United States
Environmental Protection
Agency
Office of
Solid Waste
Washington, D.C 20460
EPA/530-SW-88-0009-r
May 1988
Solid Waste
Proposed
Amendment
to the Best
Demonstrated
Available Technology
(BDAT) Background
Document Volumes 1 and
2forF001-F005;
Spent Solvents
Volume 10
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PROPOSED
BEST DEMONSTRATED AND AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT
SUPPORTING THE PROPOSED
LAND DISPOSAL RESTRICTIONS RULE
FOR
FIRST THIRD WASTES
VOLUME 10
AMENDMENT TO THE
BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR F001-F005 SPENT SOLVENTS - VOLUMES 1 AND 2
U.S. Environmental Protection Agency
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief Monica Chatmon
Treatment Technology Section Project Manager
May 1988
U S. Environmental Protection Agency
Region 5, Library (PI-12J)
77 West Jackson Boulevard, 12th NOW
Chicago, ft 60604-3590
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TABLE OF CONTENTS
Section Page
EXECUTIVE SUMMARY i
1.0 AMENDMENT TO SECTION 1.0 OF THE BDAT BACKGROUND DOCUMENT
FOR F001-F005 SPENT SOLVENTS 1-1
2.0 AMENDMENT TO SECTION 3.2.4 OF THE BDAT BACKGROUND DOCUMENT
FOR F001-F005 SPENT SOLVENTS 2-1
3.0 AMENDMENT TO SECTION 4.3 OF THE BDAT BACKGROUND DOCUMENT
FOR F001-F005 SPENT SOLVENTS 3-1
3.1 Applicable Treatment Technologies 3-1
3.2 Demonstrated Treatment Technologies 3-1
3.3 Available Treatment Technologies 3-1
3.4 Detailed Description of Steam Stripping 3-2
4.0 AMENDMENT TO SECTION 5.5.16 OF THE BDAT BACKGROUND DOCUMENT
FOR F001-F005 SPENT SOLVENTS 4-1
4.1 Identification of Best Demonstrated and Available
Technology 4-1
4.1.1 Analysis of Operation of Plant A 4-2
4.1.2 Determination that Plant B F002 Wastewaters are
Similar to Plant A F001-F005 Wastewaters 4-4
4.1.3 Analysis of Operation of Plant B 4-5
4.2 Calculation of Treatment Standards 4-6
5.0 REFERENCES 5-1
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LIST OF TABLES
Table
2-1 AVAILABLE CHARACTERIZATION DATA FOR F001-F005 WASTEWATERS
AT PLANT A 2-2
2-2 AVAILABLE CHARACTERIZATION DATA FOR F002 WASTEWATERS AT
PLANT B 2-3
4-1 TREATMENT PERFORMANCE DATA COLLECTED BY EPA FOR F001-F005
WASTEWATERS CONTAINING METHYLENE CHLORIDE, PLANT A -
STEAM STRIPPING 4-10
4-2 TREATMENT PERFORMANCE DATA COLLECTED BY EPA FOR F002
WASTEWATERS CONTAINING METHYLENE CHLORIDE, PLANT B -
STEAM STRIPPING 4-12
4-3 DESIGN AND OPERATING DATA COLLECTED BY EPA
PLANT A - STEAM STRIPPING 4-13
4-4 DESIGN AND OPERATING DATA COLLECTED BY EPA
PLANT B - STEAM STRIPPING 4-14
4-5 VOLATILE MATRIX SPIKE RECOVERIES FOR STEAM STRIPPER
BOTTOMS FROM PLANT B 4-15
4-6 CORRECTED METHYLENE CHLORIDE CONCENTRATIONS FOR STEAM
STRIPPER BOTTOMS (F002 TREATED WASTEWATER) FROM PLANT B ... 4-16
4-7 CALCULATION OF THE TREATMENT STANDARD FOR METHYLENE
CHLORIDE IN F001-F005 WASTEWATERS FROM THE PHARMACEUTICALS
MANUFACTURING INDUSTRY 4-17
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LIST OF FIGURES
Figure
3-1 STEAM STRIPPING 3-5
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EXECUTIVE SUMMARY
On November 7, 1986, pursuant to the Hazardous and Solid Waste
Amendments (HSWA) enacted on November 8, 1984, EPA established treatment
standards for the land disposal of EPA listed hazardous wastes F001-F005.
These standards apply to wastewaters and nonwastewaters for 25 spent solvents,
including methylene chloride.
EPA established a separate F001-F005 treatment standard for
methylene chloride in wastewaters from the Pharmaceuticals manufacturing
industry. EPA has acquired additional data and is proposing to revise the
treatment standard. The treatment standard promulgated on November 7, 1986 is
12.7 ppm; the revised treatment standard is proposed to be 0.44 ppm. All
other treatment standards promulgated on November 7, 1986, are not being
revised, and therefore, remain unchanged.
This proposed amendment to the Best Demonstrated and Available
Technology (BDAT) Background Document for F001-F005 Spent Solvents presents
the new data received by EPA, and provides EPA's rationale for revising the
treatment standard for methylene chloride in F001-F005 wastewaters from the
Pharmaceuticals manufacturing industry. Section 1.0 provides EPA's legal
authority for revision of the treatment standard. Sections 2.0 through 4.0
describe the specific revisions to the November 7, 1986 BDAT Background
Document for F001-F005 Spent Solvents.
