as Co-monomer This technology was developed by Samco International Inc. in Kyoto and uses a radio-frequency plasma to copolymerize CFCs with ethylene or ethane. The resultant copolymer is highly crosslinked. A lab-scale apparatus treated 10 g/h of CFC-113 with an efficiency of 80% in 1994. Samco has already done all of the basic development work for this CFC stabilization process, and has patents in the US and Japan. Commercialized equipment is expected to have a treatment capacity of 1 kg/h, and maximum recovery efficiency would be achieved with multi-stage units. Samco International Inc. has no immediate plans to develop equipment for higher volumes of CFC. The technology could be licensed, and it could represent an interesting alternative technology if applications for the copolymer were found. Despite the above, the technology was classified as an emerging technology because of the lack of a commercial-scale operation and because the vendor is apparently not developing and promoting the technology for such larger scale operations. A-2.2.2 Destruction of ODS in Dilute Exhaust Stream Using Energetic Electron Induced Plasma - Adsorbent Filter Hybrid System This is a low temperature plasma technology developed at McMaster University in Hamilton, Ontario. Reaction by-products are adsorbed into an activated carbon bed. A destruction efficiency of greater than 90% was achieved with trichloroethylene. The development of the technology is at the bench-scale and it has not been demonstrated for ODS destruction. It was not thought that this technology would become commercially available by 2003, particularly since other plasma technologies are further developed. A-2.2.3 High Voltage Gliding Arc Plasma Discharge Reactor for CFC Destruction This plasma technology was developed by GREMI (Université d’Orléan, France). CFCs are fed into the plasma along with water vapor. There is potential formation of synthesis gas (CO and H2) that could be recovered. HCl and HF could be scrubbed or recovered. Destruction efficiency of CFCs greater than 90% was demonstrated. The development of this technology is limited to bench-scale tests. It was thought unlikely that this technology would become commercially available by 2003, particularly since other plasma technologies are further developed. A-2.2.4 Freon 113 Destruction in Air Under the Effect of Nanosecond Corona and Microwave Discharge This technology is described in a study to develop better understanding of CFC destruction mechanisms in plasma, and is at the R&D developmental stage only.
A-2.3.1 Chemical Reduction of ODS Using Metallic Sodium on a Solid Substrate The ODS gas stream is fed to a column filled with a solid substrate coated with sodium metal. The process operates under an inert atmosphere. In bench-scale tests, destruction efficiency for CFCs was shown to be greater than 99%, and greater than 98% for halons. No toxic gaseous or liquid effluents are generated. This is a relatively simple destruction process, however, the preparation of the solid substrate with coated sodium metal may be more complicated. The process was developed by a German company, and E.A. Technology Ltd. has also developed such a process. The technology was expected to be available within 5 years in 1992. No additional information was found, however, confirming development beyond bench-scale testing, and it was not considered likely to be commercially available in 2003 on that basis. A-2.3.2 Chemical-Thermal Destruction of Halogenated Hydrocarbon with Calcium Silicate or Oxide Waste is fed to a reactor along with calcium silicate or oxide at 700°C and 98 kPa. The halogen reacts with the solid reagent. A destruction efficiency of greater than 99.99% was obtained with halogenated hydrocarbons, and no dioxins were detected. The process has not been tested for ODS destruction.. The solid reagent can be recovered by superheated steam, which produces HCl. The process has been demonstrated at the pilot scale. In 1992, a commercial facility was expected to be in operation within 2-3 years. No additional information could be located to confirm development beyond bench-scale testing, and it was not considered likely to be commercially available in 2003 on that basis. A-2.3.3 Mineralization of CFCs with Sodium Oxalate This process was developed at the Department of Chemistry of Yale University, New Haven. Gaseous CFCs are fed into a packed bed filled with sodium oxalate powder at 290°C, which generates NaF(s), NaCl(s), C(s) and CO2. Residual sodium oxalate can be pyrolysed to carbonate at 350°C if desired. The inventors claim complete destruction of CFCs and CCl4. This is a relatively simple process that could likely be scaled up with little difficulty. Economical success would depend on cost and availability of sodium oxalate. It was classified as emerging technology because it was believed that it will not be available by year 2003, based on the current state of development. A-2.3.4 Aerosol Mineralisation of CFCs by Sodium Vapour Reduction The process was developed by the National Institute of Standards and Technology, Maryland, USA. Gaseous CFCs are fed along with argon (Ar) and sodium (Na) vapour into a reactor maintained at 1400°C, which generates NaF(s), NaCl(s) and C(s). The fine solids are separated from the argon by filtration. Residual sodium vapour can be condensed and the argon recompressed for recovery and recycle. The carbon can be separated by washing out the salt. A destruction efficiency for CF4 greater than 99% was obtained. The technology development was at the bench scale in 1997, no additional development has been done since, and there are apparently no intentions to continue development.
