Technology Transfer
EPA-625/10-84-004
Environmental
Regulations
and Technology
Fugitive VOC Emissions in the
Synthetic Organic Chemicals
Manufacturing Industry
December 1984
This report was prepared jointly by
Office of Air Quality Planning and Standards
Office of Air and Radiation
Research Triangle Park, NO 27711
and
Center for Environmental Research Information
Office of Research Program Management
Office of Research and Development
Cincinnati, OH 45268
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This report was prepared by JACA Corp., Fort Washington, PA, and
Radian Corp., Research Triangle Park, NC. EPA would like to thank PEDCo
Environmental, Arlington, TX for technical review, and the American Petroleum
Institute for Figure 8 (reprinted from API Standard 617, Centrifugal
Compressors for General Refinery Services, Fourth Edition, 1979).
Cover photo courtesy of Atlantic Richfield Co.
This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of
trade names or commercial products does not constitute endorsement or
recommendation for use.
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Contents
1. Overview 1
2. Applicabilityof the Standard 3
Intermediate Products, Co-Products and By-Products 3
Equipment "In VOC Service" 3
Exemptions , 4
Modification and Reconstruction Provisions 4
3. Fugitive Emission Sources 6
Valves 6
Pumps 8
Compressors 10
Pressure Relief Devices 12
Open-Ended Valves and Lines 13
Sampling Connection Systems 13
Flanges and Other Connectors 13
Comparing Emissions from Different Types of
Fugitive Emission Sources 14
4. Standard Provisions '... 15
Delay of Repair Provisions 15
Provisions for Leakless Equipment 16
Closed Vent Systems 16
Equivalency Determinations 16
Vacuum Service 16
Reporting 17
5. Detailed Provisions of the Standards 18
Valves 18
Pumps 20
Compressors 20
Pressure Relief Devices 21
Open-Ended Valves or Lines 21
Sampling Connection Systems 21
Miscellaneous Sources 22
Closed Vent Systems and Control Devices 22
6. Leak Detection Methods 23
Noninstrument Methods 23
Instrument Techniques 23
7. Other Standards 25
8. Sources of Information 26
Federal Register Notices 26
Control Technique Guidelines Documents 27
Background Information Documents for Standards 27
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Illustrations
Figures
1. Contribution of Source Subcategories to Total SOCMIVOC Emissions 6
2. Primaty Valve Maintenance Points 7
3. Typical Design of a Bel lows Seal 7
4. Typical Designs of Diaphragm Valves 8
5. Typical Design of a Packed Seal 8
6. Basic pesign of a Single Mechanical Pump Seal 9
7. Typical Arrangements of Dual Mechanical Pump Seals 10
8. Typical Designs of Mechanical Compressor Seals 11
9. Typical Design of a Pressure Relief Valve Mounted on a Rupture Disk
Device 12
10. Examples of Closed Purge Sampling Systems 13
Tables
1. New Source Performance Standards for Synthetic Organic Chemicals
Manufacturing Industry Fugitive VOC Emission Requirements 2
2. Classification of VOC Services 4
3. Emission and Control Efficiency Factors Used in Estimating VOC
Emissions fora Process Unit 5
4. Emission Factors for Fugitive Emission Sources 14
5. Recordkeeping Requirements for Detected Equipment Leaks 19
6. Specifications and Performance Criteria for Portable VOC Monitors ... 24
iv
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1. Overview
Section 111 of the Clean Air Act, as
amended in 1977, directed the U.S.,
Environmental Protection Agency
(EPA) to set standards of perform-
ance for any newly constructed,
modified, or reconstructed sources
of air pollution which may endanger
public health or welfare. These New
Source Performance Standards
(NSPS) were to be promulgated for
each of the dozens of industries
recognized as being significant
contributors to air pollution. To direct
standards-setting activities in an
orderly fashion, industries were
prioritized according to: (1) total
emissions from the source industry,
(2) the extent to which each pollutant
endangers public health or welfare,
and (3) the mobility and competitive
nature of each source industry.
This ranking process resulted in a
Priority List of industries (categories)
for which EPA was mandated to pro-
mulgate standards within a given
time. After the list and its supporting
materials were reviewed, the final
Priority List was promulgated on
August 12,1979. The Synthetic
Organic Chemicals Manufacturing
Industry (SOCMI) was first on the list
as the single most significant contri-
butor to air pollution.
In this same period, an extensive
assessment of emissions from
petroleum refineries showed that
fugitive emissions of volatile organic
compounds (VOC) were a major
contributor of VOC emissions to the
atmosphere. Used in this context,
fugitive emissions refer to leaks of
VOC from equipment such as valves,
pumps, compressors, pressure relief
devices, and connectors.
Using the results of the refinery
assessment and information
gathered in an EPA research study of
SOCMI, standards of performance for
fugitive emissions of VOC in SOCMI
were developed and proposed by
EPA in January 1981. Coincident with
the development of the proposed
standards, EPA's research group
conducted additional studies of
fugitive emissions from chemical
plants to validate the transfer of
technical information from the
refining industry. Twenty-four
separate chemical process units
were evaluated, six of which were
investigated more closely to examine
the effectiveness of emission control
techniques and programs. From
these and previous studies, sufficient
information was gathered to permit
development of emission factors for
types of equipment in SOCMI, as
well as procedures for estimating the
effectiveness of emission reduction
techniques.
These new findings were compiled
into an Additional Information
Document (AID) on fugitive
emissions of VOC in SOCMI. In
addition to the new findings, the AID
presented a comprehensive review of
the fugitive emissions studies
completed to date. More importantly,
the AID set forth EPA's conclusions
about fugitive emissions in SOCMI,
including:
How to estimate emissions
What emission reductions are
achievable
The costs of controlling
emissions.
Thus, the AID established the
technical framework on which EPA
based its final standards for
equipment leaks in SOCMI. The final
standards were promulgated on
October 18,1983.
The standards, summarized in Table
1, apply only to facilities constructed
or modified after January 5,1981
which produce (as a product, co-
product, or intermediate) one or more
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of the 378 organic chemicals listed
Inside the back cover of this
publication. The standards also apply
only to specific pieces of equipment
which contain 10 percent or more
VOC.
The standards require a leak detec-
tion and repair program to reduce
VOC emissions from valves. They
require the use of certain equipment
to reduce VOC emissions from
pumps, compressors, process
sampling connections, and open-
ended lines. In addition, records
must be maintained and semiannual
reports must be submitted to EPA by
the owners and operators of facilities
subject to these standards.
This Environmental Regulations and
Technology publication is intended
as an introduction to these SOCMI
fugitive VOC emissions standards. It
Is not intended as a detailed
discussion of them. This publication
also does not cover other standards
with which;owners or operators of
organic chemical units may have to
comply such as those for distillation
unit operations, benzene equipment
leaks, volatile organic liquid storage
vessels, air oxidation unit processes,
and vinyl chloride.
The standards for fugitive VOC
emissions in SOCMt can be found in
the notice of the final regulation in
the Federal Register of October 18,
1983; they will eventually appear in
updated copies of Title 40, Part 60 of
the Code of Federal Regulations (40
CFR 60). Title 40, Part 60 also con-
tains general requirements for all
new source standards. Details on
how to obtain these and other
documents| relating to this standard
are provided below under "Sources
of Information." The numbers
appearing in brackets throughout
this text refer to specific sections in
40 CFR 60.
Table 1.
New Source Performance Standards for Synthetic Organic Chemicals
Manufacturing Industry Fugitive VOC Emission Requirements
Requires monthly leak detection and repair of valves
Requires monthly leak detection and repair of pumps
Requires control equipment for compressors
Requires no detectable emissions from safety relief devices
Requires caps, plugs, blinds, or second valves oh open-ended lines
Requires repairs of pipe connections
Requires closed-purge or closed-vent systems for sampling connections
Requires control devices on vented systems
Requires recordkeeping and semiannual reporting
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2. Applicability of the
Standards
Any chemical plant producing one or
more of the SOCMI chemicals may
be subject to the standards for
fugitive VOC emissions in SOCMI.
Before discussing the applicability of
these standards to a plant, a few
definitions are in order:
An affected facility is defined, for the
purposes of this standard, as the
group of all equipment within a
process unit. The owner or operator
of any affected facility on which
construction or modification is
begun after January 5,1981 must be
able to demonstrate that the require-
ments of fugitive VOC emissions
standards have been met within 180
days after initial startup.
Equipment refers to sources of
fugitive VOC emissions including
pumps, compressors, valves,
pressure relief devices, sampling
connection systems, and open-ended
lines or flanges.
A process unit consists of the
components assembled to produce
one or more SOCMI chemicals as an
intermediate chemical or a final
product. The production of the
chemicals may entail separation or
purification techniques; it is not
merely limited to the production of
chemicals through reaction process-
es. As such, what is generally
accepted as a "chemical plant" may
actually consist of several process,
units under this definition. There are,
of course, several qualifications and
exemptions to this statement. These
are the subject of the remainder of
this section.
Intermediate Products,
Co-Products, and By-Products
The production of intermediate
chemicals and co-products as well as
final products are covered by the
standards. Intermediate chemicals
are produced from raw materials;
their production, however, is typically
for captive use in the production of
the desired final product. If there is
sufficient storage for raw materials
and for the intermediate chemical,
the equipment used to produce the
intermediate chemical would
constitute a process unit. Ketene is
an example of an intermediate
chemical produced for captive use; it
is an acetylating agent used to
produce a variety of products. Co-
products are produced together and
both could be recovered for
subsequent use. Again, they are
covered if there is sufficient storage
for the raw materials and for the co-
products. Phenol and acetone
produced from the cleavage of
cumene hydroperoxide are examples
of co-products subject to the
standards.
By-products occur as a consequence
of producing other chemicals and are
not .necessarily of subsequent
purpose or use; they may be found
as trace contaminants in the final
product of a chemical production
unit. Production of a SOCMI
chemical as a by-product would only
bring a process unit under the
standard if the unit produces it for
subsequent use.
Equipment "In VOC Service"
Because the standards are intended
to reduce fugitive emissions from
significant sources of VOC, only
those sources "in VOC service" in an
affected facility must comply with
the standards. Equipment is in VOC
service if the fluid it contains
comprises 10 percent or more VOC
by weight. All organic compounds
are regulated as VOC with the
following exceptions:
Methylene chloride, 1,1,1-
trichloroethane, trichlorofluoro-
methane, dichlorodifluoro-
methane, and chlorodifluoro-
methane are not regulated as
VOC but their manufacture is
covered by the standards because
their manufacture involves the
use or production of VOC.
Methane, ethane, trifluoro-
methane, trichlorotrifluoro-
methane, dichlorotetrafluoro-
ethane, and chloropentafluoro-
ethane are not regulated as VOC
and their manufacture is not
covered by the standards.
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If there is a question about whether
equipment is considered to be in
VOC service, ASTM Methods E-260,
E-168, and E-169 may be used to
determine the VOC content of the
process fluid contained in the equip-
ment. The standards also allow the
owner or operator to elect to use
engineering judgment in making this
determination. However, the ASTM
methods will always be used if there
is any disagreement between EPA (or
the state or local agency) and the
owner or operator of an affected
facility.
When equipment has been judged
not to be in VOC service, the data
and the Information developed by the
owner or operator supporting this
determination must be recorded
[60.486{i) (3) and (j)j.
