&EPA
United States
Environmental Protection
Agency
Preliminary Study of Carbon Disulfide
Discharges from Cellulose Products
Manufacturers
December 2011
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U.S. Environmental Protection Agency
Office of Water (43 03 T)
1200 Pennsylvania Avenue, NW
Washington, DC 20460
EPA-821-R-11-009
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Preliminary Study of Regenerated Cellulose Manufacturers
CONTENTS
Page
1.0 STUDYING DISCHARGES FROM REGENERATED CELLULOSE MANUFACTURERS 1
1.1 Introduction 1
1.2 Background - Manufacturing Process 1
1.3 Background - Existing Effluent Guidelines and Regenerated Cellulose
Manufacturing 2
1.3.1 40 CFR Part 414 2
1.3.2 40 CFR Part 463 3
1.3.3 Potential New Subcategories for the OCSPF Category 4
1.3.4 NPDES Permit Basis 4
1.4 Background-Industry Profile of U.S. Cellulose Manufacturers 5
2.0 CARBON BISULFIDE PROPERTIES 7
2.1 Chemical Properties of Carbon Bisulfide 7
2.2 Carbon Bisulfide - Potential Pathways into the Environment 9
3.0 WASTEWATER SOURCES 9
3.1 Unloading and Storage 9
3.2 Process Steps 11
3.3 Air Pollution Control 12
4.0 REGENERATED CELLULOSE PROCESS WASTEWATER TREATMENT 13
5.0 FACILITY BISCHARGE BATA 15
5.1 Innovia Films, Inc in Tecumseh, KS 15
5.1.1 Waste Streams 15
5.1.2 Wastewater Treatment 16
5.1.3 Bischarge Bata 17
5.2 Viskase Corporation inLoudon, TN 19
5.2.1 Wastewater Source and Treatment 19
5.2.2 Bischarge Bata 19
6.0 CONCLUSIONS 20
7.0 REFERENCES 20
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Preliminary Study of Regenerated Cellulose Manufacturers
LIST OF TABLES
Page
Table 1. Applicability of Subcategories in the PMF Category 3
Table 2. Existing ELGs for Regenerated Cellulose Materials 4
Table 3. Operating U.S. Cellulose Products Manufacturers and Corresponding 2009 TRI and
DMR Discharges 6
Table 4. Closed or Idled Cellulose Manufacturers in the United States 7
Table 5. Chemical Properties of Carbon Bisulfide, Acetone, and Ethanol 7
Table 6. Inhalation Exposure Limits for Carbon Bisulfide, Acetone, and Ethanol 8
Table 7. TRI 2009 Carbon Bisulfide Air Emissions and Water Bischarges for Cellulose
Products Manufacturers 9
Table 8. Facility Carbon Bisulfide Unloading and Storage Practices as of 2000 11
Table 9. Cellulose Products Wastewater Treatment 13
Table 10. Confirmed Sources of Wastewater and Wastewater Treatment at Cellulose
Manufacturing Facilities 14
Table 11. Innovia Films, Inc Waste Streams 15
Table 12. 2008, 2009, and 2010 Carbon Bisulfide Concentration Bata for Innovia Films,
Inc 17
Table 13. Carbon Bisulfide Concentration Bata for Viskase Corporation in Loudon, TN 19
Table A-l. Applicability of Subcategories in the OCPSF Category 1
11
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Preliminary Study of Regenerated Cellulose Manufacturers
1.0 STUDYING DISCHARGES FROM REGENERATED CELLULOSE MANUFACTURERS
1.1 Introduction
EPA is studying wastewater discharges from regenerated cellulose manufacturers
because these facilities report large discharges of carbon disulfide (CS2) (U.S. EPA, 2006, U.S.
EPA, 2010). Currently no existing regulation sets federal effluent limitations for CS2 discharges
from the seven regenerated cellulose manufacturers that operate in the United States. Cellulose
products manufacturers use CS2 in the viscose process to break down aged alkali cellulose prior
to regeneration. CS2 can enter the wastewater stream at these facilities from CS2 unloading and
storage, the viscose process, CS2 recovery, and/or air pollution control.
The main pollutant of concern discharged from these facilities, CS2, is a volatile organic
compound. EPA researched how the CS2 enters the wastewater and its fate in the facilities'
existing wastewater treatment systems. EPA also collected data on whether the CS2 discharges
would impact human health or aquatic life. EPA continues to resolve the overall question of how
significant concentrations of CS2 remain in the wastewater, although CS2is highly volatile.
1.2 Background - Manufacturing Process
Regenerated cellulose products manufacturers use the viscose process to form cellulose
film, sponge, food casings, and rayon from dissolving-grade wood pulp. In the viscose process,
sheets of dissolving-grade cellulose pulp are saturated with caustic (e.g., sodium hydroxide) to
convert the cellulose into alkali cellulose. The alkali cellulose partially oxidizes and degrades by
aging in ambient air. Gaseous CS2 is mixed with the aged alkali cellulose in a vessel to form
sodium cellulose xanthate. The sodium cellulose xanthate is dissolved in aqueous caustic
solution, creating the viscose solution. The viscose solution is ripened, filtered, degassed, and
extruded, and then sulphuric acid is added to the viscose solution to form regenerated cellulose
(Schmidtke, 2000). Figure 1 presents a simplified flow diagram of the general viscose process
and the different process steps for each type of regenerated cellulose (cellulose film or
cellophane, sponge, food casings, and rayon) (Schmidtke, 2000).
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Preliminary Study of Regenerated Cellulose Manufacturers
Liquid Caustic
Dissolving Grade
Wood Pulp
Steep
Alkali Cellulose
Shredder
White Crumbs
Carbon Disulfide
I
Xanthate
Liquid Caustic
Water
Extrude Through Slit
into Acid Bath
Sodium Cellulose Xanthate
Mix with Salt and
Fibers; Extrude Into
Molds
Cellophane
Submerge in Hot Salt
Solution or Place in
Electro-Coagulation
Oven
Extrude Through
Nozzle into Acid
Bath
i
r
Force Through
Spinnerette into Acid
Bath
Food Casings
Rayon
Sponge
1.3
Figure 1. Simplified Process Flow Diagram for the Generic Viscose Process and
Regenerated Cellulose Products
Background - Existing Effluent Guidelines and Regenerated Cellulose
Manufacturing
The regenerated cellulose manufacturing process is closely related to two effluent
limitation guidelines and standards (ELGs) point source categories: Organic Chemicals, Plastics,
and Synthetic Fibers (OCPSF, 40 CFR Part 414) and Plastics Molding and Forming (PMF, 40
CFR Part 463). However, wastewater discharges from the manufacture of several cellulose
products are not covered by any existing categorical ELGs or pretreatment standards.
1.3.1 40 CFR Part 414
The OCPSF ELGs (40 CFR Part 414, Subpart B) apply to wastewater discharged from
the manufacture of rayon, a regenerated cellulose fiber. However, these regulations specifically
exclude discharges from the manufacture of cellulose film, sponge, and meat casings (40 CFR
§414.20). Further, these regulations do not include limitations for CS2 and there are no rayon
facilities currently operating in the United States. Appendix A includes further information on
the applicability and subparts of 40 CFR Part 414.