A-2.3.5 Molten Metal Technology (MMT) This technology involves the injection of the wastes along with oxygen in a reactor containing metallic solvent at 1650°C, which dissociates the wastes into their atomic constituents. The resultant acid gases are then required to be scrubbed. The technology was being tested for CFCs destruction at the bench scale in 1992. If successful, a prototype was anticipated. No information was available confirming the further development of this technology. A-2.3.6 Pressurized Coal Iron Gasification (P-CIG) P-CIG is a process for the gasification of coal that is injected into a slag-covered iron bath along with oxygen at 1450°C. The technology was tested at the lab scale for halon destruction, and pilot-scale development of this technology was being planned in 1992. No information was available confirming the further development of this technology. A-2.3.7 Dormier Incineration Process in Steel Smelter The volume of wastes is first reduced by pyrolyzing the organic material at 700°C in a rotary kiln. Wastes are then fed into a molten-steel bath at 1600°C to reduce waste to their chemical constituents. The resultant acid gases are then be scrubbed. The first pilot plant was expected to be in operation in a West German steel plant in 1992. No information was available confirming the further development of this technology. A-2.3.8 Destruction of CFCs During Chemchar Gasification In a process developed at the University of Missouri (Columbia, Mo.), CFCs are oxidized in a heated column filed with char and 5% KOH. The chlorine from the CFCs is recovered as KCL and the fluorine recovered as non-leachable carbon fluoride. A destruction efficiency of greater than 99.996% was obtained with CFC 113 and CFC 13 in bench-scale tests in 1998. The formation of carbon fluoride was considered to be problematical, and furthermore it was though unlikely that the technology would become commercially available by 2003. A-2.4
Photochemical Technologies
A-2.4.1 UV Laser Photolysis for the Destruction or Transformation of Halon 1301 into CF3I This technology was developed in Israel by Spectronix Ltd.. It uses an ArF excimer laser to irradiate Halon 1301 in the presence of I2 to generate CF3I. The inventors claim that CF3I is a potential halon replacement. The technology is fully described in the U.S Patent 5,211,821. Technology development is at the bench scale. The development of a working prototype was not continued due to lack of resources and timing considerations. This was classified as an emerging technology because will likely not be available by 2003.
