FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
BACKGROUND DOCUMENT
FOR WASTES FROM THE PRODUCTION OF
DINITROTOLUENE, TOLUENEDIAMINE, AND TOLUENE DIISOCYANATE
K027, K111, K112, K113, K114, K115, K116, U221, and U223
Jose E. Labiosa
Work Assignment Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
May 1989
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TABLE OF CONTENTS
Section Page
1.0 INTRODUCTION 1-1
1.1 Background 1-1
1.2 Rationale For Treatment Standards 1-2
1.3 Organization of Background Document 1-7
2.0 INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-2
2.2 Waste Characterization 2-8
2.3 Determination of Waste Treatability Groups 2-11
3.0 APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.1.1 K027, K113-K116, U221, and U223 Organics 3-2
3.1.2 K115 Metals 3-4
3.1.3 K111 and K112 Organics 3-5
3.2 Demonstrated Treatment Technologies 3-6
3.2.1 K027, K113-K116, U221, and U223 Organics 3-6
3.2.2 K115 Metals 3-8
3.2.3 K111 and K112 Organics 3-9
4.0 TREATMENT PERFORMANCE DATABASE 4-1
5.0 IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY
(BDAT) 5-1
5.1 Determination of BDAT for K027, K113-K116, U221, and
U223 Nonwastewater Organics 5-2
5.1.1 Identification of BDAT 5-2
5.1.2 Evaluation of Substantial Treatment by
Incineration and Fuel Substitution 5-3
5.2 Determination of BDAT for K027, K113-K116, U221, and
U223 Wastewater Organics 5-11
5.2.1 Identification of BDAT 5-11
5.2.2 Evaluation of Substantial Treatment by
Carbon Adsorption 5-13
5.3 Determination of BDAT for Nickel in K115 5-14
5.4 Summary of BDAT for the K027 Treatability Group 5-16
5.5 Determination of the Regulatory Approach for the K111
and K112 Treatability Group 5-16
6.0 SELECTION OF REGULATED CONSTITUENTS 6-1
7.0 CALCULATION OF TREATMENT STANDARDS 7-1
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TABLE OF CONTENTS
(Continued)
Section Page
8.0 REFERENCES 8-1
APPENDIX A: CBI WASTE CHARACTERIZATION DATA A-1
APPENDIX B: APPLICATION OF THE SECTION 5.1.2 METHODOLOGY B-1
TO THE K027 TREATABILITY GROUP
APPENDIX C: CARBON ADSORPTION FOR THE TREATMENT OF K027 C-1
TREATABILITY GROUP WASTEWATERS
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LIST OF TABLES
Table Page
2-1 FACILITIES THAT MAY GENERATE K027, Kill, K112, K113, K114,
K115, AND/OR K116 r BY STATE AND EPA REGION 2-3
2-2 SUMMARY OF PUBLICLY-AVAILABLE WASTE CHARACTERIZATION DATA
FOR WASTE CODES K027, K111, K112, K113, K114, K115, AND
K116 2-9
4-1 WASTE CHARACTERIZATION DATA FOR K027, K113-K116 4-6
4-2 TREATMENT PERFORMANCE DATA FOR K015: LIQUID INJECTION
INCINERATION 4-7
4-3 TREATMENT PERFORMANCE DATA FOR K086: ROTARY KILN
INCINERATION 4-8
4-4 TREATMENT PERFORMANCE DATA FOR F024: ROTARY KILN
INCINERATION 4-9
4-5 SUMMARY OF OPERATING DATA FOR INCINERATION OF K015, K086,
F024, AND K027 4-10
4-6 TREATMENT PERFORMANCE DATA FOR K103 AND.K104: CARBON
ADSORPTION STEP 4-11
4-7 TREATMENT PERFORMANCE DATA FOR NICKEL TRANSFERRED FROM
STABILIZATION OF F006 NONWASTEWATER 4-12
4-8 TREATMENT PERFORMANCE DATA FOR NICKEL TRANSFERRED FROM
LIME AND SULFIDE PRECIPITATION FOLLOWED BY VACUUM
FILTRATION OF K062 AND METAL-BEARING CHARACTERISTIC
WASTEWATER 4-13
5-1 COMPARISON OF CONSTITUENTS IN K015, K086, AND F024 THAT
ARE MORE DIFFICULT TO TREAT THAN THE CONSTITUENTS OF
CONCERN IN K027, K113-K116, U221, AND U223 5-8
7-1 CALCULATION OF TREATMENT STANDARDS FOR
NICKEL IN K115 7-2
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LIST OF FIGURES
Figure Page
2-1 FLOW DIAGRAM OF PROCESSES GENERATING THE K027,
K111-K116 WASTE CODES 2-U
5-1 FLOWCHART ILLUSTRATING THE PROCEDURE USED TO SHOW
SUBSTANTIAL TREATMENT BY INCINERATION OR FUEL
SUBSTITUTION 5-5
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EXECUTIVE SUMMARY
BDAT Treatment Standards for K027, K113, K114, K115, K116, U221, and U223
Pursuant to section 3004(m) of the Hazardous and Solid Waste Amend-
ments (HSWA) enacted on November 8, 1984, the Environmental Protection Agency
(EPA) is establishing best demonstrated available technology (BDAT) treatment
standards for the listed wastes identified in 40 CFR 261.32 and 40 CFR 261.33
as K027, K113, K114, K115, K116, U221, and U223. Compliance with these BDAT
treatment standards is a prerequisite for placement of these wastes in units
designated as land disposal units according to 40 CFR Part 268. The effective
date of these treatment standards is June 8, 1989.
The background document provides the Agency's treatment standards
for K027, K113-K116, U221f and U223. The Agency is not proposing treatment
standards for the newly listed wastes Kill and K112 at this time.
The EPA pamphlet entitled Methodology for Developing BDAT Treatment
Standards summarized the Agency's legal authority and promulgated methodology
for establishing treatment standards. The background document presents
waste-specific information — the number and locations of facilities affected
by the land disposal restrictions for K027, K113-K116, U221, and U223 wastes,
the waste generating process, characterization data, and the technologies used
to treat the waste (or similar wastes). The document also explains EPA's
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determination of'BDAT, selection of constituents to be regulated, and calcula-
tion of treatment standards.
According to 40 CFR 261.32 and 40 CFR 261.33, waste codes K027,
K111-K116, U221, and U223, which are generated by the production of
dinitrotoluene (DNT), toluenediamine (TDA), and toluene diisocyanate (TDI) are
listed as follows:
K027 Centrifuge and distillation residues from toluene diisocyanate
production.
K111 Product washwaters from the production of dinitrotoluene via
nitration of toluene.
K112 Reaction by-product water from the drying column in the produc-
tion of toluenediamine via hydrogenation of dinitroluene.
K113 Condensed liquid light ends from the production of toluenediamine
via hydrogenation of dinitroluene.
K114 Vicinals from the purification of toluenediamine in the produc-
tion of toluenediamine via hydrogenation of dinitrotoluene.
K115 Heavy ends from the purification of toluenediamine in the produc-
tion of toluenediamine via hydrogenation of dinitrotoluene.
K116 Organic condensate from the solvent recovery column in the
production of toluene diisocyanate via phosgenation of
toluenediamine.
U221 Toluenediamine (TDA)
U223 Toluene diisocyanate (TDI)
EPA has estimated that eight domestic facilities that produce DNT,
TDA, and TDI are potential generators of the K027, K111-K116, U221 and U223
wastes. In addition, U221 and U223 wastes may be generated by users of TDA
and TDI.
Treatment standards are established for both nonwastewater and
wastewater forms of K027, K113-K116, U221, and U223. For the purpose of
determining the applicability of the treatment standards, wastewaters for
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K027, K113-K116,~U221, and U223 are designed as wastes containing less than 1
percent (weight basis) total suspended solids1 and less than 4 percent (weight
basis) total organic carbon (TOC). Wastes not meeting this definition must
comply with the treatment standards for nonwastewaters.
For K027, K113-K116, U221, and U223 nonwastewaters, the Agency is
establishing a technology treatment standard of either incineration or fuel
substitution. In addition, a treatment standard is established for nickel in
K115 based on stabilization.
For K027, K113—K116, U221, and U223 wastewaters, the Agency is
establishing a technology treatment standard of either carbon adsorption
followed by regeneration or incineration of spent carbon or incineration. In
addition, a treatment standard is established for nickel in K115 based on lime
and suffide precipitation followed by vacuum filtration.
The following tables present the treatment standards for K027,
K113-K116, U221, and U223 wastes. The treatment standards are specified
technologies for organics in wastewater and nonwastewater forms of the wastes
and a numerical treatment standard for nickel in wastewater and nonwastewater
1The term "total suspended solids" (TSS) clarifies EPA's previously
used terminology of "total solids" and "filterable solids". Specifically,
total suspended solids is measured by method 209C (total suspended solids
dried at 103-105°C) in Standard Methods For The Examination Of Water and
Wastewater. 16th edition.
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forms of K115. The numerical standards are TCLP for nonwastewater forms of
K115 and total composition for wastewater forms of K115. The units are mg/kg
(parts per million on a weight-by-weight basis) for nonwastewater and mg/1
(parts per million on a weight-by-volume basis) for wastewater. K027,
K113-K116, U221, and U223 wastes must be treated by the promulgated BDAT as a
prerequisite to land disposal.
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1.0 INTRODUCTION
1.1 Background
The Hazardous and Solid Waste Amendments Act (HSWA), enacted on
November 8, 1984, amended the Resource Conservation and Recovery Act (RCRA) of
1976. Pursuant to HSWA, Section 3004(g) of RCRA requires the U.S. Environmen-
tal Protection Agency (EPA) to promulgate regulations that restrict the land
disposal of hazardous wastes beyond specified dates. Under Section 3004(m) of
RCRA, the Agency is required to-set "levels or methods of treatment, if any,
which substantially reduce the likelihood of migration of hazardous constitu-
ents from the waste so that short-term and long-term threats to human health
and the environment are minimized." As specified in the promulgated regula-
tory framework for implementing the land disposal restrictions, these "treat-
ment standards" are based on the performance of the best demonstrated avail-
able technologies (BDAT) for a waste. If a waste or treatment residual, as
generated or treated, meets the BDAT treatment standard established by EPA for
that waste, then the prohibition on land disposal does not apply and the waste
may be land disposed.
HSWA requires EPA to establish treatment standards for all listed
hazardous wastes according to the following schedule:
DATE GOAL
August 8, 1988 Treatment standards for at least
one-third of all listed hazardous wastes
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DATE GOAL
June 8, 1989 Treatment standards for at least
two-thirds of all listed hazardous wastes
May 8, 1990 Treatment standards for all remaining
listed hazardous wastes and all wastes
identified as of November 8, 1984
If EPA fails to set a treatment standard by the statutory deadline
for any hazardous waste in the first-third or second-third of the schedule,
the waste may be disposed in a landfill or surface impoundment, provided that
the disposal unit is in compliance with the minimum technological requirements
specified in Section 3004(o) of RCRA. This so-called "soft hammer" provision
applies until May 8, 1990 ("hard hammer" provision date), at which time such
wastes will automatically be prohibited from all methods of land disposal that
are not otherwise determined to be protective through the "no-migration"
petition process (53 FR 11765, April 8, 1988). For any hazardous waste that
is newly identified or listed in 40 CFR Part 261 after November 8, 1984, EPA
is required to set a treatment standard for that waste within six months of
the date of identification or listing. However, the statute does not provide
for an automatic prohibition on the land disposal of such wastes if EPA fails
to set a treatment standard within the six-month period.
1.2 Rationale For Treatment Standards
This background document provides the Agency's rationale and techni-
cal support for the treatment standards for the listed wastes identified in 40
CFR 261.31 and 40 CFR 261.33 as K027, K113, K114, K115, K116, U221, and U223.
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K027, which is generated from the production of toluene diisocyanate (TDI), is
part of the second-third of the scheduled listed wastes to be evaluated by the
Agency for land disposal restrictions. Wastes listed as K111, K112, K113,
K1141 K115, and K116, which are generated from the production of dinitro-
toluene (DNT), toluenediamine (TDA), or toluene diisocyanate (TDI), are "newly
listed" (i.e., listed as hazardous wastes after November 8, 1984). Treatment
standards for K113-K116 are being promulgated as part of this second-thirds
rulemaking. The Agency is not promulgating treatment standards for the newly
listed wastes K111 and K112 at this time. In addition, the Agency is promul-
gating treatment standards for soft-hammered first-third U wastes, U221 and
U223. These wastes are generated from spills, leaks, or discard of chemicals
associated with the production of TDA and TDI or from the use of TDA or TDI as
active or additive ingredients in manufacturing processes. Treatment stan-
dards are also being promulgated for K027-, K113-K116-, U221-, and U223-
containing wastewaters generated from RCRA corrective actions and CERCLA
remedial orders (as either contaminated ground or surface water).
Wherever EPA believes that wastes represented by different codes can
be treated to similar concentrations using identical technologies, the Agency
has combined the codes into one treatability group (53 FR 31145, August 17,
1988). Based on a review of waste generation data, waste management prac-
tices, and waste characterization data for the wastes, EPA believes that these
wastes can be combined into two waste treatability groups: (1) the K027,
K113-K116, U221, and U223 treatability group (hereafter referred to as the
"K027 treatability group"), and (2) the K111 and K112 treatability group.
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EPA may establish treatment standards either as a specific treatment
technology or as a performance level of treatment monitored by measuring the
concentration levels of the hazardous constituents in the waste, treatment
residual, or extract of the waste. While EPA prefers to establish treatment
standards as performance levels, this approach is not always possible. As
discussed in this background document, EPA is promulgating BDAT treatment
standards for K027, K113, K114, K115, K116, U221, and U223 (the K027 treat-
ability group) as specific treatment technologies. For the K115 waste code,
EPA is also promulgating performance level treatment standards for nickel in
wastewaters and nonwastewaters, since this BDAT List metal constituent is
present at treatable concentrations in the waste, and treatment performance
data are available for this constituent.
The Agency's decision to establish treatment standards as specific
treatment technologies for the K027 treatability group (except nickel in K115,
which is being promulgated at a concentration level in the treatment residual)
is based on the following rationale. EPA does not currently have any treat-
ment performance data for any of the wastes in the K027 treatability group.
The Agency has not pursued treatment performance testing for these wastes
because EPA has determined that available analytical methods cannot satisfac-
torily measure the principal hazardous organic constituents (aromatic rings
containing nitrogen compounds) contained in K027, K113-K116, U221, and U223
wastes and treatment residuals. In addition, the Agency currently has not
identified any organic constituents in these wastes that could be used as
surrogates or indicator constituents in order to develop alternative numerical
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standards for these wastes. Therefore, the Agency is unable to develop
concentration-based BDAT treatment standards for these wastes at this time.
Instead, the Agency is promulgating treatment standards for the
organic hazardous constituents expressed as specific methods of treatment.
