United States Office of Enforcement 340/1-80-005
Environmental Protection Office of General Enforcement May 1978
Agency Washington, DC 20460
v>EPA National Emission
Standards for Hazardous
Air Pollutants Inspection
Manual for Vinyl Chloride
-------
NATIONAL EMISSION STANDARDS
FOR HAZARDOUS AIR POLLUTANTS
INSPECTION MANUAL
for
VINYL CHLORIDE
EPA Contract No. 340/1-80-005
RTI Project No. 41U-3172-2
EPA Project Officer
John R. Busik
Prepared for
U. S. ENVIRONMENTAL PROTECTION AGENCY
Office of Enforcement
Office 'of General Enforcement
Washington, D. C. 20460
May 1978
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ACKNOWLEDGMENT
This Inspection Manual was prepared by Mr. Michael F. Lamorte of
the Research Triangle Institute. Project Officer for the Environmental
Protection Agency - Enforcement Division was Mr. John R. Busik. The
Task Manager was Mr. Richard Biondi assisted by Ms. Libby Scopino. The
author appreciates the many contributions made by Mr. Biondi and
Ms. Scopino during the preparation of this Manual. The author also
appreciates the assistance of Surveillance and Analysis and of Enforcement
Division personnel of Region 6 in applying the Inspection Forms under
field conditions.
In addition, discussions with Mr. Ben Carpenter and Dr. Forest
Mixon of the Research Triangle Institute were very helpful. Mr. R. N.
Wheeler, Jr., of the Union Carbide Corporation, provided information of
the more recent solvent polymerization process. Finally, many thanks
are in order to Mr. John R. Lawrence, The Society of the Plastics
Industry, Inc., and to industry representatives for the hospitality
extended to the author during the numerous plant site visits.
ii
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TABLE OF CONTENTS
Page
ACKNOWLEDGMENT ii
LIST OF FIGURES v
LIST OF TABLES ix
LIST OF INSPECTION FORMS x
LIST OF CHEMICAL FORMULAS xi
LIST OF ABBREVIATIONS xli
1.0 INTRODUCTION 1
1.1 Background 1
1.2 Authority 2
1.3 Applicability 2
1.4 Definitions 3
2.0 EDC, VC AND PVC INDUSTRIES 6
2.1 Ethylene dichloride (EDC) 6
2.2 Vinyl chloride (VC) 7
2.3 Polyvinyl chloride (PVC) 8
3.0 PROCESS FLOW DESCRIPTION AND EMISSION POINT IDENTIFICATION 9
3.1 Ethylene dichloride--oxychlorination 9
3.2 Vinyl chloride 12
3.2.1 Hydrochlorination of acetylene 12
3.2.2 Dehydrochlorination of ethylene dichloride 16
iii
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TABLE OF CONTENTS
(Continued)
3.3 Polyvinyl chloride 18
3.3.1 Suspension polymerization 18
3.3.2 Emulsion (i.e., dispersion) polymerization 23
3.3.3 Latex dispersion polymerization 26
3.3.4 Bulk polymerization 26
3.3.5 Solvent polymerization 29
3.4 Clarifying note on the balanced oxychlorination-
dehydrochlorination process 36
3.5 Photographs of equipment 38
4.0 LEAK DETECTION MONITORING INSTRUMENTATION, RECORDS AND REPORTS 55
4.1 Leak detection monitoring instrumentation 55
4.2 Leak detection monitoring recordkeeping 59
4.3 Routine leak detection and relief discharge recordkeeping 59
5.0 INSPECTOR SAFETY 60
6.0 INSPECTION PROCEDURES AND INSPECTION FORMS 61
6.1 Summary of compliance status 62
6.2 Checklist 62
6.3 On review of records 62
6.4 Pre-test equipment checklist for stack emission test 63
6.5 Equipment checklist for vinyl chloride concentration in
inprocess wastewater, resin, slurry, wet cake and
latex samples 63
APPENDIX A: Mean value calculation 86
APPENDIX B: National Emission Standards for Hazardous Air
Pollutants - Standard for Vinyl Chloride,
October 21, 1976 87
APPENDIX C: National Emission Standards for Hazardous Air
Pollutants - Standard for Vinyl Chloride: Cor-
rections and Amendments, June 7, 1977 103
REFERENCES 109
iv
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LIST OF FIGURES
Page
3.1 Ethylene dichloride process flow diagram using 10
oxychlorination which involves the reaction of
oxygen and hydrogen chloride with ethylene.
3.2 Vinyl chloride monomer process flow diagram using 13
hydrochi orination of acetylene.
3.3 Vinyl chloride monomer process flow diagram using 17
dehydrochlorination of ethylene dichlorade.
3.4 Polyvinyl chloride process flow diagram using 20
suspension polymerization.
3.5 Polyvinyl chloride process flow diagram using 24
emulsion (i.e., dispersion) polymerization.
3.6 Polyvinyl chloride latex process flow diagram using 27
emulsion (i.e., dispersion) polymerization.
3.7 Polyvinyl chloride process flow diagram using bulk 30
polymerization.
3.8 Polyvinyl chloride process flow diagram using solvent 32
polymerization.
3.9 More recent polyvinyl chloride process flow diagram 33
using solvent polymerization.
3.10 Block diagram of a balanced oxychlorination- 37
dehydrochlorination process.
3.11 Large capacity VC reactor using the oxychlorination 40
process is located in the tall vessel. The oxychlori-
nation manual vent is the open ended pipe, rising
above the top of the reactor on the left side.
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LIST OF FIGURES
(continued)
3.12 The tops of medium capacity, side-by-slde PVC 40
reactors using the emulsion process may be seen.
Individual RD/SRV and manual vents may also be seen
mounted on top of each reactor.
3.13 Small size PVC reactor with cover removed to clean 41
reactor in preparation for next polymerization run.
Prior to removing cover the PVC and water solution
were removed and transferred to stripper. "Elephant
trunk" is placed through the opening to vent vinyl
chloride gas through "trunk" to the recovery system
in order to be in compliance with emissions standard
reactor opening loss. This type reactor is used in
the suspension, emulsion and latex polymerization
processes.
3.14 Medium capacity side-by-side PVC reactors using 41
solvent process. Individual RD/SRV and manual vents
connected to vinyl chloride recovery system may also
be seen. Lower portion of reactors comprise the
heating elements to raise the contents to the tem-
perature required for polymerization.
3.15 The top of medium capacity, side-by-side PVC reactors 42
using solvent process. Foreground shows a motor
valve for emergency venting through to the VC monomer
recovery system.
3.16 The top of a small capacity PVC stripper vessel used 42
in the suspension, emulsion and latex processes,
showing an SRV.
3.17 A stripper column is shown that removes VC from a 43
PVC-varnish solution resulting from the solvent
polymerization process.
3.18 A typical wastewater stripper column is shown that 43
may be found in EDC, VC and PVC plants.
3.19 The top of an EDC storage tank is shown with its 44
vent.
3.20 Cylindrical, side-by-side, above ground VC storage 44
tanks are shown. RD/SRV vents may be seen on pipe
rack above tanks.
vi
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LIST OF FIGURES
(continued)
3.21 Spherical, above ground vinyl chloride storage 45
tanks. RD/SRV vents may be seen perched on top of
sphere.
3.22 Underground VC storage tank area. 45
3.23 Mash water stripper storage tank. 46
3.24 Upper portion of tar storage tank shown with vent. 46
>
3.25 PVC suspension resin rotary dryer and dust col- 47
lector. Drying is accomplished by the application
of heat and rotary action.
3.26 PVC dispersion resin spray drying takes place in the 47
cylindrical building. Large diameter feed pipe,
seen at the left of the dryer, carries drying air
to the top of the dryer. Housing for the atomiza-
tion system is perched at top of dryer.
3.27 An EDC light ends distillation column is shown 48
with its RD/SRV vent.
3.28 VCM column condenser and condenser vent motor valve. 48
3.29 The top of an EDC light ends column reflex 49
accumulator showing the RD/SRV vent.
3.30 In the foreground the light ends dryer regeneration 49
liquid knockout vessel is shown in balanced EDC-VC
plant.
3.31 An EDC finishing column with the RD/SRV and its vent 50
mounted on the top. (In some installations the
finishing column performs the function of the light
ends distillation column while in others it en-
compasses the functions of both the light and heavy
ends columns.)
3.32 Foreground shows the insulated vent piping and motor 50
valve from the reactor refrigerator condenser vessel
in a balanced EDC osychlorination plant.
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LIST OF FIGURES
(continued)
3.33 Typical RD/SRV assembly with the vents from each 51
connected to a manifold of the vent system.
3.34 Dual RD/SRV vents mounted at top of spherical 51
vinyl chloride storage tank.
3.35 Typical pump and double mechanical seal. 52
3.36 Top connections on railroad tank car shown with 52
flexible hose attached for VC loading. Smaller
diameter flexible hose in the foreground is
connected to recovery system.