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1.0 AMENDMENT TO SECTION 1.0 OF THE BOAT BACKGROUND DOCUMENT FOR
F001-F005 SPENT SOLVENTS
This section of the amendment reinforces Section 1.1, Legal Back-
ground, of the BOAT Background Document for F001-F005 Spent Solvents.
On November 7, 1986 (51 Federal Register 40572), EPA promulgated
treatment standards for regulated constituents in F001-F005 spent solvent
wastewaters and nonwastewaters, including methylene chloride in F001-F005
wastewaters from the Pharmaceuticals manufacturing industry. Since November
7, 1986, new data have become available to the Agency on the steam stripping
of methylene chloride in wastewaters determined to be similar to the F001-F005
wastewaters from the Pharmaceuticals manufacturing industry. RCRA Section
3004(m) states that the Agency has the right to revise a treatment standard
provided that rulemaking procedures are followed; therefore, EPA is revising
the treatment standard for methylene chloride in F001-F005 wastewaters from
the Pharmaceuticals manufacturing industry based on the new data.
On January 14, 1986, the Agency proposed treatment standards for
regulated constituents in F001-F005 wastewaters and nonwastewaters. In that
proposed rule, EPA established BOAT treatment standards based on health-based
standards, and the Agency determined that both biological treatment and steam
stripping could achieve BOAT levels of performance for methylene chloride in
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F001-F005 wastewaters. F001-F005 wastewaters from the Pharmaceuticals
manufacturing industry were not determined to be a separate waste treatability
group in the proposed rule.
After the January 14, 1986 proposal, EPA received comments from
industry (Reference 1), presenting data from plant A on the steam stripping of
methylene chloride in F001-F005 wastewaters from the Pharmaceuticals manu-
facturing industry. These data indicate that F001-F005 wastewaters from the
Pharmaceuticals manufacturing industry warrant a separate waste treatability
group due to high concentrations of methylene chloride in the wastewaters as
compared to the levels of methylene chloride in other F001-F005 wastewaters.
Therefore, on September 5, 1986, EPA published a Notice of Data Availability
presenting the data from plant A and asking for data and comments concerning
the proposed rule.
On November 7, 1986, EPA promulgated treatment standards for regu-
lated constituents in F001-F005 wastewaters and nonwastewaters, including a
treatment standard of 12.7 ppm for methylene chloride in F001-F005 wastewaters
from the Pharmaceuticals manufacturing industry. The value of 12.7 ppm was
based on the data for steam stripping of methylene chloride in F001-F005
wastewaters from plant A. Documentation for the calculation of this treatment
standard is shown in Reference 2. For the November 7, 1986 promulgation, the
data from plant A were reviewed to determine whether the steam stripper was
well-operated. The Agency determined that 28 of the 40 data points were
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collected while the stripper was not well-operated; the Agency did not use
these 28 data points for the calculation of the treatment standard.
Since the November 7, 1986 promulgation, the Agency collected steam
stripping treatment performance data on F002 wastewaters from plant B. The
F002 wastewaters sampled at plant B contained methylene chloride at concentra-
tions similar to those found in F001-F005 wastewaters from the Pharmaceuticals
manufacturing industry. A review of the data shows that the steam stripper at
plant B was well-operated during the sampling episode and achieved better
treatment performance than the steam stripper at plant A. Therefore, the
Agency is using these new data to propose a revised treatment standard of 0.44
ppm for methylene chloride in F001-F005 wastewaters from the Pharmaceuticals
manufacturing industry.
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2.0 AMENDMENT TO SECTION 3.2.4 OF THE BOAT BACKGROUND DOCUMENT FOR
F001-F005 SPENT SOLVENTS
This section amends the discussion in Section 3.2.4 of the BOAT
Background Document for F001-F005 Spent Solvents. This section presents
characterization data for the spent solvent wastewaters from plant A and plant
B.
Table 2-1 presents the ranges of constituents identified in F001-
F005 wastewaters from plant A, which is a Pharmaceuticals manufacturing
facility. Table 2-2 presents the ranges of constituents identified in F002
wastewaters from plant B, which is an agricultural chemicals manufacturing
facility. The F002 wastewaters from plant B have been determined to be
similar to F001-F005 wastewaters from the Pharmaceuticals manufacturing
industry. This determination is based on available characterization data and
is further discussed in Section 4.1.2.
The data presented in Tables 2-1 and 2-2 were obtained from sampling
and analysis episodes conducted by the Agency. The wastes are characterized
by high concentrations of methylene chloride.
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Table 2-1
AVAILABLE CHARACTERIZATION DATA FOR F001-F005 WASTEWATERS AT PLANT A
Concentration in the
Untreated Waste (ppm)
Constituent Source of Data: i ii
Methylene Chloride 225-12,000 8,879-11,837
Methanol NA 369-1,684
Diethyl Ether NA 32-45
Pyridine NA 289-600
(i) Plant A Data from the Development Document For Final Effluent Limitation
Guidelines, New Source Performance Standards and Treatment Standards For
the Pharmaceuticals Manufacturing Point Source Category (Reference 3).
