FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT
FOR
U AND P WASTES AND MULTI-SOURCE LEACHATE (F039)
VOLUME E:
GASEOUS U AND P WASTES
Richard Kinch
Acting Chief, Waste Treatment Branch
Lisa Jones
Project Manager
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Solid Waste
401 M Street, S.W.
Washington, DC .20460
May 8, 1990
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TABLE OF CONTENTS
Page
1.0 INTRODUCTION 1-1
1.1 Regulatory Background 1-1
1.2 User's Guide to the Five-Volume U and P Waste and
Multi-Source Leachate (F039) Background Document Set . . 1-3
1.3 Summary of Contents: Volume E 1-4
2.0 INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected 2-1
2.2 Waste Characterization 2-1
2.3 Determination of Waste Treatability Groups 2-2
3.0 IDENTIFICATION OF APPLICABLE, DEMONSTRATED, AND BEST
TECHNOLOGY 3-1
3.1 Applicable Treatment Technologies 3-1
3.1.1 Nonwastewaters 3-2
3.1.2 Wastewaters 3-5
3.2 Demonstrated Treatment Technologies 3-7
3.2.1 Nonwastewaters 3-8
3.2.2 Wastewaters 3-9
3.3 Identification of Best Demonstrated and Available
Technology (BOAT) 3-10
3.3.1 Nonwastewaters 3-10
3.3.2 Wastewaters 3-11
4.0 TREATMENT PERFORMANCE DATA 4-1
5.0 ACKNOWLEDGEMENTS 5-1
6.0 REFERENCES . ' 6-1
APPENDIX A - LIST OF FACILITIES THAT MAY GENERATE U AND P
GASEOUS WASTES A-l
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LIST OF TABLES
Page
1-1 BOAT TREATMENT STANDARDS FOR GASEOUS U & P WASTES
(METHODS OF TREATMENT) 1-6
2-1 CONSTITUENTS IN WASTE TREATABILITY GROUPS FOR GASEOUS
U & P WASTES 2-4
3-1 CONSTITUENTS IN BOAT TREATMENT STANDARDS FOR GASEOUS
U & P WASTES (METHODS OF TREATMENT) 3-13
4-1 ETHYLENE OXIDE WASTEWATER AND NONWASTEWATER TREATMENT DATA . 4-2
ii
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1.0 INTRODUCTION
1.1 Regulatory Background
Section 3004(m) of the Resource Conservation and Recovery Act
(RCRA), as amended by the Hazardous and Solid Waste Amendments (HSWA) on
November 8, 1984, requires the U.S. Environmental Protection Agency (EPA or
the Agency) to promulgate treatment standards for certain hazardous wastes
based on the Best Demonstrated Available Technology (BOAT) for those wastes.
More than 500 of these hazardous wastes were listed as of December 1988 (see
Title 40, Code of Federal Regulations. Part 261 (40 CFR Part 261)). The
Agency divided the listed hazardous wastes into five groups. The wastes in
each group were examined to determine whether further land disposal is protec-
tive of human health and the environment (see 40 CFR Part 268) . The five
groups and their respective dates of promulgation of treatment standards are:
• Solvent and dioxin wastes November 7, 1986
"California List" wastes July 8, 1987
• "First Third" wastes August 8, 1988
• "Second Third" wastes June 8, 1989
• "Third Third" wastes On or before May 8, 1990
Several wastes included in this schedule were regulated ahead of schedule, and
several wastes in the "First Third" or "Second Third" group of wastes were
deferred to the "Third Third" group of wastes. Treatment standards for the
Third Third wastes will become effective no later than May 8, 1990. On and
after this date, wastes regulated in the "Third Third" rulemaking will have to
comply with applicable treatment standards prior to "land disposal" as defined
in 40 CFR Part 268.
This document provides the Agency's rationale and technical support
for developing method-based treatment standards for the three gaseous U and P
wastes: ethylene oxide (U115), nitric oxide (P076), and nitrogen dioxide
(P078). These standards are applicable to the wastes as listed as well as to
any wastes generated by the management or treatment of the listed waste.
Treatment standards are specified for both nonwastewater and wastewater forms
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of each listed hazardous waste. For the purpose of determining the applic-
ability of the treatment standards, wastewaters are defined as wastes contain-
ing less than 1% (weight basis) total suspended solids1 and less than 1%
(weight basis) total organic carbon (TOC). Wastes not meeting the wastewater
definition must comply with treatment standards for nonwastewaters. In
general, numerical treatment standards were developed for wastes that are
amenable to quantification in hazardous waste matrices, and treatment stan-
dards specifying methods of treatment were developed for wastes that are not
amenable to quantification in hazardous waste matrices using current analyti-
cal methods.
The Agency's legal authority and promulgated methodology for
establishing treatment standards and the petition process for requesting a
variance from the treatment standards are summarized in EPA's Methodology for
Developing BOAT Treatment Standards (Reference 1).
U wastes include discarded commercial chemical products, manufactur-
ing chemical intermediates, off-specification commercial chemical products,
container and inner liner residues, and residues, including contaminated
water, soil, or debris resulting from the cleanup of a spill, that are iden-
tified as toxic wastes. P wastes include discarded commercial chemical
products, manufacturing chemical intermediates, off-specification commercial
chemical products, container and inner liner residues, and residues, including
contaminated water, soil, or debris resulting from the cleanup of a spill,
that are identified as acutely hazardous wastes. Section 2.0 discusses the
definition of U and P wastes in greater detail.