3.37 Railroad tank car loading platform shown with 53
pipe rack support for flexible hose VC feed and
recovery system in VC plant.
3.38 Oxychlorination vent scrubber stack. 53
3.39 Incinerator and stacks of a PVC plant showing the 54
platform (center stack) on which stack samples
are taken to determine VC emission concentration.
4.1 Schematic diagram of continuous monitoring system 58
for vinyl chloride emissions.
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LIST OF TABLES
Page
3.1 The potential emission points identified by the 11
keys in Figure 3.1 in the oxychlorination
process for ethylene dichloride.
3.2 Hydrochl on" nation of acetylene product gases and 14
their boiling point temperatures.
3.3 The potential emission points identified by the 15
keys in Figure 3.2 in the hydrochlorination of
acetylene for vinyl chloride monomer.
t
3.4 The potential emission points identified by the 19
keys in Figure 3.3 in the dehydrochlorination of
ethylene dichloride for vinyl chloride monomer.
3.5 The potential emission points identified by the 22
keys in Figure 3.4 in the suspension polymerization
process for polyvinyl chloride.
3.6 The potential emission points identified by the 25
keys in Figure 3.5 in the emulsion (i.e., dispersion)
polymerization process for polyvinyl chloride.
3.7 The potential emission points identified by the 28
keys in Figure 3.6 in the emulsion (i.e., dispersion)
polymerization process for polyvinyl chloride latex.
3.8 The potential emission points identified by the keys 31
in Figure 3.7 in the bulk polymerization process for
polyvinyl chloride resin.
3.9 The potential emission points identified by the keys 34
in Figure 3.8 in the solvent polymerization process
for polyvinyl chloride and copolymers.
3.10 The potential emission points identified by the keys 35
in Figure 3.9 in the solvent polymerization process
for polyvinyl chloride and copolymers.
3.11 Figure number of photographs and corresponding 39
equipment category.
ix
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LIST OF INSPECTION FORMS
Page
Summary of Compliance Status 64
Checklist 65
On Review of Records 74
Pre-Test Equipment Checklist for Stack Emission Test 80
Equipment Checklist for Vinyl Chloride Concentration In Inprocess
Wastewater, Resin, Slurry, Wet Cake and Latex Samples 83
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LIST OF CHEMICAL FORMULAS
Name
Acetylene HC = CH
Chlorine C12
Ethylene CH2 = CH2
Ethyl ene Di chloride C1CH2 " CH2C1
Hydrogen Chloride
HC1
Oxygen 2
= CHC1
Polyvinyl Chloride -
Vinyl Chloride Monomer H2C * CHC1
Water H2°
xi
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LIST OF ABBREVIATIONS
BOD Biological oxygen demand
COO Chemical oxygen demand
EDC Ethylene dichloride
EPA U.S. Environmental Protection Agency
Eq. Equation
FR U.S. Federal Register
HCL Hydrogen chloride
NESHAP National Emission Standards for Hazardous Air Pollutants
PVC Polyvinyl chloride
RO Rupture disc
SOP Standard operating procedure
SRV Safety relief valve
TSS Total suspended solids
VAC Vinyl acetate comonomer
VC Vinyl chloride
VCM Vinyl chloride monomer
xii
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1.0 INTRODUCTION
1.1 BACKGROUND
Pursuant to Section 112 of the Clean Air Act (42-U.S.C. 1857), the
Administrator of the U.S. Environmental Protection Agency (EPA) has
added vinyl chloride to the list of hazardous air pollutants (40 FR
59477) and established a national emission standard (40 FR 59532) for
facilities which manufacture ethylene dichloride, vinyl chloride, and/or
polyvinyl chloride. The National Emission Standards for Hazardous Air
Pollutants (NESHAPs) regulations are applicable to plants producing the
following: ethylene dichloride by the reaction of oxygen and hydrogen
chloride with ethylene; vinyl chloride by any process; and one or more
polymers containing any fraction of polymerized vinyl chloride. The
regulations do not apply to equipment used in research and development
if the reactor used to polymerize the vinyl chloride processed in the
equipment has a capacity of no more than 0.19 m (50 gal). Research and
development facilities containing a polymerization reactor capacity
greater than 0.19 m (50 gal) but no more than 4.07 m3 (1100 gal) are
exempt from all parts of the regulations except the 10 ppm limit. The
proposed emission standards for existing and new plants were advanced in
the Federal Register. December 24, 1975 for vinyl chloride in plants
manufacturing ethylene dichloride, vinyl chloride, and/or polyvinyl
chloride. Final standards (4T-FJ?-October 21, 1976, pages 46560-46573)
became effective October 21, 1976 and apply to existing and new plants [1].
EPA decided to regulate vinyl chloride because it has been implicated
as the causal agent of angiosarcoma (a rare form of liver cancer) and
other serious disorders, both carcinogenic and non-carcinogenic, in people
subjected to occupational exposure and in laboratory animals exposed to
controlled concentrations of vinyl chloride [2]. Reasonable extrapolations
from these findings cause concern that vinyl chloride may cause or
contribute to the same or similar disorders at present ambient concentration
levels. The purpose of the standard is to set limits of vinyl chloride
1
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emissions from all known process and fugitive emission sources 1n ethy-
lene dichloride, vinyl chloride, and/or polyvinyl chloride plants. This
will have the effect of furthering the protection of public health by
minimizing the health risks to people living In the vicinity of these
plants and to any additional people who are exposed as a result of new
construction [3].
This Inspection Manual contains the guidelines for the benefit of
and the standardized procedures to be followed by EPA field inspectors
or their designated representatives. In conjunction with the operator's
testing and monitoring results and the required recording and recordkeep-
ing of these results, the basic enforcement tools are readily available
to properly trained field inspectors. The degree to which this portion
of the NESHAPs program is successful depends critically on the effective-
ness and efficiency with which inspectors conduct field inspections.
1.2 AUTHORITY
Authority for promulgation of the NESHAPs standards and regulations
of Air pollutants is contained in Section 112 of the Clean Air Act (42
U.S.C. 1857). It directs the Administrator of the U.S. Environmental
Protection Agency to establish emission standards and regulations for
hazardous air pollutants (40 PR 59477), and to maintain a current listing
of these pollutants.
1.3 APPLICABILITY
The applicability of the NESHAPs standards and regulations is
specified with respect to the function of the facility, product and
process by which the product is produced.
There are no exemptions to the NESHAPs vinyl chloride emissions
standards and regulations for production plants which employ reactors of
any capacity to produce one or more of the following: ethylene dichlo-
ride by reaction of oxygen and hydrogen chloride with ethylene; vinyl
chloride by any process; and one or more polymers containing any fraction
of polymerized vinyl chloride [1].
Equipment employed in research and development of the polymerization
of vinyl chloride for which the reactor capacity 1s not greater than 0.19 rt
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(50 gal) is not subject in any way to the vinyl chloride emission standards
and regulations [1].
Equipment employed in research and development of the polymerization
o
of vinyl chloride for which the reactor capacity is greater than 0.19 m
n
(50 gal) and less than 4.07 m (1100 gal) is subject only to the 10 ppm
vinyl chloride emission limit into the atmosphere from each reactor,
stripper, monomer recovery system, and mixing, weighing, and holding
containers [1].
1.4 DEFINITIONS
The definitions of terms used in this Inspection Manual are precise
and this precision is required to conduct inspections properly. The terms
requiring this precision are defined below [1].
(a) "Ethylene dichloride plant" includes any plant which produces
ethylene dichloride by reaction of oxygen and hydrogen chloride
with ethylene.
(b) "Vinyl chloride plant" includes any plant which produces vinyl
chloride by any process.
(c) "Polyvinyl chloride plant" includes any plant where vinyl
chloride alone or in combination with other materials is
polymeri zed.
(d) "Slip gauge" means a gauge that has a probe that moves through
the gas/liquid interface in a storage or transfer vessel and
indicates the level of vinyl chloride in the vessel by the
physical state of the material the gauge discharges.
(e) "Type of resin" means the broad classification of resin
referring to the basic manufacturing process for producing
that resin, including, but not limited to, the suspension,
dispersion, latex, bulk, and solution processes.
(f) "Grade of resin" means the subdivision of resin classification
that describes it as a unique resin, i.e., the most exact
description of a resin with no further subdivision.
(g) "Dispersion resin" means a resin manufactured in such a way as
to form fluid dispersions when dispersed in a plasticizer or
plasticizer/diluent mixtures.
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(h) "Latex resin" means a resin that is produced by a polymerization
process that initiates from free radical catalyst sites and is
sold undried.
(i) "Bulk resin" means a resin which is produced by a polymerization
process in which no water is used.