(ii) Correspondence from Plant A to EPA, September 20, 1983 (Reference 4).
NA Not available.
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Table 2-2
AVAILABLE CHARACTERIZATION DATA FOR F002 WASTEWATERS AT PLANT B
Constituent
Carbon Tetrachloride
Chloroform
Methylene Chloride
Hexachloroethane
Benzoic Acid
Methanol
Percent Water
Concentration in the
Untreated Waste (ppm)
<2.5-3.1
23-110
2,500-7,400
0.26-1.3
0.52
55-81
91.97-97.11 (wt. %)
Parameter
Total Dissolved Solids
Concentration in the
Untreated Waste (ppm)
1,900-122,300
Volatile Dissolved Solids
300-3,100
Data Source: Onsite Engineering Report for Plant B (Reference 5)
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3.0 AMENDMENT TO SECTION 4.3 OF THE BDAT BACKGROUND DOCUMENT FOR
F001-F005 SPENT SOLVENTS
This section amends Section 4.3 of the BDAT Background Document for
F001-F005 Spent Solvents.
3.1 Applicable Treatment Technologies
For the November 7, 1986 promulgation, the Agency identified batch
distillation, thin film evaporation, fractionation, incineration, steam
stripping, biological treatment, carbon adsorption, air stripping, wet air
oxidation, and fuel substitution as applicable treatment technologies for
F001-F005. The Agency is not revising this list for this reproposal.
3.2 Demonstrated Treatment Technologies
The demonstrated technology that the Agency has identified for
treatment of methylene chloride in F001-F005 wastewaters from the pharmaceuti-
cal manufacturing industry is steam stripping (Reference 2). A detailed
description of steam stripping is presented in Section 3.4.
3.3 Available Treatment Technologies
An available treatment technology is one that (1) is not a propri-
etary or patented process that cannot be purchased or licensed from the
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proprietor (is commercially available), and (2) substantially diminishes the
toxicity of the waste or substantially reduces the likelihood of migration of
hazardous constituents in the waste. For treatment of methylene chloride in
F001-F005 wastewaters from the Pharmaceuticals manufacturing industry, the
demonstrated technology (steam stripping) meets these criteria and is there-
fore considered to be available.
3.4 Detailed Description of Steam Stripping
This section replaces the discussion of steam stripping in Section
4.3.1 of the BDAT Background Document for F001-F005 Spent Solvents.
Steam stripping is a technology that can separate more volatile
materials from less volatile materials by a process of vaporization and
condensation. As such, it is a type of distillation process.
Applicability and Use of Technology. Steam stripping is applicable
to wastewaters that contain BDAT organics that are sufficiently volatile such
that they can be removed by the application of steam. Waste parameters that
affect the performance of steam stripping are filterable solids, total organic
carbon (TOG), and the presence of BDAT organics that are either not volatile
or only minimally volatile.
Underlying Principles of Operation. The basic principle of oper-
ation for steam stripping is the volatilization of hazardous constituents
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through the application of heat. The constituents that are volatilized are
then condensed and either reused or further treated.
An integral part of the theory of steam stripping is the principle
of vapor-liquid equilibrium. When a liquid mixture of two or more components
is heated, a vapor phase is created above the liquid phase. The vapor phase
will be more concentrated in the constituents having the higher vapor pres-
sure. If the vapor phase above the liquid phase is cooled to yield a conden-
sate, a partial separation of the components results. The degree of separa-
tion would depend on the relative differences in the vapor pressures of the
constituents; the larger the difference in the vapor pressure, the easier the
separation can be accomplished.
If the difference between the vapor pressures is extremely large, a
single separation cycle or single equilibrium stage of vaporization and
condensation may achieve a significant separation of the constituents. If the
difference between the vapor pressures is small, then multiple equilibrium
stages are needed to achieve effective separation. In practice, the multiple
equilibrium stages are obtained by stacking trays or placing packing into a
column. The vapor phase from a tray rises to the tray above it and the liquid
phase falls to the tray below it. Essentially, each tray represents one
equilibrium stage. In a packed steam stripping column, the individual equi-
librium stages are not discernible, but the number of equivalent trays can be
calculated from mathematical relationships.
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The vapor liquid equilibrium is expressed as relative volatility or
the ratio of the vapor to liquid concentration for one constituent divided by
the ratio of the vapor to liquid concentration of the other constituent. The
relative volatility is a direct measure of the ease of separation. If the
numerical value is 1, then separation is impossible because the constituents
have the same concentrations in the vapor and liquid phases. Separation
becomes easier as the value of the relative volatility becomes increasingly
greater than unity.
Physical Description of the Process. A steam stripping unit con-
sists of a boiler, a stripping section, a condenser, and a collection tank as
shown by Figure 3-1. The boiler provides the heat required to vaporize the
liquid fraction of the waste. The stripping section is composed of a set of
trays or packing in a vertical column. The feed (waste influent) enters at
the top.