A-2.4.2 Photochemical Degradation of Organic Wastes with a TiO2 Catalyst This technology involves irradiation of the organic waste with an UV lamp over a TiO2 catalyst. The technology was tested for the destruction of chlorinated organics, but has not been tested for ODS. In 1992, commercialization was expected to occur in the “near future,” however, no information was available confirming the further development of this technology. A-2.4.3 UV Laser Controlled Decomposition of CFCs This technology was presented in a patent held by the U.S. as represented by the Secretary of the Navy. CFCs are decomposed by UV light, and decomposition products are reacted with Group IV chemical element-based mediating species (Si, SiO2, etc), prior to being scrubbed into water. The acid scrubbing solution requires neutralization. Tetrachloroethylene is a product of the CFC decomposition. This process was used in the electronics industry and was not considered to be applicable to large-scale CFC destruction. A-2.5
Catalytic Technologies
One of the challenges of the catalytic destruction of ODS is to prevent catalyst deactivation due to the presence of halogens. The development of all catalytic technologies presented below is at the bench scale. The duration of the catalyst would need to be quantified to determine replacement costs. A-2.5.1 Dry Distillation Disposal System for Waste Foam and Refrigerators This technology was developed by Toshiba Co., Japan. This is a two-step technology for treating foam containing CFCs. The foams are first dry distillated at 200°C to release the CFCs. The gaseous CFCs are then decomposed in a catalytic reactor using a Cr2O3-based catalyst. The oil from the resin may be reclaimed. Waste CFCs can also be treated directly with the catalytic reactor. A continuous bench-scale system was being developed in 1996, but no information confirming further development could be located. A-2.5.2 Halohydrocarbon Destruction Catalyst This process use a proprietary catalyst to decompose ODS along with water vapour or hydrocarbon to provide the hydrogen source. In 1992, a full-scale system was scheduled for start-up in Taiwan. No information was available confirming the further development of this technology. A-2.5.3 Catalytic Oxidation of CFCs with a Pt/ZrO2-PO4 Based Catalyst The catalyst was developed by Sumitomo Metal Mining Company, Japan. CFCs are oxidized in an air-water vapour environment at 500°C. The generated acid gases are required to be scrubbed. In bench-scale tests in 1994, the destruction efficiency for CFCs was greater than 93%. Catalyst activity was maintained for a 300-hr trial. Longer-term activity would require to be validated. The technology was classified as emerging because it was not thought likely to be commercially available by the year 2003.
A-2.5.4 CFC Oxidation in a Catalyst-Sorbents Packed Bed The process was developed by the Department of Chemical Engineering of Lehigh University, USA. Diluted CFCs streams (30-350 ppm) are oxidized with air into a catalyst bed. The Cu/Mn catalyst is supported on Na2CO3. The generated acid gases are absorbed by the Na2CO3 catalyst support, which help minimizing catalyst deactivation. A destruction efficiency for CFC 11 of greater than 80% was achieved in bench-scale tests. The inventors claim their catalyst is better than noble metal and metal oxide. The technology was classified as emerging because it was not thought likely to be commercially available by the year 2003. A-2.5.5 Transformation of CFCs to HFCs Using Dehalogenation Catalysts in a H2 Environment The Department of Chemistry of Simon Fraser University, Canada has done work to develop this technology. Bench-scale tests of various catalysts showed that a Pt/charcoal catalyst was the most efficient. The process generates HFCs that are presumed to degrade in the troposphere. Further development was realized by the Department of Chemical Process Technology of Delft University of Technology, The Netherlands. Bench-scale tests were performed for the conversion of CFC 12 into HFC 32 over a Pd/charcoal catalyst in an H2 Environment. No catalyst deactivation was observed after an 800-hr trial. The inventors claim to be able to achieve 100% destruction efficiency of CFC using multi-fixed bed reactor, but this has not be demonstrated. The technology was classified as emerging because it was not thought likely to be commercially available by the year 2003. A-2.6
Other Technologies
A-2.6.1 Use of Waste CFC in an Antimony Process This technology was presented in an abstract, and few details were given. The process exists at a commercial scale in Lanstar, Manchester UK. Waste CFCs and HCFCs come from ICI in Runcorn, UK. About 200 TM/y of CFCs were destroyed in 1994. This was considered to be a specialized technology application that is unlikely to be available for significant quantities of Canadian surplus ODS. A-2.6.2 CFC Destruction into Biocatalytic System [Ref 20, 29c] An INRS-Santé paper concluded that biocatalytic destruction of CFCs was feasible, but only with limited potential capacity. Experimental scale tests with CFCs achieved up to 99.9% destruction efficiency in an anaerobic liquid stream. No test data on gaseous CFC streams were presented. A-2.6.3 Supercritical Water Oxidation (SCWO) This technology is available from Weatherly Inc and is used commercially to destroy organic waste. Diluted organic wastes into water are mixed with pure oxygen, heated and pumped to 600°C and 25.4 Mpa in a tubular reactor. Under these extreme conditions, the presence of halogen salts lead to severe corrosion of the equipment. It would not be economically feasible to treat ODS due to these corrosion issues.
A-2.6.4 Electrohalogenation of CFC-113 on Pb/Pd Cathodes Combined with H2 Diffusion Anode This technology was developed at the University of Barcelona, Spain. It treats CFCs in a 70-80% MeOH solution. The development of the technology is at the early R&D stage.
