502"
F.IP0PT DQTJ!£NTA?rON j 1. REPORT NO. ; 2. 13. "
="i2£ EPA/530-SW-99-048J •• I j PBaS-2^»lA?I .
4, Title i,?/. Sutt:t!e I 5. ftecort Date
BE£* lE'C-JBTRATE: AVAILABLE TECHNOLOGY (BOAT) BACKGROUND DOCUMENT FOR KOU. ! JUNE 199c
•/i:: S\D "'C;4 - FINAL
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Psrfori»;n3 Organization ftept. No
ad^:./:^t«dn-i!:eaddy/os«
ci :=--;..T:r,q o-^anizatior Name aid Address
i 10.
Project/Task/Swrl: Unit No.
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40' y. ctr"Sct
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-------
ACKNOWLEDGMENTS
This document was prepared by the U.S. Environmental Protection
Agency, Office of Solid Waste, with the assistance of Versar Jnc. under
Contract No. 68-01-7053. Mr. Robert April, Chief, Treatment Technology
Section, Waste Treatment Branch, served as the EPA Program Manager during
the preparation of this document and the development of treatment
standards for the wastes generated from the production of acrylonitrile.
The technical project officer for these wastes was Ms. Monica Chatmon-
McEaddy. Mr. Steven Silverman served as legal advisor.
Versar personnel involved in the preparation of this document included
Mr. Jerome Strauss, Program Manager; Mr. Stephen Schwartz, Task Manager;
Ms. Laura Fargo, Staff Engineer; Ms. Barbara Malczak, Technical Editor;
and Ms. Sally Gravely, Project Secretary. Mr. Alan Corson of Jacobs
Engineering Group and Mr. Mark Hereth of Radian Corporation assisted in
the review of this document.
We greatly appreciate the cooperation of the individual companies that
permitted their plants to be sampled and that submitted detailed informa-
tion to the U.S. EPA on treatment of these wastes.
i i
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TABLE OF CONTENTS
Section Page
1. INTRODUCTION 1-1
2. INDUSTRY AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industry Affected and Process Description 2-1
2.2 Waste Characterization 2-4
2.3 Determination of Waste Treatability Group 2-6
3. APPLICABLE AND DEMONSTRATED TECHNOLOGIES 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-3
4. PERFORMANCE DATA BASE 4-1
4.1 Nonwastewaters 4-2
4.2 Wastewaters 4-3
5. IDENTIFICATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BDAT) 5-1
5.1 BDAT for Nonwastewaters 5-2
5.2 BDAT for Wastewaters 5-3
6. SELECTION OF REGULATED CONSTITUENTS 6-1
6.1 Identification of Constituents in the Untreated
Waste and Waste Residuals 6-1
6.2 Determination of Significant Treatment from BDAT .... 6-2
6.2.1 BDAT List Organic Constituents and
Inorganics Other Than MetaVs 6-2
6.2.2 BDAT List Metals 6-3
6.3 Rationale for Selection of Regulated Constituents ... 6-4
7. DEVELOPMENT OF BOAT TREATMENT STANDARDS 7-1
8. REFERENCES 8-1
APPENDIX A - ANALYTICAL QA/QC A-l
APPENDIX B - INCINERATION B-l
APPENDIX C - WET AIR OXIDATION C-l
i i i
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LIST OF TABLES
Table Page
1-1 BOAT Treatment Standards 1-5
2-1 Major Constituent Analysis of Untreated
KOI 1, K013, and K014 Listed Wastes 2-8
2-2 BOAT Constituent Composition and Other Data for KQ11 .. 2-9
2-3 BDAT Constituent Composition and Other Data for K013 .. 2-11
2-4 BOAT Constituent Composition and Other Data for K014 .. 2-13
2-5 BDAT Constituent Composition and Other Data for
KOI1/K013/K014 Mixed Waste 2-14
4-1 Performance Data Collected by EPA for Incineration
of KOI 1/K013/K014 4-4
5-1 Summary of Accuracy Adjustment of Performance Data
for Incineration of K011/K013/KQ14 Nonwastewater 5-5
6-1 BDAT Constituents Detected or Not Detected in the
KOI1/K013/K014 Wastes and Waste Residuals 6-5
6-2 Constituents for Regulations of K011/K013/K014
Nonwastewaters 6-13
6-3 Calculated Bond Energies for the Organic Constituents . 6-14
7-1 Calculation of Nonwastewater Organic and Cyanide
Treatment Standards for the Regulated Consitituents
Based on Rotary Kiln Incineration Performance Data 7-2
7-2 BDAT Treatment Standards 7-3
LIST OF FIGURES
Figures Page
2-1 Schematic Flow Diagram of the Sohio Process for
Production of Acrylonitrile 2-3
i v
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1. INTRODUCTION
Pursuant to section 3QQ4{m) of the Resource Conservation and Recovery
Act, as enacted by the Hazardous and Solid Waste Amendments on November 8,
1984, the Environmental Protection Agency (EPA) is establishing treatment
standards based on the best demonstrated available technology (BOAT) for
nonwastewater forms of the wastes generated from the production of
acrylonitrile. These wastes are identified in 40 CFR 261.32 as K011,
K013, and K014. Compliance with these BOAT treatment standards is a
prerequisite for the placement of these wastes in units designated as land
disposal facilities according to 40 CFR Part 268. The effective date of
these nonwastewater treatment standards is June 8, 1989. The applicabili-
ty of the restrictions for K0I1, K013, and K014 wastewaters and the effec-
tive date are discussed in the preamble to the final rule for the Second
Third wastes.
This background document presents the Agency's technical support for
selecting and developing the treatment standards for the constituents to
be regulated in the acrylonitrile nonwastewaters. This document also
contains some information relevant to the acrylonitrile wastewaters. The
EPA will summarize any additional information used to develop performance
standards for the wastewaters from acrylonitrile production in an addendum
to this background document. Section 2 presents waste-specific informa-
tion—the number and location of facilities affected by the land disposal
restrictions, the waste generating process, and waste characterization
data. The technologies used to treat the waste (or similar wastes) are
238<»g
1-1
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discussed in Section 3. All the available performance data, including
data on which the treatment standards are based, are presented in
Section 4. Section 5 explains EPA's determinations of 8DAT, and Section
6 discusses the selection of constituents to be regulated. The treatment
standards are determined in Section 7.
EPA wishes to point out that, because of facility claims of
confidentiality, this document does not contain all of the data that EPA
used in its regulatory decision-making process. Under 40 CFR Part 2,
Subpart B, facilities may claim any or all of the data that are submitted
to EPA as confidential. EPA will make determinations regarding the
validity of the facility's claim of confidential business information
(CBI) according to 40 CFR Part 2, Subpart B. In the meantime, the Agency
will treat the data as C8I. Additionally, the Agency would like to empha-
size that it evaluated all available data (including CBI data) in develop-
ing the BOAT treatment standards for KOI1/K013/K014 nonwastewaters.
The BOAT program and EPA's promulgated methodology are more thoroughly
described in two additional documents: Methodology for Developing BDAT
Treatment Standards (USEPA 1988a) and Generic Quality Assurance Project
Plan for Land Disposal Restrictions Program (BDAT) (USEPA 1987). The
petition process to be followed in requesting a variance from the BDAT
treatment standards is discussed in the methodology document.
The Agency has information indicating that generators of the K011,
K013, and K014 listed wastes currently mix them together before treatment
and disposal. Consequently, EPA has developed treatment standards for
233-ig
1-2
-------
these wastes as KOI1/K013/K014 mixed nonwastewaters. However, each
individual waste, if disposed of separately, must also meet the treatment
standards. (For the purpose of determining the applicability of the
treatment standards, wastewaters are defined as wastes containing less
it
than 1 percent (weight basis) total suspended solids and less than
1 percent (weight basis) total organic carbon (TOC). Waste not meeting
this definition must comply with the treatment standards for
nonwastewaters.)
The acrylonitrile wastes contain cyanide and BDAT list organic
constituents. Rotary kiln incineration was determined to be the BDAT for
both the organics and cyanides in the KOI1/KO13/KO14 nonwastewaters. The
Agency is regulating four organic constituents and cyanide in nonwaste-
water forms of the acrylonitrile wastes. For the BOAT list organics and
cyanide, the treatment standards reflect total waste concentration. The
units for total waste concentration are mg/kg (parts per million on a
weight-by-weight basis). Because the Agency is not regulating any BDAT
list metal constituents, there are no treatment standards based on the
metal concentrations in the leachate from the toxicity characteristics
The term "total suspended solids" (TSS) clarified 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 to 1Q5°C) in Standard Methods for the
Examination of Water and Wastewater, 16th Edition (APHA, AWWA, and WPCF
1985).
23o4g
1-3
-------
leaching procedure (TCLP). Testing procedures for all sample analyses
performed for the regulated constituents are specifically identified in
Appendix A of this background document.
The treatment standards for the KOI1/K013/K014 nonwastewater forms
are shown in Table 1-1. Nonwastewaters that, as generated, contain the
regulated constituents at concentrations that do not exceed the treatment
standards are not prohibited from land disposal units untreated.
In the January II. 1989, proposed rule (54 FR 1066-1071), the Agency
proposed wastewater treatment standards based on the performance of wet
air oxidation followed by biological treatment for amenable cyanides,
total cyanides, and organic constituents, and chemical precipitation,
settling, and filtration for metal constituents. The Agency received
many comments concerned with EPA's rationale for transferring performance
data for the cyanide constituents from wet air oxidation of F007 wastes,
and for organic constituents from the effluent limitations for facilities
in the Organic Chemical Plastics and Synthetic Fibers (OCPSF) industry
for biological treatment. Because of these comments and the additional
treatment data that are being compiled by the Ad Hoc Acrylonitrile
Producers UIC Group, the Agency believes that additional data collection
and analysis is necessary prior to promulgation of these treatment
standards.
Therefore, the Second Third land disposal restriction rule does not
promulgate treatment standards for the wastewater forms of K011, KOI3 and
KOI4. These wastes were originally scheduled for regulation in the First
2384g
1-4
-------
Third, with a statutory deadline of August 8, 1988. Since the Agency
still has not promulgated standards for the wastewater forms of K011,
K013 and KO14, land disposal of these wastewaters shall continue to be
regulated by the "soft hammer" provisions in 40 CFR 268.8. EPA intends to
promulgate concentration-based treatment standards for cyanides, organics,
and metals constituents for these wastes prior to May 8, 1990.
2384g
1-5
-------
Table 1-1 BDAT Treatment Standards
BOAT Treatment Standards for K021/K013/KO14 Nonwastewaters
Maximum for any
single grab sample
Total composition TCLP
Constituent (mg/kg) (mg/1)
Acetonitrile 1.8 Not Applicable
Acrylonitrile 1.4 Not Applicable
Acrylamide 23 Not Applicable
Benzene 0.03 Not Applicable
Cyanides (Total) 57 Not Applicable
BDAT Treatment Standards for K011/K013/K014 Wastewaters
Maximum for any
single grab sample
Total composition
Constituent (mg/1>
(EPA intends to propose and promulgate
K011/K013/K014 wastewater treatment
standards prior to May 8, 1990.)
2334g
1-6
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2. INOUSTRY AFFECTED AND WASTE CHARACTERIZATION
This section includes a description of the industry affected by the
land disposal restrictions for waste codes K011, K013, and K014 and the
production processes employed in this industry. Also included is a
discussion of how K011, K013, and KQ14 wastes are generated as well as
characterization of both the individual K011, K013, and K014 wastes and
the KOII/K013/KO14 mixed wastes. This section concludes with a discussion
of the basis for combining listed acrylonitrile waste codes into one
treatability group.
The full list of hazardous waste codes from specific sources is given
in 40 CFR 261.32. Within this list, three specific hazardous waste codes
are generated by acrylonitrile manufacturers:
KOI 1: Bottom stream from the wastewater stripper in the production
of acrylonitrile.
K013: Bottom stream from the acetonitrile column in the production
of acrylonitrile.
KQ14: Bottoms from the acetonitrile purification column in the
production of acrylonitrile.
2.1 Industry Affected and Process Description
The four-digit standard industrial classification (SIC) code reported
for the acrylonitrile industry is 2869. The Agency has identified six
facilities in the United States that actively manufacture acrylonitrile
and could generate K011, K013, and K0I4 listed wastes (Standford Research
Institute 1988). Of the six acrylonitrile manufacturers, one is located
in Ohio (EPA Region V), one in Louisiana (EPA Region VI), and four in
Texas (EPA Region VI).
£ 38*ig
2-1
-------
Acrylonitrile is manufactured in the United States by the Sohio
Process. This process involves vapor-phase catalytic air oxidation of
propylene and ammonia, also known as ammoxidation, to yield acrylonitrile.
The principal byproducts of the process are hydrogen cyanide,
acetonitrile, and acrylamide. The process flow diagram is illustrated in
Figure 2-1. Approximate stoichiometric quantities of propylene, ammonia,
and oxygen (as air) are reacted in a fluidized bed reactor to yield
acrylonitrile and other byproducts. The gaseous effluents from the reac-
tor are quenched and scrubbed in a quenching column using sulfuric acid
solution. Unreacted ammonia is converted to soluble ammonium sulfate in
the presence of sulfuric acid. Liquid effluents from the quench column
are treated in a wastewater stripping column to recover the low boiling
point organics. The bottom stream from the stripping column constitutes
one of the listed wastes (K011). Typical generation rates for this waste
stream vary from 100 to 200 gallons per minute.
Gaseous effluents from the quench column are sent to an absorber,
where the acrylonitrile and byproducts are absorbed in water. The aqueous
solution from the absorber is treated in an acrylonitrile recovery column
to obtain acrylonitrile and hydrogen cyanide (HCN) as the overhead
products. The overhead products are treated further in a heads column to
recover hydrogen cyanide. The acrylonitrile bottom stream from the heads
column is dried and purified further to yield polymer-grade acrylonitrile.