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Preliminary Study of Regenerated Cellulose Manufacturers
1.3.2 40 CFR Part 463
The PMF industry includes facilities that are engaged in blending, molding, forming, or
other types of processing of plastic materials. These processes commonly include extrusion,
coating and laminating, thermoforming, calendaring, casting, foaming, cleaning, and finishing
(U.S. EPA, 1984). EPA first promulgated ELGs for the PMF Category (40 CFR Part 463) on
December 17, 1984 (49 FR 49040). There are three subcategories, all of which have best
practicable control technology (BPT), new source performance standards (NSPS), pretreatment
standards for existing sources (PSES), and pretreatment standards for new sources (PSNS)
limitations.
The manufacture of cellulose products are not covered by Part 463 (the PMF Category).
The product is made of regenerated cellulose using the viscose process, and Part 463 specifically
excludes products manufactured from regenerated cellulose, as well as the molding and forming
of regenerated cellulose (U.S. EPA, 1984).
40 CFR §463.1 (g) Processes used to regenerate cellulose and to
produce a product (e.g., rayon) from the regenerated cellulose are not
subject to the effluent limitations guidelines and standards in this part.
Processes that mold or form cellulose derivatives (e.g., cellulose
acetate) are subject to the effluent limitations guidelines and standards
in this part if they discharge process water.
The regenerated cellulose manufacturing process is similar to the operations regulated by
40 CFR Part 463 because water contacts extrusion equipment and regenerated cellulose products
for cooling, cleaning, and finishing; however, regenerated celluloses are not plastic materials and
are not regulated by the PMF ELGs. Table 1 describes the three subcategories regulated by the
PMF ELGs.
Table 1. Applicability of Subcategories in the PMF Category
Subpart
A
B
C
Description
Contact Cooling and Heating Water
Cleaning Water
Finishing Water
Applicability
Processes where water contacts plastic material or plastic
products for the purpose of heat transfer.
Processes where water contacts the plastic products or
shaping equipment for the purpose of cleaning.
Processes where water contacts plastics products during
finishing.
Source: Preliminary Review of Prioritized Categories of Industrial Dischargers, (U.S. EPA, 2005a)
The Technical Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Plastics Molding and Forming Point Source Category
(PMF TDD) provides the rationale for excluding regenerated cellulose manufacturers from the
PMF ELGs. It states that plastic materials are a group of synthetic, organic materials composed
of high molecular weight, long chain molecules. The definition of plastic materials in the PMF
regulation also includes natural polymers that are combined with synthetic organic materials,
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Preliminary Study of Regenerated Cellulose Manufacturers
such as cellulose acetate. However, wholly natural organic materials, such as regenerated
cellulose, are not included in the PMF definition of plastic materials.
The PMF TDD also states that the final step in the xanthate process used to regenerate
cellulose is to wash the regenerated cellulose to remove dissolved salts and sulfur compounds
within the product. Process water used in this step is not considered cleaning water as defined in
the final PMF ELGs because it does more than just clean the surface of the regenerated cellulose.
Therefore, wastewater discharges from the manufacture of several cellulose products,
including film, sponge, and food casings, are not covered by any existing categorical ELGs or
pretreatment standards. Table 2 provides an overview of the cellulose products that are covered
by existing ELGs and corresponding €82 limitations.
Table 2. Existing ELGs for Regenerated Cellulose Materials
Regenerated Cellulose Product
Rayon3
Cellulosic Film (Cellophane)
Cellulosic Sponge
Food Casing
40 CFRPart 414 (OCPSF)
Included, but no CS2 limits
Excluded
Excluded
Excluded
40 CFR Part 463 (PM&F)
Excluded
Excluded
Excluded
Excluded
Source: 40 CFR §414.20 and 40 CFR §463.l(g)
a - There are not rayon manufacturers currently operating in the United States.
1.3.3 Potential New Subcategories for the OCSPF Category
EPA reviewed the information provided in Tables 1 and 2 and determined that the
cellulose products manufacturers using the viscose process to manufacture cellophane, cellulosic
sponge, and food casings have processes, operations, wastewaters, and pollutants identical to the
rayon manufacturers regulated by the OCPSF Category (Subpart B - Rayon Fibers). The end
products at these facilities are all considered regenerated cellulose materials and are all produced
using the same viscose process. For future screening level data review, EPA will classify the
discharges from these facilities as a potential new subcategory of the OCPSF Category.
1.3.4 NPDES Permit Basis
Because wastewater discharges from the manufacture of several cellulose products,
including film, sponge, and food casings are not covered by any existing categorical ELGs or
pretreatment standards, permit writers have used state water quality standards, historical
performance effluent data (HPED), other similar ELGs (i.e., OCSPF Subpart D - Thermoplastic
Resins BPT), and best professional judgment (BPJ) as the basis for permit limits. The permits for
wastewater discharges from cellulose products manufacturing include limits for the following
pollutants: biological oxygen demand (BOD), total suspended solids (TSS), ammonia, ammonia
nitrogen, total residual chlorines, oil and grease, and total organic carbon.
Only one NPDES permit (for Innovia Films, Tecumseh, KS, a cellulose products
manufacturer), includes monitoring requirements for CS2. Innovia Films is required to monitor
CS2 to avoid process upsets to the facility's activated sludge treatment system. Other permitted
facilities are not required to monitor CS2, likely because there are no national water quality
criteria for it, and other similar ELGs do not have limitations for CS2.
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Preliminary Study of Regenerated Cellulose Manufacturers
1.4 Background - Industry Profile of U.S. Cellulose Manufacturers
EPA identified seven cellulose products manufacturers operating in the U.S. as of 2009.
The final products of these facilities compete in markets with products made from alternative
materials, especially plastics. Cellulose products have generally been declining in market share
over time as newer non-cellulose products have been introduced (Beach, et al., 2000). The
cellophane manufacturing industry has been declining since the 1950s due to new regulations
and economic issues. The domestic market for rayon has also been eliminated because textile
production has moved out of the United States (Beach, Houtven, Buckley, and Depro, 2000).
Table 3 lists the operating U.S. cellulose products manufacturers and their discharges from the
2009 TRI and DMR databases, in pounds per year (LEY) and toxic-weighted pound equivalents
(TWPE). Table 4 lists those manufacturing operations that appear to have been idled or closed
prior to 2009.
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Preliminary Study of Regenerated Cellulose Manufacturers
Table 3. Operating U.S. Cellulose Products Manufacturers and Corresponding 2009 TRI and DMR Discharges
Facility a
1
2
3
4
5
6
7
3M
Corporation
3M
Corporation
Innovia Films
Inc.
Spontex Inc.
Viscofan
USA Inc.
