FINAL
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT ADDENDUM FOR
ACRYLONITRILE WASTES (K011, K013, AND K014)
Larry Rosengrant, Chief
Treatment Technology Section
Monica Chatman-McEaddy
Project Manager
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, DC 20460
May 1990
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ACKNOWLEDGMENTS
This document was prepared for the U.S. Environmental Protection
Agency, Office of Solid Waste, by Versar Inc., under Contract No.
68-W9-00-68. Mr. Larry Rosengrant, Chief, Treatment Technology Section,
Waste Treatment Branch, served as the EPA Program Manager for the BOAT
program. Ms. Monica Chatman-McEaddy served as the Project Manager for
regulatory development for K011, K013, and K014 wastes. Mr. Steven
Silverman served as EPA legal advisor.
The following personnel from Versar Inc. were involved in preparing
this document: Mr. Jerome Strauss, Program Manager; Mr. Stephen
Schwartz, Assistant Program Manager; Ms. Roberta Eelman and Ms. Laura
Fargo, Staff Engineers; Ms. Sally Gravely, Program Secretary; and
Ms. Martha Martin, Technical Editor.
ii
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TABLE OF CONTENTS
Section Page No.
1. INTRODUCTION AND SUMMARY 1-1
2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION 2-1
2.1 Industries Affected 2-1
2.2 Waste Characterization 2-2
3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES 3-1
4. PERFORMANCE DATA 4-1
5. DETERMINATION OF BEST DEMONSTRATED AVAILABLE
TECHNOLOGY (BOAT) 5-1
6. SELECTION OF REGULATED CONSTITUENTS 6-1
7. CALCULATION OF BOAT TREATMENT STANDARDS 7-1
7.1 Correcting the Remaining Data 7-1
7.2 Editing the Data 7-2
7.3 Calculating the Variability Factors 7-3
7.4 Calculating the Treatment Standards 7-4
8. REFERENCES 8-1
APPENDIX A - Determination of Wastewater Definition for
K011/K013/K014 Wastes A-l
APPENDIX B - Analytical Information B-l
APPENDIX C - ANOVA Test C-l
iii
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LIST OF TABLES
Page No.
Table 1-1 BOAT Treatment Standards for K011/K013/K014 Wastewaters 1-2
Table 2-1 Additional K011 Waste Characterization Data 2-4
Table 2-2 Additional K013 Waste Characterization Data 2-6
Table 2-3 Additional K014 Waste Characterization Data 2-8
Table 2-4 Additional K011/K013 Waste Characterization Data 2-8
Table 2-5 Additional K011/K013/K014 Waste Characterization Data . 2-9
Table 4-1 Performance Data for K011/K013/K014 Treatment
by a Proprietary Wet Air Oxidation Process 4-4
Table 4-2 Performance of Wet Air Oxidation on K011 Wastes 4-5
Table 4-3 Performance of Pilot-Scale Wet Air Oxidation on
K011/K013 Wastes (Waste 1) 4-6
Table 4-4 Performance of Pilot-Scale Wet Air Oxidation on
K011/K013 Wastes (Waste 2) 4-7
Table 4-5 Performance of Laboratory-Scale Wet Air Oxidation
on K011 Wastes 4-8
Table 4-6 Wet Air Oxidation of K011, K013, and Mixtures of the
Two Streams 4-9
Table 7-1 Calculation of Treatment Standards for
Acrylonitrile Wastewaters 7-4
Table A-l Calculation of 99.9th Percentile of TOC Content A-3
Table B-l Analytical Methods for Regulated Constituents in
K011/K013/K014 Wastes B-3
Table B-2 Matrix Spike Recoveries B-4
Table C-l F Distribution at 95 Percent Confidence Level C-4
Table C-2 Accuracy-Corrected Data for ANOVA C-5
Table C-3 F Value Determination C-6
IV
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1. INTRODUCTION AND SUMMARY
This background document presents the technical support and rationale
for the development of treatment standards for K011/K013/K014
wastewaters. The effective data for these standards is August 8, 1990.
Treatment standards for nonwastewater forms of K011/K013/K014 were
promulgated in the Second Third final rulemaking (54 FR 26594,
June 23, 1989). This background document is issued as an addendum to the
June 1989 background document for K011/K013/K014 (USEPA 1989a), which
accompanied the rulemaking for nonwastewater forms of K011/K013/K014.
Treatment standards for wastewater forms of K011/K013/K014 were not
promulgated as part of the Second Third rulemaking in order to allow the
Agency time for additional data collection and analysis. Information
contained in the June 1989 background document is not repeated in this
document.
This document presents information specific to the treatment of
K011/K013/K014 wastewaters and the technologies that were evaluated in
the determination of best demonstrated available technology (BDAT) for
K011/K013/K014 wastewaters. The Agency is regulating the same five BDAT
list constituents that are regulated in K011/K013/K014 nonwastewaters
(acetonitrile, acrylonitrile, acrylamide, benzene, and cyanide). These
standards are based on the treatment performance of wet air oxidation.
The treatment standards for K011/K013/K014 wastewaters are presented in
Table 1-1.
Compliance with these BDAT treatment standards is a prerequisite for
placement of these wastes in units designated as land disposal facilities
according to 40 CFR Part 268. For the purpose of determining the
treatment standards, K011/K013/K014 wastewaters are defined as wastes
containing less than 5 percent (weight basis) total organic carbon and
less than 1 percent (weight basis) total suspended solids. Information
about the wastewater definition is presented in Appendix A.
1-1
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Table 1-1 BDAT Treatment Standards for K011/K013/K014 Wastewaters
Maximum
for anv single grab sample
Constituent Total composition (mg/1)
Acetonitrile 38
Acrylonitrile 0.06
Acrylamide 19
Benzene 0.02
Cyanide (total) 21
1-2
336<.g
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Wastes not meeting this definition must comply with the treatment
standards for K011/K013/K014 nonwastewaters.
Consistent with the background document for nonwastewaters, the
treatment performance standard was developed based on a K011/K013/K014
mixed waste. The term K011/K013/K014 can refer to K011, K013, and K014
wastes individually; any combination of K011, K013, and K014 wastes;
treatment residuals resulting from treatment of K011, K013, and K014
wastes individually; and treatment residuals resulting from treatment of
any combination of K011, K013, and K014 wastes and treatment residuals.
Hence, all combinations, and individual wastestreams, if disposed of
separately, must meet the treatment standards.
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 CBI. Additionally, the Agency would like to
emphasize that it evaluated all available data (including CBI data) in
developing the BOAT treatment standards for K011/K013/K014 wastewaters.
The BDAT 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 1987a). The petition process to be followed in requesting a
variance from the BDAT treatment standards is discussed in the
methodology document.
1-3
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2. INDUSTRIES AFFECTED AND WASTE CHARACTERIZATION
KOll, K013, and K014 are waste streams generated by the production of
acrylonitrile. KOll is the bottom stream from the wastewater stripper,
K013 is the bottom stream from the acetonitrile column, and K014 is the
bottom stream from the acetonitrile purification column.
