TECHNOLOGIES "
FOR
CFC/HALON DESTRUCTION
CORPORATION
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DCN 39-239-004-71-05 AEERL-503
April 19, 1989
FINAL REPORT '
TECHNOLOGIES '
.FOR
/HALON DESTRUCTION
MAY 03 1989
by:
J. C. Dickerman, T. E. Emmel
G. E. Harris, and K. E. Hummel
Radian Corporation
Post Office Box 13000
Research Triangle Park, North Carolina 27709
EPA Contract No. 68-02-4286
Work Assignment 71
EPA Project Officer: Paul M. Lemieux
Air and Energy Engineering Research Laboratory
Research Triangle Park, North Carolina 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
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CONTENTS
Tables iii
1. Introduction 1-1
Purpose of Study 1-1
Methodology/Approach 1-1
2. Summary of Key Findings 2-1
General Comments 2-1
Technologies to Destroy CFCs and Halons 2-4
• Environmental Implications of CFC Destruction 2-10
Monitoring Methods for CFC Destruction 2-12
Implications for CFC Destruction 2-16
Regulatory Impacts 2-18
Data Caps and Research Needs 2-21
3. Bibliography 3-1
References 3-1
Personal Contacts 3-2
Appendices
A. List of Experts A-l
B. Control Technology Summaries B-l
C. Preliminary List of Technologies C-l
D. Trial Burn Data Tables D-1
E. List of Contacts E-l
F. Japanese MITI Attachment F-l
ii
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TABLES
1. Estimated U.S. Bank of CFCs and Halons in 1988
by End Use and Compound 2-3
2. Summary of Existing and Promising Future Destruction
Technologies 2-7
FIGURES
1. Simplified Flow Diagram of a Thermal Destruction Process 2-8
DISCLAIMER
This report has been reviewed by the U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
iii
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SECTION 1
INTRODUCTION
This report presents an overview of the current status of possible
technologies used to destroy chlorofluorocarbons and halons, chemicals
implicated in the destruction of the stratospheric ozone layer. The Montreal
Protocol, an international treaty to control the production and consumption of
these chemicals, allows countries to increase production by the volume of CFC
or halon destroyed, provided that the destruction technology had been approved
by the Parties to the Protocol. The Parties have not yet approved nor
considered possible destruction technologies. This document is the first step
in the United States' review of such technologies, and will serve as the basis
for additional work in this area.
PURPOSE OF STUDY
The U.S. Environmental Protection Agency (EPA) has requested an
investigation into several areas related to destruction technologies:
• A review of the currently and potentially available destruction
technologies:
• a review of potential environmental or health effects posed by
destruction by-products; and
• review of methods to monitor destruction efficiency.
METHODOLOGY/APPROACH
Due to the limited scoping exercise of this assignment, this report is
based on publicly-available articles and reports, and personal contacts with
various individuals who are knowledgeable in the field (see Section 3).
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Results of this evaluation are presented in the following sections.
Section 2 presents a summary of the key findings which include:
• The ability of the various technologies to effectively destroy CFCs;
• The environmental consequences of such destruction; •
• The ability of current emission monitoring systems to verify that
the CFCs have indeed been destroyed;
• The impacts of current regulations on CFC destruction; and
• The existence of any significant data gaps, along with recommen-
dations of future required work to resolve any unanswered issues
resulting from the data gaps.
Se.ction 3 contains the bibliography for this report. This report also
includes a series of Appendices. The first consists of a list of experts in
this field. Other appendices provide technology overviews of the most
promising destruction technologies including their relative advantages and
disadvantages, a preliminary listing of technologies which were considered,
trial burn data tables, a brief description of phone contacts, and information
on CFC destruction provided by the Japan Ministry of International Trade and
Industry (MITI).
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SECTION 2
SUMMARY OF KEY FINDINGS
GENERAL COMMENTS
CFCs and Halons are Difficult to Destroy
CFCs and halons are very stable compounds. They are resistant to
oxidation, thus making them difficult to destroy by incineration.
Furthermore, CFCs and halons are nonflammable and do not support combustion by
themselves (halons are primarily used as fire extinguishing agents). The
stability of these chemicals is attributed to the presence of
fully-substituted halogens.
CFCs and halons may be broken down by hydrolysis. Hydrolysis involves
splitting the CFC with water as shown in the example below for CFC-12:
CC12F2 + 2H20 > C02 + 2HF +2HC1
This reaction occurs in the combustion chamber of an incinerator, where
supplemental fuel is burned to create the high temperature (to increase the
reaction rate) and also furnish some of the water for hydrolysis.
The primary products of CFC or halon destruction are carbon compounds
(such as carbon dioxide (C0«)] and potentially corrosive and dangerous halogen
acids [such as hydrogen chloride (HC1) and hydrogen fluoride (HF)]. It is
also possible to form free halogen gases [such as chlorine (Cl«), or fluorine
(F^)] which are also corrosive and hazardous chemical by-products.
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Potential Volume of CFCs and Halons to be Destroyed
The Montreal Protocol allows Parties to the Protocol to implement a
system of credits that allow CFC and halon production and use to be offset by
their destruction. In order to estimate the potential magnitude of such a
program which would grant "production credits" for destroying CFCs or halons,
this section examines those end use applications which would be attractive
sources of CFCs for capture and destruction.
Examples of end use applications which contain CFCs or halons that could
be captured and destroyed are:
• Refrigeration systems;
• Halon fire extinguishers;
• Rigid polyurethane foam;
• Solvent uses; and
• Sterilant gas systems.
The estimated inventory or "bank" for these applications in the U.S. is shown
in Table 1 which indicates that over one million metric tons of CFC and halons
exist. The banked emission sources store or retain the CFCs over a period of
months or years. Most of the banked CFCs or halons are only emitted when the
product is disposed. Depending on the application, some of the banked CFCs
and halons may be recycled or destroyed rather than emitted.
Among the major categories, those sources which contain concentrated CFCs
or halons (e.g., refrigeration or solvents) would be the better candidates for
destruction. In contrast, the banked CFCs contained in rigid polyurethane
foam will be less attractive for destruction because of th'e more dilute CFC
content as well as the difficulties of collection and transportation.
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7?
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TECHNOLOGIES TO DESTROY CFCs AND HALONS
There are many technologies chat could potentially be used to destroy
CFCs and Halons (see Table 2 and Appendices B and C). Host of these
technologies are at a preliminary level of development for application to CFCs
and halons. Only thermal incineration is currently available and demonstrated
for CFC and halon destruction. The following section presents a brief
discussion of each potentially applicable technology.
Existing and Future Technologies for Destruction
Destruction technologies can be divided into several broad classes.
These include thermal, chemical, biological, and electrical (see Table 2).
Contacts both with firms engaged in the disposal.of hazardous wastes and
producers of CFCs indicate that current practice is limited to thermal
destruction processes (i.e., conventional thermal incineration).
Thermal destruction processes achieve destruction of the CFC or halon
molecules by exposure to high temperatures for relatively long residence times
in the presence of excess oxygen. CFCs and halons do not have enough heat of
combustion to provide the temperatures necessary for thermal incineration.
The necessary heat must be supplied through firing a supplemental fuel or by
co-firing other wastes that have a substantial net heat of combustion.
The thermal decomposition of CFCs and halons produces either halogen
acids (HC1, HF, HBr) or free halogen molecules (C12, F., Br.). These
decomposition products are very corrosive and pose one of the most significant
problems in CFC/halon destruction. In particular, the attack on the
refractory materials used to insulate and protect the incinerator walls has
been a problem, requiring development of special refractory materials. The
halogen acids or free halogens must also be scrubbed from the stack gases
before emission. This can be done using a water scrubber for the acid
species, but the free halogen species require an alkaline scrubbing liquor.
The decomposition products can be forced towards the easier to scrub halogen
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TABLE 2.
SUMMARY OF EXISTING AHP PROMISIHG FUTURE DESTRUCTION TECHHOLOGIES
OT
O
O
K)
Process
Classification
Thermal Processes
Process
Thermal Incineration
Catalytic Incineration
Description
Destruction or dissociation of CFCs
or halons by exposure to high
temperature In the presence of excess
oxygen.
Destruction or dissociation of CFCs
or halons by exposure to lower
temperatures than thermal Incineration
In the presence of a solid catalyst
and excess oxygen.
Development Status
Commercially available for CFCs and
halons, both for dedicated CFC or
ha Ion destruction and for co-firing
with other waste materials.
Commercially available for other waste
materials, but only at bench scale
research level for CFCs and halons.
Pyrolysls
Destruction or dissociation of CFCs
or halons by exposure to high
temperatures In the absence of
oxygen.
Commercially available for other
waste materials, but only at bench
scale research level for CFCs and
halons.
Chemical Processes
Metals Scrubbing/
Destruction
Chemical Scrubbing/
Destruction
Active metals (such as sodium, zinc,
or aluminum) suspended In an Inert
liquid medium chemically dehalogenate
the CFCs or halons, producing a metal
salt (e.g., NaCl).
Highly alkaline, non-aqueous scrubbing
liquor absorbs and destroys CFCs and
halons.
Pilot scale research level.
Laboratory scale research level.
Wet Air Oxidation
Moderate temperature aqueous stream
with oxygen destroys organic materials
by oxidation, and possibly by
hydrolysis for CFCs and halons.
Commercially available for other
waste materials, but only bench
scale research level for CFCs and
halon*.
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TABLE 2.
(Continued)
OP
o
O
N>
Process
Classification
Chemical Processes
(Continued)
Process
Supercritical Water
Oxidation
Description
Similar to Wet Air Oxidation, but
at supercritical conditions (higher
temperature and pressure), to
Increase the reaction rate.
Development Status
Commercially available for other
waste materials, but only bench
scale research level for CFCs and
halons.
Biological Processes
No promising processes
were Identified
Destruction of CFCs or halons by
mlcroblal attack.
Commercially available for other
waste materials, but only at
conceptual research level for CFCs
and halons.
Electrical Processes
Corona Discharge
to
High voltage discharge generates an
Ionized corona field and the energized
electrons from the field are capable
of dissociating many types of wastes.
Bench scale for other waste
materials, but only at conceptual
research level for CFCs and halons.
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acids by providing ample hydrogen in the incinerator. The hydrogen may be
supplied by a high-hydrogen supplemental fuel (like natural gas) or through
steam or water injection. Figure 1 illustrates an incinerator with associated
scrubber and auxiliary equipment.
Thermal incineration is the only technology for CFC or halon destruction
that was found to be currently available at commercial scale. Examples of
dedicated CFC incinerators were found, as well as general hazardous waste
incinerators that can co-fire CFCs with other wastes. The dedicated CFC
incinerators were found only at CFC manufacturing facilities (e.g., DuPont and
Pennwalt in the United States, ICI in Great Britain, and Hoechst A.G. in West
Germany). The co-fired CFC incinerators were found at commercial hazardous
waste disposal facilities (e.g., Rollins, GSX, LWD, and Chemical Waste
Management). The co-fired incinerators are limited by permit as to how much
CFC they can feed, with limits ranging from a maximum of 5 percent to as
little as 100 parts per million.
Other technologies have been proposed for destruction of CFCs or halons.
Some of these technologies have been commercially used for destruction of
other types of wastes, but they have not been demonstrated for CFCs and
halons. Each of these promising technologies is discussed below.
• Catalytic Incineration is similar to thermal incineration, but the
destruction is achieved at lower temperatures by use of a catalyst.
The lower temperatures represent a potential savings in fuel costs,
but the application to date, of catalytic incineration has been
limited to destruction of hydrocarbons or chlorinated organics. If
tests of chloride-resistant catalysts are successful with CFCs or
halons, catalytic incineration could be commercially available in
the near term (3 to 5 years).