For the nonwastewater forms of K027, K113—K116, U221, and U223, the treatment
methods are either incineration or fuel substitution. Incinerators must
comply with the requirements of 40 CFR 264 Subpart 0, or 265 Subpart 0. Fuel
substitution units must comply with the requirements of 40 CFR Part 266,
Subpart D. For the wastewater forms of K027, K113-K116, U221, and U223, the
methods are either carbon adsorption followed by incineration of spent carbon,
or direct incineration of the wastewaters. It should be noted that the use of
other treatment technologies prior to carbon adsorption is not prohibited by
this rule. In addition, for K115 wastes, the Agency is promulgating concen-
tration-based treatment standards for nickel. Since EPA is specifying a
treatment method as the treatment standard, residues resulting from the
required treatment method are no longer prohibited from land disposal (unless
EPA should otherwise specify other requirements as it is doing for nickel in
K115 and for organics concentrated in the spent carbon from the treatment of
K027 group wastewaters). In addition, any nonwastewater residues from treat-
ment technologies prior to carbon adsorption must meet the same treatment
standards applicable to the spent carbon (i.e., incineration). The wastewater
effluent from carbon adsorption is considered to meet the treatment standard.
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In order to specify a method of treatment for a waste, EPA must show
that the technology is BDAT for that waste. For a technology to be considered
BDAT, it must provide substantial treatment of the constituents of concern,
similar constituents, or constituents that are harder to treat than the
constituents of concern. In the absence of treatment performance data, EPA
may show that a technology provides substantial treatment for similar wastes
that are believed to be more difficult to treat than K027, K113-K116, U221,
and U223. This background document presents EPA's documentation that the
demonstrated and required treatment technologies (incineration or fuel substi-
tution for nonwastewaters and carbon adsorption or incineration for
wastewaters) provide substantial treatment of hazardous constituents in the
K027 treatability group, based on a review of treatment performance data for
other wastes.
The Agency is not promulgating BDAT treatment standards for the
newly listed wastes K111 and K112 at this time. As is the case for wastes in
the K027 treatability group, EPA does not have any treatment performance data
for Kill or K112, and the Agency has determined that available analytical
methods cannot satisfactorily measure the principal hazardous organic constit-
uents (aromatic rings containing nitrogen compounds) contained in K111 and
K112 wastes and treatment residuals. Since these wastes were listed after the
enactment of HSWA, land disposal of these wastes is not subject to either the
"soft hammer" provisions or the May 8, 1990 "hard hammer" provisions. Conse-
quently, land disposal of K111 and K112 may continue until regulations
restrict their disposal.
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Additional information on the Agency's legal authority and promul-
gated methodology for establishing treatment standards, and the petition
process necessary for requesting a variance from the treatment standards, is
provided in the EPA pamphlet Methodology for Developing BDAT Treatment Stan-
dards^) .
1.3 Organization of Background Document
Section 2.0 of this document presents information on the industry
affected by the land disposal restrictions and on waste characterization data
available for K027 and K111-K116. A more detailed discussion is also provided
for the determination of waste treatability groups identified for the K027,
K111-K116, U221, and U223 waste codes. Section 3.0 presents the applicable
and demonstrated treatment technologies for the treatability groups, while
Section 4.0 presents treatment performance data used in determining BDAT for
the treatability groups. (As discussed above, treatment performance data are
not available for use in determining BDAT for the K111 and K112 treatability
group.) Section 5.0 explains EPA's determination of BDAT for the treatability
groups. Section 6.0 discusses the selection of nickel for regulation in K115,
and Section 7.0 explains the calculation of the treatment standard for nickel
in K115.
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BDAT Treatment Standards
for K027, K113-K116, U221 and U223
(Nonwastewaters)
EITHER INCINERATION OR FUEL SUBSTITUTION*
AS A METHOD OF TREATMENT
* - Incinerators must comply with 40 CFR 264 Subpart 0 or 265 Subpart 0.
Fuel substitution units must be in compliance with 40 CFR Part 266
Subpart D.
BDAT Treatment Standards
for K027, K113-K116, U221 and U223
(Wastewaters)
CARBON** ADSORPTION OR INCINERATION*
AS A METHOD OF TREATMENT
* - Incinerators must comply with 40 CFR 264 Subpart 0 or 265 Subpart 0.
Fuel substitution units must be in compliance with 40 CFR Part 266
Subpart D.
** - Spent carbon and any other nonwastewater residuals generated upstream
from a carbon adsorption unit must meet the nonwastewater standards
applicable to these wastes prior to land disposal. Carbon adsorption
units must be operated such that breakthrough of TDI and TDA does not
occur. Selection of a surrogate or indicator compound as a measure
of breakthrough should be considered on a case-by-case situation.
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BDAT Treatment Standards for K115
(Nonwastewaters)
Maximum For Any
Single Grab Sample
Total Composition TCLP
Constituent (mg/kg) (mg/1)
Nickel Not Applicable 0.32
BDAT Treatment Standards for K115
(Wastewaters)
Maximum For Any
Single Grab Sample
Total Composition TCLP
Constituent (mg/1) (mg/1)
Nickel 0.47 Not Applicable
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2.0 INDUSTRY AFFECTED AND WASTE CHARACTERIZATION
The purpose of this section is to describe the industry affected by
the land disposal restrictions for K027, K111, K112, K113, K114, K115, K116,
U221, and U223 and to present available characterization data for these
wastes.
Wastes identified as K027, K111, K112, K113, K114, K115, K116, U221,
and U223 are specifically generated by dinitrotoluene (DNT), toluenediamine
(TDA), and toluene diisocyanate (TDI) manufacturing processes and are listed
in 40 CFR 261.32 and 261.33(f) as follows:
Waste Code Listed Waste
K027 Centrifuge and distillation residues from toluene
diisocyanate production
K111 Product washwaters from the production of dinitrotoluene
via nitration of toluene
K112 Reaction by-product water from the drying column in the
production of toluenediamine via hydrogenation of dinitro-
toluene
K113 Condensed liquid light ends from the production of
toluenediamine via hydrogenation of dinitrotoluene
K114 Vicinals1 from the purification of toluenediamine in the
production of toluenediamine via hydrogenation of dinitro-
toluene
1Vicinals are the ortho isomers of TDA. Ortho isomers are removed
before phosgenation of TDA to TDI to avoid the formation of methylbenzi-
midazolone which reduces the reaction yield.
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Waste Code Listed Waste
K115 Heavy ends from the purification of toluenediamine in the
production of toluenediamine via hydrogenation of dinitro-
toluene
K116 Organic condensate from the solvent recovery column in the
production of toluene diisocyanate via phosgenation of
toluenediamine
U221 Toluenediamine
U223 Toluene diisocyanate
2.1 Industry Affected and Process Description
The Agency estimates that there are eight domestic facilities that
produce dinitrotoluene (DNT), toluenediamine (TDA), and/or toluene diisocya-
nate (TDI). The majority of these facilities are located in the southern and
eastern sections of the United States. Table 2-1 lists the number of facili-
ties manufacturing each product, along with potential wastes generated, by
state and EPA region. A simplified flow diagram illustrating the manufactur-
ing processes generating dinitrotoluene, toluenediamine, and toluene diiso-
cyanate is presented in Figure 2-1. DNT and TDA are generally produced for
use in TDI manufacturing. Additionally, TDA may be produced for use in the
manufacture of dyes or other chemical products; however, the production level
of TDA for these purposes is believed to be quite low. Almost all of the TDI
produced is used to manufacture polyurethanes, including polyurethane foam
products, coatings, elastomers, and adhesives.
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Table 2-1
FACILITIES THAT MAY GENERATE K027, Kill, K112, K113,
K114, K115, AND/OR K116, BY STATE AND EPA REGION*
State (EPA Region)
Louisiana (VI)
New Jersey (II)
Texas (VI)
West Virginia (III)
Number of Facilities
DNT TDA TP I
1 3 3
1 0 0
Wastes Potentially
Generated
K027, K111, K112, K113,
K114, K115, K116
K111
2 2 2
1 1 1
K027, K111, K112, K113
K114, K115, K116
K027, K111, K112, K115,
K116
DNT = Dinitrotoluene
TDA = Toluenediamine
TDI = Toluene Diisocyanate
"Any facility generating TDA and TDI might also generate U221 and U223
wastes. See reference 21.
Source: Telephone Survey conducted in July 1988 by Radian Corporation,
Herndon, VA.
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Figure 2— 1.
Flow Diagram of Processes Generating the
K027, K1 1 1 - K116 Waste Codes
Phosgene
Solvent
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The manufacture of toluene diisocyanate (TDI) typically involves
three chemical processes: 1. Nitration of toluene to form dinitrotoluene
(DNT) 2. Hydrogenation of DNT to form toluenediamine (TDA), and 3. Phosgen-
ation of TDA to form toluene diisocyanate (TDI).
As shown in Figure 2-1, toluene is nitrated with nitric acid in the
presence of sulfuric acid, which acts as a solvent and a catalyst. The
two-phase product from the nitration reactor is separated into organic and
acid layers. Spent acid is then sent to a recovery unit, where the recovered
acid solution is recycled to the reactor. Water, a by-product of the nitra-
tion reaction, is separated in the acid recovery step and is used in the DNT
washing process following acid separation. The organic layer from the acid
separation step, which contains the desired product dinitrotoluene (DNT), is
purified through a two- or three-stage washing process. Washwaters from the
washing process form the listed waste K111.
The DNT product is dissolved in a solvent (typically methanol) and
is combined with a catalyst (either palladium on carbon or Raney nickel). The
mixture is then sent to a pressurized reactor where hydrogen is introduced.
The product from the hydrogenation reaction is sent to a catalyst recovery
unit, where the catalyst is recovered. The crude TDA product is then dis-
tilled through a series of columns. Solvent is removed from the solvent
recovery column and is completely recycled. By-product water resulting from
the hydrogenation of dinitrotoluene is removed in the TDA drying column. The
by-product water forms the listed waste K112. Light ends are removed from the
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light ends separation column and form the listed waste K113- Vicinals (the
ortho isomers of TDA) are removed from the vicinals separation column and form
the listed waste K114. In the final distillation step, heavy ends are removed
from the residue separation column and form the listed waste K115.
Following distillation, the purified TDA is dissolved in a solvent,
typically chlorobenzene or o-dichlorobenzene. The resulting mixture is then
sent to a series of reactors. Phosgene liquid is fed into the bottom of these
reactors, which are referred to as phosgenators. The crude TDI product from
the phosgenation reaction is then distilled through a series of columns.
Phosgene is recovered in the phosgene recovery column and recycled to the
phosgenators. Solvent is removed from the solvent recovery column and sent to
a separation column, where the organic liquid condensate (K116) and excess
phosgene are separated. The organic condensate from the solvent recovery step
forms the listed waste K116. Bottoms from the solvent recovery column are
sent to the residue separation column, where TDI residue is separated from the
overhead TDI product. The TDI residue forms the listed waste K027.
The wastes listed as U221 (TDA) and U223 (TDI) under Section 261.33
(a) and (d) of the Code of Federal Regulations (CFR) are those materials con-
taining TDA or TDI, intended for disposal, and which meet any of the listing
criteria of Section 261.3 CFR. The listing criteria involve a commercial
chemical product or manufacturing intermediate which is either reagent grade
of the chemical, technical grade, crude product, or a formulation in which the
listed chemical (i.e. TDA or TDI) is the sole active ingredient. Technical
2-6
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grade generally refers to the chemical in various stages of purification.
There are no exact criteria, such as percent purity, to define a technical
grade of a substance. Also included are off-specification products which, if
they met specification, would have the generic name included in 40 CFR 261.33.
Therefore, U221 and U223 may be generated from spills, leaks, or discard of
chemicals associated with the production of TDA and TDI or from the use of TDA
or TDI as an active or additive ingredient in manufacturing processes. To
determine if a material or substance that meets these criteria is subject to
regulation as a "U" waste, at least one of the following additional criteria
must characterize the material.' A "U" waste is either: discarded or intended
for discard; mixed with another material and applied to the land for dust
suppression; applied to the land in lieu of its original intended use;
remaining residue that will not be recycled, reclaimed or reused in an
original container or liner; used as a fuel additive in lieu of its original
purpose or; be contained in soil, water or debris resulting from cleanup of a
spill.
While the reaction of amines (TDA) with phosgene is the most common
method of manufacturing isocyanates, other processes exist that may produce a
TDA or TDI product or manufacturing intermediate. These manufacturing pro-
cesses may therefore also result in generation of U221 and/or U223 (e.g., an
off-spec batch containing TDA or TDI as an active ingredient which cannot be
used and must therefore be discarded). U221 and U223 generated by these other
processes are subject to the promulgated standards established for wastewater
and nonwastewater forms of U221 and U223. Examples of other methods for the
production of isocyanates are the Curtius, Hofman, and Lossen Rearrangements,
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Metathesis, preparation from isocyanate derivatives, and preparation from
isocyanic acid. Facilities that formulate other commercial products such as
urethane polymers, foam plastics, or fire retardant materials may also gener-
ate U221 and U223 if the unused pure commercial product or intermediate is
spilled or intended to be discarded and the TDA or TDI is the manufacturer's
commercial product or intermediate having as its sole active ingredient TDI or
TDA.
2.2 Waste Characterization
Table 2-2 presents a summary of the publicly available characteriza-
tion data for K027, Kill, K112, K113, K114, K115, and K116. Characterization
data are not available for U221 or U223. The summary in Table 2-2 was com-
piled from data in the Listing Background Document for DNT, TDA, and TDI
production, from data based on theoretical calculations, and from patent
information supported by unspecified industry data. All available data for
each waste code may be found in Appendix A - Confidential Business Information
(CBI) Waste Characterization Data. Data listed in this Appendix is located in
the confidential portion of the EPA RCRA docket for this rulemaking.
As shown in Table 2-2, K027 contains high levels of TDI and TDA and
up to 90% polymers and tar-like materials; K111 and K112 contain <1% organic
compounds; K113, K114, and K115 consist of organic waste streams that contain
high levels of TDA; and K116 contains high levels of chlorinated hydrocarbons,
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Table 2-2
SUMMARY OF PUBLICLY-AVAILABLE WASTE CHARACTERIZATION DATA
FOR WASTE CODES K027, K111, K112, K113, K114, K115, AND K116
Estimated Untreated Waste Concentration (%)a
Ma1or Constituents KQ27 Kill K112 K113 K114 K115 K116
ORGANIC CONSTITUENTS
BDAT List Constituents
7. Carbon tetra- — — — — — — 0-75
chloride
14. Chloroform — — — — — — 0-7
42. Tetrachloroethene — — — — — — 0-15
43. Toluene — — — — — — CBI
56. Aniline — — CBI 0.01-0.1 0-5
Non-BDAT List
Constituents
Toluenediisocyanate 0-50
Isocyanates 3
Dinitrotoluenes — 0-0.3b
Mononitrotoluenes — 0.0045
Dinitrocresols — 0.06
(mostly 2,6-
dinitro p-cresol)
Nitrophenols — 0.0035
Nitroaromatics — 0.0035
(nitrobenzoic acids
and nitrocresols)
2,4-TDA & 2,6-TDA 10-50e — 0.05-0.3 0-37.5 4.5-50 10-50
3,4-TDA & 2,3-TDA — — 0.05-0.3 0-37.5 40-95 0-2.5
o-Toluidine — — 0-0.06 0.6-6 0-3
p-Toluidine — — 0-0.04 0.4-4 0-2
Polymers & Tar-Like 90
Materials
Phosgene — — — — — — 0-30
Karathane 10-50
Methylcyclohexylamine — — CBI
Methylcyclohexanone — — CBI
= Data are not available for these constituents
CBI = Confidential Business Information
TDA = Toluenediamine
a Most of the data shown for K027 and K111-K116 represent
analysis for organics using capillary GC/MS Method 8270.