Exemptions
In a further effort to exclude from
coverage those pieces of equipment
with little potential for significant
VOC emissions, specific subcate-
gories of VOC service were identified
by EPA. This classification scheme is
shown in Table 2.
Using these classifications, two
exemptions from the standards are
allowed. A facility is exempt from the
SOCMI fugitive emissions standard if
it:
Is designed to process light
liquids and gaseous VOC at less
than 1,000 Mg/yr [60.480(d) (2)j
Produces only heavy liquids
[60.480(d)(3)].
In addition, a facility is exempt from
the SOCMI standards if it:
Has no equipment in VOC service
[60.480(d) (5)]
Produces only beverage alcohol
[60.480(d) (4)].
Table 2.
Classification of VOC Services
VOC Service
Gas/Vapor Gaseous state at operating conditions
Light Liquid Liquid state at operating conditions
Vapor pressure of at leastone component is greater than
0.3 kPa at 20ฐC
Concentration of all components (with vapor pressure above
0.3 kPa) is not less than 20 percent
Heavy Liquid Not gas/vapor or light liquid service
The last exemption applies only to
fermentatioh alcohol process units
making products for human con-
sumption, process units within
beverage albohol manufacturing
operations are covered by the
standards if they process non-
beverage alcohol products.
To qualify for any of these exemp-
tions, the owner or operator must
maintain proper records [60.486(i)j.
These records basically consist of
the information, data, and analyses
necessary tb demonstrate (1) pro-
cessing rate, or (2) composition and
nature of raw materials, intermedi-
ates, and products.
Modification and
Reconstruction
Modification and reconstruction
provisions pertain to facilities whose
construction was begun before
January 5,1981. As a result, older
process uni;ts may be subject to
these standards.
Modification is defined as any
physical or operational change (with
a few exceptions) to an existing
facility that results in an increase in
emissions from that facility [60.14].
The key point for invoking the modifi-
cation provisions is that there must
be an overall increase in emissions.
Therefore, if an increase in VOC
emissions resulting from changing or
adding equipment (i.e., valves or
pumps) is offset by a reduction in
VOC emissions from other
equipment within the same process
unit, the owner or operator may avoid
being covered by the NSPS standard
under the modification provisions.
Estimates of fugitive emissions from
a process unit may be made by using
the techniques described in the
Background Information Document
for Promulgated Standards and in the
Additional Information Document for
Fugitive Emissions in Organic
Compounds (see "Sources of
Information"). For each equipment
type, the number of pieces of
equipment before changes were
made is multiplied by an emission
factor and 8760 hours/year to
estimate emissions on an annual
basis. The total fugitive emissions
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for a process unit is simply the sum
of the annual emissions for each
equipment type. The same is done
for the number of pieces of
equipment after changes are made.
The difference is the increase or
decrease in uncontrolled emissions
resulting from changes to the
existing facility. Estimates of
controlled emissions can be made by
applying control efficiency estimates
to the uncontrolled emissions
estimates for each type of
equipment. Emissions estimates
made in this manner allow evaluation
of emissions increases for a deter-
mination of modification. Table 3
includes emission factors and
estimated control efficiencies for
equipment operating in compliance
with the standards.
The three changes (physical or
operational) that are considered
exceptions under the modification
provisions are:
Changes such as routine
maintenance, repair, and
replacement
An increase in the number of
hours of operation
An increase in production rate
that is effected without a capital
expenditure. NOTE: Capital
expenditure is defined in the
General Provisions [60.2] and in
the standards [60.481].
Table 3.
Emission and Control Efficiency Factors Used in Estimating VOC Emissions
for a Process Unit
Valves (Gas/Vapor)
Valves (Light Liquid) . . .
Pumps (Light Liquid)
Compressors
Pressure Relief Valves (G
Sampling Connections .
Open-Ended Lines
Equipment Type
(Service)
i as/Vapor)
Emission
Factor
(kg/hr)
00056
0 0071
00494
0 2280
01040
0.0150
00017
Estimated
Control
Efficiency
0.73
0.58
0.61*
1.00
1.00
1.00
1.00
"Average estimated control efficiency for pumps complying with leak detection and repair program.
SOURCE: Fugitive Emission Sources of Organic Compounds Additional Information on
Emissions, Emission Reductions, and Costs. U.S. Environmental Protection Agency. 1982.
A specific clarification was added to
the SOCMI standards on this last
point. The addition or replacement of
equipment such as valves or pumps
for the purpose of process improve-
ment does not of itself constitute a
modification. More simply stated,
this modification provision is not trig-
gered merely because equipment
components have been added or
replaced to keep the process
operating efficiently.
Reconstruction is determined solely
on the basis of capital costs
expended on an affected facility. A
facility is reconstructed if the fixed
capital cost of the components
replaced in the existing facility
exceeds 50 percent of the fixed
capital cost of constructing an
entirely new facility. The key concept
here is "affected facility." Since the
affected facility consists solely of
fugitive emission sources, other
process sources and equipment are
not included in the cost analysis.
Reconstruction determinations are
generally evaluated on a case-by-case
basis [60.15].
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3. Fugitive Emission
Sources
The term fugitive emissions in this
context means the loss of VOC
through sealing mechanisms
separating process fluid from the
atmosphere. Fugitive emissions are
also referred to as equipment leaks
and come fi;om the hundreds or
thousands of valves, pumps, com-
pressors, pressure relief devices,
open-ended, valves or lines, sampling
connection systems, and flanges and
other connectors within a processing
plant. As shown in Figure 1, they
comprise a large percentage of total
VOC emissions in the industry (about
35 percent) leven though the emis-
sions on a "per component" basis
may be small.
The techniques used to control
fugitive VOC emissions are quite
different frqm those used to control
process emissions, due in large part
to the fact that process emissions
are generally vented from a definable
point or stack, while fugitive
emission sources are more diffuse.
Combustion control techniques are
generally used in controlling process
emissions. No single control tech-
nique is applicable to the control of
all types of [fugitive emissions, nor is
a single emission limit universally
applicable. Each type of fugitive
emission source must be considered
separately in establishing
appropriate, applicable control tech-
niques. The following discussion
describes each of these sources with
respect to the origin and control of
potential emissions.
Valves
Valves, among the more common
elements in the chemical plant, are
available in numerous designs for
widely varying applications: gate,
globe, control, plug, ball, check,
diaphragm, and relief. Most of these
designs (check and relief valves
excepted) have a valve stem which
operates to restrict or to open the
valve for fluid flow. Typically the
stem is sealed by a packing gland or
O-ring to prevent the leakage of
process fluids to the atmosphere.
Packing glands are most commonly
used and a wide variety of packing
materials are available to suit most
operational requirements of tempera-
ture, pressure, and compatibility.
Process Sources
Non-Process Sources
Air Oxidation
Processes
t f ;'* i'* t;^ : |*;\ Equipment
-.' * * ป "-< , -'*'.'' A Leaks
.%<>%;. V/*->V'*V\P5*)
Other
Reactor [
Processes
(6%) ;
Storage of
Organic Liquids
(8%)
Secondary Sources
(5%)
Figure 1. Contribution of Source Subcategories to Total SOCMI
VOC Emissions
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O-rings are much less common
because of design and materials
limitations. With time and prolonged
use, both the packing gland and
O-ring fail, resulting in VOC
emissions.
Repair techniques range from simple
on-line maintenance to complex
techniques. Basic repairs that can be
performed on a valve while it remains
in place and in service include
tightening or replacing bonnet bolts,
and tightening packing gland nuts.
These valve components are illustrat-
ed in Figure 2.
However, on-line repair techniques
are not always applicable or effective
in reducing emissions. For example,
operational or safety requirements
may preclude the repair of valves by
simple means. Other valves simply
cannot be repaired effectively on-line
or easily removed from service. In
some instances, repair of valves can
be effected through more
sophisticated repair techniques.
Though relatively expensive, sealant
injection has been proven effective in
petroleum refining applications in
California, where complete
elimination of VOC leaks has been
mandated. In cases where
maintenance or repair of valves is not
possible, valve replacement may be
required.
Valve designs that have little or no
potential for leaking of process fluids
are referred to as "leakless" or
"sealless." Two examples are
bellows sealed valves and diaphragm
valves. Bellows seals are the most
effective gland seal mechanism for
valves and have been used primarily
in the nuclear power industry, where
their relatively high cost can be
justified by stringent safety require-
ments. A typical design of a bellows
seal is shown in Figure 3.
Packing
Gland
Packing
Figure 2. Primary Valve Maintenance Points
Bellows
Body Bonnet
Figure 3. Typical Design of a Bellows Seal
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Diaphragm
Disk
Stem
Diaphragm
Rgure 4. Typical Designs of Diaphragm Valves
Diaphragm valves use a diaphragm of
some appropriate material to seal the
process fluid from the stem of the
valve. In some designs, the dia-
phragm acts as the flow control
element as well as the sealing
mechanism. Diaphragm valves, how-
ever, may be a source of fugitive
emissions if the diaphragm fails. Two
typical designs of diaphragm valves
are shown in Figure 4.
Pumps
Pumps are integral pieces of equip-
ment in most chemical processes,
providing the motive force for trans-
porting liquids throughout a plant.
The centrifugal pump is the chief
design used in SOCMI, but other
pump types are also used. Packed
seals and mechanical seals are
commonly used to prevent leakage of
process fluid to the atmosphere
where the moving pump shaft meets
the stationary casing.
Possible Leak
Area
Pump Stuffing Box
-Packing Gland
Figure 5. Typical Design of a Packed Seal
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Packed seals are used on pumps
with either reciprocating or rotating
shafts. Specially selected packing
materials (chosen on the basis of the
process materials and environment)
are compressed into a "stuffing box"
in the pump casing and retained by a
packing gland, resulting in a tight
seal around the shaft. Figure 5
shows an example of a packed seal.
Lubrication must be applied to
prevent excessive heat generation
from friction between the moving
shaft and the stationary packing.
Pumps with packed seals have a
greater leak potential than do pumps
with more sophisticated sealing
mechanisms. Leaks from packed
seals typically result from the
degradation of the packing. These
leaks can often be reduced by
tightening the packing gland. But at
some point, the packing will have
deteriorated so much that it must be
replaced. In most cases, pump pack-
ing can be replaced only when the
pump is out of service.
Mechanical seals are used to seal
pumps with rotating shafts only. A
variety of designs are in common
use; all have a lapped seal face
between a stationary element and a
rotating seal ring. The leakage of
process fluid from the seal is mini-
mized by maintaining close toler-
ances on the interface between the
shaft and the sealing mechanism.
Figure 6 shows the basic design of a
single mechanical seal.
Since a mechanical seal also may
leak occasionally, redundant sealing
mechanisms can be used. For
instance, a single mechanical seal
Pump
Stuffing
Box
Gland
Ring
Shaft
Rotating
Seal Ring
Figure 6. Basic Design of a Single Mechanical Pump Seal
may also have a packed seal as an
auxiliary sealing mechanism to
reduce fugitive emissions. The same
purpose might also be accomplished
with a dual mechanical seal arrange-
ment, either back-to-back or tandem,
as shown in Figure 7. In the back-to-
back arrangement, a barrier fluid
(also referred to as a seal or buffer
liquid) circulates between the two
seals. The barrier fluid pressure is
maintained above the pump operat-
ing pressure. As a result, leakage is
normally of the barrier fluid across
the primary seal into the process
fluid and across the secondary seal
to the atmosphere. The tandem
arrangement basically has a single
seal backed up by another single
seal; both seals face the same
direction. The barrier fluid is
circulated through the space
between the seals.