The bottom stream from the recovery column consists of a dilute
aqueous solution of acetonitrile, which is treated in a steam stripping
column to obtain acetonitrile and hydrogen cyanide as the overhead
2-2
2384g
-------
TO
Alfl POLLUTION
CONTROL DEVICE
PROPYLENE
AMMONIA
IN)
¦
U>
AIR
DILUTE
SULFURIC
ACID
STEAM
STEAM
f *\ WATER
V
A
A
a z z
GEO
ft 1
HON
(TO PURIFICATION
OR INCINERATOR)
AcimoNnnii e
TO STORAGE
ACRYLONITfllLE
DRYING
—»~
PURIFICATION
COLUMN
(TO INCINERATOR)
TO
ACiTONITRILE
STORAGE
COLUMN BOTTOMS
(KOtl)
T
COLUMN BOTTOMS
(K013)
COLUMN BOTTOMS
(KO14)
FIGURE 2-1. SCHEMATIC FLOW DIAGRAM OF THE SOHIO
PROCESS FOR PRODUCTION
OF ACRYLOHITHILE
-------
products. The bottom stream from this column constitutes a listed waste
stream (K013). Typical generation rates for this stream vary from 100 to
200 gallons per minute. Depending upon the demand for acetonitri1e, some
acrylonitrile production plants treat the crude acetonitrile stream in a
purification column to obtain commercial-grade acetonitrile. The bottoms
from the acetonitrile purification column represents the third listed
waste stream (K014). Typical generation rates for this stream vary from
4 to 14 gallons per minute. In acrylonitrile production facilities where
the acetonitrile is not refined, the crude acetonitrile stream is usually
incinerated in an off-gas incinerator, thus eliminating the generation of
K014.
2.2 Waste Characterization
The waste streams are identified in Figure 2-1. The listing constitu-
ents for <011, K013. and K014 include acrylonitrile, acetonitrile, and
hydrocyanic acid. The approximate percent concentrations of major
constituents making up individual K011, K013, and K014 listed wastes,
K011/K013/K014 wastewater mixtures, and K011/K013/K0I4 nonwastewater
mixtures are summarized in Table 2-1 at the end of this section. (For
the purposes of this rule, the Agency's definition of a wastewater is a
waste that contains less than 1 percent (weight basis) total suspended
solids and less than 1 percent (weight basis) total organic carbon
(TOC). Wastes not meeting this definition are defined as nonwastewaters.)
Typically, the K011 waste stream contains about 100 to 4,000 ppm of
cyanide, 40 to 3,000 ppm of acetonitrile, 0.2 to 8,000 ppm of
acrylonitrile, 1,000 to 2,000 ppm of acrylamide, and less than 200 ppm of
2-4
2334g
-------
acrolein. In addition to the primary contaminants listed above, this
stream also contains approximately 4 percent suspended solids. The
suspended solids consist largely of spent, inorganic catalyst particles
and polymeric acrylonitrile. Also, the KO11 stream contains about
10 percent dissolved sulfates. Waste characterization data for KO11 are
presented in Table 2-2. These data indicate that KO11 is a nonwastewater
by definition.
The K013 waste stream typically is 99 percent water and contains about
26 to 60 ppm of cyanide, less than 35 ppm of acetonitrile, less than
10 ppm of acrylonitrile, less than 120 ppm of acrylamide, and less than
1 ppm of acrolein. Waste characterization data for K013 are presented in
Table- 2-3. These data indicate that K013 is a wastewater by definition.
Primary pollutants in the K014 waste stream are acetonitrile and
cyanide. Generally, the KO14 waste stream contains 1,000 to 60,000 ppm
of acetonitrile and up to 10,000 ppm of ethyl cyanide and is 83 to 99
percent water. Waste characterization data for K014 are presented in
Table 2-4. These data indicate that K014 is a nonwastewater by defini-
tion.
It is current practice to mix the waste streams in settling ponds/
tanks where the suspended solids are separated as a sludge that is gener-
ally land disposed or incinerated and a liquid that is usually injected
into a deep well. Waste characterization data for mixed K011/K013/K014
wastewaters and mixed K011/K013/KO14 nonwastewaters are presented in
Table 2-5.
i23ig
2-5
-------
2.3 Determination of Waste Treatability Group
In cases where EPA believes that constituents present in different
listed wastes can be treated to similar concentrations by using the same
technologies, the Agency may combine the listed wastes into one treatabil-
ity group.
The Agency has determined that the acrylonitrile waste codes (K011,
K013. and KOI4) represent a single waste treatability group. This deter-
mination was made because these wastes originate from the same industry
and similar processes and have similar chemical characteristics. Although
concentrations of specific constituents will vary from one listed waste
to another, 'all of the above wastes contain similar constituents and are
expected to be treatable to similar levels using the same technology.
Furthermore, in a typical production facility, the acrylonitrile waste
streams (K011, K013, and possibly KOI4) are cowningled prior to their
ultimate disposal. The mixed waste is sent to settling ponds/tanks,
where the suspended solids are- removed as an underflow sludge and the
liquid is disposed of in deep wells.
The Agency is aware that all acrylonitrile production facilities
generate K011 and K013 waste streams and only those facilities that purify
the crude acetonitrile generate the K014 waste stream. However, the
Agency believes the KOI1/K013/KOI4 waste matrix is more difficult to
treat than the KOI1/KO13 matrix, hence, the K011/K013 waste mixture can
be treated to the same levels as the K011/K013/K014 waste mixture. This
assumption is based on the characterization data for the individual
2384g
2-6
-------
wastes showing K014 typically has the highest concentrations of the regu-
lated BOAT constituents among these wastes. Consequently, EPA examined
the characteristics of the KQ11/K013/K014 mixed wastes, applicable
treatment technologies, and treatment performance levels attainable in
order to support a single regulatory approach for the three wastes as a
KOI1/K013/K014 nonwastewater mixture and a K011/K013/K014 wastewater
mixture.
23S4g
2-7
-------
?J79g
Iable 2-1 Major Constituent Analysis of Untreated
KOI I. K013, and K0I4 listed Wastes
Major constituents
KOI I
Concent rat ion M X>
K0I3
KOM
Mixed KOI1/K0I3/K0I4
wastewater
Mixed KOI1/K013/K014
nonwastewater
Arnnoniun sulfate
BOAI list volatile constituents
(including acrolein, acetonitrile,
acrylonitrile. benzene, ethyl
cyanide)
10
0.5
*0 1
10
0 9
Cyanide
Inert solids (including silicon,
¦olybdenun. iron, aluninin oxides)
0.5
<0 1
0 8
<1
0 1
<1.0
16
50
Water
85
99
93
97
30
= No analysis performed.
-------
2779g
Idble 2-2 BDAI Constituent Composition and Other Oata for KOI 1
Untreated KOII waste characterization (mg/kg)
Analysis (a) (b) (c) (d) (e) (f) (g) (h) (i) (j)
BDAI list Volatile*:
Acrolein
Acetonitrile
Acrylamide
Aery Ionitrile
Benzene
[thyI cyanide
Pyridine
200
3,000
1.000
>500
<0.2
3.000
<500
30.1
2,300
2.040
5,420
60 120
40-2.800
100-2.500
1.100
B.000
100
4/
300
BOAI List Sewivolat i les:
Phenol - <0.03 - - 0 13
pDAI List Netals:
Antimony - - - 0.20
Arsenic - - - 0.21
Bariua - - - 0.004
Nickel ------- o 59
Lead - ' - - - - - - - 0.04
Zinc - - - - - - - 0.02
Other BDAI List Inorganics:
Cyanide 270 700 100 1,240 3,700
Cyanide (as
hydrogen cyanide) 4,000 - <0.2 7,000
Fluoride - - - - -47
Others:
Acetaldehyde 1,000 --------
Acetic acid 2.000 --------
Acrylic acid 300 --------
Aery Ion itrile polymer
Amnonia 16.500 19,000 24,000 9.300 15.000 -
Amnonia sulfate - 100.000 100,000-120.000
Ash content 1.000
-------
Iable 2-2 (continued)
Untreated K.01I waste charactert/at ion Img/kg)
Analysis (a) (b) (c) (d) (e) (f) (g) (h) (i) (j)
Others (continued):
BOO . . . . . 46.300
Boron - 0.4
Btu content (Btu/lb) - - - 524
COO 6b.bOO
Funaronitri le 500 -
Hydrogen sulfide 6
Nitriles 2,800 • -----
Nitrogen (as amide) 3,100 -
Nitrogen (as aimonia) 13,700 ¦
Nitrogen (as nitrate) 61 -
Nitrogen (as nitrite) 4,200 --------
Nitrogen (as nitrite) 540 -
pH 4.9-5.0 ------
Phosphorous 0.4
Polymeric Material 60,000 --------
Sulfates 32.000 74.000 86,000 90,000 32,000 -
Sulfur -- - - - 1.4
Suspended solids - - - 40,000 -
IOC ----- 26,000
Water (X) 90 90
- = No analysis performed.
(a) Reference: USIPA 1966a.
(b) Reference: USEPA 1986a.
(c) Reference: USCPA 1986a.
(d) Reference: USIPA 1986a.
(e) Reference: USEPA 1980.
(f) Reference: Nennrandun from Samuel I . Hayes. EER Laboratory Manager, to Lisa Brown. HWERL Project Officer, on November 25, 1987,
concerning sanple results.
(g) Rgference: Hemorandifn from Radha Kristman. PCI, to Ron turner, EPA-0R0. on October 23. 1987. concerning telephone conversation Milh Steve Lang.
Environmental Superintendent for the Sohio Lima Plant.
(h) Reference: Hemorandifn frun Ouane Parker. Oyanamac, to Yvonne Garbe. IPA-0SU. on January 2, 1987.
(i) Reference: USCPA 1988a.
(j) Reference: Hemorandun from Radha Krislman, PU. to Ron lurner. LPA-0HD. on Dec enter 9. 19B7, concerning site visit to Schio Chemical.
-------
if//Hg
lable 2-3 BOAT Constituent Conjiosition and Other Data for K013
Analysis
(a)
(b)
Untreated KOI3 waste characterization (mq/ltql
(c)
(d)
(e)
if)
(9)
(h)
BDAI tist Vo tat lies:
Acetone
Acetonitri le
Acrolein
Aerylamide
Acrylonitrile
35
<10
0.8
2 5
35
<10
26 5
0.34
120
1.61
0.45
6.8
2.1
BDAI list Seaivolat i les:
PhenoI
<0 01
BOAT tist Metals:
Arsenic
Pariui
Nickel
Lead
I inc
0.019
0.030
0.02
0 003
0.02
Other BDAI List Inorganics:
Cyanide
Cyanide (as hydrogen cyanide) 225
35
26
60
225
34
31
Others:
Acetic acid
Anmonia
Ash
BOO
Boron
Btu content (Btu/lb)
COD
Nitrites
ptl
Phosphorous
Sulfates
|0C
Water (X)
120
220
6,700
500
143
4.000
6 7
153
500
300
0.2
5.2
19
36
46,300
15.800
4,810
1,000
99
103
4.800
99 5
-------
<•/ /ay
table 2-3 (continued)
Nu analysis performed
(a)
Reference:
USE PA
1986a.
(b)
Reference:
USLPA
l98Ga.
(c)
Reference:
USIPA
1986a.
(d)
Reference:
USLPA
1966a.
(e|
Reference:
USfPA
1980
(f)
Reference:
Mtsnorandua f
sanyle results.
Samuel L. Ilayes. £TR laboratory Manager, to I isa Brown, HWERL Project Officer, on November 25. 198/, concerning
sanyle results
(g) Reference: Mcmurandun frem Radha Kristman. PEI, to Ron Turner. TPA ODD, on October 23. 1987, concerning telephone conversation with Steve Lany,
invironmental Superintendent for the Sohio LIm Plant.
(h) Reference: USfPA 1988b.
-------
2779g
lable 2-4 BUAI Constituent Conposition and Other Data for K014
Analysis
Untreated KOI4 waste characterization (mq/kq)
(a)
(b)
(c)
(d)
(e)
BDAI 1 ist Volat iles:
Acetone
Acelonitri le
Dichlorodif luoromethane
Ethyl cyanide
Pyr idine
1.000-?.000
22.000
60.000
10,000
1.700
4 3
3.000
9 1
130
99
BDAI list Sen) t volat i les:
2-Picol ine
l?0
BDAI I ist Hetals:
Ant imony
Bariun
Cadniun
Chromiun
Copper
Nickel
Lead
I inc
<0 85
<0 05
<0.10
<0.18
<0.15
<0.38
<0 05
0.07
0 05
0 01
0 006
0.03
0 05
0.04
0.011
0 03
<0.034
0.009
0.02
0.01
0.03
0.02
0.04
0.04
Other BDAI List Inorganics:
Cyanide
5,000
4.3
300
4.500
Others:
Btu content (Btu/lb)
P"
IOC
Water (X)
2.0 2.5
1,000
99
1.589
83.4
718
93.2
435
96
- - No analysis performed.
(a) Bottoms from the acetonitrile purification colimn in the production of aerylonitrile (Reference: UStPA 1985).
(b) Reference: Mcmorandun from Radha Krishman. PI I. to Ron turner EPA-OHO, on October 23, 1987. concerning Telephone
conversation with Steve Lang. Environmental Superintendent for the Sohio Lima Plant.
(c) Reference: USfPA 1988b
(d) Reference: DM HA 1988b.
(e) Reference: USfl'A 1988b
-------
27/9g
Table 2-5 BOAI Constituent Canposition and Other Data for KOII/K013/K014 Nixed Wastes
Untreated wined KOI 1/IC0I3/K0I4 waste characterization Imq/fcql
Analysis (a) (b) (c) (d) (e)
BOAI list VoUtiles:
Acelonitrile
Acetone
Aery Ianide
Aerylonitrile
Benzene
Chloroforn
Methylene chloride
1.1.1 -1r ich loroethane
Irichloroethene
0 68 2 /
0.04 0.09S
2 4 2 9
0 41-0 95
48 61
0.030 0.042
0.023 0.042
0 026 0 045
0 014 0.019
177
217
500-50.000
420 490
<5 65
575
24 4
270
Other volat iles
Styrene
14-19
BDAI tist Sonivolat i les:
Phenol
4.2
BDAT list Hetals:
Arsenic
Barius
Cadmiun
Chronim
lead
N icke I
Z inc
2.7-6.2
82-200
2 0-2.9
95-200
35 41
280 470
140 210
0.02
0 1/
3.2
0.28
<0 05
15 4
<0.04
0.38
0.012
1.08
18
Other BDAI list Inorganics:
Cyan ide
Cyanide (as hydrogen cyanide)
Fluoride
5,000-5.200
56 73
391
500-50.000
20.000 250,000
240-350
.211
-------
27/9g
I able 2-5 (continued)
Untreated mixed KOI I/K0I3/K0M waste characteri/ation (mti/kq)
Analysis (a) (b) (c| (d) (e)
Other:
Aerylonitrile polymer - 20,000-260,000
Aliminw 500-1,100
Aluninun oxide 20.000-500,000
Amnonia 4,000
BOD (biological oxygen demand) .... 7,207
COD (chemical oxygen demand) 6,440 26,100 37,900
Copper 12-22 0 20
Iron 2.000-4.000 5 9 20,000 500.000
Holybdenua 0,300 17,000 40 1 20,000 500.000 73.6
pH 8 1
Phosphorous 2.4 -
Silicon 45 200 -
Sulfate 33.000 36.000 12.000 20.000 500.000 29,000-45.000
lota I solids - - 100.000 400.000 91,000
IDS (total dissolved solids) - 53,000-75,000
IOC (X carbon) 17-31 ...