The stripping process uses multiple equilibrium stages, with the
initial waste mixture entering the uppermost equilibrium stage. The boiler is
located below the lowermost equilibrium stage so that vapor generated moves
upward in the column coming into contact with the falling liquid. As the
vapor comes into contact with the liquid at each stage, the more volatile
components are removed or "stripped" from the liquid by the vapor phase. The
concentration of the emerging vapor is slightly enriched (as it is in equi-
librium with the incoming liquid), and the liquid exiting the bottom of the
boiler ("bottoms") is considerably enriched in the lower vapor pressure
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VENT OF
NON-CONDENSED
VAPORS
CONDENSER
WASTE
INFLUENT
TREATED
EFFLUENT
RECOVERED SOLVENT
FOR REUSE
OR TREATMENT
FIGURE 3-1.
STEAM STRIPPING
3-5
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constituent(s). The process of stripping is very effective for wastewaters
where the relative volatilities are large between the organics of concern and
wastewater. Steam stripping is used to strip the organic volatiles from
wastewater. The water effluent from the bottom of the stripper is reduced in
organic content, but in some circumstances may require additional treatment,
such as carbon adsorption or biological treatment. The steam and organic
vapors leaving the top of the column are condensed. Organics in the conden-
sate that form a separate phase in water usually can be separated and recov-
ered or disposed. After separation the aqueous condensate is usually recycled
to the stripper.
Characteristics of a Waste that Affect Performance. In determining
whether steam stripping is likely to achieve the same level of performance on
an untested waste as a previously tested waste, EPA focuses on the following
characteristics of a waste: boiling point, total dissolved solids, total
dissolved volatile solids, and oil and grease. EPA recognizes these charac-
teristics have some limitations in assessing transfer of performance; never-
theless, the Agency believes that they provide the best possible indicator of
relative volatility. Below is a discussion of relative volatility, as well as
EPA's rationale for evaluating the above described waste characteristics in
determining transfer of treatment performance.
As discussed earlier, the term relative volatility (a) refers to the
ease with which a substance present in a solid or liquid waste will vaporize
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from that waste upon application of heat from an external source. Hence, it
bears a relationship to the equilibrium vapor pressure of the substance.
£
For an ideal binary mixture, the relative volatility (a) is
expressed as:
a = .
K
j
YJ/XJ
where Kj_ and Kj are equilibrium concentrations for components i and j respec-
tively, Y is the mole fraction of the component in the vapor, and X is the
mole fraction of the component in the liquid.
For non-ideal binary mixtures, the relative volatility (a) is
expressed as:
a =
V
A
where f is the fugacity. The term "fugacity" is a thermodynamic term that
accounts for departures from ideal behavior of the gas and liquid; it can only
be determined empirically.
The term "ideal" refers to whether the vapor pressures of the two
components can be linearly related to their respective compositions in the
liquid phase; this is known as Raoult's law. In general, binary solutions at
low pressures follow this law and are, therefore, "ideal"; most mixtures do
not follow Raoult's law.
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EPA recognizes that the relative volatilities can not be measured or
calculated directly for the types of wastes generally treated by steam strip-
ping even if these wastes behaved in an ideal manner. Determining relative
volatilities is further complicated by the fact that the relative volatility
changes as the temperature conditions change throughout the steam stripper.
Accordingly, EPA will use the following surrogates: boiling point, oil and
grease content, total dissolved inorganic solids, and total dissolved volatile
solids.
For a given pressure and temperature, compounds with lower boiling
points will have higher vapor pressures. Therefore, in the case of waste-
waters containing low concentrations of organics where relative volatility is
effectively a comparison of vapor pressures, the ratio of boiling points of
the constituents in the untested and tested wastes will indicate whether the
untested waste can be treated to the same degree as the tested waste. Boiling
point alone would not account for any non-ideal behavior of the solution.
Accordingly, EPA will examine the concentrations of oil and grease, total
dissolved solids, and total dissolved volatile solids. All of these charac-
teristics affect the partial pressures of the individual organic constituents
of concern as well as the solubility. Accordingly, these characteristics will
affect relative volatility of a constituent and, hence, the ability of the
constituent to be treated using steam stripping.
Design and Operating Parameters. EPA's analysis of whether a steam
stripping system is well-designed will focus on the degree of separation the
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system is designed to achieve and the controls installed to maintain the
proper operating conditions. The specific parameters are presented below.
(1) Concentrations of Constituents in the Treated and Untreated
Wastes. In determining whether to sample a particular steam stripper as a
candidate for BDAT, EPA considers the concentration to which the system is
designed to treat the waste. This evaluation is important for two reasons: a
treatment system will usually not perform as well as designed; and if an
untreated waste has concentrations of constituents in excess of the concentra-
tions that the treatment system is designed to treat, the system performance
will be poor. Therefore, in evaluating the performance of a steam stripper,
data on the characteristics of the untreated waste are necessary to determine
whether treatment performance conformed with design specifications.
(2) Vapor-Liquid Equilibrium Data. The vapor-liquid equilibrium
data are determined in laboratory tests unless already available. The use of
these data are required for several reasons. First, they are used to calcu-
late the number of theoretical stages required to achieve the desired separa-
tion. Using the theoretical number of stages, the actual number of stages can
then be determined through the use of empirical tray efficiency data supplied
by an equipment manufacturer.
Second, the vapor-liquid equilibrium data are used to determine the
liquid and vapor flow rates that ensure sufficient contact between the liquid
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and vapor streams. These rates are, in turn, used to determine the column
diameter.