'The term "total suspended solids" (TSS) clarifies EPA's previously used
terminology of "total solids" and "filterable solids." Specifically, total
suspended solids are measured by Method 209c (Total Suspended Solids Dried at
103 to 105°C in Standard Methods for the Examination of Water and Wastewater
(Reference 2).
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1.2 User's Guide to the Five-Volume U and P Waste and Multi-Source
Leachate (F039) Background Document Set
In the interest of clarity, the Agency has reorganized the "Third
Third" background documents that were prepared for proposal of the Third Third
Rule. Multi-source leachate (F039) and the majority of the U and P waste
codes addressed in the Third Third Rule are now covered in a five-volume set
of background documents.
The five-volume background document set is organized as follows:
• Volume A - Wastewater forms of organic U and P wastes and
multi-source leachate (F039) for which there are concentration-
based treatment standards;
• Volume B - U and P wastewaters and nonwastewaters with methods
of treatment as treatment standards;
• Volume C - Nonwastewater forms of organic U and P wastes and
multi-source leachate (F039) for which there are concentration-
based treatment standards;
• Volume D - Reactive U and P wastewaters and nonwastewaters with
methods of treatment as treatment standards; and
• Volume E (this document) - Gases.
The development of treatment standards for the majority of the
U and P wastes is described in Volumes A, B, C, and D. However, three of
these wastes, ethylene oxide (U115), nitric oxide (P076), and nitrogen dioxide
(P078), are significantly different in form (i.e., gases), and therefore have
been assigned to a separate volume. Methods of treatment are being promul-
gated as BOAT treatment standards for these wastes, as listed in Table 1-1.
This background document provides the Agency's rationale and technical support
for selecting the constituents to be regulated and for developing treatment
methods for these wastes.
The Agency considers as empty any cylinder at ambient pressure that
held hazardous waste that is a compressed gas (see 40 CFR 261.7(b)(2)), even
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if the cylinder previously contained any of the three gaseous U and P wastes.
As a result, an empty cylinder would not be considered a nonwastewater form of
a hazardous waste. A cylinder that is above ambient pressure, that contains
any of these gases, and that is to be disposed of, is considered a nonwaste-
water form of the particular U or P gaseous waste it held, and thus would be
subject to the BOAT treatment standards for that waste discussed in this
document. Pressurized cylinders containing any of the three gaseous U and P
wastes may not be land-disposed in their present form but must undergo treat-
ment before land disposal can occur.
1.3 Summary of Contents: Volume E
This background document provides the Agency's rationale and techni-
cal support for developing treatment standards for the three gaseous U and P
wastes: ethylene oxide (U115), nitric oxide (P076) and nitrogen dioxide
(P078). Section 2.0 of this document presents a description of the industry
that may be affected by the land disposal restrictions and the waste charac-
terization data for these wastes. The Agency estimates that there are approx-
imately 33 facilities that may be affected by this rule. The four-digit
Standard Industrial Classification (SIC) codes associated with the industry
generating these gases are 2869 (Industrial Organic Chemicals, Not Elsewhere
Classified) and 2819 (Industrial Inorganic Chemicals, Not Elsewhere Classi-
fied). Section 2.0 also*includes EPA's rationale for combining these waste
codes into two treatability groups.
Section 3.0 lists the applicable and demonstrated treatment tech-
nologies for the gaseous wastes. EPA's rationale for identifying BOAT and
methods of treatment as treatment standards for these wastes is also included
in Section 3.0. The BOAT treatment standard for P076 (nitric oxide) and P078
(nitrogen dioxide) nonwastewaters is contact with a caustic reducing solution.
For P076 and P078 wastewaters, the BDAT treatment standard is also contact
with a caustic reducing solution. For U115 (ethylene oxide) nonwastewaters,
the BDAT treatment standard is thermal or chemical oxidation. For U115
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wastewaters, the BDAT treatment standard is any one of the following treatment
trains:
• Thermal oxidation;
• Chemical oxidation followed by carbon adsorption; or
• Wet air oxidation followed by carbon adsorption.
Section 4.0 describes the Agency's rationale for establishing
methods of treatment for these wastes rather than concentration-based treat-
ment standards. Section 5.0 acknowledges the persons involved in developing
these waste regulations. Section 6.0 lists the references cited in this
document. Appendix A provides a list of facilities that may potentially
generate U and P gaseous wastes.
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Table 1-1
BOAT TREATMENT STANDARDS FOR GASEOUS U AND P WASTES
(METHODS OF TREATMENT)
U115 (ETHYLENE OXIDE) WASTEWATERS
Thermal oxidation;
Chemical oxidation followed by carbon adsorption; or
Wet air oxidation followed by carbon adsorption
U115 (ETHYLENE OXIDE) NONWASTEWATERS
Thermal oxidation; or
Chemical oxidation.
P076 (NITRIC OXIDE) WASTEWATERS AND NONWASTEWATERS
Contact with a caustic reducing solution.
P078 (NITROGEN DIOXIDE) WASTEWATERS AND NONWASTEWATERS
Contact with a caustic reducing solution.
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2.0 INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
This section describes the industries affected by the land disposal
restrictions for U115, P076, and P078, the available waste characterization
data, and the determination of waste treatability groups.