One facility reported analysis of K027 using "Total Amine
equivalent ASTM Method D-1638".
b Includes nitrophenolics.
c 2,4-TDA isomer only.
^ "Karathane" is the common name of the compound "Dinocap."
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Table 2-2 (Continued)
SUMMARY OF PUBLICLY-AVAILABLE WASTE CHARACTERIZATION DATA
FOR WASTE CODES K027, Kill, K112, K113, K114, K115, AND K116
Estimated Untreated Waste Concentration ($)a
Malor Constituents K027 Kill K112 K113 K114 K115 K116
INORGANIC CONSTITUENTS
Water
Ferric chloride
Inorganics
(H2SO4 + HNO3,
Sulfate + Nitrate
Salts)
Spent catalyst (Ni)
OTHER PARAMETERS
Ash content {%)
Specific gravity
Heating value
(Btu/lb)
= Data are not available for these constituents
CBI = Confidential Business Information
TDA = Toluenediamine
a Most of the data shown for K027 and K111-K116 represent
analysis for organics using capillary GC/MS Method 8270.
One facility reported analysis of K027 using "Total Amine
equivalent ASTM Method D-1638".
b Includes nitrophenolics.
c 2,4-TDA isomer only.
^ "Karathane" is the common name of the compound "Dinocap."
Source: USEPA. Listing Background Document for Dinitrotoluene. Toluene-
diamine and Toluene Diisocyanate Production. 1985. (10).
CBI
6
CBI
1-4
CBI
CBI
CBI
6
1.22
6020-9993
0-5
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including carbon" tetrachloride and chloroform. Additionally, based on manu-
facturing processes generating K027 and K111-K116, these wastes are expected
to contain very low concentrations of metals, if any, except K115, which may
contain 0-5% spent nickel catalyst. As shown in Table 2-2, K027 has a low ash
content of 6 percent. Waste codes K113-K116 are also expected to have low ash
contents based on the manufacturing processes generating these wastes.
2.3 Determination of Waste Treatability Groups
EPA's approach to regulating first-third wastes grouped the waste
codes into waste treatability groups that were addressed together in develop-
ing the BDAT land disposal restrictions. Where EPA believes that wastes
represented by different codes can be treated to similar concentrations using
identical technologies, the Agency has combined the codes into one treatabil-
ity group (53 FR 31145, August 17, 1988).
For waste codes K027, K111-K116, U221, and U223, a careful review of
waste generation data, waste management practices, and waste characterization
data was conducted to determine whether these waste codes could be combined
into one or more waste treatability groups. Based on this review, two waste
treatability groups have been determined: (1) the K027 and K113-K116, U221,
and U223 treatability group (K027 treatability group), and (2) the K111 and
K112 treatability group.
K027, K113-K116, U221, and U223, as generated, are usually nonwaste-
waters containing high concentrations of aromatic organo-nitrogen compounds.
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Specifically, the Agency believes that K027 and K113-K116 are expected to
contain high concentrations of TDA. In addition to the organo-nitrogen
compounds TDA and TDI, K116 is expected to contain high concentrations of
chlorinated hydrocarbons, such as carbon tetrachloride and phosgene. K027,
K113, K114, and K116 are expected to contain very low concentrations of
metals, if any. However, available data show that K115 may contain treatable
concentrations of nickel (up to approximately 5%). The Agency has information
showing that facilities generating K027 and K113-K116 usually either treat or
dispose of these wastes in the same unit or in similar units.
Although CPA lacks characterization data for U221 and U223, the
Agency believes that the major organic constituents that will be present in
these wastes are TDA in U221 and TDI in U223. Since TDI and TDA products are
generated from similar manufacturing processes, EPA believes that any impuri-
ties in the commercial products or off-specification products meeting the
listing criteria for U221 and U223 will consist of chemicals similar to those
typically shown or expected to be contained in K027, K115, and K116. As a
result, the Agency expects U221 and U223 to show treatment characteristics
similar to K113-K116 and K027. Based on these similarities, the Agency
believes that U221 and U223 are amenable to treatment by the same treatment
technologies that are applicable to K027 and K113-K116. In fact, available
literature (see Reference 27) and current industry practices indicate that
U221 and U223 are typically treated by the same processes treating the other
K027 treatability group wastes. Therefore, K027, K113-K116, U221, and U223
are considered to represent a single waste treatability group.
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K111 and K112 are generated by similar industries (production of
nitrated aromatic compounds) and similar processes. These two wastes, as
generated, are normally wastewaters containing low concentrations of organic
compounds (0-U). K111 and K112 are expected to contain very low concentra-
tions of metals, if any. K111 and K112 are often co-disposed or co-treated in
wastewater treatment systems. Therefore, based on a similarity in waste
generation, waste management practices, and waste characteristics, Kill and
K112 represent a separate, distinct waste treatability group.
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3.0 APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
In Section 2.0, the processes generating K027, K111 —K116, U221, and
U223 were described and characterization data were presented for the wastes.
In addition, two treatability groups were identified. This section identifies
the treatment technologies that are applicable for treatment of wastes in
these treatability groups and determines which of the applicable technologies
can be considered demonstrated for the purpose of establishing BDAT.
To be applicable, a technology must theoretically be usable to treat
the waste in question or a similar waste. To be demonstrated, the technology
must be employed in full-scale operation for the treatment of the waste in
question or of a similar waste. Technologies available only at research
facilities or at pilot- and bench-scale operations are not considered in
identifying demonstrated technologies.
3.1 Applicable Treatment Technologies
The following subsections present applicable treatment technologies
for (1) organic constituents in nonwastewater and wastewater forms of K027,
K113—K116, U221, and U223, (2) metal constituents in nonwastewater and waste-
water forms of K115, and (3) organic constituents in wastewater and nonwaste-
water forms of K111 and K112. For the purpose of the land disposal restric-
tions rule, wastewaters are defined as wastes containing less than (weight
basis) total suspended solids and less than 1f (weight basis) total organic
3-1
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carbon (TOC). Wastes not meeting this definition are classified as nonwaste-
waters.
3.1.1 K027. K113-K116. U221. and U223 Organics
Nonwastewaters
As generated, K027, K113-K116, U221, and U223 are generally non-
wastewaters containing high concentrations of aromatic organo-nitrogen com-
pounds. Applicable treatment technologies, therefore, include technologies
that destroy or reduce the total amount of various organic compounds in the
waste. The Agency has identified incineration, fuel substitution1, solvent
extraction followed by recovery or incineration of the contaminated solvent,
and recycle or reuse as potentially applicable for treatment of K027, K113-
K116, U221, and U223 nonwastewaters.
The Agency believes that incineration of K027, K113-K116, U221, and
U223 will generate low volumes, if any, of ash residue, since the ash content
of these wastes is typically low (less than 6% in the case of K027). Treat-
ment (such as filtration) of incineration/fuel substitution scrubber waters
may also result in a nonwastewater residual that may be classified as K027,
K113-K116, U221, or U223. Since organics are destroyed during incineration,
1Fuel substitutes should meet the criteria discussed in 48 FR
11157-11160.
3-2
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nonwastewater residues resulting from burning these listed wastes or those
generated from filtration of scrubber waters would contain low levels, if any,
of organic constituents. Therefore, additional treatment of these residuals
would not be required.
Wastewaters
Incineration of K027, K113-K116, U221, and U223 nonwastewaters may
result in the generation of scrubber water residuals that may be classified as
K027, K113-K116, U221, and U223 wastewaters. Since organics are destroyed
during incineration, these scrubber waters would contain low levels, if any,
of organic constituents. Therefore, additional treatment of these residuals
for hazardous organic constituents would not be required.
Other cases in which wastewater forms of K027, K113-K116, U221, and
U223 may be generated include wastewaters in which these codes are mixed with
other wastes, wastewaters from containment sumps for storm water or spills,
and wastewaters from wash stations for cleaning trucks or equipment. Additionally,
the Agency believes that RCRA corrective actions and CERCLA remediations may
result in the generation of wastewaters containing K027, K113-K116, U221, and
U223 (as either contaminated groundwater, surface water, or treatment resi-
due). These types of wastewaters are "derived from" K027, K113-K116, U221,
and U223 and are also subject to the land disposal restrictions. The Agency
has identified carbon adsorption followed by regeneration or incineration of
the spent carbon, incineration, solvent extraction, and biological treatment,
3-3
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as potentially applicable for treatment of hazardous organic constituents in
these wastewaters. These applicable technologies destroy or re-^ce the total
concentration of hazardous organic compounds in the waste (incineration and
biological treatment) or selectively remove hazardous organic compounds from
the waste stream (carbon adsorption and solvent extraction).
3.1.2 K115 Metals
Nonwastewaters
As generated, K115 is usually a nonwastewater and may contain 0-5/6
spent nickel catalyst. Incineration or fuel substitution of K115 nonwaste-
waters would be expected to generate small amounts of ash that may contain
concentrated levels of nickel (since nickel is not destroyed in the combustion
process). A nonwastewater residual may also be generated from treatment of
incineration/fuel substitution scrubber waters (e.g., spent filter cart-
ridges). The Agency has identified stabilization as a potentially applicable
technology for treatment of these K115 nonwastewater residuals.
Wastewaters
Incineration or fuel substitution of K115 nonwastewaters may result
in the generation of a scrubber water residual that may be classified as a
K115 wastewater. The residual may contain concentrated levels of nickel
(since nickel is not destroyed in the combustion process). The Agency has
3-4
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identified lime and sulfide precipitation followed by vacuum filtration as
potentially applicable for treatment of nickel in this K115 wastewater resi-
dual.
3.1.3 Kill and K112 Organics
Wastewaters
As generated, K111 and K112 are normally wastewaters containing low
concentrations of organic compounds (less than 1£) and very low concentrations
of metals. The Agency has identified biological treatment, carbon adsorption,
and solvent extraction as potentially applicable for treatment of the organic
constituents in these K111 and K112 wastewaters.
Monwastewaters
All of the treatment processes presented as potentially applicable
for organic constituents in K111 and K112 wastewaters generate nonwastewater
residuals (e.g., spent biomass, spent carbon, and solvent extract). The
Agency has identified fluidized-bed, multiple hearth, or rotary kiln incinera-
tion technologies as potentially applicable for treatment of these Kill and
K112 nonwastewaters.
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3.2 Demonstrated Treatment Technologies
The following subsections present demonstrated treatment technolo-
gies for (1) organic constituents in nonwastewater and wastewater forms of
K027, K113-K116, U221, and U223, (2) metal constituents in nonwastewater and
wastewater forms of K115, and (3) organic constituents in wastewater and
nonwastewater forms of K111 and K112.
3.2.1 K027. K113-K116, U221. and U223 Organlcs
Nonwastewaters
As stated in section 3.1.1, potentially applicable treatment tech-
nologies for K027, K113-K116, U221, and U223 nonwastewaters include incinera-
tion, fuel substitution, solvent extraction followed by recovery or incinera-
tion of the contaminated solvent, and recycle or reuse. The Agency has been
unable to identify any facilities using solvent extraction for treatment of
these nonwastewaters. One facility recycles K116 nonwastewaters but also
occasionally co-incinerates this waste with K027.
Several of the facilities that generate one or more of K027, K113-
K116, U221, and U223 incinerate them in liquid injection or fluidized-bed
incinerators or burn them in high-temperature boilers on a full-scale level.
The Agency is currently aware of three facilities that incinerate these wastes
(two on site and one off site) and of at least three facilities that treat
these wastes by fuel substitution in high-temperature boilers. (One facility
that incinerates K027 also treats one or more of K113-K116 by fuel
3-6
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substitution, and one facility treats K027 by fuel substitution.) Based on
this information, the Agency has determined that incineration and fuel substi-
tution are demonstrated treatment technologies for nonwastewater forms of
K027, K113-K116, U221, and U223.
Wastewaters
As stated in Section 3.1.1, potentially applicable treatment tech-
nologies for K027, K113-K116, U221, and U223 wastewaters include carbon
adsorption followed by regeneration or incineration of the spent carbon,
incineration, solvent extraction, and biological treatment. As discussed
previously, additional treatment of scrubber waters generated from incinera-
tion/fuel substitution is not required. However, other K027-, K113-K116-,
U221-, and U223-containing wastewaters may be generated that contain hazardous
organic constituents requiring treatment. While the Agency is not aware of
any specific facilities that treat wastewater forms of the K027 treatability
group, carbon adsorption, solvent extraction, and biological treatment are
demonstrated on a full-scale level for treatment of wastes that contain
organo-nitrogen compounds (e.g., K103 and K104 wastewaters). Therefore, the
Agency believes that since these technologies are demonstrated for treatment
of wastes containing similar organic constituents, these technologies are also
demonstrated for treatment of wastewater forms of the K027 treatability group.
In addition, industry comments indicate that there are facilities that from
time to time generate wastewaters contaminated with K027 group wastes and
these facilities stated further, that they often treat such wastewaters by
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incineration. Therefore, the Agency believes that incineration is also a
demonstrated treatment technology for K027, K113-K116, U221, and U223 waste-
waters.
3.2.2 K115 Metals
Nonwastewaters
The Agency is not aware of any facilities that treat nickel in K115
nonwastewater residuals using the applicable technology identified in Section
3.1.2. However, EPA has examined its BDAT treatment performance database and
determined that stabilization of nonwastewater residuals from incineration and
fuel substitution is demonstrated for a similar waste, F006 nonwastewaters.
The Agency also believes that none of the constituents present in K115 non-
wastewater residuals are likely to interfere with the treatability of nickel
because the requirement for thermally destroying organics in K115 will concen-
trate the concentration of nickel in treated residuals such as ash and incin-
erator scrubber water. Therefore, the Agency believes that stabilization is
demonstrated to treat nickel in K115 nonwastewater residuals.