(3) Column Temperature and Pressure. Column temperature and
pressure are integrally related to the vapor liquid equilibrium conditions.
Column temperature design includes performing a heat balance around the steam
stripping unit, which accounts for the heat removed in the condenser, the heat
input in the feed, the heat input from steam injectors, and the heat loss from
the column. Column pressure influences the boiling point of the liquid. For
example, the column temperature required to achieve the desired separation can
be reduced by operating the system under vacuum. During treatment, it is
important to continuously monitor these parameters to ensure that the system
is operated at design conditions.
(4) Column Internals. Column internals are designed to accommodate
the physical and chemical properties of the wastewater to be stripped. Two
types of internals may be used in steam stripping: trays or packing. Tray
types include bubble cap, sieve, valve and turbo-grid. Trays have several
advantages over packing. Trays are less susceptible to blockage by solids,
they have a lower capital cost for large diameter columns (greater than or
equal to 3 feet), and they accommodate a wider range of liquid and vapor flow
rates. Packing types include raschig rings, pall rings, saddles, and sulzer-
structures. Compared to trays, packing has the advantages of having a lower
pressure drop per theoretical stage, being more resistant to corrosive materi-
als, having a lower capital cost for small diameter column (less than 3 feet),
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and finally being less susceptible to foaming because of a more uniform flow
distribution.
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4.0 AMENDMENT TO SECTION 5.5.16 OF THE BOAT BACKGROUND DOCUMENT FOR
F001-F005 SPENT SOLVENTS
This section amends Section 5.5.16 of the BOAT Background Document
for F001-F005 Spent Solvents.
4.1 Identification of Best Demonstrated and Available Technology
For the November 7, 1986 promulgation, EPA determined steam strip-
ping to be BOAT for methylene chloride in F001-F005 wastewaters from the
Pharmaceuticals manufacturing industry. The treatment standard for methylene
chloride in F001-F005 wastewaters from the Pharmaceuticals manufacturing
industry is being revised in this proposal. This revision is based on new
data for steam stripping of F002 wastewaters that have been determined to be
similar to F001-F005 wastewaters from the Pharmaceuticals manufacturing
industry.
The Agency has 40 data points from plant A (Reference 3) for treat-
ment of methylene chloride in F001-F005 wastewaters from the Pharmaceuticals
manufacturing industry. Table 4-1 presents the methylene chloride concentra-
tions detected in the untreated and treated wastewaters at Plant A. These
data are from a sampling episode conducted by the EPA's Industrial Technology
Division. The Agency also has 13 data points from plant B (Reference 5) for
treatment of F002 wastewaters with concentrations of methylene chloride that
are similar to the concentrations in wastewaters from the Pharmaceuticals
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manufacturing industry. Table 4-2 presents the methylene chloride concen-
trations detected in the untreated and treated wastewaters at plant B. These
data are from a sampling episode conducted by EPA's Office of Solid Waste.
The data from plant A were used for the November 7, 1986 promulgation; the
data from plant B were obtained by EPA after the November 7, 1986 promulgation
date.
The treatment performance data were assessed to determine whether
they represent operation of a well-designed and well-operated system, whether
quality assurance/quality control measures were employed to ensure the accura-
cy of the data, and whether appropriate analytical tests were used to assess
the performance of the treatment technology. Section 4.1.1 presents the
analysis of operation of plant A, and Section 4.1.3 presents the analysis of
operation of plant B. Section 4.1.2 presents the Agency's determination that
the F002 wastewaters from plant B are similar to F001-F005 wastewaters from
the Pharmaceuticals manufacturing industry.
4.1.1 Analysis of Operation of Plant A
The performance data for steam stripping of F001-F005 wastewaters
containing methylene chloride at plant A were reviewed to determine whether
the steam stripper was well-designed and well-operated during the sampling
episode. Design and operating data collected at plant A during the sampling
episode are presented in Table 4-3. Design conditions are available for
overhead temperature; therefore, only overhead temperature data are presented.
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Other operating data, including feed temperature, bottoms temperature, feed
rate, and steam rate, can be found in Reference 3.
As discussed in Section 3.0 of this amendment, temperature is an
important operating parameter. The steam stripping column must be designed to
achieve the proper operating conditions to obtain optimal treatment perfor-
mance. The steam stripper at plant A is designed to effectively treat the
waste at an overhead temperature of 98°C. As shown in Table 4-3, many data
points were collected during operation at overhead temperatures below 98°C.
During the sampling episode, the overhead temperature ranged from 82°C to
98°C, with only one data point collected while the stripper was operated at
the design temperature of 98°C. This wide fluctuation of overhead temperature
indicates poor operation of the steam stripper.
For the November 7, 1986 promulgation, the treatment performance
data from plant A were examined to determine the minimum temperature repre-
sentative of a well-operated system. As a method of evaluating the data, the
concentration of methylene chloride in the effluent was plotted as a function
of overhead temperature. The data indicate that, as the overhead temperature
drops below the design temperature, there is an increase in the variability in
the effluent concentrations achieved at a given overhead temperature. This
increased variability is an indication of increased instability or poor
control of the steam stripping system. Since the variability in the effluent
concentrations increased as the overhead temperature dropped below 90°C, the
minimum overhead temperature for a system that was well-operated was estimated
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as 90°C. As a result of this evaluation, for the November 7, 1986 rule, 28 of
the 40 data points were deleted from the data set because the overhead temper-
ature was below 90°C.