2.1 Industry Affected
Industries that generate U115, P076, and P078 include both the
organic chemical and inorganic chemical industries. Appendix A identifies 33
facilities that may generate these wastes.
2.2 Waste Characterization
Ethylene oxide (U115) is a colorless gas that is used as a petroleum
demulsifier, fumigant, rocket propellant, industrial sterilant, and fungicide,
as well as a reagent in the manufacture of glycol and higher glycols, surfac-
tants, acrylonitrile, and ethanolamines.
Nitric oxide (P076) is a colorless gas that is used to bleach rayon,
in the preparation of nitrosyl carbonyls, and as an intermediate in the
production of nitric acid from ammonia.
Nitrogen dioxide (P078) is a red to brown gas that is used as a
nitrating agent, an oxidizing agent, a catalyst, an oxidizer for rocket fuels,
a polymerization inhibitor for acrylates, and as a reagent in the manufacture
of nitric acid.
In the proposed rule, EPA stated that while U115, P076, and P078 are
highly toxic, it is unlikely that they will exist as wastes that require land
disposal. For example, since it is difficult to "spill" a gas onto soil or
into water, it is unlikely that these wastes could exist as spill residues.
Since the Agency could not determine the existence of any land disposal
scenarios for these wastes, the only concern addressed in the proposed rule
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was the possibility that containers of these wastes could be land-disposed in
a cleanup situation. EPA solicited comments from anyone who might already be
land-disposing these wastes or anyone who might do so in the future.
In response, several commenters pointed out that U115, P076, and
P078 share two unique disposal problems: (1) the treatment and disposal of
damaged or otherwise nonrecyclable or nonreusable cylinders (such as ethylene
oxide cylinders stored past their expiration date), and (2) the treatment and
disposal of wastewater forms of these wastes (generated from emergency blow-
down of processing equipment or routine plant maintenance). The wastewater
forms of these wastes are currently diluted and injected into deep wells.
Other nonwastewater forms of gaseous wastes potentially requiring land dis-
posal include contaminated soil or debris from cleanup of an ethylene oxide
spill (ethylene oxide is used in industry in the liquid state and may not
immediately "flash" to vapor if spilled), and process vessel residues gener-
ated during routine cleaning operations. Another wastewater form of gaseous
waste potentially requiring land disposal includes scrubber water. Therefore,
these gaseous wastes are expected to range from low levels of toxic constitu-
ents in water to pure gaseous forms of the compound.
2.3 Determination of Waste Treatability Groups
In the course of developing treatment standards, EPA combined the
wastes included in this document (U115, P076, and P078), as well as all other
Third Third U and P wastes, into treatability groups based on similarities in
composition, structure, and functional groups present within the structure of
the chemical. The industries that generate these wastes were also considered
in establishing these groups. These waste treatability groups take into
account differences in the applicability and effectiveness of treatment for
those particular wastes.
Although ethylene oxide, nitric oxide, and nitrogen dioxide exhibit
similar physical properties, they have significantly different chemical
properties. These differences affect the applicability and effectiveness of
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treatment technologies on the wastes, to the extent that ethylene oxide, an
organic gas, requires some form of oxidation as treatment while nitric oxide
and nitrogen dioxide, both inorganic gases, require treatment in a reducing
solution. As a result, these wastes have been divided into two treatability
groups, an ethylene oxide group and a nitrogen oxide group. Table 2-1 lists
the constituents in the ethylene oxide and nitrogen oxide waste treatability
groups.
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Table 2-1
CONSTITUENTS IN WASTE TREATABILITY GROUPS FOR GASEOUS U AND P WASTES
ETHYLENE OXIDE WASTE TREATABILITY GROUP
U115 - Ethylene Oxide
NITROGEN OXIDE WASTE TREATABILITY GROUP
P076 - Nitric Oxide
• P078 - Nitrogen Dioxide
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3.0 IDENTIFICATION OF APPLICABLE, DEMONSTRATED, AND BEST TECHNOLOGY
This section presents the Agency's rationale for determining the
best demonstrated-available technology (BOAT) for treatment of gaseous U and P
wastes, including the Agency's determination of:
• Applicable technologies;
• Demonstrated technologies; and
• The best demonstrated available technology (BOAT) for treatment
of these wastes.
In determining BOAT, the Agency first determines which technologies
are potentially applicable for treatment of the waste(s) of interest. The
Agency then determines which of the applicable technologies are demonstrated
for treatment of the waste(s) of interest. Next, the Agency determines which
of the demonstrated technologies is "best" for the purpose of establishing
BOAT. Finally, the Agency determines whether the best demonstrated technology
is available for treatment of the waste(s) of interest.
3.1 Applicable Treatment Technologies
To be applicable, a technology must theoretically be usable to treat
the waste in question or to treat a waste that is similar in terms of param-
eters that affect treatment selection. Detailed descriptions of technologies
that are applicable to treat listed hazardous wastes are provided in this
section and in EPA's Treatment Technology Background Document (Reference 3).
When the Third Third treatment standards were proposed, the Agency
believed that all three of the U and P gaseous wastes (U115, P076, and P078)
were probably generated as gases and that industry typically reused or recov-
ered compressed gases. In addition, the Agency had very limited treatment
data for U115, no treatment data for P076 and P078, and no information with
which to determine applicable treatment technologies. As a result, EPA
proposed a treatment standard of "Recovery as a Method of Treatment" for all
P076, P078, and U115 wastes. Following proposal, EPA received several com-
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ments supplying information on treatment technologies for all three wastes.