Water (X) 97 10 30
- = No value reported.
(a) Nonwastewater spent catalyst from the bottom of a surface impounctnent containing KOI I, K0I3. and K0I4. (Reference:
USEPA 1988a )
(b) Combined K0U. K013. and K0I4 wastewater. Aqueous waste includes plant washdown water, transport vehicle flush
water, and rainwater runoff from the wnufacturing unit. (Reference: USEPA 1985.)
(c) Combined KOI I, K013. and K0I4 nonwastewater. (Reference: USfPA 1985.)
(d) Combined K01I. K0I3, and K0I4 wastewaters. (Reference: Hemorandun to Ronald Turner, EPA-0SW, from Radha Krishnan, PEI,
on February I, 1988)
(e) Combined K011. K013. and K014 wastewaters. (Reference: Mcmorandun to James Ber low. EPA-0SW. from Ronald Turner,
EPA-0RD. on June 21, 1988. concerning the results of wet air oxidation bench-scale tests of K011. K013. and K0I4 mixed
sludge.)
-------
3. APPLICABLE AND DEMONSTRATED TECHNOLOGIES
Section 2 established one treatability group for the management of
K011, K013, and K0I4 nonwastewaters. This section identifies the treat-
ment technologies that are applicable to this group and determines which,
if any, of the applicable technologies can be considered demonstrated for
the purposes of establishing BOAT.
To be applicable, a technology must be theoretically capable of
treating the waste in question or of treating a waste that is similar in
terms of the parameters that affect treatment selection. The applicable
technologies are discussed in Appendix B and Appendix C. To be
demonstrated, the technology must be employed in full-scale operation for
the treatment of the waste in question or a similar waste. Technologies
that are available only at pilot- and bench-scale operations are not
considered in identifying demonstrated technologies.
3.1 Applicable Treatment Technologies
Initial data gathering on the treatment of K011, K013, and K014- wastes
included phone contacts with industry, review of the technical literature,
and contacts with the EPA Office of Research and Development.
Characterization data presented in Section 2 show that the K011, KOI3,
and K014 listed wastes contain treatable quantities of BDAT list organics
and cyanide. By definition, the KOI] and K014 listed wastes are nonwaste-
waters and K013 is a wastewater; however, most generators of the
acrylonitrile wastes mix them together in a settling pond/tank, which
?3S4g
3-1
-------
generally results in a KOI1/K013/K014 wastewater and nonwastewater. The
treatment technologies considered applicable for the nonwastewater forms
are those that destroy or recover BOAT list organic compounds and cyanide.
The applicable technologies that the Agency has identified for
treatment of BDAT list organics and cyanide present in KOI1/K013/K014
nonwastewater are rotary kiln incineration and wet air oxidation.
Incineration is a technology that destroys the cyanide and organic
components in the waste. Wet air oxidation is a. technology used to treat
aqueous wastes that contain certain organics and oxidizable inorganics
such as cyanide. Wet air oxidation reduces but typically does not totally
destroy the organic concentrations in the treatment residuals (i.e.,
wastewater effluent and reactor still bottoms). That is, these residues
may still contain quantities of BDAT list organic and cyanide concentra-
tions that may require further treatment prior to disposal.
3.2 Demonstrated Treatment Technologies
The Agency believes that incineration is demonstrated to treat the
BOAT list organics and cyanide present in the KOI1/K013/K014 nonwaste-
waters. The Agency has identified one facility performing pilot-scale
incineration tests on the K011/K013 nonwastewaters. Incineration of the
KOI1/K013/K014 nonwastewaters has also been tested at an EPA test facili-
ty. Furthermore, incineration is a proven full-scale technology for
destroying organics and cyanides in numerous hazardous waste streams.
Hence, the Agency believes that incineration is demonstrated for
KOI1/K013/K014 nonwastewaters.
Zioig
3-2
-------
Wet air oxidation is demonstrated to treat KOi1/K013/K014 nonwaste-
waters. EPA has identified one facility that is currently performing
pilot-scale tests on the K011/K013/K014 nonwastewaters. In addition, wet
air oxidation is a proven full-scale technology for treating organics and
cyanides in numerous hazardous wastes. Thus, the Agency considers wet
air oxidation to be demonstrated for KOI1/K013/K014 nonwastewaters.
Detailed discussions of incineration, and wet air oxidation are
presented in Appendix B and Appendix C.
2384=
3-3
-------
4. TREATMENT PERFORMANCE DATA BASE
This section presents the data available to EPA on the performance of
demonstrated technologies in treating the K011, K013, and K014 listed
wastes. These data are used elsewhere in this document for determining
which technologies represent BOAT (Section 5), for selecting constituents
to be regulated (Section 6), and for developing treatment standards
(Section 7). In addition to full-scale demonstration data, the data used
to develop treatment standards may include data developed at research
facilities or obtained through other applications at less than full-scale
operation, as long as the technology is demonstrated in full-scale opera-
tion for a similar waste or wastes as defined in Section 3.
Performance data., to the extent that they are available to EPA,
include the untreated and treated waste concentrations for a given
constituent, values of operating parameters that were measured at the
time the waste was being treated, values of relevant design parameters
for the treatment technology, and data on waste characteristics that
affect performance of the treatment technology.
Where data are not available on the treatment of the specific wastes
of concern, the Agency may e1e„ct to transfer data on the treatment of a
similar waste or wastes, using a demonstrated technology. To transfer
data from another waste category, EPA must find that the wastes covered
by this background document are no more difficult to treat (based on the
waste characteristics that affect performance of the demonstrated treat-
ment technology) than the treated wastes from which treatment performance
levels are being transferred.
4-1
233«g
-------
4.1 Nonwastewaters
EPA tested incineration to demonstrate the actual performance
achievable by this technology for treatment of the BOAT list organics and
cyanide present in the KOI1/K013/K014 nonwastewaters. Since EPA is not
aware of any generator or treatment, storage, and disposal (TSD) facility
currently using full-scale incineration for treatment of K011, K013, and
K014 listed wastes, the K011/K013/K014 nonwastewaters were collected from
a generator and incinerated using a pilot-scale unit at a commercial
facility, John Zink Company in Tulsa, Oklahoma.
The Agency has received incineration performance data from an
industrial source testing incineration as a treatment for K011/K013
nonwastewaters; however, no BOAT list constituent concentrations for the
treatment residuals (i.e., scrubber water, ash) were reported.
EPA has collected untreated and treated data for KOI1/KO13/K014 non-
wastewaters using rotary kiln incineration at the commercial facility.
These data are shown in Table 4-1 at the end of this section. Four of
the data sets show significant treatment for two organics (i.e., benzene,
styrene) and cyanide detected in the untreated KO12/K013/KO14 nonwaste-
waters. (For a discussion on significant treatment, see Section 5.) The
treated data represent total waste concentration found in the scrubber
water and ash residuals. Operating data and design data collected during
the test are also shown in Table 4-1. These data indicate that the system
was operated within the design specifications.
The Agency has received wet air oxidation performance data from an
industrial source. These data show reductions for some of the organics
4-2
228Cg
-------
and cyanide concentrations in the treatment residuals. However, these
data and all treatment process information have been classified as confi-
dential business information and cannot be presented in the KQ11/K013/K014
background document. These data are located in the RCRA CBI docket.
4.2 Wastewaters
Treatment performance data specifically for the K011/K013/K014
wastewaters are being compiled by the Ad Hoc Acrylonitrile Producers UIC
Group. These data will be presented in an addendum to this background
document.
23345
4-3
-------
5. IDENTIFICATION OF BEST DEMONSTRATED
AVAILABLE TECHNOLOGY (BDAT)
This section presents the Agency's rationale for determining the best
demonstrated available technology (BDAT) for KOI1/K013/K014 nonwaste-.
waters. Based on the lack of available data specifically for treatment of
acrylonitrile wastewaters as described in Section 4, the Agency intends
to collect additional data on treatment of KOI1/K013/K014 wastewaters and
to identify the BDAT by May 8, 1990.
To determine BDAT, the Agency examines all available performance data
on technologies that are identified as demonstrated to determine (using
statistical techniques) whether one or more of the technologies performs
significantly better than the others. All performance data used for
determination of best technology must first be adjusted for accuracy, as
discussed in EPA's publication, Methodology for Developing BDAT Treatment
Standards. (Accuracy adjustment accounts for the ability of an analytical
technique to recover a particular constituent from the waste in a
particular test. The recovery of a constituent is usually determined by
spiking a sample with a known amount of the target constituent and then
comparing the spiked sample amounts with results from unspiked samples.)
The accuracy-corrected performance data for the K011/K013/K014 wastes are
presented in Table 5-1 at the end of this section. BDAT must be
specifically defined for all streams associated with the management of
the listed waste or wastes; this pertains to the original waste as well
as to any residual waste streams created by the treatment process.
238-g
5-1
-------
The technology that performs best on a particular waste or waste
treatment is then evaluated to determine whether it is "available." To
be available, the technology must (1) be commercially available to any
generator and (2) provide "substantial" treatment of the waste, as
determined through evaluation of accuracy-adjusted data. In determining
whether treatment is substantial, EPA may consider data on the performance
of a waste similar to the waste in question, provided the similar waste
is at least as difficult to treat. If the best technology is found to be
not available, then the next best technology is evaluated, and so on.
5.1 BOAT for Nonwastewaters
As mentioned in Section 2, the K011/K013/K014 nonwastewaters contain
BOAT list organics and cyanide. These wastes can have a total organic
carbon content of greater than 1 percent and a total suspended solids
content of greater than 1 percent.
The two demonstrated technologies identified for organics and cyanide
treatment of KQ11/K013/K014 nonwastewaters for which the Agency has data
are rotary kiln incineration and wet air oxidation. Operating data
collected during both the incineration and wet air oxidation tests show
that both data sets represent the performance of systems operating within
the design specifications. Therefore, all data were used in the selection
of BOAT.
Next, the Agency examined both data sets to determine whether inciner-
ation performs better than wet air oxidation. The results of the compari-
son of incineration and wet air oxidation indicate that incineration pro-
vides better treatment for the organics and cyanide in the KOI1/K013/K014
5-2
?3o4g
-------
nonwastewaters. Because the wet air oxidation data are confidential,
reasons for this decision are presented as confidential business informa-
tion and are located in the RCRA CBI docket.
Using the incineration performance data, EPA's determination of
substantial treatment for organics is based on the reduction of BOAT list
organic constituents from levels as high as 61 mg/kg to nondetectable
levels of less than 0.01 mg/kg in the ash residual. EPA's determination
of substantial treatment for cyanide is based on the reduction of total
cyanide from levels as high as 2,000 mg/kg to levels of less than 38 mg/kg
in the ash. The concentrations of cyanide in the ash residual may
actually be lower than the values reported, but the complex ash residual
matrix caused a higher than desired detection limit.
The Agency has determined that these reductions are substantial and
that incineration is available to treat organics and cyanide present in
K011/K013/K014 nonwastewaters because it is commercially available.
Therefore, incineration represents BOAT for the organics and cyanide
present in the K011/K013/K014 nonwastewaters.
5.2 BOAT for Wastewaters
The characterization data presented in Section 2 reveal that the
K011/K013/K014 wastewaters contain BOAT list organics and cyanide. The
wastewaters usually contain less than 1 percent total organic carbon and
less than 1 percent total suspended solids.
The Agency received several comments on the proposed rule indicating
that treatability studies on actual KOI1/K013/K014 wastewaters will be
available in the future. EPA has decided to review these additional data
5-3
-------
before establishing BOAT for the K011/K013/K014 wastewaters, since the
Agency believes that these treatability tests may show better treatment
than the available data.
23S4g
5-4
-------
27169
Table 5-1 Smmary of Accuracy Adjustment of Perforwnce Data for
Incineration of K011/K013/K014 Nonwastewater
Analytical Data BOAT list constituent concentrations
Saagle Set #1
Percent
recovery
Mixed
for
Accuracy-
KOI1/K013/K014
¦atrix
Accuracy
adjusted
norwastevaters
Ash
spike
correction
concentrat ion
Constituents
(rag/kg)
(mg/kg)
test
factor
(mg/kg)
BDAT list wolatiles
Acetonitrile
0.870
<0.5
79
1.266
<0.63
Aery lonitri 1e
0.410
<0.5
100
1.0
<0.5
Acrylaaide
2.8
<6.5
79
1.266
<8.2
Acetone
<0.04
<0.25
100
1.0
<0.25
Benzene
57
<0.01
100
1.0
<0.01
Chloroform
0.03Z
<0.01
100
1.0
<0.01
Methylene Chloride
0.034
<0.ZS
100
1.0
<0.25
1,1,1-Trichloroethane
0.045
<0.01
100
1.0
<0.01
Trichloroethene
0.016
<0.01
100
1.0
<0.01
Other volatiles
Styrene
16
<0.01
100
1.0
<0.01
BOAT list inoroanics
Cyanide (total)
1ZOO
10
58
1.724
17
5-5
-------
2716g
Table 5-1 (continued}
Analytical Data BOAT list constituent concentrations
Saile Set 12
Percent
Constituents
Mixed
CQU/K.013/K014
norwastewaters
(ag/kg)
Ash
(¦g/kg)
recovery
for
¦atrix
spike
test
Accuracy
correction
factor
Accuracy-
adjusted
concentrat ion
(¦gAg)
BOAT list volatiles
Acetonitri1«
0.68
<0.5
79
1.266
<0.63
Acrylonitri le
0.52
<0.5
100
1.0
<0.5
Acrylande
2.4
<6.5
79
1.266
<8.2
Acetone
<0.04
<0.25
100
1.0
<0.25
Benzene
61
<0.01
100
. 1.0
<0.01
Chlorofor*
0.39
<0.01
100
1.0
<0.01
Methylene chloride
0.023
<0.25
100
1.0
<0.25
1,1.1-Tr ichloroethane
0.026
<0.01
100
1.0
<0.01
Trichloroethene
0.019
<0.01
100
1.0
<0.01
Other volatiles
Styrene
19
<0.01
100
1.0
<0.01
BOAT list inoraanics
Cyanide (total)
1400
5.8
58
1.724
10
5-6
-------
2716g
Table 5-1 (continued)
Analytical Data
BDAT list constituent concentrations
le Set >3
Constituents
Mixed
K011/K013/K014
nonvastewaters
(ag/kg)
Ash
(ng/kg)
Percent
recovery
for
¦atrix
spike
test
Accuracy-
Accuracy adjusted
correction concentration
factor (ag/kg)
BDAT list volatiles
Acetonitrile 1.?