4.1.2 Determination that Plant B F002 Wastewaters are Similar to Plant A
F001-F005 Wastewaters
Since November 7, 1986, data from plant B for steam stripping
treatment of methylene chloride in F002 wastewaters have become available to
the Agency. The data for the untreated F002 wastewaters from plant B were
compared to the data for the untreated F001-F005 Pharmaceuticals manufacturing
industry wastewaters from plant A. To compare the data for these wastewaters,
the Agency considered the characteristics of a waste that affect the perfor-
mance of a steam stripper, as well as other characteristics of the waste that
provide information on the treatability of the waste by steam stripping.
Methylene chloride concentration data are available to the Agency
for the untreated wastewaters at plant A and at plant B. The methylene
chloride concentration in the untreated F001-F005 wastewaters at plant A
ranged from 225 ppm to 12,000 ppm, while the methylene chloride concentration
in the untreated F002 wastewaters at plant B ranged from 2,500 ppm to 7,400
ppm.
In Section 3.4, the Agency identified the following waste character-
istics that affect performance of steam stripping: boiling point, oil and
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grease, total dissolved inorganic solids, and total dissolved volatile solids.
Methylene chloride is the only constituent in either waste being reproposed at
this time; the boiling point of pure methylene chloride is 39-75°C. EPA has
data from plant B on total dissolved inorganic solids and total dissolved
volatile solids, but does not have data from plant B on oil and grease. EPA
does not have data from plant A on these three characteristics. Therefore,
EPA cannot compare total dissolved inorganic solids, total dissolved volatile
solids, and oil and grease; however, the Agency has no reason to believe that
they are not similar.
Based on the above discussions, the Agency has determined that the
untreated F002 wastewaters from plant B are similar to the untreated F001-F005
wastewaters from plant A. EPA thus considered data from plant B in revising
the treatment standard for methylene chloride in F001-F005 wastewaters from
the Pharmaceuticals manufacturing industry.
4.1.3 Analysis of Operation of Plant B
The performance data for steam stripping of F002 wastewaters con-
taining methylene chloride at plant B were reviewed to determine whether the
steam stripper could be considered well-designed and operated. Design and
operating data for plant B are presented in Table 4-4. Design conditions are
available for mid-column temperature; therefore, only mid-column temperature
data are presented. Other operating data, including feed flowrate and column
overhead temperature, can be found in Reference 5.
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A comparison of the mid-column operating temperature (99°C-102°C)
and the minimum mid-column design temperature (80°C) shows that the mid-column
temperature was well above the minimum during the sampling episode. Also, the
mid-column temperature showed very slight fluctuation during sampling.
Therefore, the Agency has concluded that the steam stripper at plant B was
well-operated during the sampling episode.
EPA believes that because the stripper at plant B consistently
attained a 99°C operating temperature (5-12°C better than plant A), it better
reflects proper design and operation of the treatment system. In light of the
new data collected from plant B, EPA is not including the data from plant A in
the proposed revision of the treatment standard for methylene chloride.
Instead, EPA is using only the treatment data from plant B to calculate the
revised treatment standard.
4.2 Calculation of Treatment Standards
The best demonstrated and available technology for treatment of
methylene chloride in F001-F005 wastewaters from the Pharmaceuticals manufac-
turing industry has been identified as steam stripping based on available
performance data. The best measure of performance of a destruction, recovery,
or separation technology, such as steam stripping, is the total amount of
constituent remaining after treatment. Therefore, the BOAT treatment standard
for methylene chloride in F001-F005 wastewaters from the Pharmaceuticals
manufacturing industry was calculated based on total waste concentration data.
4-6
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The Agency used the data from plant B, consisting of 13 data points,
to calculate the revised treatment standard for methylene chloride in
F001-F005 wastewaters from the Pharmaceuticals manufacturing industry. Table
4-2 presents the 13 values of the concentration of methylene chloride in the
treated waste. EPA adjusted these data to account for analytical inter-
ferences associated with the chemical makeup of the treated wastes. General-
ly, performance data are corrected for accuracy as follows: (1) a matrix
spike recovery is determined for the constituent as explained below, (2) an
accuracy correction factor is determined for the constituent by dividing 100
by the matrix spike recovery (percent); and (3) treatment performance data for
the constituent are corrected by multiplying the reported concentration of the
constituent by the corresponding accuracy correction factor.
Matrix spike recoveries are developed by analyzing a sample of a
treated waste for a constituent and then reanalyzing the sample after the
addition of a known amount of the same constituent (i.e., spike) to the
sample. The matrix spike recovery represents the total amount of constituent
recovered after spiking minus the initial concentration of the constituent in
the sample, and the result divided by the known amount of constituent added.
Table 4-5 presents the matrix spike recoveries for volatile organic
constituents for which matrix spike analyses were performed at plant B. A
matrix spike analysis was not performed for methylene chloride. Matrix spike
analyses were performed on Sample 1 and Sample 7 for other volatile organic
constituents. Therefore, the recoveries determined for the volatile organic
4-7
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constituents for which matrix recoveries were performed were averaged separ-
ately for the two matrix spike analyses. The average matrix spike recovery
for volatiles in Sample 1 was 102$; the average recovery for volatiles in
Sample 7 was 110/5. The lower average percent recovery, 102$, was used in
accuracy correction calculations for methylene chloride.