Based on these comments, EPA has determined treatment technologies applicable
to the specific land disposal problems associated with the gaseous wastes.
These wastes include damaged cylinders unacceptable for recycling or reuse
(nonwastewater forms) and rinsewater used to clean such cylinders (wastewater
forms), as well as tank washwater, spill residue, and emergency blowdown
water. The following subsections present applicable treatment technologies
for nonwastewater and wastewater forms of the three U and P gaseous wastes.
3.1.1 Nonwastevaters
Since nonwastewater forms of the U and P gaseous wastes may contain
hazardous constituents at treatable concentrations, applicable treatment
technologies include those that destroy or reduce the total amount of hazard-
ous constituents in the waste. The Agency has identified the following
treatment technologies as applicable for treatment of nonwastewater forms of
these wastes:
Ethylene Oxide Waste Treatabilitv Group
• Chemical oxidation;
• Thermal oxidation; and
• Recovery.
Nitrogen Oxide Waste Treatabilitv Group
. • Contact with a caustic reducing solution; and
• Recovery.
These treatment technologies were identified based on current waste
treatment practices and engineering judgment.
Chemical Oxidation
Chemical oxidation is a destruction technology in which dissolved
organic compounds are chemically oxidized to yield carbon dioxide, water,
salts, and simple organic acids. This technology generates one treatment
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residual, treated effluent. The treated effluent may require further treat-
ment for organic constituents by carbon adsorption.
Thermal Oxidation
Thermal oxidation (incineration) is a destruction technology in
which energy, as heat, is transferred to the waste to destabilize chemical
bonds and destroy organic constituents. The three types of incinerator design
applicable to U and P organic wastes are fluidized-bed, rotary kiln, and
liquid injection incineration.
In a fluidized-bed incinerator, solid and semi-solid wastes are
injected into the fluidized-bed material (generally sand and/or incinerator
ash), where they are heated to their ignition temperature. Heat energy from
the combustion reactions is then transferred back to the fluidized bed. Ash
is removed periodically during operation and during bed change-outs.
In a liquid injection incinerator, liquid wastes (such as equipment
wash water or scrubber water) are atomized and injected into the incinerator.
In general, only wastes with low or negligible ash contents are amenable to
liquid injection incineration. Therefore, this technology does not generate
an ash residual.
In a rotary kiln incinerator, solid and semi-solid wastes (such as
contaminated soil) are fed into the elevated end of the kiln, and the rotation
of the kiln mixes the waste with hot gases to heat the waste to its ignition
temperature. Ash is removed from the lower end of the kiln. Combustion gases
from the kiln enter the afterburner for complete destruction of organic waste
constituents. Other wastes (such as liquids and gases) may also be injected
into the afterburner.
Combustion gases from the incinerator are then fed to a scrubber
system for cooling and removal of entrained particulates and acid gases, if
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necessary. This process generates scrubber water. Fluidized-bed and rotary
kiln incinerators also generate ash.
Recovery
Recovery of gases consists of recycling and reusing the gases from
damaged or otherwise unusable cylinders. Total recycle and reuse of a waste
in the same process or another process eliminates the generation of the waste
and consequently generates no residuals.
Contact with a Caustic Reducing Solution
One commenter (Reference 4) supplied information describing the
treatment of nitric oxide and nitrogen dioxide in a caustic reducing solution.
Nitric oxide and nitrogen dioxide undergo hydrolysis reactions in aqueous
solutions to form nonhazardous nitrites and nitrates. Industrial application
of this process as a treatment technology consists of dispersing nitric oxide
or nitrogen dioxide wastes into a caustic solution containing an appropriate
concentration of a weak reducing agent. The reducing agent and caustic pH
ensure a neutral effluent solution with no oxidation potential.
The chemistry behind this technology consists of nitric oxide and
nitrogen dioxide reacting simultaneously with water to form nitrous acid:
NO + N02 + H20 -> 2HN02
In addition, nitrous acid will react to form nitric acid, nitric oxide, and
water:
3HN025^ HN03 + 2NO + H20
The alkaline solution helps drive this reaction to the less cor-
rosive nitrous oxide.
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The presence of reducing agents also helps drive the HN03^HN02
equilibrium to the less corrosive HN02. For example, iron(II) sulfate will
react with nitric acid to form nitrous acid:
HN03 + 2Fe2* + 2H* -> HN02 + 2Fe3* + H20
Finally, the alkaline solution will convert the nitrous acid and nitric acid
to nitrites and nitrates:
HN03 + OH- -> N03- + H20
HN02 + OH'S^NCV + H20
These reactions are just two of many possible reactions taking place
with a NO, mixture, most with similar equilibrium constants and potential.
Different chemical compounds exist and react on a micro level, depending on
local stoichiometry. Individual facilities using this treatment technology
would have to monitor the reaction conditions carefully, using oxidation/
reduction indicators and tests for remaining oxidation potential, to ensure
complete conversion of the NO, wastes to nitrites and nitrates. The indica-
tors chosen, as well as the tests for residual oxidation potential, will
depend to a large extent on the reducing agents and types of caustic solution
selected.