2.1 Industries Affected
The Agency has no new data that would change the description of the
acrylonitrile manufacturing industry that was contained in the June 1989
K011/K013/K014 background document (USEPA 1989).
2.2 Waste Characterization
The June 1989 K011/K013/K014 background document contained
characterization data for K011/K013/K014 wastes. Additional
K011/K013/K014 characterization data submitted after promulgation of the
treatment standards for nonwastewaters are presented in Tables 2-1
through 2-5 at the end of this section. The data in the tables were
submitted to the Agency by or on behalf of several United States
acrylonitrile producers to help EPA characterize the K011/K013/K014
wastewaters.
In the background document for K011/K013/K014 nonwastewaters, it was
determined that management of the K011/K013/K014 stream typically
involves a settling or filtration process to remove suspended solids
followed by deep-well injection of the liquid effluent and land disposal
of the filtered solids. The settled filtered solids are considered
nonwastewaters, and the liquid effluent is usually considered a
wastewater by the generators.
The data in Table 2-1 show that KOll wastewaters typically contain
about 400 to 2000 mg/1 of acetonitrile, 90 to 1000 mg/1 acrylamide, less
2-1
336*6
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than 1020 mg/1 acrylonitrile, nondetectable levels of benzene and less
than 500 mg/1 cyanide. Nickel appears to be present in one K011
wastewater sample; however, the generator of that particular stream
claims that the stream is usually filtered to remove suspended catalyst
particles containing nickel so these data do not reflect waste
characteristics of K011, K013, and K014 wastewaters (Cyanamid 1989c).
Wastes defined as K011 also contain 0.85 percent to 3.15 percent total
organic carbon (TOC) and 25 to 1100 mg/1 total suspended solids (TSS).
The data presented in Table 2-2 show that K013 wastewaters usually
contain less than 20 mg/1 acetonitrile, less than 100 mg/1 acrylamide,
less than 20 mg/1 acrylonitrile, less than 150 mg/1 of cyanide, and
nondetectable levels of benzene and nickel. These data show that the TOC
range for the K013 wastewaters is 0.29 to 0.55 percent and the TSS range
is 2 to 30 mg/1. However, the Agency has confidential data that show the
TOC content can average 2 percent (Sterling 1989).
The only additional data for K014 show a waste with about 20,000 mg/1
acetonitrile, 3.3 to 8.0 percent TOC, and 8 to 831 mg/1 TSS. These data
are presented in Table 2-3.
The additional data for K011/K013 mixed wastewaters are presented in
Table 2-4. Generally, the K011/K013 mixture contains acetonitrile
ranging from 180 to 600 mg/1, acrylamide ranging from 500 to 1000 mg/1,
acrylonitrile from 10 to 200 mg/1, and less than 1,100 mg/1 cyanide. The
TOC ranges from approximately 1.4 to 3.0 percent, and the TSS ranges from
100 to 550 mg/1.
Table 2-5 presents the available data for the K011/K013/K014
mixture. This waste typically contains 1.1 to 2.0 percent TOC and 20 to
700 mg/1 TSS. The K011/K013/K014 mixture usually contains less than
700 mg/1 acetonitrile, less than 1600 mg/1 acrylonitrile, less than
1100 mg/1 acrylamide, less than 0.42 mg/1 benzene, and less than 1900 mg/1
total cyanide.
2-2
3364g
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In summary, K011, K013, and K011/K013 mixtures and the K011/K013/K014
mixtures are aqueous wastes containing low TSS (i.e., less than 1100
mg/1) and low TOC (i.e., less than 3.15 percent). The K014 wastes can
contain low TSS (i.e., less than 850 mg/1) and a considerably higher TOC
content (i.e., 8.0 percent). Based on these data, the Agency has
determined that K011/K013/K014 wastewaters are defined as wastes
containing less than 5.0 percent TOC and less than 1 percent TSS;
K011/K013/K014 nonwastewaters are defined as all other wastes not meeting
this definition. The development of the total organic carbon level is
presented in Appendix A of this document.
2-3
3364g
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3337g
Table 2-1 Additional K011 Naate Cbaractarization Data
Untreated 1011 waata
Panwtar (onita) (a) (a) (a)
HtA
Aeetone
Aeetonitrile 420 1,030 630
Aeryljenide 780. 730 273
Aorylonitrile 760 310 330
Beniene ~
(a) (a) (a) (a) (a) (a)
333 440 1.700
87 1.200 1.200
673 <0.3 2.6 18 47.8+93.5 90
<0.005 <0.005 ~ <10
(a)
23.3
1.119
748
1.020
(b)
~
Cyanide (total) 431
273 306 308 490 0.3+0.04 302/138 379
<.02 <.02 <.02 24.3
nitrogen (/!) 21,100 12,800 13.900 17.000 17.000
Ballet* (/I) 68.400 33.700 42.800 31.000 30.000
(B/l) ~ 31,000
Total auapondod
olid* (/I) 47 189 23 34 27
Total ozcanie
eacboa (X) 2.13 1.33 2.03 2.24 1.1
Total diaaotod
olid* (X)
26000
400-1100
1.1 2.6
6-13.8
2-4
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3337g
Tabl* 2-1 (eontiaawl)
K011
(vita) (c) (e) (e) (e) (e) (e) (c) (e) (e) (c) (c) (c) (c) (e) (e) (c) (e) (c)
Act
ACflbGDl&CllB * ~ ~ * "~ " ~ ~ ~ " ""~ " ~ "
(total) _--__
Oth«r An«lT»«»
Sulfat*
ftnainal
ollda (BK/1) ITS 34 25 47 2B ~
Total ozganie
ortWD (Z) 1.96 2.24 2.03 2.13 1.33 2.01 1.81 2.60 1.31 2.10 1.90 3.13 1.37 1.63 0.83 2.63 1.46 1.93
Total dlMolvvd
olid* (Z) 13.2 9.91 8.03 12.21 8.37 6.60 -- _ _ _
Source*: Tt xihl «r/Kocur«k 1989.
b - BP 1989*.
e Crmt^U 1989*.
2-5
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3337g
Tabl* 2-2 ArlrtU.imal K013 Hut* CbaractariMtion Data («s/l)
K013 *m*t»
() () () () () () () (b)
AMtonitcilB ' <1
AcrylrflBiito 1
Aery Inn Itrilfr <1
<1 3
10 02
6 2
<0.003 10.0
a H ^^ ^^ ^^
6.4 2.6 1.2 11.3±7.0 2.2
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3337g
Tabla 2-2 (cantim-d)
Dntraatad rn!3
fira-il.r (onitaHe) (e) (e) (e) (e) (e) (e) (c) (c) (c) (c)
Ae-ylaBida
aczylonitrila
Cranid- (total)
ickal
oitrosan (MB/1)
Total aaapandad
ollda (/!) 7 2 2 5 18 __
Total organic
carbon (Z) 0.42 0.28 0.48 O.S9 0.83 0.7S 0.61 0.57 1.03 0.63 0.45
Total dlMOlv-d
(Z) 0.41 0.25 0.43 0.57 2.34
: a - Tiaehlar/Xooar*- 1888.
b - BP 1888a.
e - Cyan-aid 1868a.