Acrylonitri le 0.54
Acrylaaide 2.6
Acetone 0.095
Benzene 48
Chloroform 0.030
Methylene chloride 0.24
1.1.1-Trichloroethane 0.029
Trichloroethene 0.014
Other volatiles
Styrene 15
BOAT list inorganics
Cyanide (total) 2000
- * No value available because no analysis perfoiwd on treatment residuals.
5-7
-------
2716g
Table 5-1 (continued)
Analytical Data
BDAT list
constituent concentrations
Sanole Set #4
Percent
recovery
Mixed
for
Accuracy-
K011/M13/K014
aatrix
Accuracy
adjusted
nonoastetMters
Ash
spike
correction
concentration
Const ituents
(¦g/kg)
(og/kg)
test
factor
(¦gAg)
BOAT list volatiles
Acetonitri le
1.9
<0.5
79
1.266
<0.63
Acrylonitri le
0.63
<0.5
100
1.0
<0.5
Acrylaaide
2.7
<6.5
79
1.266
<8.2
Acetone
<0.04
<0.25
100
1.0
<0.25
Benzene
59
<0.01
100
1.0
<0.01
Ch lorofora
0.034
<0.01
100
1.0
<0.01
Methylene chloride
0.041
<0.25
100
1.0
<0.25
1,1.1-Trichloroethane
0.02
<0.01
100
1.0
<0.01
Inch loroethene
0.017
<0.01
100
1.0
<0.01
Other volatiles
Styrene
16
<0.01
100
1.0
<0.01
BOAT list inorganics
•
Cyanide (total)
1300
22
58
1.724
38
5-8
-------
2716g
Table 5-1 (continued)
Analytical Data
BOAT list
constituent
concentrations
Sarnie Set
#5
Percent
recovery
Nixed
for
Accuracy-
K011/K013/KQ14
matrix
Accuracy
adjusted
nomMsteaaters
Ash
spike
correction
concentration
Constituents
(¦9/kg)
(¦g/kg)
test
factor
(¦g/kg)
8DAT list »olatites
Acetonitri le
2.7
<0.5
79
1.266
<0.63
Acrylonitrile
0.95
<0.5
100
1.0
<0.5
Acrylaaide
2.9
<6.5
79
1.266
<8.2
Acetone
0.081
<0.25
100
1.0
<0.25
Benzene
55
<0.01
100
1.0
<0.01
Chlorofora
0.042
<0.01
100
1.0
<0.01
Methylene chloride
0.21
<0.25
100
1.0
<0.25
1,1,1-Trichloroethane
0.032
<0.01
100
1.0
<0.01
Trichloroethene
0.018
<0.01
100
1.0
<0.01
Other volat i les
Styrene
18
<0.01
100
1.0
<0.01
BOAT list inorganics
Cyanide (total)
1500
4.8
58
1.724
8.3
5-9
-------
27l6g
Table 5-1 (continued)
Analytical Data
BDAT list constituent concentrations
Set #6
Mixed
K0U/K013/K014
norwasteMters
Percent
recovery
for
¦itrix
Accuracy-
Accuracy adjusted
correction concentration
factor (ng/kgj
Constituents
(ag/kg)
Ash spike
(mg/kg) test
BDAT list volatilea
Acetonitrile - - - -
Aery lonitri le - -
Acrylaaide -
Acetone -
Benzene - - - - -
Chlorofora -
Methylene chloride - -
1.1,1-Trichloroethane -
Trichloroethene - -
Other volatiles
Styrene - -
BOAT list inorganics
Cyanide (total) - 9.0 58 1.724 16
- = No value available because no analysis performed on untreated aaste or treatnent residuals.
5- 10
-------
2716g
Table 5-1 (continued)
Analytical Data
BOAT list constituent concentrations
Const 1 tuents
Mixed
KOI1/K013/K014
nomwstewaters
(¦g/kg)
Sanole Set <7
Ash
(ng/ka)
Percent
recovery
for
aatrix
spike
test
Accuracy-
Accuracy adjusted
correction concentration
factor (ng/kg)
BDAT list volatiles
Acetonitrile - - - - -
AeryIonitrile - -
Acrylaaida -
Acetone - -
Benzene -
Chlorofom -
Methylene chloride - -
1.1,1-Trichloroethane - - -
Trichloroethene - -
Other volatiles
Styrene - -
BOAT list inorganics
Cyanide (total) - 12 58 1.724 21
- = No value available because no analysis performed on untreated waste or treaaent residuals.
Reference: USEPA 1988a.
5-11
-------
-------
6. SELECTION OF REGULATED CONSTITUENTS
This section presents the rationale for the selection of regulated
constituents for the treatment of KO11/KO13/KO14 nonwastewaters. The
Agency will determine regulated constituents for K011/K013/K014 wastewater
forms prior to May 8, 1990.
Constituents selected for regulation must satisfy the following
cri teri a:
1. They must be on the BOAT list of regulated constituents.
(Presence on the BDAT list implies the existence of approved tech-
niques for analyzing the constituent in treated waste matrices.)
2. They must be present in, or be suspected of being present in, the
untreated waste. For example, in some cases, analytical difficul-
ties (such as masking) may prevent a constituent 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 performance data are transferred, the selected constituents
must be easier to treat than the waste constituent(s) from which
performance data are transferred. Factors for assessing ease of
treatment vary according to the technology of concern. For
instance, for incineration the factors include bond dissociation
energy, thermal conductivity, and boiling point.
From the group of constituents that are eligible to be regulated, EPA
may select a subset of constituents as representative of the broader
group. For example, out of a group of constituents that react similarly
to treatment, the Agency might name only those that are the most diffi-
cult to treat as regulated constituents for the purpose of setting a
standard.
6.1 Identification of Constituents in the Untreated Waste and Waste
Residuals
The first step in selecting candidate constituents to be regulated is
to identify the BDAT list constituents present in the K011/K013/K014
6-1
2384g
-------
wastes in quantities treatable by the selected BOAT. Table 6-1 (at the
end of this section) shows which of the 231 BOAT list constituents were
detected, not detected, and not analyzed for in the K011/K013/K014
nonwastewaters and incinerator ash residual. In addition to reviewing
the constituents detected in the nonwastewater streams as summarized in
Table 6-1, the Agency evaluated all available characterization data
presented in Section 2 and the waste-generating process to identify
constituents that are generally present in the nonwastewater. Table 6-2
presents all constituents known to be present in any KOI1/K013/K014
nonwastewater and treatment residuals.
6.2 Determination of Significant Treatment from BOAT
The next step in selecting the constituents to be regulated is to
identify those constituents in the waste that were significantly treated
by the technology designated as BDAT. The determined BOAT for organic
and cyanide treatment of K011/K013/K014 nonwastewaters is rotary kiln
incineration.
6.2.1 BDAT List Organic Constituents and Inorganics Other Than Metals
The incineration data presented in Table 4-1 demonstrate significant
treatment for cyanides, and benzene. The concentrations of the other
BDAT list organics in the untreated wastes are too low to demonstrate
significant reduction. However, as discussed in the incineration write-up
presented in Appendix B, the Agency is using theoretical bond energies as
a surrogate for measuring combustibility. In general, the higher the bond
energy for a constituent, the more difficult it is to combust. Of all
the organics determined to be present in K011/K013/K014 wastes (as shown
6-2
3384g
-------
in the waste characterization data in Section 2 and the performance data
in Section 4), styrene and benzene rank as the most difficult to treat
based on their high bond energy (see Table 6-3). Since these constituents
were significantly treated to nondetectable concentrations in the treat-
ment residuals, EPA believes that the other organic constituents can also
be significantly treated to nondetectable levels if they are present in
high concentrations in the untreated waste. Therefore, all BOAT list
organic constituents expected to be present in the K011/K013/K014
nonwastewaters will be considered for regulation. (Table 6-3 shows the
calculated bond energies for the candidate organic constituents.)
Fluoride and sulfide were detected in the K011/K013/K014 nonwastewater
untreated waste and treated waste streams. Since fluoride and sulfide
were detected in the incineration treatment residuals, it does not appear
that incineration is BOAT for sulfide and fluoride. Therefore, these two
constituents are not being regulated at this time as the Agency currently
has not completed its evaluation of treatment information for sulfide and
fluoride.
6.2.2 BOAT List Metals
EPA reviewed information on the possible origin of the BOAT list
metals in the EPA-tested KOI1/K013/K014 nonwastewaters, such as the metal
catalyst used to improve process efficiency and reduce the amount of by-
products, and concluded that the catalyst is the source of the high iron
and molybdenum but not the BOAT list metal concentrations. Therefore, EPA
is not regulating any BDAT list metals because the Agency has insufficient
data that indicate that arsenic, barium, cadmium, chromium, copper, lead,
6-3
2364<3
-------
nickel, and zinc are present in treatable quantities in most KOI1/K013/
K014 nonwastewaters. If additional treatment performance and characteri-
zation data for nickel becomes available, the Agency is not precluded from
regulating nickel as a nonwastewater treatment standard for KOI 1, K013,
and K014 wastes.
6.3 Rationale for Selection of Regulated Constituents
Table 6-2 presents all of the candidate constituents that were
detected in the untreated waste and nonwastewater treatment residual
generated from treatment with the identified BOAT.
The Agency selected acrylonitrile, acetonitrile, acrylamide, and
benzene as the BOAT organic constituents for regulation. These organic
constituents were present in the untreated waste in large quantities rela-
tive to the presence of the other constituents. Cyanide has been selected
for regulation because of its high concentration in the untreated
KOI1/K013/K014 wastes.
The Agency believes that regulation of the constituents selected will
ensure that treatment occurs for the remaining BOAT list organic candi-
dates since BOAT treatment of the selected constituents will, at the same
time, effectively treat those constituents not selected. Table 6-2 pre-
sents the selected regulated constituents for the K011/K013/K014 wastes.
2384g
6-4
-------
2706g
Table 6-1 BOAT Constituents Detected or Hot Detected in the
K011/K013/K014 Wastes and Waste Residuals
BOAT
reference
no. Para
ster
K011/K013/K014
CAS no. nonwastewater
Incinerator
ash
residual
Volatile Organics
222
Acetone
67-64-1
0
NO
I
Acetonitrile
75-05-8
0
NO
2
Acrolein
107-02-8
HO
NO
Aery 1 aside
79-06-1
0
Ml
3
Aery lonitr i le
107-13-1
0
NO
4
Benzene
71-43-2
0
NO
5
Bnndichlorcaethan*
75-27-4
NO
NO
6
Bronethane
74-83-9
NO
NO
223
n-Butyl alcohol
71-36-3
NO
NO
7
Carbon tetrachloride
56-23-5
NO
NO
8
Cartoon disulfide
75-15-0
NO
NO
9
Chlorobenzene
108-90-7
NO
NO
10
2-Chlore-1,3-butad iene
108-90-7
NO
NO
11
Ch 1 orod i brronettane
108-90-7
NO
NO
12
Chloroethane
75-00-3
NO
NO
13
2-Chloroethyl vinyl ether
110-75-8
NO
NO
14
Chlorofona
67-66-3
0
NO
15
Ch loro«e thane
74-87-3
NO
NO
16
3-Chloropropene
107-05-1
NO
NO
17
1,2-0 i brono-3-chloropropane
96-12-8
NO
NO
IB
1,2-Oibroaoethane
106-93-4
NO
NO
19
Oibrmcaethane
74-95-3
NO
NO
20
Trans-l,4-0ichloro-2-butene
110-57-6
NO
NO
21
Dichlorodifluoroaethane
75-71-8
NO
NO
22
1,1-Oichloroethane
75-35-3
NO
NO
23
1,2-0ichloroethane
105-06-2
NO
NO
24
1,1-0 ichloroethy lene
75-35-4
NO
NO
25
Trans-1.2-0ichloroethene
156-60-5
NO
NO
26
1,2-0ichloropropane
78-87-5
NO
NO
27
Trans-1.3-0ichloropropene
10061-02-6
NO
NO
26
cis-l,3-0ichloropropene
10061-01-5
M)
NO
29
1.4-0ioxane
123-91-1
NO
NO
224
2-Ethoxyethanol
110-80-5
NO
NO
225
Ethyl acetate
141-78-6
K0
NO
226
Ethyl benzene
100-41-4
NO
NO
6-5
-------
2706g
Table 6-1 (continued)
BOAT
reference
no.
Paraaeter
IC011/K023/IC014
CAS no. nomaasteMter
Incinerator
ash
residual
Volati le Oroamcs (continued)
30 Ethyl cyanide 10712-0
227 Ethyl ether 60-29-7
31 Ethyl nethacrylate 97-53-2
214 Ethylene oxide 75-21-8
32 I oa (methane 74-88-4
33 Isobutyl alcohol 78-83-1
228 Methanol 67-56-1
34 Methyl ethyl ketone 78-93-3
229 Methyl isobutyl ketone 108-10-1
35 Methyl nethacrylate 80-62-6
36 Methyl iKthancsulfonate 66-27-3
37 Methylacrylonitrile 126-98-7
38 Methylene chloride 75-09-2
230 2-Nitropropane 79-46-9
39 Pyridine 110-86-1
40 1,1,1,2-Tetrachloroethane 530-20-6
41 1,1,2,2-Tetrachloroethane 79-34-5
42 Tetrachloroethene 127-18-4
43 Toluene 108-88-3
44 TribroBoaethane 75-25-2
45 1,1,1-Trichloroethane 71-55-6
46 1,1,2-Trichloroethane 79-00-5
47 Trichloroethene 79-01-6
48 Trichlorononof luorcaettttne 75-69-4
49 1,2,3-Trichloropropane 96-18-4
231 1.1.2-Trichloro-l,2.2-
trifluoroethane 76-13-1
50 Vinyl chloride 75-01-4
215 1,2-Xylene 97-47-6
216 1,3-Xylene 108-38-3
217 1.4-Xylene 106-44-5
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0
NO
NO
NO
NO
NO
NO
NO
0
NO
0
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
Saiivolatiles
51
52
Acenaphthalene
Acenaphthene
208-96-8
83-32-9
NO
NO
NO
NO
6-6
-------
2706g
Table 6-1 (continued)
BOAT
reference
no.