• Pvrolvsis is destruction using high temperatures, but without excess
oxygen for direct combustion. This approach offers potential for
reduced exhaust gas volume (resulting in smaller, less costly gas
scrubbers), but has not been tested with CFCs or halons. If
demonstration tests were initiated, pyrolysis could be commercially
available for CFCs or halons in the near term (3 to 5 years).
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CLEANED
EXHAUST GAS
COMBUSTION „
AIR
STEAM
NATURAL GAS £
CFC - CONTAINING i
WASTE GAS
;
V
•>
i
,AS
LIQUID
CFC - CONTAINING -J
WASTE LIQUIDS *
WATER (
WATER
i
\
DEMISTER
£ WATER
PACKED
TOWER
SCRUBBER
TO
WASTEWATER
TREATMENT
SYSTEM
Figure 1. Simplified Flow Diagram of a Thermal Destruction Process
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• Active metals scrubbing is a process which uses sodium, zinc, or
aluminum metal to rapidly react with halogenated compounds. It has
only been commercialized for destruction of PCB-containing wastes.
Active metals scrubbing could be commercialized in the moderate term
(5 to 10 years).
• Chemical scrubbing is a process that uses a highly alkaline reagent
to destroy halogenated compounds. It has only been demonstrated on
the bench-scale for PCB destruction. Chemical scrubbing would
probably be a long term commercial possibility (10 to 15 years).
o Wet air oxidation is a process that uses a moderate temperature
aqueous stream with oxygen to destroy organic compounds. Limited
test data show that CFC-113 can be destroyed by this process, but
its.use is limited to dilute aqueous wastes. The ultimate
application of wet air oxidation is questionable because of the
requirement for a dilute aqueous form, but it could probably be
commercialized for some CFC or halon applications in the moderate
term (5 to 10 years).
• Supercritical water oxidation is similar to wet air oxidation, but
it operates at higher temperatures and pressures. The current
application of supercritical water oxidation is limited to
destruction of aqueous wastes containing chlorinated organics. It
is possible that this technology could be commercialized for
specialty CFC or halon streams in the moderate term (5 to 10 years).
• Corona discharge is a process that uses energized electrons from an
ionized corona field to destroy many organics. It is currently a
development project, but shows possibility for future development.
The commercialization of corona discharge for destroying CFCs or
halons is a long term possibility (10 to 20 years).
CFC Destruction Efficiencies
A common measure of the performance of a CFC destruction technology is
its destructions and removal efficiency (ORE), which is an indicator of the
amount of input feed material that actually gets destroyed or removed.
Although there are limited amounts of actual test burn data on CFCs, the
available data show high destruction efficiencies. For example, a trial burn
at Olin Corporation (Brandenburg, KY) in November 1984 showed a DRE of
>99.9998 percent for co-fired CFC-11 and CFC-12 (2). To put this destruction
efficiency into perspective, if 100 kilograms of CFC-12 were fed to a
destruction device with a destruction efficiency of 99.9998 percent, only
20 grams of CFC-12 would be released. Appendix D presents additional trial
kgo/102 2-9
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burn data conducted with CFCs in the waste feed. Most of this data is on
CFC-11 and CFC-12. Since these are two of the most stable CFCs, it is
anticipated that other CFCs (like CFC-113) would have similar, or possibly
slightly better, destruction efficiencies.
Lack of Halon Destruction Efficiency Data
Information on the destruction of halons has been difficult to obtain.
Inquiries to halon producers did not yield any information nor are there any
publicly available test data. Sweden is beginning a research program to study
destruction technologies for CFCs and halons, but tests to date have been
limited to the bench scale, and no results are available. Halons do not
actually "burn," and in fact their primary use is as a fire suppressing. They
will thermally decompose, however, so the application of thermal destruction
processes is feasible. There is believed to be some concern over generation
of free bromine in a thermal decomposition process, so careful control of the
combustion conditions and supplemental fuels would be required.
ENVIRONMENTAL IMPLICATIONS OF CFC DESTRUCTION
Environmental concerns surrounding CFC and halon destruction include
possible formation of potentially hazardous products of incomplete combustion
(PIC), and acid and/or halogenated gas emissions. Although the acid gases can
be scrubbed, the scrubber by-products create the need for disposal and
handling.
PIC Formation
Incineration processes for CFC or halon destruction require supplemental
fuel, such as methane or propane, or other hydrocarbon-containing wastes to
sustain combustion. Co-firing waste fuels with CFCs or halons may make it
more difficult to control formation of incomplete combustion products or PICs,
since waste fuels are often complex mixtures containing aromatic compounds.
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Some of the aromatic compounds may become partially halogenated as the CFCs or
halons are destroyed which can result in release of halogenated aromatic
compounds which as a class, have been shown to be toxic.
PIC formation, in general, is a poorly understood phenomena, which is
further complicated for CFC destruction systems since no data on PIC formation
exist. Incomplete combustion products are formed due to localized areas of
poor mixing of fuel and oxygen, and temperature deficiencies in the
incinerator. Data from hazardous waste incinerators have indicated that PIC
formation in a properly operated system is typically less than 1 ppm. At
these low levels, the volumes of any PIC's formed would be small. The overall
toxicity, however, is an unresolved issue that requires additional data to
resolve.
Acid Gases
Thermal destruction of CFCs or halons also produces acid gases (HC1, HF,
or hydrogen bromide [HBr]) and/or free halogen gases (chlorine (C1-), fluorine
(F,,) , or bromine [Br«]) when the halogen-containing parent compound is broken
down in the incinerator. Although both types of gases are hazards because of
their toxicity and corrosivity, acid gases can be more easily scrubbed from
the exhaust gases and are, therefore, less of a problem than the free halogen
gases from a pollution control perspective. Excess hydrogen or water is
desirable because it promotes the formation of acid gases rather than the free
halogen gases.
Large quantities of acid gases are generated by thermal destruction of
CFCs. For each pound of CFC-12 incinerated, roughly 0.6 pounds of HC1 and 0.3
pounds of HF are produced. The current environmental permitting regulations
for hazardous waste incinerators require that HC1 emissions be controlled
below 1.8 kg/hr or removed at an efficiency of 99 percent, whichever is
greater (4). At present, there is no federal regulation directly applicable
to HF or HBr emissions, although state or local agencies may set conditions in
operating permits.
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Removal of the acid gases requires scrubbing with either a water or
caustic solution to react with the acid/halogen gases. Both water and caustic
scrubbers are used for cleaning CFG destruction flue gases. These aqueous
waste streams must be sent to wastewater treatment facilities before
discharge. Large quantities of waste salts are generated. For each pound of
CFC-12 incinerated, neutralization of the acid gases produced results in the
generation of roughly 1.5 pounds of salts.
Combustion Products
In addition to PIC formation and the formation of acid gases, destruction
of CFC's will also produce such combustion products as carbon dioxide (CO.),
water, nitrogen oxides (NO ) and carbon monoxide (CO). These combustion
X
products include "criteria" pollutants (e.g., NO and CO), as well as
so-called "greenhouse" gases (e.g., CO. and NO ). However, the relative
amount of greenhouse gases that would be emitted from the destruction of CFC's
is very small when compared to the amount of similar combustion products
emitted by the power generation industry and from automobiles.
MONITORING METHODS FOR CFG DESTRUCTION
To monitor destruction, record keeping procedures must be in place to
track the quantities of CFC compounds in the waste fed to the incinerator, and
then methods must be available to monitor the destruction efficiency achieved
during incineration.
Tracking. Procedures
The basic tracking procedure now in use involves the preparation of a
feed record and a certificate of destruction for each waste load that is
incinerated. The feed record includes information on the weight and
composition of the waste load. This information is gathered when the waste
load is received by the incinerator facility. After the waste has been
kgo/102 2-12
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incinerated, the certificate of destruction is prepared to document that the
waste was destroyed. This certificate is sent to the waste originator to
complete the recordkeeping process.
As discussed above, information on both the weight and composition of
each waste load is documented in the feed record. It was indicated during the
phone contacts with incinerator operators that wastes containing CFCs or
halons may arrive at an incinerator facility in drums, tank trucks, or tank
cars. Scales located at the facility are used to obtain gross weights on the
containerized waste loads. Information on the empty (tare) weights of the
containers are then used to determine the net weight of each waste load, and
this weight is then entered on the feed record.
Composition information on each waste load is obtained by chemical
analysis. Typi'cally, both the waste generator and the incineration facility
operator analyze a composite sample of each waste load. The generator
normally provides the results of his analysis with the waste shipment. The
analysis performed by the incinerator facility then serves as a check on the
information provided by the generator. The composition information obtained
from this two-step'process is entered on the feed record along with the net
weight of the waste load.
Although it is possible to determine the quantity of waste CFCs or halons
fed to the incinerator based on the weight and composition information entered
on the waste feed record, extra care is required to obtain a representative
sample if a waste is not homogeneous. In addition, if a waste load is stored
in tanks at the incinerator facility prior to destruction, CFCs and halons may
be emitted to the atmosphere. For this reason, the waste should be analyzed
just prior to incineration so that a more accurate measure of the CFC or halon
content is obtained.
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Determination of Destruction Efficiency
As discussed above, incineration has been demonstrated as an effective
technology for destruction of wastes containing CFCs. Performance standards
developed by EPA under the Resource Conservation and Recovery Act (RCRA) apply
to incinerators burning wastes that contain CFCs. The approach adopted by EPA
is to require prelicense testing or a trial burn on each waste incinerator
unit to 1) ensure that the requisite destruction and removal efficiency (DRE)
is demonstrated; and 2) define a range of operating parameters for which the
unit would be in compliance. During a trial burn, a 99.99% DRE for each
principal organic hazardous constituent (POHC) in the waste feed must be
attained. The POHCs are selected on the basis of projected high concentration
in the waste stream, large annual volumes, and/or high resistance to
combustion. The current RCRA incineration standards regulate only the POHCs.
Emissions of products of incomplete combustion (PICs) are not covered by the
standards, although future rulemaking may indirectly regulate PICs through
limitations on CO.
RCRA also requires that if HC1 stack emissions are greater than
1.8 kg/hr, at least 99 percent removal of HC1 from the exhaust gas is required
during the trial burn. RCRA incinerator operating permits will also specify
continuous monitoring of CO concentration in the stack gas, with an operating
limit of 100 parts per million by volume (ppmv). Additional requirements may
also be specified by the State or local agency on the incinerator performance
depending on waste feed composition (e.g., limitations on HF or HBr
emissions). During the trial burn, incinerator operating parameters monitored
include temperature, waste feed composition, waste feed rate, combustion air
velocity, residence time, 0., and CO.
Once the license to operate the incinerator is granted, the license
mandates that operating parameters be selected from the range specified during
the trial burn. The permit is generally valid for five years. During this
period, the federal or the designated state agency conducts, at a minimum,
annual inspections of the incinerator operation, including records on CO,
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temperature, waste feed, waste composition, and scrubber operation. Any
change in incineration operation (e.g., waste feed rate, composition,
combustion temperature), other than what was represented in the permit
application or is allowable under the permit, requires a modification be made
to the permit, with a potential requirement to conduct another trial burn.
Sampling and Analytical Methods
Measurement of several incinerator operating parameters are necessary to
maintain thermal destruction conditions which are equivalent to those observed
during a successful trial burn. The principal candidate species for
continuous monitoring is one of the compounds selected for the trial burn.
However, the sampling and analytical methods are not practical for continuous
performance monitoring on a day to day basis. One alternative is to
indirectly monitor incineration performance using commercially available
continuous monitors to measure combustion intermediates (e.g., CO or
hydrocarbons) and thereby infer waste destruction efficiency. CO is a good
indicator of incomplete combustion (the lower the CO level, the more complete
the combustion) and is therefore often used as a surrogate indicator of
combustor performance. Currently, continuous monitoring of CO concentration
in the stack is the only RCRA requirement after a permit is granted.