In general, mechanical seals have the
advantage of low leak potential.
However, their repair can be both
costly and time consuming. To repair
a leak from a pump equipped with a
mechanical seal, the pump must be
taken off-line and dismantled. In
addition, care must be taken to
minimize emissions when dismantl-
ing the pump.
In addition to these pump types and
seal designs, there are several "seal-
less" technologies available. Three
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Possible Leak
Into Sealing
Fluid /}
Fluid End /
\/
Primary
Seal
V
Secondary
Seal
Back-to-Back Arrangement
Seal Liquid
Out In
(Top) (Bottom)
Fluid
End
Primary
Seal
^Secondary
Seal
Tandem Arrangement
Figure 7. Typical Arrangements of Dual Mechanical Pump Seals
designs have been applied in SOCMI
where leakage cannot be tolerated.
The canned-motor pump is a shaft-
less design in which the pump
bearings run in the process fluid. The
motor rotor housing and pump
casing are interconnected. Dia-
phragm pumps use a flexible dia-
phragm as the driver for moving the
fluid; as a result, seals and packing
are not exposed to the process fluid.
Magnetic-drive pumps also have no
seals in contact with the process
fluid; the impeller in the pump casing
Is driven by an externally mounted
magnet coupled to the motor.
Compressors
Compressors transport gases
throughout a process unit in much
the same manner that pumps
transport liquids. They are driven by
rotating or reciprocating shafts.
Thus, the sealing mechanisms for
compressorjs are similar to those for
pumps, i.e.,jpacked and mechanical
seals. Agair^, it is the sealing
mechanism! that is the greatest
potential sojurce of fugitive VOC
emissions. Packed seals are
generally restricted to reciprocating
compressors where mechanical seal
designs cannot be used. Leakage
from packed seals may be reduced
by tightening the packing gland. On
some reciprocating compressors
(particularly newer compressors), the
distance piece, which is the housing
connecting the compressor cylinder
and the drive crankcase, can be
vented to a control device to treat
any leakage through the packing. On
older models, however, this practice
may not be possible without
recasting the distance piece to
accommodate the vent line.
The mechanical seals used on
compressors reduce but do not
eliminate leakage of the process
fluid. The types of seals commonly
used on compressors include:
Labyrinth, comprising interlocking
teeth to restrict flow
Restrictive ring, comprising
multiple stationary carbon rings
Mechanical contact, similar to the
mechanical seal for pumps
Liquid film, employing an oil film
between the rotating shaft and
stationary gland.
These mechanical seals, as shown in
Figure 8, can be vented in various
ways to a control device for the
elimination of VOC which may leak
from the process.
The repair of mechanical seals
requires removing the compressor
from operation. Since compressors
in SOCMI do not typically have
spares, immediate repair may not be
practical or possible without a
process unit shutdown. Optional
control techniques for controlling
emissions from these mechanical
seals are available, such as venting
the barrier fluid system or the seal to
a control device.
10
-------
Port May Be Added
For Scavenging Or
Inert-Gas Sealing
Internal
Gas Pressure
Atmosphere
Labyrinth Seal
Internal
Gas Pressure
Clean Oil In
Pressure
/ Breakdown
Stationary Seat \ N
Carbon Ring
Oil Out
Atmosphere
Contaminated
Oil Out
Single Mechanical Seal
Port May Be
Added For
Sealing
Internal
Gas
Pressure
Scavenging
Port May Be
Added For
Vacuum
Application
Restrictive Ring Seal
Clean Oil In
Internal
Gas
Pressure
ihere
Contaminated
Oil Out
Oil Out
Liquid Film Seal
Figure 8. Typical Designs of Mechanical Compressor Seals
Reprinted courtesy of the American Petroleum Institute.
11
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Pressure Relief Devices
Pressure relief devices are safety
devices commonly used throughout
SOCMI to prevent operating
pressures from exceeding the
maximum allowable working
pressures of the process equipment.
The most common pressure relief
device is a spring-loaded pressure
relief valve (PRV), such as that shown
in Figure 9. The PRV is designed to
open when the operating pressure
exceeds a set pressure, and to reseat
after the operating pressure has
decreased to below the set pressure.
Leaks of VOC from pressure relief
devices occur through the valve seat
as a result of the improper reseating
of the valve after a release, and of the
process being operated at or near the
valve set pressure. In addition,
leakage is possible from seating
element degradation over a period of
time. Leakage as a result of improper
reseating is often referred to as
"simmering" or "popping." Reseating
problems can be resolved by soft-
seat technology, which consists of
an elastomeric O-ring to provide an
improved seal when the valve reseats
after an overpressure release.
Rupture disks (RD) are pressure relief
devices that allow no fugitive
emissions unless the disk is
ruptured. Excessive pressure causes
the disk to burst. Rupture disks can
be used in conjunction with PRVs to
eliminate potential fugitive emissions
from the PRVs. When mounted
upstream of a relief valve, fugitive
emissions are blocked prior to the
potential leak source, the valve seat.
Fugitive emissions from PRVs can
also be eliminated by routing the
discharge of the PRV to an
appropriate control device. The most
common example of this procedure
is a flare header.
Tension-adjustment
Thimble
to
Atmospheric
Vent
Seat
_Pressure Relief Valve r-\_
Rupture Disk Device *-
Connection for
Pressure Gauge
& Bleed Valve
CI3
From System
Figure 9. Typical Design of a Pressure Relief Valve Mounted on
a Rupture Disk Device
12
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Process Line
0
Sample I
Container!
X
Sample
Container
Figure 10. Examples of Closed Purge Sampling Systems
Open-Ended Valves and Lines
Open-ended valves and lines are
found throughout chemical plants to
drain, purge, or vent a process fluid
to the atmosphere, a container, or to
a closed system for recovery.
Process fluids may be emitted
directly to the atmosphere through
incompletely closed or faulty valve
seats. To prevent such atmospheric
emissions, a pipe plug, cap, or blind
flange can be installed on the open
end of the valve or its drain pipe.
Another option is using a second
valve in a "block-and-bleed"
arrangement. In these cases it is best
to close the valve upstream first so
that no process fluid will be trapped
between the two valves, as this may
cause leakage of VOC as a result of
temperature expansion.
Sampling Connection
Systems
Periodic checks of process
operations are often made by
sampling process streams to
evaluate the performance of reactors,
distillation units and other
operations, and to verify the purity
and composition of feedstocks,
intermediates, and products. Process
fluids already in the sample lines
must be purged prior to sampling in
order to obtain a representative
sample for analysis. The purged fluid
is often merely drained onto the
ground or into the sewer drains,
releasing VOC into the atmosphere.
Sampling emissions can be reduced
by using a closed purge sampling
system which returns the purged
VOC back to the process, or by
routing the purged VOC to a control
device. Two examples of closed
purge sampling systems are shown
schematically in Figure 10. In one
case, the sample is collected as a
side-cut stream from the purge
stream, which flows around a flow-
restricting device (such as an orifice
or valve) in the main proess line. In
the second example, the purge is
directed through the sample
container. Closed purge sampling
may also be done with partially
evacuated sample containers.
Flanges and Other
Connectors
In terms of total numbers, flanges
and other connectors comprise the
single largest class of fugitive
emission sources in a process unit.
Flanges are gasket-sealed junctions
used to mate pipe and other
equipment such as valves, vessels,
and pumps. Flanges may be used in
pipe 50 mm (0.2 inches) or greater in
diameter. Other connectors, such as
13
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Table 4.
Emission Factors for Fugitive Emission Sources
Equipment Type
Volva . ,
ProssurB Relief Valve . . ......
Flange
Process Fluid
Gas/Vapor
Light Liquid
Heavy Liquid
, Light Liquid
Heavy Liquid
Gas/Vapor
Emission Factor
.(kg/hi)
0.0056 ~~|
6.0071
p.00023j
0.0494 "I
0.0214 J
0.228
0.1040
0.0150
0.0017
0.00083
Percent of Total
VOC Fugitive
Emissions
47
16
4
g
3
6
15
100
SOURCE: Fugitive Emission Sources of Organic Compounds Additional Information on
Emissions, Emission Reductions, and Costs.
threaded connections and nut-and-
ferrule connections, are used on
smaller lines and perform the same
function as flanges.
Flanges and other connectors may
leak VOC as a result of improperly
selected gaskets, poorly assembled
flanges, poorly assembled nut-and-
ferrule combinations, or poorly
assembled pipe connections.
However, the major cause of VOC
leakage from flanges and other
connectors is the deformation of
sealing surfaces as a result of
thermal stress. In some cases,
merely tightening the bolts on a
flange is effective in sealing a VOC
leak. Generally, however, correction
of a leaking connector by, for
example, replacing a flange gasket
requires partial or complete
shutdown of the process unit.
Comparing Emissions from
Different Types of Fugitive
Emission Sources
There are two ways to compare
emissions associated with the
fugitive emission sources described
above. First, the emissions from
each type of fugitive source (or
component) can be considered.
Individual emission factors for
components are shown in Table 4.
This Table indicates that compressor
seals and pressure relief devices are
the most significant VOC emitters,
and that flanges are the least
significant VOC emitters on a "per
component" basis.
However valves, which have one of
the smaller emission factors, are
responsible for 47 percent of total
VOC emissions because of their
relative abundance. Compressors,
which have a larger emission factor,
represent only a small portion of the
total emissions for the unit.
14
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4. Standard Provisions
Each type of equipment is covered
by specific provisions in the
standards. For some types of
equipment such as open-ended lines,
the choice of controls is limited by
the standards to a single technique.
For other sources, several control
options are allowed, providing that
the desired emissions reduction is
achieved. For sources such as
valves, a basic standard has been
written, but several options are
allowed as long as each achieves an
equivalent level of control. Finally,
since new emissions reduction
techniques may yet be developed,
the standards are structured to
permit the use of equivalent means
of emissions reduction not already in
the standards. The source-specific
requirements will be discussed
below. There are, however, a number
of provisions and concepts which
apply to all or several equipment
types, or to the process unit as a
whole. They include:
Delay of repair provisions
Provisions for "leakless"
equipment
Provisions for closed vent
systems
Equivalency determination
provisions
Provisions for equipment in
vacuum service
Reporting.
Delay of Repair Provisions
Each of the standards for the
individual equipment types specify a
schedule for repairing the equipment
once a "leak" is detected. Precisely
what constitutes a "leak" varies from
one equipment type to another.
However, the schedule for repair
typically requires that an attempt be
made to repair the leak within five
days of detection, and that repairs be
successfully completed within 15
days of detection.
This compliance schedule is not
unreasonable providing the repairs
can be effected without requiring
that the entire process unit be shut
down. This is often possible, but
some fugitive emission sources may
not be repairable by on-line
repair techniques. Under certain
conditions, specific provisions of the
standards permit a repair delay
[60.482-9].