3439 River Road South Gloucester, Ontario Canada K1A 0H3
Gary Cranny
DASCEM Holdings
Ted (Edward) Grandmaison
Queen’s University Dept of Chemical Engineering USEPA, Stratosphere Protection Division
Michael Forlini
Gerry Getman VP, R&D
Commodore Advanced Sciences Inc
Ian Glew
Bovar Waste Management
Brian Hobsbawn Assistant Director
Environment Australia Ozone Protection
C.W. Lee
U.S. EPA
Address
Area of Expertise
Phone/Fax/E-mail
Chemistry of refrigerants; technologies for destruction of refrigerants Destruction and transformation of toxic chemicals using UV; photochemistry; physical chemistry
Argon plasma arc destruction of halons, CFCs, HCFCs [Australian process] Gas combustion technologies
6205J (mail code), 41 M Street SW, Washington, DC, 20460 2340 Menaul Blvd Suite 400 Albuquerque, NM 87103 P.O. Box 303 Swan Hills, Alberta T0G 2C0 P.O. Box 787 Canberra, Australia ACT 2601 Research Triangle Park North Carolina
DuPont Canada Inc Technical Service Dept of National Defence Environmental Protection Public Works And Government Services Canada (PWGSC, Environment) DND, Defence Construction Canada, Contract Services Directorate
Ministère de l'Environnement et de la faune Service de la qualité de l'atmosphère Direction des politiques du secteur industriel
101 Colonel By Drive Ottawa, Ontario K1A 0K2 Place du Portage, Phase III, 8B3 Hull, Quebec K1A OS5 Place de Ville, Tower B 112 Kent Street, 17th Floor Ottawa, Ontario Canada K1A 0K3 3439 River Road South Gloucester, Ontario Canada K1A 0H3
Place Vincent Massey 351 St. Joseph Blvd. Hull, Quebec K1A 0H3 675 Boulevard René Lévesque Est 9ième étage Édifice Marie-Guyart Québec, Québec G1R 5V7
Philippe Chemouny Program Officer Donald Connor Halon Specialist
Vipond Fire Protection Inc.
Janot De Lacroix Manager of Protection and Prevention Service Abe Finkelstein Manager
Centre Canadien d’Architecture Candian Centre for Architecture
1920 rue Baile Montreal, Quebec H3H 2S6
Environment Canada, Cleaner Production & Technologies
Jim W. Flowers
Protocol Resource Management Inc
Place Vincent Massey 351 St. Joseph Blvd. Hull, Quebec K1A 0H3 Aurora, ON
Ian Glew
Bovar Waste Management
Elio Guglielmi
Warren Healey President
Heating, Refrigerants, and Air Conditioning Institute (HRAI)
Dr. John Hewings Senior Advisor
Ontario Ministry of the Environment Air Policy and Climate Change Branch
John Hilborn
Environment Canada
P.O. Box 303 Swan Hills, Alberta T0G 2C0 2906 West Broadway, Suite 241 Vancouver, British Columbia V6K 2G8 5045 Orbitor Drive Building 11, Suite 300 Mississauga, ON L4W 4Y4 135 St. Clair Ave. West - 4th Floor Toronto, Ontario M4V 1P5
Stakeholder Working Group: Participating Members Name/Title
Organization
Address
Phone/Fax/E-mail
Adam Richardson
Control Fire Systems
63 Advance Road Toronto, ON M8Z 2S6
Adrian Steenkamer
Environment Canada, Cleaner Production & Technologies
Art Stelzig Head
Environment Canada, Chemical Producers
Monique Thériault Environmental Technical Program Manager Pierre Vaillancourt Director, Corporate Security
Public Works And Government Services Canada (PWGSC, Environment)
Place Vincent Massey 351 St. Joseph Blvd. Hull, Quebec K1A 0H3 Place Vincent Massey 351 St. Joseph Blvd. Hull, Quebec K1A 0H3 Place du Portage, Phase III, 8B3 Hull, Quebec K1A OS5
Stakeholder Working Group: Corresponding Members Name/Title
Organization
Address
Phone/Fax/E-mail
Fred Dawson
DuPont Canada Inc
(Mississauga office)
Alexandre Dubé Robert Eno Manager