Wastewaters
The Agency is not aware of any facilities that treat nickel in K115
wastewater. However, EPA has examined its BDAT treatment performance database
and determined that lime and sulfide precipitation followed by vacuum
3-8
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filtration of wastewaters is demonstrated for a similar waste, K062 and metal-
bearing characteristic wastes. The Agency also believes that none of the
constituents present in K115 scrubber waters are likely to interfere in the
treatability of nickel because the requirements for removing the organics in
K115 wastewaters will minimize the potential interferences of organics with
the treatment of nickel. Therefore, the Agency believes that lime and sulfide
precipitation followed by vacuum filtration is demonstrated to treat nickel in
K115 wastewaters.
3.2.3 K111 and K112 Organics
Wastewaters
As stated in Section 3.1.3, potentially applicable treatment tech-
nologies for K111 and K112 wastewaters include biological treatment, carbon
adsorption, and solvent extraction. The Agency has been unable to identify any
facilities that currently use solvent extraction to treat either K111 or K112
wastewaters. However, facilities have been identified that treat these wastes
by biological treatment or carbon adsorption on a full-scale level. Of the
several facilities that generate K111 and/or K112 wastewaters, three facili-
ties currently treat these wastes in biological treatment units, while three
facilities use carbon adsorption either alone or as a polishing step prior to
disposal. Therefore, the Agency has identified biological treatment and
carbon adsorption as the demonstrated treatment technologies for wastewater
forms of K111 and K112.
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Nonwastewaters
As stated in Section 3.1.3, potentially applicable treatment tech-
nologies for Kill and K112 nonwastewaters include fluidized-bed, multiple
hearth, or rotary kiln incineration. The Agency is aware of at least one
facility that currently treats the nonwastewater residuals derived from the
treatment of K111 and K112 by fluidized-bed incineration on a full-scale
level. Therefore, the Agency has determined that incineration is the demon-
strated treatment technology for nonwastewater forms of K111 and K112.
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4.0 TREATMENT PERFORMANCE DATABASE
This section presents the treatment performance data that EPA used
to develop BDAT treatment standards for K027, K113-K116, U221, and U223. As
discussed previously, the Agency does not have any treatment performance data
for the treatment of K027, K113-K116, U221, or U223. However, data are
available for treatment of similar wastes and are presented below. The
treatment performance data are used in this document to determine which
technologies represent BDAT (Section 5.0) and to develop BDAT treatment
standards (Section 7.0).
The Agency believes that nickel will be present in treatable concen-
trations in the wastewater and nonwastewater residuals of treated K115 because
metals are not treated by the technologies promulgated for organics in K115.
Therefore, treatment performance data were transferred from other previously
tested wastes to develop numerical treatment standards for nickel in K115
nonwastewaters and wastewaters. The basis for the data transfer and the
sources of treatment performance data are discussed below. For organic
constituents in K027, K113-K116, U221, and U223 nonwastewaters and waste-
waters, numerical treatment standards cannot be developed because EPA lacks
analytical methods that can satisfactorily analyze for the constituents of
concern in such complex waste matrices. As a result, EPA chose to specify a
method of treatment as the BDAT treatment standard for these wastes. To
determine whether the demonstrated technologies identified in Section 3.0
provide substantial treatment for the constituents of concern in K027,
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K113-K116, U221, and U223, performance data from treatment of other similar
wastes were examined. The data that were examined are presented in this
section.
Treatment performance data, to the extent that they are available to
EPA, include the concentrations of constituents in the untreated and treated
wastes, values of treatment technology operating parameters that were moni-
tored at the time the waste was being treated, values of relevant design
parameters for the treatment system, and data on waste characteristics that
affect performance of the treatment technology. A discussion of the methodol-
ogy used to identify treated wastes from which treatment performance data are
being transferred is included in Appendix B of this document.
Table U-1 presents data on waste characteristics that affect perfor-
mance of the demonstrated treatment technologies, incineration and fuel
substitution, for organic constituents in waste codes K027, and K113-K116,
(all tables are presented at the end of this section). Available treatment
performance data and data for waste characteristics that affect performance of
incineration for waste codes K015, K086, and F024 are presented in Tables 4-2
through 4-4, respectively. Table 4-5 summarizes the operating data that
correspond to the information presented in Tables 4-1 through 4-4.
Table 4-6 presents available treatment performance data and operat-
ing data for carbon adsorption treatment of K103 and K104 wastewaters.
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The Agency does not have treatment performance data for biological
treatment or incineration of wastewaters that are similar to K027, K113-K116,
U221, or U223 wastewaters.
Sources of treatment performance data that demonstrate treatment of
nickel, for potential transfer to K115, include those wastes previously tested
by stabilization (for nonwastewaters) and by lime and sulfide precipitation
followed by vacuum filtration (for wastewaters). EPA presented data for
stabilization of metals in nonwastewaters in the California List Notice of
Data Availability (52 FR 29992, August 12, 1987). EPA screened these data to
determine whether any wastes were generated from similar industries or had
similar processing steps or similar waste characteristics as those for ash
generated from the incineration of K115.
The Agency has determined that stabilization of wastewater treatment
sludge from electroplating operations, F006, is the best source of data for
transfer to K115 nonwastewaters (nickel treatment). The F006 stabilization
data were chosen since (1) this waste represents a sludge containing high
concentrations of nickel, similar to the nickel concentrations (in the percent
range) of untreated K115 when compared to other wastes treated by metal
stabilization, (2) the numerical standard for nickel in F006 is more
conservative than the standard for nickel in other waste codes treated by
stabilization (i.e., K062 and metal-bearing characteristic wastes), and (3)
the Agency has determined in the past that transfer of data from a sludge to
4-3
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an ash is technically feasible. In addition, constituents present in K115
nonwastewater-treated residuals are not expected to interfere with the
treatment of nickel in K115. Treatment performance data for stabilization of
F006 are presented in Table 4-7.
EPA's database for chemical precipitation treatment of wastewaters
is included in the California List Notice of Data Availability (52 FR 29992,
August 12, 1987). EPA screened these data to determine whether any wastes
were generated from similar industries, had similar processing steps, or had
similar waste characteristics as those expected for scrubber water generated
from the incineration of K115. Data are available for chemical precipitation
and vacuum filtration of K062 and metal-bearing characteristic wastes. The
K062 and metal-bearing characteristic wastes and K115 scrubber water are both
wastewaters and are expected to contain similar concentrations of nickel.
EPA then examined the relative treatability of K115 scrubber water
and K062 and metal-bearing characteristic wastes. Waste characteristics that
affect treatment performance for chemical precipitation include the concentra-
tions and types of metals in the waste, the concentrations of dissolved
solids, the content of oil and grease, and whether the metal exists in the
wastewater as a complex. Both wastes are expected to contain the constituent
of concern, i.e., nickel. Suspended solids, dissolved solids, and complexed
metals are not considered to be significant parameters in either waste. Since
K115 scrubber waters are generated from incineration, the presence of oil and
grease are not considered to be significant. However, K062 and metal-bearing
4-4
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characteristic wastewaters contain oil and grease and may therefore be more
difficult to treat than K115 scrubber water. In addition, the Agency does not
expect any of the constituents present in K115 wastewater treated by carbon
adsorption or incineration to interfere with the treatment of nickel in K115.
Based on this analysis, transfer of nickel treatment performance
data from K062 and metal-bearing characteristic wastes to K115 wastewaters is
valid. Treatment performance data for lime and sulfide precipitation followed
by vacuum filtration of K062 and metal-bearing characteristic wastes are
presented in Table 4-8.
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Table 4-1
WASTE CHARACTERIZATION DATA FOR K027, K113-K116
Waste Characteristics Affecting the
Performance of Incineration or Fuel Substitution
Constituents in
Untreated Wastes
K027
TDI
Polymerized TDI
2,4-TDA
Karathane
K113-K115
2,4- & 2,6-TDA
2,3- 4 3,4-TDA
o- p-Toluidinec
Aniline0
K116
Concentration in
Untreated Waste3
(ppm)
0-500,000
900,000
100,000-500,000
100,000-500,000
0-500,000
0-950,000
0-100,000
100-50,000
Boiling Point
(°C)
134
NA
283-285
138-140
283-285
283-285
200-202
184-186
Bond
Dissociation
Energy
(kcal/mole)
2,350
NA
1,940
4,911
1,940J
1,940°
2,480"
1,495
Phosgene
Carbon tetrachloride
Chloroform
Tetrachloroethene
0-300,000
0-750,000
0-70,000
0-150,000
8.2
76.7-77
61-62
121
335
320
340
465
U221
TDA
NA
283-285
1,940
U22-
TDI
NA
283-285
2,350
NA = Not available
TDA = Toluenediamine
TDI = Toluene diisocyante
a = From Table 2-2, Section 2.0
c = Constituent in K113 and K114 only
b = Bond dissociation energy for each isomer
Sources: References (22), (23), (24), (25), and (26).
4-6
-------
Table 4-2
TREATMENT PERFORMANCE DATA FOR K015: LIQUID
INJECTION INCINERATION
Bond
Boiling
Dissociation
Regulated
Concentration (ppb)a
Point
Energy
Constituent
Untreated Scrubber Water°
(°C)
(kcal/mole)
Anthracene
<5,000 <50-210
242
2,900
Benzal Chloride
910,000-1,100,000 <50-94
205
1,600
Benzo(b and/or k)
<5,000 <50-96
NA
3,990
fluoranthene
Phenanthrene
<5,000 <50-58
340
2,900
Toluene
<10 15-59
110.6-111
1,620
a = The operating ranges for the liquid injection incinerator and scrubbing
system during the performance test are summarized in Table 4-5.
b = Values have not been adjusted for analytical precision and accuracy.
Source: U.S. EPA, Proposed Best Demonstrated Available Technology (BDAT)
Background Document for K015, Volume 1, EPA/530-SW-88-0009-a. (13)
4-7
-------
Table 4-3
TREATMENT PERFORMANCE DATA FOR K086: ROTARY
KILN INCINERATION
Bond
Concentration
Boiling
Dissociatioi
Regulated
in
Waste (DPm)a
Point
Energy
Constituent
Untreated
Scrubber Water^
(°C)
(kcal/mole)
Acetone
CBI
<0.005
56.5
945
Bis(2-ethylhexyl)
CBI
<0.010
385
6,565
phthalate
n-Butyl alcohol
+
—
117-118
1,635
Cyclohexanone
CBI
<0.005
155.6
1,685
1,2-Dichlorobenzene
+
—
180.5-181
1,325
Ethyl acetate
««
—
77
1,305
Ethyl benzene
CBI
<0.005
136.3
1,905
Methanol
+
--
64.7
495
Methylene chloride
CBI
<0.005-<0.010
39.75
360
Methyl ethyl ketone
+
—
79.6
1,230
Methyl isobutyl ketone
CBI
—
117-118
1,800
Naphthalene
CBI
<0.010
217.9-218
2,120
Nitrobenzene
+
--
210-211
933
Toluene
CBI
<0.005-<0.010
110.6-111
1,620
1,1,1-Trichloroethane
+
—
74-74.1
625
Trichloroethylene
+
—
86.7-87
485
CBI = Confidential Business Information
+ = Concentration unknown. This constituent was regulated because EPA
believes it to be present in the untreated waste.
— = Treated waste concentration not available.
** = Untreated waste concentration not available,
a = The operating ranges for the rotary kiln incinerator during the
performance test are summarized in Table 4-5.
b = Values have not been adjusted for analytical precision and accuracy.
Source: U.S. EPA, Proposed Best Demonstrated Available Technology (BDAT)
Background Document for K086, Volume 15, Non CBI Version,
EPA/530-SW-88-0009-n.(15)
Footnote: Although a rotary kiln incinerator was used to treat the K086
(solvent wash), the data effectively represents liquid injection
because the waste was fed through the liquid injection nozzle on
the rotary kiln.
4-8
-------
Table 14-4
TREATMENT PERFORMANCE DATA FOR F021: ROTARY
KILN INCINERATION
Concentration in Waste (ppm)a
Boiling
Regulated
Untreated
Scrubber
Point
Constituent
Waste
Ash
Water
<°C)
2-Chloro-1,3-
<0.5-<200,000
0.10
0.101
59.1
butadiene
3-Chloropropene
<0.5-285,186
0. 10
0.101
11-15
1,1-Dichloroethane
<0.25-<10,000
<0.005
<0.005
57-57.3
1,2-Dichloro-
<0.25-26,068
0.005
0.005
83-81
ethane
1,2-Dichloro-
<0.025-230,000
0.005
0.005
96.1
propane
cls-1,3-Di-
<0.025-160,000
0.005
0.005
108
chloropropene
trans-1,3-
<0.025-290,000
0.005
0.005
112
Dichloropro-
pene
0.58-<196
0.632-0.666
Bis(2-ethylhexyl)
<0.012-0.011
385
phthalate
<0.010l-<0.0121
385
Di-n-octyl phthalate
<0.351
<0.333-<0.351
Hexachloroethane
<0.351-<196
0.632-0.666
0.012-0.011
186.8-18*;
Pentachlorobenzene
<1.76-<915
1.6x10"'-0.01
< 1.67—<1.79
<0.052-<0.06l
275-277
Tetrachloro-
0.00003
0.00001
100-500
dibenzofurans
2.0x10~7-0.03
Pentachloro-
0.00003
0.0001
100-500
dibenzofurans
Pentachloro-
5.0x10*'-0.002
0.00001
0.00001
100-500
dibenzo-p-
dioxins
2.7x10*7-0.05
Hexachloro-
0.00001
0.0003
100-500
dibenzofurans
rj
Hexachloro-
5.3x10"'-0.01
0.0001
0.00001
100-500
dibenzo-p-
dioxins
a = The operating ranges for the rotary kiln incinerator during the performance
are summarized in Table 1-5.
Bond Diss-
ociation
Energy
(kcal/mole)
955
810
615
615
930
790
790
6,165
6,565
565
1,310
1,000
980
2,190
960
2,170
test
Source: U.S. EPA, Proposed Best Demonstrated and Available (BDAT) Background Document for F021.(12)
-------
Table 1-5
SUMMARY OF OPERATING DATA
FOR INCINERATION OF K015, K086, F021, AND K027
Waste Code:
Type of Incinerators:
OPERATING PARAMETERS
Incineration Chamber
Temperature (UF)
Feed Rate (lb./min.)
Residence Time (sec.)
Afterburner Chamber
Temperature (UF)
Excess oxygen (%)
Carbon monoxide (ppm)
Off-Gas Scrubber
Flow rate (gal./min.)
Pressure drop (in. of
H20)
K027
Liquid
Injection
{*1
2,000-2,300
83.3«
1.7
NA
10-12
75-150
NA
NA
K027
Fluidized-Bed
ihl
1585.1-1752.8f
18.3-30.0
NA
NA
7.19-12.21
28-255
11-18-1
NA
K015
Liquid
Injection
(c)
1,780-2,077
1.11-6.22
NA
NA
3.17-5.771
0-6111
17.11
38-11
KO86
Rotary Kiln
(d)
1,880-2,053
NA
0.2h
2,032-2,056
5.0-6.2
3.7-5.0
NA
NA
F021
Rotary Kiln
(e)
1,207-1,601
NA
0.1-0.58h
1,877-2,112
5-15
1-70
NA
NA
(a) Source: Reference 17.