3.1.2 Wastewaters
Since wastewater forms of the gaseous U and P wastes may contain
hazardous constituents at treatable concentrations, applicable treatment
technologies include those technologies that destroy or reduce the total
amount of hazardous constituents in the waste. The Agency has identified the
following treatment technologies as applicable for treatment of wastewater
forms of these wastes:
Ethvlene Oxide Waste Treatabilitv Group
• Chemical oxidation;
• Thermal oxidation;
• Wet air oxidation;
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• Biological treatment; and
• Carbon adsorption.
Nitrogen Oxide Waste Treatability Group
• Contact with a caustic reducing solution.
These treatment technologies were identified based on current waste
treatment practices and engineering judgment.
The concentrations and types of waste constituents present in the
gaseous U and P wastewaters generally determine which technology is most
applicable. Carbon adsorption, for example, is often used as a polishing step
following primary treatment by biological treatment or wet air oxidation.
Typically, carbon adsorption is applicable for treatment of wastewaters
containing less than 0.1% total organic constituents. Wet air oxidation and
biological treatment are applicable for treatment of wastewaters containing up
to 1% total organic constituents.
Chemical Oxidation
The description of chemical oxidation was given previously for
nonwastewaters in Section 3.1.1. This description also applies to waste -
waters.
Thermal Oxidation
The description of thermal oxidation was given previously for
nonwastewaters in Section 3.1.1. This description, particularly that of
liquid injection incineration, also applies to wastewaters.
Wet Air Oxidation
Wet air oxidation is a destruction technology in which organic
constituents in wastes are oxidized and destroyed under high pressure at
elevated temperatures in the presence of dissolved oxygen. This technology is
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applicable for wastes comprised primarily of water and up to 10% total organic
constituents. Wet air oxidation generates one treatment residual, treated
effluent. The treated effluent may require further treatment for organic
constituents by carbon adsorption.
Biological Treatment
Biological treatment is a destruction technology in which organic
constituents in wastewaters are biodegraded. This technology generates two
treatment residuals, treated effluent and waste biosludge.
Carbon Adsorption
Carbon adsorption is a separation technology in which organic
constituents in wastewaters are selectively adsorbed onto activated carbon.
This technology generates two treatment residuals, treated effluent and spent
activated carbon. The spent activated carbon can be reactivated and recycled,
or can be incinerated.
Contact With a Caustic Reducing Solution
The description of contact with a caustic reducing solution was
given previously for nonwastewaters in Section 3.1.1. This description also
applies to wastewaters.
3.2 Demonstrated Treatment Technologies
To be demonstrated, a technology must be employed in full-scale
operation for treatment of the waste in question or a similar waste. Tech-
nologies available only at pilot- or bench-scale operations are not considered
in identifying demonstrated technologies. The demonstrated treatment tech-
nologies for nonwastewater and wastewater forms of ethylene oxide and nitrogen
oxide wastes are:
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Ethylene Oxide Wastes
Nitrogen Oxide Wastes
Nonwastewaters
• Thermal oxidation
• Chemical oxidation
Contact with a caustic
reducing solution
Wastewaters
• Thermal oxidation
• Chemical oxidation
• Wet air oxidation
• Carbon adsorption
Contact with a caustic
reducing solution
3.2.1
Nonwastewaters
The Agency has identified contact with a caustic reducing solution
as a demonstrated technology for treatment of nonwastewater forms of the
nitrogen oxide wastes, and thermal and chemical oxidation as demonstrated
technologies for treatment of nonwastewater forms of ethylene oxide wastes.
EPA has received numerous comments from industry describing their use of a
reduction treatment technology for treatment of nitrogen oxide wastes and use
of oxidation treatment technologies for treatment of ethylene oxide wastes.
The Agency believes that oxidation is demonstrated for treatment of
ethylene oxide nonwastewaters based on industry comments and because ethylene
oxide is similar in chemical structure to other organic U and P wastes that
have been successfully treated by oxidation on a full-scale operational basis.
Nitrogen oxide wastes, on the other hand, are not amenable to
oxidation, since they are inorganic oxidation products. Therefore, the Agency
believes that a reduction technology would effectively treat these wastes, and
based on industry's comments (Reference 4), believes that contact with a
caustic reducing solution is a demonstrated treatment technology for nitrogen
oxide nonwastewaters.
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The Agency no longer believes that recovery is a demonstrated
technology for treatment of either ethylene oxide or nitrogen oxide nonwaste-
waters, based on information obtained during the comment period. Industry
commented that recovery often poses health and safety problems. In the
specific case of ethylene oxide cylinder recovery, commenters reported that
damaged cylinders pose significant risk of explosion and thus are very danger-
ous to store and handle; moreover, most cylinder-handling firms refuse to take
damaged cylinders. Commenters reported that they have been promptly treating
their damaged cylinders on site using chemical and thermal treatment.
3.2.2 Wastewaters
The Agency has identified contact with a caustic reducing solution
as a demonstrated technology for treatment of wastewater forms of the nitrogen
oxide wastes, and thermal oxidation, chemical oxidation, wet air oxidation,
and carbon adsorption as demonstrated technologies for treatment of wastewater
forms of ethylene oxide wastes. EPA has received numerous comments from
industry describing their use of a reduction treatment technology for treat-
ment of nitrogen oxide wastes and oxidation treatment technologies for treat-
ment of ethylene oxide wastes.