(j) "Inprocess wastewater" means any water which, during manufacturing
or processing, comes into direct contact with vinyl chloride
or polyvinyl chloride or results from the production or use of
any raw material, intermediate product, finished product,
by-product, or waste product containing vinyl chloride or
polyvinyl chloride but which has not been discharged to a
wastewater treatment process or discharged untreated as
wastewater.
(k) "Wastewater treatment process" includes any process which
modifies characteristics such as BOD, COD, TSS, and pH, usually
for the purpose of meeting effluent guidelines and standards;
it does not include any process the purpose of which is to
remove vinyl chloride from water to meet requirements of this
subpart.
(1) "In vinylchloride service" means that a piece of equipment
contains or contacts either a liquid that is at least 10 percent
by weight vinyl chloride or a gas that is at least 10 percent
by volume vinyl chloride.
(m) "Standard operating procedure (SOP)" means a formal written procedure
officially adopted by the plant owner and/or operator and available
on a routine basis to those persons responsible for carrying out
the procedure.
(n) "Run" means the net period of time during which an emission
sample is collected.
(o) "Ethylene dich1oride purification" includes any part of the process
of ethylene dichloride production that follows ethylene dichloride
formation and in which finished ethylene dichloride is produced.
(p) "Vinyl chlori de puri ficati on" includes any part of the process of
vinyl chloride production that follows vinyl chloride formation
and in which finished vinyl chloride is produced.
4
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(q) "Reactor" includes any vessel In which vinyl chloride is partially
or totally polymerized into polyvinyl chloride.
(r) "Reactor opening loss" means the emissions of vinyl chloride
occurring when a reactor is vented to the atmosphere for any
purpose other than an emergency relief discharge as defined in
§61.65(a).
(s) "Stripper" includes any vesselin which residual vinyl chloride
is removed from polyvinyl chloride resin, except bulk resin, in
slurry form by the use of heat and/or vacuum. In the case of
i
bulk resin, "stripper" includes any vessel which is used
to remove residual vinyl chloride from polyvinyl chloride
resin immediately following the polymerization step in
the plant process flow.
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2.0 EDC, VC AND PVC INDUSTRIES
Polyvinyl chloride is a polymer employed in the fabrication of
literally thousands of consumer and industrial products. The manu-
facturers of these products purchase the polyvinyl chloride resin from
a relatively small number of producers. Polyvinyl chloride is polymerized
from the vinyl chloride monomer. In turn vinyl chloride is produced.from
ethylene dichloride by cracking ethylene dichloride during dehydrochlorina-
tion or from the hydrochlorination of acetylene.
In the following brief presentation, the attributes of ethylene
dichloride, vinyl chloride, and polyvinyl chloride production facilities
are discussed with respect to those considerations that are pertinent
to plant inspections.
2.1 ETHYLENE DICHLORIDE (EDC)
The principal process for ethylene dichloride production in the
U.S. is oxychlorination which involves the reaction of oxygen and hydrogen
chloride with ethylene [4], In 1974, there were nine plants using this
process to produce 5.05 billion pounds of ethylene dichloride per year
[6].
While refined ethylene dichloride is sold for other industrial uses,
its major use is for vinyl chloride monomer production. Typically the
economics of the industry dictates that an ethylene dichloride plant be
in close proximity to a vinyl chloride monomer plant in which case the
shipping cost of large, continuous flows of pure ethylene dichloride to
a vinyl chloride plant is minimal [4]. This has led to the concentration
of these plants in Texas, Louisiana and the northern states [4]. In most
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cases, the unconverted ethylene dichloride from the vinyl chloride plant
is recycled back with the crude ethylene dichloride [4].
Vinyl chloride emissions occur in an ethylene dichloride plant using
the oxychlorination process from three sources: side reactions in the
oxychlorination process and dissolved vinyl chloride in recycled hydrogen
chloride and in recycled unconverted ethylene dichloride. Physically,
the major vinyl chloride emission sources are the EDC reactor, EDC
refining and the fugitive emissions that may be present.
2.2 VINYL CHLORIDE (VC)
There are four processes to produce vinyl chloride monomer [6].
There are fifteen plants producing vinyl chlorjde having a production
capacity of 6.8 billion pounds per year [6]. Two plants use the hydro-
chlorination of acetylene, nine use the chlorination-oxychlorination of
ethylene (with oxygen from air) and dehydrochlorination, one uses the same
process, except that pure oxygen is used in place of air, and three plants
use the direct chlorination of ethylene and dehydrochlorination [6].
The main sources of vinyl chloride emissions in plants using the
hydrochlorination of acetylene are reactor condenser vent (continuous),
scrubber vent (continuous), heavy ends storage vent (intermittent), and
assorted fugitive sources [6].
The sources of emissions from the chlorination-oxychlorination of
ethylene and dehydrochlorination processes using oxygen from air or using
pure oxygen are the same. The main sources of emissions are those dis-
cussed in Section 2.1 and not repeated here, purification system vents
(continuous), scrubber vent (continuous), loading area (intermittent),
and vinyl chloride emissions from the purification process; but the loss
per unit product produced is greater from the purification portion of
the plant.
The process using direct chlorination and dehydrochlorination is
used in vinyl chloride production when the manufacturing facility has
other uses for the hydrogen chloride by-product. This process also uses
ethylene dichloride in a dehydrochlorination process to produce vinyl
chloride.
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2.3 POLYVINYL CHLORIDE (PVC)
Polyvlnyl chloride Is produced by a polymerization process from
the vinyl chloride monomer. There are five processes used to polymerize
the monomer: suspension polymerization is the most widely used and
accounts for 78% of the U.S. plant capacity; dispersion polymerization
(i.e., emulsion) accounts for 13%; bulk polymerization for 6% [4]. The
latex polyvinyl chloride is produced by dispersion polymerization
and is sold and transported in a water suspension; solution polymeri-
zation is adaptable to a continuous process for copolymers and is
used by one company in the U.S. [4].
Emissions may occur at any point of the processes, such as
storage, reactors, strippers, mixers, weighers, blenders, recovery
systems, inprocess wastewater, loading facilities, etc. [6].
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3.0 PROCESS FLOW DESCRIPTION AND EMISSION POINT IDENTIFICATION
The manufacturing processes covered in the vinyl chloride emissions
Final Standard are discussed in this chapter with the aid of process
flow diagrams. The emission points covered in the Standard are listed
and keyed on the corresponding flow diagrams for each process.
3.1 ETHYLENE DICHLORIDE--OXYCHLORINATION*
One of the major processes for ethylene dichloride (see Section
3.4) production in the U.S. is oxychlorination which involves the reaction
of oxygen and hydrogen chloride with ethylene [4]. The oxygen may be
introduced into the process in concentrated form or by an air stream as
shown in Figure 3.1 [6]. The two processes are similar and will be
discussed together since the emission sources are identical. The generic
reaction equation for the process is given by
CH2 = CH2 + 1/2 02 + 2HCL + C1CH2 - CHgCl + H20. (3-1)
This reaction takes place in the reactor, shown in Figure 3.1, at elevated
temperature. The oxychlorination process typically exhibits a 98%
conversion of hydrogen chloride to ethylene dichloride per pass from the
reaction represented in Eq. (3-1) [6]. The raw materials (ethylene,
hydrogen chloride and oxygen/air) are made to pass through a catalyst.
In the presence of oxygen, the catalyst concentrates the ethylene and
chlorine allowing for the reaction, Eq. (3-1), to take place at a lower
temperature. Because the reaction is highly exothermic, a water flow
over the reaction tube surface is required to control the temperature in
the reactor. The result is that steam evolves at the exit port of the
water jacket.
*While this process is usually identified as oxychlorination, it is more
precisely an oxyhydrochIon*nation process.
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ETHYLENG
AIR/OXYGEN
HYDROGEN
CHLORIDE
VENT
WATER-
nn
HOT WATER-
-»STEAM
OXYGEN
REACTOR
CSl.
WATERWASH
COLUMN
FRIG.
SEPARATION
TANK
J VENT
WASH WATER
WATER FROM OXYCHLORINATION AND VCM I
t-*TO REACTOR OR SALES STORAGE
WASTE -
^
-»TO EDC RECOVERY SYSTEM
IS)
HEAVY ENDS TAR
REMOVAL COLUMN
TAR STORAGE
—•DISPOSAL
EOC PRODUCT
STORAGE
Figure 3.1. Ethylene Dichloride process flow diagram using oxychlordination which involves the
reaction of oxygen and hydrogen chloride with ehtylene.
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Table 3.1: The potential emission points identified by the
keys in Figure 3.1 in the oxychlorination process
for ethylene dichloride.