2-7
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3337g
Tabla 2-3 *hHt.iona1 K014 Hut* Cbaractariaation Data
Pntraatad KOI* waata
(nits) (a) (b)
Acatenitrila 11,281.7 + 9.888.6
Total ozsanic eacbon (Z) 3.3 - 8.0
Total mpanrtarl aoUdaiaa/l) 8-831
« fc» reported
Soorow: - TiMhlox/Koconk 1888.
b - BP 1888a.
Tabla 2-4 aiMltinnal X011/K013 Hasta Charaetarisatioa Data (a«/l)
Paraaatar (onita) (a) (a) (a) (a) (b)
BOAT Liat £mft£itBrafi_
AcatnnltriU
Aecylavlda
Aexylonitrila
CyaBida (total)
f Iff I'll
979
880
90
1.100
178
920
12
1.100
470
787
189
1.100
328
808
182
1.100
6.634 4.380 9.674 9.363
17.770 12.017 19.883 16.361
33.170 33.863 38,632 40,643
938 322 230 223 100-900
Total ozcanic cacbon 13,698 13.024 18.244 23,000-30.000
Total diaaolvad aollda 100.000-130.000
- Bo rvportad
a TiMhlar/Koennk 1888.
b - BP 1888a.
2-8
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3337g
Table 2-5 additional K011/KD13/K014 Wait* Charaetarisation Data
Otatroatad BJ1VDJ13/I014
(trnit*)
OO
BOAT 1.1 at. CIKU
Aorylxnltxil*
Cyanide (total)
104-684
330 - 1390
743 - 1078
0.07 - 0.42
1244 - 1899
Total raapandod solid* U«/l)
Total organic oacfaon (Z)
Total diMolvvd aolid* (Z)
20-700
1.1 - 2.0
.3 - 7.0
- HP 198Ba.
b - BP !MOb.
2-9
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3. APPLICABLE AND DEMONSTRATED TREATMENT TECHNOLOGIES
For K011/K013/K014 wastewaters, the Agency believes that wet air
oxidation is an applicable technology. In addition, the Agency believes
biological treatment is applicable for treatment of some K013
wastewaters. The Agency has identified these technologies because they
are designed to reduce the concentration of organics and oxidizable
inorganics such as cyanide in wastewaters. EPA also believes that carbon
adsorption is applicable as a polishing step for both wet air oxidation
and biological treatment to reduce the organic compounds in the
effluents.
Wet air oxidation is potentially applicable for wastewaters containing
up to 10 percent organic concentration (USEPA 1987b). It is a treatment
technology that oxidizes hazardous organic compounds at elevated tempera-
tures and pressures. The Agency notes that the term "wet air oxidation"
is used throughout this document to identify a process whereby wastes are
oxidized in an aqueous liquid phase under conditions of elevated
temperature and pressure. The oxidant could be air, oxygen-enriched air,
"pure" oxygen, or other oxidants.
Biological treatment is a technology that uses living microorganisms
to decompose organic constituents into carbon dioxide, water, and simple
organic compounds. It is generally applicable for wastewaters containing
dilute concentrations of organics.
Carbon adsorption is a technology in which the wastewater is passed
through a column packed with activated carbon. The contaminants in the
wastewaters are adsorbed by the carbon because the contaminant has a low
solubility in the waste and/or the contaminant has a greater affinity for
the carbon than for the waste.
3-1
3364g
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The Agency believes that wet air oxidation is demonstrated to treat
the BOAT list organics and cyanide present in the K011/K013/K014
nonwastewaters. The Agency has identified several facilities performing
pilot-scale wet air oxidation tests on K011/K013/K014 wastewaters.
Furthermore, wet air oxidation is a proven full-scale technology for
destroying organics and cyanides in numerous hazardous waste streams
(USEPA 1987b). Hence, the Agency believes that wet air oxidation is
demonstrated for K011/K013/K014 wastewaters.
It is believed that biological treatment is not applicable for K011,
K011/K013 mixtures, or K011/K013/K014 mixtures because of the greater
concentrations of organic constituents (i.e., up to 3.1 percent) and
ammonium sulfate. Additionally, the organic concentration of K014 is
high (i.e., up to 8.0 percent) for biological treatment to be effective
(USEPA 1987b). Moreover, some K013 wastes contain approximately
2 percent TOC and biological treatment would not be applicable because of
the organic content.
EPA believes that biological treatment is demonstrated to treat some
K013 wastewaters. The Agency has identified one facility testing
biological treatment for K013 wastewaters containing low concentrations
of BDAT list organics; thus the Agency considers biological treatment to
be demonstrated to treat K013 wastewaters containing low concentrations
of organics. However, the Agency believes that it is inappropriate to
identify biological treatment as demonstrated for K011/K013/K014
wastewaters based solely on the biological treatment of dilute K013
wastewaters because K011/K013/K014 wastewater streams consisting of K011
and K013 combined or K011, K013, and K014 combined would contain much
higher concentrations of dissolved ammonia and sulfate. It is conceivable
that the high concentrations of dissolved ammonia and sulfate would
interfere with biological treatment. Additionally, because some K013
wastewaters are known to contain TOC concentrations of 2 percent
(Sterling 1989), biological treatment would be inappropriate.
3-2
336*8
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The Agency has not identified any facilities performing carbon
adsorption treatment on K011/K013/K014 wastewaters. Consequently, EPA
does not believe that carbon adsorption is demonstrated to treat these
wastes. Detailed discussions of wet air oxidation, biological treatment,
and carbon adsorption are presented in the Treatment Technology
Background Document (USEPA 1988b).
3-3
3364g
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4. PERFORMANCE DATA
This section presents the data available to EPA on the performance of
demonstrated technologies in treating K011/K013/K014 wastewaters. 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). Eligible data, in addition to full-scale demonstration
data, 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 operation for similar
wastes.
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.
Tables 4-1 through 4-6 present performance data for wet air oxidation
treatment of K011/K013/K014 wastewaters. All six evaluations were
performed using different process equipment, operating conditions, and
waste matrices.
Table 4-1 contains treatment performance data for pilot-scale
treatment of K011/K013/K014 mixed waste by a proprietary wet air
oxidation process. The data consist of four sets of untreated and
treated wastewater effluent samples. These data show reductions of the
organics and cyanide concentrations in the wastewater effluent. The
operating conditions and all process information have been classified as
Confidential Business Information (CBI) and cannot be presented in the
K011/K013/K014 addendum. These data are located in the RCRA CBI docket.
4-1
3364g
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Table 4-2 presents performance data for treatment of K011 wastewaters
by wet air oxidation process. These data consist of one set of untreated
K011 wastewater and treated wastewater effluent sample results.