Viskase
Corporation
Viskase
Corporation
Location
Elyria, OH
Tonawanda,
NY
Tecumseh,
KS
Columbia,
TN
Danville, IL
Osceola, AR
Loudon, TN
Product Type
Cellulosic
Sponges
Cellulosic
Sponges
Cellophane
Cellulosic
Sponges
Food Casings
Food Casings
Food Casings
2009 TRI Data
Discharge
Type"
Indirect
Indirect
Direct
Direct
Indirect
Direct
Indirect
Basis of
Estimate c
M2
0
M2
M2
M2
0
M2
CS2
Pounds
Released
from
Facility d
NR
4,700
26,500
223
14,000
473
13,000
CS2 Pounds
Released to
Stream e
NR
752
26,500
223
2,240
473
2,080
CS2
TWPE
NR
2,105
74,300
624
6,270
1,320
5,820
2009 DMR Data
Average
Flow
(MGD)
NA
NA
2.22
0.38
NA
1.16
NA
CS2
LEY
NR
NR
24,100
NR
NR
NR
NR
CS2
TWPE
NR
NR
53,100
NR
NR
NR
NR
Source: Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S. (Schmidtke, 2000), DMRLoads2009_v2, TRIReleases2009_v2.
a - Cellulose manufacturing facilities that are currently operating in the United States.
b - ELGs control pollutant discharges at the point of discharges from industrial facilities and cover discharges directly to surface water (direct discharges) and
discharges to POTWs (indirect discharges).
c - Basis of Estimate Descriptions: Ml: continuous monitoring data or measurements; M2: periodic or random monitoring data or measurements; C: mass balance
calculations, such as calculation of the amount of the toxic chemical in streams entering and leaving process equipment; E: published emission factors;E2: site-
specific emission factors; and O: other approaches, such as engineering calculations.
d - Discharges include transfers to POTWs and do not account for POTW removals.
e - Discharges include transfers to POTWs and account for POTW removals.
NR - No data reported.
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Preliminary Study of Regenerated Cellulose Manufacturers
Table 4. Closed or Idled Cellulose Manufacturers in the United States
Facility Name
Lenzing Fibers Corp.
Lenzing Fibers Corp.
3M Corporation
Location
Axis, AL
Lowland, TN
Prairie du Chien, WI
Product Type
Rayon
Rayon
Cellulosic Sponges
Facility Status
in 2011
Closed
Closed
Idled
Type of
Discharger a
Direct
Direct
Indirect
Source: Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S. (Schmidtke, 2000)
2.0 CARBON BISULFIDE PROPERTIES
All cellulose products manufacturers use €82 in the viscose process to regenerate
cellulose. The €82 is used to react with aged alkali cellulose to form sodium cellulose xanthate.
CS2is an extremely flammable and highly volatile chemical that is slightly soluble in water.
2.1 Chemical Properties of Carbon Bisulfide
Table 5 presents chemical properties for €82 compared to acetone and ethanol. The
Henry's Law Constant for CS2 is 1,748 Pa mVmol at 25° C (Love, 2011). Henry's Law Constant
is the measure of the solubility of a gas in a liquid at a particular temperature, proportional to the
pressure of that gas above the liquid (Kotz and Treichel, 1999). Chemicals with a higher Henry's
Law Constant are more volatile. For example, CS2 is highly volatile: the gas constant for CS2 is
approximately 403 times higher than that for acetone (4.02 Pa m3/mol).
Table 5. Chemical Properties of Carbon Bisulfide, Acetone, and Ethanol
Chemical Properties
Henry's Law Constant at 25°C
Water Solubility
Evaporation Rate a
National Fire Protection Association (NFPA)
Flammability Rating b
CS2
1,748 Pa nrVmol
0.2% at 20° C
22.6
4
Acetone
4.02 Pa nrVmol
Soluble
5.7
3
Ethanol
0.585 Pa nrVmol
Miscible
NA
3
Sources: EPA On-line Tools for Site Assessment Calculation; Fischer Scientific MSDS for Acetone and Ethanol;
Love, 2011; Ohio EPA, 2010; and OSHA Guidelines for Carbon Disulfide.
a - The rate at which a material will vaporize when compared to the known standard rate of butyl acetate
(evaporation rate = 1.0).
b - The NFPA flammability rating ranks the relative danger for a chemical. The higher the rating, the higher danger
associated with the chemical flammability.
CS2 is also hazardous to humans when inhaled. Table 6 presents the Occupational Safety
& Health Administration (OSHA) and National Institute for Occupational Safety and Health
(NIOSH) established permissible exposure limits (PELs) and recommended exposure limits
(RELs) for CS2, acetone, and ethanol. These exposure limits correspond to the amount or
concentration of the substance in the air and may also contain skin designation. As part of the
Occupation Safety and Health Guidelines, OSHA also established CS2PELs of 30 ppm
(acceptable peak concentration for a 30 minute exposure) and 100 ppm (instantaneous maximum
peak). NIOSH RELs also include a 10 ppm short-tern exposure limit.
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Preliminary Study of Regenerated Cellulose Manufacturers
Table 6. Inhalation Exposure Limits for Carbon Disulfide, Acetone, and Ethanol
Exposure Limits
OSHA PELS (TWA)a
NIOSH RELs (TWA)a
CS2
20 ppm b
1 ppm
Acetone
1000 ppm
250 ppm
Ethanol
1000 ppm
1000 ppm
Sources: Fischer Scientific MSDS for Acetone and Ethanol and OSHA Guidelines for Carbon Disulfide.
a - Time weighted average.
b - OSHA PEL for CS2 is an 8-hour time weighted average (TWA) concentration.
Because €82 is highly volatile and flammable, facilities take additional precautions to
reduce emissions to the air and sparks during the transfer of €82. These precautions include
submerging the pipelines from storage tanks to the process in water trenches, transporting
recovered €82 underground from the process to storage tanks, and transferring €82 by gravity or
magnetically sealed pumps.
EPA contacted the Carbon Disulfide Coalition to determine its toxicity levels and fate
and transport in water. The Akzo Nobel contact, a Carbon Disulfide Coalition member and a
manufacturer of CS2, provided the following freshwater toxicity levels:
• Freshwater, acute: 3 mg/L; and
• Freshwater, chronic: 1 mg/L.
The Akzo Nobel contact also stated that CS2 volatilizes quickly from water. Historically,
Carbon Disulfide Coalition scientists had difficulty measuring the solubility of CS2, due to the
rapid volatilization of free CS2 into the vapor space. They found that the dissolved levels quickly
dropped during the experiment. The Coalition concluded that the fate and transport of CS2 in
water would be volatilization, i.e., none would stay in solution (Love, 2011).
Table 7 presents the total air emissions and water discharges (to surface water or POTW)
for the seven cellulose products manufacturers. The reported data confirm that the majority of
the CS2 evaporates, which corresponds with the physical/chemical properties. However, the
estimated concentration of CS2 in the water discharged from four facilities exceeds the CS2
solubility at 25° C (0.2 %) (Love, 2011).
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Preliminary Study of Regenerated Cellulose Manufacturers
Table 7. TRI 2009 Carbon Disulfide Air Emissions and Water Discharges for Cellulose
Products Manufacturers
Facility
1
2
3
4
5
6
7
3M Corporation
3M Corporation
Innovia Films Inc.
Spontex Inc.
Viscofan USA Inc.
Viskase Corporation
Viskase Corporation
Location
Elyria, OH
Tonawanda, NY
Tecumseh, KS
Columbia, TN
Danville, IL
Osceola, AR
Loudon, TN
Discharge
Type8
Indirect
Indirect
Direct
Direct
Indirect
Direct
Indirect
Water Releases
% of Total CS2
Discharges
NA
1.22%b
3.1 %b
0.03 %
0.41 %b
0.05 %
0.68 %b
Total CS2
Air
Emissions
187,000
379,000
820,000
618,000
3,360,000
924,000
1,890,000
CS2
Discharge
before POTW
Removals
NR
4,700
26,500
223
14,000
473
13,000
Source: TRIReleases2009_v2.
a - ELGs control pollutant discharges at the point of discharges from industrial facilities and include discharges
directly to surface water (direct discharges) and discharges to POTWs (indirect discharges).
b - The estimated CS2 concentrations discharged to water from these facilities exceeds the CS2 solubility at 25° C
(0.2 %)
NR - No data reported.