ParasKter
K.011/K.013/IC014
CAS no. rcorma3te*ater
incinerator
ash
residual
Saaivolatiles (continued)
53
Acetophenone
96-86-2
NO
NO
54
2-Acetylaainofluorene
53-36-3
NO
NO
55
4-Aainobiphenyl
92-67-1
NO
56
Aniline
62-53-3
IS
NO
57
Anthracene
120-12-7
NO
NO
S8
Araaite
140-57-8
NO
59
Ben*(a(anthracene
56-55-3
NO
NO
218
Benzal chloride
98-87-3
NO
NO
60
Benzal chloride
98-87-3
NO
NO
61
Benzenethiol
108-98-5
NO
NO
62
Benzo(aIpyrene
50-32-8
NO
NO
63
Benzo(b)fluoranthene
205-99-2
NO
NO
64
Benzo(ghi)perylene
191-24-2
NO
NO
65
Benzo(k)fluoranthene
207-08-9
NO
NO
66
p-Benzoquinone
106-51-4
NO
NO
67
Bis(2-ch1oroethoxy )methane
111-91-1
NO
NO
68
Bis(2-chloroethyl)ether
lli-44-4
NO
NO
69
Bis(2-chloroisop ropy 1)ether
39638-32-9
NO
NO
70
Bis(2-e thy lhexyUphtha late
117-81-7
NO
NO
71
4-Bramphenyl phenyl ether
101-55-3
NO
NO
72
Butyl benzyl phthalate
85-68-7
NO
NO
73
2-sec-Buty1-4,6-dlnitropheno1
88-85-7
NO
NO
74
p-Chloroam line
106-47-8
NO
NO
75
Chlorobenzi late
510-15-6
NO
NO
76
p-Chloro-*-cresol
59-50-7
NO
NO
77
2-Ch loronaphthalene
91-58-7
NO
NO
78
2-Chlorophenol
95-57-8
NO
NO
79
3-Chloropropionitnle
542-76-7
NO
NO
80
Chrysene
218-01-9
NO
NO
81
ortho-Cresol
95-48-7
NO
NO
82
para-Cresol
106-44-5
NO
NO
232
Cyelohexanone
108-94-1
NO
NO
83
0ibenz(a.h)anthracene
53-70-3
NO
NO
84
0ibenzo(a.e)pyrene
192-6S-4
NO
NO
85
0ibenzo(a,i)pyrene
189-55-9
NO
NO
86
it-0 ich lorobenzene
541-73-1
NO
NO
87
o-Dichlorobenzene
95-50-1
NO
NO
6-7
-------
2706g
Table 6-1 (continued)
BOAT
reference
no. Para
eter
K0U/K013/M14
CAS no. nonvasteMter
Incinerator
ash
residual
Sanivolatiles (continued)
88
P'D i chlorobenzene
106-46-7
NO
NO
89
3.3'-0ichlorobenzidine
91-94-1
NO
NO
90
2,4-Dichloropheno1
120-83-2
NO
NO
91
2,6-0ichlorophtno1
87-65-0
NO
NO
92
Diethyl phthalate
84-66-2
NO
NO
93
3,3"-0ioethoxybenzid ine
119-90-4
NO
NO
94
p-Diorttiylaainoazobenzene
60-11-7
KG
NO
95
3.3'-0i«ethylbenzidine
119-93-7
NO
NO
96
2,4-0 isethyIpheno1
105-67-9
NO
NO
97
Oiaethyl phthalate
131-11-3
NO
NO
98
Di-n-butyl phthalate
84-74-2
NO
NO
99
1,4-0initrobenzene
100-25-4
NO
NO
100
4.6-0initro-o-creso1
S34-52-1
NO
NO
101
2,4-Oinitrophenol
51-28-5
NO
NO
102
2.4-Oinitrotoluene
121-14-2
NO
NO
103
2,6-0inltrotoluene
606-20-2
NO
NO
104
Oi-n-octyl phthalate
117-84-0
NO
NO
105
Di-n-propyInitrosanine
621-64-7
NO
NO
106
Diphenylaaine
122-39-4
NO
NO
219
Dipheny1nitrosaa ine
86-30-6
NO
NO
107
1.2-0iphenylhydrazine
122-66-7
NO
NO
108
Fluoranthene
206-44-0
NO
NO
109
riuorene
86-73-7
NO
NO
110
Hexachlorobenzene
118-74-1
NO
NO
111
Hexach lorobutad iene
87-68-3
NO
NO
112
Hexachlorocyc lopentad iene
77-47-4
NO
NO
113
Hexachloroethane
67-72-1
NO
NO
114
Hexachlui uphaw
70-30-4
NO
NO
115
Indeno(1,2.3-cd)pyrene
193-39-5
NO
NO
116
Isoaafrole
120-58-1
NO
NO
117
Nethapyrl lone
91-80-5
NO
NO
118
3-Methylcholanthrene
56-49-5
NO
NO
119
4.4'-Hethylenebis
NO
NO
120
(2-chloroaniline)
101-14-4
NO
NO
121
Naphthalene
91-20-3
NO
NO
122
1.4 - Napht hoqu i none
130-15-4
NO
NO
123
I-Naphthy laatne
134-32-7
NO
NO
G-,
-------
2706g
Table 6-1 (continued)
BOAT Incinerator
reference K011/K013/K014 ash
no. Parajneter CAS no. nomastewter residual
Sewivolatiles (continued)
124 2-Naphthylaaine
125 p-Nitroani1ine
126 Nitrobenzene
127 4-Nitrophenol
128 N-Nitrosodi-n-butyla»we
129 N-Nitrosodiethylasine
130 N-Nitrosodioethylaaine
131 N-Nitrosoaethylethylaaine
132 N-Nitrosonrphol ine
133 N-Nitrosopiperidine
134 n-Nitrusopyrrolidine
135 5-Nitro-o-toluidine
136 Pentachlorobenzene
137 Pentachloroethane
138 Pentachloronitrobenzene
139 Pentachloropheno1
140 Phenacet in
141 Phenanthrene
142 Phenol
220 Phthalic anhydride
143 2-Picoline
144 Pronaaide
145 Pyrene
146 Resortinol
147 Safrole
148 1,2.4.5-Tetrachlorobenzene
149 2,3.4,6-Tetrachlorophenol
150 1,2,4-Trichlorobenzene
151 2,4,5-Trichloropheno1
152 2.4.6-T r ichloropheno1
153 Tris(2,3-dibraopropy 1}
phosphate
91-59-8
100-01-6
98-95-3
100-02-7
924-16-3
55-18-5
62-75-9
10595-95-6
59-89-2
100-75-4
930-55-2
99-65-8
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
85-44-9
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
58-90-2
120-82-1
9S-95-4
88-06-2
126-72-7
NO
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
ND
NO
NO
ND
NO
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
Netals
154
155
Antiaony
Arsenic
7440-36-0
7440-38-2
NO
0
KA
0
6-9
-------
2706q
Table 6-1 (continued)
BOAT Incinerator
reference KD11/KD13/K014 ash
no. Parameter CAS no. nonwasteMter residual
Hetals (continued)
156 Dariua
157 Berylliia
158 Cat*) i mi
159 Chnanis
160 Copper
221 Hexavalent Chroanua
161 Lead
162 Aercury
163 Nickel
164 Seleniia
165 Silver
166 Thalliia
167 Vanadii*
168 Zinc
7440-39-3
7440-41-7
7440-43-9
7440-47-32
7440-50-B
NA
7439-92-1
7439-97-6
7440-02-0
7782-49-2
7440-22-4
7440-28-0
7440-62-2
7440-66-6
0
NO
D
D
D
MA
0
NO
0
NO
NO
ND
NO
D
0
NA
NO
0
0
NA
0
NO
0
0
0
NA
NA
0
Inorganics
169
170
171
Cyanide
Fluoride
Sulfide
57-12-5
16964-48-8
8496-25-8
0
0
NO
NO
0
D
Oroanochlorine Pesticides
172
173
174
175
176
177
178
179
180
181
182
183
184
185
Aldrin
alpha-BHC
beta-BHC
delta-BHC
Chlordane
Oieldrin
Endosulfan I
tndosulfan II
Endrin
Endrin aldehyde
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
939-98-8
33213-6-5
72-20-8
7421-93-4
ND
NO
NO
ND
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
ND
NO
ND
ND
ND
NO
m
NO
ND
NO
NO
NO
NO
6-i0
-------
Z706g
Table 6-1 (continued)
BOAT Incinerator
reference K011/K013/K0I4 ash
no. Parameter CAS no. namMsteMter residual
Oroarcochlonne Pesticides (continued)
186 Heptachlor
16/ Heptachlor epoxide
1B8 Isodrin
18$ Kepone
190 Nethoxyclor
191 Toxaphene
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
8001-35-2
NO
NO
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
Phenoxvacetic Acid Herbicides
192 2,4-Oichlorophenoxyacetic acid 94-75-7
193 Silvex 93-72-1
194 2.4.5-T 93-76-5
NO
NO
NO
ND
NO
NO
Organophosphorous Insecticides
195 Oisulfoton
196 Faajihur
197 Methyl parathion
198 Parathion
199 Phorate
298-04-4
52-85-7
298-00-0
56-38-2
298-02-2
ND
ND
0
NO
D
NO
NO
NO
NO
NO
PCBs
200
201
202
203
204
205
206
Aroclor 1016
Aroclor 1221
Aroc lor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
12674-U-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
N0
ND
NO
NO
NO
NO
NO
ND
NO
NO
NO
NO
NO
NO
Oioxins and Furans
207 Hexachlorodibenzo-p-dioxins
208 Hexachlorodibenzofuran
209 Pentachlorodibenzo-p-dioxins
210 Pentach lorodlbenzofu ran
NA
NA
NA
NA
NO
NO
NO
NO
NO
NO
NO
NO
6-11
-------
27063
Table $-1 (continued)
BOAT Incinerator
reference W11/K013/K014 ash
no. Parameter CAS no. nomMstevatar residual
Dioxins ami Furans (continued)
211 Tetrachlorodibenzo-p-dioiins NA M NO
212 Tetrachlorodibef«ofuran NA NO NO
213 2.3.7.8-TetrachlorodibeniO-p-dioxin NA NO NO
NL 3 Not on list at the tine of analysis
NO = Not detected
0 = Detected
KA = Not applicable
Reference: USEPA 1988b.
6-12
-------
Z779g
Table 6-2 Constituents for Regulation of K011/K013/K014
NonaasteMaters
Candidate BOAT list
constituents determined
to be present in KOIX/ Eliminated based Selected
K013/K014 nonwastewaters on treatabi1itya constituents
Volatiles
Acetone
Acetonitrile X
Acrolein
Acrylonitri le X
Acrylanide X
Benzene X
Chloroform
0 ichlorod i fluoroaethane
Ethyl cyanide
Methylene chloride
Pyridine
1,1,1-Trichloroethane
Trichloroethene
Sanvolati lea
Phenol
2-Picoline
Inorganics Other Than Metals
Cyanide X
Fluoride X
Sulfide X
Metals
Arsenic X
Bar ii* X
Cacteiiai X
Chnsiia X
Copper X
Lead X
Nickel X
Seleniw X
Silver X
Zinc X
aConstituents eliminated because they Mere determined not to be present in
treatable quantities in most K011/K013/K014 nonwasteMters and/or cannot be
significantly treated by the technologies designated as BOAT.
6-13
-------
22&4q
Table 6-3 Calculated Bond Energies for the Organic Constituents
Constituent Calculated bond energy9
(Kcal/vl)
Acetone
945
Acrolein
805
Acetonitrile
590
Acrylaaide
985
Acrylonitrile
860
Benzene
1320
Chloroform
340
Oichlorodif luoraethane
390
Ethyl cyanide
880
Methylene chloride
355
Pyridine
1210
Phenol
1421
1,1.1 - Tnch loroethane
625
Trichloroethene
485
Styrene
1750
a Calculations are based on information in Sanderson 1971.
6-14
-------
7. DEVELOPMENT OF THE BOAT TREATMENT STANDARDS
The Agency bases the treatment standards for the regulated constitu-
ents on the performance of wel1-designed and well-operated BDAT treatment
systems. These standards must account for analytical 1 imitations in
available performance data and must be adjusted for variabilities related
to treatment, sampling, and analytical techniques and procedures.
The BDAT standards are determined for each constituent by multiplying
the arithmetic mean of accuracy-adjusted constituent concentrations
detected in treated waste by a "variability factor" specific to each
treatment technology defined as BDAT. Accuracy adjustment of performance
data was discussed in Section 5 in relation to defining "substantial
treatment." Variability factors correct for normal variations in the
performance of a particular technology over time. They are designed to
reflect the 99th percentile level of performance that the technology
achieves in commercial operation. For more information on the principles
of calculating variability factors, see EPA's publication, Methodology
for Developing BDAT Treatment Standards.
The calculations of the organic and cyanide standards are presented in
Table 7-1. The Agency is establishing the treatment standards as shown
in Table 7-2 for K011, K013, and K014 nonwastewaters. For nonwastewater
forms of these wastes, the BDAT list organic and cyanide treatment
standards are based on the performance of incineration.
?384g
7-1
-------
fable 7-1 Calculation of the Proposed Nomastewater Organic and Cyanide Treatment Standards for
the Regulated Constituents Based on Rotary Kiln Incineration Performance Data
Unadjusted concentration (ag/kg)
Accuracy-corrected concentration (og/kg)
Treatment
Sawle Set Ho.
Correct ion
Saaple Set No.
Mean
Variability
standard
Constituent 1
2
3 4
5 6 7
factor
1
2
3
4 5 6
7
(mg/kg)
factor
(«9/kg)
8DA1 List Volatile Oraanics
Acetonitrile O.S
O.S
0.5
0.5
1.266
0.63
0.63
-
0.63 0.63 -
-
0 63
2.8
18
Acrylonitrile 0.5
O.S
0 5
0.5
1.000
0.5
0.5
-
0.5 0.5 -
-
0.5
2 8
1.4
Acrylaaide 6.S
6.S
6.5
6.5
1.266
8.2
8.2
-
8.2 8.2 -
-
8.2
2.8
23.
Benzene 0.01
0.01
0.01
0.01 -
1.000
0.01
0.01
~
0.01 0.01 -
~
0.01
2.8
0.03
BOAT List Inoroanics
Other Than Netals
Cyanide (total) 10
5.8
- 22
4.8 9.0 12
1.724 17
10
-
38 8.3 16
21
18.3
3.1
57
- = No value available.
-------
Table 7-2 BOAT Treatment Standards
BOAT Treatment Standards for KOI1/KO13/KO14 Nonwastewaters
Maximum for any
single grab sample
Total composition TCLP
Constituent (mg/kg) (mg/1)
Acetonitrile 1.8 Not Applicable
Acrylonitrile 1.4 Not Applicable
Acrylamide 23 Not Applicable
Benzene 0.03 Not Applicable
Cyanides (Total) 57 Not Applicable
BOAT Treatment Standards for K011/KO13/KO14 Wastewaters
Maximum for any
single grab sample
Total composition
Constituent (mg/1)
(EPA intends to propose and promulgate
K011/K013/K014 wastewater treatment
standards prior to May 8, 1990.)