Concentration of organics have been reduced from concentrations as high
as 1700 mg/1 to 77 rag/1, and total cyanide has been reduced from 302 mg/1
to 7.1 mg/1. Operating data collected during the test are also shown on
the table.
The data in Table 4-3 show the performance of wet air oxidation for
treatment of K011/K013 mixed wastes. These data consist of one untreated
sample result and eight different treated effluent sample results. The
same untreated waste was treated using eight different combinations of
operating conditions. The operating conditions are shown in the table
for each separate test. The results show reductions for acetonitrile and
total cyanide during all tests. Test #4 reported an increase in
acrylonitrile concentration, while test #2, test #3, test #5, and test #8
reported an increase in acrylamide concentration.
Table 4-4 presents performance data for treatment of another
K011/K013 mixed waste. For this evaluation there are three sets of
untreated and treated results. Test #1 shows reductions for all
constituents except acrylamide. Test #2 and Test #3 show reductions for
all constituents. The operating conditions are shown in the table.
Table 4-5 presents performance data for the laboratory-scale wet air
oxidation process of K011 waste. The data consist of one untreated
sample and the results of two treated wastewater effluents generated at
different operating temperatures. The results show reductions of certain
organic constituents and cyanide; however, both treated effluents show
increases in the total organic carbon content.
Table 4-6 presents wet air oxidation performance data for treatment
of K011, K013, and mixtures of the two streams. The operating conditions
are shown on the table and are constant for all three evaluations. The
4-2
3364g
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first evaluation consists of two sets of untreated and treated results
for K011/K013 mixed wastes. Reductions are noted for all four organic
constituents and cyanide. The second evaluation is for treatment of K013
waste. These data consist of one set of untreated and treated results.
The concentration of acetonitrile increased in the treatment effluent,
while the other three organics and cyanide concentrations decreased. For
the K011 wastewater, reductions in the constituents of concern in the
treatment effluent are shown for all four organics consistuents and
cyanide.
4-3
336*6
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Table 4-1 Performance Data for K011/K013/K014 Treatment
by a Proprietary Wet Air Oxidation Process
Test number
Test f1 Test *2 Test #3 Test *4
Parameter (units) Untreated Treated Untreated Treated Untreated Treated Untreated Treated
BDAT List Constituent (mn/1)
Acetonitrile 166 3.8 229 3.3 104 13.8 684 11.8
Acrylonitrile 1,560 <0.02 1,590 <0.02 728 <0.02 550 <0.02
Benzene 0.17 0.007 0.18 0.007 0.07 <.006 0.42 <.006
Acrylamide 844 2.59 770 1.81 1.078 S.S4 745 8.24
Cyanide (total) 1,244 3.9 1,300 4.0 1,460 0.7 1,899 4.6
Other Analyses (mn/1)
pB 5.9 2.0 6.0 2.0 5.9 7.1 5.9 7.2
Chemical oxygen demand 55,900 3,300 57,200 4,100 60,900 3,800 47,900 3,400
Total organic carbon 20,700 1,700 20,600 2,100 22,300 2,100 14,800 1.800
Operating Conditions:
Reactor temperature: CBI
Residence time: CBI
Off-gas oxygen concentration: CBI
Reactor pressure: CBI
CBI = Confidential Business Information.
Source: BP 1989b.
4-4
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Table 4-2 Performance of Net Air Oxidation on K011 Hastes
Parameter (units) Untreated Treated
BOAT List Constituent (rnn/l)
Acetonitrile 1,700 77
Acrylonitrile 90 <10
Acrylamide 1,200 <20
Benzene <10 <10
Cyanide (total) 302 7.1
Cyanide (amenable) 138 <1
Operating conditions: Reactor temperature: 280*C
Residence time: 60 minutes
Off-gas oxygen concentration: unknown
Reactor pressure: 3,300 psig
Source: Tiachler/Kocurek 1989.
4-5
3364g
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3038g
Table 4-3 Performance of Pilot-Scale Wet Air Oxidation on K011/K013 Hastes (Haste 1)
Untreated
Parameters (units) K011/K013
BOAT list constituents (TO/1)
Acetonitrile 575
Acrylamide 980
Acrylonitrile 50
Cyanide (Total) 1100
Other analyses (m/1)
Anmonia-nitrogen 6634
Sulfate 17770
Chemical orygen demand 55170
Total suspended solids 538
Total organic carbon 20488
Operating conditions
Reactor temperature (*C)
Residence time (minutes)
Off-gas oxygen (percent)
Reactor pressure (psig)
Treated K011/K013
Test *1
110
0
1
2.4
10923
19094
20220
1461
12390
249
70
3
900
Test 02
254
1120
0
2.2
10760
18037
19463
1263
12390
260
70
3
1100
Test 03
245
1205
12
0.3
10741
18494
18293
915
10927
260
70
6
1100
Test 04
270
107
100
5
10829
18285
23013
1527
13366
238
70
3
900
Test 05
295
1007
0
2.5
10894
17571
22047
1210
12195
238
70
6
900
Test 06
0
200
20
0.6
10984
19220
19315
897
10927
249
70
6
900
Test 07
407
69
43
1.7
10683
17183
22839
1468
12488
249
52
3
900
Test 08
215
1057
8
0
9424
15676
33475
1961
14829
249
60
0
900
Reference: Tischler/Kocurek 1989.
-------
Table 4-4 Performance of Pilot-Scale Wet Air Oxidation
on K011/K013 Wastes (Haste 2)
Parameter (units)
Test 41
Untreated _ Treated
Test #2 Test #3
Untreated _ Treated Untreated Treated
BDAT List Constituents (ra/1)
Acetonitrile
Acrylamide
Acrylonitrile
Total cyanide
178
520
12
1100
221
972
11
0.6
470
797
195
1100
SO
156
5
2.1
329
809
162
1100
114
12
13
1.7
Others Analyses (rnn/l)
Ammonia-nitrogen
Sulfate
Chemical oxygen demand
Total suspended solids
Total organic carbon
4390
12017
3S983
322
13659
7698
11816
16539
790
12098
5644
15895
39652
230
15024
7883
17434
19639
839
7317
5363
16561
40643
223
18244
9151
17628
18961
932
9951
Operating Conditions
Reactor temperature ( C)
Residence time (minutes)
Off-gas oxygen (percent)
Reactor pressure (psig)
249
70
3
900
249
70
3
900
249
60
3
900
Source: Tischler/Kocurek 1989.
4-7
336*6
-------
Table 4-5 Performance of Laboratory-Scale Net Air Oxidation
on K011 Wastes
Parameter (units)
BOAT List Constituents (mK/1)
Acetonitrile
Acrylamide
Acrylonitrile
Total cyanide
Chemical oxygen demand
Total organic carbon
Operating Conditions
Reactor temperature (*C)
Residence time (minutes)
Reactor pressure (psig)
Untreated Treated Treated
Test #1 Test 42
1119 255 399
748 143 186
1020 21 32
379 0.63 3.1
26000 5760 6540
11000 13090 15160
290 270
120 120
2540 2540
Source: Tiscbler/Kocurek 1989.