(b) Source: Reference 18.
(c) Source: Reference 13.
(d) Source: Reference 15.
(e) Source: Reference 12.
(f) = This number represents the temperature range measured in the free board area of the fluidized bed
incinerator
(g) = This number was calculated using a heating value of 10,000 Btu/lb.
(h) = This number represents the rotational speed of the rotary kiln incinerator in rotations per minute, a
surrogate measure of residence time.
(i) = The liquid injection incinerator consists of a single chamber. These parameters were measured in that
chamber.
(J) = Make-up flow rate.
NA = Not Available
-------
Table 4-6
TREATMENT PERFORMANCE DATA FOR K103 AND K104:
CARBON ADSORPTION STEP
REGULATED CONSTITUENT
Aniline
Benzene
2,4-Dinitrophenol
Nitrobenzene
Phenol
Cyanides (Total)
K103 and K104
Concentration (ppm)
Untreated
<1.5-<3.0
<0.005-0.008
16-57
<3.0-4.5
< 1.5—<3 - 0
1.7-4.77
Treated5
<0.03-4.20
<0.005-0.42
0.23-0.38
<0.03-0.15
<0.03-0.15
0.129-0.597
K103 and K104
OPERATING PARAMETERS
Feed Rate to the System
(lbs/hr)
Feed pH to the System
(standard pH units)
Feed Temperature to
the System (°C)
Total Organic Carbon in
Treated Waste (mg/1)
Calculated Residence Time
(minutes)
Design
Value
65,300 (max)
7.0 (min)
40
250 (max)
85 (min)
Operating
Range
52,200-76,000
3.1-10.6
25-44
7-79.3
73-107
a = Values have not been adjusted for analytical precision and accuracy.
Source: U.S. EPA, Proposed Best Demonstrated Available Technology (BDAT)
Background Document for Aniline Production Treatability Group
(K103, K104), Volume 7, EPA/530-SW-88-0009-g.(16)
4-11
-------
Table 4-7
TREATMENT PERFORMANCE DATA FOR NICKEL TRANSFERRED
FROM STABILIZATION OF F006 NONWASTEWATER
Untreated Waste
Concentration
Treated Wastea
Concentration
Total
(msc/kd)
TCLP
(mR/1)
TCLP
(mR/1)
435
0.71
0.05
989
22.7
0.03
259
1.1
0.27
37
0.52
0.02
701
9.78
0.04
19,400
730
<0.06
13,000
152
0.11
23,700
644
0.04
5,730
16.1
0.02
a = Values have been adjusted for analytical precision and accuracy.
Source: U.S. EPA, Proposed Best Demonstrated Available
Technology (BOAT) Background Document for F006,
Volume 13, EPA/530-SW-88-0009-1. (11)
4-12
-------
Table 4-8
TREATMENT PERFORMANCE DATA FOR NICKEL TRANSFERRED FROM LIME
AND SULFIDE PRECIPITATION FOLLOWED BY VACUUM FILTRATION
OF K062 AND METAL-BEARING CHARACTERISTIC WASTEWATER
Untreated K062
Waste Concentration
(PPrc)
669
712
382
Treated K062
Wastewater3
(PP")
0.36
0.33
0.39
a = Values have not been corrected for analytical precision and accuracy.
Source: U.S. EPA, Final Best Demonstrated Available Technology
(BDAT) Background Document for K062. August 1988. (14)
4-13
-------
5.0
IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BDAT)
This section presents the Agency's rationale for determining best
demonstrated available technology (BDAT) for K027, K113, K114, K115, K116,
U221, and U223 nonwastewaters and wastewaters. The Agency's rationale for
addressing the K111 and K112 treatability group at a later date is also
presented in this section. BDAT is specified for all streams associated with
the management of the listed wastes (this pertains to the original waste as
well as to any residual waste streams generated by the treatment process).
The Agency determines BDAT based on a review of the available
treatment performance data. If data are available for only one treatment
technology for a waste, then that technology is "best." If data are available
for more than one technology, the data are examined to determine whether one
or more of the technologies performs significantly better than the others.
All treatment performance data used to determine whether a technology performs
significantly better is first corrected for accuracy, as discussed in EPA's
Methodology for Developing BDAT Treatment Standards (18).
The technology that performs best on a particular waste or waste
treatability group is then evaluated to determine whether it is "available."
To be available, the technology must (1) be commercially available, and (2)
provide "substantial" treatment of the waste, as determined through an evalua-
tion of treatment performance data. To determine whether treatment is sub-
stantial, EPA may consider data on a treatment technology's performance on a
5-1
-------
waste similar to the waste in question, provided that the similar waste is at
least as difficult to treat. If it is determined that the best technology is
not available, then the next best technology is evaluated, and so on.
The determination of BDAT for organics in K027, K113-K116, U221, and
U223 is discussed in Section 5.1 for nonwastewaters and in Section 5.2 for
wastewaters. The determination of BDAT for nickel in nonwastewater and
wastewater forms of K115 is presented in Section 5.3. A summary of BDAT for
the K027 treatability group is provided in Section 5.4. The Agency's ration-
ale for addressing the Kill and K112 treatability group at a later date is
presented in Section 5.5.
5.1 Determination of BDAT for K027. K113-K116. U221. and U223 Nonwaste-
water Organics
5.1.1 Identification of BDAT
As discussed in Section 3.2.1, incineration and fuel substitution
are demonstrated technologies for treating organics in nonwastewater forms of
K027, K113-K116, U221, and U223. The Agency has been unable to identify any
other demonstrated technologies for these wastes; therefore, incineration and
fuel substitution are the "best" technologies for treatment of organics in
K027, K113-K116, U221, and U223 nonwastewaters.
5-2
-------
The Agency evaluated these technologies to determine whether they
met the two criteria identified above and could therefore be considered
"available" for these wastes. The first criterion was satisfied since incin-
eration and fuel substitution are commercially available technologies. The
Agency then evaluated available treatment performance data to determine
whether incineration and fuel substitution provide substantial treatment of
the hazardous organic constituents in K027, K113-K116, U221, and U223. As
described below and in Appendix B, incineration and fuel substitution do
provide substantial treatment for these wastes and therefore, are available
technologies. The Agency has thus determined that incineration and fuel
substitution are BDAT for organics in K027, K113-K116, U221, and U223 non-
wastewaters.
5.1.2 Evaluation of Substantial Treatment by Incineration and Fuel Substi-
tution
The procedure described in this section and more fully described in
Appendix B was used to show that incineration and fuel substitution provide
substantial treatment for hazardous organic constituents in K027, K113-K116,
U221, and U223. This procedure was used to establish treatment standards as
specific technologies rather than concentration-based numerical standards
because (1) no analytical methods are available that can satisfactorily
analyze for the constituents of concern in these wastes, and (2) surrogate
constituents to measure performance have not been identified for the hazardous
constituents in these wastes.
5-3
-------
Figure 5-1 presents a flowchart illustrating the procedure used to
show that incineration and fuel substitution provide substantial treatment for
constituents of concern in K027, K113-K116, U221, and U223 nonwastewaters.
This procedure is consistent with EPA's methodology for transfer of treatment
data from a tested waste to an untested waste to establish treatment standards
as concentration-based performance levels. Each step shown in Figure 5-1 is
described in Appendix B. The results of these steps for K027, K113-K116,
U221, and U223 are discussed briefly below.
Step 1: Available waste characterization data for K027, K113-K116,
U221, and U223 were examined to identify "major" constituents of concern.
"Major" constituents of concern include but are not limited to those constitu-
ents listed in 40 CFR Part 261 Appendix VII and/or VIII at treatable concen-
trations. For a constituent to be considered at a treatable concentration, it
should be shown or believed to be in the waste, should be highly toxic (e.g.,
dioxins and furans may be present at low concentrations but are still of
concern due to their high toxicity), be present in the waste at high concen-
trations, or is relatively difficult to incinerate (e.g., high boiling points
and high bond dissociation energies) than other constituents in the waste.
The major constituents of concern for K027 and K113—K116 are shown in Table
4-1. Waste characterization data are not available for U221 and U223; how-
ever, these wastes are expected to contain constituents similar to or identi-
cal to those listed for K027 and K113—K116 and the major constituents of
concern for these wastes are transferred from the listing background document
information.
5-4
-------
* Note that regulated constituents are, by definition, substantially
treated by the BOAT treatment technology. Substantial treatment Is
demonstrated by comparing constituent concentrations in the
untreated waste with corresponding concentrations in the treatment
residuals.
Figure 5—1. Flow Chart Illustrating the Procedure Used to Show
Substantial Treatment by Incineration or Fuel Substitution
5-5
-------
Step 2: The BDAT treatment performance database was examined to
identify all waste codes previously tested by incineration or fuel substitu-
tion. The database included only those tests for which the treatment system
was well-designed and well-operated during the treatment test and for which
substantial treatment of hazardous organic constituents was demonstrated.
Step 3: The tested wastes that were identified in Step 2 were
"screened" to identify waste codes that were similar to K027, K113-K116, U221,
and U223 or that contain constituents more difficult to treat than those in
the untested wastes. Specifically, tested wastes were identified that:
o Were generated from similar industries or similar processes
and/or had similar waste characteristics as K027, K113-K116,
U221, and U223;
o Had similar or lower thermal conductivities than K027, K113-
K116, U221, and U223; and
o Contained regulated BDAT List constituents that were equally or
more difficult to incinerate than the constituents of concern
in K027, K113-K116, U221, and U223.
The specific tested wastes that met these criteria are K015, K086, and F024.
EPA's BDAT methodology for determining the relative incinerability
of a waste includes a comparison of the thermal conductivities of the untested
waste with the thermal conductivities of other wastes that have been treatment
tested by incinerators or fuel substitution units. EPA's approach is based on
the belief that the lower the thermal conductivity of a waste, the harder it
is to transfer heat to a constituent in the waste and thus to volatilize and
destroy the constituent.
5-6
-------
The degree of difficulty of incineration of a particular constituent
is based on the boiling point and bond dissociation energy (BDE) of the
constituent. The boiling point represents the degree of difficulty associated
with volatilization. The lower the boiling point, the easier it is to vola-
tilize the constituent in the incinerator or fuel substitution unit. Once
volatilized, a constituent is destroyed by combustion. EPA believes that the
energy required to destroy constituents can be assessed through a comparison
of each constituent's BDE. Constituents with higher BDE's are more difficult
to destroy than are those with lower BDE's. A detailed discussion of EPA's
BDAT methodology for determining the relative incinerability of a waste and
specific waste constituents is included in the Treatment Technology Background
Document (19)•
Step 4: Specific constituents that were regulated in the wastes
identified in Step 3 that had higher boiling points and bond dissociation
energies (and were therefore more difficult to treat) than the constituents of
concern in K027, K113-K116, U221, and U223 were identified for each of the
tested waste codes. The constituents of concern in K027, K113-K116, U221, and
U223 and the corresponding constituents in tested wastes that are more diffi-
cult to treat are listed in Table 5-1.
Constituents that have been regulated in the tested codes are
substantially treated by incineration, since substantial treatment was a
requirement for determination of incineration as BDAT for those wastes.
Constituents are considered to be substantially treated if constituent
5-7
-------
Table 5-1
COMPARISON OF CONSTITUENTS IN K015, K086, AND F024 THAT ARE MORE DIFFICULT
TO TREAT THAN THE CONSTITUENTS OF CONCERN IN K027, K113-K116, U221, AND U223
Constituents of Concern in
K027. K113-K116. U221. and U223
Boiling BDE
Constituent Point,°C kcal/mole
1. TDI
134
2. TDA
283-285
2,350
1,940
Constituents in K015, K086, and F024
That are More Difficult to Treata
Boiling
BDE
Constituent
Point,°C
kcal/mole
Anthracene
242
2,900
Phenanthrene
340
2,900
Benzo(b and/or k)
NA
4,030
fluoranthene
Bis(2-ethylhexyl)
385
6,465
phthalate
Di-n-octyl phthalate
385
6,565
Pentachlorodibenzo-
400-500
2,490
p-dioxin
Phenanthrene
340
2,900
Benzo(b and/or k)
NA
4,030
fluoranthene
Bis(2-ethylhexyl)
385
6,465
phthalate
Di-n-octyl phthalate
385
6,565
Pentachlorod ibenzo-
400-500
2,490
p-dioxin
Hexachlorodibenzo-
400-500
2,470
NA = Not available.
BDE = Bond dissociation energy.
TDA = Toluenediamine
TDI = Toluene Diisocyanate
a = The listed constituents are more difficult to treat because they have
higher boiling points and higher bond dissociation energies than the
constituents of concern in K027, K113-K116, U221, and U223. The listed
constituents are substantially treated by incineration and/or fuel
substitution.
5-8
-------
Table 5-1 (Continued)
COMPARISON OF CONSTITUENTS IN K015, K086, AND F024 THAT ARE MORE DIFFICULT
TO TREAT THAN THE CONSTITUENTS OF CONCERN IN K027, K113-K116, U221, AND U223
Constituents of Concern in Constituents in K015, K086, and F024
K027. K113-K116. U221, and U223 That are More Difficult to Treata
Boiling
BDE
Boiling
BDE
Constituent
Point,°C
kcal/mole
Constituent
Point,°C
kcal/mole
3. o- and
200-202
2,480
Anthracene
242
2,900
P-
Phenanthrene
340
2,900
Toluidine
Benzo(b and/or k)
NA
4,030
fluoranthene
Bis(2-ethylhexyl)
385
6,465
phthalate
Di-n-octyl phthalate
385
6,565
Pentachlorodibenzo-
400-500
2,490
p-dioxin
4. Kara-
138-140
4,911
Bis(2-ethylhexyl)
385
6,465
thane
phthalate
Di-n-octyl phthalate
385
6,565
NA = Not available
BDE = Bond dissociation energy.
TDA = Toluenediamine
TDI = Toluene Diisocyanate
a = The listed constituents are more difficult to treat because they have
higher boiling points and higher bond dissociation energies than the
constituents of concern in K027, K113-K116, U221, and U223. The listed
constituents are substantially treated by incineration and/or fuel
substitution.
5-9
-------
concentrations in the untreated waste are significantly higher than corre-
sponding concentrations in the treatment residuals. If incineration or fuel
substitution has been shown to provide substantial treatment in a tested waste
for a constituent that is equally or more difficult to treat than a constitu-
ent in an untested waste (with respect to thermal conductivity, boiling
points, and bond dissociation energies, as described above), then these
technologies will also provide substantial treatment of the constituent of
concern in the untested waste. EPA also believes that destruction of hazard-
ous organic constituents in a waste is similar whether it occurs in an incin-
erator, high-temperature boiler, or industrial furnace providing that these
treatment technologies are well designed and well operated.
Step 5: As shown in Table 5-1, EPA identified several constituents
that were regulated in previously tested waste codes that are more difficult
to treat than the constituents of concern in K027, K113-K116, U221, and U223.