?384g
7-3
-------
-------
8. REFERENCES
APHA, AWWA, and WPCF. 1985. American Public Health Association,
American Waste Works Association, and Water Pollution Control
Federation. Standard method for the examination of water and
wastewater. 16th ed. Washington, D.C.: American Public Health
Association.
Federal Register. 1986. Hazardous waste management systems; land
disposal restrictions; Final Rule; Appendix I to Part 268-Toxicity
Leaching Procedure (TCIP). Vol. 51, No. 216. November 7, 1986.
pp. 40643-40654.
Rich. 1987. Hazardous Waste Treatment Technologies. Second Printing.
Northbrook, 1L: Pudran Publishing Co.
Sanderson. 1971. Chemical bond and bond energy. Vol. 21 in Physical
chemistry. New York: Academic Press.
Stanford Research Institute. 1988. Directory of chemical producers.
SRI International. 1988.
USEPA. 1980. U.S. Environmental Protection Agency. RCRA listing
background document waste. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1985. U.S. Environmental Protection Agency. Characterization of
waste streams listed in 40 CFR; Section 261, Waste Profiles. Prepared
for the Waste Identification Branch, Characterization and Assessment
Division, U.S. Environmental Protection Agency. Prepared by Environ
Corporation, Washington, D.C.
USEPA. 1986a. U.S. Environmental Protection Agency. Summary of
available waste composition data from review of literature and data
bases for use in treatment technology application and evaluation for
"California List" waste streams. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1986b. U.S. Environmental Protection Agency, Office of Solid
Waste and Emergency Response. Test methods for evaluating solid waste;
physical/chemical methods. 3rd ed. Washington, D.C.; U.S.
Environmental Protection Agency.
USEPA. 1987a. U.S. Environmental Protection Agency. Generic quality
assurance project plan for Land Disposal Restrictions Program ("BOAT").
Washington, D.C.: U.S. Environmental Protection Agency.
Z384g
8-1
-------
USEPA. 1987b. Effluent Guidelines Division. Development document for
effluent limitations guidelines and standards for the organic chemicals,
plastics and synthetic fibers point source category. EPA 440/1-87/009.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988a. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for
incineration of KOI1/K013/K014 sludge at John Zink Test Facility.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988b. U.S. Environmental Protection Agency. Engineering
summary report on K011, K013, and K014 wastewater characterization and
treatment. Prepared by PEI Associates, Cincinnati, Ohio.
USEPA. 1988c. U.S. Environmental Protection Agency. Methodology for
developing BOAT treatment standards. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1988d. U.S. Environmental Protection Agency. Best demonstrated
available technology background document for cyanide wastes.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988e. U.S. Environmental Protection Agency. Best demonstrated
available technology background document for K062. Washington, D.C.:
U.S. Environmental Protection Agency.
USEPA. 1988f. U.S. Environmental Protection Agency. Treatment
technology background document. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1988g. U.S. Environmental Protection Agency. Onsite engineering
report of treatment technology performance and operation for wet air
oxidation of F007 at Zimpro/Passavant, Inc., in Rothschild, Wisconsin.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1988h. U.S. Environmental Protection Agency. Autoclave
oxidation results and pilot plant run proposal for an acrylonitrile
production wastewater. Prepared by PEI Associated, Inc. Cincinnati,
Ohio.
USEPA. 19881. U.S. Environmental Protection Agency. Best demonstrated
available technology background document for F006. Washington, O.C.:
U.S. Environmental Protection Agency.
Z364g
8-2
-------
APPENDIX A
Analytical QA/QC
The analytical methods used for analysis of the regulated
constituents identified in Section 6 are listed in Table A-l. SW-846
methods (EPA's Test Methods for Evaluation of Solid Waste;
Physical/Chemical Methods, SW-846, Third Edition, November 1986) were
used in most cases for determining total constituent concentrations.
In some instances SW-846 allows for the use of alternative or
equivalent procedures or equipment. Table A-2 presents the specific
procedures or equipment used in extraction of organic compounds. The
specific procedures or equipment used for analysis of organic compounds
are shown in Table A-3.
As stated in the introduction, all concentrations for the regulated
constituents will be corrected to account for analytical interference
associated with the chemical makeup of the waste matrix. The correction
factor for a constituent is based on the matrix spike recovery values.
Table A-4 presents the organic matrix spike recoveries used to determine
the correction factor for the nonwastewater organic and cyanide data.
A-l
-------
??8
-------
2284g
table A 2 Specific Procedures or Equipment Used in Extraction of Organic Canj>oiinds When
Alternatives or Equivalents Are Allotted in the SW-846 Methods
Analysis
SW 846 method
Saddle aliquot
Alternatives or equivalents allowed
by SW 84ti Methods
Specific procedures or
equipment used
Purge and trap
5030
5 Milliliters of liquid
lhe purge and trap device to be •
used is specified in the method in
f igure I. the desorbcr to be used
is described in f igures ? and 3.
and the packing Mterials are
described in Section 4.10.? of SW-846.
lhe method allows equivalents of this
equipment or these materials to be used.
lhe purge and trap equipment and
the desorber used were as specified
in SU-846. lhe purge and trap
equipment is a leckmar I SC 2 with
standard purging chambers (Supclco
cat. ?-0?93). The packing materials
for the traps were 1/3 silica gel
and 2/3 2.6-diphenylene.
The method specifies that the
trap must be at least 25 cm long
and have an inside diameter of at
least 0.105 cm.
The length of the trap was 30 cm
and the diameter was 0.105 cri.
lhe surrogates recoranended are
to luene - d8.4-bromof luorobeti/ene.
and l,2-dichloroethane d4. The
reconaended concentration level is
50 ug/l.
lhe surrogates were added as
specified in SW-846.
References: USEPA 1988a.
USEPA 1986b
-------
?3?Sq
lable A3 Specific Procedures or fquipment Used for Analysis of Organic Compounds
When Alternatives or tquivalenls Are Allowed in SV 846
Saofile Alternatives or equivalents
SW 846 preparation a I loved in SW-846 for
Analysis Method Method equipment or in procedure Specific equifnent or procedures used
Organic Cawwunds
Recanvnended GC/MS operating conditions:
Actual GC/HS operating conditions:
Gas Chromatography/
Mass Spectrometry
for volat i le
organics
i
8?40 5030 Ilectron energy:
Mass range:
Scan time:
Initial colum temperature:
Initial colum holding tine
Colum temperature program:
Final coluan tofierature:
Final colum holding time:
Injector tnjierature:
Source twyerature:
Transfer line teafierature:
Carrier gas:
70 ev (nominal)
35-?60 ami
lo give 5 scans/peak but
not to exceed / sec/scan
45"C
3 nin
8'C/min
200*C
15 min
200 225*C
According to manufacturer's
specif Icatlon
250 300*C
Hydrogen at 50 cm/sec or
hellua at 30 cm/sec
flectron energy:
Mass range:
Scan t imc:
70 ev
35-260 ami
2.5 sec/scan
Initial colum tenperature: 38*C
Initial colum holding time: 2 nin
Colum tenperature program: 10'C/nin
Final colum temperature:
Final colum holding time
Injector temperature:
Source to^ierature:
transfer line tenperature:
Carrier gas:
225'C
30 nin or xylene elutes
225*C
Manufacturer's recanmended
value of I00*C
275*C
Heliua at 30 cm/nin
cm/sec
• Additional Information on Actual System Used:
Equtpment: Finnegan Model 5100 GC/MS/0S system
Data system: SUPER INCOS Autoquan
Mode: Electron impact
NBS library available
Interface to MS - Jet separator
• I he colum should be 6 ft x 0.1 In I.D. glass,
packed with IX SP-1000 on Carbopack B (60/80 mesh) or
an equivalent.
• Sanples may be analyzed by purge and trap technique
or by direct injection.
• Ihe colum used Mas an 8 ft x 0.1 in I.D. glass,
packed tilth IX SP-1000 on Carbopack B (60/80 nesh).
• The singles were analyzed using the purge and trap
technique.
-------
?3?5g
lable A 3. (continued)
Analysis
SW 846
Method
Sanjile
preparat ion
Method
Alternatives or equivalents
allowed in SM 846 for
equipment or in procedure
Specific equipment or procedures used
lota I and Amenable
Cyanide
Color iaetric
901? 500 al Pretreatment with bismuth nitrate May be
necessary if sulfides are present.
PretreatMent with sulfamic acid May be
necessary if nitrites/nitrates are present.
Pretreatmenl was not necessary.
Pretreatment was not necessary.
J»
cn
A risher-Nu11igan absorber or equivalent
should be used.
A spectrophotometer suitable for Measurements
at 578 re* with a 1.0-cm cell or larger Is
required.
An ACE smog bubbler absorber was used
A Bausch and loifi Model Spec Ironic ?| wds used.
References: USEPA 1986b
USEPA 1988a.
-------
lable A 4 Hdlrix Spike Recoveries Used to Calculate Correction factors for
K01I/KOI3/KOI4 Nonwastewater Organic and Cyanide Concent rat ions
Sawple
Pup I icate
BOAI list
const ituent
Original
awunt found
(1*9/9)
Amount
spiked
(fq/g)
Spike
resu It
W9)
Percent
a
recovery
Sp ike
result
Percent
recovery8
Accuricy-
correct ion
factor'*
Acetonitri Ic
NO
l?5
9'J
79
100
80
1.266
Acrolein
ND
IPS
100
80
38
47
2.128
Acrylonitri le
NO
125
138
110
119
108
1.000
Benzene
ND
25
35
141
206
146
1 000
Chlorobenrene
NO
25
27
107
115
107
1 000
1.1-Dichloroethene
ND
25
24.8
99
103
104
1010
toluene
ND
25
28
113
132
117
1.000
Irlchloroethene
ND
25
26
m
109
105
1.000
Average
104
102
1.000
Acrylaaide
ND
56
45
81
44
79
1.266
Cyanide (total)
NO
4.9
0
0
2.8
58
1.724
'Percent recovery ¦= [(spike result - original amount)/spike added].
''Accuracy-correction factor = 100/percent recovery (using the lowest percent recovery values).
Reference: USIPA 1988a.
-------
APPENDIX B
TECHNOLOGY - INCINERATION
This section addresses the commonly used incineration tech
liquid injection, rotary kiln, fluidized bed, and fixed hearth,
appropriate, the subsections are divided by type of incineration u
Add!icabilitv
Liquid Injection
Liquid injection is applicable to wastes that have viscosity values
low enough that the waste can be atomized in the combustion chamber. A
range of maximum viscosity values are reported in the literature, with
the low being 100 Saybolt Seconds Universal (SSU) and the high being
10,000 SSU. It is important to note that viscosity is temperature
dependent so that while liquid injection may not be applicable to a waste
at ambient conditions, it may be applicable when the waste is heated.
Other factors that affect the use of liquid injection are the presence of
suspended solids and particle size. Both of these can cause plugging of
the burner nozzle.
Rotary Ki1n/Fluidized Bed/Fixed Hearth
These incineration technologies are applicable to a wide range of
hazardous wastes. They can be used on wastes that contain high or low
total organic content, high or low filterable solids, various viscosity
ranges, and a range of other waste parameters. EPA has not found these
technologies to be demonstrated on most wastes that are composed
essentially of metals with low organic concentrations. In addition, the
Agency expects that the incineration of some of the high metal content
B-l
-------
wastes may not be compatible with existing and future air emission limits
without emission controls far more extensive than those currently in use.
Underlying Principles of Operation
Liquid Injection
The basic operating principle of this incineration technology is that
incoming liquid wastes are volatilized and then additional heat is
supplied to the waste to destabilize the chemical bonds. Once the
chemical bonds are broken, these constituents react with oxygen to form
carbon dioxide and water vapor. The energy needed to destabilize the
bonds is referred to as the energy of activation.
Rotary Kiln and Fixed Hearth
There are two distinct principles of operation for these incineration
technologies, one for each of the two chambers involved. In the primary
chamber, energy, in the form of heat, is transferred to the waste to
achieve volatilization of the various organic waste constituents. During
this volatilization process some of the organic constituent bonds
destabilize and oxidize to carbon dioxide and water vapor. In the
secondary chamber, additional heat is supplied to overcome the energy
requirements needed to destabilize the remaining chemical bonds and allow
the constituents to react with excess oxygen to form carbon dioxide and
water vapor. The principle of operation for the secondary chamber is
similar to that of liquid injection.
Fluidized Bed
The principle of operation for this incinerator technology is
somewhat different from that for rotary kiln and fixed hearth
B-2
-------
incineration, in that there is only one chamber, which contains the
fluidizing sand and a freeboard section above the sand. The purpose of
the fluidized bed is to both volatilize the waste and combust the waste.
Destruction of the waste organics can be accomplished to a better degree
in this chamber than in the primary chamber of the rotary kiln and fixed
hearth because of (a) improved heat transfer from fluidization of the
waste using forced air and (b) the fact that the fluidization process
provides sufficient oxygen and turbulence to convert the organics to
carbon dioxide and water vapor. The freeboard volume generally does not
include an afterburner; however, additional time is provided for
conversion of the organic constituents to carbon dioxide and water vapor
(and hydrochloric acid if chlorine is present in the waste).
Description of Incineration Technologies
Liquid Injection
The liquid injection system is capable of incinerating a wide range
of gases and liquids. The combustion system has a simple design with
virtually no moving parts. A burner or nozzle atomizes the liquid waste
and injects it into the combustion chamber, where it burns in the
presence of air or oxygen. A forced draft system supplies the combustion
chamber with air to provide oxygen for combustion and turbulence for
mixing. The combustion chamber is usually a cylinder lined with
refractory (i.e., heat-resistant) brick, and it can be fired
horizontally, vertically upward, or vertically downward. Figure 1
illustrates a liquid injection incineration system.
B-3
-------
WAIER
AUXILIARY FUEL
LIQUID OR GASEOUS.
WASTE INJECTION
BURNER
AIR
BURNER
PRIMARY
COMBUSTION
CHAMBER
AFTERBURNER
(SECONDARY
COMBUSTION
CHAMBER)
T
rm
SPRAY
CHAMBER
GAS TO Ain
POLLUTION
CONTROL
HORIZONTALLY FIREO
LIQUID INJECTION
INCINERATOR
ASH
WATER
FIGURE 1
LIQUID INJECTION INCINERATOR
-------
Rotary Kiln
A rotary kiln is a slowly rotating, refractory-lined cylinder that is
mounted at a slight incline from the horizontal (see Figure 2). Solid
wastes enter at the high end of the kiln, and liquid or gaseous wastes
enter through atomizing nozzles in the kiln or afterburner section.