33648
4-8
-------
Table 4-6 Met Air Oxidation of K011, K013, and Mixtures of the Two Strea
K011/K013 mixed wastes K013 K011
Test *1 Test #2 Test Test
Parameter (units) Untreated Treated Untreated Treated Untreated Treated Untreated Treated
BDAT List Constituents (mm)
Acetonitrile 690 1S.S 720 11.4 0.40 SO 1160 10
Aerylonitrlie 420 0.6S 215 0.2 1.30 0.30 380 0.04
Acrylamide 680 <1 690 <1 6 <1 1260 <1
Benzene
-------
5. DETERMINATION OF BEST DEMONSTRATED
AVAILABLE TECHNOLOGY (BDAT)
This section presents the Agency's rationale for determining the best
demonstrated available technology (BDAT) for K011/K013/K014 wastewaters.
The Agency examines all available performance data on technologies that
are identified as demonstrated for treatment of K011/K013/K014
wastewaters.
The performance data are evaluated according to the BDAT methodology
(USEPA 1988). First, the available design and operating data are
examined to ensure proper design and operation of the treatment system.
Data that indicate that the treatment system was not well-designed and
well-operated at the time of testing are not used in the determination of
BDAT. Next, the "best" performing treatment technology is evaluated to
determine whether the resulting treatment is substantial. If the best
technology provides substantial treatment and it has been determined that
the technology is also available to the affected industry, then the
technology represents BDAT.
The only demonstrated technology identified for treatment of
K011/K013/K014 wastewaters is wet air oxidation, hence, it is best. The
Agency has treatment performance data from several different wet air
oxidation processes. Upon examination of the performance data, it was
determined that some data showed that organic constituent concentrations
increased in value after treatment. Consequently, EPA determined that
the operating conditions for those tests were not optimized and deleted
those data from the evaluation of substantial treatment. The deleted
data sets include data from Table 4-3, Test #2, Test #3, Test #4,
Test #5, and Test #8; data in Table 4-4, Test #1; and all data in
Table 4-5.
5-1
3364g
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Using the remaining wet air oxidation 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
1590 mg/1 to levels of less than 0.02 mg/1 in the wastewater effluent.
EPA's determination of substantial treatment for cyanide is based on the
reduction of total cyanide from levels as high as 1899 mg/1 to levels of
less than 4.6 mg/1 in the wastewater effluent.
The Agency believes that these reductions are substantial and that
wet air oxidation is available to treat organics and cyanide present in
the K011/K013/K014 wastewaters because the technology is commercially
available. The Agency notes that one of the wet air oxidation processes
is proprietary; however, the company has stated in writing that it
"... is fully committed to the commercial availability of this
technology" (BP 1989b). Therefore, EPA believes that wet air oxidation
represents BDAT for the organics and cyanide present in the
K011/K013/K014 wastewaters.
5-2
3364g
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6. SELECTION OF REGULATED CONSTITUENTS
The Agency presented its selection of regulated constituents for
K011/K013/K014 nonwastewaters in Section 6 of the K011/K013/K014
background document (USEPA 1989) . These regulated constituents are
acetonitrile, acrylonitrile, acrylamide, benzene, and cyanide.
The Agency has no data that would lead it to believe that
K011/K013/K014 wastewaters contain other constituents that may warrant
regulation. Furthermore, it is clear from examination of the performance
data presented earlier in this addendum that wet air oxidation
substantially treats each of the above regulated constituents in
K011/K013/K014 wastewaters. Therefore, the Agency is selecting the same
regulated constituents for the purpose of regulating K011/K013/K014
wastewaters that were selected for K011/K013/K014 nonwastewaters.
6-1
336*8
-------
7. CALCULATION OF BOAT TREATMENT STANDARDS
This section presents the calculation of treatment standards for the
regulated constituents described in Section 6. These standards are
calculated based on the performance of the demonstrated treatment system
that was determined to be BDAT (i.e., wet air oxidation). Analytical
methods used to calculate concentrations of the regulated constituents
are discussed in Appendix B.
Consistent with the background document for K011/K013/K014
nonwastewaters, the Agency used only treatment performance data for mixed
K011/K013/K014 wastes to develop the numerical performance standards.
Therefore, data in Table 4-2, and some data in Table 4-6, will not be
used in the standard calculations. The rationale for developing the
standards as a mixture is described in the K011/K013/K014 background
document (USEPA 1989).
As discussed in the methodology (USEPA 1989), the Agency calculates
the treatment performance standards by following a four-step procedure:
(1) correcting the remaining performance data for analytical
interference; (2) editing the data; (3) calculating adjustment factor
(variability factors) to account for process variability; and
(4) calculating the actual treatment standards using variability factors
and average treatment values. The four steps in this procedure are
described in detail in Sections 7-1 through 7-4.
7.1 Correctine the Remaining Data
After the data were deleted in Section 5 because of the poor
operating conditions and single waste stream performance data were
deleted, the data remaining to be used in the calculation consisted of
treatment data in Table 4-1, some data in Table 4-3, some data in
Table 4-4, and some data in Table 4-6. All data values were corrected
7-1
3364g
-------
to take into account analytical interferences associated with the
chemical makeup of the treated samples. This was accomplished by
calculating an accuracy factor from the percent recoveries for the
selected regulated constituents in the K011/K013/K014 wastewaters. The
actual recovery values, accuracy factors, and corrected concentrations
for the selected constituents are presented in Appendix B. The corrected
concentration values were obtained by multiplying the accuracy factors by
the concentration values in the treated waste.
7.2 Editine the Data
To use all the remaining performance data to calculate treatment
standards, the Agency must determine whether the data are homogeneous
(i.e., represent approximately the same treatment efficiencies). The
remaining performance data for wet air oxidation treatment of
K011/K013/K014 wastewaters are contained in Section 4 of this addendum.
It should be noted that each table contains data for a different wet air
oxidation technology operated at different levels of temperature,
pressure, and reactor residence time. In particular, the wet air
oxidation technology used to produce the data in Table 4.1, which is
claimed to be proprietary by BP Chemicals Inc., differs in certain
aspects from the wet air oxidation technologies used to produce the data
in Tables 4-3, 4-4, and 4-6.
The data in Tables 4-1, 4-3, 4-4, and 4-6 were compared by using an
analysis of variance (ANOVA) test to reveal whether the treatment
performance represented by each system is homogeneous to the treatment
performance represented by the other systems. The ANOVA calculation is
presented in Appendix C. The ANOVA test proved that the system
represented by the data in Table 4-1 is not homogeneous with the other
data and demonstrates significantly better treatment. Therefore, the
Agency is using only Table 4-1 data to develop the treatment standards
for K011/K013/K014 wastewaters.
7-2
3364g
-------
7.3 Calculatine the Variability Factors
It is expected that in normal operation of a well-designed and
well-operated treatment system, there will be some variability in
performance. Based on the test data, a measure of this variability is
expressed by the variability factor. The methodology for calculating
variability factors is explained in the BOAT methodology document
(USEPA 1989a). Table 7-1 presents the results of the variability
calculations for the selected constituents in K011/K013/K014 wastewaters.