Therefore, based on the above analyses, EPA believes that incineration and
fuel substitution provide substantial treatment of major constituents of
concern in K027, K113-K116, U221, and U223, since it was shown in Step 4 that
these treatment technologies provided substantial treatment for constituents
that were more difficult to treat in similar wastes.
Step 6: In Table 4-5, design and operating data for incineration
and/or fuel substitution systems currently treating K027, K113—K116, U221,
and/or U223 were compared to design and operating data for treatment systems
from the BDAT performance database for the waste codes selected in Step 3. As
5-10
-------
shown in the table, the operating ranges for BDAT incineration units (liquid
injection for K015, rotary kiln for K086 and F024) on tested waste codes are
similar to the operating ranges for the liquid injection and fluidized-bed
incineration units treating K027. EPA believes that the similarities in
design and operation of incinerators and fuel substitution units treating
these wastes provides additional support for the conclusion that incineration
and/or fuel substitution provide substantial treatment for K027, K113—K116,
U221, and U223 nonwastewaters and therefore are appropriate as BDAT for these
wastes.
5.2 Determination of BDAT for K027, K113-K116, U221, and U223 Wastewater
Organics
5.2.1 Identification of BDAT
As discussed in Section 3.2.1, carbon adsorption, incineration,
solvent extraction, and biological treatment have been identified by the
Agency as demonstrated treatment technologies for treating organics in waste-
waters similar to K027, K113-K116, U221, and U223. Treatment performance data
are available on carbon adsorption for the waste codes K103 and K104. These
wastewaters contain cyclic organo-nitrogen compounds at concentrations similar
to those expected for K027, K113-K116, U221, and U223 wastewaters. As out-
lined in Section 5.1.2, the Agency also has treatment performance data for
incineration of nonwastewaters that contain constituents harder to incinerate
than the constituents of concern in K027, K113-K116, U221, and U223.
5-11
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Treatment performance data on solvent extraction of K103 and K104 wastewaters
represents treatment of wastewaters containing high concentrations of organo-
nitrogen compounds. However, since the organo-nitrogen compound concentra-
tions for K103 and K104 are significantly higher than the organo-nitrogen
compound concentrations expected in K027 treatability group wastewaters, the
Agency does not believe these data can be used to evaluate treatment of K027,
K113-K116, U221, and U223 by solvent extraction. The Agency also does not
have treatment performance data for biological treatment that can be used to
evaluate treatment of K027 treatability group wastes. Therefore, carbon
adsorption and incineration are the "best" technologies for treatment of
organics in K027, K113-K116, U221, and U223 wastewaters.
The Agency evaluated the carbon adsorption and incineration technol-
ogies to determine whether they met the two criteria identified above and
could therefore be considered "available" for these wastes. The first crite-
rion was satisfied since carbon adsorption and incineration are commercially
available technologies. The Agency then evaluated available treatment perfor-
mance data to determine whether carbon adsorption and incineration provide
substantial treatment of the hazardous organic constituents in K027, K113—
K116, U221, and U223. As described in Section 5.1.2 and Appendix B, incinera-
tion shows substantial treatment of constituents harder to treat than the
constituents of concern in the K027 treatability group. Carbon adsorption
will also provide substantial treatment for these wastes and substantial
treatment by this technology is discussed below in Section 5.2.2. Therefore,
both carbon adsorption and incineration are available technologies. The
5-12
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Agency has thus determined that carbon adsorption and incineration are BDAT
for organics in K027, K113-K116, U221, and U223 wastewaters.
5.2.2 Evaluation of Substantial Treatment by Carbon Adsorption
The information discussed in this section and in Appendix C was used
to show that carbon adsorption provides substantial treatment for hazardous
organic constituents in K027, K113-K116, U221, and U223 wastewaters. This is
necessary because (1) no analytical methods are available that can satisfacto-
rily analyze for the constituents of concern in K027 treatability group, and
(2) surrogate constituents to measure performance have not been identified for
the hazardous constituents in these wastes.
The Agency evaluated carbon adsorption for substantial treatment by
examining the treatment of similar wastes (K103 and K104) by this treatment
technology and by evaluating the ability of carbon adsorption to absorb
organic constituents similar to those expected in K027, K113-K116, U221, and
U223 wastewaters.
The available data for carbon adsorption on wastes similar to K027
treatability group wastes are presented in Table 4-6. The data for K103 and
K104 show substantial treatment of wastewaters containing cyclic organo-
nitrogen compounds at concentrations similar to those expected for K027,
K113-K116, U221, and U223 wastewaters. Hazardous organic constituents that
are expected to be present in K027 treatability group wastewaters are toluene
5-13
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diisocyanates, toluenediamines, karathane, aniline, tetrachloroethene, chloro-
form, carbon tetrachloride, o- and p-toluidine, and phosgene. The treatment
performance data available for K103 and K104 do not include treatment of any
of these constituents; however, since carbon adsorption provides substantial
treatment for other organo-nitrogen compounds, the Agency believes that the
technology will also provide substantial treatment for the organo-nitrogen
compounds expected to be present in K027, K113—K116, U221, and U223 waste-
waters .
In addition, carbon adsorption is a commercially available waste-
water treatment technology that is commonly used for the removal of organic
constituents. Appendix C provides additional information on the ability of
carbon absorption to provide substantial treatment for organics in wastewater.
Furthermore, the large molecular size, and the complex, branched ring struc-
ture of the constituents in K027, K113-K116, U221, and U223 makes them amena-
ble to removal by adsorption on activated carbon. The Agency therefore
believes that a properly designed and operated carbon adsorption unit treating
K027 group wastes will provide substantial treatment; therefore, carbon
adsorption is appropriate as BDAT for these wastes.
5.3 Determination of BDAT for Nickel in K115
Treatment performance data for nickel are transferred from F006 and
K062 and metal-bearing characteristic wastes determined by the Agency to be
similar to the range of nickel concentrations in untreated nonwastewater and
5-14
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wastewater forms of K115 respectively. The treatment performance data are
presented in Tables 4-7 and 4-8. As discussed in the background documents for
F006 and K062, these treatment performance data were reviewed and assessed to
determine whether they represented operation of a well-designed and
well-operated system, whether sufficient quality assurance/quality control
measures were employed to ensure that the detected effluent concentrations
were adjusted for analytical precision and accuracy, and whether the appropri-
ate measures of performance were used to assess the performance of the treat-
ment technologies.
Since the Agency does not have data for any other technologies for
treatment of nickel in nonwastewaters and wastewaters that are similar to
K115, the Agency has determined that stabilization and lime and sulfide
precipitation followed by vacuum filtration are the best technologies for K115
nonwastewaters and wastewaters.
The Agency then evaluated the available data to determine whether
these technologies are "available." The demonstrated technologies for treat-
ment of nickel in K115—stabilization, and lime and sulfide precipitation
followed by vacuum filtration—are commonly used for the treatment of metals
in nonwastewaters and wastewaters and are considered to be commercially
available. These technologies also provide substantial treatment for nickel.
Therefore, stabilization and lime and sulfide precipitation followed by vacuum
filtration are "available" for the purpose of establishing BDAT.
5-15
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Based on the above discussion, EPA is promulgating (1) stabilization
as BDAT for nickel in K115 nonwastewaters and (2) lime and sulfide precipita-
tion followed by vacuum filtration as BDAT for nickel in K115 wastewaters.
5.4 Summary of BDAT for the K027 Treatability Group
As discussed in Section 5.1, EPA is promulgating incineration and
fuel substitution as BDAT for organics in K027, K113-K116, U221, and U223
nonwastewaters. As discussed in Section 5.2, EPA is promulgating carbon
adsorption and incineration as BDAT for the treatment of organic constituents
in K027 treatability group wastewaters. EPA is promulgating concentration
levels for nickel based on the performance of stabilization as BDAT for nickel
in K115 nonwastewaters, and lime and sulfide precipitation followed by vacuum
filtration as BDAT for nickel in K115 wastewaters, as discussed in Section
5.3. These BDAT treatment standards do not preclude a facility from using
recycling operations in accordance with the conditions specified in 40 CFR
Part 261.2.
5.5 Determination of the Regulatory Approach For the K111 and K112
Treatability Group
As described in Section 3.1.3, Kill and K112, as generated, norm-
ally consist of wastewater forms and generally contain 0-\% organic compounds.
Applicable technologies for treatment of K111 and K112 wastewaters include
those that destroy or reduce the total amount of various organic compounds in
5-16
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the wastes. The following technologies were identified as potentially appli-
cable for treatment of K111 and K112 wastewaters: (1) biological treatment,
(2) carbon adsorption, and (3) solvent extraction. The technology identified
as potentially applicable for treatment of K111 and K112 nonwastewaters was
incineration.
Based on telephone contacts with the eight facilities producing DNT,
TDA, and/or TDI, the Agency identified two demonstrated treatment technologies
for K111 and K112 wastewaters: biological treatment and carbon adsorption.
The Agency also identified fluidized-bed incineration as a demonstrated
technology for treatment of sludge derived from wastewater treatment of K111
and K112 where the wastewater treatment sludge is a "derived-from" nonwaste-
water form of K111 and K112.
To be considered an "available" treatment for K111 and K112, the
demonstrated technology must provide substantial treatment in the wastes or
similar wastes for constituents of concern. As discussed previously, treat-
ment performance data are not available for biological treatment or carbon
adsorption treatment of K111 and K112 wastewaters. Additionally, treatment
performance data are not available from other wastes for transfer to the K111
and K112 treatability group. Therefore, at this time the Agency has been
unable to show that these technologies provide substantial treatment for
constituents of concern in K111 and K112. Thus, EPA is not setting treatment
standards for K111 and K112.
5-17
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Since K111 and K112 were listed after the November 8, 1984 effective
date of HSWA and land disposal of these wastes is not subject to either "soft
hammer" or "hard hammer" provisions, the Agency believes further study should
be made of these wastes and treatment options before proposing BDAT treatment
standards.
5-18
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6.0
SELECTION OF REGULATED CONSTITUENTS
This section presents the rationale for the selection of constitu-
ents for regulation in the K027 treatability group. Generally, constituents
selected must satisfy the following criteria:
1. The constituent must be on the BDAT List of regulated consti-
tuents. (Presence on the BDAT List implies the existence of
approved methods for analyzing the constituent in treated waste
matrices.)
2. The constituent must be present in. or be suspected of being
present in. the untreated waste. For example, in some cases,
analytical difficulties (such as masking) may prevent a con-
stituent from being identified in the untreated waste, but its
identification in a treatment residual may lead the Agency to
conclude that it is present in the untreated waste.
3. Where treatment performance data from other constituents are
being transferred, the constituents) from which performance
data are transferred must be as difficult to treat as the
selected constituent(s) being regulated. Assessing ease of
treatment varies according to the technology of concern. For
instance, factors to consider for incineration include bond
dissociation energies, thermal conductivities, and boiling
points.
Waste characterization data for the K027 and K113-K116 waste codes
were presented in Section 2.0. Major organic constituents of concern in these
wastes, such as karathane, TDI, TDA, and o- and p- toluidine, would be consid-
ered for regulation; however, these constituents cannot be analyzed due to a
lack of satisfactory analytical methods (Section 1.0). As a result, no
treatment performance data are available for these constituents (Section 4.0).
Therefore, EPA is specifying a treatment technology as the BDAT treatment
standard for organics in the K027 treatability group, rather than develop
concentration-based treatment performance levels for individual constituents.
6-1
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Incineration or fuel substitution are the BDAT treatment standard for organics
in K027 treatability group nonwastewaters, and carbon adsorption and incinera-
tion are the BDAT treatment standard for organics in K027 treatability group
wastewaters.
A review of the inorganic waste characterization data identified
spent nickel catalyst in untreated K115. Since metals are not treated in
either incineration, fuel substitution, or carbon adsorption processes, which
are the specified BDAT technologies for the K027 treatability group, the
Agency is regulating nickel in nonwastewater and wastewater residuals of K115
based on treatment performance data from other waste codes (Section 4.0).
6-2
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7.0 CALCULATION OF TREATMENT STANDARDS
The Agency bases treatment standards for constituents on the perfor-
mance of well-designed and well-operated BDAT treatment systems. These
standards must account for analytical limitations in available treatment
performance data, and the data must be adjusted for variabilities related to
treatment, sampling, and analytical techniques and procedures.
BDAT treatment standards are determined for each constituent by
multiplying the arithmetic mean of accuracy-adjusted constituent concentra-
tions detected in treated waste by a "variability factor" specific to each
constituent. Variability factors correct for normal variations in the perfor-
mance of a particular technology over time and are designed to reflect the
99th percentile level of performance that the technology achieves in commer-
cial operation. (The principles of calculating variability factors are
described in more detail in EPA's Methodology for Developing BDAT Treatment
Standards (18).) Table 7-1 below shows the calculation of treatment standards
for nickel in nonwastewaters and wastewater forms of K115.
In cases where EPA has identified a treatment technology for a
particular waste or waste treatability group as BDAT, but cannot develop
specific concentration-based treatment standards for that waste because of
7-1
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Table 7-1
CALCULATION OF TREATMENT STANDARDS FOR NICKEL IN K115
NONWASTEWATERS
Regulated Constituents
Metals
Nickel
F006 Constituent
From Which
Treatment Performance
Data Were
Transferred
Nickel
Arithmetic
Average of
Corrected
Treatment Values
(PPm>
0.071
Variability
Factor
(VF)
4.H7
Treatement
Standard3
(Average x VF)
(ppm)
0.32
Regulated Constituents
Metals
K062 Constituent
From Which
Treatment Performance
Data Were
Transferred
Arithmetic
Average of
Corrected
Treatment Values
(ppm)
Variability
Factor
(VF)
Treatement
Standard3
(Average x VF)
(ppm)
Nickel
Nickel
0.387
1.21
0.47
7-2
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analytical limitations, the Agency can require the use of that treatment
technology as the BDAT treatment standard.
For the K027 treatability group, the Agency is promulgating inciner-
ation or fuel substitution as the BDAT treatment standard for organics in
nonwastewaters, and carbon adsorption and incineration as the BDAT treatment
standard for organics in wastewaters. For K115 nonwastewater and wastewater
residuals, the Agency is promulgating concentration-based treatment standards
for nickel. These standards are shown below.
K115 Nonwastewater Residual
BDAT: Stabilization
Maximum for any Single Grab Sample
Total Composition TCLP
Constituent (mg/kg) (mg/1)
Nickel Not Applicable 0.32
K115 Wastewater Residual
BDAT: Lime and Sulfide Precipitation followed by Vacuum Filtration
Maximum for any Single Grab Sample
Total Composition TCLP
Constituent (mg/1) (mg/1)
Nickel 0.47 Not
Applicable
7-3
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8.0 REFERENCES
1. U.S. EPA. Test Methods for Evaluating Solid Waste. SW-846, Third Edition.
Office of Solid Waste and Emergency Response, Washington, D.C., 1986.