The Agency believes that both oxidation and carbon adsorption
technologies are demonstrated for treatment of ethylene oxide wastewaters
based on industry comments and because ethylene oxide is similar in chemical
structure to other organic U and P wastes that have been successfully treated
by oxidation and carbon adsorption technologies (separately) on a full-scale
operational basis.
Nitrogen oxide wastes, on the other hand, are not amenable to
oxidation, since they are inorganic oxidation products. Therefore, the Agency
believes that a reduction technology would effectively treat these wastes, and
based on industry's comments (Reference 4), believes that contact with a
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caustic reducing solution is a demonstrated treatment technology for nitrogen
oxide wastewaters.
The Agency is not aware of any facilities that recover (recycle and
reuse) ethylene oxide or nitrogen oxide wastewaters on a full-scale opera-
tional basis; therefore, recycle and reuse is not considered to be demon-
strated for these wastewaters at this time.
The Agency is aware of facilities that use biological treatment for
ethylene oxide wastewaters, and therefore believes biological treatment is
demonstrated for these wastewaters. The Agency is not aware of any facilities
that use biological treatment for nitrogen oxide wastes, and therefore does
not believe that biological treatment is demonstrated for these wastewaters.
3.3 Identification of Best Demonstrated and Available Technology (BOAT)
Best demonstrated and available technology (BDAT) is determined
based on a thorough review of all the treatment performance data available on
the waste of concern or wastes judged to be similar. The treatment perfor-
mance data that were evaluated for these wastes are presented in Section 4.0.
Following the identification of "best," the Agency determines whether the best
demonstrated technology is "available." An available treatment technology is
one that (1) is not a proprietary or patented process that cannot be purchased
or licensed from the proprietor (i.e., it must be commercially available), and
(2) substantially diminishes the toxicity of the waste or substantially
reduces the likelihood of migration of hazardous constituents from the waste.
3.3.1 Nonwastewaters
The Agency is considering oxidation processes to be BDAT for treat-
ment of ethylene oxide nonwastewaters and contact with a caustic reducing
solution to be BDAT for treatment of nitrogen oxide nonwastewaters. The
oxidation processes identified as BDAT for ethylene oxide nonwastewaters are
either thermal oxidation (incineration) or chemical oxidation. Both of these
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treatment methods are expected to destroy the organic constituents of concern
in these wastes and therefore are both considered "best."
The Agency is promulgating thermal and chemical oxidation for
ethylene oxide nonwastewaters and contact with a caustic reducing solution for
nitrogen oxide nonwastewaters as treatment standards, rather than specifying
recovery as the treatment standard, which was the proposed treatment standard.
EPA recognizes that in some cases cylinder recovery may not be feasible. As
such, EPA is establishing chemical or thermal oxidation treatment methods as
treatment standards for cylinder recovery. The promulgation of BOAT treatment
standards as methods of treatment, however, does not preclude a facility from
utilizing recycle or reuse operations in accordance with 40 CFR 261.
The Agency believes that both oxidation treatment processes are
commercially available and provide substantial reduction of waste toxicity,
based on industry comments (see Section 4.0). Likewise, the Agency believes
that contact with a caustic reducing solution is commercially available and
provides substantial reduction of waste toxicity, based on an industry comment
(Reference 4).
3.3.2 Wastewaters
The Agency is considering oxidation processes to be BDAT for treat-
ment of ethylene oxide wastewaters and contact with a caustic reducing solu-
tion to be BDAT for treatment of nitrogen oxide wastewaters. The oxidation
processes identified as best for ethylene oxide wastewaters are thermal
oxidation (incineration), chemical oxidation, and wet air oxidation. In
addition, carbon adsorption is to follow chemical or wet air oxidation to
ensure effective treatment of ethylene oxide. The Agency believes that it is
sound engineering judgment to include a final step of carbon adsorption
following oxidation. This step will ensure that ethylene oxide is removed
from the wastewater matrix. Additionally, spent carbon from treating these
wastewaters becomes a nonwastewater form of this waste (54 Federal Register
26630-1, June 23, 1989) and would thus have to undergo a final oxidation step,
3-11
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most likely thermal oxidation (incineration). EPA believes that incineration
is the most successful method of treatment for a wide variety of organic
wastes, and would assure ultimate destruction of all ethylene oxide present in
the wastewater.
The Agency believes that all three oxidation treatment processes are
commercially available and provide substantial reduction of waste toxicity,
based on industry comments (see Section 4.0). Wet air oxidation was not
specifically discussed by commenters; however, EPA believes that wet air
oxidation is an effective technology for treating ethylene oxide wastewaters
(see the BOAT Treatment Technology Background Document. Reference 3), and
therefore is also setting it as BOAT, when performed in series with carbon
adsorption.
The Agency is not promulgating biological treatment as BOAT for
treatment of ethylene oxide wastewaters, because of the concern that possible
shock loads of these wastes would disable a plant's working organisms and
allow these wastes to exit untreated in the effluent.
The BOAT treatment standards for ethylene oxide and nitrogen oxide
nonwastewaters and wastewaters are listed in Table 3-1.