Methylene chloride was not detected in 11 of the 13 treated waste-
water samples. In these cases, the detection limits were presented as the
corrected treatment concentrations for methylene chloride. For the two cases
where methylene chloride was detected in the samples, the treatment concen-
trations were adjusted by multiplying the treatment concentrations by the
accuracy correction factor (0.98).
The corrected treatment concentrations for methylene chloride in
F002 wastewaters treated by steam stripping at plant B are presented in Table
4-6.
The revised treatment standard for methylene chloride in F001-F005
wastewater from the Pharmaceuticals manufacturing industry has been calculated
as shown in Table 4-7. The steps used to calculate the revised treatment
standard are as follows. The arithmetic average of the corrected treatment
data for methylene chloride was calculated for the data set using the data
points presented in Table 4-6. Using the corrected treatment data, a vari-
ability factor was calculated for the data set. The variability factor
represents the variability inherent in performance of treatment systems,
4-8
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collection of treated samples, and analyses of samples. For cases where
methylene chloride was not detected in the treated wastewater, the Agency used
the detection limit in calculation of the variability factor. Variability is
still expected in concentrations below the detection limit since the actual
concentrations would range from zero to the detection limit. Methylene
chloride was present at concentrations greater than the detection limit in two
samples (samples 8 and 11); methylene chloride was not detected in the other
eleven samples. Therefore, the variability factor was calculated based on
eleven data points set at the detection limits and two data points represent-
ing methylene chloride concentrations that were detected in the samples.
The revised treatment standard for methylene chloride was calculated
by multiplying the average corrected treatment concentration of methylene
chloride in the treated waste by the variability factor. As shown in Table
4-7, the proposed revision of the treatment standard for methylene chloride in
F001-F005 wastewaters from the Pharmaceuticals manufacturing industry is 0.44
ppm.
4-9
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Table 4-1
TREATMENT PERFORMANCE DATA COLLECTED BY EPA
FOR F001-F005 WASTEWATERS CONTAINING METHYLENE CHLORIDE
PLANT A - STEAM STRIPPING
Untreated Wastewater Treated Wastewater
Sample Methylene Chloride Methylene Chloride
Number Concentration (ppm) Concentration (ppm)
1 8,250 0.926
2 8,250 5.10
3 8,250 4.94
4 8,250 3.00 *
5 8,250 1.99 *
6 8,250 5.70 *
7 8,250 22.80 *
8 8,250 38.05 *
9 225 3.90 *
10 225 8.36 *
11 225 20.60 *
12 225 4.07
13 225 10.70 *
14 225 20.30 *
15 225 4.80 *
16 225 7.87 *
17 7,000 1.72
18 7,000 1.63
19 7,000 3.60 *
20 7,000 14.25 *
21 7,000 39.30 *
22 7,000 138.0 *
23 7,000 110.0 *
24 7,000 60.80 *
25 11,200 10.10 *
26 9,900 22.85 *
27 9,100 57.50 *
28 9,400 115.0 *
29 10,200 59.90 *
30 11,800 127.0 *
31 10,000 3.18
32 12,000 3.73 *
4-10
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Table 4-1 (Continued)
TREATMENT PERFORMANCE DATA COLLECTED BY EPA
FOR F001-F005 WASTEWATERS CONTAINING METHYLENE CHLORIDE
PLANT A - STEAM STRIPPING
Untreated Wastewater
Sample Methylene Chloride
Number Concentration (ppm)
33 9,500
34 9,500
35 9,500
36 9,500
37 9,500
38 9,500
39 9,500
40 9,500
Treated Wastewater
Methylene Chloride
Concentration (ppm)
7.
4,
20
04
4.27
,47
.62
.63
.83
15.80
Reference 3
*This data point was deleted in data analysis for the November 7, 1986
promulgation because the overhead temperature was less than 90°C. See
Section 4.1.1 of this document for a discussion of this data editing
procedure.
4-11
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Table 4-2
TREATMENT PERFORMANCE DATA COLLECTED BY EPA
FOR F002 WASTEWATERS CONTAINING METHYLENE CHLORIDE
PLANT B - STEAM STRIPPING
Untreated Wastewater Treated Wastewater
Sample Methylene Chloride Methylene Chloride
Number Concentration (ppm) Concentration (ppm)
1 3,400 <0.250
2 2,900 <0.250
3 2,500 <0.170
4 3,000 <0.170
5 5,400 <0.250
6 7,400 <0.250
7 3,900 <0.110
8 3,200 0.120
9 3,100 <0.125
10 3,600 <0.170
11 2,800 0.400
12 3,400 <0.170
13 5,500 <0.125
Reference 5.