Several studies have been conducted to determine if incinerator emissions
can be correlated with surrogate compound, like CO or total hydrocarbon,
concentrations in the stack gases. Some of these studies have shown a
relationship between CO and/or total hydrocarbon concentrations and
incinerator emissions while other studies have found no correlation. It
should be noted that these studies have been done on other types of wastes,
not CFCs or halons. Therefore, additional research needs to include not only
the validation of the PIC to surrogate correlation approach, but also the
applicability of that approach to CFCs and halons.
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IMPLICATIONS FOR DESTRUCTION
This section highlights a number of issues which will likely effect the
implementation of a CFC destruction program.
Need for Central Facilities
Destruction processes for CFCs and halons are likely to be operated as a
central facility, rather than as portable or user-sited units. This is
because 1) destruction facilities must comply with stringent regulations (and
it is simpler and less costly to permit a few central facilities, rather than
a multitude of smaller units); and 2) considerable expertise is required to
safely and efficiently destroy these, compounds, which is not generally
available to the user population. A central destruction facility would
require that individual users collect and transport the compounds for
disposal. As such, it is likely that current CFC manufacturing and recycle
facilities, and commercial hazardous waste incineration facilities will be the
location of most destruction facilities. This is because many of these
facilities already have incinerators and have the needed technical and
management expertise. It may also be easier to get permits for CFC
destruction at locations which already are permitted for CFC manufacturing and
recycling or waste destruction.
Conversion of CFCs
An alternative to destruction of certain CFCs is chemical conversion into
fluoromonomers. Fluoromonomers are used to make chemically-resistant plastics
such as Teflon* or Kel-F* (3) as is currently practiced with partially-
halogenated hydrochlorofluorocarbons (HCFC), and also with CFC-113. For
example, CFC-113 is converted to chlorotrifluoroethylene which is then
polymerized to form KEL-F* (sold by 3M Corporation). CFC-11 and CFC-12 also
have been reacted with methane or ethylene (but only .in the laboratory) to
form vinylidene fluoride, which could then be polymerized to make Kynar* (sold
by Pennwalt).
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Limitations to this approach include: the demand for these plastics
versus the amount of CFCs and HCFCs, the ability to purify the CFC/HCFC's to
make saleable grade plastic and the economics. However, polymerization to a
plastic whether saleable or not may be environmentally and economically more
attractive than other destruction options.
Recycling of CFCs
Although recycling is not a destruction process, it is an interim measure
which can be actively promoted to reduce emissions of used or contaminated
CFCs and lessen the production of new CFCs. Once substitute chemicals become
available to replace CFCs or halons, recycling should ease the transition by
providing users a continuing supply of the regulated compounds.
Recycling of contaminated CFCs is currently practiced on a commercial
scale by Omega Recovery (Whittier, CA). Also, some solvent suppliers (such as
DuPont) operate central solvent reclamation facilities. These facilities
generally accept CFCs from solvent distributors or firms which service large
commercial building chillers. Recovered CFCs may contain contaminants such as
water, oil, other solvents, acids, and noncondensible gases. The reclamation
process involves such steps as neutralization, filtration, drying or
adsorption, and distillation to return the material to purity specifications
which meet or exceed those for new, virgin CFCs.
Costs for recycling used CFCs were found to be in the same range as costs
charged for destructing used CFCs. A significant difference exists, however,
in that the recycling process produces a replacement for the used CFCs as part
of the recycling cost, whereas make-up CFCs must be purchased when used CFCs
are destroyed. For this reason, recycling will likely be less costly than
destruction.
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REGULATORY IMPACTS
This section addresses current U.S. environmental regulations which
pertain to emissions and disposal of CFCs and halons, and discusses potential
regulatory changes that may affect CFC or halon disposal operations.
Currently, the regulations that would have the most effect on CFC disposal
operations are: 1) the Resource Conservation and Recovery Act (RCRA) which
can affect the handling and processing of spent CFC wastes, and 2) the Clean
Air Act which affects the allowable emissions of acid gases. All regulatory
provisions should be able to be met and thus should not create impediments to
implementing a CFC destruction program.
Resource Conservation and Recovery Act (RCRA)
The Resource Conservation and Recovery Act (RCRA) establishes the
Environmental Protection Agency's authority to regulate solid and hazardous
wastes. The RCRA regulations require that hazardous wastes be tracked from
generation to ultimate disposal.
In uncontaminated form, CFCs and halons are not regulated wastes, nor are
they likely to be considered characteristically hazardous. However, as
previously indicated, recovered CFCs and halons may contain contaminants
controlled by RCRA. Thus, recovered CFCs and halons may be defined under RCRA
as hazardous wastes by virtue of being mixed with other regulated wastes, such
as solvents, or by being mixed with corrosive wastes. Thus, RCRA regulations
may be applicable to CFC and halon destruction processes, such as
incineration. Anticipated revisions to the current RCRA incineration rules
may particularly impact CFC and halon destruction since PICs will likely be a
primary focus of future changes. To the extent that recycling becomes a
viable option and the CFC and halon wastes are defined by RCRA to be hazardous
then the recycling provisions of RCRA may also apply.
kgo/102 2-18
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In addition to possible application of the federal hazardous waste rules,
some states (such as California) have designated contaminated CFCs as
hazardous wastes due to the corrosive and acidic nature of some wastes.
Designation of CFC and halon wastes as hazardous under federal and/or state
laws will significantly affect the economics of destruction and recycling
options, and will tend to create a disincentive to utilization of these
methods.
Clean Air Act (CAA)
The Clean Air Act (CAA) establishes the authority of the U.S.
Environmental Protection Agency to regulate emissions of air pollutants from
both stationary and mobile sources. The CAA requires EPA to establish
National Ambient Air Quality Standards (NAAQS) as well as source specific
emission limits' for pollutants of concern. The primary mechanism for
controlling emissions is through a national permitting system that imposes
technology based limits on point sources.
The Federal CAA does not directly address emissions of CFCs or halons.
For example, the National Emission Standards for Hazardous Air Pollutants
(NESHAPs) do not regulate these pollutants, nor is there an applicable New
Source Performance Standard (NSPS). However, under Prevention of Significant
Deterioration (PSD) regulations both HF and HBr emissions can fall under the
CAA if they are emitted at more than 3 tons per year (TPY) from a source which
also emits one or more of the six criteria pollutants (e.g., CO, NO , SO.,) at
X £
more than 250 tons per year.
State or local air pollution regulatory agencies may regulate CFC and
halon emissions or emissions from destruction or recycling processes through
their own permitting programs.
kgo/102 2-19
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Clean Water Act (CWA)
The Clean Water Act, also known as the Federal Water Pollution Control
Act, gives the Environmental Protection Agency the authority to regulate the
discharge of pollutants into waters of the United States. This language has
been interpreted to include virtually all U.S. surface waters and the
territorial sea. The Acts primary mechanism for controlling discharge is
through a national permit system which imposes technology based limits on
point sources.
Effluent from CFC or halon incinerator scrubbers will require treatment
before direct discharge to a watercourse under the National Pollutant
Discharge Elimination System (NPDES) program or may require pretreatment
before being discharged to a publicly owned treatment works (POTW). In either
case, treatment of the effluent will generate sludges which may themselves be
considered as RCRA hazardous wastes.
Toxic Substances Control Act (TSCA)
The Toxic Substances Control Act (TSCA) provides the Environmental
Protection Agency with the authority to regulate the many chemical substances
and mixtures which are constantly being developed and produced in this
country. TSCA provides for the compilation of an inventory of chemicals
manufactured, imported or processed for commercial purposes in the U.S. TSCA
gives the Environmental Protection Agency broad authority to regulate
chemicals found to pose unreasonable risk to human, health or the environment.
The statute specifically requires the phase-out of the manufacture of
polychlorinated biphenyls (PCBs) except for uses that are "totally enclosed."
Fully halogenated chlorofluoroalkanes (in aerosol propellant use) are
subject to certain manufacturing, processing, and distribution in commerce
restrictions under TSCA (40 CFR Part 762) except as otherwise exempted. Other
than these restrictions, the TSCA rules do not address CFC and halon use or
disposal.
kgo/102 2-20
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Comprehensive Environmental Response Compensation and Liability Act (CERCLA)/
Superfund Amendments and Reauthorization Act (SARA)
The Comprehensive Environmental Response Compensation and Liability Act
(CERCLA) provides federal authority for responding to releases of hazardous
substances into the environment. The Act created a "Superfund" generated from
taxes levied on the chemical and petroleum industries which produce the
hazardous substances specified in the implementing regulations. The fund is
used to respond to sites where uncontrolled hazardous substances are found;
though liability for the cleanup ultimately belongs to the parties responsible
for the contamination.
The Superfund Amendments and Reauthorization. Act (SARA) provides for the
continuation of the provisions of CERCLA and strengthens many of its parts.
In addition to the $8.6 billion provided by the Amendments for site
remediation, SARA seeks to streamline the clean-up process, to require that
permanent solutions be used, and to increase the citizen participation and
access to the site remediation activities. In addition, Section 313 of SARA
establishes reporting requirements for all compounds regulated by the Act.
CFC-113 is included in the list of toxic chemicals for Section 313 of
SARA. Under these rules, producers and users of CFC-113 must comply with the
reporting provisions of Section 313 which require annual estimates of routine
substance releases to air, water, or ground.
DATA GAPS AND RESEARCH NEEDS
Four major areas of data gaps identified in this evaluation are: 1) PIC
formation resulting from CFC destruction; 2) technical design data on CFC
thermal destruction systems, particularly in the area of corrosion and
materials of construction; 3) all aspects of halon destruction; and 4)
availability of continuous CFC or halon monitors to verify destruction.
kgo/102 2-21
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These data gaps can be addressed through short-term (2-5 years) research
initiatives which would be focused on better characterizing thermal
destruction systems to make data available for future developments. In
addition to short-term research initiatives, a more long-term (5-15 years)
research program should also be considered to promote the development of the
most promising destruction technologies now in various stages of development.
Short-Term Research Initiatives (2-5 years)
The objective of short-term research is to quickly resolve any data gaps
that exist with the current technology so that existing concerns over
secondary environmental impacts and specialized design requirements can be
resolved. A viable program could consist of three main elements:
Characterization of Thermal Destruction Systems--Several issues/data
gaps exist concerning CFC destruction which could readily be
resolved through a well-designed fundamental research program. This
fundamental research can be supported by field tests at selected
commercial or pilot-scale facilities. Issues that can be resolved
through short-term research are:
a. CFC PIC Formation--Under what operating conditions are they
formed? How does the role of mixed fuel firing affect PIC
formation? Are there any potential human health effects from
exposure to PICs? One approach to generate some PICs and
health effects data would be to require PICs sampling and
analysis as part of the RCRA trial burns.
b. Specialized Design Requirements--Correlations of corrosive
off-gases as a function of operating conditions will determine
how to minimize free halogen species, and will provide data for
specifying appropriate materials of construction for future
designs, and for designing the acid gas scrubbing systems.
c. Halon Destruction Data--Since no data currently exists, the
test program could be designed to answer: What operating
conditions and supplemental fuel requirements are necessary for
Halon destruction? What materials of construction are
required? What conditions will result in PIC formation? What
is the Destruction Efficiency? What is the proportion of free
bromine to HBr? What type of scrubbing is require to control
bromine and/or HBr emissions?
kgo/102 . 2-22
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2. Develop accurate cost estimates for a CFC/Halon destruction using
the results of the data from the fundamental research and
demonstration programs.