NA - Not applicable.
2.2 Carbon Disulfide - Potential Pathways into the Environment
Releases of €82 from manufacturing facilities are almost exclusively to the atmosphere
(ATSDR, 1996). However, facilities transfer €82 to wastewater during feedstock unloading and
storage and air pollution control. Other than cellulose products manufacturing, industries that use
€82 as a raw material or form it as a by-product include the manufacturing of soil disinfectant,
development restrainer for instant color photography, aging of roasting coffee, pesticide
intermediates, degreasing, chemical analysis, electroplating of gold and nickel, oil extraction,
and dry cleaning (ATSDR, 1996). Natural sources of €82 in the environment include anaerobic
ocean floors, wetlands, microbial activity in solids, certain crop plants and trees, volcano and
marsh emissions, and vapor space above liquid sulfur (ATSDR, 1996).
3.0 WASTEWATER SOURCES
At cellulose products manufacturing facilities, the primary sources of wastewater
containing €82 are railcar unloading, storage, viscose process steps, and air pollution control
(Schmidtke, 2000). After reviewing the available data, the majority of the €82 enters the
wastewater from the viscose processes used to regenerate the cellulose (KDHE, 2005; Martin,
2011).
3.1 Unloading and Storage
Most cellulose products manufacturing facilities receive €82 in the liquid or gas form by
railcar. Because €82 is highly flammable, facilities unload €82 by water and/or nitrogen
displacement to prevent fire or explosion. Water displacement is a method of unloading liquid
€82 from railcars where water enters the railcar at the same flow rate that the €82 is expelled to
the storage container. Nitrogen displacement is the same process; however, the inert gas fills the
railcar as €82 is expelled. Facilities use water and/or nitrogen displacement to prevent
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Preliminary Study of Regenerated Cellulose Manufacturers
flammable, gaseous €82 emissions to the atmosphere and to preclude contact with oxygen (§40
CFR63.5610).
Once in the storage pool and/or tank, water or inert gas is again used to contain the €82.
If nitrogen is used, a nitrogen blanket is applied with enough pressure to keep the CS2 in liquid
form. If water is used, the liquid €82 is more dense than water, and a water blanket will also keep
the €82 in liquid form. The liquid €82 remains at the bottom and is recovered or discharged to
the wastewater treatment system. €82 does not evaporate from the unloading/storage system
because the systems are closed to the atmosphere and are not mixed/aerated, the process that
allows €82 to volatilize. Figure 2 shows the €82 unloading and storage processes by
displacement.
Nitrogen Gas
or Water
Unloading
Displacement
Rate(Rl GPM)
CS2 to Storage
(Rl GPM)
Nitrogen Gas
or Water
Legend
Headspace occupied by
Nitrogen Gas or Water
CS2
Rail car
Process Use
Displacement Rate
(R2 GPM)
Loading/Unloading Waste
Displacement Rate (Rl GPM)
CS2 to Process
(R2 GPM)
Recovered
CS2 from Process
(R3 GPM)
Wastewater to
Treatment or Nitrogen
^ Gas to Atmosphere
(R3 GPM)
Wastewater to
Treatment or Nitrogen
Gas to Atmosphere
Figure 2. CSi Unloading and Storage System Using Containment Pool/Tank
Facilities using water displacement for raw material unloading generate CS2-saturated
wastewater during railcar unloading; water displaced from the CS2 storage tank is sent to the
facility's wastewater treatment system (Schmidtke, 2000).
After unloading €82, facilities store pressurized, liquid €82 in large tanks. Because €82 is
extremely flammable, the facilities store the tanks with one or a combination of the following
methods:
10
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Preliminary Study of Regenerated Cellulose Manufacturers
• Submerged under water in a containment pool;
• Raised above a water containment pool; or
• Covered by a nitrogen blanketing system.
Because liquid €82 has a higher specific gravity than water, any €82 that leaks during
storage will settle to the bottom of the containment pool that a storage tank is submerged in or
stored above.
In addition to underwater or nitrogen blanket storage, the facilities use a water or nitrogen
padding system to fill headspace in the tank and further prevent contact with oxygen. The water
or nitrogen padding is displaced into the water pool as €82 is loaded into the storage vessel.
Conversely, the water or nitrogen padding in the storage tank fills the headspace as €82 is
expelled for use in the manufacturing process, also shown in Figure 2.
Any water that is displaced from the unloading or storage in the pool and water padding
is sent to the wastewater treatment system (Schmidtke, 2000). Table 8 presents the unloading and
storage practices for each cellulose products manufacturing facility.
Table 8. Facility Carbon Disulfide Unloading and Storage Practices as of 2000
Facility
1
2
3
4
5
6
7
3M Corporation
3M Corporation
Innovia Films Inc. b
Spontex Inc.
Viscofan USA Inc.
Viskase Corporation
Viskase Corporation
Facility
Location
Elyria, OH
Tonawanda, NY
Tecumseh, KS
Columbia, TN
Danville, IL
Osceola, AR
Loudon, TN
Facility Unloading
Procedures
Unloading
System
N2
N2
N2
Water
N2
N2
N2
Water
Displacement a
NA
Yes
No
NA
No
NA
Yes
Facility Storage Procedures
Tank Location
Submerged in
Water Pool
Mounted Over
Water Dike
Mounted Over
Water Dike
NA
Submerged in
Bottom Sloped
Water Pool
Submerged in
Water Pool
Submerged in
Water Pool
Padding
System
Water
Water
N2
Water
Water
N2
N2
Source: Schmidtke, 2000
a - Some facilities use nitrogen to displace CS2 from the railcar into storage tanks, but use a water dike or pool for
the storage tank. Therefore, they create a wastewater stream as CS2 enters the storage tank.
b - Innovia Films is the only facility where the CS2 is not directly in contact with water as part of the unloading or
storage processes at the facility. The facility contact confirmed that the majority of the facility's discharges are from
the viscose processes and CS2 recovery at the plant.
3.2 Process Steps
€82 is combined with aged alkali cellulose to form sodium cellulose xanthate. After this
reaction, the sodium cellulose xanthate is combined with liquid caustic and water in a
coagulation bath. In order to control the sodium sulfate levels of the coagulation bath, water is
continuously drained from this process step. Because the sodium cellulose xanthate contains
some €82 from previous process steps, €82 is discharged with the wastewater (Martin, 2011).
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Preliminary Study of Regenerated Cellulose Manufacturers
Any wastewater overflow from the viscose solution steps also contains €82 discharges
(Schmidtke, 2000). At this time, EPA is unable to determine what causes overflow from the
viscose solution steps or the amount of wastewater that results from process overflow.
At one facility, CS2 used in the viscose process is recovered through condensation. The
facility uses steam to condense the €82, which is ultimately sent to the recovery plant. The €82
not captured from condensation is oil-scrubbed and recovered. Because some €82 is soluble in
water, the steam condensate may contain €82. The steam condensate is sent to the facility's
wastewater treatment plant (Martin, 2011).