Position Name
Reactor Vent
Reactor Refrigerator
Condenser Vent
Wastewater from
Water Wash Column
Wastewater from
Wash/Crude Storage
Wash Water Stripper Vent
Wash Water Stripper
Storage Vent
Wash Crude Product
Storage Vent
Light-Ends Column
Condenser Vent
Finishing Column Vent
Light-Ends Purification
Column Vent
Refined EDC Storage
Tank Vent
Heavy-Ends, Tar-Removed
Column Vent
Heavy-Ends Storage Tank Vent
Tar Storage Tank Vent
Fugitive
Key
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Entire
Plant
Frequency
Intermittent
Continuous
Continuous
Conti nuous
Continuous
Continuous
Intermittent
Continuous
Continuous
Intermittent
Intermittant
Continuous
Intermittent
Intermittent
Intermittent/
Continuous
11
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The gas stream that exits the reactor contains ethylene dichloride
in the form of a gas. In the process represented In Figure 3.1 this
stream also contains ethylene, hydrogen chloride and air or pure oxygen.
The stream is passed through a hot water wash column to remove impurities
from the ethylene dichloride, and to maintain its gaseous state. The
ethylene dichloride gas and water vapor stream are passed through a cold
water condenser prior to entering the separation tank. The separated,
purified ethylene dichloride is then transported to a storage tank [6].
The water from the hot water wash and from the separation tank is
passed through a stripping column to separate ethylene dichloride and
waste by-products. The separated ethylene dichloride is passed on to
the EDC storage tank, while the waste by-products are disposed.
The potential emission points are listed in Table 3.1 and
identified by the keys shown in Figure 3.1. The emission sources are
listed to correspond with operational steps in the generalized hydrochlori-
nation process. Fugitive emission sources (pumps, pump maintenance
valves, pressure relief valves, samplers, etc.) are not identified
because the locations of these sources are unique for each plant. The
emission from any point, whether listed or not, depends on the operating
condition (batch or continuous, reaction efficiency, etc.) of the plant
at the time of inspection and in some cases on the immediate past history
of operating conditions [6].
3.2 VINYL CHLORIDE
3.2.1 Hydrochlorination of acetylene
In this process vinyl chloride monomer is produced by the hydro-
chlorination of acetylene. The reaction occurs between hydrogen chloride
and acetylene at 85-141°C in the reactor shown in Figure 3.2, in the
presence of a catalyst, mercuric chloride on activated carbon [6]. The
reaction is governed by the equation
HC = CH + HCL »• H2C = CHCL. (3-2)
The reaction typically exhibits a 90% conversion to vinyl chloride per
pass. As a result, acetylene and hydrogen chloride gases exit the
reactor as well as vinyl chloride. These gases are compressed, cooled
12
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VENT
.SCRUBBING LIQUID
VENT GAS REACTOR
HEAVY ENDS
DISTILLATION
LIGHT ENDS
DISTILLATION
Figure 3.2. Vinyl chloride monomer process flow diagram using hydrochlorination
of acetylene.
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and pumped to a purification system consisting of a light-ends distillation
column and a heavy-ends distillation column. In the light ends distillation
column acetylene is separated and transported back into the reactor for
another pass. Other volatile gases are passed to the vent gas reactor
and vent condenser. Table 3.2 lists the main products and their boiling
point temperatures. This shows that acetylene has the lowest boiling
point temperature and is separated easily from the other compounds.
Table 3.2: Hydrochlorination of acetylene product gases
and their boiling point temperatures.
Gas
Acetyl ene
Hydrogen Chloride
Vinyl Chloride
Ethyl ene Di chloride
Symbol
HC = CH
HC1
H2C = CHC1
C1CH2 - CH2C1
Boiling Point
Temperature
- 84°C
- 85° C
- 13°C
+ 83°C
The reaction represented in Eq. (3-2) is exothermic. Therefore,
the heavy-ends that are transported to the heavy-ends distillation
column from the light-ends distillation column will contain some poly-
merized material as well as vinyl chloride monomer. The vinyl chloride
is distilled, subsequently liquefied and placed in a storage tank. The'
heavy-ends are transported to a temporary storage tank and ultimately
incinerated.
The potential emission points are listed in Table 3.3 and identified
by th2 keys shown in Figure 3.2. The emission sources are listed to
14
-------
correspond with operational steps in the generalized hydrochlorination
process. Fugitive emission sources (pumps, pump maintenance valves,
pressure relief valves, samplers, etc.) are not identified because the
locations of these sources are unique for each plant. The emission from
any point, whether listed or not, depends on the operating conditions
(batch or continuous, reaction efficiency, etc.) of the plant at the
time of inspection and in some cases on the immediate past history of
operating conditions.
Table 3.3: The potential emission points identified by the
keys in Figure 3.2 in the hydrochlorination of
acetylene for vinyl chloride monomer.
Position Name
Reactor Condenser Vent
Scrubber Vent
VCM Condenser Vent
VCM Storage Vent
Heavy-Ends Storage Vent
VCM Loading Vent
Fugitive
Key
1
2
3
4
5
6
Entire
Plant
Frequency
Continuous
Continuous
Conti nuous
Continuous
*
Intermittent
Intermittent
Intermi ttent/
Continuous
Intermittent is used in the sense that if the rate of incineration is
greater than the rate of storage, emission is probably intermittent.
When the reverse is true, emission will be continuous.
15
-------
3.2.2 Dehydrochlor1nation of ethylene dlchloride
The production of vinyl chloride monomer by dehydrochlorination
(removal of hydrogen chloride) involves the thermal dehydrochlorination
of dry ethylene dichloride. Thermal dehydrochlorination is sometimes
referred to as a cracking process. Vinyl chloride results when ethylene
dichloride is placed in a cracking furnace at approximately 510°C [4].
For most efficient operation", the furnace is packed with a catalyst such
as pumice or charcoal. Typically, the conversion efficiency per pass is
94 to 97%.
The reaction is represented by the equation
C1CH2 - CH2C1 » H2C = CHC1 + HC1. (3-3)
In an integrated ethylene dichloride-vinyl chloride plant, where the
oxychlorination process is employed to produce ethylene dichloride, the
hydrogen chloride by-product in Eq. (3-3) is returned to the ethylene
dichloride reactor as an input crude shown in Eq. (3-1) [4,6].
Figure 3.3 shows the process flow diagram [6], The ethylene dichlo-
ride is transported as a liquid (boiling point +83°C, see Table 3.2) and
is vaporized completely prior to entering the cracking furnace. The
hydrogen chloride is generated in the cracking furnace. The gas flow
exiting the cracking furnace consists of mainly vinyl chloride, but also
present are ethylene dichloride, hydrogen chloride and other hydrocarbons.
The quenching column uses liquid ethylene dichloride to liquify the ethy-
lene dichloride in the mixture while the gaseous vinyl chloride passes
on to the partial condenser and condenser.
The liquid ethylene dichloride is transported to the washed crude
storage in the ethylene dichloride section of the plant and ultimately
transported back to the cracking furnace for another pass.
The vinyl chloride and hydrogen chloride gases are cooled, compressed
and pumped to a purification system consisting of a light-ends distilla-
tion column and a heavy-ends distillation column. In the light-ends
column the vinyl chloride is separated from the hydrogen chloride. The
hydrogen chloride is recycled to the ethylene dichloride reactor if the
oxychlorination process is used. Other volatile by-products are passed
to the vent gas reactor.
16
-------
RECYCLED TO
HCL RECOVERY
»VEHT
EWMATOft
iFEEO
Figure 3.3. Vinyl chloride monomer process flow diagram using dehydrochlorination
of ethylene dichloride.
-------
The potential emission points are listed in Table 3.4 and identified
by the keys shown in Figure 3.3. The emission sources are listed to
correspond with operational steps in the generalized dehydrochlorination
process. Fugitive emission sources (pumps, pump maintenance valves,
pressure relief valves, samplers, etc.) are not identified because the
location of sources is unique for each plant. The emission from any
point, whether listed or not, depends on the operating conditions (batch
or continuous, reaction efficiency, etc.) of the plant at the time of
inspection and in some cases on the immediate past history of operating
conditions.
3.3 POLYVINYL CHLORIDE
3.3.1 Suspensionpolymerization
The suspension polymerization process is the most common process
for polyvinyl chloride production [4]. The resin produced is sometimes
referred to as suspension resin. Polymerization of vinyl chloride
requires the mixing of weighed amounts of vinyl chloride (weighed amounts
of a comonomer where desired to change the polyvinyl chloride properties),
catalyst, water and suspending agents [4]. The raw materials are mixed
in a clean glass or stainless steel lined reactor. Air is removed from
the reactor by a steam jet or vacuum pump. Reaction temperature is
controlled by either cooling or heating, depending on the details of the
process used. The reaction is initiated by the catalyst. As the reaction
proceeds, polyvinyl chloride is produced in particle form. Agitation is
employed to prevent a slurry from agglomerating in the reactor and the
suspending agent disperses the vinyl chloride droplets. The polymeriza-
tion process is allowed to continue until 85 to 90% of the vinyl chloride
has polymerized; this requires approximately 6 hours [4], If allowed to
continue beyond this point, the product becomes increasingly less
uniform with respect tp molecular weight and, therefore, the physical
properties are less uniform. The vinyl chloride residue is in vapor
form in the reactor, dissolved in water, and/or trapped in the polyvinyl
chloride granules.