3. Develop approved monitoring techniques. CFC Monitoring--Either
initiate development of continuous monitors to verify the
destruction of CFCs and halons or conduct studies to correlate
CFC/halon destruction other easily monitored surrogate parameters
(e.g., carbon monoxide, temperature, etc.).
Long-Term Research Initiatives (5-15 vears)
The objective of a long-term research program would be to promote the
development of some alternative CFC/halon destruction technologies. Such a
program could probably begin with a detailed conceptual evaluation of all
alternatives to incineration in order to prioritize their relative merits.
The conceptual study could be followed by bench-scale proof-of-concept tests
for the most promising alternatives, and then a pilot-scale demonstration.
Also, associated cost and environmental assessments could be conducted. The
overall objective would be to develop and demonstrate a superior alternative
to the point that it could be commercialized by the private sector.
It is possible that some of the potential alternative destruction
technologies could be adapted to CFCs or halons on a more accelerated basis.
This would apply to those technologies that are already commercially available
for other waste materials. It might be possible to conduct a commercial-scale
test in the near term for some of these techniques, and, if successful, to
make them commercially available in the near term. This type of accelerate
development would best be accomplished by private industry, but EPA could help
to promote such activity by developing information that demonstrates the
market potential for CFC or halon destruction systems.
kgo/102 2-23
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SECTION 3
BIBLIOGRAPHY
REFERENCES
1. Handbook: Permit Writer's Guide to Test Burn Data - Hazardous Waste
Incineration. Prepared for U.S.EPA/ORD by PEI Associates and JACA
Corporation. EPA-625/6-86-012, August 1986.
2. Kirk-Othmer Encyclopedia of Chemical Technology. Third Edition.
Wiley-Interscience, 1983.
3. Code of Federal Regulations 40 "Protection of Environment". Parts 264
and 270, Revised 7/1/88.
4. Polcyn, A.J., and H.E. Hesketh. A Review of Current Sampling and
Analytical Methods for Assessing Toxic and Hazardous Organic Emissions
from Stationary Sources. JAPCA, 35(1), January 1985.
5. La Fond, R.K., J.C. Kramlich, W.R. Seeker, and G.S. Samuelsen.
Evaluation of Continuous Performance Monitoring Techniques for Hazardous
Waste Incinerators. JAPCA, 35(6), June 1985.
6. Staley, L.J., M.K. Richards, G.L. Huffman, R.A. Olexsey, and B.
Dellinger. On the Relationship Between CO, POHC, and' PIC Emissions from
a Simulated Hazardous Waste Incinerator. JAPCA, 39(3), March 1989.
kgo/102 3-1
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7. Chang, D.P.V., et al. Evaluation of a Pilot-Scale Circulating Bed
Combustor as a Potential Hazardous Waste Incinerator. JAPCA,
37(3):266-274, March 1987.
8. Cundy, V.A., et al. Practical Incinerator Implications From a
Fundamental Flat Flame Study of Dichloromethane Combustion. JAPCA,
36(7):824-828, July 1986.
PERSONAL CONTACTS
1. Personal Communication. Hemby, J., U.S. Environmental Protection Agency,
with Hummel, K., Radian Corporation, March 13, 1989.
2. Personal Communication. Bellinger, B., University of Dayton Research
Institute, .with Hummel, K., Radian Corporation, February 27, 1989.
3. Personal Communication. Lukosius, E., DuPont, with Hummel, K., Radian
Corporation, February 27, 1989.
4. Personal Communication. Irrgang, G., T-Thermal, with Hummel, K. , Radian
Corporation, February 28, 1989.
5. Personal Communication. Dwyer, F., Allied/Signal, with Hummel, K.,
Radian Corporation, February 28, 1989.
6. Personal Communication. Keller, M., John Zink Company, with Hummel, K.,
Radian Corporation, March 7, 1989.
7. Personal Communication. Buice, J., Dow Chemical USA, with Hummel, K.,
Radian Corporation, March 7, 1989.
8. Personal Communication. Brunner, C., Incineration Consultants, Inc.,
with Hummel, K., Radian Corporation, March 7, 1989.
kgo/102 3-2
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9. Personal Communication. Weitzmann, L., Acurex, with Hummel, K., Radian
Corporation, March 7, 1989.
10. Personal Communication. Turner, R., LaRoche Chemicals, with Hummel, K.,
Radian Corporation, March 7, 1989.
11. Personal Communication. Santoleri, J., Four Nines Corporation, with
Herndon, D., Radian Corporation, March 6, 1989.
12. Personal Communication. Sweval, M., Great Lakes Chemical Corporation,
with Herndon, D., Radian Corporation, March 8, 1989.
13. Personal Communication. Hudson, L., International Technology (IT)
Corporation, with Herndon, D., Radian Corporation, March 8, 1989.
14. Personal Communication. Vlick, R., Air Conditioning Company, with
Hummel, K., Radian Corporation, March 7, 1989.
15. Personal Communication. Pershing, D., University of Utah, with Emmel,
T., Radian Corporation, March 8, 1989.
16. Personal Communication. Backlund, J., Coen Company, with Hummel, K.,
Radian Corporation, March 8, 1989.
17. Personal Communication, Scofield, B., Chemical Waste Management, with
Hummel, K., Radian Corporation, March 7, 1989.
18. Personal Communication. Turner, M., Racon, with Hummel, K., Radian
Corporation, March 8, 1989.
19. Personal Communication. O'Meara, D., Omega Recovery, with Hummel, K.,
Radian Corporation, March 9, 1989.
kgo/102 3-3
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20. Personal Communication. Aker, J., DuPont, with Hummel, K., Radian
Corporation, March 13, 1989.
21. Personal Communication. Spivey, J., Research Triangle Institute, with
Hummel, K., Radian Corporation, March 14, 1989.
22. Personal Communication. Leonard, L., Radian Corporation (Sacramento),
with Hummel, K., Radian Corporation, March 14, 1989.
23. Personal Communication, von Klahr, W., Hoechst-Celanese, with
Hummel, K., Radian Corporation, March 17, 1989.
24. Personal Communication. Hedlund, T., Swedish National Environmental
Protection Board, with Hummel, K., Radian Corporation, March 17, 1989.
25. Personal Communication. Bakken, P., Norway Ministry of Environment, with
Hummel, K., Radian Corporation, March 14, 1989.
26. Personal Communication. Kim, Y.J., U.S.EPA Region 5 (Chicago, IL), with
Horstman, J., Radian Corporation, March 15, 1989.
27. Personal Communication. Wilson, J., U.S.EPA Region 6 (Dallas, TX), with
Horstman, J., Radian Corporation, March 15, 1989.
28. Personal Communication. Reiser, Mr., U.S.EPA Region 7 (Kansas City, KS),
with Horstman, J., Radian Corporation, March 15, 1989.
29. Personal Communication. Silverstien, M., U.S.EPA Region 8 (Denver, CO),
with Horstman, J., Radian Corporation, March 15, 1989.
30. Personal Communication. Wilson, S., U.S.EPA Region 10 (Seattle, WA),
with Horstman, J., Radian Corporation, March 15, 1989.
kgo/102 3-4'
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31. Personal Communication. Gross, G., U.S.EPA Region 3 (Philadelphia, PA),
with Horstman, J., Radian Corporation, March 20, 1989.
32. Personal Communication. Urvarsky, J., U.S.EPA Region 9
(San Francisco, CA), with Horstman, J., Radian Corporation, March 20,
1989.
33. Personal Communication. Craig, J., Ross Incineration, with Horstman, J.
Radian Corporation, March 21, 1989.
34. Personal Communication. Conveser, M., Rollins Environmental, with
Horstman, J., Radian Corporation, March 22, 1989.
35. Personal Communication. Trivedi, G., LWD Incorporated, with Herndon, D.
Radian Corporation, March 22, 1989.
36. Personal Communication. Smith, S., Caldwell Systems, with Horstman, J.,
Radian Corporation, March 20, 1989.
37. Personal Communication. Brogart, J., U.S.EPA Region 2 (New York City,
NY), with Horstman, J., Radian Corporation, March 20, 1989.
38. Personal Communication. Fisher, W., Chemical Waste Management, with
Horstman, J., Radian Corporation, March 22, 1989.
39. Personal Communication. Tew, L., Olin Corporation, with Horstman, J.,
Radian Corporation, March 23, 1989.
40. Personal Communication. Cundy, V., Louisiana State University, with
Hummel, K., Radian Corporation, March 20, 1989.
41. Personal Communication. Ziman, R., Demtrol, with Shareef, G., Radian
Corporation, March 21, 1989.
kgo/102 3-5
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42. Personal Communication. Dietrich, P., Dedert Topsoe, with Shareef, G.,
Radian Corporation, March 21, 1989.
43. Personal Communication. Misaki, S., Daikin Industries, with Hummel, K.,
Radian Corporation, March 24, 1989.
44. Personal Communication. Munekata, S., Asahi Glass Co. Ltd., with
Hummel, K., Radian Corporation, March 22, 1989.
45. Personal Communication. Harris, M., ICI Americas, with Horstman, J.,
Radian Corporation, March 20, 1989.
46. Personal Communication. Crocker, J., Texas Air Control Board, with
Horstman, J., Radian Corporation, March 15, 1989.
47. Personal Communication. Darrington, D., Versar, with Horstman, J.,
Radian Corporation, March 20, 1989.
48. Personal Communication. Fore, K., Martin Marietta (U.S.DOE), with
Horstman, J., Radian Corporation, March 20, 1989.
49. Personal Communication. Lee, C.C., U.S.EPA (Cincinnati, OH), with
Horstman, J., Radian Corporation, March 29, 1989.
50. Personal Communication. Stewart, C., U.S.EPA Region 4 (Atlanta, GA),
with Shareef, G., Radian Corporation, March 29, 1989.
51. Personal Communication. Willis, B., U.S.EPA Region 4 (Atlanta, GA), with
Horstman, J., Radian Corporation, March 28, 1989.
52. Personal Communication. Walbach, D., Acurex, with Hummel, K., Radian
Corporation, March 27, 1989.
kgo/102 3-6
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53. Personal Communication. Swager, Mr., Netherlands Ministry of
Environment, with Hummel, K., Radian Corporation, March 30, 1989.
kgo/102 3-7
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APPENDIX A
List of Experts
(List of Experts organized by specialization, with affiliation/organization
and address).
kgo/102 A-l
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GENERAL
AREA
NAME
ORGANIZATION
ADDRESS
SPECIFIC
EXPERTISE
THERMAL Mr. Donald A. Oberacker U.S. EPA
PROCESSES HWERL
Thermal Destruction Branch
Risk Reduction Engineering Lab
26 West Martin Luther King Or.
Cincinnati, OH 45268
Thermal Destruction Processes
Trial Burn Testing
SITE Program
Or. Paul H. Lemteux
U.S. EPA
AEERL
Combustion Research Branch
MD-6S
Research Triangle Park. NC 27711
Thermal Destruction Processes
Products of Incomplete
Combustion
Mr. Joseph A. McSorley U.S. EPA
AEERL
Combustion Research Branch
MD-65
Research Triangle Park. NC 27711
Thermal Destruction Processes
Products of Incomplete
Combustion
I
ro
Dr. Barry Del linger
Univ. of Dayton
Research Institute
Environmental Sciences
300 College Park
Dayton. OH 45469
Thermal Destruction Kinetics
Products of Incomplete
Combustion
Mr. Harold Oiot
Qgden Environmental Services P.O. Box 85178
San Diego, CA 92138-5178
Circulating Bed Combustion
System Vendor
Ms. Carrie Penman
Uestinghouse Electric
Waltz Hill Site
P.O. Box 286
Mad Ison. PA 15663
Plasma System Vendor
Mr. Gene Irrgang
T-Thermal
Brook Road
Conshohocken. PA 19428
Incinerator/Burner Vendor with
Installations Handling CFCs
Mr. Mike Keller
John Zlnk Co.