3.3 Air Pollution Control
On June 11, 2002, EPA promulgated a NESHAP for Cellulose Products Manufacturing
(40 CFR Part 63, Subpart UUUU, 67 FR 40055). The Cellulose Products Manufacturing
NESHAP regulates the Miscellaneous Viscose Processes and Cellulose Ethers Production
Categories. The Miscellaneous Viscose Process category includes cellulose food casings, rayon,
cellulosic sponge, and cellophane manufacturing facilities. The NESHAP established emissions
limits for hazardous air pollutants (HAPs), such as CS2, carbonyl sulfide, ethylene oxide,
methanol, methyl chloride, propylene oxide, and toluene. The resulting additional air pollution
control may be transferring more CS2 to the water via scrubbers (U.S. EPA, 2006).
Gaseous by-products formed during the regeneration of cellulose, including hydrogen
sulfide and CS2, are off-gassed from the process equipment. Facilities control emissions of these
toxic gases using either a wet gas scrubber, a direct-contact condenser, or a biofilter system. In a
wet gas scrubber, the air pollutants are absorbed by an aqueous solution. The wet scrubber
removal efficiency for C$2 varies depending on facility specific operations. For example, some
systems can remove up to 65 percent of CS2 prior to the stack (Marshall, 1998). The majority of
the scrubbed CS2 is either recovered or sent to wastewater treatment as scrubber effluent
wastewater. At other facilities, CS2 removal is low but the scrubber effluent wastewater may
contain some CS2 (Schmidtke, 2000).
In direct-contact condensers, water vapors are condensed out of the vent stream. The
condensed water is sent to the wastewater treatment system. The remaining CS2 vapors are
pulled by a vacuum jet to a second direct-contact condenser. The CS2 condenses because of the
decrease in temperature and is sent to a settling tank with other process by-products. The
condensed CS2 is piped underground to the storage tanks in the water containment pool. The CS2
emission reduction for these condenser systems is 99 percent (Schmidtke, 1998a).
Biofilters are also used as air pollution control at cellulose products manufacturing
facilities. Each biofilter (bed) has a plenum at the bottom (air space), a midsection that contains
grating and media that contain microbes, and a cover on top. The gases enter the bottom of the
bed and exit from the top. The removal efficiency of the biofilter varies based on process
conditions; however, normal CS2 reductions across the bed are approximately 80 percent
(Nicholson, 2000). Wastewater from the biofilter, which may contain some CS2, is sent to
wastewater treatment facilities. The spent media from the biofilter are neutralized with lime and
hauled offsite (Nicholson, 2000).
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Preliminary Study of Regenerated Cellulose Manufacturers
4.0 REGENERATED CELLULOSE PROCESS WASTEWATER TREATMENT
Table 9 summarizes the wastewater treatment used by the three cellulose products
manufacturers where EPA obtained data (Schmidtke, 2000). Table 10 summarizes the possible
sources of wastewater containing CS2 and the methods of wastewater treatment specific to each
plant.
Table 9. Cellulose Products Wastewater Treatment
Product
Cellophane
Food Casings
Cellulosic Sponges
Pretreatment Used by Indirect
Dischargers
NA
Neutralization, filtration and
settling. Achieved CS2
concentrations of 5-20 parts per
million (ppm).
Neutralization and oxidization
Treatment Used by Direct Dischargers
Neutralization, settling, equalization,
second neutralization, aeration, and
clarification (i.e., activated sludge)
Neutralization using lime, equalization, and
clarification.
Equalization, aeration, and clarification
(activated sludge).
Source: Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S. (Schmidtke, 2000).
NA - Not applicable.
In addition to wastewater treatment, facility management practices also affect how much
€82 is discharged in wastewater. For example, the Loudoun, TN Viskase facility formerly used a
water blanket during €82 unloading. This led to 10,000 gallons of €82 saturated water being
discharged to the wastewater treatment facility every time €82 was unloaded. By converting to
the nitrogen blanket system, the Viskase facility eliminated a significant source of €82
wastewater discharges (Schmidtke, 1998b).
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Preliminary Study of Regenerated Cellulose Manufacturers
Table 10. Confirmed Sources of Wastewater and Wastewater Treatment at Cellulose Manufacturing Facilities
Facility Name
1
2
3
4
5
6
7
3M
Corporation
3M
Corporation
Innovia Films
Inc.
Spontex Inc.
Viscofan USA
Inc.
Viskase
Corporation
Viskase
Corporation
Location
Elyria, OH
Tonawanda,
NY
Tecumseh, KS
Columbia, TN
Danville, IL
Osceola, AR
Loudon, TN
Product
Type
Cellulosic
Sponges
Cellulosic
Sponges
Cellophane
Cellulosic
Sponges
Food
Casings
Food
Casings
Food
Casings
Possible Sources of Wastewater
- Biofilter
- Storage tank displaced water
- Rotary vacuum filters
- Viscose steps
- Extrusion/regeneration
- Storage tank displaced water
- Railcar blowoff
- H2S scrubber vacuum pump discharge
- Overflow of storage tank submersion water
- Viscose steps (slurry, ripening, filtration)
- Extrusion/regeneration
- Washing
- Acid systems (acid recovery, basement systems,
anhydrous department)
- Viscose steps (ripening room trenches)
- Extrusion/regeneration (extrusion wash water, extrusion
acid)
- Deaerator condensate
- Waste handling
- Extrusion/regeneration
- Washing
Wastewater
Treatment
- Oxidation
- Neutralization
- Holding tanks
- Neutralization
- Neutralization
- Settling basin
- Equalization basin
- Activated Sludge
- Equalization
- Activated Sludge
- Mixing basin
- Neutralization
- Settling basins
- Discharge basin
(stack)
- Neutralization
(lime)
- Equalization
- Clarifiers
- Filter
- Neutralization
Type of
Discharger a
Indirect
Indirect
Direct
Direct
Indirect
Direct
Indirect
Source: Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S. (Schmidtke, 2000).
a - ELGs control pollutant discharges at the point of discharges from industrial facilities and cover discharges directly to surface water (direct discharges) and
discharges to POTWs (indirect discharges).
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Preliminary Study of Regenerated Cellulose Manufacturers
5.0 FACILITY DISCHARGE DATA
EPA reviewed all available €82 concentration data for facilities presented in Table 3.
EPA located wastewater treatment information for two facilities: Innovia Films, Inc in
Tecumseh, KS and Viskase Corporation in Loudon, TN.
5.1 Innovia Films, Inc in Tecumseh, KS
Innovia Films, Inc in Tecumseh, KS manufactures cellophane used primarily in food
packaging. EPA obtained 2009 discharge monitoring report (DMR) data for this facility, the only
cellulose products manufacturing facility required to monitor for CS2. EPA obtained facility-
specific waste stream and wastewater treatment data from the facility's permit and fact sheet.
5.1.1 Waste Streams
Acid, alkaline, and neutral waste streams are generated from the cellulose production
process. All process wastewaters are commingled, treated, and discharged through the treatment
plant discharge (outfall 001). Approximately 2.0 MOD wastewater is treated and discharged
through Outfall 001. Table 11 describes the facility waste streams and typical flow.