Rotation of the kiln exposes the solids to the heat, vaporizes them, and
allows them to combust by mixing with air. The rotation also causes the
ash to move to the lower end of the kiln, where it can be removed.
Rotary kiln systems usually have a secondary combustion chamber or
afterburner following the kiln for further combustion of the volatilized
components of solid wastes.
Fluidized Bed
A fluidized bed incinerator consists of a column containing inert
particles such as sand, which is referred to as the bed. Air, driven by
a blower, enters the bottom of the bed to fluidize the sand. Air passage
through the bed promotes rapid and uniform mixing of the injected waste
material within the fluidized bed. The fluidized bed has an extremely
high heat capacity (approximately three times that of flue gas at the
same temperature), thereby providing a large heat reservoir. The
injected waste reaches ignition temperature quickly in the hot fluidized
bed. Continued bed agitation by the fluidizing air allows larger
particles to remain suspended in the combustion zone. (See Figure 3)
Fixed Hearth
Fixed hearth incinerators, versions of which are also called
controlled air or starved air incinerators, are another major technology
B-5
-------
GAS TO
AIR POLLUTION
CONTROL
A
SOLID
waste
'.n FluE nt
AUXILIARY
FUEL.
AIR
! COMBUSTION
'GASES
rotary
KILN
UOUIO OR
GASEOUS
WASTE
AFTERBURNER
FEED
MECHANISM
UOUIO OR
GASEOUS
WASTE
INJECTION
~
ASH
FIGURE 2
ROTARY KILN INCINERATOR
B-6
-------
GAS TO
^ AIR POLLUTION
CONTROL
FREEBOARD
MAKE-UP
SAND
SAND BED
BURNER
AIR
ASH
FIGURE 3
FLUIDIZED BED INCINERATOR
B-7
-------
used for hazardous waste incineration. Fixed hearth incineration is a
two-stage combustion process (see Figure 4). Waste is fed into the first
stage, or primary chamber, and usually burned at less than stoichiometric
conditions (less than the theoretically required amount of air). The
resultant smoke and pyrolysis products, consisting primarily of volatile
hydrocarbons and carbon monoxide, along with the normal products of
combustion, pass to the secondary chamber. Here, additional air is
usually injected to complete the combustion. This two-stage process
generally yields low stack particulate and carbon monoxide (CO)
emissions. The primary chamber combustion reactions and combustion gas
volumes are maintained at low levels by the starved air conditions so
that particulate entrainment and carryover are minimized.
Air Pollution Controls
Following incineration of hazardous wastes, combustion gases are
generally further treated in an air pollution control system. The
presence of chlorine or other halogens in some waste requires a scrubbing
or absorption step to remove hydrogen chloride (HC1) and other halo-acids
from the combustion gases. Ash in the waste is not destroyed in the
combustion process. Depending on its composition, ash will exit either
as bottom ash, at the discharge end of a kiln or hearth for example, or
as particulate matter (fly ash) suspended in the combustion gas stream.
Particulate emissions from most hazardous waste combustion systems
generally have particle diameters of less than 1 micron and require
high-efficiency collection devices to minimize air emissions. In
B-8
-------
AIR
AIR
WASTE
injection'
BURNER
1
GAS lO All)
POLLUTION
CONTflOl
PRIMARY
COMBUSTION
CHAMBER
GRATE
T
SECONOARY
COMBUSTION
CHAMBER
AUXILIARY
FUEL
2-STAGE FIXED HEARTH
INCINERATOR
ASH
FIGURE H
FIXED HEARTH INCINERATOR
-------
addition, scrubber systems provide an additional buffer against
accidental releases of incompletely destroyed waste products resulting
from poor combustion efficiency or combustion upsets.
Waste Characteristics Affecting Performance fWCAPs)
Liquid Injection
In determining whether liquid injection will achieve the same level
of performance on an untested waste as on a previously tested waste, and
whether performance levels can be transferred, EPA examines the
dissociation bond energies of the constituents in the untested and tested
wastes. This parameter is being used as a surrogate indicator of
activation energy which, as discussed previously, destabilizes molecular
bonds. In theory, the bond dissociation energy would be equal to the
activation energy; however, in practice this is not always the case.
Other energy effects (e.g., vibrational effects, the formation of
intermediates, and interactions between different molecular bonds) may
have a significant influence on activation energy.
Because of the shortcomings of bond energy calculations in estimating
activation energy, EPA analyzed other waste characteristic parameters to
determine whether these parameters would provide a better basis for
transferring treatment standards from an untested waste to a tested
waste. These parameters include heat of combustion, heat of formation,
use of available kinetic data to predict activation energies, and general
structural class. All of these were rejected for the reasons provided
below.
B-10
-------
The heat of combustion measures only the difference in energy of the
products and reactants; it does not provide information on the transition
state (i.e., the energy input needed to initiate the reaction). Heat of
formation is used as a tool to predict whether reactions are likely to
proceed; however, there are a significant number of hazardous
constituents for which these data are not available. The use of kinetic
data was rejected because these data are limited and could not be used to
calculate dissociation requirements for the wide range of hazardous
constituents. Finally, EPA decided not to use structural classes because
the Agency believes that evaluation of bond dissociation energies allows
for a more direct determination of whether a constituent will be
destabilized.
Rotary Kiln/Fluidized Bed/Fixed Hearth
Unlike liquid injection, these incineration technologies always
generate a residual ash. Accordingly, in determining whether these
technologies will achieve the same level of performance on an untested
waste as on a previously tested waste and whether performance levels can
be transferred, EPA examines the following waste characteristics that
affect volatilization of organics from the waste, as well as destruction
of the organics once volatilized. Relative to volatilization, EPA
examines the thermal conductivity of the entire waste and the boiling
points of the various constituents. As with liquid injection, EPA
examines bond energies in determining whether treatment standards for
scrubber water residuals can be transferred from a tested waste to an
B-11
-------
untested waste. Below is a discussion of how EPA arrived at thermal
conductivity and boiling point as the best means to assess volatilization
of organics from the waste; the discussion relative to bond energies is
the same for these technologies as for liquid injection and is therefore
not repeated.
(1) Thermal conductivity. Consistent with the underlying principles
of incineration, a major factor with regard to whether a particular
constituent will volatilize is the transfer of heat through the waste.
In the case of rotary kiln, fluidized bed, and fixed hearth incineration,
heat is transferred through the waste by three mechanisms: radiation,
convection, and conduction. For a given incinerator, heat transferred
through various wastes by radiation is more a function of the design and
type of incinerator than of the waste being treated. Accordingly, the
type of waste treated has a minimal impact on the amount of heat
transferred by radiation. With regard to convection, EPA also believes
that the type of heat transfer is generally more a function of the type
and design of incinerator than of the waste itself. However, EPA is
examining particle size as a waste characteristic that may significantly
impact the amount of heat transferred to a waste by convection and thus
may impact volatilization of the various organic compounds. The final
type of heat transfer, conduction, is the one that EPA believes has the
greatest impact on volatilization of organic constituents. To measure
this characteristic, EPA uses thermal conductivity; an explanation of
this parameter, as well as how it can be measured, is provided below.
B-12
-------
Heat flow by conduction is proportional to the temperature gradient
across the material. The proportionality constant is a property of the
material and is referred to as the thermal conductivity. (Note: The
analytical method that EPA has identified for measurement of thermal
conductivity is described in Section 5, High Temperature Metals Recovery
in the Treatment Technology Background Document (USEPA 1989)). In
theory, thermal conductivity would always provide a good indication of
whether a constituent in an untested waste would be treated to the same
extent in the primary incinerator chamber as the same constituent in a
previously tested waste.
In practice, thermal conductivity has some limitations in assessing
the transferability of treatment standards; however, EPA has not
identified a parameter that can provide a better indication of heat
transfer characteristics of a waste. Below is a discussion of the
limitations associated with thermal conductivity, as well as other
parameters considered.
Thermal conductivity measurements, as part of a treatability
comparison of two different wastes to be treated by a single incinerator,
are most meaningful when applied to wastes that are homogeneous (i.e.,
uniform throughout). As wastes exhibit greater degrees of nonhomogeneity
(e.g., significant concentration of metals in soil), thermal conductivity
becomes less accurate in predicting treatability because the measurement
essentially reflects heat flow through regions having the greatest
conductivity (i.e., the path of least resistance) and not heat flow
through all parts of the waste.
B-23
-------
Btu value, specific heat, and ash content were also considered for
predicting heat transfer characteristics. These parameters can no better
account for nonhomogeneity than can thermal conductivity; additionally,
they are not directly related to heat transfer characteristics.
Therefore, these parameters do not provide a better indication of the
heat transfer that will occur in any specific waste.
(2) Boilino point. Once heat is transferred to a constituent within
a waste, removal of this constituent from the waste expends on its
volatility. As a surrogate for volatility, EPA is using the boiling
point of the constituent. Compounds with lower boiling points have
higher vapor pressures and, therefore, would be more likely to
volatilize. The Agency recognizes that this parameter does not take into
consideration the impact of other compounds in the waste on the boiling
point of a constituent in a mixture; however, the Agency is not aware of
a better measure of volatility that can easily be determined.
Design and Operating Parameters
Liquid Injection
For a liquid injection unit, EPA's analysis of whether the unit is
well designed focuses on both the likelihood that sufficient energy is
provided to the waste to overcome the activation level for breaking
molecular bonds and whether sufficient oxygen is present to convert the
waste constituents to carbon dioxide and water vapor. In assessing the
effectiveness of the design and operaton of a liquid injection unit, EPA
examines the following parameters: (a) the temperature, (b) the excess
B-14
-------
oxygen concentration, (c) the carbon monoxide concentration, and (d) the
waste feed rate. Below is a discussion of why EPA believes that these
parameters are important, as well as a discussion of how these parameters
are monitored during operation.
It is important to point out, relative to the development of land
disposal restriction standards, that since liquid injection generally
does not produce bottom ash, EPA is concerned with these design
parameters only when a quench water or scrubber water residual is
generated from treatment of a particular waste. If treatment of a
particular waste in a liquid injection unit would not generate a
wastewater stream, then the Agency, for purposes of land disposal
treatment standards, would be concerned only with the waste
characteristics that affect selection of the unit, not with the
above-mentioned design parameters.
(1) Temperature. Temperature provides an indirect measure of the
energy available (i.e., Btu/hr) to overcome the activation energy of
waste constituents. As the design temperature increases, it becomes more
likely that the molecular bonds will be destabilized and the reaction
completed.
The temperature is normally controlled automatically through the use
of instrumentation that senses the temperature and automatically adjusts
the amount of fuel and/or waste being fed. The temperature signal
transmitted to the controller can be simultaneously transmitted to a
recording device and thereby continuously recorded. To fully assess the
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operation of the unit, it is important to know not only the exact
location in the incinerator at which the temperature is being monitored
but also the location of the design temperature.
(2) Excess oxygen concentration. It is important that the
incinerator contain oxygen in excess of the stoichiometric amount
necessary to convert the organic compounds to carbon dioxide and water
vapor. If insufficient oxygen is present, then destabilized waste
constituents could recombine to form the same or other BOAT list organic
compounds and potentially cause the scrubber water to contain higher
concentrations of BOAT list constituents than would be the case for a
well-operated unit.
In practice, the amount of oxygen fed to the incinerator is
controlled by continuous sampling and analysis of the stack gas. If the
amount of oxygen drops below the design value, then the analyzer
transmits a signal to the valve or damper controlling the air supply and
thereby increases the flow of oxygen. The analyzer simultaneously
transmits a signal to a recording device so that the amount of excess
oxygen can be continuously recorded. Again, as with temperature, it is
important to know the location from which the combustion gas is being
sampled.
(3) Carbon monoxide concentration. The carbon monoxide
concentration is an important operating parameter because it provides an
indication of the extent to which the waste organic constituents are
being converted to carbon dioxide and water vapor. An increase in the
carbon monoxide level indicates that greater amounts of organic waste
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constituents are unreacted or partially reacted. Increased carbon
monoxide levels can result from insufficient oxygen, too much oxygen
(causing cooling), insufficient turbulence in the combustion zone, or
insufficient residence time of combustion gases.
(4) Waste feed rate. It is important to monitor the waste feed rate
because it is correlated to the residence time. The residence time is
associated with a specific Btu energy value of the feed and a specific
volume of combustion gas generated. Prior to incineration, the Btu value
of the waste is determined through the use of a laboratory device known
as a bomb calorimeter. The volume of combustion gas generated from the
waste to be incinerated is determined from a waste analysis referred to
as an ultimate analysis. This analysis determines the amount of
elemental constituents present, which include carbon, hydrogen, sulfur,
9
oxygen, nitrogen, and halogens. Using this analysis plus the total
amount of air added, the volume of combustion gas can be calculated.
After both the Btu content and the expected combustion gas volume have
been determined, the feed rate can be fixed at the desired combustion gas
residence time. Continuous monitoring of the feed rate determines
whether the unit was operated at a rate corresponding to the designed
residence time.
Rotary Kiln
For this incineration technology, EPA examines both the primary and
secondary chamber in evaluating the design of a particular incinerator.
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Relative to the primary chamber, EPA's assessment of design focuses on
whether it is likely that enough energy is provided to the waste to
volatilize the waste constituents. For the secondary chamber, analogous
to the sole liquid injection incineration chamber, EPA examines the same
parameters discussed previously under liquid injection incineration.
(These parameters will not be discussed again here.)
In assessing the effectiveness of the design and operation of the
primary chamber, EPA examines the following parameters: (a) the kiln
temperature, (b) the residence time of the waste solids, and (c) the
revolutions per minute. Below is a discussion of why EPA believes that
these parameters are important, as well as a discussion of how these
parameters are monitored during operation.
(1) Temperature. The primary chamber temperature is important
because it provides an indirect measure of the energy input (i.e.,
Btu/hr) available for heating the waste. The higher the design
temperature in a given kiln, the more likely it is that the constituents
will volatilize. As discussed earlier in the Liquid Injection summary,
temperature should be continuously monitored and recorded. Additionally,
it is important to know the location of the temperature sensing device in
the kiln.
(2) Residence time of the waste solids. This parameter is important
in that it affects whether sufficient heat is transferred to a particular
constituent for volatilization to occur. As the time that the waste is
in the kiln is increased, a greater quantity of heat is transferred to
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the hazardous waste constituents. The residence time is a function of
the specific configuration of the rotary kiln, including the length and
diameter of the kiln, the waste feed rate, and the rate of rotation. .