In general, a repair delay is allowed
for any piece of equipment if it is
technically infeasible to accomplish
the repair without a process unit
shutdown. Repair delay is also
allowed for equipment which can be
isolated from the process and
removed from VOC service. Where a
repair is delayed due to "technical
infeasibility," the repair must be
made before the end of the next
process unit shutdown.
These delay of repair provisions
apply to any fugitive emission source
in a facility. There are additional
delay of repair provisions for valves
and pumps under certain
circumstances. These additional
provisions are addressed in the
discussions on valves and pumps.
There are strict recordkeeping
requirements for delay of repair of
leaking equipment. Records for the
following must be made and the
records maintained for at least two
years:
The reasons for the delay
Signature of the owner or operator
(or designee) who determined that
a process unit shutdown would be
necessary to repair the leak
Expected date of repair
Dates of process unit shutdowns
while the equipment leak
remained unrepaired
Date of successful repair.
15
-------
Provisions for Leakless
Equipment
Certain valves, pumps and
compressors are exempt from most
of the monitoring and repair
requirements. Examples of
equipment to which leakless
technology provisions apply include
diaphragm valves and canned pumps.
A valve, pump or compressor
designated for no detectable
emissions must operate with
monitoring instrument readings of
less than 500 ppmv above
background. Upon initially
determining that the equipment
qualifies for no detectable emissions
status, the identification number of
the component must be entered into
a permanent log. After the initial
determination is made, the
equipment must be monitored
annually and must continue to
exhibit instrument readings of less
than 500 ppmv above background
[60.482-2(3), 482-3(1), and 482-7(f)].
Closed Vent Systems
Several portions of the standards
require the use of a closed vent
system coupled with a control
device. A closed vent system
consists of the piping, connections,
and flow-inducing devices (e.g., fans,
compressors) necessary to transport
gas or vapor from a piece of equip-
ment to a control device. Systems
which are open to the atmosphere
are not considered closed vent
systems. Control devices include
enclosed combustion devices, vapor
recovery systems, and flares. The
design and operational requirements
for each of these systems are
specified in the standards [60.482-10].
Equivalency Determinations
The standards for control of fugitive
emissions of VOC incorporate a
number of techniques ranging from
work practices (e.g., leak detection
and repair programs) which achieve
only a degree of emissions reduc-
tion, to leakless technology (e.g.,
sealed bellows valves and canned
pumps). However, there is always the
possibility that new techniques may
be developed that achieve emission
reductions equivalent to those which
would be achieved under the
standards. ;
The fugitive jemissions standards
account for this situation in the
equivalency [determinations provision
[60.484]. An equivalent means of
emission reduction is allowed
through a petitioning procedure, not
unlike the standards-setting process.
The owner or operator of a SOCMI
plant or the hnanufacturer of control
equipment may petition EPA for an
equivalency determination by
documenting the equivalency of the
technique in reducing emissions. The
petitioning procedure is available for
all equipment, design, operational,
and work practice standards.
The owner or operator desiring an
equivalency ^determination must
present data on emissions and
control effectiveness to support a
determination. In each instance,
emission reductions must at least
equal the control techniques required
by the applicable standard. In
requesting an equivalency determina-
tion, the owner or operator must
commit in writing to the equivalent
means of emission reduction, if
granted. The evidence presented to
date on the required control
techniques will then be assessed. If
approval appears justified, a public
hearing on the equivalency deter-
mination will be requested. Finally,
based upon evaluation of the request
and input from the public hearing,
EPA may (a) grant approval of the
control technique as equivalent, (b)
approve the control technique as
equivalent with conditions, or (c)
deny the equivalency request.
Any determination of equivalence
granted through the petitioning
procedure is proposed and
promulgated in the Federal Register.
Such "equivalent" practices then
become adopted as appropriate
means of emissions reduction for
fugitive VOC emissions control under
the Clean Air Act. Any owner or
operator may then elect to use the
equivalent practice in his process
units, without further equivalency
determination.
Vacuum Service
Equipment in vacuum service is
exempt from the monitoring and
equipment requirements of the
standards. Equipment is considered
to be in vacuum service if it operates
at an internal pressure at least 5 kPa
below ambient pressure. Records
must be kept for equipment in
vacuum service.
16
-------
Reporting
To comply with the standards for
fugitive VOC emissions from the
SOCMI, four types of reports must be
submitted to EPA [60.8 and 60.487]:
Routine semiannual reports
Notifications of construction and
startup
Notifications of performance
testing to demonstrate
compliance
Reports of performance test
results.
The reporting requirements may
change slightly where the EPA has
delegated enforcement authority to a
state and has approved alternative
reporting requirements.
The initial semiannual report must be
submitted within six months after
the initial startup date of the process
unit. It must identify the process unit
and contain the following information
about equipment in the process unit:
The number of valves subject to
the leak detection and repair
provisions
The number of pumps subject to
the monthly leak detection and
repair program, and to the dual
mechanical seal requirements
The number of compressors,
excluding those designated NO
DETECTABLE EMISSIONS (NDE)
and those with seals connected
to a closed vent system and
control device.
Subsequent semiannual reports must
provide an accounting of leak
identification data for each month
during the reporting period. The
numbers of valves, pumps, and
compressors that were determined to
be leaking and the corresponding
numbers of those equipment types
not found leaking must be reported
for each month. .
The semiannual reports also include
a monthly accounting of the facts
explaining each delay of repair (if
applicable). The reasons for the
technical infeasibility of a process
unit shutdown must be reported if
that was a cause of a delay of repair.
The dates of any process unit shut-
downs during the semiannual report-
ing period are noted in the report as
well. Finally, if any information
reported in the initial semiannual
report changed during the current
semiannual period, these changes
must be noted.
According to the General Provisions
(40 CFR Part 60, Subpart A),
notification must be made of
construction and startup. There are
two other circumstances where
notification is required as stipulated
in Subpart VV. First, with respect to
certain options allowed for valves, an
owner or operator must give
notification at least 90 days prior to
implementing an option's provisions.
Second, EPA must be notified of the
schedule of initial performance
testing at least 30 days prior to
testing. The results of each test must
also be reported.
17
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5. Detailed Provisions
of the Standards
For each type of fugitive emission
source which is covered by the
standards there is a basic standard
and its associated leak definition,
there may be options or exclusions
from the standard, and there are
reporting and recordkeeping require-
ments. These will be discussed
below for each equipment type.
These sources and the reference to
the relevant standard in the Code of
Federal Regulations are:
Valves [60.482-7, 483-1, 483-2]
Pumps [60.482-2]
Compressors [60.482-3]
Pressure relief devices [60.482-4]
Sampling connection systems
[60.482-5]
Open-ended valves and lines
[60.482-6]
Miscellaneous sources [60.482-8]
Closed vent systems and control
devices [60.482-10].
Valves
The requirements for valves
described iii this section apply only
to valves in ;gas/vapor and light liquid
VOC service. The requirements for
valves in heavy liquid service are
minimal and are described under
Miscellaneous Sources, below.
Requirements. The valve standard is
a work practice standard based on a
monthly leak detection and repair
program. While the concept of the
program is rather straightforward,
there are numerous requirements for
monitoring,: identification of leak
sources, repair, and recordkeeping. In
its simplest form, the standard
requires monthly monitoring of all
valves with a portable VOC analyzer
to identify sources that are leaking. A
valve is leaking if the instrument
reading at the leak interface (for
example, at the packing gland or at
the bonnet) is 10,000 ppmv or greater.
A valve identified as leaking must be
tagged for repair and repaired within
15 days of detection. An initial
attempt at repair must be made
within five days of detection.
Repair of a valve means reducing the
instrument reading below 10,000
ppmv. The recommended practices
for initial repairs include tightening
bonnet bolts, replacing bonnet bolts,
tightening packing gland nuts, and
injecting lubricant into lubricated
packing. Repair methods are not
restricted to these techniques. The
VOC purged from the equipment at
the time of repair should be collected
and recovered or destroyed at that
time.
If the repair cannot be made within
the allotted time period, the general
delay-of-repair provisions may apply
as well as the following valve-specific
provisions.
First, a delay of repair is allowed if
the VOC emissions resulting from
immediate repair would be greater
than the emissions resulting from
the equipment leak if allowed to leak
until the next process unit shutdown.
Furthermore, a delay of repair for
valves may be permitted beyond a
process unit shutdown if repair is
contingent upon valve replacement
parts, and if the replacement parts
which are otherwise adequately
stocked are not available due to
depletion through extraordinary
demand for replacements. This
provision provides some flexibility for
owners or operators facing
unscheduled shutdowns and parts
shortages through no fault or
negligence on their part.
The standards require that only
leaking valves be tagged. An owner
or operator may, however, choose to
identify those valves in the process
unit that require routine monitoring
(especially since only valves in VOC
gas/vapor and light liquid services
must be monitored under the rule).
Options. There are at least four
options to the basic standard for
valves. All are related to the monthly
leak detection and repair program.
Option 1 is the basic requirement of
the standard. It permits a quarterly
monitoring program of those valves
that have not leaked for two
consecutive monthly monitoring
periods [60.482-7(c)]. Only leaking
valves must receive monthly
attention.
Option 2 is not a work practice
standard; rather it is a performance
standard. In meeting and maintaining
a certain performance level, routine
monitoring and maintenance are not
required. The performance standard
requires that no more than 2 percent
of all valves (the composite total) in
gas/vapor and light liquid service can
leak at any given time. In lieu of
18
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Table 5.
Recordkeeping Requirements for Detected Equipment Leaks
When a leak is detected:
Instrument and operator identification numbers
Equipment identification number
Date of leak detection
When repairs are attempted:
Dates of each attempt to repair the leak
Repair methods used for each attempt at repair
Notation of failed repair attempt (if the maximum instrument reading after the repair
attempt is equal to or greater than 10,000 ppmv
When repairs are delayed more than 15 days:
The reasons for the delay
Signature of the owner or operator (or designee) who determined that a process unit
shutdown would be necessary to repair the leak
Expected date of repair
Dates of process unit shutdowns while the equipment leak remained unrepaired
Date of successful repair
monthly or quarterly monitoring,
initial and annual compliance tests
are used to demonstrate compliance.
All monitoring under this option
must be completed within one
calendar week. EPA must be notified
at least 90 days prior to the planned
performance test [60.483-1]. Failure to
maintain this performance level
constitutes a violation of the
standard. This is a significant
difference between Option 2 and
Option 1. Under Option 1, a violation
only occurs if the required
monitoring and maintenance is not
performed correctly.
Option 2 is best suited for well-
designed, low-leak process units.
EPA test results show that there are
many units that could meet such a
performance standard. The option
provides maximum flexibility in that
the owner/operator can determine the
means (equipment or work practice)
to achieve and maintain the per-
formance level.
Option 3 allows less frequent
monitoring if, in implementing the
basic requirements (Option 1), a level
of performance in which fewer than 2
percent of the valves are leaking can
be maintained for two quarters.
Under these circumstances, monitor-
ing can be performed on a semi-
annual basis. If the percentage of
leaking valves exceeds 2 percent, the
standard requires implementation of
Option 1. Option 3 may be reinstated
but to qualify, EPA must be notified
and the performance history (i.e.,
fewer than 2 percent leaking) must
again be demonstrated [60.483-2(b)
(2)].