P.O. Box 70220
Tulsa. OK 74170
Incinerator/Burner Vendor with
Installations Handling CFCs
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>
GENERAL
AREA
THERMAL
PROCESSES
(cont.)
CHEMICAL
PROCESSES
NAME
Mr. Jack Buice
Mr. Jim Aker
Mr. Don Matter
Or. James Spivey
Or. Vic Cundy
Mr. Joe Santoleri
Mr. Garry Howe 11
Mr. Charles Russell
Mr. Leo Veitzmann
ORGANIZATION
ADDRESS
SPECIFIC
EXPERTISE
Dow Chemical USA
E.I. DuPont de Nemours
Rollins Environmental
Texas Operations
OC-1120
Freeport..TX 77541
"U"
Chambers Works
Deepwater. NJ 08023
P.O. Box 609
Deer Park. TX 77536
Research Triangle Institute P.O. Box 12194
Thermal Oxidation of
Chlorinated Organics
Thermal Destruction of CFCs
Thermal Destruction of CFCs
Catalytic Destruction of
Research Triangle Park, NC 27709 Chlorinated Organics
Louisiana State University Department of Mech. Engrg.
Baton Rouge. LA 70803
Four Nines Corp.
U.S. EPA
KUERL
Detox International
Acurex
Conshohocken, PA 19428
Thermal Destruction Kinetics
Products of Incomplete
Combustion
Trial Burn Testing
Incineration Consultant
Risk Reduction Engineering Lab Chemical Destruction Processes
26 West Hartin Luther King Dr. SITE Program
Cincinnati, OH 45268
525 Dunham Road
St. Charles, IL 60174
Active Metals Destruction
(Molten Aluminum)
P.O. Box 13109 Active Metals Destruction
Research Triangle Park. NC 27709 (Acurex PCB process)
-------
GENERAL
AREA NAME ORGANIZATION
CHEMICAL Mr. Ralph Morgan Modar
PROCESSES
(cont.)
ADDRESS
3200 Uilcrest
Houston. TX 77042
SPECIFIC
EXPERTISE
Supercritical
F luid Oxidation
Mr. Will lam Copa
Z impro
301 W. Military Road
Rothschild. WI 54474
Wet Air Oxidation of CFCs
ELECTRICAL Dr. Norm Plaks
PROCESSES
U.S. EPA
AEERL
MD-61 Electrostatic Destruction
Research Triangle Park. NC 27711 (Corona Discharge)
OTHER AREA Mr. Tom Hedlund
Swedish Nations)
Environmental Protection
Board
Box 1302
S-1007125
Solna. SWEDEN
Sweden's Programs to Evaluate
CFC/halon Destruction Technology
>
Or. Koicht Mlzuno
Atmospheric Environmental
Protection Department
Nat'l Research Instit. for
Pollution and Resources
Ministry of International
Trade and Industry (M.I.T.I.)
16-3 Onogawa Tsukuba
Ibaraki 305 JAPAN
Japan's Program to Evaluate
CFC/halon Destruction Technology
Dr. Hugh Re illy
Sandia National Lab
Solar Energy Department
Division 6227
Albuquerque. NM 87185
Solar Destruction
Mr. Dennis O'Meara Omega Recovery
12504 East Whittier Blvd.
Whittter. CA 90602
Recycling Processes
Dr. Louis Thibodeaux Louisiana State University
Department of Chem. Engrg.
Baton Rouge, LA 70803
Biological Processes
Land Treatment
Mr. Dale L. Harmon U.S. EPA
AEERL
MD-62B
CFC Control Technologies
Research Triangle Park, NC 27711 Recycling Processes
-------
APPENDIX B
Control Technology Summaries
(Control Technology Summaries providing additional information on destruction
processes for CFCs and halons as (1) currently practiced or (2) considered by
experts to have the greatest potential, for future applicability).
kgo/102 B-l
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CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: CONVENTIONAL THERMAL OXIDATION
OPERATING PRINCIPLE: Conventional thermal oxidation refers to various
types of incineration processes using a high temperature flame. With
CFCs or halons, the destruction process might be dissociation at the
elevated temperature followed by rapid hydrolysis rather than oxidation.
DEVELOPMENT STATUS: Commercial
DESTRUCTION EFFICIENCY: Very high (>99%).
RELIABILITY/OPERABILITY: Careful selection of refractory material necessary to
prevent rapid erosion by HF at high temperature. Also, combustion
conditions must be maintained with excess H- or H?0 to ensure formation
of acid gases rather than free CK, F2, or Br^ (wnich are generally more
difficult to clean up). Incinerator should use a high energy auxiliary
fuel burner to create a high temperture zone for thermal dissociation,
followed by steam or water injection to effect a rapid hydrolysis of the
chlorine and fluorine to form HC1 and HF.
SECONDARY ENVIRONMENTAL CONCERNS: Acid gases generated by destruction of CFCs
and halons include HF, HC1, and HBr. Also, there is potential for
formation of toxic and hazardous products of incomplete combustion (PICs)
which may also be potential ozone depleters.
COSTS - CAPITAL: Incinerator refractory may have to be expensive high
alumina type.
- OPERATING AND MAINTENANCE: Fuel requirement for burner, steam or water
for hydrolysis, and reagents for neutralization of acid gases. Rough
calculation for fuel cost and caustic indicates approximately $0.35 per
kilogram ($0.16 per pound) of CFC destroyed. Disposal costs for scrubber
sludge.
LIMITATIONS/BARRIERS: Typical CFC incinerator installations are specially
designed units with extensive air pollution control devices. They are
often limited to firing low concentrations of CFCs to avoid severe
refractory damage.
SUMMARY - PROS: Conventional thermal oxidation is currently the only
available method for complete destruction of CFCs and halons. Industrial
contacts contend that high destruction efficiencies and insignificant PIC
formation are typical.
- CONS: Possible formation of PICs which may be toxic, hazardous,
or ozone depleters. Sparse data on destruction efficiency. Refractory
damage caused by HF can result in costly repairs and downtime.
B-2
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: CATALYTIC THERMAL DESTRUCTION
OPERATING PRINCIPLE: Catalytic thermal destruction involves using a solid
catalyst to provide an alternate reaction pathway for destruction at
lower temperatures than conventional thermal destruction.
DEVELOPMENT STATUS: Commercial (For CFCs:Bench-scale)
DESTRUCTION EFFICIENCY: High (>90%).
RELIABILITY/OPERABILITY: Careful selection of catalyst and construction
material (esp. catalyst bed support) necessary to prevent deactivation or
rapid corrosion, respectively. Conditions must be maintained with
available H- or H«0 to ensure formation of acid gases rather than free
CK, F2> or Br- (which are generally more difficult to clean up).
SECONDARY ENVIRONMENTAL CONCERNS: There is potential for formation of toxic
and hazardous products of incomplete combustion (PICs) which may also be
potential ozone depleters. Also, acid gases or neutralized salts may be
regulated.' Disposal of used catalyst may also be a potential concern.
COSTS - CAPITAL: Potential cost savings compared to thermal incineration
since reduced temperature minimizes the need for special refractory or
materials of construction.
- OPERATING AND MAINTENANCE: Fuel requirement for incinerator and
reagents for neutralization of acid gases. Disposal costs for scrubber
sludge. Periodic replacement of catalyst.
LIMITATIONS/BARRIERS: Catalytic incineration of CFCs is an adaptation of
existing technology available for destruction of chlorinated organics.
However, current practice has been limited to destruction of dilute
gaseous streams containing chlorinated organics. There are no data
available for catalysts used for CFC destruction.
SUMMARY - PROS: The primary advantage of catalytic incineration over
conventional thermal incineration is the potential cost savings from
reduced fuel requirements since destruction may be possible at a lower
temperature. Cost of metal oxide catalysts are lower than noble metal
catalysts; metal oxide catalysts are the preferred type for this stream.
- CONS: Some early data on catalytic incineration of chlorinated
organics showed rapid deactivation and low destruction efficiency with
noble metal catalysts. No data on destruction efficiency for CFCs or
halons. No proven technology in this area.
B-3
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: PYROLYSIS
OPERATING PRINCIPLE: Pyrolysis involves destruction of CFCs or halons by
heating to very high temperatures in the absence of air. Since CFCs and
halons can be destroyed through bond homolysis, simple heating without
air is sufficent to break the bonds. This technology includes the plasma
torch and other sub-stoichiometric burners.
DEVELOPMENT STATUS: Commercial (For CFCs:Bench-sca1e)
DESTRUCTION EFFICIENCY: Very high (>99%).
RELIABILITY/OPERABILITY: Careful selection of pyrolyzer material necessary to
prevent rapid erosion by HF at high temperature. Conditions must be
maintained with available H^ or H,0 to ensure formation of acid gases
rather than free CK, F2, or Br2 fwhich are generally more difficult to
clean up).
SECONDARY ENVIRONMENTAL CONCERNS: Pyrolysis of CFCs or halons without H2 or
H-0 would likely result in formation of free CK, F~, or Br-. Also;
tnere is higher potential for formation of toxic ana hazardous products
of incomplete combustion (PICs) when operating under "reducing"
conditions which may also be potential ozone depleters.
COSTS - CAPITAL: Potential cost savings compared to thermal incineration
since reduced gas flow may allow significantly smaller scrubbers. Some
test data with pyrolysis destruction has shown a need for an incinerating
afterburner to clean up PICs. This would add significantly to the cost.
- OPERATING AND MAINTENANCE: Energy requirement for pyrolyzer and
reagents for neutralization of acid gases. Disposal costs for scrubber
sludge.
LIMITATIONS/BARRIERS: Pyrolysis is less developed than conventional thermal
oxidation for the destruction of hazardous wastes. Some critics feel
that when an afterburner is required for the pyrolyzer exit gas, an
incinerator alone is a more cost effective choice.
SUMMARY - PROS: The primary advantage of pyrolysis over conventional
thermal incineration is the potential cost savings from smaller
downstream scrubbing equipment (made possible by heating without air).
- CONS: Commercial development of pyrolysis systems may be limited
by possible formation of large quantities of PICs which may be toxic,
hazardous, or ozone depleters. Sparse data on destruction efficiency.
Potential damage caused by HF can result in costly repairs and downtime.
B-4
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: METALS SCRUBBING/DESTRUCTION
OPERATING PRINCIPLE: Active metals such as sodium, zinc, or aluminium are
suspended in an inert liquid medium. The active metals chemically
dehalogenate the halogenated organic waste feed, producing a metal salt
(e.g., Nad).
DEVELOPMENT STATUS: Pilot-scale
DESTRUCTION EFFICIENCY: Very high (>99%)
RELIABILITY/OPERABILITY: The active metals are highly reactive with water or
air. Also, there may be difficulties in terms of materials of
construction.
SECONDARY ENVIRONMENTAL CONCERNS: One advantage of active metals scrubbing is
that the metal salts can be precipitated out of concentrated solution in solid
form, possibly allowing easier disposal of this secondary waste. Fluoride
salts are a potential concern.
COSTS - CAPITAL: Moderate to low compared to baseline thermal incineration.
- OPERATING AND MAINTENANCE: For CFCs: Costs are unknown, probably high.
LIMITATIONS/BARRIERS: The primary limitation of active metals scrubbing is
uncertainty regarding the ability to maintain the reactivity of the metal
in the presence of air and water. Feed pretreatment might be required to
remove water, and the process might have to be run under slight nitrogen
pressure to exclude air.