Figure 3.4 shows the process flow diagram for suspension polymeriza-
tion [4]. Vinyl chloride is supplied to the weighing station from the
vinyl chloride source (plant or tank car) and from the recovery system.
The comonomer (if required) for a batch is weighed in its own weighing
station. In addition to the weighed quantities of vinyl chloride monomer
18
-------
Table 3.4: The potential emission points Identified by the
keys In Figure 3.3 In the dehydrochlorination
of ethylene dlchloride for vinyl chloride
monomer.
Position Name
Recycling of EDC to
Washed Crude Storage
Light-ends Distillation
Column Vent
Heavy-ends Distillation
Column Vent
Heavy-ends Storage Vent
VCM Storage Vent
Light-ends Column
Waste Water
Quench Column Vent
Fugitive
Key
1
2
3
4
5
6
7
Entire
Plant
Frequency
Intermittent
*
Intermittent
Intermittent
Intermittent
Intermittent
Continuous
Continuous
Intermittent/
Continuous
19
-------
I )AVENT
rsj
o
(
I
VCM
RECOVERY
TANK
VCM » ,
FROM TANK CAR' I
)
J— 1— \
VCM
CONDENSER
/
DISTILLED
CMSTORASEJ
c
VCM
STORAGE
TANK
VCM
EVAPORATOR (Optional)
CO MONOMER
TANK CARS
C
COMONOMER
STORAGE
TANKS
)
1
1
R\
REC. VCM CONO.
a COMR
INITIATOR CATALYST
SUSPENDING 8
SURFACE ACTIVE
AGENTS
PUMP
SOLUTION MIXING
TANK 8 CHARGE PUMP
Figure 3A. Polyvinyl chloride process flow diagram using suspension polymerization.
-------
and comonomer, the initiator catalyst and suspending agent are transported
to the reactor. The polymerization takes place at elevated temperatures
and at a pressure in the range of 5.1 to 8.0 atmospheres.
The contents of the reactor (polyvinyl chloride granules, gases,
water and initiator catalyst) are subjected to a stripping process to
remove unreacted vinyl chloride. The stripping process may take place
in the reactor or the contents may be transferred to a stripper vessel
where stripping takes place. Vinyl chloride is stripped by the application
of heat alone or by the application of the combination of heat and
vacuum. The vinyl chloride and other volatilized chemicals drive off are
transferred to the recovery system. In some plants the vinyl chloride
is processed through a distillation column and parsed on to the recovery
system storage tank. The other gases are vented, and included will be
some vinyl chloride. The remaining slurry is transported to a slurry
blend tank where several batches are blended together to obtain a more
uniform product [4].
The blended slurry is then pumped to a centrifuge where most of the
water is removed. The wet polyvinyl chloride is then dried to remove
remaining water and vinyl chloride. The resin is then transferred to
storage or bagging stations.
Table 3.5 lists the potential emission sources for the suspen-
sion process with the key referred to Figure 3.4. The Key(T)denotes the
recovery system vent through which the noncondensable gases are vented.
The venting may take place manually or automatically and may be intermit-
tent or continuous depending on the system design and the pressures
employed.
Keys(T)and^)are the weighing stations for the vinyl chloride
monomer and comonomer. High pressure may build up at these stations, in
which case the emission will contain vinyl chloride.
The reactor emissions, Key(T), may arise when a run-away condition
develops and due to residual vinyl chloride vapor that may be present when
the reactor manhole is opened for cleaning.
21
-------
Table 3.5: The potential emission points Identified by the keys
In Figure 3.4 1n the suspension polymerization
process for polyvinyl chloride.
POSITION NAME
Vinyl Chlbride
Recovery Vent
Vinyl Chloride
Weighing Tank Vent
Comonomer
Weighing Tank Vent
Reactor Vent and
Opening Loss
Stri pper
Vent
Slurry Blend
Tank Vent
Centrifuge
Vent
Product Collection
Vent
Silo
Vent
Waste
Water
Dryer
Exhaust
Bulk
Loading
Fugitive
KEY
1
2
3
4
5
6
7
8
9
10
11
12
Entire
Plant
FREQUENCY
Intermittent/Continuous
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Continuous
Continuous
Intermittent
Intermittent
Interim' ttent/Conti nuous
22
-------
Keys(T)j^6)and(7)are all associated with the stripping, blending and
drying operations of the polyvinyl chloride slurry. In each of these
operations vinyl chloride emissions may occur [4]. Keys(^8)and(^9)are
points where emissions may occur in the storage and bagging of the
resins, while Key(lO)is the emission point from the waste water treatment
process.
3.3.2 Emulsion (i.e., dispersion) polymerization
The emulsion polymerization process uses equipment basically similar
to that of the suspension process described in Section 3.3.1 [4]. The resin
produced is sometimes called an emulsion resin. Emulsion resins can be
polymerized at lower temperatures and at a higher rate than suspension
resins. However, emulsion resins are also more s'ensitive to heat and shear
stresses. When subjected to either or a combination of heat and shear
stresses, the resultant changes in the resin's physical characteristics may
make it unsuitable for use. The resin obtained from the emulsion process is
of smaller particle size than obtained from the suspension process [4].
The emulsion process flow diagram is shown in Figure 3.5 and the cor-
responding keyed emission sources are presented in Table 3.6. A study of
Figures 3.4 and 3.5 show that the processes are identical in the following
ways: batch reactor process; water is used as the suspending medium to
suspend liquid vinyl chloride; all process equipment is identical except
for the dryer. In addition, the suspension process uses a centrifuge to
aid in drying while the emulsion process does not.
In the emulsion process soap and water are used as the emulsifier.
The emulsion process differs from the suspension in the following ways:
more soap is added to the slurry in the reactor which stablizes the
monomer droplets and results in the absence of agglomerates; a spray dryer
is used because it does not produce excessive temperature or shear stresses
during the drying, while the rotary, flash, or fluidized bed dryer used
in the suspension process may produce these stresses [4].
23
-------
ro
(
VCM
RECOVERY
TANK
VCM ,_
FROM TANK CAR' j
VCM
CONDENSER
DISTILLED
/CM STORAGE
A
,/
(
VCM
STORAGE
TANK •
VCM
EVAPORATOR(Opllonol)
L
CO MONOMER
TANK CARS
C
STORAGE
TANKS J
REC. VCM COND.
a COMP.
WEIGHT
TANK
5/
VENT
WEIGHT
TANK
A VENT
BATCH
REACTOR
n
MITIATOR CATALYST
8U5PENDIHC • -
AGENTS
SOLUTION MIXING x-x
TANK a CHARGE PUMP^S/
£P—»©
BULK
SHIPPING
Figure 3.5. Polyvinyl chloride process flow diagram using emulsion (i.e., dispersion)
polymerization.
-------
Table 3.6: The potential emission points identified by the
the keys in Figure 3.5 in the emulsion (i.e.,
dispersion) polymerization process for poly-
vinyl chloride.
POSITION NAME
Vinyl Chloride
Recovery Vent
Vinyl Chloride
Weighing Tank Vent
Comonomer
Weighing Tank Vent
Reactor Vent and
Opening Loss
Stripper
Vent
Slurry Blend
Tank Vent
Spray Dryer
Vent
Product Collection
Vent
Silo
Vent
Process
Water
Bulk
Loading
Fugitive
KEY
1
2
3
4
5
6
7
8
9
10
11
Entire
Plant
FREQUENCY
In termi ttent/Cont i nuous
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Continuous
Intermittent
Intermittent
Intermi ttent/Conti nuous
25
-------
3.3.3 Latex dispersion polymerization
Latex resins are produced by the emulsion process [4]. The latex
resin Is polymerized vinyl chloride monomer suspended In water. It 1s sold
and transported in this solution form. The process is identical in almost
all ways to the suspension and emulsion processes. It differs 1n that
there is no drying process step and more soap is added in the reactor than
for the emulsion or suspension processes [4]. The result is a latex resin which
is a colloidal suspension of polyvinyl chloride. The process flow diagram
and most probable emission sources are shown in Figure 3.6 and Table 3.7,
respectively.
3.3.4 Bulk polymerization
The bulk polymerization process is a batch process and consists of
two polymerization steps [4]. In the pre-polymerization reactor there is
liquid vinyl chloride in the presence of a polymerization initiator. The
reactor is of a similar design to that used in the suspension process. The
conversion to polyvinyl chloride from vinyl chloride is in the range 7 to
12% [4]. This suspended polyvinyl chloride in liquid vinyl chloride is
then transferred to a larger, high pressure, horizontal-type reactor.