In instances where a selected constituent was not detected in the
treated waste, the treated value for that constituent was assumed to be
at the detection limits. For example, acrylonitrile was not detected in
the treated wastewater effluent and concentration values were set at the
detection limit. This resulted in no apparent variation among the
treated values and a calculated variability factor of 1.0. A variability
factor of 1.0 represents test data from a process measured without
variation and analytical interferences. Instead of using the calculated
value of 1.0, the variability factors for acrylonitrile were fixed at 2.8
as justified in the methodology document (USEPA 1988a).
7.4 Calculatine the Treatment Standards
The treatment standards for the selected constituents were determined
first by calculating an arithmetic average value for the accuracy-
corrected concentrations of each constituent. Next, the variability
factors were multiplied by the average concentration values. The
treatment standards are presented in Table 7-1.
7-3
3364g
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Table 7-1. Calculation of Treatment Standards for Acrylonltrile Hastewaters
Effluent concentrations
Hastewater (ng/l) Percent
constituents #1 #2 #3 #4 recovery
Acetonitrile 3.8 3.3 13.8 11.8 100
Acrylonitrile <0.02 <0.02 <0.02 <0.02 100
Acrylamide 2.59 1.81 5.54 8.24 100
Benzene 0.007 0.007 <0.006 <0.006 53
Cyanide (total) 3.B 4.0 0.70 4.6 100
Accuracy* Treatment
correction Corrected Variability Standard **
factor average factor (mg/1)
1 8.2 4.66 38
1 0.02 2.8 0.06
1 4.55 4.22 19
1.89 0.012 1.24 0.02
1 3.3 6.47 21
* Accuracy Correction Factor = 100/percent recovery.
Treatment standard = (Accuracy-corrected average concentration) X (variability factor)
7-4
3364g
-------
8. REFERENCES
BP. 1988. BP Chemical America Inc. Letter dated August 31, 1988, from
S. Schoger (BP) to J. Berlow (EPA) and attached report. (The attached
report is CBI.)
BP. 1989a. BP Chemicals Inc. Letter dated August 15, 1989, from
P. Huff (BP) to L. Rosengrant (EPA).
BP. 1989b. BP Chemicals Inc. Letter dated July 28, 1989, from
K. Madliger (BP) to L. Rosengrant (EPA) and attached report,
Demonstration of a wet oxidation process for treating acrylonitrile
wastewater, by BP Chemicals Inc., dated June 1989.
Cyanamid. 1989a. Letter dated September 11, 1989, from J. Schneller
(Cyanamid) to M. Chatmon-McEaddy (EPA).
Cyanamid. 1989b. Letter dated September 7, 1989, from J. Schneller
(Cyanamid) to M. Chatmon-McEaddy (EPA).
Cyanamid. 1989c. American Cyanamid. Letter dated August 2, 1989, from
J. Schneller (Cyanamid) to M. Chatmon-McEaddy (EPA).
Gilbert, Richard D. 1987. Statistical methods for environmental
pollution monitoring. NY: Van Nostrand. pp. 174-5.
Sterling. 1989. Letter dated September 11, 1989, from David W. Dunn
(Sterling) to M. Chatmon-McEddy (EPA).
Tischler/Kocurek. 1989. Supplemental waste characteristics and BOAT
performance data for K011, K013, and K014 wastewaters. Prepared for Ad
Hoc Acrylonitrile Producers Group.
USEPA. 1987a. U.S. Environmental Protection Agency. Generic quality
project plan for Land Disposal Restrictions Program ("BOAT").
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1987b. U.S. Environmental Protection Agency. Technical resource
document treatment technologies for solvent containing wastes. NTIS,
Springfield, Virginia.
USEPA. 1988a. U.S. Environmental Protection Agency. Methodology for
developing BOAT treatment standards. Washington, D.C.: U.S.
Environmental Protection Agency.
USEPA. 1988b. U.S. Environmental Protection Agency. Treatment
technology background. Washington, D.C.: U.S. Environmental
Protection Agency.
USEPA. 1989. U.S. Environmental Protection Agency, Office of Solid
Waste Final best demonstrated available technology (BOAT) background
document for K011, K013, and K014. Washington, D.C.: U.S.
Environmental Protection Agency.
8-1
3364g
-------
APPENDIX A
DETERMINATION OF WASTEWATER DEFINITION FOR K011/K013/K014 WASTES
The Agency identified incineration as BOAT for K011/K013/K014
nonwastewaters in the Second Third rulemaking (54 FR 26594, June 23,
1989), basing its identification on performance data for incineration of
K011/K013/K014 sludge that had resulted from allowing as-generated
K011/K013/K014 wastes to settle in a settling basin. The K011/K013/K014
sludge was the bottoms (underflow) stream from the settling basin. This
waste consisted of 17 to 31 percent TOC and approximately 10 to 40
percent TSS.
Since making the determination of BOAT for K011/K013/K014
nonwastewaters in the proposed rule, the Agency has collected additional
data regarding K011/K013/K014 waste characterization and treatment; these
additional data are reported in Table A-l. The waste characterization
for K011/K013/K014 shows that many as-generated K011/K013/K014 wastes
consist of between 1 percent and 3 percent by weight total organic carbon
and less than 1 percent by weight total suspended solids.
The Agency does not believe that incineration is BOAT for most
as-generated K011/K013/K014 wastes because of the large volume and low
Btu content of those wastes. It would require extensive amounts of
energy and incineration capacity to incinerate those aqueous wastes.
However, the K011/K013/K014 as-generated wastes are ideal candidates for
wet air oxidation because of the relatively low organic content (compared
to most incinerated wastes), low TSS, and aqueous nature. Additionally,
EPA has treatment performance data for only wet air oxidation for the
K011/K013/K014 wastes as-generated. EPA does not have performance data
for wastes defined as wastewaters by the original BOAT definition (i.e.,
less than 1 percent TOC and less than 1 percent TSS).
A-l
3364g
-------
The Agency is proposing to extend the definition of wastewaters for
K011/K013/K014 wastes to include wastes containing less than 5 percent
TOC and less than 1 percent TSS. The Agency determined the upper limit
of 5 percent based on a calculation of the 99.9th percentile for all the
available TOC values for mixed K011/K013/K014 waste streams. Mixed waste
streams have been used as the basis in the development of the
nonwastewater and wastewater standards for reasons presented in the
background document for K011/K013/K014. The calculation for the 99.9th
percentile is presented in the following table. The actual value is 4.2
percent, but the Agency rounded to 5 percent for analytical convenience.
A-2
3364g
-------
Table A-l Calculation of 99.9th Percentile of Total Organic
Carbon (TOC) Content
Source
Total organic carbon (TOC)
(mg/1)
Waste Matrix
Tischler/Kocurek
Tischler/Kocurek
Tischler/Kocurek
Tischler/Kocurek
BP July 18, 1989
BP July 18, 1989.