Table 11. Innovia Films, Inc Waste Streams
Waste Stream
Alkaline
Acid
Neutral
Description
Domestic waste flows and alkaline waste
streams from the mix house, finishing,
coating, casting, and the viscose
manufacturing areas (VMA)
Acid waste process flows from casting
areas and the powerhouse a
Condensate flow from the hot well area
Typical Flow (MGD)
0.67
0.6
0.68
Source: Facility Fact Sheet (KDHE, 2005).
a - The powerhouse discharge also includes water from reverse osmosis cleaning and demineralizer washes.
€82 enters the wastewater from different processes at the plant (Martin, 2011):
• Start up procedures that call for the dumping of liquid viscose (alkaline waste
stream);
• Overflow from the viscose process, which results in various losses of CS2 as
liquid viscose (alkaline waste stream);
• Continuous dumping of the coagulation bath solution to the wastewater treatment
system, which is dumped to control the balance of sodium sulfate in the viscose
process (alkaline waste stream);
• Casting area water and wash water (acid waste stream); and
• CS2 recovery system (neutral waste stream), which is described below.
Because CS2 is volatile valuable feedstock, the facility recovers volatilized CS2 used in
the process in the CS2 recovery system (Martin, 2011). The following process steps result in
excess or liberated CS2 air emissions:
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Preliminary Study of Regenerated Cellulose Manufacturers
• The xanthation step in the viscose process, where €82 is sprayed on alkali
cellulose to produce xanthate (an intermediate product in the cellophane process);
• The extrusion/casting step, where the viscose solution is soaked in concentrated
and dilute sulfuric acid baths, which liberates €82 and hydrogen disulfide; and
• The extrusion/casting step where the cellulose is washed in a hot water bath,
which also liberates €82.
At the €82 recovery plant, the facility uses steam to recover the €82. Although the
majority of the €82 is recovered, the facility contact stated that some €82 is captured in the steam
condensate which is transferred to the wastewater treatment system (Martin, 2011).
5.1.2 Wastewater Treatment
The plant uses an activated sludge extended aeration process to treat the wastewater. The
acid wastestream is first neutralized using hydrated lime in settling pond #1. The neutralized acid
stream is then commingled with the alkaline and neutral wastestreams in settling pond #2. The
combined wastestream is pumped to the equalization basin. As the wastestream is pumped from
the equalization basin to the activated sludge aeration basin, the plant adds phosphoric acid and
ammonium hydroxide to provide supplemental nutrients for biological treatment. The excess
activated sludge is settled in clarifiers, and the treated effluent is discharged to the Kansas River
through a long outfall sewer. The sludge is concentrated by a centrifuge and land applied
(KDHE, 2005). Figure 3 diagrams the Innovia Films wastewater treatment system (Mester,
2011).
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Preliminary Study of Regenerated Cellulose Manufacturers
Acid
Wastestream
Lime
Alkaline
Wastestream
Neutral.
Wastestream
Settling Basin #1
Holding Ponds
Settling Pond #2
Post Neutralization
Post Neutralization
Equalization Tank
Sodium Hydroxide (if
necessary)
Diversion Tank
Aeration Basin
If
a 55
Splitter Box
100' Clarifier
Clarifier Overflow
(Effluent) Discharge
to Kansas River
60' Clarifier
Waste Sludge
(Hauled Offsite)
Figure 3. Block Diagram of Innovia Films Wastewater Treatment System
5.1.3 Discharge Data
Innovia Films' permit requires the facility to monitor for CS2 because concentrations at
35 mg/L or greater inhibit the activated sludge process. The permit requires remedial action if the
€82 concentration exceeds 17.5 mg/L. The facility analyzes the €82 samples using EPA Method
624.
The facility samples for CS2 at the splitter box, which receives flow from the aeration
basin and feeds the flow to the clarifiers. The overflow (treated effluent) from the clarifiers is
piped underground by gravity to the outfall. The outfall discharges to the receiving stream
approximately 7,000 feet from the splitter box. Table 12 shows the 2008, 2009, and 2010 CS2
concentration data for Innovia Films, Inc.
Table 12. 2008, 2009, and 2010 Carbon Bisulfide Concentration Data for Innovia Films,
Inc.
Outfall
001
001
Date
31-Jan-08
29-Feb-08
Monthly Minimum
Concentration
(mg/L)
0.63
1.58
Monthly Average
Concentration
(mg/L)
2.03
4.98
Monthly Maximum
Concentration
(mg/L)
2.86
8.45
17
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Preliminary Study of Regenerated Cellulose Manufacturers
Table 12. 2008, 2009, and 2010 Carbon Bisulfide Concentration Data for Innovia Films,
Inc.
OutfaU
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
001
Date
31-Mar-08
30-Apr-08
31-May-08
30-Jun-08
31-M-08
31-Aug-08
30-Sep-08
31-Oct-08
30-Nov-08
31-Dec-08
31-Jan-09
28-Feb-09
31-Mar-09
30-Apr-09
31-May-09
30-Jun-09
31-M-09
31-Aug-09
30-Sep-09
31-Oct-09
30-Nov-09
31-Dec-09
31 -Jan- 10
28-Feb-10
31 -Mar- 10
30-Apr-10
31-May-10
30-Jun-10
31-M-10
31-Aug-10
30-Sep-10
31-Oct-10
30-Nov-lO
31-Dec-10
Monthly Minimum
Concentration
(mg/L)
7.11
0.56
0.52
0.13
0.26
0.75
3.23
0
3.51
0
6.02
5.19
6.63
0.25
0.21
0.07
0.06
0.25
0.1
0.16
0
4.14
1.18
1.74
2.42
0.88
2.84
0
0.28
0.24
0.88
0.79
0.52
2.94
Monthly Average
Concentration
(mg/L)
9.48
0.56
0.74
0.55
0.36
0.75
5.76
0
8.34
2.14
9.77
5.19
10.67
0.39
0.66
0.22
0.86
0.25
0.15
0.85
0.12
4.14
2.79
3.22
2.42
1.54
2.84
0.07
0.42
0.27
0.88
0.84
1.10
3.50
Monthly Maximum
Concentration
(mg/L)
12.5
0.56
0.98
0.99
0.56
0.75
8.29
0
13.1
4.29
17.1
5.19
14.5
0.52
1.53
0.33
1.67
0.25
0.21
1.55
0.25
4.14
4.62
4.7
2.42
2.14
2.84
0.14
0.55
0.30
0.88
0.88
1.79
4.07
Source: Envirofacts
As shown in Table 12, a total of 10 average concentrations (28 percent) exceed 3 mg/L,
the acute freshwater toxicity level for CS2, and a total of 17 average concentrations (47 percent)
exceed 1 mg/L, the chronic freshwater toxicity level for €82 (Love, 2011). There are no
concentrations above the 17.5 mg/L permit monitoring concentration. The Carbon Bisulfide
Coalition finds these concentrations are inconsistent with their experiences. The coalition
reviewed analytical values from a wastewater treatment system consisting of aeration and
neutralization only. The concentrations of CS2 at the discharge points were less than 1 mg/L,
with an overall CS2 removal over 99 percent (Love, 2011). The final effluent concentrations are
likely less than those taken at the splitter box, because after the sampling point, the wastewater
goes through clarification and travels over 1.3 miles through a pipe to the surface water, allowing
for further volatilization.