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Table 3-1
BOAT TREATMENT STANDARDS FOR GASEOUS U AND P WASTES
(METHODS OF TREATMENT)
U115 (ETHYLENE OXIDE) WASTEWATERS
Thermal oxidation;
Chemical oxidation followed by carbon adsorption; or
Wet air oxidation followed by carbon adsorption.
U115 (ETHYLENE OXIDE) NONWASTEWATERS
Thermal oxidation; or
Chemical oxidation.
P076 (NITRIC OXIDE) WASTEWATERS AND NONWASTEWATERS
Contact with a caustic reducing solution.
P078 (NITROGEN DIOXIDE) WASTEWATERS AND NONWASTEWATERS
Contact with a caustic reducing solution.
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4.0 TREATMENT PERFORMANCE DATA
This section discusses the data used to identify the applicable,
demonstrated, and available technologies for treatment of ethylene oxide and
nitrogen oxide nonwastewaters and vastewaters.
Two commenters (References 6 and 7) suggested establishing con-
centration-based treatment standards based on chemical or thermal oxidation
(incineration) for nonwastewaters, and on incineration, biological treatment,
or carbon adsorption for nonwastewaters. One commenter (Reference 6) supplied
limited process and treatment information on incineration for nonwastewaters
and on incineration or biological treatment for wastewaters. This informa-
tion is summarized in Table 4-1. Unfortunately, these limited data did not
fulfill the data quality requirements specified in the Generic Quality
Assurance Project Plan for Land Disposal Restrictions Program ("BOAT") (Refer-
ence 10); therefore, concentration-based treatment standards cannot be calcu-
lated based on these data. However, the data indicate substantial treatment
of ethylene oxide nonwastewater by incineration and of ethylene oxide waste -
water by incineration and biological treatment.
One commenter (Reference 4) described their treatment method of
venting nitrogen oxide gases into a caustic reducing solution, which yields a
neutral, nonhazardous solution of nitrates and nitrites. Due to the lack of
supporting technical data, the Agency is unable to calculate concentration-
based treatment standards based on this treatment method; however, based on
this information, the Agency is considering "contact with a caustic reducing
solution" as an available and demonstrated treatment technology for nitric
oxide and nitrogen dioxide wastewaters and nonwastewaters.
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Table 4-1
ETHYLENE OXIDE WASTEWATER AND
NONWASTEWATER TREATMENT DATA
Waste:
Treatment A:
Treatment B:
Wastewater
Ethylene Oxide Underground Storage Tank Washwater at Concentra-
tion of 26.23 ppm Ethylene Oxide.
Absorbed in Nitrogen and Destroyed in Flare.
Wastewater Residual at Concentration of <0.5 ppm Ethylene
Oxide.
Biological Waste Treatment Wastewater Residual at Concentration
of <0.5 ppm Ethylene Oxide.
Nonwastewater
Waste: Ethylene Oxide Underground Storage Tank Sandblasting Residue at
Concentrations of 1 to 10 ppm Ethylene Oxide.
Treatment: Commercial Hazardous Waste Incineration 99.99% ORE (Destruction
and Removal Efficiency) for Ethylene Oxide.
Source: Union Carbide Corporation (Reference 6).
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5.0 ACKNOWLEDGEMENTS
This background document was prepared for the U.S. Environmental
Protection Agency, Office of Solid Waste, by Radian Corporation under Con-
tract No. 68-W9-0072. This document was prepared under the direction of
Richard Kinch, Acting Chief, Waste Treatment Branch; Larry Rosengrant, Section
Head, Treatment Technology Section; Jerry Vorbach, Project Officer, and Lisa
Jones, Project Manager. Steve Silverman served as EPA legal advisor.
The following personnel from Radian Corporation were involved in
preparing this document: John Williams, Program Manager; Mary Willett,
Project Director; and John Horstman, Task Leader.
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6.0 REFERENCES
1. USEPA. 1988. U.S. Environmental Protection Agency, Office Solid Waste.
Methodology for Developing Treatment Standards. Washington, D.C.: U.S.
Environmental Protection Agency.
2. American Public Health Association, American Water Works Association, and
the Water Pollution Control Federation. 1985. Standard Methods for the
Examination of Water and Wastewater. Sixteenth Edition. Washington,
D.C.: American Public Health Association.
3. USEPA. 1988. U.S. Environmental Protection Agency. Treatment Technology
Background Document. Washington, D.C.: U.S. Environmental Protection
Agency.
4. Aqua-Tech-Groce Laboratories. 1990. Comment LD12-0015 on the Proposed
Rule for Land Disposal Restrictions or Third Scheduled Wastes (54 FR
48372, November 22, 1989). Washington, D.C.: U.S. Environmental Protec-
tion Agency.
5. Versar, Inc. 1989. Phone Survey of Gas Manufacturers, Packagers, and
Distributors on the Management of Compressed Waste Gases. Memorandum to
the Record. Washington, D.C.: U.S. Environmental Protection Agency.
6. Union Carbide Corporation. 1990. Comments LD12-00190 and LD12-00190.A
on the Proposed Rule for Land Disposal Restrictions for Third Scheduled
Wastes (54 FR 48372, November 22, 1989). Washington, D.C.: U.S.
Environmental Protection Agency.
7. Olin Chemicals. 1990. Comment LD12-00129 on the Proposed Rule for Land
Disposal Restrictions for Third Scheduled Wastes (54 FR 48372, November
22, 1989). Washington, D.C.: U.S. Environmental Protection Agency.