Univesité de Sherbrooke N.W.T. Department of Renewable Resources Environmental Protection Ontario Power Technologies Department of Environmental Technologies Safety-Kleen Inc. Environment Canada Atlantic Region
APPENDIX D: SUMMARY OF LITERATURE SEARCH The following section describes the literature search strategy to find and retrieve information relating to technology used to dispose, destroy or transform Ozone-Depleting Substances (ODS). The databases listed below were chosen for their direct relevance to the science and technology literature. A total of 17 databases were used in the search. The keywords listed below were chosen so that all facets of the subject area would be covered without the risk of missing any important information. Databases Used for Search
Abstracts in New Technologies and Engineering Chemical Engineering and Biotechnology Abstracts Conference Papers Index Ei Compendex Ei Engineering in Brief Energy Science and Technology Federal Research in Progress Inside Conferences INSPEC (1969-present) ISMEC: Mechanical Engineering Abstracts JICST – Eplus – Japanese Science and Technology Meteorological and Geoastrophysical Abstracts NTIS – National Technical Information Service Pollution Abstracts Science SciSearch – a Cited Reference Science Database (1990) Wilson Applied Science and Technology Abstracts
Keywords Used in Search Strategy Chemical names of interest CFCs or chlorofluorocarbons HFCs or hydrofluorocarbons HCFCs or hydrochlorofluorocarbons Halons Carbon tetrachloride ODS Ozone-depleting substances (or chemicals)
Phrases relating to technologies Destruction Destroy Disposal Transformation Stabilisation WITH Technologies Technology Process Once on-line in the DIALOG database, the search strategy was implemented. After completion of the initial search strategy, a total of 554 records were obtained. These records were saved and printed in title form (with dates of publication included), so that a preliminary screening of the titles could be performed. Overall Search Strategy On-line call up of 17 databases in Dialog database Search for: [Chemical names of interest] AND [Phrases relating to technologies] Date restriction of 1990 to present for all records Listing of all related records (Titles only) was obtained All titles were reviewed and only relevant records (i.e. by date and relevance of title) were chosen for further evaluation. In order to evaluate these records further, the chosen titles were re-entered into the Dialog database, and a recall of the full abstract was performed. The abstracts were then saved and reviewed again for relevance (i.e., by date, information, and language of document5). Consideration of Patent Databases The use of databases containing patent information was considered as part of the search strategy. The Derwent World Patents Index and the U.S. Patents Full Text were two examples of optional databases in Dialog which were considered. Patent information that could have been obtained from the search would not have included information on the actual use of the process in currently running facilities, and would have resulted in non-specific technology information due to the generalized search strategy. Furthermore, the likelihood of obtaining information on technologies that are no yet at the commercial development stage was considered to be quite high. In view of the high costs associated with the use of these databases and the limited quality of the data obtainable for the purposes of this project, it was decided that more specific and relevant technological information could be obtained from other known sources and contacts.