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Preliminary Study of Regenerated Cellulose Manufacturers
5.2 Viskase Corporation in London, TN
The Viskase Corporation in Loudon, TN is a food casings manufacturer, one of two
operated by Viskase Corporation, the world's largest producer of small-sized food casings
(Schmidtke, 1998b).
5.2.1 Wastewater Source and Treatment
The Viskase Corporation plant uses approximately 1.95 MGD of water. Wastewater from
the extrusion, regeneration, and washing areas is sent to the wastewater treatment facility. At the
wastewater treatment plant, coarse materials are removed from the waste stream and the
wastewater is neutralized with lime. The wastewater is sent off site for treatment at a POTW.
The C$2 levels in the wastewater sent to the POTW typically vary between 5 and 20 ppm
(Schmidtke, 1998b).
5.2.2 Discharge Data
In 2009, EPA contacted Viskase Corporation and the local pretreatment coordinator to
confirm CS2 discharges. The facility's industrial user permit limit for CS2 is 5 mg/L. Viskase
collects samples at the point where the discharge leaves the facility and enters a pipe connected
to the adjacent POTW. In addition, the POTW collects samples at the other end of this pipe,
where the Viskase discharge enters the POTW. These samples are analyzed for CS2. The
combined data show that the facility releases close to 100,000 pounds of CS2 to the POTW, but
the POTW receives less than 3,000 pounds per year from the discharge pipe per year. This
decrease in pollutant load suggests the possible volatilization of 97,000 pounds per year of CS2
within the discharge pipe (Birkholtz, 2009; Glarrow, 2009; U.S. EPA, 2009).
The POTW provided CS2 concentration measurements taken at the influent to their
treatment system. Table 13 shows the results of these sampling events.
Table 13. Carbon Disulfide Concentration Data for Viskase Corporation in Loudon, TN
Date
13-Feb-06
14-Aug-06
20-Feb-07
19-Sept-07
l-Apr-08
19-Aug-08
3-Feb-09
POTW Measurement at Treatment
Works Influent (mg/L)
12
O.001
0.001
1.1
1.4
0.001
O.001
Discharge Limit (mg/L)
5
5
5
5
5
5
5
Source: Facility Contact (Birkholz, 2009).
The CS2 concentrations for Viskase Corporation do not exceed the discharge limit of 5
mg/L, except for the February 2006 concentration. More importantly, these discharges represent
the CS2 concentrations prior to treatment through the POTW. Therefore, the CS2 concentrations
are likely below levels of detection in the POTW effluent, and are likely of no concern to human
health and aquatic life.
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Preliminary Study of Regenerated Cellulose Manufacturers
6.0 CONCLUSIONS
The conclusions of the cellulose products manufacture review are as follows:
• From available data, EPA identified seven active regenerated cellulose
manufacturers in the U.S. These facilities use and discharge wastewater
containing €82 generated from €82 storage, recovery, and the viscose process.
EPA continues to resolve the overall question of how significant concentrations of
CS2 (ranging from values below detection to 17.1 mg/L) remain in the water after
treatment, although €82 is highly volatile (430 times more volatile than acetone,
for example).
• There are three direct dischargers, but only one facility collects data on €82 in
their wastewater. This facility, Innovia Films, Inc, discharges up to 17.1 mg/L of
€82 after activated sludge wastewater treatment. There are 17 of 36 monthly
average concentrations in the facility's 2008 through 2010 CS2 data that are above
the chronic freshwater toxicity level of 1 mg/L. The concentration of €82 entering
the receiving stream is likely lower, because the sample point is more than one
mile from the final discharge point, allowing for further €82 volatilization in the
discharge pipe. The measurements reported by Innovia Films are inconsistent
with information received from the Carbon Bisulfide Coalition. Based on
Coalition solubility and volatility data, the CS2 concentrations would be less than
1 mg/L following aeration.
• There are four indirect dischargers, but EPA obtained data from only one facility
on CS2 in their wastewater. Because facilities pre-treat their wastewater, and it is
processed through a POTW, CS2 concentrations for indirect dischargers likely are
well below aquatic life criteria.
• The cellulose products manufacturers using the viscose process include a small
number of U.S. facilities. For this reason, EPA considers these discharges are best
controlled by facility-specific permitting assistance.
EPA prioritizes point source categories with existing regulations for potential revision
based on the greatest estimated toxicity to human health and the environment, measured as
TWPE. Based on the above conclusions, EPA will categorize these discharges with Part 414,
OCPSF for future annual reviews. EPA is assigning this category with a lower priority for
revision (i.e., this category is marked with "(3)" in the "Findings" column in Table V-l in the
Federal Register notice that presents the 2011 annual review of existing effluent guidelines and
pretreatment standards).
7.0 REFERENCES
1. Acetone. MSDS No. 00140 [Online]; Fischer Scientific: Fair Lawn, NJ. February 28,
2008, http://fscimage.fishersci.com/msds/00140.htm (accessed August 2, 2011).
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Preliminary Study of Regenerated Cellulose Manufacturers
2. Agency for Toxic Substances and Disease Registry (ATSDR). 1996. Toxicological
Profile for Carbon Bisulfide. Atlanta, GA. U.S. Department of Health and Human
Services, Public Health Service. EPA-HQ-OW-2010-0824. DCN 07673.
3. Beach, Robert, et al. 2000. Economic Analysis of Air Pollution Regulations:
Miscellaneous Cellulose Manufacturing Industry, Industry Profile. Research Triangle
Institute. (February). EPA-HQ-OW-2010-0824. DCN 07674.
4. Birkholtz, Dave. 2009. Telephone conversation with Dave Birkholtz of City of Loudoun,
TN POTW and Eleanor Codding of Eastern Research Group, Inc. "Carbon Disulfide
Discharges Reported to TRI by Viskase Facility in Loudoun, TN." (March 12). EPA-HQ-
OW-2008-0517 DCN 07300.
5. ERG, 2010. Quality Assurance Project Plan for the Plastics Molding and Forming
Preliminary Category Review. (November). EPA-HQ-OW-2010-0824. DCN 07675.
6. Ethanol. MSDS No. 91467 [Online]; Fischer Scientific: Fair Lawn, NJ. September 26,
2007, http://fscimage.fishersci.com/msds/91467.htm (accessed August 2, 2011).
7. Glarrow, Patrick. 2009. Telephone communication with Patrick Glarrow of Viskase in
Loudoun, TN and Eleanor Codding of Eastern Research Group, Inc. "Carbon Disulfide
Discharges Reported to TRI by Viskase Facility in Loudoun, TN." (March 10). EPA-HQ-
OW-2008-0517-0074.
8. KDHE, 2005. Kansas Department of Health and Environment - Bureau of Water.
NPDES Permit Fact Sheet for Innovia Films, Inc. NPDES KS0003204. Tecumseh, KS.
(September). EPA-HQ-OW-2010-0824. DCN 07676.
9. Kotz, John and Treichel, Paul. 1999. Chemistry and Chemical Reactivity, Fourth Edition.
Saunders College Publishing, pp. 653-654.
10. Love, Brian. 2011. Notes from E-mail Communication between Brian Love, Akzo Nobel,
and Elizabeth Sabol, ERG. "RE: Carbon Disulfide - Fate and Transport." (July 1). EPA-
HQ-OW-2010-0824. DCN 07677.