8. Phillips Petroleum Company. 1990. Comment LD12-00080 on the Proposed
Rule for Land Disposal Restrictions for Third Scheduled Wastes (54 FR
48372, November 22, 1989). Washington, D.C.: U.S. Environmental Protec-
tion Agency.
9. Hoechst Celanese Corporation. 1990. Comment LD12-00047 on the Proposed
Rule for Land Disposal Restrictions for Third Scheduled Wastes (54 FR
48372, November 22, 1989). Washington, D.C.: U.S. Environmental Protec-
tion Agency.
10. USEPA. 1987. U.S. Environmental Protection Agency, Office of Solid
Waste. Generic Quality Assurance Project Plan for Land Disposal Restric-
tions Program ("BOAT"). Washington, D.C.: U.S. Environmental Protection
Agency.
11. Lowenheim, F. A., Moran, M. K., ed. 1975. Industrial Chemicals. 4th ed.
New York, New York: John Wiley & Sons, Inc.
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12. Windholz, M., ed. 1983. The Merck Index. 10th ed. Rahway, New Jersey:
Merck & Company.
13. Sax, N. I., Lewis, R. J. Sr., ed. 1987. Hawlev's Condensed Chemical
Dictionary, llth ed. New York: Van Nostrand Reinhold Company.
14. SRI International. 1987. 1987 Directory of Chemical Producers-United
States of America. SRI International, Menlo Park, California.
15. USEPA. 1989. U.S. Environmental Protection Agency. Potential
Generators. Waste Characterization, and Current Waste Management Prac-
tices for Third Third Wastes. Draft. Washington, D.C.: U.S.
Environmental Protection Agency.
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Appendix A
LIST OF FACILITIES THAT MAY GENERATE U AND P GASEOUS WASTES
Ethylene oxide (U1I5) is a colorless gas that is used as a petroleum
demulsifier, fumigant, rocket propellant, industrial sterilant, and fungicide,
as well as a reagent in the manufacture of ethylene glycol and higher glycols,
surfactants, acrylonitrile, and ethanolamines.
Nitric oxide (P076) is a colorless gas that is used to bleach rayon,
in the preparation of nitrosyl carbonyls, and as an intermediate in the
production of nitric acid from ammonia.
Nitrogen dioxide (P078) is a red to brown gas that is used as a
nitrating agent, an oxidizing agent, a catalyst, an oxidizer for rocket fuels,
a polymerization inhibitor for acrylates, and as a reagent in the manufacture
of nitric acid.
The facilities listed in Table A-l are producers or users of ethyl-
ene oxide, nitric oxide, and nitrogen dioxide, and are therefore potential
generators of these U and P wastes.
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Table A-l
FACILITIES THAT MAY GENERATE U115, P076, AND P078
U115 (Ethvlene Oxide)
Plant Name
BASF Corporation, Chemicals Division
Celanese Chemical Company, Inc.
Dow Chemical U. S. A.
Eastman Kodak Company
ICI Americas, Inc.
National Distillers and Chemical Corporation
PD Glycol
Shell Oil Company
Sun 01in Chemical Company
Texaco Chemical Company
Union Carbide Corporation
Union Carbide Corporation
Conoco
Balchem Corporation
Scott Specialty Gases
Liquid Air Corporation
Liquid Air Corporation
Matheson Gas Products
Phillips Petroleum Company
P076 Nitric Oxide
Plant Name
Matheson Gas Products, Inc.
Matheson Gas Products, Inc.
Matheson Gas Products, Inc.
Matheson Gas Products, Inc
Matheson Gas Products, Inc.
Matheson Gas Products, Inc.
Matheson Gas Products, Inc.
Matheson Gas Products, Inc.
Matheson Gas Products, Inc.
Air Products & Chemicals, Inc.
Scott Specialty Gases
Liquid Air Corporation
Sardoz Chemical Company
Aldrich Chemical Company
Plant Location
Geismar, LA
Clear Lake, TX
Plaquemine, LA
Longview, TX
Bayport, TX
Morris, IL
Beaumont, TX
Geismar, LA
Claymont, DE
Port Neches, TX
Seadrift, TX
Taft, LA
Houston, TX
Statehill, NY
Plumsteadville, PA
Georgia
Washington
Secaucus, NJ
Bartlesville, OK
Plant Location
Cucamonga, CA
East Rutherford, NJ
Gloucester, MA
Gonzales, LA
Joliet, IL
La Porte, TX
Morrow, GA
Newark, CA
Twinsberg Township, OH
Allentown, PA
Plumsteadville, PA
Texas
North Carolina
Wisconsin
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Table A-l (Continued)
FACILITIES THAT MAY GENERATE U115, P076, AND P078
P078 Nitrogen Dioxide
Plant Name
Cepex Midwest
Aldrich Chemical Company
Air Products & Chemicals, Inc.
Scott Specialty Gases
Liquid Air Corporation
Matheson Gas Products, Inc.
Plant Location
Nebraska
Wisconsin
Allentown, PA
Plumsteadville,
Texas
Secaucus, NJ
PA
Note: This list of facilities was compiled from information in References 4,
5, 6, 7, 8, 9, 11, 12, 13, 14, and 15. Some of these facilities may no
longer use or manufacture these chemicals, and some may be corporate
headquarters for companies that handle the chemicals at other sites.
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