To this is added more liquid vinyl chloride and initiator. This reactor,
sometimes called an autoclave, serves as the post polymerization reactor
resulting in a reaction efficiency of approximately 85 to 90% [4]. The post-
polymerization reactor is more rugged and the agitation more vigorous
than the pre-polymerization reactor [4],
The post-polymerization reactor must be cleaned after each batch;
less frequent cleaning is required for the pre-polymerization
reactor.
The bulk process is similar in most aspects to the suspension process.
Since there is no water or water vapor in the suspension, low temperature
(-35°C or -31°F as opposed to 7°C or 44.6°F in the suspension and dispersion)
condensers may be employed in the recovery system. Moreover, the drying
operation is not needed, and no in-process waste water system is present [4],
The remaining monomer in the post-polymerization vessel may be removed
by a number of processes. The monomer may be removed by vacuum alone.
Another method is to introduce steam into the autoclave and the steam and
released vinyl chloride are removed by vacuum. The steam-vacuum
26
-------
ro
VCM
FROM TANK CAR'
C
VCM
fvENT
(ra
VCM
CONDENSER
DISTILLED A
VCM STORAGE^
CVCMN
STORAGE 1
TANK J
VCM
EVAPORATOR (Optional)
T.
CO MONOMER
TANK CARS
C:OMONOMERN
STORAGE )
TANKS J
REC. VCM COND.
ft COMP.
INITIATOR CATALYST
SUSPENDING ft
'SURFACE ACTIVE
AGENTS
JPUMP
SOLUTION 'MIXING
TANK 8 CHARGE PUMP
Figure 3.6. Polyvlnyl chloride latex process flow diagram using emulsion (i.e., dispersion)
polymerization.
-------
Table 3.7: The potential emission points Identified by the keys
in Figure 3.6 in the emulsion (i.e., dispersion)
polymerization process for polyvlnyl chloride latex.
POSITION NAME
Vinyl Chloride
Recovery Vent
Vinyl Chloride
Weighing Tank Vent
Comonomer
Weighing Tank Vent
Reactor Vent and
Opening Loss
Stripper
Vent
Slurry Blend
Tank Vent
Product Collection
Vent
Loading
Station
Fugitive
KEY
1
2
3
4
5
6
7
8
Entire
Plant
FREQUENCY
Intermi ttent/Cont i nuous
Intermittent
Intermittent
Intermittent
Intermittent
Intermittent
Continuous
Continuous
Intermittent/Continuous
28
-------
procedure may be repeated as many times as required to meet the emission
standard. Those plants using the steam-vacuum process require wastewater
stripping to bring the wastewater in compliance with the emission
standard. Whichever method is used, the recovered monomer is placed in
a temporary holding tank and recycled back to the pre-polymerization
reactor through a filter [4].
The process flow diagram and the potential emission points are
given in Figure 3.7 and the keyed_emission points listed in Table 3.8 [4],
3.3.5 Solvent polymerization
The solvent polymerization product is considered a speciality product
and is a small segment of the total PVC industry [5]. However, it serves a
large number of important needs that usually involve thin PVC coatings,
such as for the food and beverage industries [5]. The early developed process
is shown in Figure 3.8 and the more recently developed process is shown
in Figure 3.9 [5]. The processes are similar in most aspects, differing
more in the technological developments of recent years than in the basic
process operations. The early process is described below followed by
the points of difference.
The early process flow diagram is shown in Figure 3.8 and the cor-
responding source emission points listed in Table 3.9. The emission
points in Table 3.10 correspond to the process flow diagram shown in
Figure 3.9. The comonomers. initiators and solvents are continuously
introduced into the reactor.
The process flow shows that the VCM, comonomer and initiator are
introduced into the reactor along with the solvent, usually n-butane [4"].
The comonomer is almost always vinyl acetate. The continuous process
provides a degree of turbulence among the constituents in the reactor
that results in a copolymer conversion efficiency approaching 100%. A
continuous copolymer stream is drawn off from the reactor and filtered.
The filter cake is passed on to a flash evaporator where it is dried
and the monomers recycled. The solvent is drained from the filter and
recycled back into the reactor along with the recovered monomers. During
any one pass of the solvent stream, some solvent is lost to the process;
therefore a solvent make-up stream is also required [4],
29
-------
NITROGEN
CO
O
INITIATOR
VENT
COMPRESSOR
-O-D
RECYCLE
CONDENSER A
PRESSURE
REDUCER
n—*
o—-a
AIR COLLECTOR
POST
POLYMERIZATION
REACTOR
MILL
Figure 3.7. Polyvinyl chloride process flow diagram using bulk polymerization.
-------
Table 3.8: The potential emission points identified by the
keys in Figure 3.7 in the bulk polymerization
process for polyvinyl chloride resin.
POSITION NAME
Pre-Polymerization
Reactor Vent
Post-Polymerization
Reactor Vent
Monomer Holding
Tank Vent
Recycle Condenser
Vent
Pressure Reducer
Vent
First Bag House
Vent
Second Bag House
Vent
Reject Vent
Fugitive
KEY
1
2
3
4
5
6
7
8
Entire
Plant
FREQUENCY
Intermittent
Intermittent
t
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Intermittent/
Continuous
31
-------
CO
INi
VENT
f©
(VCM A
STORAGE }—
1
CO M
minii
INITIATO
VENT
f RECEIVING J
(SOLVEK
MAKE-l
rSOLVENT \
•UP J
VENT
I SOLVENT
I a
VMONOMER
I
GRINDER
BAGGING a
SHIPPING
SCRAP
BAGGING
SHIPPING
di)
Figure 3.8. Early polyvlnyl chloride process flow diagram using solvent polymerization,
-------
co
co
Monomers
and
Solvent
Storage Area
Solvent and
Vinyl Acetate
Packaging
Figure 3.9. More recent polyvlnyl chloride process flow diagram using solvent polymerization,
-------
Table 3.9: The potential emission points Identified by the
keys In Figure 3.8 1n the solvent polymerization
process for polyvlnyl chloride and copolymers.
POSITION NAME
Receiving Tank Vent
VCM Storage Vent
Reactor Vent
Flash Evaporator (Stripper)
Solvent and Monomer
Recovery
Bag Filter
Bag Filter- Screen
Grinder Filter
Grinder Filter-Screen
Storage S1lo
kilk Loading
:ugitive
KEY
1
2
3
4
5
6
7
8
9
10, 11
12, 13
Entire
Plant
FREQUENCY
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Intermittent
Intermittent/
Continuous
34
-------
Table 3.10: The potential emission points Identified by the
keys 1n Figure 3.9 in the solvent polymerization
process for polyvinyl chloride and copolymers.
POSITION NAME
Reactor
Monomer Condenser
Resin Drying
Silo
Solvent and Vinyl
Acetate Condenser
Fugitive
KEY
1
2,3,4
5
6
7
Entire
Plant
FREQUENCY
Continuous
r, Continuous
Continuous
Continuous
Continuous
Intermittent/
Continuous
35
-------
Vinyl chloride emissions from the reactor area in a continuous
process are relatively lower than from batch processes [4]. There is some
evidence to suggest that the vinyl chloride is more easily removed
from the resin than in other polymerization processes.
The most important difference between the processes is that the
earlier process produced a slurry as a result of polymerization while the
later process produces a solution. The stripping operation from solution
gives a lower VCM concentration and,typically produces less emissions.
Moreover, inprocess water comes into contact with the polymerized material
after the stripping operation. This avoids the requirement of an inprocess
water stripper, and the inprocess water storage and treatment equipment
should not give any emissions. Finally, drying is accomplished by means
of hot air rather than flash evaporator.
3.4 CLARIFYING NOTE ON THE BALANCED OXYCHLORINATION - DEHYDROCHLORINATION
PROCESS
Oxychlorination and direct chlorination are the two major processes
used for e'thylene dichloride production [4]. EDC plants operate a balanced
process which consists of a vinyl chloride plant and a direct chlorination
plant [4].
A block diagram of the balanced process is shown in Figure 3.10.
Typically ethylene dichloride refining is common to both the direct chlori-
nation and to the oxychlorination plants. Therefore, the ethylene dichloride
crudes are refined through the same equipment. In Figure 3.10 the EDC
refining equipment is shown to be part of the EDC oxychlorination plant. The
crude oroduced from the oxychlorination plant may contain vinyl chloride
monomer. Therefore, the common receiving point of the monomer and all down-
stream parts of the direct chlorination plant are subject to the Standard.
That the crude from the oxychlorination plant may contain vinyl chloride
arises because of recycled ethylene dichloride and because the recycled hydrogen
chloride used is a by-product of the monomer cracking. In Figure 3.10 this
is shown by the flow of HC1 and EDC from the dehydrochlorination to the
oxychlorination reactors and EDC refining, respectively.