4-12
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Table 4-3
DESIGN AND OPERATING DATA COLLECTED BY EPA
PLANT A - STEAM STRIPPING
Overhead Overhead
Sample Temp(°C) Sample Temp(°C)
Number (Design=98°C) Number (Design=98°C)
1 97 21 84*
2 98 22 83*
3 94 23 83*
4 89* 24 83*
5 89* " 25 89*
6 86* 26 86*
7 84* 27 84*
8 84* 28 83*
9 87* 29 83*
10 89* 30 82*
11 86* 31 93
12 90 32 89*
13 89* 33 90
14 86* 34 90
15 87* 35 95
16 85* 36 90
17 97 37 89*
18 90 38 90
19 88* 39 88*
20 85* 40 88*
Reference 3.
*This data point was deleted in data analysis for the November 7, 1986
promulgation because the overhead temperature was less than 90°C. See
Section 4.1.1 of this document for a discussion of this data editing
procedure.
4-13
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Table 4-4
DESIGN AND OPERATING DATA COLLECTED BY EPA
PLANT B - STEAM STRIPPING
Mid-Column
Sample Temp(°C)
Number (Min.80°C)
1 102
2 102
3 101
4 100
5 99
6 100
7 100
8 100
9 99
10 101
11 100
12 100
13 101
Reference 5.
4-14
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Table 4-5
VOLATILE MATRIX SPIKE RECOVERIES FOR STEAM STRIPPER BOTTOMS FROM PLANT B
Sample 1
Sample 7
Spike Constituent
4.
9.
38.
43.
45.
JN. 47.
1
H"1
<_n
Benzene
Chlorobenzene
Methylene Chloride
To 1 uene
1 , 1 , 1-Trichloroethane
Trichl oroethene
Original
Amount
Found
(ppm)
<0.25
<0.25
No mat r i x
chl oride
The 1 ower
<0.25
<0.25
<0.25
Amount
Spiked
(ppm)
2.5
2.5
Amount
Recovered
(ppm)
2.
2.
625
4
spike was performed
is based
average
2.5
2.5
2.5
on the
percent
2.
2.
2.
1 ower
Original
Percent* Amount
Recovery Found
(%)
105
96
(ppm)
<0.
<0.
for this constituent
average percent
recovery is 102% from
475
6
65
99
104
106
1 1
1 1
Amount Amount
Spiked Recovered
Percent*
Recovery
(ppm) (ppm) (%)
1 .085 1
1 .085 1
The percent recove
recovery
Sampl e
<0.
<0.
<0.
1 1
1 1
1 1
of the vol at i 1 e
Set 1 .
1.085 1
1.085 1
1.085 1
. 1 18
.237
ry for
const i
. 15
.302
. 139
103
1 14
methy 1 ene
tuent s .
106
120
105
-~ ~~ 1 1 n
Average
102
*Percent Recovery = TOO x (C^ - Co)/Ct, where
Reference 5
= amount recovered, Co = original amount found, and Ct = amount spiked.
-------
Table 4-6
CORRECTED METHYLENE CHLORIDE CONCENTRATIONS
FOR STEAM STRIPPER BOTTOMS (F002 TREATED WASTEWATER)
FROM PLANT B
Corrected Concentration**
Sample Number in the Treated Wastewater, ppm
Plant B
1 0.250
2 0.250
3 0.170
4 0.170
5 0.250
6 0.250
7 0.110
8* 0.118
9 0.125
10 0.170
11* 0.392
12 0.170
13 0.125
Average 0.196
*Methylene chloride was present at concentrations above the detection limit
in samples 8 and 11; methylene chloride was not detected in the other
samples.
**Corrected concentrations are equal to the actual concentration multiplied by
the accuracy correction factor for samples where methylene chloride was
found above the detection limit. Corrected concentrations are equal to the
detection limit in samples where methylene chloride was not detected.
4-16
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Table 4-7
CALCULATION OF THE TREATMENT STANDARD FOR METHYLENE CHLORIDE
IN F001-F005 WASTEWATERS FROM THE PHARMACEUTICALS MANUFACTURING INDUSTRY
Arithmetic Treatment
Average Standard
Range in of Corrected (Average
Untreated Treated Variability x VF)
Data Set Waste (ppm) Values (ppm) Factor (VF) (ppm)
Plant B 2,500- 7,400 0.196 2.26 0.44
4-17
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5.0 REFERENCES
1. Chemical Manufacturers Association. 1986. Comment on EPA's Proposed
Rule on Land Disposal Restrictions, pp. 111-25, 26, and 28. Volume IX,
Commenter No. 85.
2. USEPA. 1986. U.S. Environmental Protection Agency, Office of Solid
Waste. Best Demonstrated Available Technology (BOAT) Background Document
For F001-F005 Spent Solvents. Vol 2, pp. 5-62 to 5-70, 5-159 to 5-162.
November 1986.
3. USEPA. 1983. U.S. Environmental Protection Agency, Office of Water.
Development Document for Final Effluent Guidelines, New Source Perfor-
mance Standards and Pretreatment Standards for the Pharmaceutical Manu-
facturing Point Source Category, pp. 124-128. September 1983.
4. Correspondence from Hoffman-LaRoche, Inc., to EPA. September 3, 1983.
5. USEPA. 1988. U.S. Environmental Protection Agency, Office of Solid
Waste. Draft Onsite Engineering Report of Treatment Technology Perfor-
mance and Operation for Olin Chemicals, Rochester, New York, pp. 8, 12,
35-46, 64. February 1, 1988.
5-1
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