11. Marshall, Amy and Rebecca Nicholson. 1998. Site Visit Notes from 3M Corporation,
(NESHAP for the Miscellaneous Cellulose Manufacturing Industry). Tonawanda, NY.
(November 3). EPA-HQ-OW-2010-0824. DCN 07678.
12. Martin, Tony. 2011. Notes from Telephone Communication between Tony Martin,
Innovia Films, Inc, and Elizabeth Sabol, ERG. "RE: Carbon Disulfide - Wastewater
Discharges and Recovery System." (August 1). EPA-HQ-OW-2010-0824. DCN 07679.
13. Mester, Joe. 2011. Notes from Telephone Communication between Joe Mester, KDHE,
and Elizabeth Sabol, ERG. "RE: Carbon Disulfide - Wastewater Discharges at Innovia
Films, Inc." (July 22). EPA-HQ-OW-2010-0824. DCN 07680.
14. Nicholson, Rebecca and Amy Marshall. 2000. Site Visit Notes from Nylonge
Corporation, (NESHAP for the Miscellaneous Cellulose Manufacturing Industry). Elyria,
OH. (May 1, 2000). EPA-HQ-OW-2010-0824. DCN 07681.
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Preliminary Study of Regenerated Cellulose Manufacturers
15. Ohio EPA, 2010. National Pollutant Discharge Elimination System (NPDES); BADCT
Limits for Volatile Organic Compounds. (November 8). EPA-HQ-OW-2010-0824. DCN
07683.
16. OSHA, 1994. Guidelines for Carbon Bisulfide. Available online at:
http://www.osha.gov/SLTC/healthguidelines/carbondisulfide/recognition.html
17. Schmidtke, Karen and Rebecca Nicholson. 1998a. Site Visit Notes from Lenzing Fibers
Corporation in Lowland, TN (Miscellaneous Cellulose Manufacturing Industry
NESHAP). Lowland, TN. (May 22). EPA-HQ-OW-2010-0824. DCN 07682.
18. Schmidtke, Karen and Rebecca Nicholson. 1998b. Site Visit Notes from Viskase
Corporation in Loudon, TN (Miscellaneous Cellulose Manufacturing Industry NESHAP).
Loudon, TN. (August 4). EPA-HQ-OAR-2003-0193-0006.
19. Schmidtke, Karen and Thomas Holloway. 2000. Industry Profile of the Cellulose
Products Manufacturing Facilities in the U.S. Prepared for U.S. EPA National Emissions
Standards for Hazardous Air Pollutants: Cellulose Products Manufacturing. Gary, NC.
(April 11). EPA-HQ-OAR-2003-0193-0004.
20. U.S. EPA. EPA On-line Tools for Site Assessment Calculation. Available online at:
http://www.epa.gov/athens/learn2model/part-two/onsite/sparcproperties.html
21. U.S. EPA. 1984. Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Plastics Molding and Forming Point Source
Category. EPA 440/1-84/069. Washington, DC. (December).
22. U. S. EPA. 1987. Development Document for Effluent Limitations Guidelines and
Standards for the Organic Chemical, Plastics, and Synthetic Fibers Point Source
Category-Final. EPA 4401-87-009. Washington, DC. (October).
23. U. S. EPA. 2005a. Preliminary Review of Prioritized Categories of Industrial
Dischargers. EPA-821-B-05-004. Washington, DC. (August). EPA-HQ-OW-2004-0032-
0053.
24. U. S. EPA. 2005b. Product and Product Group Discharges Subject to Effluent Limitations
and Standards for the Organic Chemicals, Plastics, and Synthetic Fibers Point Source
Category - 40 CFR 414. Washington, DC. EPA-HQ-OW-2004-0032-0941.
25. U. S. EPA. 2006. Technical Support Document for the 2006 Effluent Guidelines Program
Plan. EPA-821-R-06-018. Washington, DC. (December). EPA-HQ-OW-2004-0032-
2782.
26. U. S. EPA. 2009. Technical Support Document for the Preliminary 2010 Effluent
Guidelines Program Plan. EPA-821-R-09-006. Washington, DC. (October). EPA-HQ-
OW-2008-0517-0515.
27. U. S. EPA. 2011. Technical Support Document for the 2010 Effluent Guidelines Program
Plan. Washington, D.C. (October). EPA-820R-10-021. EPA-HQ-OW-2008-0517 DCN
07320.
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Preliminary Study of Regenerated Cellulose Manufacturers
APPENDIX A
40 CFR Part 414
EPA first promulgated ELGs for the OCPSF Category (40 CFR Part 414) on November
5, 1987 (52 FR 42568). This category consists of seven subcategories that apply to the
manufacture of products and product groups, as shown in Table A-l with corresponding
Standard Industrial Classification (SIC) codes and applicability. Subparts B through H have
limitations for biochemical oxygen demand (BODs), total suspended solids (TSS), and pH. The
regulation also includes limitations and/or pretreatment standards for certain toxic pollutants in
three additional subparts:
Subpart I — Direct Discharge Point Sources That Use End-of-Pipe Biological Treatment;
Subpart J — Direct Discharge Point Sources That Do Not Use End-of-Pipe Biological
Treatment; and
Subpart K — Indirect Discharge Point Sources.
Table A-l. Applicability of Subcategories in the OCPSF Category
Subpart Subcategory Title Corresponding SIC Code(s) a
Subcategory Applicability
B
Rayon Fibers
2823: Cellulosic Manmade
Fibers
Cellulosic manmade fiber (Rayon)
manufactured by the Viscose process.
Other Fibers
2824: Synthetic Organic Fibers,
Except Cellulosic
All other synthetic fibers (except Rayon)
including, but not limited to, products
listed in Section 414.30.
D
Thermoplastic Resins
28213: Thermoplastic Resins
Any plastic product classified as a
thermoplastic resin including, but not
limited to, products listed in Section
414.40.
Thermo setting Resins
28214: Thermosetting Resins
Any plastic product classified as a
thermosetting resin including, but not
limited to, products listed in Section
414.50.
Commodity Organic
Chemicals
2865: Cyclic Crudes and
Intermediates, Dyes and
Organic Pigments
2869: Industrial Organic
Chemicals, NEC
Commodity organic chemicals and
commodity organic chemical groups
including, but not limited to, products
listed in Section 414.60.
Bulk Organic
Chemicals
2865: Cyclic Crudes and
Intermediates, Dyes and
Organic Pigments
2869: Industrial Organic
Chemicals, NEC
Bulk organic chemicals and bulk organic
chemical groups including, but not limited
to, products listed in Section 414.70.
H
Specialty Organic
Chemicals
2865: Cyclic Crudes and
Intermediates, Dyes and
Organic Pigments
2869: Industrial Organic
Chemicals, NEC
All other organic chemicals and organic
chemical groups including, but not limited
to, products listed in the OCPSF
Development Document (Vol. II,
Appendix II-A, Table VII).
Source: Product and Product Group Discharges Subject to Effluent Limitations and Standards for the Organic
Chemicals, Plastics, and Synthetic Fibers Point Source Category — 40 CFR 414, Table 2-2 (U.S. EPA, 2005b).
a - During the 2009 annual review EPA developed a crosswalk between SIC codes and NAICS codes. Because there
is not a direct match EPA did not report NAICS codes.
NEC - Not elsewhere classified.
A-l
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