Option 4 is a work practice which is
implemented much like Option 3. It
too is initiated with implementation
of the basic requirements (Option 1).
Option 4 permits annual monitoring if
the performance level of 2 percent or
fewer valves leaking is maintained for
five consecutive quarterly monitoring
periods. As with Option 3, the
standard requires implementation of
Option 1 if the 2 percent level is
exceeded. Upon notification to the
Administrator and demonstration of
performance, Option 4 can be
reinstated in the same manner as
Option 3, except that a five-quarter
period of 2 percent performance is
necessary before beginning annual
monitoring.
Option 4 and Option 2 appear to be
annual monitoring programs. But
there are some fundamental differ-
ences. Option 4 is an extension of
the basic standard's leak detection
and repair program through the
application of skip-period sampling
techniques. Skipping to annual moni-
toring is permitted, and is based on
demonstrated performance. Since it
is an extension of the basic standard,
exceedance of the 2 percent limit
again requires only that the basic
requirements of Option 1 be
reinstituted. On the other hand,
under Option 2, exceeding the 2
percent performance limit
constitutes a violation of the
standard.
Recordkeeping. Recordkeeping is a
key element in demonstrating com-
pliance with work practice standards.
Records on the valve leak detection
and repair programs that are part of
the SOCMI fugitive emissions stan-
dards must be maintained and avail-
able for inspection for two years. The
information that must be recorded
for all valve leaks is listed in Table 5.
These requirements apply to the
basic standard and all of the options.
Options 3 and 4 are based on a
demonstrated performance level,
thus they have additional record-
keeping requirements: the schedule
for monitoring, and the percentage of
valves found leaking during each
monitoring period.
Exemptions. Provided certain record-
keeping requirements are met,
exemptions from the routine
monitoring requirements are allowed
for valves designated as "leakless,"
"unsafe-to-monitor," or "difficult-to-
monitor." Leakless valves need only
be monitored annually, as described
earlier in this section.
A valve may be considered unsafe-to-
monitor if the owner or operator can
demonstrate that monitoring
personnel would be exposed to an
immediate danger or hazard as a
result of screening the valve. A plan
must be developed that provides for
monitoring as frequently as is practi-
cal. The plan, a list of the sources,
and the reasons for their listing must
be recorded [60.482(g)].
A valve is difficult-to-monitor if the
owner or operator can demonstrate
that monitoring personnel must be
elevated more than 2 meters (or
about 6 feet) above a support
structure to screen the valve. This
exemption is only applicable to
existing process units to which the
standards apply as a result of
modification or reconstruction.
Difficult-to-monitor valves must be
listed along with the reason(s) for
listing each valve. Also, a plan for
monitoring these valves as frequently
as practical (but at least annually)
must be recorded and implemented
[60.486(f) (2)].
19
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Pumps
The pump standard applies only to
pumps in light liquid VOC service. It
is a work practice standard calling
for monthly instrument inspections
and weekly visual inspections. A leak
from a pump is defined as a 10,000
ppmv or greater instrument reading
when using a portable VOC analyzer,
or as evidence of liquids dripping
from a pump seal observed during
the weekly visual inspections of each
seal.
The repair required by the pump
standard is the elimination of liquids
dripping from the seal and the
reduction of the instrument reading
below the 10,000 ppmv value. Pumps
in SOCMI processes are generally
installed in pairs, which allows one
to be used as a spare. This allows
continued operation during repair.
In addition to the general delay-of-
repair provisions, there is an addi-
tional delay-of-repair provision for
pumps. Repair of a chronic pump
leak may eventually warrant the
Installation of a dual seal system and
associated barrier fluid system, con-
nected to a closed vent system and
control device. In this event, the
repair may be delayed beyond the
15-day period until the installation
has been completed. The delay of
repair may not exceed six months.
Exemptions. Routine monitoring is
not required for sealless pumps,
some pumps with dual mechanical
seal systems, and some pumps with
enclosed seal areas. To be eligible
for an exemption, the dual
mechanical seal system must have a
barrier fluid system either:
With a degassing reservoir
connected to an accepted closed
vent system and control device, or
Operated at a pressure higher
than the pump stuffing box
pressure, or
That purges the barrier fluid into
the process with no VOC emis-
sions to the atmosphere.
The barrier fluid must be a heavy
liquid or a non-VOC, and the barrier
fluid system must have a sensor to
indicate failure of the seal, the barrier
fluid system, or both. The owner or
operator selects the type of sensor
to be used in the barrier fluid system
based on design considerations and
operating experience [60.482-2(d)].
Records must be maintained on the
design criteria for the barrier fluid
system sensor, including an explana-
tion of these criteria, changes to the
criteria, and reasons for the changes.
While pumps with these systems are
exempt from monthly instrument
monitoring, they must still be visually
inspected op a weekly basis for indi-
cations of liquids dripping from the
seal. For pumps so equipped, a leak
is detected by the sensor (indicating
failure of the seal, barrier fluid
system, or both) or by visual evi-
dence of liquids dripping from the
seal. Upon detection of a leak, the
same repair requirements for the
basic standard apply for pumps with
dual mechanical seal systems.
Pumps equipped with an enclosed
seal that are vented to a closed vent
system/control device have an
exemption from the monthly monitor-
ing requirements of the basic pump
standard. However the recordkeeping
requirements for these pumps are
the same as the requirements for
pumps complying with the basic
standard. There are, however, addi-
tional requirements for the closed
vent system/control device
[60.482-2(f)J.
Compressors
Rather than relying upon work
practices, the standards for
compressors are directed toward the
installation of equipment, since
spare compressors are not generally
used in SOCMI. The compressor
standard requires a seal system to be
installed to prevent VOC emissions
to the atmosphere. The seal system
must include a barrier fluid system
and a sensor, such as a pressure
indicator or level indicator, which will
indicate a failure of the system.
Failure of the seal or barrier fluid
system, as indicated by an audible
alarm or through daily inspections of
the sensor, is indicative of a leak and
requires repair. The owner or opera-
tor must determine the specific
criteria which indicates a failure of
the seal system. The design details
of the barrier fluid system and any
changes to the system must be
recorded in a log that is available for
inspection.
After a leak is detected repairs must
be effected as soon as practicable on
the seal or barrier fluid system, or
both. The first attempt at repair must
be within five days of leak detection;
repair must be completed within 15
days of leak detection, unless a delay
of repair is warranted.
In addition to installing this equip-
ment, certain operational require-
ments for the barrier fluid system are
the same as the requirements for
pumps.
Exemptions. The standard for
compressors allows three
exemptions:
Compressors equipped with
enclosed seal areas connected
through a closed vent system to
an acceptable control device are
exempt from the control equip-
ment requirements provided the
arrangement captures, transports,
and treats any VOC leakage from
the seal.
Compressors complying with the
NDE limit are also exempt from
the equipment requirements,
provided they meet certain
testing, recordkeeping, and
reporting requirements.
20
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Certain existing reciprocating
compressors may be completely
exempt from compliance with the
standard. The linear shaft motion
of reciprocating compressors
makes sealing extremely difficult.
Most newer reciprocating
compressor designs provide for
venting of the distance piece
(between the compressor and
drive) in accordance with ASME
Codes. (Venting the distance
piece through a closed vent
system to a control device would .
essentially meet the requirements
of the first exemption.) Older
designs, however, may not
incorporate this venting capability.
An exemption is allowed for such
older compressors, provided the
owner or operator can
demonstrate that the distance
piece must be recast (not merely
replaced) with a vent port or that
the entire compressor would have
to be replaced to comply with the
standard.
Pressure Relief Devices
These standards apply only to
pressure relief devices in gas/vapor
service; other pressure relief devices
are covered by the standard on Mis-
cellaneous Sources. The VOC
emitted to the atmosphere during
unplanned process upsets are not
considered fugitive emissions, and
are not subject to the standard.
The standard is a performance
standard with a limit of no detectable
emissions (NDE). NDE is defined as a
difference of 500 ppmv or less
between the instrument reading at
the leak surface and the reading for
the background. In addition there
must be no visible evidence of
leakage. A test of each pressure
relief device is required at least
annually to verify compliance. No
specific equipment or operational
requirements are given in the regula-
tion; the owner or operator is free to
select any means of controlling the
fugitive emissions that will meet the
NDE limit. However, an exceedance
of the NDE limit is considered
noncompliance. Connection of the
discharge of a pressure relief device
through a closed vent system to a
control device would effectively
eliminate emissions from a relief
device; this practice is specifically
exempt from the annual monitoring
requirements for pressure relief
devices.
Additional Requirements. When
emergency releases through the
pressure relief device do occur, leaks
may result from a poorly seated valve
or the loss of seal in a rupture disk.
The repair requirements associated
with this standard refer to returning
the relief device to a condition of
NDE after the device is activated. For
example, replacing the failed rupture
disk or reseating the relief valve
properly would generally return the
pressure relief device to an NDE
status. This repair must be made
within five days of the release, and
the pressure relief device must be
monitored at that time to ensure its
return to a condition of NDE.
Meeting this time constraint is
facilitated if a dual relief valve
arrangement is used.
Recordkeeping for all equipment
designated for NDE is minimal. Only
the identification numbers of the
pressure relief devices, the dates,
and results (that is, the maximum
instrument reading at the leak
interface and the instrument reading
of the surroundings) of each com-
pliance test need to be recorded and
available for inspection. The results
of monitoring after each overpres-
sure release are considered test
results and thus must be recorded.
Open-Ended Valves or Lines
Emissions from open-ended valves or
lines (not pressure relief devices)
must be eliminated through the use
of a pipe cap, plug, blind flange, or a
second valve. The open end must be
sealed at all times, except during the
operation of the open end, such as
during sampling, draining, or vessel
purging.
If a second valve is used to close the
open end, the valve closest to the
process must be closed first. This
procedure ensures that the space
between the two valves will not
contain fluid, creating a leak
potential if the trapped fluid expands
with increasing temperature.
Sampling Connection
Systems
A closed purge system or a closed
vent system must be used on all
sampling connection systems.
Certain operational requirements
also apply. For example, when taking
liquid samples in a process unit,
some process fluid would typically
be bled from the sample lines into a
waste container before collecting the
sample for analysis. To comply with
the rule, this "waste" material and
any unused sample (after analysis)
must either be returned to the
process, or be treated in a control
device. One option is to capture and
transport any purged fluid through a
closed vent system to a control
device. This option is particularly
useful for gaseous VOC sampling
systems. Another alternative is the
use of In situ (in-line or nonextractive)
sampling systems, which are
specifically exempt from the
standard.
21
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Miscellaneous Sources
Miscellaneous sources are those
fugitive emission sources with a
somewhat smaller potential to leak
VOC to the atmosphere. They
include:
Pumps and valves in heavy liquid
service
Pressure relief devices in liquid
service
Flanges and other connectors.
There is no established emission
reduction plan for these sources.
They need only be monitored with a
portable instrument if a VOC leak is
suspected by visual, audible, sense
of smell, or other means. Potential
leaks from miscellaneous sources
are verified through instrument
monitoring using an instrument
reading of 10,000 ppmv as the leak
definition.
Any verified leak must be repaired so
that the instrument reading is
reduced below the 10,000 ppmv leak
definition. Typical on-line repair tech-
niques include tightening packing
glands, reseating pressure relief
valves, or tightening flange bolts and
screwed connections. As with all
source leaks, repair must begin as
soon as is practical, with an initial
attempt within 5 days of leak
detection, and repair completed
within 15 days.