SUMMARY - PROS: The process has been used to destroy another class of
toxic chemicals which are fairly unreactive, PCBs (using the Acurex
process), so there is some experience with the technique. Metals
scrubbing is claimed to provide a high degree of destruction at
near-ambient temperatures and may be tailored to produce a solid salt
which would be easier to dispose of.
- CONS: Reaction of CFCs or halons with active metals is untested
and unproven. The active metals themselves are often pyrophoric (they
spontaneously react with air) or they may be water-reactive. This would
complicate the operation of such a process.
B-5
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: CHEMICAL SCRUBBING/DESTRUCTION
OPERATING PRINCIPLE: This technology involves the use of a highly
alkaline, non-aqueous scrubbing liquor to absorb and destroy halogenated
organics. One example of this is the K-PEG process (KOH is the alkaline
component; poly-ethylene glycol is the solvent).
DEVELOPMENT STATUS: Bench-scale
DESTRUCTION EFFICIENCY: High, but may be lower than active metals scrubbing.
RELIABILITY/OPERABILITY: The alkaline component is highly reactive with water.
Absorption of carbon dioxide (C02) from air by the sorbent may be a
problem. Also, there may be difficulties in terms of materials of
construction.
SECONDARY ENVIRONMENTAL CONCERNS: One advantage of the K-PEG process is that
the salts formed by dehalogenation can be precipitated out of
concentrated solution in solid form, possibly allowing easier disposal of
this secondary waste. Fluoride salts are a potential concern.
COSTS - CAPITAL: Low to moderate
- OPERATING AND MAINTENANCE: For CFCs: Costs are unknown, but may be
less expensive than active metals process.
LIMITATIONS/BARRIERS: The primary limitation of chemical scrubbing with an
alkaline reactant is uncertainty regarding the degree of destruction.
Also, there may be limitations to treatment of water-contaminated CFCs or
halons.
SUMMARY - PROS: Chemically reactive scrubbing of air streams containing
CFCs or halons might be superior to ordinary scrubbing processes (such as
lean oil scrubbing). The process has been demonstrated on the
bench-scale for the destruction of PCBs. Control of the pH may allow
precipitation of a solid salt which could be easily separated and
disposed of.
- CONS: Reaction of CFCs or halons with alkaline scrubbing liquors
is untested and unproven. The alkaline components are water-reactive and
could be very corrosive.
B-6
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: SUPERCRITICAL WATER OXIDATION
OPERATING PRINCIPLE: This process involves using water at supercritical
conditions (i.e., temperature > 374°C (705.5eF) and pressure > 218 atm
(3208 psia)) with oxygen to achieve rapid destruction of organic
compounds. With CFCs or halons, the destruction process might involve
hydrolysis as well as oxidation.
DEVELOPMENT STATUS: Commercial (For CFCs:Bench-scale)
DESTRUCTION EFFICIENCY: Potentially higher than wet air oxidation.
RELIABILITY/OPERABILITY: Possible metallurgy considerations which might affect
rel iabil ity/operability or produce high capital costs.
SECONDARY ENVIRONMENTAL CONCERNS: Unknown; possible neutralization of acidic
aqueous waste stream. Fluoride salts are a potential concern.
COSTS - CAPITAL: Possible requirement for exotic materials of construction.
- OPERATING AND MAINTENANCE: Higher energy requirements than wet air
oxidation due to higher temperature and pressure. Requires oxygen
supply.
LIMITATIONS/BARRIERS: Supercritical water oxidation is a new technology
which is basically a modification of wet air oxidation. Both
supercritical water oxidation and wet air oxidation are typically used
with aqueous streams only. Since CFCs and halons do not have an
abstractable hydrogen or a double bond, they are resistant to oxidation.
This may make them difficult to destroy using this process, although
initial hydrolysis could occur to destabilize the target molecule.
SUMMARY - PROS: Limited data exist for destruction of CFC-113 by wet air
oxidation. Since supercritical water oxidation is touted as faster than
wet air oxidation, it may be capable of more efficient destruction of
CFCs and halons.
- CONS: Destruction of CFCs or halons by supercritical water
oxidation is untested and unproven. The possibility of high energy
consumption and possible metallurgical limitations are unresolved
concerns.
B-7
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: WET AIR OXIDATION
OPERATING PRINCIPLE: This process involves using a high temperature
(temperature > 300"C (570*F)) aqueous stream with oxygen to destroy many
organic compounds. With CFCs or halons, the destruction process might
involve hydrolysis as well as oxidation.
DEVELOPMENT STATUS: Commercial (For CFCs:Bench-scale)
DESTRUCTION EFFICIENCY: High, but limited to aqueous streams only.
RELIABILITY/OPERABILITY: Possible metallurgy considerations which might affect
reliability/operability and cost.
SECONDARY ENVIRONMENTAL CONCERNS: Unknown; possible neutralization of acidic
aqueous waste stream. Fluoride salts are a potential concern.
COSTS - CAPITAL: Possible requirement for exotic materials of construction.
- OPERATING AND MAINTENANCE: High energy requirements due to high
temperature. Requires oxygen supply.
LIMITATIONS/BARRIERS: Wet air oxidation is typically used with aqueous
streams only. Since CFCs and halons do not have an abstractable hydrogen
or a double bond, they are resistant to oxidation. This may make them
difficult to destroy using this process.
SUMMARY - PROS: Limited data exist for destruction of CFC-113 by wet air
oxidation. Effective on aqueous streams. May be able to enhance by
adding solid catalyst.
- CONS: Possible limitation to dilute aqueous streams only. Wet
air oxidation may be considered slow compared to other types of
destruction processes.
B-8
-------
CONTROL TECHNOLOGY SUMMARY
TECHNOLOGY NAME: CORONA DISCHARGE
OPERATING PRINCIPLE: This process uses a high voltage AC or DC discharge
to generate an ionized corona field. The energized electrons are capable
of dissociating many types of hazardous wastes.
DEVELOPMENT STATUS: Bench-scale
DESTRUCTION EFFICIENCY: High, when several stages are connected in series to
obtain long residence times.
RELIABILITY/OPERABILITY: Insufficient data to estimate reliability and
operability.
SECONDARY ENVIRONMENTAL CONCERNS: Possible modification to the basic design
may offer potential for simultaneous destruction and neutralization.
Otherwise, the acid gases generated as a result of CFC/halon destruction would
have to be scrubbed and neutralized.
COSTS - CAPITAL: Could require multiple stages. Power supply may be
expensive.
- OPERATING AND MAINTENANCE: Possible high electrical costs.
LIMITATIONS/BARRIERS: The process is still in development phase. Current
research efforts are directed towards modeling the corona field and
scaling up the technology. Also, studies to establish power consumption
as a function of destruction efficiency are needed, as well as
investigating the properties of an ionized bed of reactive pellets.
SUMMARY - PROS: The corona destruction process is fairly rapid, and is
performed at ambient temperatures and pressures. The possibility of
simultaneous destruction and neutralization is potentially valuable, but
unproven.
- CONS: Destruction of CFCs or halons in a corona discharge is
untested. The possibility of high power consumption and difficulty in
modeling and scaling up to commercial size are unresolved concerns.
B-9
-------
APPENDIX C
Preliminary List of Technologies
(Listing of all technologies considered for destruction of hazardous wastes to
determine applicability towards CFC and halon destruction)
kgo/102 C-l
-------
LEGEND FOR CODES:
1. Waste Streams
G
L
S
SI
Gas
Liquid
Solid
Sludge
2. State of Development
Co Conceptual
B Lab or Bench scale
P Pilot scale
C Commercial
C* Commercial on other than hazardous wastes
3. Applicable to CFCs
1
2
3
Data available for CFCs
No data for CFCs but appears feasible
Doubtful application
C-2
-------
General
Category Process Name
THERMAL Infrared Thermal
PROCESSES Destruction
Circulating Fluidized
Bed Combustor
Multisolid Fluidized
Bed
Advanced Electric
Reactor
Fluid Wall Reactor
o
i
Electric Pyrolyzer
Pyroplasma System
Waste
Description Stream
Wastes are metered on a woven belt and pass S
under an Infrared heating element. Combust-
ible off-gases are burned in a secondary
chamber .
Uses injection of limestone to neutralize L,S,S1
acid gases.
Uses a moving bed of heated inert material All
to Incinerate wastes.
Performs well only on finely ground material. S
Technology is currently shelved.
Uses electrically induced radiant heat to S
pyrolyze organic constituents. Same as Huber
technology.
Reaction chamber heated to 3000 F where or- S
ganics are volatilized and solids are
vitrified.
Doing extensive testing with commercial L,S1
scale equipment in the laboratory. Wastes
State of Applicable
Development to CFCs Contact
C 3 ECOVA, Inc. (formerly
Shirco). Dallas. TX
C 1 Ogden Environmental Ser-
vices, San Diego, CA
C* 3 Battelle Memorial
Institute, Columbus, Oil
C 2 J.M. Huber, Co.
Borger, TX
Unk I Thagard Research Corp.
Costa Mesa, CA
Unk 3 Westinghouse
Madison, PA
P 2 Westinghouse
Madison, PA
must be pumpable.
Plasma Pyrolyzer
Built around the Westinghouse torch.
Currently not working with this technology.
L.S1
Pyrolysis Systems
Niagara Falls, Ontario
Canada
Pyrolytic Decom-
position
Heats waste materials in the absence of
oxygen to drive off volatiles for incin-
eration or recovery.
L,S1
Midland-Ross Corp
Toledo, OH
-------
General
Category Process Name
THERMAL High Temperature
PROCESSES Pyro lysis with 02
(cont.)
Applied Energetics
Plasma Temperature
Incinerator
Joule Heated Glass
He Her
Electromelt Pyro
Converter
o Consertherm Rotary
*~ Kiln
Fast Rotary Reactor
"Cyclin" Cyclone
Incinerator
Pyretron Oxygen-
enhanced burner
Liquid Injection
Incineration
Description
Uses oxygen induced high temperature to
pyrolyze waste.
Burns wastes in a pressurized stream of
preheated oxygen.
Applies electric current directly to waste
material for combustion and for creation
of a glass matrix.
Uses a bed of molten glass to oxidize
organics and to capture ash and inorganics.
A modular controlled air incinerator.
A rapidly rotating cylinder using dryer
technology for waste incineration.
A cylindrical shaped combustion chamber
provides for intensive mixing of fuel and
air.
Oxygen enhancement allows higher feed
rates while still maintaining performance.
Common technology.
Waste State of Applicable
Stream Development to CFCs
L.S C* 2
L,S P 2
L.S P 3
L.S C* 3
L.S. SI C 2
S.S1 P 3
G.L C 2
G.L C 2
L C 1
Contact
Russell and Axon
St. Louis, MO
Applied Energetics, Inc.
Tullahoma. TN
Battelle Pacific NW Labs
Richland, UA
Penberthy Electomelt
International, Inc.
Seattle. UA
Industronics, Inc.
South Windsor, CT
PEDCo Technology Corp
Cincinnati. OH
Institute of Gas Tech-
nology, Chicago. IL
American Combustion
Several
Thermal and Catalytic
Incineration
Common technology.
1 Several
-------
General
Category Process Name
CHEMICAL Wet Air Oxidation
PROCESSES
IT Catalyzed Wet Air
Oxidation
High Temperature Wet
Oxidation
Supercritical Fluid
Oxidation
Molten Salt
^ Destruction
Metal Oxide
Destruction
Battelle Northwest
Aqueous Phase Alkaline
• Destruction of Halo-
genated Organics
Waste
Description Stream
Uses elevated temperature and pressure to Aq
oxidize organics in water.
Uses selective catalysts and elevated Aq .
temperature and pressure to oxidize organics.