BP July 18, 1989
BP July 18, 1989
BP July 18, 1989
BP July 18, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
BP November, 1989
20,488
13,659
15,024
18,244
20,700
20,600
22,300
14,800
30,000
20,000
24,000
23,400
23,100
22,300
28,800
26,000
27,200
20,200
23,600
22,300
22,100
24,000
16,500
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013/K014
K011/K013/K014
K011/K013/K014
K011/K013/K014
K011/K013
K011/K013/K014
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
K011/K013
The original data are approximately normally distributed with a
possible outlier (i.e., the 30,000 mg/1 value). The log-transformed data
are more normally distributed with no suspected outlier. Using
log-transformed data, a 99.9th percentile estimate of TOC equaling 4.2
percent is obtained from the following equation:
99.9th percentile TOC - exp (y + Zgg gSy) = expUO.Ol + 3.0 x 0.205) ~ 42,000
where:
y » InX
X - TOC (mg/1)
y " average log TOC
Sy - standard deviation log TOC
Zgg 9 - 99.9th percentile value of the standard normal variate.
Reference: Richard J. Gilbert. 1987.
A-3
3364g
-------
APPENDIX B
ANALYTICAL INFORMATION
The analytical methods used for analysis of the regulated
constituents identified in Section 6 are listed in Table B-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 determining total constituent concentrations except for the
acrylamide analysis.
Acrylamide was determined by a Waters 600 HPLC with a Waters 494 UV
detector at 218 nm. Samples were analyzed by direct injection onto a
Chromegabond C~~ (30 cm x 4.6 mm) column and eluted with
methanol-acetonitrile-water eluent. Analyte identification and
quantification were based on retention time matching to external
standards. Multipoint external standard calibration to the UV detector
was used to quantify the amount of acrylamide present. Calibration
included determination of instrumental response over a range of standard
concentrations. Instrumental calibration was routinely checked by the
analysis of a mid-range standard. The acceptance criteria were
established at 15 percent relative percent difference for the absolute
instrumental response of a calibration check standard relative to initial
calibration data. If results were outside the 15 percent range,
calibration was reestablished.
As stated in the BOAT methodology, 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 B-2 presents the available matrix spike recoveries used to
determine the correction factors for some wastewater organic and cyanide
data. It should be mentioned that if a recovery value is above
B-l
3364g
-------
100 percent, the Agency uses 100 percent to determine the accuracy
adjustment so that the adjusted values do not decrease when corrected for
accuracy. EPA believes this is a conservative approach for calculating
treatment standards. For the Cyanamide data, values were not available
for all volatile organic constituents (i.e., acetonitrile). Therefore,
the Agency used an average percent recovery to calculate the accuracy
correction factor for acetonitrile.
B-2
336
-------
3038g
Table B-l Analytical Methods for Regulated Constituents In K011/K013/K01* Wastes
Regulated
constituents
Volatile
Acatonitrlle
Acrylonitrils
Acrylamide
Bens ana
Extraction
nethod
Purge and trap
Purge and trap
Dlraet Injection
Purge and trap
Method
number
5030
5030
3030
Analytical
athod
Gas Chromatographr/Mata Spectrometry
Gat Chrometography/Hesa Spectrooetry
HPLC*
Gaa Chromatography/Maia Spactrometry
SH-848
Method
nunber
8030
8030
8030
Inornanlca Other Than Hetal»
Cyanide (total) Specified in analytical method
Colorioetric
8012
*A high-performance liquid chromatography (HPLC) method has bean used to perform acrylamlde analysis. Mora information
about the method is described in the text of this Appendix.
References: BP 1080b.
-------
3036g
Table B-a Matrix Spike Recoveries Used to Calculate Corrections Factor* Cor Wet Air Oxidation Treated Hastewaters
Swmle
Data
source Constituent
Cyanamide 1989b Aerylonltrlle
Acrylonltrlle
Benzene
Benzene
Acrylaalda
Acetonltrlle
Cyanide (total)
BP 19B9b Aeetonltrlle
Acrylonltrlle
Acrylanlde
Beniene
Cyanide (total)***
Original
t ample
0.63 ppn
0.20 ppn
0.006 ppn
0.01 ppn
<1 ppn
0.73 ppn
3.6 ug/1
14 ug/1
334 s«/l
6.1 us/1
0.6 ng/1
Spike
added
0.20 ppn
0.20 ppn
0.22 ppn
0.216 ppn
30 ppn
3.0 ppn
1.7 us/1
420 ug/1
1990 mg/1
32 ug/1
0.1 og/1
Spike
result
1.04 ppn
0.46 ppn
0.236 ppn
0.201 ppn
36 ppn
3.03 ppn
7.2 ug/1
397 ug/1
2640 m/1
36 ug/1
0.7 Bg/1
Percent Accuracy correction
recovery* factor**
193
130
113
86
113
126 (average)
86
197
ISO
103
33
100
1.00
1.00
1.00
1.14
1.00
1.00
1.16
1.00
f.OO
1.00
1.89
1.00
Percent recovery « {(Spike Result - Original Amount)/Spike amount] x 100.
* Accuracy correction factor " 100/Percent Recovery (using the lowest percent recovery values).
* The recovery results for cyanide are actually for the product feed and not the treated wast*. They are used since they are the only
spike recoveries presented for cyanide.
-------
APPENDIX C
ANOVA TEST
EPA is using the statistical method known as an analysis of variance
(ANOVA) in the determination of the level of performance that represents
the best treatment. Since the Agency has data from more than one wet air
oxidation process, this method provides a measure of the differences
between data sets. If the differences are not statistically significant,
the data sets are said to be homogeneous.
If the Agency found that the levels of performance for one or more
wet air oxidation processes are not statistically different (i.e., the
data sets are homogeneous), EPA would average the long term performance
values achieved by each wet air oxidation process and then multiply this
value by the largest variability factor associated with any of the
acceptable wet air oxidation processes. If EPA found that one process
performs significantly better (i.e., the data sets are not homogeneous),
BDAT would be the level of performance achieved by the best wet air
oxidation process multiplied by its variability factor.
To determine whether any or all of the treatment performance data
sets are homogeneous using the analysis of variance method, it is
necessary to compare a calculated "F value" to what is known as a
"critical value" (see Table C-l). These critical values are available in
most statistics tests (see, for example, Statistical Concepts and Methods
by Bhattacharyya and Johnson, 1977, John Wiley Publications, New York).
Where the F value is less than the critical value, all treatment data
sets are homogeneous. If the F value exceeds the critical value, it is
necessary to perform a "pair wise F" test to determine whether any of the
C-l
336*6
-------
sets are homogeneous. The "pair wise F" test must be done for all of the
various combinations of data sets using the same method and equation as
the general F test.
The F value is calculated as follows:
(i) All data are natural logtransformed.
(ii) The sum of the log transformed data points for each data set is
computed (T.).