Closed Vent Systems and
Control Devices
Closed vent systems must be
operated with NDE to the
atmosphere (i.e., the difference-in
instrument readings between the
leak interface and the surroundings
is less than 500 ppmv, and there is
no visible evidence of leakage). The
closed vent system and its control
device must be monitored for
compliance initially and at least
annually thereafter.
Three options are available for VOC
emission control devices:
Vapor recovery systems
Enclosed combustion devices
Flares.
All three options are capable of
achieving VOC emissions reductions
of at least 95 percent. But since each
is very different in terms of design
and operating characteristics, there
are separate requirements for each.
Vapor recovery systems include
devices which recover VOC without
destroying them. Adsorbers,
absorbers, and condensers are all
examples of vapor recovery systems.
Any vapor recovery system achieving
a VOC removal efficiency of at least
95 percent is an allowable control
device under the standards.
Enclosed combustion devices, such
as incinerators, boilers, and process
heaters, are destructive control
devices. At least 95 percent
efficiency in removing VOC is
required for enclosed combustion
devices. In lieu of demonstrating the
95 percent efficiency, an owner or
operator may elect to comply with .
the requirements by maintaining an
operating temperature of 816ฐC
(1500ฐF) and a residence time of 0.75
seconds.
Flares may also be used to comply
with the standard for control devices,
provided some important design and
operational criteria are met: it must
be designed and operated with
smokeless federation, and a flame
must be present at all times.
Smokeless operation means that
visible emissions may be present for
no more than a cumulative five
minutes during any consecutive two-
hour period, using EPA Reference
Method 22.
There are specific requirements for
flares relating to the velocity and the
net heating value of the gas; these
must be periodically tested. The net
heating value is computed based
upon chemical analyses and/or
established data. Concentrations of
individual components in the flared
gas are determined using gas
chromatography as prescribed in
Reference Method 18 and ASTM
D2504-67 (reapproved 1977).
Specific monitoring requirements
have been established for flares used
to comply with the standards. The
presence of a flare pilot flame must
be monitored at all times using a
thermocouple or equivalent sensor.
Monitoring is also required for the
other control devices, but no specific
requirements are listed in the regula-
tion. Owners or operators must
select an appropriate parameter to
monitor that ensures the control
device is maintained and operated
within the specified design. Several
options for monitoring methods for
control devices are discussed in the
Background Information Document
for the promulgated standards.
The recordkeeping requirements for
control devices focus on design
specifications and periods when the
device is not in service. For each
control device, the following
information must be recorded and
maintained:
Schematics, drawings, and design
specifications
Dates and changes to the design
specifications
Parameters) monitored with a
rationale for the selection of each
parameter
Dates for periods during which the
control device was not operating
Dates of startup and shutdown of
the control device.
22
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6. Leak Detection
Methods
The detection of leaks is a critical
aspect of complying with the fugitive
VOC emissions standards. All leak
detection procedures must be in
accordance with the specific require-
ments detailed in the standards
[60.485] and in Reference Method 21
(located in Appendix A of 40 CFR 60).
Noninstrument Methods
Noninstrument leak detection can be
done visually, audibly, or by sense of
smell. The standard for
miscellaneous sources (pumps and
valves in heavy liquid service;
pressure relief devices in liquid
service; and flanges and other
connectors) cites the use of these
noninstrument techniques for deter-
mining leaks. The standard for
pumps in light liquid service relies
upon weekly visual inspections for
determining liquid leaks dripping
from the seal.
Soap bubble testing, or soaping, is
one noninstrument technique which
Reference Method 21 cites as an aid
to screening certain sources for VOC
leaks. Soaping is only applicable to
sources with nonmoving seals, with
moderate surface temperatures,
without large openings to the atmos-
phere, and without evidence of liquid
leakage. Thus, soaping cannot be
used to screen pump seals, sources
with surface temperatures above the
boiling point or below the freezing
point of the soap solution, open-
ended lines or valves, or pressure
relief valves.
Basically, the technique involves the
application of a soap solution around
the potential leak surface such as a
valve stem packing gland. A potential
leak is indicated by the appearance
of bubbles. The leak must then be
verified using the instrument tech-
niques given in Reference Method 21
and the applicable standard [60.485].
The absence of bubbles is indicative
of NDE or no leak. However, soaping
is only a supplemental method for
screening sources prior to
instrument monitoring.
Instrument Techniques
Instrument techniques include fixed
point monitors and portable VOC
analyzers. Based upon an evaluation
by EPA, fixed point monitoring
systems (or area monitors) may be
subject to outside influences such as
meterological conditions. Further,
they are not as effective in deter-
mining leaks as individual compo-
nent screening with portable
monitors. Area monitors, however,
are useful in monitoring continuously
for the appearance of large leaks.
For the SOCMI standards, a leak is
identified if an instrument measure-
ment is above one of two levels. In
routine monitoring for leak detection,
an instrument reading of 10,000
ppmv or greater indicates a leak. This
should trigger several actions:
tagging, recording, and repairing. The
10,000 ppmv leak definition is
applicable to pumps (light liquid
service), and valves (gas/vapor and
light liquid services). NDE is also
determined with instrument
screening. A reading of 500 ppmv or
greater above background is a leak
and violates the performance
standard.
Compliance Monitoring Program. For
any affected process unit, com-
pliance with the fugitive emission
standard must be demonstrated
within 180 days after the initial
startup of the process unit. A leak
detection program, then, must be
designed in advance of the startup
so that it can be fully implemented
23
-------
within the six-month period. As part
of the program design, instrumenta-
tion should be promptly acquired so
that operating personnel can begin
training. These instruments include
portable VOC analyzers that meet the
performance criteria specified in
Method 21. In addition, calibration
gases for the selected monitoring
system (i.e., instrument and calibrant)
should be procured well in advance
of implementing the program so that
calibration and monitoring techni-
ques can be mastered prior to
routine monitoring.
Portable Instruments. Reference
Method 21 describes the procedure
for leak detection using a portable
analyzer and specifies the requisite
performance characteristics for the
analyzer. The instrument detector
must respond to the VOC that is to
be measured. The instrument
may be calibrated using one easily-'
obtainable reference gas in order to
measure the VOC if the relationship
between the calibration gas and the
VOC (the so-called response factor)
is known. Response factors differ for
different combinations of
compounds and instruments. A
response factor of less than 10 is
required for the individual
compounds, if a measured or pub-
lished response factor is greater than
10, it may be necessary to use a
different type of analyzer to obtain
reasonable precision.
The types of detectors that may be
used include catalytic oxidation,
flame ionization, infrared absorption,
and photoionization. The instrument
must:
Sample continuously at a nominal
rate of 0.5 to 3 liters per minute
Be intrinsically safe for use in an
explosive atmosphere
Have a scale readable to within 5
percent of the defined leak
concentration level.
Table 6.
Specifications and Performance Criteria for Portable VOC Monitors
Instrument Specification
Detector
Detection Range..
Readable Range ..
Sample Flow Rate.
Safety
. Examples: Catalytic oxidation
Flame ionization
Infrared absorption
Photoionization
. Leak definition concentrations
. To 5 percent of the leak definition
. Nominally 0.5 to 3.0 liters per minute
. Intrinsically safe operation in explosive atmospheres
Performance Criteria
Response Factor ...
Response Time
Calibration Precision
. Less than 10 for each constituent
. Less than or equal to 30 seconds
. Less than or equal to 10 percent of the calibration
gas value
SOURCE: Reference Method 21
Table 6 shows additional perform-
ance criteria in terms of response
and precision. Century Systems'
Organic Vapor Analyzer (OVA)ฎ, the
Bacharach Instruments' TLV Sniffer
(TLA/)ฎ, and the H-Nuฎ photoioniza-
tion instrument have been used
successfully in some of the fugitive
emissions research projects
conducted by the EPA and other
groups.*
Calibration. Portable monitoring
instruments are calibrated in terms
of concentration (ppmv) of a refer-
ence compound. At least two calibra-
tion gases must be used. First, a
zero gas, which is air containing less
than 10 ppmv VOC, is used to set the
instrument baseline. Second, a cali-
bration gas, which contains a refer-
ence compound (methane or
n-hexane) in air at the leak definition
concentration, is used to set the
instrument span. Calibrants, either
purchased or prepared by the user,
must be analyzed and certified to
within ฑ 2 percent accuracy. The
shelf life must be specified for
purchased calibrants; prepared
calibrants must be replaced daily,
unless no degradation can be proved.
How Sources Are Monitored. In
general, sources are monitored by
placing the instrument probe inlet at
the surface where leakage would
occur (i.e., the leak interface). For
each component, the entire leak
interface must be traversed. For
example, valves are monitored at the
seal between the stem and the
housing and at the interface of the
packing gland take-up flange seat.
For compressors and pumps, the
probe is traversed around the circum-
ference at the interface of the shaft
and seal. For pressure relief devices
and open-ended lines and valves, the
probe is placed at the center of the
opening to the atmosphere. To deter-
mine the instrument reading of the
background for evaluation of NDE,
the probe inlet is moved randomly 1
to 2 meters upwind and downwind of
the source.
'Mention of trade names does not constitute
endorsement by EPA.
24
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7. Other Standards
In addition to the fugitive emissions
standards there are other standards
with which owners or operators of
organic chemical units may have to
comply. Standards have been
proposed or promulgated for the
following source categories:
Standards of Performance for
New Stationary Sources; VOC
Emissions from the Synthetic
Organic Chemical Manufacturing
Industry (SOCMI) Distillation Unit
Operations proposed on
December 30,1983 (48 FR
57538-57561).
National Emission Standards for
Hazardous Air Pollutants;
Benzene Equipment Leaks
(Fugitive Emission Sources)
promulgated on June 6,1984 (49
FR 23498-23520).
Standards of Performance for
New Stationary Sources, Volatile
Organic Liquid Storage Vessels
(including Petroleum Liquid
Storage Vessels) constructed
after July 23,1984 proposed on
July 23, 1984 (49 FR 29698-29718).
National Emission Standards for
Hazardous Air Pollutants; Vinyl
Chloride promulgated on
October 21,1976 (41 FR
46559-46573).
Standards of Performance for
New Stationary Sources; VOC
Emissions from the Synthetic
Organic Chemical Manufacturing
Industry (SOCMI) Air Oxidation
Unit Processes proposed on
October 21,1983 (48 FR
48932-48958).
25
-------
8. Sources of
Information
There is no one reference that
describes i'n detail how to comply
with the SOCMI fugitive emission
standards. This publication is
designed to help owners and
operators 4f SOCMI plants by
explaining [in plain English what the
standards require. There are other
references iand documents that
provide additional information.
References that may be helpful are
listed in this section with some
comments on the material each
contains.
Federal Register Notices
The Federal Register contains
notices of regulations and notices of
proposed final regulatory actions. It
is published by the Office of the
Federal Register, National Archives
and Records Service of the General
Services Administration and is avail-
able for sale from:
Superintendent of Documents.
U.S. Government Printing Office.
Washington, DC 20402.