Uses long vertical underground tubular Aq
reactor to oxidize suspended organics in
water.
Uses high temperatures and very high L
pressures to oxidize organics.
Uses a bed of molten sodium carbonate to L.S
destroy wastes and scrub acid gases.
Uses an inexpensive metal oxide (such as G
alumina. A1203) to react with CFCs at 500
to 800 deg C.
Converts halogenated organics into an oil L.S
using mild alkali under pressure
State of Applicable
Development to CFCs Contact
C 1 Zimpro Environmental
Systems. Rothschild. WI
B 2 IT Envirosciences, Inc
Knoxville, TN
Co 2 Methods Engineering Inc.
Angleton, TX
P 2 MODAR. Inc.
Natick. MA
P 2 Rockwell International
Canoga Park, CA
Co 2 Dr. Dan Blake
SERI
1617 Cole Blvd.
Golden, CO 80401
B ,2 Battelle Pacific
Northwest Laboratories
P.O. Box 999
Richland, WA 99352
CARD Catalytic
Dehalogenation of
Hazardous Wastes
Acurex Process
Dehalogenizej- compounds by replacing
halogen atom with hydrogen atom.
Sodium reagent with a. proprietary
constituent reacts to form NaCl and
nontoxic product.
L.S1
Chamberlain National
GARD Division
7501 N. Natchez Ave.
Niles, IL 60648
Acurex
P.O. Box 13109
Research Triangle Park. NC 27709
-------
Genera)
Category Process Name
CHEMICAL PPM Process
PROCESSES
(cont.) ,
Description
Uses a proprietary sodium reagent to
dechlorinate organic molecules. Can not be
used on aqueous streams.
Waste
Stream
L
State of
Development
Appl icable
to CFCs
3
Contact
o
1
Sunohio PCBX
Potassium polyethylene
glycolate (KPEG) wash
Ozonation
Uses proprietary reagent to convert PC8
molecules to metal chlorides and polyphenol
compounds
Effective in dehalogenating aromatics and
aliphatic organic materials. Has been tested
on wood preservatives and spent solvent with
dioxin.
Injection of ozone to react with organics
and form nontoxic materials
UV photolysis/APEG * UV radiation is used to convert halogenated
detoxification materials. Needs a hydrogen donor.
'(alkaline polyethylene
glycols)
L.S1
Several
2 IT Enviroscience
(Cnoxville, TN
BIOLOGICAL
PROCESSES
Biological Degradation
Microbes are injected into the ground or
ground removed and slurried with organisms.
Will be demonstrated with pentachlorophenol
and creosote wastes.
3 DETOX Industries. Inc.
Sugarland. TX
Fluid bed biological
Systems
Air Products & Chemicals
Allentown, PA
Liquid/solid contact
digestion
Motec. Inc.
Mt. Juliet. TN
-------
Genera 1
Category
Process Name
Description
Waste State of Applicable
Stream Development to CFCs
Contact
o
BIOLOGICAL Ion exchange
PROCESSES (biological)
(cont.)
Powdered activated
carbon (biological)
White Rot Fungus
(Phanerochaete
chrysosporium)
Pseudomonas cepacia
(AC1100)
Pseudomonas putidas
Activated sludge
ELECTRICAL Corona Discharge
PROCESSES
OTHER Solar Destruction
PROCESSES
Used to degrade lignin, but is also
effective in degrading organo-halides.
Developed to dechlorinate a variety of
chlorophenols.
Developed for PCB degradation
Common technology
High energy electrons are capable of
dissociating the compounds of interest.
Solar energy is focussed to generated high
temperatures.
Sunitech, Inc.
Twinburg, PA
Zimpro Environmental
Control Systems
Rothschild. WI
S Unk 3 General Electric
All C 3 Several
G B 2 Or. Norm Plaks
U.S. EPA/AEERL
Research Triangle Park. NC 27711
L P 2 Dr. Hugh Re illy
Sandla National Lab
Albuquerque, NH B7185
Microwave discharge Similar to incineration
Unk
-------
APPENDIX D
Trial Burn Data Table
(Data for destruction efficiency collected from trial burn testing for RCRA
Part B permit)
kgo/102 D-l
-------
RCRA PART B TRIAL BURN TEST DATA SUMMARY
Fao 1 ity
Name Test
;Tvoe of Incinerator) Location Number
Glin Brandenburg, KY No.
i'.iquiC. Injection) No.
No.
No.
3ennwalt Calvert City. KY No.
(Liquid Injection) No.
No.
No.
No.
No.
No.
2
2
3
3
22-1
22-2
22-3
22-4
23-1
23-2
23-3
Waste Feed Destruction
Type of Concentration Efficiency Temperature
Feed (Percent) (Percent) (Oeg F)
CFC-11
CFC-12
CFC-11
CFC-12
HCFC-141b
HCFC-141b
HCFC-141b
HCFC-141b
HCFC-141b
HCFC-141b
HCFC-141b
10
5
14
5
6
10.
17,
15,
9.
15.
14.
.3
.8
.0
.6
.9
,2
.6
.0
.2
.1
5
>99.
>99.
>99.
>99.
99
99
>99
>99
>99
>99
>99
9998
9998
9999
9998
.997
.995
.999
.999
.999
.999
.999
2.
2.
2.
2.
2.
2,
2.
2.
2.
2.
2.
088
088
095
095
220
220
220
220
300
300
300
Test
Date
11-28-84
11-28-84
11-29-84
H-29-84
12-3-83
12-4-83
12-5-83
12-9-83
12-6-83
12-7-83
12-8-83
Source
(A)
(A)
(A)
(A)
(A)
(A)
(A)
(A)
(A)
(A)
(A)
<3SX/Therma 1
Oxlaat ion Corp.
lliq-jid Injection)
Columbia, SC
No. 3 CFC-11
8.3
99.999
Honeywell Pi'nellas Co., FL No. 1
(Liquid Injection) . No. 2
No. 3
LWO
(Rotary 99.9999
0.71 >99.9996
0.71 >99.9999
3.0 99.994
3.6 99.9995
3.9 99.9917
2.8 99.9801 (1)
23.6
7.1
13.9
10.0
99.9993
99.9997
99.9985
SOURCES
A. Bermu Writers uuiae to Test Burn Data
=. RCRA Part B Permit File Search at EPA Region 4 (Atlanta, GA)
C. Hazaroous Waste Facility Perm.it File Search at New Jersey Department of
Enviromental Protection (Trenton, NJ).
NOTES
:. According to plant, low destruction efficiency was cue to a portion of
waste feeo CFC-11 was contained in glass bottles wnicn remained partially intact.
2. This is a ouplicate of Pennwalt's unit in Calvert City, KY.
3. Test results have not yet been reported.
D-2
1,800 3-19-87
1,647 12-16-88
6-7-88
6-8-88
6-8-88
2,000
2.300
2,000
(3)
1.788 6-14-88
1,819 6-14-88
1.799 6-15-88
1,861 12-14-88
1.828 12-14-88
1,640 12-15-88
(8)
(8)
(8)
(B)
(B)
(B)
(8)
(c;
(0
(O
(C)
(O
(C)
-------
APPENDIX E
List of Contacts
(List of Contacts by letter or phone with date, name, organization, and brief
summary).
kgo/102 E-l
-------
SUBJECT
Discussed difficulties in destroying CFCs and
formation of PICs.
Requested any information that DuPont may have
developed on destruction technologies.
Requested information on experience I-Thermal has
In CFC incinerator field. Mr. Irrgang did not want
disclose info without assurances of secrecy. He
felt that PICs are not a problem for well-run unit.
Requested any information on destruction of CFCs
or ha Ions. Mr. Dwyer said that Allied has not been
very active in the area. Another division of the
company (Baron Blakeslee) has been more active in
recovery of CFCs.
Planning a trial burn in April 1989 which will
include CFCs in the waste feed.
Recently performed a trial burn with CFC-11.
Preliminary results indicate a ORE of 99.99%.
Assisted Pennwalt on their trial burn with
HCFC-142b. Suggested EPA publication "Permit
Writers Guide to Trial Burn Data."
Racon does not incinerate any off-spec product or
still bottoms. Instead, they recycle back to the
reactor. Trade-off versus incineration since they
require more frequent catalyst changeout.
DATE NAME
ORGANIZATION
2/27/89 Dr. Barry Del Iinger
University of Dayton
Research Institute
2/27/89 Mr. Ed Lukosius
E.I. OuPont de Nemours
2/27/89 Mr. Gene Irrgang
T-Thermal
2/28/89 Mr. Frank Owyer
Allied/Signal
3/3/89 Mr. Wayne Fisher
Chemical Waste Management.
3/3/89 Mr. Gary Trivedi
LWD Incorporated
3/6/89 Mr. Joe Santoleri Four Nines, Inc.
3/6/89 Mr. MarshaII Turner Racon
-------
DA IE NAME ORGANIZAUON
SUBJECT
3/6/89 Or. Hike Harris
ICI Americas
fl
I
U)
3/6/89 Mr. Mark Sweval
3/6/89 Mr. Rick Turner
3/7/89 Mr. Scott Kuhn
3/7/89 Ms. Betty Willis
Great Lakes Chemicals
LaRoche Chemicals
GSX Thermal Oxidation Corp.
EPA Region 4
1C1 does not incinerate any CFCs or ha Ions at their
U.S. halon plant. Later, he said that ICI does
pyrolyze CFC-22 in a polymer production facility
in Bayonne, NJ.
Great Lakes Chemical recycles about 95% of their
off-spec or waste materials. They are looking into
destruction processes with a professor at Purdue.
LaRoche does not incinerate any CFCs or ha Ions.
Mr. Turner raised the issue that contaminated CFCs
may be classed as hazardous wastes.
Mr. Kuhn said that CFC-11 was Included in a trial
burn at their facility in Columbia (SC). He
suggested contacting Ms. Betty Willis with EPA
Region 4 (Atlanta. GA).
Ms. Willis was aware of the GSX trial burn and said
that results were on file in Region 4. She also
suggested contacting Kathy Fore (Martin Marietta-
OOE at Oak Ridge (TN)) or Ten Schearer (EPA/ORO at
Cinncinati (Oil)). They are developing a database
with trial burn data.
3/7/89 Mr. Robert Vlick
3/7/89 Mr. Mike Keller
Air Conditioning Co.
John Zink Co.
Mr. Vlick explained how his firm (a large chiller
service organization) uses recycling with Omega
to reduce the cost of refrigerant.
Mr. Keller disputed T-Thermal's claim to being the
only company in the world with experience with high
concentrations of CFCs in incinerator waste feeds.
-------
OAIE NAME
3/7/89 Mr. Jack Buice
ORGANIZATION
Oow Chemical USA
SUBJECT
3/7/89 Mr. Leo Weitzmann
3/7/89 Mr. Bill Scofield
3/8/89 Mr. John Backlund
3/9/89 Mr. Dennis O'Meara
3/13/89 Mr. Jim Aker
3/14/89 Dr. James Spivey
Acurex
Chemical Waste Management
Coen Company
Omega Recovery
E.I. OuPont de Nemours
Chambers Works
Research Triangle Institute
Mr. Buice has extensive experience in thermal
oxidation of chlorocarbons. He said that Oow has
burned some fluorinated compounds in the past; he
thought it was a CFC-contaminated oil.
Mr. Weitzmann was knowledgeable about several types
of chemical destruction processes for halogenated
organics. He felt that active metals reaction has
good potential for destruction of CFCs and ha Ions.
Mr. Scofield explained how their Port Arthur (TX)
facility handles wastes containing CFCs. They are
limited to 100 ppm fluoride in the waste feed, so
they can blend on-site to dilute wastes with a high
CFC concentration.