(3) Revolutions per minute (RPM). This parameter provides an
indication of the turbulence that occurs in the primary chamber of a
rotary kiln. As the turbulence increases, the quantity of heat
transferred to the waste would also be expected to increase. However, as
the RPM value increases, the residence time of waste solids decreases,
resulting in a reduction of the quantity of heat transferred to the
waste. This parameter needs to be carefully evaluated because it
provides a balance between turbulence and residence time.
Fluidized Bed
As discussed previously, the primary chamber accounts for almost all
of the conversion of organic wastes to carbon dioxide and water vapor
(and acid gas if halogens are present). The freeboard volume will
generally provide additional residence time for combustion gases for
thermal oxidation of the waste constituents. Relative to the primary
chamber, the parameters that EPA examines in assessing the effectiveness
of the design are temperature, residence time, and bed pressure
differential. The first two were included in the rotary kiln discussion
and will not be discussed here. The last, bed pressure differential, is
important in that it provides an indication of the amount of turbulence
and, therefore, indirectly the amount of heat supplied to the waste. In
general, as the pressure drop increases, both the turbulence and heat
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supplied increase. The pressure drop through the bed should be
continuously monitored and recorded to ensure that the designed valued is
achieved.
Fixed Hearth
The design considerations for this incineration unit are similar to
those for a rotary kiln with the exception that rate of rotation (i.e.,
RPMs) is not an applicable design parameter. For the primary chamber of
this unit, the parameters that EPA examines in assessing how well the
unit is designed are the same as those discussed under Rotary Kiln; for
the secondary chamber (i.e., afterburner), the design and operating
parameters of concern are the same as those discussed under Liquid
Injection.
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References
Ackerman, D.G., McGaughey, J.F., and Wagoner, D.E. 1983. At sea
incineration of PCB-containing wastes on board the M/T Vulcanus. USEPA
600/7-83-024. Washington, D.C.: U.S. Environmental Protection
Agency. 1981.
Bonner, T.A., et al. 1981. Engineering handbook for hazardous waste
incineration. SW-899. Prepared by Monsanto Research Corporation for
US EPA. NTIS PB 81-248163.
Novak, R.G., Troxler, W.L., and Dehnke, T.H. 1984. Recovering energy
from hazardous waste incineration. Chemical Engineering Progress
91:146.
Oppelt, E.T. 1987. Incineration of hazardous waste. JAPCA. Vol. 37,
no. 5, May 1987.
Santoleri, J.J. 1983. Energy recovery-a by-product of hazardous
waste incineration systems. In Proceedings of the 15th Mid-Atlantic
Industrial Waste Conference on Toxic and Hazardous Waste.
USEPA. 1986. U.S. Environmental Protection Agency. Best demonstrated
available technology (BOAT) background document for F001-F005 spent
solvents. Vol. 1, EPA/530-SW-86-056. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1989. U.S. Environmental Protection Agency. Treatment
Technology Background Document. Washington, D.C.: U.S. Environmental
Protection Agency.
Vogel, G., et al. Incineration and cement kiln capacity for hazardous
waste treatment. In Proceedings of the 12th Annual Research Symposium.
Incineration and Treatment of Hazardous Wastes. Cincinnati, Ohio,
April 1986.
Mitre Corp. 1983. Guidance manual for hazardous waste incinerator
permits. NTIS PB84-100577.
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APPENDIX C
TECHNOLOGY - WET AIR OXIDATION
ApdIicability
Wet air oxidation is a treatment technology applicable to wastewaters
containing organics and oxidizable inorganics such as cyanide. The
process is typically used to oxidize sewage sludge, regenerate spent
activated carbon, and treat process wastewaters. Wastewaters treated
using this technology include pesticide wastes, petrochemical process
wastes, cyanide-containing metal finishing wastes, spent caustic
wastewaters containing phenolic compounds, and some organic chemical
production wastewaters.
This technology differs from other treatment technologies generally
used to treat wastewaters containing organics in several ways. First,
wet air oxidation can be used to treat wastewaters that have higher
organic concentrations than are normally handled by biological treatment,
carbon adsorption, and chemical oxidation, but may be too dilute to be
effectively treated by thermal processes such as incineration. Wet air
oxidation is most applicable for waste streams containing dissolved or
suspended organics in the 500 to 15,000 mg/1 range. Below 500 mg/1, the
rates of wet air oxidation of most organic constituents are too slow for
efficient application of this technology. For these more dilute waste
streams, biological treatment, carbon adsorption, or chemical oxidation
may be more applicable. For more concentrated waste streams (above
15,000 mg/1), thermal processes such as incineration may be more
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applicable. Second, wet air oxidation can be applied to wastes that have
significant concentrations of metals (roughly 2 percent), whereas
biological treatment, carbon adsorption, and chemical oxidation may have
difficulty in treating such wastes.
It is important to point out that wet air oxidation proceeds by a
series of reaction steps and the intermediate products formed are not
always as readily oxidized as are the original constituents. Therefore,
the process does not always achieve complete oxidation of the organic
constituents. Accordingly, in applying this technology it is important
to assess potential products of incomplete oxidation to determine whether
further treatment is necessary or whether this technology is appropriate
at all.
Studies of the wet air oxidation of different compounds have led to
the following empirical observations concerning a compound's
susceptibility to wet air oxidation based on its chemical structure:
1. Aliphatic compounds, even with multiple halogen atoms, can be
destroyed within conventional wet air oxidation conditions.
Oxygenated compounds (such as low molecular weight alcohols,
aldehydes, ketones, and carboxylic acids) are formed, but these
compounds are readily biotreatable.
2. Aromatic hydrocarbons, such as toluene, acenaphthene, or pyrene,
are easily oxidized.
3. Halogenated aromatic compounds can be oxidized provided there is
at least one nonhalogen functional group present on the ring
(e.g., pentachlorophenol (-0H) or 2,4,6-trichloroanil ine
(-NH2)).
4. Halogenated aromatic compounds, such as 1,2-dichlorobenzene, and
PCBs, such as Aroclor 1254, are resistant to wet air oxidation
under conventional conditions.
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5. Halogenated ring compounds, such as the pesticides aldrin,
dieldrin, and endrin, are expected to be resistant to
conventional wet air oxidation.
6. DOT can be oxidized, but results in the formation of intractable
oils in conventional wet air oxidation.
7. Heterocyclic compounds containing oxygen, nitrogen, or sulfur are
expected to be destroyed by wet air oxidation because the 0, N,
or S atoms provide a point of attack for oxidation reactions to
occur.
Underlying Principles of Operation
The wet air oxidation of aqueous wastes occurs at high temperatures
and pressures. The typical operating temperature for the treatment
process ranges from 175 to 325"C (347 to 617°F). The pressure is
maintained at a level high enough to prevent excessive evaporation of the
liquid phase at the operating temperature, generally between 300 and
3000 psi. At these elevated temperatures and pressures, the solubility
of oxygen in water is dramatically increased, thus providing a strong
driving force for the oxidation. The reaction must take place in the
aqueous phase because the chemical reactions involve both oxygen
(oxidation) and water (hydrolysis). The wet air oxidation process for a
specific organic compound generally involves a number of oxidation and
hydrolysis reactions in series, which degrade the initial compound by
steps into a series of compounds of simpler structure. Complete wet air
oxidation results in the conversion of hazardous compounds into carbon
dioxide, water vapor, ammonia (for nitrogen-containing wastes), sulfate
(for sulfur-containing wastes), and halogen acids (for halogenated
wastes).
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However, treatable quantities of partial degradation products may
remain in the treated wastewaters from wet air oxidation. Therefore,
effluents from wet air oxidation processes may be given subsequent
treatment including biological treatment, carbon adsorption, or chemical
oxidation before being discharged.
Description of Wet Air Oxidation Process
A conventional wet air oxidation system consists of a high-pressure
liquid feed pump, an oxygen source (air compressor or liquid oxygen
vaporizer), a reactor, heat exchangers, a vapor-liquid separator, and
process regulators. A basic flow diagram is shown in Figure 1.
A typical batch wet air oxidation process proceeds as follows.
First, a copper catalyst solution may be mixed with the aqueous waste
stream if preliminary testing indicates that a catalyst is necessary.
The waste is then pumped into the reaction chamber. The aqueous waste is
pressurized and heated to the design pressure and temperature,
respectively. After reaction conditions have been established, air is
fed to the reactor for the duration of the design reaction time. At the
completion of the wet air oxidation process, suspended solids or gases
are removed and the remaining treated aqueous waste is either discharged
directly or fed to a biological treatment, carbon adsorption, or chemical
oxidation treatment system if further treatment is necessary prior to
discharge.
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PRESSURIZED
WASTE FEED
T
PRESSURIZED
AIR OR
OXYGEN
FEED HEAT
EXCHANGERS
reactor
STEAM
STEAM
QAS-UQUIP
SEPARATOR
V
TREATED
WASTE
(TO
FURTHER
TREATMENT
on
DISPOSAL)
FIGURE 1
WET AIR OXIDATION PROCESS FLOW DIAGRAM.
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Wet air oxidation can also be operated in a continuous process. In
continuous operation, the waste is pressurized, mixed with pressurized
air or oxygen, preheated in a series of heat exchangers by the hot
reactor effluent and steam, and fed to the reactor. The waste feed flow
rate controls the reactor residence time. Steam is fed into the reactor
column to adjust the column temperature. The treated waste is separated
in a gas-liquid separator, with the gases treated in an air pollution
control system and/or discharged to the atmosphere, and the liquids
either further treated, as mentioned above, and/or discharged to disposal.
Waste Characteristics Affecting Performance (WCAPs^
In determining whether wet air oxidation will achieve the same level
of performance on an untested waste as on a previously tested waste and
whether performance levels can be transferred, EPA examines the following
waste characteristics: (a) the chemical oxygen demand and (b) the
concentration of interfering substances.
Chemical Oxygen Demand
The chemical oxygen demand (COD) of the waste is a measure of the
oxygen required for complete oxidation of the oxidizable waste
constituents. The limit to the amount of oxygen that can be supplied to
the waste is dependent on the solubility of oxygen in the aqueous waste
and the rate of dissolution of oxygen from the gas phase to the liquid
phase. This sets an upper limit on the amount of oxidizable compounds
that can be treated by wet air oxidation. Thus, high-COO wastes may
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require dilution for effective treatment to occur. If the COD of the
untested waste is significantly higher than that of the tested waste, the
system may not achieve the same performance. Pretreatment of the waste
or dilution as part of treatment may be needed to reduce the COD.to
within levels treatable by the dissolved oxygen concentration and to
achieve the same treatment performance, or other, more applicable
treatment technologies may need to be considered for treatment of the
untested waste.
Concentration of Interfering Substances
In some cases, addition of a water-soluble copper salt catalyst to
the waste before processing is necessary for efficient oxidation
treatment (for example, for oxidation of some halogenated organics).
Other metals have been tested and have been found to be less effective.
Interfering substances for the wet air oxidation process are essentially
those that cause the formation of insoluble copper salts when copper
catalysts are used. To be effective in catalyzing the oxidation
reaction, the copper ions must be dissolved in solution. Sulfide,
carbonate, and other negative ions that form insoluble copper salts may
interfere with treatment effectiveness if they are present in significant
concentrations in wastes for which copper catalysts are necessary for
effective treatment. If an untested waste for which a copper catalyst is
necessary for effective treatment has a concentration of interfering
substances (including sulfide, carbonate, or other anions that form
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insoluble copper salts) significantly higher than that in a tested waste,
the system may not achieve the same performance and other, more
applicable treatment technologies may need to be considered for treatment
.of the untested waste.
Design and Operating Parameters
In assessing the effectiveness of the design and operation of a wet
air oxidation system, EPA examines the following parameters: (a) the
oxidation temperature, (b) the residence time, (c) the excess oxygen
concentration, (d) the oxidation pressure, and (e) the amount and type of
catalyst.
Oxidation Temperature
Temperature is the most important parameter affecting the system.
The design temperature must be high enough to allow the oxidation
reactions to proceed at acceptable rates. Raising the temperature
increases the wet air oxidation rate by enhancing oxygen solubility and
oxygen diffusivity. The process is normally operated in the temperature
range of 175 to 325°C (347 to 617'F), depending on the hazardous
constituent(s) to be treated. EPA monitors the oxidation temperature
continuously, if possible, to ensure that the system is operating at the
appropriate design condition and to diagnose operational problems.
Residence Time
The residence time impacts the extent of oxidation of waste
contaminants. For a batch system, the residence time is controlled
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directly by adjusting the treatment time in the reaction tank. For a
continuous system, the waste feed rate is controlled to make sure that
the system is operated at the appropriate design residence time.
Generally, the reaction rates are relatively fast for the first 30
minutes and become slow after 60 minutes. Typical residence times,
therefore, are approximately 1 hour. EPA monitors the residence time to
ensure that sufficient time is provided to effectively oxidize the waste.
Excess Oxygen Concentration
The system must be designed to supply adequate amounts of oxygen for
the compounds to be oxidized. An estimate of the amount of oxygen needed
can be made based on the COD content of the untreated waste; excess
oxygen should be supplied to ensure complete oxidation. The source of
oxygen is compressed air or a high-pressure pure oxygen stream. EPA
monitors the excess oxygen concentration (the concentration of oxygen in
the gas leaving the reactor) continuously, if possible, by sampling the
vent gas from the gas-liquid separator to ensure that an effective amount
of oxygen or air is being supplied to the waste.
Oxidation Pressure
The design pressure must be high enough to prevent excessive
evaporation of water and volatile organics at the design temperature.
This allows the oxidation reaction to occur in the aqueous phase, thereby
improving treatment effectiveness. EPA monitors the oxidation pressure
continuously, if possible, to ensure that the system is operating at the
appropriate design condition and to diagnose operational problems.
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Amount and Type of Catalyst
Adding a catalyst that promotes oxygen transfer and thus enhances
oxidation has the effect of lowering the necessary reactor temperature
and/or improving the level of destruction of oxidizable compounds. For
waste constituents that are more difficult to oxidize, the addition of a
catalyst may be necessary to effectively destroy the constituent(s) of
concern. Catalysts typically used for this purpose include copper
bromide and copper nitrate. If a catalyst is required, EPA examines the
amount and type added, as well as the method of addition of the catalyst
to the waste, to ensure that effective oxidation is achieved.
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References
Dietrich, M.J., Randall, T.L., and Canney, P.J. 1985. Wet air oxidation
of hazardous organics in wastewater. Environmental Progress 4:171-197.
Randall, T.L. 1981. Wet oxidation of toxic and hazardous compounds,
Zimpro technical bulletin 1-610. Presented at the 13th Mid-Atlantic
Industrial Waste Conference, June 29-30, 1981, University of Delaware,
Newark, Del.
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