2. U.S. EPA. Test Methods for Evaluating Solid Waste, SW-846, Second Edition.
Office of Solid Waste and Emergency Response, Washington, D.C., 1982.
3. U.S. EPA "Appendix I". Federal Register. Volume 51, Number 216, November
7, 1986, P40647.
4. American Water Works Association, and Water Pollution Control Federation.
Standard Methods for the Examination of Water and Wastewater, Sixteenth
Edition. American Public Health Association, Washington, D.C., 1985.
5. American Society for Testing and Materials. 1986 Annual Book of ASTM
Standards Petroleum Products. Lubricants, and Fossil Fuels. Philadelphia,
Pennsylvania, 1986.
6. U.S. EPA. Methods for Chemical Analysis of Water and Wastes. Environmen-
tal Monitoring and Support Laboratory, Cincinnati, Ohio, EPA-600/4-79-020,
1983.
7. U.S. EPA. Generic Quality Assurance Project Plan for Land Disposal Re-
strictions Program (BDAT). Office of Solid Waste, Washington, D.C.
EPA/530-SW-87-011, 1987.
8. U.S. EPA. Methodology for Developing BDAT Treatment Standards. 1988.
9. U.S. EPA. Listing Background Document Toluene Diisocyanate Production.
1980.
10. U.S. EPA. Listing Background Document for Dinitrotoluene, Toluene-
diamine and Toluene Diisocyanate Production. 1985.
11. U.S. EPA. Best Demonstrated Available Technology (BDAT) Background
Document for F006. Proposed. Vol. 13. EPA/530-SW-88-0009-1, 1988.
12. U.S. EPA. Best Demonstrated Available Technology (BDAT) Background
Document for F024, Proposed. 1988.
13. U.S. EPA. Best Demonstrated Available Technology (BDAT) Background
Document for K015. Proposed. Vol. 1, EPA/530-SW-88-0009-a, 1988.
14. U.S. EPA. Best Demonstrated Available Technology (BDAT) Background
Document for K062, Final. 1988.
8-1
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15. U.S. EPA. Best Demonstrated Available Technology (BDAT) Background
Document for K086. Proposed. Vol. 15, EPA/530-SW-88-0009-n, 1988.
16. U.S. EPA. Best Demonstrated Available Technology (BDAT) Background
Document for Aniline Production Treatability Group (K103, K104), Pro-
posed. Vol. 7, EPA/530-SW-88-0009-g, 1988.
17. Olin Corporation. "Response to 3007 Letter". September 9, 1988 Letter.
18. Mobay Corporation. "Report of RCRA Trial Burn Results for Fluidized Bed
Incinerator". July 1988.
19. U.S. EPA. Treatment Technologies Background Document. 1989.
20. Kirk-Othmer. Encyclopedia of Chemical Technology. Second Edition, Volume
12, pp. 45-64.
21. Memorandum: Preliminary Data Gathering Effort on K027 Waste Group.
From C. Hong, H. Welner, Radian; To J. Labiosa, EPA/OSW, 5/11/88.
22. Verschurern, Karel. 1983. Handbook of Environmental Data on Organic
Chemicals, 2nd edition, pp. 575-576. NY: Van Nostrand Reinhold Co.,
Inc.
23. Sanderson, R.T. 1971. Chemical Bonds and Bond Energy, pp. 28-29,
150-153, 200-211. NY and London: Academic Press.
24. Dean, J.A., editor. 1979. Lange's Handbook of Chemistry. 12th edition,
pp. 3-126 to 3-128. McGraw-Hill.
25. Weast, R.C., editor. 1980. CRC Handbook of Chemistry and Physics. 61st
edition, p. C-134. Boca Raton, FL: CRC Press, Inc.
26. Windholz, Martha, editor. 1983. The Merck Index. 10th edition.
Rahway, NJ: Merck and Company.
27. Peer Consultants, Inc. Appendices Supporting Documentation for the RCRA
Incinerator Regulations. 40 CFR 264. Subpart 0 - Incinerators. September
1984.
28. Memorandum: Guidance on Chlordane and Heptachlor Pesticides Wastes.
From Sylvia K. Lowrance, Director 0SW; to Susan H. Wayland, Deputy
Director, Office of Pesticide Programs, 5/3/88.
29. Memorandum: Pesticide Standards for Formaldehyde and Paraformaldehyde.
From Devereaux Barnes, Director Characterization and Assessment Division;
To Chet McLaughlin, Chief, State Programs Section, Region VII, 3/14/88.
8-2
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Appendix A
CBI WASTE CHARACTERIZATION DATA
A-1
-------
USEPA. 1988. U.S. Environmental Protection Agency, Office of Solid Waste.
Appendix A, CBI Waste Characterization Data. Proposed Best Demonstrated
Available Technology (BDAT) Background Document for Wastes from the Production
of Dinitrotoluene, Toluenediamine. and Toluene Diisocyanate (K027. K111-K116,
U221, and U223). Washington, D.C.: U.S. Environmental Protection Agency.
This Appendix contains RCRA Confidential Business Information (CBI). Only
persons with RCRA CBI clearance may access this document. If you have further
questions, please contact the U.S. Environmental Protection Agency, Office of
Policy, Planning, and Information Management Staff, at (202) 382-4697.
A-2
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Appendix B
APPLICATION OF THE SECTION 5.1.2 METHODOLOGY
TO THE K027 TREATABILITY GROUP
B-1
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Application of the Section 5.1.2
Methodology to the K027 Treatability Group
The methodology outlined in Section 5.1.2 was applied to the K027
treatability group to show that incineration and/or fuel substitution will
provide substantial treatment of the hazardous constituents in nonwastewater
forms of K027, K113-K116, U221, and U223. Each step, shown in the flowchart
of Figure 5-1 and described in Section 5.1.2, is repeated below along with
results of its application to the K027 treatability group.
Step 1: Examine available waste characterization data for K027 and
K113-K116 and identify major constituents of concern.
Characterization data for K027 and K111-K116 are presented in Table
2-2 of Section 2.0. Many of the constituents that characterize these waste
codes are not on the BDAT List of hazardous constituents because of the
difficulties associated with analyzing for the constituents in complex waste
matrices (as discussed in Section 1.0). However, these constituents are major
constituents of concern for the K027 waste treatability group, as discussed
below.
Major constituents of concern include but are not limited to those
constituents listed in 40 CFR Part 261 Appendix VII and/or VIII at treatable
concentrations. For a constituent to be considered at a treatable concentra-
tion, it should be shown or believed to be in the waste, should be highly
toxic (e.g., dioxins and furans may be present at low concentrations but are
8-2
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still of concern due to their high toxicity), be present at high concentra-
tions in the untreated wastes, and/or has a high degree of difficulty for
treatment. EPA's BDAT methodology for determining the relative difficulty in
incineration of different hazardous constituents includes a comparison of the
boiling points and bond dissociation energies of the constituents. As shown
in Table 2-2, karathane, TDI, TDA, and carbon tetrachloride are present in the
untreated wastes at the highest concentrations. In addition, karathane, TDI,
and o- and p-toluidine have the highest bond dissociation energies of the
constituents present in the untreated wastes (4,911 kcal/mole; 2,350
kcal/mole; and 2,480 kcal/mole, respectively). 2,4-TDA and 2,6-TDA also have
the highest boiling points (283-285°C). Therefore, based on their high
toxicities, high concentrations in the untreated wastes, and high degrees of
difficulty to incinerate, the following constituents have been identified as
the major constituents of concern for the K027 waste treatability group:
karathane, TDI, 2,4- and 2,6-TDA, and o- and p-toluidine.
Step 2: Examine the BDAT performance database to identify all waste
codes previously tested by incineration processes (e.g., incinera-
tion and/or fuel substitution).
As discussed in Section 5.0 (Step 2), the BDAT incineration database
was selected for examination in this methodology. This incineration database
consists of performance data obtained from 12 incineration treatment tests
performed by the BDAT program. The incineration database includes both
treatment performance data (concentrations of hazardous constituents detected
B-3
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in the untreated and treated wastes) and corresponding design and operating
data for the incineration systems.
For the BDAT program, incineration tests were performed only on
incinerators operating under 40 CFR Part 264 Subpart 0 or Uo CFR Part 265
Subpart 0, or on fuel substitution units operating under 40 CFR Part 266.
Subsequent to each treatment test, EPA performed an engineering analysis of
the treatment system's operation during the treatment test to determine
whether the treatment system was well-designed and well-operated. The deter-
mination of whether a treatment system was well-designed and well-operated was
based on whether the treatment system was operating within design operating
parameters during the treatment test. Additionally, EPA reviewed the perfor-
mance data to determine whether the treatment system provided substantial
treatment for the constituents of concern (i.e., regulated constituents) in
the tested waste. If the treatment was determined to be well-designed and
well-operated and substantial treatment was shown, the Agency included the
data in the development of treatment standards for the tested waste. In cases
where the treatment system was determined to be poorly-designed or poorly-
operated, the Agency excluded that performance data from the incineration
database, precluding the use of that data in the development of treatment
standards.
Based on a review of the existing BDAT performance database, the
waste codes previously tested by incineration were identified and are shown on
Table B-1.
B-4
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Table B-1
WASTE CODES PREVIOUSLY TESTED BY INCINERATION
Waste Code Definition in UP CFR Part 261
K001 Bottom sediment sludge from the treatment
of wastewaters from wood preserving
processes that use creosote and/or
pentachlorophenol
K015 Still bottoms from the distillation of
benzyl chloride
K019 Heavy ends from the distillation of
ethylene dichloride in ethylene dichloride
production
K024 Distillation bottoms from the production
of phthalic anhydride from naphthalene
K037 Wastewater treatment sludge from the
production of disulfoton
K048 Dissolved air flotation (DAF) float from
the petroleum refining industry
K051 API separator sludge from the petroleum
refining industry
K086 Solvent washes and sludges, caustic washes
and sludges, or water washes and sludges
from cleaning tubs and equipment used in
the formulation of ink from pigments,
driers, soaps, and stabilizers containing
chromium and lead
K087 Decanter tank tar sludge from coking
operations
K101 Distillation tar residues from the distil-
lation of aniline-based compounds in the
production of veterinary pharmaceuticals
from arsenic or organo-arsenic compounds
K102 Residue from the use of activated carbon
for decolorization in the production of
veterinary pharmaceuticals from arsenic or
organo-arsenic compounds
Type of
Incineration Test
Rotary kiln
Liquid injection
Rotary kiln
Rotary kiln
Rotary kiln
Fluidized-bed
Fluidized-bed
Rotary kiln
Rotary kiln
Rotary kiln
Rotary kiln
B-5
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Table B-1 (Continued)
WASTE CODES PREVIOUSLY TESTED BY INCINERATION
Type of
Waste Codes Definition in 40 CFR Part 261 Incineration Test
F024 Wastes, including but not limited, distil- Rotary kiln
lation residues, heavy ends, tars, and
reactor clean-out wastes, having carbon
content from one to five, utilizing free
radical catalyzed processes (this listing
does not include light ends, spent
filters, and filter aids, spent dessicant,
wastewater, wastewater treatment sludges,
spent catalysts, and wastes listed in
Section 261.32)
B-6
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Step 3: Screen the BDAT incineration database and identify waste
codes that meet the criteria (a-c) described below.
(a) Identify wastes that are generated from similar industries or
similar processes, and/or have similar waste characteristics as
K027, K113-K116, U221, and U223.
K027, K113-K116, U221, and U223 are generated from the production of
organic chemicals; specifically, from the production of toluene diisocyanate
and/or toluenediamine. Of the wastes previously tested by incineration, K015,
K019, K024, K037, K086, and F02U were identified as waste codes also generated
from the production of organic chemicals. None of these wastes were generated
from similar processes as K027, K113-K116, U221, or U223, however, these
wastes previously tested by the Agency show the presence of organic constitu-
ents that are as difficult to treat as those organic constituents in K027,
K113-K116, U221, and U223.
(b) Identify wastes that have similar or lower thermal conductivi-
ties than the untested wastes of concern.
Analytical determinations of the thermal conductivities for these
wastes are not currently available; however, the relative thermal conductivi-
ties of the wastes can be compared based on the chemical characteristics of
these wastes. In general, organic constituents have similar thermal conduc-
tivities. Solids tend to have higher thermal conductivities than liquids.
B-7
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Metals have a high thermal conductivity, whereas inorganics, which are non-
metallic, generally act as insulators and have low thermal conductivities.
The wastes K015, K019, K024, K027, K037, K086, K113-K116, and F024,
are generated from the production of organic chemicals; therefore, these
wastes are expected to have high concentrations of organic constituents and
very low concentrations, if any, of metals. K086 treated in EPA's incinera-
tion test consisted of liquid wastes. All other waste streams are expected to
be solid or semi-solid waste mixtures. Based on the discussion above, K086 as
a liquid is expected to have a lower thermal conductivity (i.e., be more
difficult to incinerate) than K027, K113-K116, U221, and U223. The other
waste streams, K015, K019, K024, K037, and F024, are expected to have similar
thermal conductivities (i.e., similar incinerability) as K027, K113-K116,
U221, and U223.
(c) Identify wastes that contain regulated BDAT List constituents
that are equally or more difficult to incinerate than the
constituents of concern.
The boiling points and bond dissociation energies (BDE's) of regu-
lated BDAT List constituents in K015, K019, K024, K037, K086, and F024 were
examined. Of these wastes, K015, K086, and F024 were identified as the waste
codes that contained regulated BDAT List constituents that were more difficult
to incinerate (i.e., had higher BDE's and boiling points), than K027, K113-
K116, U221, and U223 constituents of concern. Characteristics of the
B-8
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regulated constituents in K015, K086, and F024, along with the performance
data, if available, are summarized in Tables 4-2 through 4-5 of Section 4.0.
Step 4; Select constituents from waste codes identified in Step 3
cnat meet the criteria delineated below.
The waste codes identified in Step 3 are K015, K086, and F024.
Characteristics of the constituents of concern in the K027, K113-K116, U221,
and U223 treatability group are summarized in Table 4-1 of Section 4.0.
Characteristics of the regulated BDAT List constituents in and treatment
performance data from K015, K086, and F024 were examined to identify constitu-
ents that:
(a) Have higher boiling points and bond dissociation energies than
the constituents of concern in K027 and K113-K116.
As mentioned in Step 1, the constituents of concern in K027 and
K113-K116 are TDI, TDA, o- and p-toluidine, and karathane.
Based'on the ¦ waste¦charaoterization and. performance data'presented
in Tables 4-2 and 4-5 of Section 4.0, anthracene, phenanthrene, and benzo(b
and/or k)fluoranthene in K015 were identified as constituents that have higher
bond dissociation energies than TDI, TDA, and o- and p-toluidine. In addi-
tion, phenanthrene has a higher boiling point than TDI, TDA, and o- and
p-toluidine. Anthracene has a higher boiling point than karathane, TDI, and
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o- and p-toluidine, but a lower boiling point (bp 242°C) than TDA (bp 283-
285°C). A boiling point is not available for benzo(b and/or k)fluoranthene.