36
-------
HCI
EDC OXYCHLORINATION
PLANT
EDC OXYCHLORINATION
REACTORS
«.
,r EDC CRUDE
EDC REFINNIN6
UNREFINED
EDC
REFINED
EDC
VCM
DEHYDROCHLORINATION
PLANT
VCM
•0, (AIR)
CH
EDC DIRECT
CHLORINATION
PLANT
Figure 3.10. Block diagram of a balanced oxychlorination-
dehydrochlorination process.
37
-------
The economics of the PVC industry demands that large producers of EDC
employ the balanced oxychlorination - dehydrochlorination type plants [4].
From Eq. (3-3) it is seen that for each vinyl chloride molecule produced
in the cracking of EDC, one HC1 molecule evolves as a by-product. This
forms the HC1 stream in Figure 3.10. However, in the oxychlorination
reaction, governed by Eq. (3-1), two HC1 molecules are required for
each EDC molecule produced. The HC1 by-product provides at a maximum
one-half the EDC required by the cracking furnace. Therefore, the
direct chlorination process must supply at least one-half of the EDC
required in a balance type plant. Presently, 95% of the EDC annual
production rate is produced in balance type plants.
3.5 PHOTOGRAPHS OF EQUIPMENT
The technology employed in the EDC, VC and PVC industries is of a
relatively higher technical level than Inspectors normally encounter in
other plant ins. ections subject to the Clean Air Act. In addition, specific
processes differ for the same general product class from plant to plant. In
many cases, if not in most, the equipment used was constructed according
to unique specifications. The operation of the equipment may be different,
in which case the materials, size, shape and their placement in the plant
may also be different. Typically, the Inspector 1s not able to draw from
experiences gained of previous inspections to the degree that is commonly
done in other industries.
To assist the Inspector in conducting complete and efficient plant
inspections, photographs of equipments are shown In Figures 3.11 to 3.39
from which VC emissions are more likely to occur. From photographs of
general types of equipment such as reactors, strippers, storage vessels,
etc., it will be less difficult to determine the function of more specialized
equipment types. No attempt has been made to present photographs of dif-
ferent types and sizes of equipments because this would require in excess
of 200 photographs. Table 3.11 gives the figure numbers and the equipment
category of those selected for reproduction in this Manual.
38
-------
Table 3.11: Figure number of photographs and corresponding
equipment category.
Figure Number
Equipment Category
3.11 to 3.15
3.16 to 3.18
3.19 to 3.24
3.25 and 3.26
3.27 to 3.32
3.33 and 3.34
3.35
3.36 and 3.37
3.38 to 3.39
Reactors
r t
Strippers
Storage Vessels
Dryers
Distillation Vessels
RD/SRV
Double Mechanical Seal
Railroad tank car loading and
unloading
Incinerators
39
-------
Manual
Vent
Figure 3.11 Large capacity EDC
reactor using the oxychlori-
nation process is located in
the tall vessel. The oxy-
chlorination manual vent is
the open ended pipe, rising
above the top of the reactor
on the left side.
EDC Reactor
RD/SRV
PVC
Reactor
Figure 3.12 The tops of medium capacity, side-by-side PVC reactors using the
emulsion process may be seen. Individual RD/SRV and manual vents
may also be seen mounted on top of each reactor.
40
-------
Elephant Trunk
RD/SRV
Vent
PVC Reactor
Figure 3.13 Small size PVC reactor with cover removed
to clean reactor in preparation for next polymerization
run. Prior to removing cover the PVC and water solu-
tion were removed and transferred to stripper.
"Elephant trunk" is placed through the opening to vent
vinyl chloride gas through "trunk" to the recovery
system in order to be in compliance with emissions
standard reactor opening loss. This type reactor is
used in the suspension, emulsion and latex polymeri-
zation processes.
Figure 3.14 Medium capacity side-by-side PVC
reactors using solvent process. Individual
RD/SRV and manual vents connected to vinyl
chloride recovery system may also be seen.
Lower portion of reactors comprise the heating
elements to raise the contents to the tem-
perature required for polymerization.
-------
Motor
Valve
PVC
Reactor
Figure 3.15 The top of medium capacity, side-by-side PVC reactors using soFvenf
process. Foreground shows a motor valve for emergency venting
through to the VC monomer recovery system.
SRV
PVC
Stripper
Vessel
•
Figure 3.16 The top of a small capacity PVC stripper vessel used in the
suspension, emulsion and latex processes, showing an SRV.
42
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-I-
oo
Stripper
Column
Waste Water
Stripper
Column
Figure 3.17 A stripper column is shown that removes
VC from a PVC-varnish solution resulting from the
solvent polymerization process.
Figure 3.18 A typical wastewater stripper column
is shown that may be found in EDC, VC and PVC
plants.
-------
Figure 3.19 The top of an EDC storage tank is shown with its vent.
RD/SRV
Vents
Figure 3.20 Cylindrical, side-by-side, above ground VC storage tanks are
shown. RD/SRV vents may be seen on pipe rack above tanks.
44
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Vents
Figure 3.21 Spherical, above
ground vinyl chloride storane
tanks. RD/SRV vents may be
seen perched on top of sphere
RD/SRV's
VC Storage
Tank
Underground
VC Storage
Tank Area
Figure 3.22 Underground VC monomer storage tank area is shown.
45
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Vent
Waste Water
Stripper Storage
Tank
Figure 3.23 Wash water stripper storage tank with its vent mounted at the top
of the tank in an EDC-VC plant.
Vent
Figure 3.24 Upper portion of tar storage tank shown with vent.
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Resin Rotary
Dryer and
Dust Collector
Figure 3.25 PVC suspension resin rotary dryer and dust collector. Drying is
accomplished by the application of heat and rotary action.
Drying Air Delivery
Pipe
Spray Dryer
Atomization
System
Figure 3.26
PVC dispersion resin spray drying takes place in the cylindrical
building. Large diameter feed pipe, seen at the left of the dryer,
carries drying air to the top of the dryer. Housing for the
atomization system is perched at top of dryer.
47
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Vent
RD/SRV
EDC Light
Ends Distil-
lation Column
Figure 3.27 An EDC light ends distillation column is shown with its RD/SRV vent,
VCM Column
Condenser
Figure 3.28 VCM column
condenser and condenser
vent motor valve.
Motor
Valve
Vent
48
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Vent
RD/SRV
Reflex
Accumulator
Regeneration
Liquid Knockout _
Vessel
Figure 3.29 The top of am EDC light ends column
reflex accumulator showing the RD/SRV vent.
Figure 3.30 In the foreground the light ends dryer
regeneration liquid knockout vessel is shown in
balanced EDC-VC plant.
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EDC
Finishing
Column
Motor Valve
Vent
Figure 3.31 An EDC finishing column with the RD/SRV and
its vent mounted on the top. (In some installations
the finishing column performs the function of the
light ends distillation column while in others it
encompasses the functions of both the light and heavy
ends columns.)
Figure 3.32 Foreground shows the insulated vent
piping and motor valve from the reactor
refrigerator condenser vessel in a balanced
EDC oxychlorination plant.
-------
Vents
Common Manifold
of Vent System
RD/SRV's
RD/SRV's
Figure 3.33 Typical RD/SRV assembly with the vents from
each connected to a manifold of the vent system.
Figure 3.34 Dual RD/SRV vents mounted at top of
spherical vinyl chloride storage tank.
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VC Loading Flexible Hose
Railroad Tank Car
en
ro
Pump
Figure 3.35 Typical pump and double mechanical seal
Recovery
System
Flexible
Hose
Figure 3.36 Top connections on railroad tank car shown
with flexible hose attached for VC loading. Smaller
diameter flexible hose in the foreground is connected
to recovery system.
-------
Railroad
Tank Car
VC Feed and
Recovery
Flexible
Hosei
Pipe
Rack
Support
Figure 3.37
Railroad tank car loading platform shown with pipe rack support for
flexible hose VC feed and recovery system in VC plant.
Vent
Scrubber
Stack
Figure 3.38 Oxychlorination
vent scrubber stack.
53
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Stacks
Stack Platform
Incinerator
Building
Figure 3.39 Incinerator and stacks of a PVC plant showing the
platform (center stack) on which stack samples are taken to
determine VC emission concentration.
54
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4.0 LEAK DETECTION MONITORING INSTRUMENTATION, RECORDS, AND REPORTS
A requirement of the Standard is that an EPA-approved leak detection
and elimination program be operational. This requirement includes an
installed continuous leak detection monitoring system, routine leak
detection monitoring with a portable hydrocarbon detector and a leak
elimination plan.
The Standard also requires recordkeeping (recording and retention
for at least two years) of data relating to leaks, detected by one of
several ways.