The final standard on fugitive VOC
emissions [in SOCMI is published in
the following Federal Register notice:
U.S. Environmental Protection
Agency. Standards of
Performance for New Stationary
Sources: Synthetic Organic
Chemical Manufacturing
Industry; Equipment Leaks of
VOC, Reference Methods 18 and
22. Federal Register, Volume 48,
48328-48361, October 18,1983.
Minor amendments to the SOCMI
standards for fugitive emissions of
VOC were published in the following
Federal Register notice:
i
U.S. Environmental Protection
Agency. Standards of
Performance for New Stationary
Sources: Equipment Leaks of
VOC Petroleum Refineries and
Synthetic Organic Chemical
Manufacturing Industry. Federal
Register, Volume 49,
22598-22608, May 30,1984.
Anyone needing to comply with the
standards should obtain a copy and
read it carefully because it contains
the official standards. It also
contains a small amount of explana-
tory material and a discussion of
comments received when the
standards were proposed.
The following Federal Register notice
contains information about EPA's
method for leak detection. It is the
final method as added to the Code of
Federal Regulations. The leak
detection required by the standards
must be done according to
Reference Method 21. Anyone
needing to comply with the SOCMI
fugitive emission standards should
obtain a copy of the final method and
read it carefully.
U.S. Environmental Protection
Agency. Addition of Reference
Method 21 to Appendix A. Federal
Register, Volume 48, 37598-37602.
August 18,1983.
As standards and reference mejhods
are finalized, they are published in
the Code of Federal Regulations.
Title 40 contains environmental rules,
standards, and regulations. Part 60 of
Title 40 deals with new source per-
formance standards. In addition to
the individual new source perform-
ance standards, there are General
Provisions which apply to all
facilities that must comply with
these standards. Anyone needing to
comply with the SOCMI fugitive
emission standards should read
carefully the General Provisions of 40
CFR Part 60.
U.S. Environmental Protection
Agency. Code of Federal
Regulations. Title 40,
Protection of Environment. Part
60, Standards of Performance
for New Stationary Sources.
Superintendent of Documents.
U.S. Government Printing
Office, Washington, DC 20402.
26
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Control Technique Guidelines
Documents
Control Techniques Guidelines
Documents are written to aid State
agencies in writing State Implemen-
tation Plans for areas which have not
attained national ambient air quality
standards. They provide information
useful in determining what
reasonably available control
technology should be. The following
guideline document has recently
been published for fugitive
emissions in SOCMI and polymer
plants. It contains sections on
emissions, control techniques,
environmental impacts of control,
and costs for control.
i
U.S. Environmental Protection
Agency. Guideline Series
Control of Volatile Organic
Compound Leaks from Synthe-
tic Organic Chemical and
Polymer Manufacturing Equip-
ment. Research Triangle Park,
NC. Publication Number
EPA-450/3-83-006. March 1984.
[NTIS: PB84-105311]
Background Information
Documents for Standards
Background information documents
present the technical information
EPA used in developing a standard.
Topics covered include descriptions
of emissions, control techniques,
costs, and environmental and energy
impacts.
There are two technical background
information documents for the
SOCMI fugitive emission standards,
one written in support of the
proposed standards and an
additional information document
which details technical information
developed after the standard was
proposed.
U.S. Environmental Protection
Agency. Background Informa-
ton for Proposed Standards for
VOC Fugitive Emissions in the
Synthetic Organic Chemicals
Manufacturing Industry.
Research Triangle Park, NC.
Publication Number EPA-450/3-
80-033a. November 1980. [NTIS:
PB81-152167]
U.S. Environmental Protection
Agency. Fugitive Emission
Sources of Organic
Compounds Additional
Information on Emissions,
Emission Reductions, and
Costs. Research Triangle Park,
NC. Publication Number
EPA-450/3-82-010. April 1982.
[NTIS: PB82-217126]
A third background document
provides support for the standards as
finally promulgated. It contains a
summary of the public comments
received on the proposed standards
and EPA's responses to those
comments.
U.S. Environmental Protection
Agency. Background Informa-
tion for Promulgated Standards
for VOC Fugitive Emissions in
the Synthetic Organic
Chemicals Manufacturing
Industry. Research Triangle
Park, NC. Publication Number
EPA-450/3-80-033b. June 1982.
[NTIS: PB84-189372]
These background documents were
prepared by EPA. In some cases the
document may still be available from
EPA and can be requested from:
U.S. EPA Library (MD-35),
Research Triangle Park, NC
27711. Telephone: (919)
541-2777
If EPA does not have the publication,
it can be obtained from:
National Technical Information
Service, U.S. Department of
Commerce, Springfield, VA 22161.
27
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Affected Synthetic Organic Chemicals
CAS No."
Chemical
CAS No.*
Chemical
CAS No."
Chemical
105-57-7 Acetal.
75-07-0 Acetaldehyde.
107-89-1 Acetaldol.
60-35-5 Acetamide.
103-84-4 Acetanilide.
64-19-7 Acetic acid.
108-24-7 Acetic anhydride.
67-64-1 Acetone.
75-86-5 Acetone cyanohydrin.
75-05-8 Acetonitrile.
98456-2 Acetophenone.
75-36-5 Acetyl chloride.
74-86-2 Acetylene.
107-02-8 Acrolein.
79-06-1 Acrylamide.
79-10-7 Acrylic acid.
107-13-1 Acrylonitrile.
124-04-9 Adipicacid.
111-69-3 Adiponitrile.
(b) , Alkyi naphthalenes.
107-18-6 Allyl alcohol.
107-05-1 Allyl chloride.
1321-11-5 Aminobenzoic acid.
111-41-1 Aminoethylethanolamine.
123-30-8 p-Amlnophenol.
628-63-7,123- . .Amyl acetates.
92-2
7141-Oc Amyl alcohols.
110-58-7 Amyl amine.
543-59-9 Amyl chloride.
110-66-7C Amyl mercaptans.
1322-06-1 Amy) phenol.
62-53-3 Aniline.
142-04-1 Aniline hydrochloride.
29191-52-4 Anisidine.
100-66-3 Anisole.
118-92-3 Anthranilic acid.
84-65-1 Anthraquinone.
100-52-7 Benzaldehyde.
55-21-0 Benzamide.
71-43-2 Benzene.
98-48-6 Benzenedisulfpnic acid.
98-11-3 Benzenesulfonic acid.
134-81-6 Benzil.
76-93-7 Benzilic acid.
65-85-0 Benzole acid.
119-53-9 Benzoin.
10047-0 Benzonitrile.
119-61-9 Benzophenone.
98-07-7 Benzotrichloride.
98-88-4 Benzoyl chloride
100-51-6 Benzyl alcohol.
100-46-9 Benzylamine.
120-51-4 Benzyl benzoate.
10044-7 Benzyl chloride.
98-87-3 Benzyl dichloride.
92-524 Biphenyl.
80-05-7 BisphenolA.
10456-1 Bromobenzene.
27497-514 .... Bromojiaphthalene.
106-99-0 Butadiene.
106-98-9 1-butene.
123-864 n-butyl acetate.
141-32-2 n-butyt acrylate.
71-36-3 n-butyl alcohol.
78-92-2 s-butyl alcohol.
7&65-0 t-butyl alcohol.
109-73-9 n-butylamine.
13952-84-6 .. ..s-butylamine.
75-64-9 t-butylamine.
98-73-7 p-tert-butyi benzole acid.
107-88-0 1,3-butylene glycol.
123-72-8 n-butyraldehyde.
107-92-6 ... .I.. Butyric acid.
106-31-0 .. Butyric anhydride.
109-74-0 .. Butyronitrile.
105-60-2 .. Caprolactam.
75-1-50 .Carbon disulfide.
558-134 '. .Carbon tetrabromide.
56-23-5 ;.. Carbon tetrachloride.
9004-35-7 ..... Cellulose acetate.
79-11-8 '.. Chloroacetic acid.
108-42-9 '. .m-chloroaniline.
95-51-2 o-chloroaniline.
106-47-8 p-chloroaniline.
35913-09-8 Chlorabenzaldehyde.
108-90-7 ...... Chlorobenzene.
118-91-2,535- .. Chlorobenzoic acid.
80-8,74-11-3c:..
2136-814,2136 . Chlorobenzotrichloride.
89-2,5216-25-ic.
1321-03-5 .... .Chlorbenzoyl chloride.
25497-294 Chlorodif luoromethane.
7545-6 Chlorodif luoroethane.
67-66-3 Chloroform.
2558643-0 Chloronapthalene.
88-73-3 o-chloronitrobenzene.
100-00-5 p-chloronitrobenzene.
25167-80-0 . .[..Chlorophenols.
126-99-8 .. Chloroprene.
7790-94-5 ..... Chlorosulfonic acid.
10841-8 .. m-chlorotoluene.
9549-8 ,. .o-chlorotoluene.
106-434 ....;.. p-chlorotoluene.
75-72-9 .Chlorotrifluoromethane.
108-394 ...... m-cresol.
9548-7 .o-cresol.
10644-5 .. p-cresol.
1319-77-3 Mixed cresols.
1319-77-3 Cresylic acid.
4170-30-0 Crotonaldehyde.
3724-65-0 Crotonic acid.
98-82-8 Cumene.
80-15-9 .Cumene hydroperoxide.
372-09-8 Cyanoacetic acid.
506-774 Cyanogen chloride.
108-80-5 Cyanuric acid.
108-77-0 .. Cyanuric chloride.
110-82-7 .. Cyclohexane.
108-93-0 I.. Cyclohexanol.
108-94-1 Cyclohexanone.
110-83-8 .. Cyclohexene.
108-91-8 . .Cyclohexylamine.
111-784 :.. Cyclooctadiene.
112-30-1 . .Decanol.
12342-2 .. Diacetone alcohol.
27576-04-1 ..:.. Diaminobenzoic acid.
95-76-1,95-82-9, Dichloroaniline.
554-00-7, 608-
27-5, 608-31'-1,
62643-7, 27134-
27-6,57311-92-9c
541-73-1 .. m-dichlorobenzene.
95-50-1 o-dichlorobenzene.
10646-7 p-dichlorobenzene.
75-71-8 .. Dichlorodifluoromethane.
11144-4 Dichloroethyl ether.
107-06-2 1,2-dichloroethane (EDC).
96-23-1 Dichlorohydrin.
26952-23-8 Dichloropropene.
101-83-7 .. Dicyclohexylamine.
109-89-7 Diethylamine.
11146-6 Diethylene glycol.
112-36-7 Diethylene glycol diethyl
ether.
111-96-6
112-34-5
124-17-7
111-90-0
112-15-2
111-77-3
64-67-5 ...
75-37-6 .. .
25167-70-8
2676140-0
27554-26-3
674-82-8 ..
12440-3 ..
121-69-7 ..
115-10-6 ..
68-12-2 .. .
57-14-7 .. .
77-78-1 ...
75-18-3 ...
67-68-5 .. .
120-61-6 . .
99-34-3 .. .
51-28-5 . . .
25321-14-6
123-91-1 . .
646-06-0 ..
122-394 ..
101-84-8 ..
102-08-9 ..
25265-71-8
25378-22-7
28675-174
27193-86-8
106-89-8 ..
64-17-5 ...
14143-5c. .
141-78-6 . .
141-97-9 ..
140-88-5 ..
75-04-7 ...
100414 ..
74-964 . . .