However, based on its structure, benzo(b and/or k)fluoranthene is expected to
have a higher boiling point than phenanthrene. Therefore, benzo(b and/or
k)fluoranthene is expected to have a higher boiling point than TDI, TDA, and
o- and p-toluidine.
Based on waste characterization and performance data presented in
Tables 4-3 and 4-5 of Section 4.0, bis(2-ethylhexyl)phthalate was identified
as the only regulated constituent in K086 that has a higher bond dissociation
energy than either karathane, TDI, TDA, or o- and p-toluidine. In addition,
the boiling point for bis(2-ethylhexyl)phthalate is also higher than the
boiling points for the K027 treatability group's constituents of concern.
Based on waste characterization and performance data presented in
Tables 4-4 and 4-5 of Section 4.0, bis(2-ethylhexyl)phthalate, di-n-octyl
phthalate, pentachloro-dibenzo-p-dioxin, and hexachloro-dibenzo-p-dioxin in
F024 were identified as constituents that have higher bond dissociation
energies (BDE's) than either TDI, TDA, o- and p-toluidine or karathane.
(Bis(2-ethylhexyl)phthalate and di-n-octyl phthalate have higher BDE's than
all four constituents of concern in the K027 treatability group; pentachloro-
dibenzo-p-dioxin has a BDE higher than TDI, TDA, and o- and p-toluidine; and
hexachloro-dibenzo-p-dioxin has a higher BDE than TDA.) In addition, the four
constituents identified in F024 all have higher boiling points than karathane,
TDI, TDA, and o- and p-toluidine in the K027 treatability group.
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(b) Are present in the untreated wastes at concentrations high
enough to allow a determination that substantial treatment was
achieved in the treated waste.
As shown in Tables 4-2 through 4-4, the selected constituents
anthracene, phenanthrene, benzo(b and/or k)fluoranthene, bis(2-ethylhexyl)-
phthalate, di-n-octyl phthalate, pentachloro-dibenzo-p-dioxin, and hexachloro-
dibenzo-p-dioxin were all present in the untreated wastes at concentrations
high enough to allow determination that substantial treatment was achieved in
the treated waste.
Step 5: Summarize demonstration of substantial treatment.
The constituents identified in Step 4, along with their characteris-
tics and the corresponding constituents of concern in the K027, K113-K116,
U221, and U223 treatability group, are summarized below.
As discussed earlier, EPA's BDAT methodology for determining the
relative difficulty of incineration of different hazardous constituents
involves the comparison of boiling points and bond dissociation energies of
the hazardous constituents. EPA's approach is based on the belief that the
higher the boiling point, the harder it is to volatilize the constituent; the
higher the bond dissociation energy, the harder it is to destabilize the
constituent. Therefore, based on the above information, anthracene, phenan-
threne, benzo(b and/or k)fluoranthene, bis(2-ethylhexyl)phthalate, di-n-octyl
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phthalate, and pentachlorodibenzo-p-dioxin are shown to be more difficult to
combust than TDI and o- and p-toluidine. Phenanthrene, benzo(b and/or k)-
fluoranthene, bis(2-ethylhexyl)phthalate, di-n-octyl phthalate, pentachlo-
rodibenzo-p-dioxin, and hexachlorodibenzo-p-dioxin are shown to be more
difficult to combust than TDA and bis(2-ethylhexyl)phthalate, and di-n-octyl
phthalate is shown to be more difficult to combust than karathane.
Furthermore, performance data from incineration of these constitu-
ents show that they are substantially treated by incineration. Therefore,
since substantial treatment is demonstrated by incineration for constituents
that are more difficult to incinerate than TDI, TDA, karathane, and o- and
p-toluidine, combustion (as incineration and/or fuel substitution) is expected
to provide substantial treatment for these major constituents of concern in
the K027 treatability group.
In summary, the above analyses demonstrate that incineration pro-
vides substantial treatment for K027, K113-K116, U221, and U223 and, there-
fore, support the determination to identify incineration and fuel substitution
as the BDAT method of treatment for K027, K113-K116, U221, and U223.
Step 6: Compare design and operating data for incineration systems
treating K015, K086, K027, K113-K116, and F02M.
To further support the determination of incineration as the BDAT
method of treatment for K027, K113—K116, U221, and U223t EPA compared design
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and operating data for incineration systems treating K015, K086, F024, K027,
and K113-K116. Table 4-5 in Section 4.0 summarizes available operating ranges
for incineration systems treating K027, K015, K086, and F024. Although
operating conditions vary from facility to facility and are waste-specific,
the operating ranges for the incinerator treating K027 are very similar to the
operating ranges for incinerators treating K015, K086, and F024, as indicated
in Table 4-5. Therefore, based on the similarity in operating ranges of these
incinerators, and since the incinerators treating K015, KO86, and F024 have
been shown to provide substantial treatment of hazardous organic constituents,
it is expected that incineration systems with similar operating conditions
also provide substantial treatment for K027, K113-K116, U221, and U223.
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Appendix C
CARBON ADSORPTION FOR THE TREATMENT OF
K027 TREATABILITY GROUP WASTEWATERS
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Carbon Adsorption for the Treatment
of K027 Treatability Group Wastewaters
The information presented in Section 5.2.2 was applied to the K027
treatability group to show that carbon adsorption will provide substantial
treatment of the hazardous organic constituents in wastewater forms of K027,
K113-K116, U221, and U223. The information presented below documents the
ability of a well-designed and well-operated carbon adsorption unit to sub-
stantially treat organics in K027 treatability group wastewaters. This
information is presented in sections that describe the underlying principles
of carbon adsorption treatment, the waste characteristics affecting perfor-
mance, and the design and operating parameters that can be used to define a
well-designed and well-operated carbon adsorption unit.
C.1 Underlying Principles of Carbon Adsorption
Activated carbon treatment is an application of the principle of
adsorption, where adsorption is the mass transfer of a molecule from a liquid
or gas into a solid surface. Adsorption with activated carbon is an important
separation method for removing organics from liquids. It occurs when the
surface of the activated carbon attracts the ions or molecules of the organic
solid to form a layer on the carbon surface and accumulate in its pores.
Activated carbon is manufactured to produce extremely porous carbon
particles, with an internal surface area that is very large (500 to 1100
square meters per gram of carbon). This porous structure, through chemical
and physical forces, attracts and holds (adsorbs) organic molecules as well as
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certain inorganic molecules. It is not unusual for activated carbon to adsorb
from aqueous solution 0.15 grams of an organic contaminant per gram of carbon,
though 0.10 gram/gram is probably a more realistic general estimate. The
principal factor that affects carbon adsorption is the chemical affinity
between the carbon and the organic compound. Other characteristics, such as
solubility, temperature, pH, type of activated carbon used, presence of other
organics, and contact time also influence the effectiveness of carbon adsorp-
tion.
Once contaminants of concern have been removed from K027 treat-
ability group waste streams onto the carbon, two options are available. The
activated carbon can (1) be disposed of by incineration in a well-designed,
well-operated incinerator, as regulated under 10 CFR Part 264 Subpart 0 and
Part 265 Subpart 0, or (2) be regenerated for further use through thermal
methods by a hazardous-waste permitted regenerator facility. However, non-
wastewater treatment residuals resulting from the thermal regeneration units
must comply with the nonwastewater standard promulgated unless the thermal
regeneration unit is already regulated under 40 CFR 264 Subpart 0, 265 Subpart
0, or 266 Subpart D.
C.2 Waste Characteristics Affecting Performance
The waste characteristics that affect an activated carbon system's
performance are: the types of organic contaminants, the concentrations of
contaminants, and the concentrations of suspended solids, grease and oil.
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C.2.1
Types of Organic Contaminants
All organic molecules can be adsorbed by activated carbon to some
degree. Generally, adsorption will increase with molecular weight until the
particle size becomes too large for carbon pore size. Activated carbon
usually has a greater affinity for aromatic compounds than for straight chain
compounds. Nonpolar compounds are usually easily adsorbed, whereas polar ones
are not. Halogenated organic compounds (HOCs), if aromatic (such as PCBs),
are readily absorbed. Finally, it has been demonstrated in practice that
adsorption will increase with decreasing solubility.
Table C-1 presents the constituents of concern for K027, K113-K116,
U221, and U223, along with some of their waste characteristics. As seen in
Table C-1, all of the constituents of concern are organic compounds with high
molecular weights, and most of the constituents of concern are either aromatic
compounds or nonpolar compounds.
For these reasons, the Agency believes that carbon adsorption can
provide substantial treatment of the constituents of concern in K027,
K113-K116, U221, and U223.
C.2.2 Concentrations of Contaminants
The process of carbon adsorption becomes ineffective at concentra-
tions exceeding a few thousand mg/1 (ppm). The carbon adsorbs concentrated
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Table C-1
CONSTITUENT CHARACTERISTICS OF K027, K113-K116, U221, AND U223
Constituent
of Concern
Molecular
Weight
Toluene diisocyante
174
Toluenediamine
122
Karathane
364
Aniline
93
Tetrachloroethene
166
Chloroform
119
Carbon tetrachloride
154
Toluidine
107
Phosgene
99
Aromatic Halogenated Non-
Compound Organic Compound Polar
Yes No *
Yes No *
Yes No *
Yes No *
No Yes Yes
No Yes Yes
No Yes Yes
Yes No *
No Yes Yes
* Polar-covalent molecules.
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contaminants so quickly that carbon consumption becomes excessive, and fre-
quent disposal and/or regeneration of carbon becomes a greater problem than
removal of the organic materials from the waste stream. In the case of K027
treatability group wastes, the wastewater forms are expected to contain
contaminants of concern at ppm concentrations. Therefore, the concentrations
in these wastes are expected to be well within the limits of the carbon
adsorption process, thereby supporting the ability of this treatment method to
provide substantial treatment of these wastes.
C.2.3 Concentrations of Suspended Solids. Grease, and Oil
Depending on the type of carbon adsorption system used, suspended
solids, oil, and grease may eventually plug, bind, or coat the activated
carbon so that it can no longer sustain the flow of wastewater. Wastewaters
which contain high amounts of total suspended solids, oil and/or grease may
therefore require pretreatment or prefilter operations prior to carbon adsorp-
tion treatment. In the case of the K027 treatability group, suspended solids
may be of concern in some of the wastewaters generated. The Agency therefore
recommends that a well-designed carbon adsorption system may include a pre-
filter to filter out the suspended solids. This nonwastewater residue would
then be considered a "derived from" K027, K113-K116, U221, or U223, and would
require incineration in a well-designed and well-operated thermal treatment
unit (regulated under 40 CFR Part 264 Subpart 0 or Part 265 Subpart 0) prior
to land disposal.
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C.3 Design and Operating Parameters
C.3.1 Design Parameters
Two types of carbon adsorption systems in general use are the
powdered activated carbon (PAC) system and the nonfluidized granular-activated
carbon (GAC) system. In the PAC system, the incoming waste stream is thor-
oughly stirred with the PAC, and after adsorption equilibrium is reached, the
mixture is settled or filtered to separate the PAC from the wastewater. In
GAC systems, the carbon is packed in columns and the liquid is passed through
the bed of carbon. The type of system to use depends on the waste stream to
be treated. In addition, the design must account for three parameters that
affect the ability of activated carbon to adsorb contaminants: contact time,
carbon particle type and size, and wastewater flow rate.
Contact Time
For both PAC and GAC systems, contact time must be determined by
testing individual wastes with different activated carbon samples. Once
contact time is determined for adequate removal of contaminants, tank sizing
is the next step and will depend on the waste flow rate.
Carbon Particle Type and Size
Activated carbon is made from a variety of substances (e.g., coal or
wood), ground to many different sizes, and manufactured with "customized" pore
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sizes. A range of surface areas and individual pore sizes will determine the
carbon's adsorptive capacity. Bench testing is recommended to determine the
most effective activated carbon product for a particular waste stream and
desired effluent.
Wastewater Flow Rate
GAC systems are designed for upflow or downflow operation. For both
types, there are practical limits to the liquid velocity. Once the velocity
and contact time are determined, the bed cross-section and depth are sized to
meet these requirements.
C.3.2 Operating Parameters
A number of parameters must be maintained during operation of a
carbon adsorption unit to ensure that the adsorption system adheres to the
design specifications. These parameters are: waste liquid concentration,
temperature, pH, suspended solids and oils, and contact time.
Waste Liquid Concentration
In GAC systems, the waste liquid concentration has a direct effect
on the operation of an adsorption system because if the concentration is
significantly higher than the design concentration, column breakthrough will
occur quickly, and excessive regeneration will be required. Conversely, if
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during the operation of a column, the waste liquid concentration decreases
significantly, previously adsorbed molecules can be desorbed from the carbon
and discharged in the effluent stream. Additionally, changes in the waste
composition can cause previously adsorbed molecules to be desorbed and re-
placed by molecules of a different constituent if the new constituent has a
higher affinity for the carbon surface. These types of situations can lead to
effluent concentrations for a particular waste constituent that are higher
than influent concentrations. Waste liquid concentration has less of an
effect on PAC systems because the PAC is removed as it is spent. Desorption
is not a problem. However, if the concentration increases significantly over
the design concentrations, excessive quantities of PAC may be required. In
any case, the effluent must be monitored for breakthrough of contaminants.
Temperature
Temperature is a critical parameter in the operating performance of
carbon adsorption systems. As the temperature is increased, the solubility of
the constituent of concern will, in general, increase and will likely result
in less effective adsorption of the constituent. Therefore, this parameter
should be continuously monitored during the operation of a carbon adsorption
unit.
E«
The pH of the waste will have an impact on the solubility of the
various constituents, as well as the potential for chemical bonding to occur.
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While these conditions are not impacted significantly by pH, this parameter
should be monitored during the operation of a carbon adsorption unit.
Suspended Solids and Oils
Suspended solids and oils are not usually a problem with PAC sys-
tems. However, in GAC systems, oils and suspended solids in the waste will
eventually plug the column. If the concentration of solids is significant
(typically greater than 200 mg/1), the waste will need to be pretreated to
remove them. In any case, suspended solids and grease present in the GAC
column influent will necessitate backwashing and/or column cleaning. The need
for such cleaning can be detected with pressure gauges which monitor the
degree of plugging.
Contact Time
Contact time requirements vary with the type of system but must be
maintained within design specifications. Typical contact times vary between
100 and 300 minutes for GAC systems and are somewhat lower for PAC systems.
For GAC systems, typical downflow rates are between 20 and 330 1/min m2 of bed
area. A typical upflow rate is 610 1/min m2 of bed area, unless the bed is
fluidized (i.e., the activated carbon is in suspension in the waste), in which
case higher velocities are necessary. Contact time is monitored by measuring
the wastewater flow rate, since system volume is predetermined.
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