5 Documents in French or in German were not necessarily excluded since CEI has capabilities in both of these languages. Environment Canada, Project # K2617-9-0037 Cantox Envronmental Inc Project # 80940
72 March 31, 2000
APPENDIX E: STAKEHOLDER WORKING GROUP MEETING SUMMARY
Ozone-Depleting Substances Disposal Technologies Stakeholder Working Group March 28, 2000 Lord Elgin Hotel, Ottawa (09:00-15:00) Attendees Mike Ascough Holmer Berthiaume Craig Boyle Jean Carbonneau Alain Carrière Alex Cavadias Daniel Champagne Philippe Chemouny Don Connor Abe Finkelstein Jim Flowers Ian Glew John Hewings John Hilborn Monty Johnston Tim Kearney Jeremy Mann Russ Martin Jason Maurier Ian McGregor Mark Miller Dan Nolan Beatrice Olivastri Colin Park Jacob Shapiro Adrian Steenkamer Art Stelzig Monique Thériault Carlo Vissani
DuPont Canada Department of National Defence Public Works Government Services Canada Environment Canada Cantox Environmental Inc Environment Canada Environnement Québec Environment Canada Vipond Environment Canada Protocol Resources Management Inc Bovar Waste Management Ontario Ministry of the Environment Environment Canada Bovar Waste Management Remtec International Environment Canada Manitoba Ozone Protection Industry Association Ontario Ministry of the Environment Fielding Chemical Technologies Inc Manitoba Ozone Protection Industry Association Cantox Environmental Inc Friends of the Earth Canadian Coast Guard Cantox Environmental Inc Environment Canada Environment Canada Public Works Government Services Canada FRC Canada
PROCESS Stakeholders were welcomed and thanked for their participation, introductions were made, and the agenda was reviewed without changes. Brief presentations were given by Environment Canada representatives on the Global ODS Agenda, the proposed ODS Phase-out Strategy, and on the history of the ODS Disposal Guidance initiative. Representatives of Cantox Environmental Inc (CEI) then gave presentations summarizing the draft Status Report, highlighting the identification of commercially available and emerging technologies as well as the technical/environmental and economic/commercial evaluations of disposal technologies. DISCUSSION All stakeholders present were given an opportunity to raise questions or concerns, and to comment on issues related to the control options presented. In general, many of the comments addressed policy issues, particularly Canada’s recently released phase-out strategy for ODS, since these are so closely associated with the development of a program to dispose of surplus ODS. The following summarizes the main points of discussion. Costs • • •
The cost estimates discussed in the Status Report were provided to give some general guidance to stakeholders. Accurate cost estimates on each process would be a very complex and involved exercise, and was beyond the scope of the current project. Transportation costs were not included in the analysis of the technologies. Some experience suggests that this would represent a relatively small though still significant percentage of the total disposal cost (about $0.60/kg, based on transport from Ontario to Alberta). Stakeholders indicated that a comprehensive economic evaluation of the ODS phase-out strategy would be appropriate.
Viability of Disposal in Canada • •
•
Several stakeholders suggested that it would be ideal to have a made-in-Canada solution to Canada’s ODS surplus, however there did not appear to be a solid business case for establishing a facility in Canada to dispose of the required quantities of surplus ODS. Government representatives suggested that in order for a disposal facility to be viable in Canada it would have to have other destruction capacities, for example for pesticides, other chlorinated organics, military wastes, etc. Environment Canada would be interested in receiving any proposals to help develop such a project. One stakeholder pointed out that CFCs will likely not be recovered and disposed of for the mobile and household appliance sectors, the former because of the rapid rate of loss and the latter because the phase-out strategy is the status quo, which means in practice very small amounts of CFCs will be recovered. Thus, the total amount of surplus CFC from the Canadian inventory available for disposal is much smaller than anticipated. Only about 26% of the total CFC inventory will be directly addressed by the phase-out plan, and not all of this will be recovered, since experience shows that recovery rates are typically well below 100%.
These considerations raise questions as to whether investing in a new or upgraded disposal facility in Canada is economically viable. Throughout the discussions, the question of the size of the market/inventory for surplus ODS was considered critical, as this would drive the creation of a disposal option in Canada. There was concern regarding the destruction of surplus halon in Canada. Given the availability of relatively inexpensive facilities in the U.S., there may be no business case for a destruction facility for halons in Canada.
Industry & Government Roles •
It was suggested by government stakeholders that only an industry-led “Product Stewardship” initiative to cover the costs of disposal could be effective (e.g., the proposed HRAI initiative. The resources and initiatives cannot come from the government, although government assistance in setting up such programs would be appropriate. Roles industry could play include: developing capital cost estimates for various processes; assessment of the economic and technical feasibility of collecting, cleaning, pressurizing, shipping, and disposing of surplus ODS. Industry stakeholders agreed with this approach in principle, but re-iterated that the business case for disposing of the quantities of ODS involved may not be viable, and may require government support if this is to be successful.