Mr. Backlund explained that Coen Co. designed the
burners for a shipboard incinerator which was able
to handle all types of waste feeds. He said that
one advantage of shipboard incineration was that
a stack scrubber system wasn't needed. .
Mr. O'Meara felt that there was essentially no
reason to destroy contaminated CFCs. He claimed
nearly everything could be recycled economically.
Mr. Aker said that DuPont has just completed a
trial burn on a new incinerator at the Chambers
Works which handles up to 10X CFC & other fluorine-
containing wastes. Data is not yet available.
Dr. Spivey has worked on catalytic incineration of
chlorinated organics. He suggested two commercial
vendors (ARI & Oedert Topsoe).
-------
DATE
NAME
ORGANIZATION
SUBJECT
3/14/89 Mr. Leon Leonard
Radian Corporation (Sacramento)
3/14/89 Mr. Per Bakken
3/17/89 Mr. Tom Hedlund
Norway Ministry of Environment
Swedish National Enviromental
Protection Board
Mr. Leonard checked on the status of Omega Recovery
project in Kern Co. (CA), which was to include some
type of incinerator for solvent wastes. He said
the project had been effectively halted because of
permitting problems.
Mr. Bakken said that he was unaware of anything in
Norway in the area of CFC or ha Ion destruction.
Mr. Hedlund explained that they are looking at two
issues in terms of destruction. First, they are
investigating the destruction of refrigerators and
freezing equipment. Second, they are part of an
inter-Nordic project to investigate destruction of
CFCs and halons. So far, results are only for
lab-scale tests.
3/17/89 Mr. Wolfgang von Klahr Hoechst/Celanese
3/20/89 Or. Vic Cundy
Louisiana State University
3/22/89 Mr. Bob Foster
Pennwalt (Calvert City. KY)
Mr. von Klahr explained that their parent company
in Germany (Hoechst AG) has a unit for complete
combustion of CFCs. Follow-up info from Sigri
Elektrographit (a subsidiary of Hoechst) provided
a European patent number and limited data.
Dr. Cundy has been working on incineration of
chlorinated methanes, but hasn't looked at CFCs or
halons. Despite the similarities, the models which
have been developed for chloroform or methylene
chloride cannot be simply extended to CFCs.
Mr. Foster explained that their facility handles
only materials from HCFC-142b production. Neither
CFC-11 or CFC-12 wastes are burned, and they do not
produce CFC-113. He said the unit in Thorofare. NJ
is a duplicate of the Calvert City unit.
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DATE
NAME
ORGAN IZAII ON
SUBJECT
3/23/89 Mr. James Hemby
i
U.S. EPA (Washington. OC)
Mr. Hemby said he could provide updated estimates
of the U.S. and world bank of CFCs and ha Ions.
3/23/89 Ms. Laura Tew
01 in Corporal ion
Ms. 'Tew explained that 01 in incinerates waste from
a urethane blending facility operated by 01 in.
They are also permitted to accept commercial waste,
they do so only on a limited basis. They monitor
CO on a continuous basis.
3/24/89 Mr. S. Misaki
m
Oaikin Industries. Ltd.
3/27/89 Or. Oean Walbach
Acurex
Mr. Misaki explained that in general, processes
which could or are being used for CFC destruction
include conversion to monomer for f luoroplastics.
incineration, or possible reaction with metal oxide.
Or. Walbach said that he has tested solvent cleaning
equipment for CFC emissions, but no incinerators.
He didn't see any special problems, and he thought
the VOST method would work best.
3/28/89 Mr. John Scott
New Jersey Department of Environ- Mr. Scott said that Rollins Environmental trial
mental Protection - Hazardous Waste burn report lists CFC-113 among the PICs, but was not
Engineering Dept. included in the feed POIICs. He suggested checking
the document "Guidance on Trial Burn Reporting and
Setting Permit Conditions" by Acurex Corp.
3/30/89 Mr. Swager
Netherlands (Environmental Board)
Mr. Swager provided information on Netherland's
Joint venture for hazardous waste incineration in
Rotterdam. The facility opened in 1987 and is
equipped with the most modern rotary kiln and
stack gas cleaning equipment. They are planning
to double capacity by expanding the scrubbers in
1991. Waste feed limits are 5.8X C1 & 0.58X F.
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APPENDIX F
Japanese MITI Attachment
(Overview of current research efforts in Japan to evaluate CFC and halon
destruction technologies. Reproduced with permission).
kgo/102 F-l
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March 2, 1989
Technologies for the Destruction of Chlorofluorocarbons
by
Koichi Mizuno
National Research Institute for Pollution and Resources
Agency of Industrial Science and Engineering
Ministry of International Trade and Industry
16-3 Onogawa, Tsukuba, Ibaraki 305 JAPAN
The destruction of chlorofluorocarbons (CFCs) has been regarded
as difficult technology. One of the reasons is that CFCs are
inflammable and chemically stable.. Secondly the released halogen
from CFCs, in particular/ fluorine species as HF, ?2' or anV
other intermediates, is difficult to treat with. Little reports
have been published and most results are fundamental because the
destruction has not been required until the global environmental
problems of stratospheric ozone depletion and climate changes
were pointed out.
The feasible technologies for the destruction are classified into
following four categories. Active works to develop the
destruction of CFCs are currently promoted in Japan.
1 . Incineration and Thermal Decomposition
Incineration of CFC-113 was reported to be performed at 800°C
with 99.99% efficiency. However, analysis of trace products were
not reported. In Japan thermal decomposition of CFCs adsorbed on
an activated carbons was carried out under nitrogen stream. The
conversion of CFCs were almost 100% below 800°C. However, CFC-11
and CFC-12 were converted to considerable amount of CF4, which
was not further decomposed below 800°C. The incineration and
thermal decomposition are low-cost destruction methods, but
released halogen attacks the furnace surface. The materials of
furnace are to be improved. It is also important to analyze
trace of hazardous by-products.
F-2
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2. Catalytic Decomposition
Reportedly an activated carbon catalyzed the decomposition of
CFC-11 under dilute concentrations. In Japan research has
revealed that some solid catalysts also accelerated the
decomposition of CFC-113 at above 300°C. Over these catalysts
conversion more than 60% was attained in a stream of 1000 ppm.
On raising the reaction temperature or increasing catalyst
amount, 100% conversion will be easily obtained. C02/ HC1 and HF
were detected. The analysis of trace by-products is under
investigation.
Photo-catalytic decomposition of CFC-11 took place on some
transition-metal oxides such as titanium dioxide at around room
temperature, although the conversion rate was slow. Platinum
loaded on titanium dioxide accelerated the decomposition.
Catalysis is one of the promising methods for the selective
decomposition of CFCs at relatively low temperatures. The
converter is -designed to be compact apparatus as compared to the
incineration.
3. Plasma Decomposition
Plasma reactor provides reactive species from stable compounds.
Recently in Japan the effectiveness for the decomposition of CFCs
was confirmed on thermal plasma at ca. 10000°C. The CFCs are
decomposed efficiently and surely, as demonstrated that
conversion more than 99.7% achieved, although apparatus is not
low-costed. HC1, HF, COX, and carbonaceous materials were formed
from CFCs and water mixture.
Low-temperature (non-equilibrium) plasma may give only partial
decomposition, since it was reported to give mainly acetylene,
carbon monoxide and solid carbon from trichloroethylene and water
mixture.
4. Chemical Reaction Using Reagents
In Japan a reducing agent of sodium naphthalene complex (Na+Naph~
) and CFCs was found to afford stoichiometric reaction. In batch
experiments reaction between Na+Naph" and CFC-113 at 150°C
F-3
-------
indicated 100% conversion of CFC-113. Continuous reaction is
under investigation. The destruction method is improved by (1)
finding low-cost reducing agents and (2)increasing selectivity to
CFCs in a mixture of CFCs and other reactive materials. It is
necessary to confirm that no hazardous products are formed in the
reaction.
5. Other Methods
There are many other methods for the detoxicification of
halocarbons, which include electrochemical reaction, UV-
irradiation, and X-ray irradiation. These were only applied to
chlorocarbons. To our knowledge no report is found on the
destruction of CFCs.
6. Conclusions
Many projects, on the destruction of CFCs have started recently in
Japan. From our experiences, the appropriate method for the
destruction requires to satisfy following several items.
(1) The destruction is to be performed surely under the
operational conditions of a wide range.
(2) No trace amounts of hazardous by-products are to be formed.
(3) Mixtures containing CFCs are to be decomposed selectively.
(4) Several kinds of destruction technologies are to be
established depending on emission types of CFCs (gas, liquid,
or solid; concentrated or dilute, etc.).
The above methods are easily applicable to the substitute
materials of CFCs as well as chlorocarbons such as
trichloroethylene, since they are more reactive than CFCs.
-------
Table Consumption of CFCs in Japan (1987 estimated: in ton).
CFC- 1 1
CFC-12
CFC-113
CFC-114
CFC- 1 1 5
Total
Hef rigeran ts
2,597
22, 139
270
179
170
25,355
(17. 1%)
Propel lanls
4,677
7,423
180
250
0
12,530
( 8.4%)
Blowing Agents
23,110
9,886
200
1 ,655
0
34,851
(23.5%)
Sol ven ts
301
0
73,136
0
0
73,437
(49.5%)
Others
230
5
1 ,910
0
0
2, 145
( 1.4%)
Total
30,915 (20.8%)
39,453 (26.6%)
75,696 (51.0%)
2,084 ( 1.4%)
170 ( 0.1%)
148.318
(100 %)
01
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RESEARCH PROJECTS RELATED TO CFCs IN OUR INSTITUTE
National Research Institute for
Pollution and Resources
AIST, MITI
ABATEMENT
1) Emission Control of Volatile Organic Halides by Adsorption
Development of Adsorbents
Development of Recovery Method from Adsorbed Phase
Proposal of Adsorption System
2) Chemical Decomposition of CFCs.
Treatment of CFCs Waste
Treatment of Mixtures and Dilute Gas
3) Combustion of Hazardous Organic Waste Mixtures
Combustion Technology for Hazardous Wastes
Analyses of Trace Products from Combustion
ASSESSMENT
1) Heterogeous Reactions of CFCs in the Atmosphere
Catalytic Reaction under Irradiation
Products Analysis of the Reaction
2) Reaction Process of Substitute CFCs in the Troposphere
Catalytic Reaction under Irradiation
Products Analysis of the Reaction
3) Behavior of Green-House Gases from Industry
4) Diffusion and Monitoring of Pollutants Including CFCs
from High-Tech Industry
Duffusion mechanism and modelling of pollutants
in the atmosphere, ground suface and undergroud
F-6
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An EXAMPLE OF ABSORPTION
Absorption Tower
Chiller UnJ
Desorption Tower
"eat Exchanger Heater
AIR
-------
clean air
concentrated CFC
ilia s nfc
gas containing CFC
IS 143^-*-
motor
^
1 5 m3/min 100 ppm
\1,500ppm '
1 m3/min 1500 pp
55
CD
AN EXAMPLE OF ROTARY ADSORPTION'
F-8
-------
tube earring adsorbent
clean exhaust
HUISS
adsorption
gas inlet.
desorption
— condenser
gas inlet for desorption.^
--'USB
sealing
inlet for earring adsorbent
seoarator
y^ (D ffil
-7
desorption tube
AN EXAMPLE OF FLUIDIZED-BED
O-Tnv
-------
I
I—
o
[ I iffffi'Jift o'ft'T.
AN EXAMPLE OF FIXED-BED ADSORPTION
Clean Air
CondenserI
m
Compressed Air
r» i
uumper f,.,,, i»
Pre-Filter
^Separated Water
m.
Gas Inlet
Separator Cooling Wate
/I
*~Recovered Solvent
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