(iii) The statistical paramater known as the sum of the squares
between data sets (SSB) is computed:
SSB
'
k
s
i - 1
2 '
Ti
ni
2 "
k
S Ii
i - 1
> j
k
n
N
number of different wet air oxidation processes
number of data points for wet air oxidation process i
number of data points for all wet air oxidation
sum of natural logtransformed data points for each wet air
oxidation process.
(iv) = the sum of the squares within data sets (SSW) is computed:
SSW -
k ni 2
S Ex
i - 1 j - 1 i,j
k
- S
i - 1
2
Ti
n
1
where:
x* .s - the natural logtransformed observations (j) for wet air oxidation
'
-------
MSB
F
MSW
where:
MSB - SSB/(k-l) and
MSW - SSW/(N-k).
A computational table summarizing the above steps is shown below.
Computational Table for the F Value
Source
Between
Within
Degrees of
freedom
K-l
N-k
Sum of
squares
SSB
SSW
Mean square
MSB - SSB/k-1
MSW - SSW/N-k
F
MSB/MSW
Table C-2 presents the values used for the accuracy-corrected data to
be used in the ANOVA calculation, and the F value results are presented
in Table C-3. The comparisons of data indicate that process 3 achieves
significantly better treatment than the other technologies.
C-3
-------
Table C-l
F Distribution at the 95 Percent Confidence Lave!
OcnoflMMtor
d«9>««* ol
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
: 17
18
19
20
21
22
23
24
25
26
27
28
29
30
40
60
120
01
1
161 4
1851
10.13
771
641
5.99
459
*SJ2
. 5.12
446
484
475
467
460
454
449
445
441
438
435
432
430
428
426
424
423
421
420
418
417
408
400
192
184
2
1995
1900
955
6.94
5.79
5.14
474
446
426
410
198
189
181
174
348
163
359
355
152
349
3.47
144
142
140
139
137
135
134
133
132
123
115
107
100
1
3
215.7
19.16
9.25
6.59
5.41
476
435
407
136
171
359
149
141
134
129
124
120
116
113
310
307
305
103
301
199
198
196
195
193
192
U4
176
168
160
V«M»««*IO<
4
2246
19.25
5.12
6J5
5.19
453
412
184
163
148
136
126
118
XII
106
301
196
193
190
187
184
182
180
178
178
174
173
171
170
169
191
153
145
137
5
230.2
19 JO
9.01
U6
SJH
4J9
197
169
148
333
330
111
103
196
190
185
181
177
174
171
168
166
164
162
160
159
157
156
155
153
145
137
12S
121
1 l«mea«n
6
234.0
19J3
8.94
6.16
4.95
428
187
158
137 -
122
109
1OO
192
133
179
174
170
166
163
160
157
155
1S3
151
149
147
146
145
143
142
134
125
117
110
7
236.8
19.35
8-39
6.09
488
421
179
ISO
129
114
101
191
183
176
171
166
161
158
154
151
2.43
2.46
144
142
140
139
137
136
135
2J3
125
117
109
101
a
23E9
1937
8.55
6.04
432
4.15
in
144
123
107
195
185
177
170
164
139
155
151
148
2.43
2.42
2.40
2J7
2J6
134
132
131
2.29
128
2.27
2.: 8
2.!0
2.02
1.94
,
2*05
1933
881
6.00
477
410
168
139
118
102
ISO
ICO
171
165
139
154
149
146
142
2.39
2.37
124
132
2.20
128
127
2JS
124
122
2.21
2.t2
104
196
taa
C-4
-------
3038g
Table C-2 Accuracy-Correct Data to Be Used in tha ANOVA Calculation
O
i
cn
Met air
oxidation
process Source
1 Tisehler/Kocurek
1989
2 Tlschler/Kocurek
1989
3 BP Chemical 1989b
4 Cyanamld
1989b
Acetonitrile
Influent Effluent
573 110
254
243
270
293
0
407
213
178 (221)
166 3.8
229 3.3
104 13.3
684 11.8
690 15. 3
720 11.4
Acrylamlde
Influent Effluent
908 0
(1.120)
(1.205)
107
(1.007)
200
69
(1.057)
320 (972)
844 2.59
770 1.81
1.089 5.54
7ks 8.24
i i
680 <1
690 <1
Acrylonitrile
Influent Effluent
SO 1
0
12
(100)
0
20
43
8
12 11
1.560 <0.02
1.590 <0.02
728 <0.02
550 <0 . 02
420 0.65
215 0.20
Total Cyanide
Influent Effluent
1.100 2.4
2.2
0.3
5
2.5
0.6
1.7
0
1.100 0.6
1.244 3.9
1,300 4.0
1.460 0.7
1.899 4.6
90 0.7
120 0.56
Benzene
Influent Effluent
--
'
--
--
--
--
--
-.
0.17 0.013
0.18 0.013
0.07 0.011
0.42 0.011
-------
3038g
Tabla C-3 F Value Determination for ANOVA last
Process
Degree of Sum of Mean Critical (Set
Constituant Source freedom iquataa square F valua Tabla C-2) Conclusion
Acatonlttila Between (B) 2 36.95
Within (H) 10 2.672
Between (B) 1 32.64
Within (W) 9 2.62S
18.48 69.14 4.10 1.3,4 Nonhomogeneous
0.2672
32.64 111.90 5.12 1.3 Nonhomogeneous
0.2917
Between (B) 1 0.6198 0.6198 1.45 7.71 3.4 Homogeneous
Within (W) 4 1.713
Acrylamlda Between (B) 2 31.90
Within (W) 6 2.010
Between (B) 1 19.74
Within (W) 3 2.010
Batwaan (B) 1 2.399
Within (W) 4 1.438
Acrylonittlla Between (B) 3 93.37
Within (W) 8 8.68
Between (B) 1 84.77
Within (MS) 7 7.986
Between (B) 1 11. IS
0.4282
15. 95 47.61 5.14 1,3.4 Nonhomogeneous
0.3350
19.74 49.11 6.61 1,3 Nonhomogeneous
0.4020
2.399 6.67 7.71 3,4 Homogeneous
0.3595
| 31.12 28.68 4.07 1,2.3,4 Nonhomogeneous
1.085
84.77 74.31 5.59 1.3 Nonhomogeneous
1.141
11.15 64.21 7.21 3.4 Nonhomogeneous
Within (H) 4 0.6946 0.1737
-------
3038g
Table C-3 (Continued)
Conitltutnt Source
Cyanide (total) Between (B)
Within (H)
Between (B)
Within (W)
Between (B)
Within (W)
Bentene Between (B)
Within (W)
o
1
Degree of
freedom
3
10
1
9
1
4
1
4
Sun of
squares
3. 567
7.957
0.7695
7.915
2.662
2.438
0.2514
0.1584
Mean
square
1.189
0.7957
0.7695
0.8794
2.662
0 . 6094
0.2514
0.03959
Process
Critical ( See
F value Table C-2) Conclusion
1.49 3.71 1.2.3.4 Homogeneous
0.87 5.12 1,3 Homogeneous
4.37 7.71 3,4 Homogeneous
6.35 7.71 3,4 Homogeneous
------- |