Inventory Issues • •
•
It was suggested that the halon inventory had been underestimated. It was pointed out the Canada’s ODS inventory is not rigorous enough to provide a “measure of success” as surplus ODS is recovered and destroyed; there will be no way to be certain of how successful such a program is. Mandatory reporting requirements (under CEPA) would be needed to get a realistic estimate of the volumes of surplus ODS. One stakeholder indicated that the announcement of Canada’s proposed accelerated phaseout strategy for ODS has already had an effect, and stakeholders are beginning to look for ways to get rid of quantities that are not yet considered surplus. Thus, the inventory available for disposal may turn out to be smaller than anticipated.
Issues With New Facilities in Canada •
• •
There are many issues associated with the approval process for a destruction facility that need to be taken into account and that represent significant barriers and delays, including: − Hazardous waste regulations − Environmental Assessment hearings (environmental & socio-economic impacts) − Cost-benefit analysis − Board and Ministerial approval processes − Process of proceeding with a pilot facility Mobile facilities may be a practical alternative, however these would involve an entire set of different regulatory issues that, again, involve barriers and delays. Given the challenges and delays associated with building and approving a new destruction facility in Canada, it was argued that it may make more sense to focus on existing facilities for ODS disposal.
Certification of destruction would be an important mechanism for assuring that ODS had been disposed of appropriately if ODS is to be exported for disposal. Destruction capacity for ODS in Canada is currently limited. The only facility licensed to destroy CFCs and halons is Bovar’s incinerator in Swan Hills, Alberta. Capacity at this facility is limited to about 40 tonnes/year at present, but could be upgraded to about 3000 tonnes/year within 6 months. It was suggested that some of the emerging technologies identified could be of interest from an environmental perspective. Others pointed out that there simply is not enough time to wait for emerging technologies to become commercially available, and that the focus has to remain on existing technologies. Representatives of the ODS recycling industry expressed concerns over the shifting perception of their operations as “bad,” now that the focus in on disposal of ODS, despite the environmental benefits of their efforts to date. Considerable investment has been made to provide these recycling services, and some consideration should be given to compensating recyclers for the impacts the new phase-out strategy will have on their business. A concern was raised regarding Canada’s policy on importing ODS surplus for destruction, should a full-capacity facility be developed in Canada. It was stated that such imports would be supported only if they were managed and disposed of in an environmentally responsible manner. One stakeholder pointed out that there is a need to re-visit environmental criteria for ODS disposal technologies since there are health issues associated with disposal, e.g., in the case of incineration, concern for dioxin/furan formation. In addition to the technical evaluation of available disposal technologies, there is an important political discussion surrounding the use of incineration in particular.
PATH FORWARD March 2000
Comment period on Status Report for all stakeholders
March 31, 2000
Guidance Document to be submitted to Environment Canada
May 2000 (?)
Guidance Document to be made available to stakeholders
Contacts for Further Information Office of the Director General Environmental Technology Advancement Directorate Environment Canada 351 St. Joseph Boulevard Hull, QC K1A 0H3 CANADA Tel: (819) 953-3090 Fax: (819) 953-9029 Mr. Philippe Chemouny International Technology Transfer Officer Environmental Technology Advancement Directorate Environment Canada 351 St. Joseph Boulevard Hull, QC K1A 0H3 CANADA Tel: (819) 997-2768 Fax: (819) 997-8427 E-mail: [email protected] Ms. Tamara Curll Assistant Director Ozone Protection Section Environment Australia AUSTRALIA Tel: (61 2) 6274 1701 Fax: (61 2) 6274 1172 E-mail: [email protected] Mr. Blaise Horisberger Adjoint scientifique Office fédéral de l'environnement, des forêts et du paysage SUISSE Tel: (41 31) 322 90 24 Fax: (41 31) 324 79 78 E-mail: [email protected]
Adrian Steenkamer Jr. Program Officer Environmental Technology Advancement Directorate Environment Canada 351 St. Joseph Boulevard Hull, QC K1A 0H3 CANADA Tel: (819) 953-0962 Fax: (819) 953-0509 E-mail: [email protected] Mr. Geoffrey Tierney Senior Environmental Affairs Officer Energy and OzonAction Unit Division of Technology, Industry and Economics United Nations Environment Programme (France) FRANCE Tel: (33 1) 4437 7633 Fax: (33 1) 4437 1474 E-mail: [email protected]