9004-57-3 .
75-00-3 ...
105-39-5 ..
105-56-6 ..
74-85-1 . ..
9649-1 . ..
107-07-3 . .
107-15-3 ..
106-934 ..
107-21-1 ..
111-55-7 ..
110-714 ..
111-76-2
112-07-2
110-80-5
111-15-9
109-864
11049-6
.Diethylene glycol
dimethyl ether.
. Diethylene glycol
monobutyl ether.
. Diethylene glycol
monobutyl ether acetate.
. Diethylene glycol
monoethyl ether.
. Diethylene glycol
monoethyl ether acetate.
. Diethylene glycol
monomethyl ether.
. Diethyl sulfate.
. Difluoroethane.
. Diisobutylene.
. Diisodecy) phathalate.
. Diisooctyl phthalate.
. Diketene.
. Dimethylamine.
. N,N-dimethylaniline.
. N,N-dimethyl ether.
. N,N-dimethylformaniide.
. Dimethylhydrazine.
. Dimethyl sulfate.
. Dimethyl sulfide.
. Dimethyl sulfoxide.
. Dimethyl terephthalate.
.3,5-dinitrobenzoic acid.
. Dinitrophenol.
. Dinitrotoluene.
. Dioxane.
. Dioxilane.
. Diphenylamine.
. Diphenyl oxide.
. Diphenyl thiourea.
. Dipropylene glycol.
. Dodecene.
.Dodecylaniline.
. Dodecylphenol.
. Epicholorhydrin.
. Ethanol.
. Ethanolamines
. Ethyl acetate.
. Ethyl acetoacetate.
. Ethyl acrylate.
. Ethylamine.
. Ethylbenzene.
. Ethyl bromide.
. Ethylcellulose.
. Ethyl chloride.
. Ethyl chloroacetate.
. Ethylcyanoacetate.
. Ethylene.
. Ethylne carbonate.
. Ethylene chlorohydrin.
. Ethylenediamine.
. Ethylene dibromide.
. Ethylene glycol.
. Ethylene glycol diacetate.
. Ethylene glycol dimethyl
ether.
. Ethylene glycol
monobutyl ether.
. Ethylene glycol
monobutyl ether acetate.
. Ethylene glycol
monoethyl ether.
. Ethylene glycol
monoethyl ether acetate.
. Ethylene glycol
monomethyl ether.
. Ethylene glycol
monomethyl ether acetate.
-------
Affected Synthetic Organic Chemicals (continued)
C/ASA/o.'
Chemical
CAS No.*
Chemical
CAS No.*
Chemical
122-99-6 .
2807-30-9
75-21-8 . . .
60-29-7 ...
104-76-7 ..
122-51-0 . .
95-92-1 ...
41892-71-1
50-00-0 ...
75-12-7 ...
64-18-6 ...
110-17-8 ..
98-01-1 ...
56-81-5 ...
26545-73-7
25791-96-2
56-40-6 . . .
107-22-2 ..
118-74-1 ..
67-72-1 . . .
36653-82-4
124-09-4 ..
629-11-8 . .
100-97-0 ..
74-90-8 ...
123-31-9 . .
99-96-7 ...
26760-64-5
78-83-1 . . .
110-19-0 ..
115-11-7 ..
78-84-2 ...
79-31-2 ...
25339-17-7
26952-21-6
78-78-4 . . .
78-59-1 ...
121-91-5 ..
78-79-5 ...
67-63-0 . . .
108-21-4 ..
75-31-0 . . .
75-29-6 . . .
25168-06-3
463-51-4 . .
123-01-3
110-16-7 ..
108-31-6 ..
6915-15-7 .
141-79-7 ..
121-47-1 ..
79-41-4 . ..
563-47-3 . .
67-56-1 . ..
79-20-9 . ..
105-45-3 ..
74-89-5 ...
100-61-8 ..
74-83-9 . ..
37365-71-2
74-87-3 ...
108-87-2 ..
1331-22-2 .
75-09-2 .. .
101-77-9 . .
101-68-8 ..
78-93-3
. Ethylene glycol
monophenyl ether.
. Ethylene glycol
monopropyl ether.
. Ethylene oxide.
. Ethyl ether.
. 2-ethylhexanol.
. Ethyl orthoformate.
. Ethyl oxalate.
. Ethyl sodium oxalacetate.
. Formaldehyde.
. Formamide.
. Formic acid.
. Fumaric acid.
. Furfural.
. Glycerol.
.Glycerol dichlorohydrin.
. Glycerol triether.
. Glycine.
.Glyoxal.
. Hexachlorobenzene.
. Hexachloroethane.
. Hexadecyl alcohol.
. Hexamethylenediamine.
. Hexamethylene glycol.
. Hexamethylenetetramine.
. Hydrogen cyanide.
. Hydroquinone.
. p-hydroxybenzoic acid.
. Isoamylene.
. Isobutanol.
. Isobutyl acetate.
. Isobutylene.
. Isobutyraldehyde.
. Isobutyric acid.
. Isodecanol.
. Isooctyl alcohol.
. Isopentane.
. Isophorone.
. Isophthalic acid.
. Isoprene.
. Isopropanol.
. Isopropyl acetate.
. Isopropylamine.
. Isopropyl chloride.
. Isopropylphenol.
. Ketene.
. Linear alkyl sulfonate.
. Linear alkylbenzene
(linear dodecylbenzene).
. Maleic acid.
. Maleic anhydride.
. Malic acid.
. Mesityl oxide.
.metanilic acid.
.Methacrylicacid.
. Methallyl chloride.
. Methanol.
. Methyl acetate.
. Methyl acetoacetate.
. Methylamine.
. n-methylaniline.
. Methyl bromide.
. Methyl butynol.
.Methyl chloride.
. Methylcyclohexane.
. Methylcyclohexanone.
. Methylene chloride.
. Methylene dianiline.
. Methylene diphenyl diiso-
cyanate.
. Methyl ethyl ketone.
107-31-3 Methyl formate.
108-11-2 Methyl isobutyl carbinol.
108-10-1 Methyl isobutyl ketone.
80-62-6 Methyl methacrylate.
77-75-8 ..- Metnylpentynol.
98-83-9 a-methylstyrene.
110-91-8 Morpholine.
85-47-2 a-napthalene sulfonic
acid.
120-18-3 b-napthlene sulfonic acid.
90-15-3 a-naphthol.
135-19-3 b-naphthol.
75-98-9 Neopentanoic acid.
88-74-4 o-nitroaniline.
100-01-6 p-nitroaniline.
91-23-6 o-nitroanisole.
100-17-4 p-nitroanisole.
98-95-3 Nitrobenzene.
27178-83-2c Nitrobenzoic acid, (o,m,
and p).
79-24-3 Nitroethane.
75-52-5 Nitromethane.
88-75-5 2-Nitrophenol.
25322-01-4 Nitropropane.
1321-12-6 Nitrotoluene.
27215-95-8 ... .Nonene
25154-52-3 Nonylphenol.
27193-28-8 .... Octylphenol.
123-63-7 Paraldehyde.
115-77-5 Pentaerythritol.
109-66-0 n-pentane.
109-67-1 1-pentene.
127-18-4 Perchloroethylene.
594-42-3 Perchloromethyl mercap-
tan.
94-70-2 o-phenetidine.
156-43-4 p-phenetidine.
108-95-2 Phenol.
98-67-9,585-38-6,Phenolsulfonic acids.
609-46-1, 1333-
39-7c
91-40-7 Phenyl anthranilic acid.
(b) Phenylenediamine.
75-44-5 Phosgene.
85-44-9 Phthalic anhydride.
85-41-6 Phthalimide.
108-99-6 b-picoline.
110-85-0 Piperazine.
9003-29-6, Polybutenes.
25036-29-7c ....
25322-68-3 Polyethylene glycol.
25322-69-4 Polypropylene glycol.
123-38-6 Propional dehyde.
79-09-4 Propionic acid.
71-23-8 n-propyl alcohol.
107-10-8 Propylamine.
540-54-4 Propyl chloride.
115-07-1 Propylene.
127-00-4 Propylene chlorohydrin.
78-87-5 Propylene dichloride.
57-55-6 Propylene glycol.
75-56-9 Propylene oxide.
110-86-1 Pyridine.
106-51-4 Quinone.
108-46-3 Resorcinol.
27138-57-4 Resorcylic acid.
69-72-7 Salicylic acid.
127-09-3 Sodium acetate.
532-32-1 Sodium benzoate.
9004-32-4 Sodium carboxymethyl
cellulose.
3926-62-3 Sodium chloroacetate.
141-53-7 Sodium formate.
139-02-6 Sodium phenate.
110-44-1 Sorbicacid.
100-42-5 Styrene.
110-15-6 Succinic acid.
110-61-2 Succinonitrile.
121-57-3 Sulfanilic acid.
126-33-0 Sulfolane.
1401-55-4 Tannic acid.
100-21-0 Terephthalic acid.
79-34-5c Tetrachloroethanes.
117-08-8 Tetrachlorophthalic
anhydride.
78-00-2 Tetraethyl lead.
119-64-2 Tetrahydronapthalene.
85-43-8 Tetrahydrophthalic
anhydride.
75-74-1 Tetramethyl lead.
100-60-1 Tetramethylenediamine.
100-18-9 Tetramethylethylened-
iamine.
108-88-3 Toluene.
95-80-7 Toluene-2,4-diamine.
584-84-9 Toluene-2,4-diisocyanate.
26471-62-5 ... .Toluene diisocyanates
(mixture).
1333-07-9 Toluenesulfonamide.
104-15-4c Toluenesulfonic acids.
98-59-9 Toluenesulfonyl chloride.
26915-12-8 Toluidines.
87-61-6,108-70-3,Trichlorobenzenes.
120-82-1c
71-55-6 1,1,1-trichloroethane.
79-00-5 1,1,2-trichloroethane.
79-01-6 Trichloroethylene.
75-69-4 Trichlorof luoromethane.
96-18-4 1,2,3-trichloropropane.
76-13-1 1,1,2-trichloro-1,2,2-tri-
fluoroethane.
121-44-8 Triethylamine.
112-27-6 Triethylene glycol.
112-49-2 Triethylene glycol
dimethyl ether.
7756-94-7 Triisobutylene.
75-50-3 Trimethylamine.
57-13-6 Urea.
108-05-4 Vinyl acetate.
75-01-4 Vinyl chloride.
75-35-4 Vinylidene chloride.
25013-15-4 Vinyl toluene.
1330-20-7 Xylenes (mixed).
95-47-6 o-xylene.
106-42-3 p-xylene.
1300-71-6 Xylenol.
1300-73-8 Xylidine.
a CAS numbers refer to the Chemical
Abstracts Registry numbers assigned to
specific chemicals, isomers, or mixtures of
. chemicals. Some isomers or mixtures that
are covered by the standards do not have
CAS numbers assigned to them. The stan-
dards apply to all of the chemicals listed,
whether CAS numbers have been assigned
or not.
b No CAS numbers(s) have been assign-
ed to this chemical, its isomers, or mixtures
containing these chemicals.
c CAS numbers for some of the isomers
are listed; the standards apply to all of the
isomers and mixtures, even if CAS
numbers have not been assigned.
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S-EPA
ฑ.- U -r _-..,;-.,
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