Conducting a meaningful inspection for the determination of com-
pliance of vinyl chloride emissions in typical EDC-VCM-PVC plants
presents a number of unique challenges. The first is that the technology
used requires a relatively high degree of expertise. The second is that
the plant area, from raw materials to finished product shipping, is
measured in acres rather than in square feet and may extend from below
ground level to several hundred feet above ground. Added to these is
the difficulty in making a definitive determination of some equipment
with respect to the specific process(es) or function(s) 1t serves.
Therefore, the NESHAPs Inspector needs to resort to complementary methods,
in addition to normal inspection procedures, to make a determination of
compliance.
To circumvent these unique challenges, a NESHAPs inspection, of
necessity, will need to rely on the in-plant continuous monitoring
instrumentation and the records obtained therefrom. In this chapter,
the typical continuous monitoring system, the resultant records and
reports are described and discussed. All are required to be in compliance.
4.1 LEAK DETECTION MONITORING INSTRUMENTATION
The Standard promulgated on October 21, 1976 requires that continuous
monitoring detection and measurement instrumentation be permanently installed
in a plant in which vinyl chloride may be emitted to the atmosphere.
55
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Typically", the instrumentation consists of a vinyl chloride or hydrocarbon
measurement instrument, mini-computer, computer program for data acquisition
and data reduction, data terminal and assorted 1/4" stainless steel tubing,
solenoid valves, vacuum pumps, etc. The measurement instrument may be a
gas chromatograph or, if the owner/operator assumes that all hydrocarbons
measured are vinyl chloride, an infrared spectrometer or flame ion detector
or an equivalent or alternative method.
The monitoring instrumentation is based on area (i.e., volume)
sampling. However, some plants will also monitor fugitive emission
sources such as pump seals, agitator seals, couplings, etc. The typical
instrumentation system uses one measurement instrument with a system of
tubing that serves to draw air samples from an area of the plant into
the detector air sample chamber where a measurement of vinyl chloride
concentration is made. The concentration value is then transmitted
to the computer memory to be printed out on the computer terminal at
a later time. The time interval between measurements is 1 to 3 minutes.
Usually, each monitoring point is measured in sequence and the sequence
is unchanging. When all points associated with a measurement instrument
have been measured for vinyl chloride emissions and transmitted to the
computer memory, the computer program provides for each measurement to
be printed in tabular form. Each measurement is identified with respect
to the time of the measurement and location within the plant. Depending
on the computer program, average vinyl chloride emissions for each point
on the basis of shift, day, week and month may also be printed out and
become a part of the record. In some instances, the data terminal does
not print any measurement made unless the vinyl chloride concentration
is greater than some defined level, such as 5 ppm. Plants that employ
this system will record each measurement for each point on the measurement
instrument's printer. It, too, becomes a part of the required recordkeeping.
Usually the concentration is measured at each point at least every 25
minutes. Each plant sets its own threshold level for the purpose of
defining a leak. In most cases, two consecutive measurements from the
56
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same monitoring point equal to or greater than the concentration threshold
value are used in the definition of a leak. The concentration threshold
level is the definition of a leak for the leak detection monitoring system.
This definition requires the approval of the EPA Administrator and it is
set at a level compared with the vinyl chloride background concentration.
When two consecutive measurements at a point indicate a leak, plant
personnel assigned to the "Leak Detection Patrol" investigate with a
portable instrument the region of the plant in which the monitoring point
is located.
The monitoring system is required to be calibrated daily by one of
two methods, described in 61.68(c). Some plants reserve one of the
points in the sequence of point measurements for calibration. Thus, the
instrument is calibrated in each sequence of measurement.
Some plants may use more than one measurement instrument when a
large number of points are being monitored. The number of points under
observation by an instrument ranges from 9 to 19, while the total number
in a plant ranges from 9 to 76. However, EPA approval is required with
respect to the position and minimum number of points.
A schematic of a monitoring system is shown in Figure 4.1 for which
there are n-air sample inlets. When a solenoid valve is activated, it
allows an air sample to be drawn by a vacuum pump from a point in the
plant into the detector air sample chamber. The pump operates continuously,
evacuating the manifold of the previous air sample so as not to influence
the vinyl chloride concentration measurement of the next air sample. In
addition, the volume of the air sample drawn prior to actual measurement
is sufficient to effectively purge the detectov air sample chamber of any
residue from previous air samples.
The switching of the solenoid valves may be accomplished by one of
two methods: a mechanical or electronic timer where the sequence is
unchanging; a computer-control led system where the sequence may be changed
according to a program. Those installations using timers usually activate
one solenoid at any one time. Computer-controlled systems may have
sophisticated programs where one or more solenoids may be operated to more
quickly assess the emission(s) in one or more plant areas.
57
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PUMP
AIR SAMPLE
FLOW
ifi
DETECTOR
AIR SAMPLE
CHAMBER
DETECTION
INSTRUMENT
J C
J L
U
#3
T
/T\
Air
Sample Inlet
Probe Location 1
Solenoid
Valve
#n-3
RINT
OUT
t
#n-2
Tubing
#n-l
#n
Figure 5.1: Schematic diagram of continuous monitoring system
for vinyl chloride emissions.
58
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4.2 LEAK DETECTION MONITORING RECORDKEEPING
The owner/operator is required to record data, retain the records
on location for a minimum of two years and to make available, upon request
of an EPA representative, those records obtained from the continuous leak
detection monitoring system.
Specific data of the detected leaks will be recorded and retained
which pertain to the location within the plant, vinyl chloride concen-
tration and the date and approximate time of measurement.
4.3 ROUTINE LEAK DETECTION AND RELIEF DISCHARGE RECORDKEEPING
The owner/operator is also required to record data, retain the
records on location for a minimum of two years and to make available,
upon request of an EPA representative, records obtained of leaks detected
during routine monitoring with a portable hydrocarbon detector and for
relief discharges from reactors.
Specific data of each leak detected during routine monitoring will
be recorded and retained which relate to location within the plant, vinyl
chloride concentration, date and time of measurement, cause of each leak,
and the action taken to repair or eliminate each leak.
59
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5.0 INSPECTOR SAFETY
Prior to inspecting an EDC-VC, VC, or PVC plant, an inspector
should check the plant's records to determine whether any leaks have
occurred in the past several days and whether any leaks are currently
being experienced.
Before entering a plant the inspector should check to assure he has
the proper safety equipment, including safety shoes, safety glasses,
hard hat, and a respirator specified for use with vinyl chloride. Any
safety regulations and plant emergency responses should be noted by the
inspector.
60
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6.0 INSPECTION PROCEDURES AND INSPECTION FORMS
The plant's compliance with the Standard will be determined through
periodic inspections by an EPA representative, in addition to data required
in the semi-annual reports on stripping and reactor opening loss and on
emission tests. The inspection entails a physical inspection as well as a
review and assessment of the plant's records.
In the following presentation, a number of forms have been developed
for the purpose of aiding the inspector to make«a definitive inspection
in the most efficient and expeditious manner. If the forms are used
properly, all major facets in the Standard will be covered. In fact,
the questions and statements that make up the forms mirror the major
facets of the Standard. Moreover, the questions and statements have been
couched so that answers and responses may elucidate or reveal non-
compliance conditions. Ideally, all questions and statements on all forms
will be answered completely during the regular or periodic inspections.
However, some plants may excel in complying with one or more sections
of the standard. An inspector having become aware of this fact may elect
not to pursue questions and statements relating to that portion of the
Standard.
The frequency of the inspections is not recommended in this document,
because this is a function of personnel being available on a regular basis.
Besides, experienced inspectors are the best judge of the required inspection
frequency.
The forms described below are self-explanatory and provide a sequence
that an inspector may choose to follow during an inspection. Questions
which may be answered prior to the actual inspection (or verified after
the inspection) are identified on the forms by an asterisk. Suggested
sources for this data, from records on file at EPA Regional Offices,
include plant Standard Operating Procedures, the Leak Detection Program
and Initial, Semi-annual and other required reports. High potential
61
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leak sources and any violations can be Identified from previous inspection
reports. If this data is recorded on the forms prior to the inspection,
it should be confirmed during the inspection and any inconsistencies
noted. Similar notations should be made on the forms when data collected
during the inspection is later compared with data from Regional Office
records.
6.1 SUMMARY OF COMPLIANCE STATUS
This form serves to summarize on one page the status of the plant
with respect to the major facets of the Standard. The questions and
statements serve to determine where emissions occur and at what levels,
the emission control devices used for each emission source and the
waivers that have been issued. This form will be most useful to personnel
of the Enforcement Division having responsibility to make a determination
of compliance.
6.2 CHECKLIST
This form contains 29 question and statements requiring responses.
They are grouped under the following categories: General, Leak Detection
Monitoring System, Stack Emission Monitoring System, Portable Instrument,
Leak Detection and Elimination, Discharges to the Atmosphere, Fugitive
Emissions, Reactors and Furnaces, Control Devices, Stack Emissions,
Inprocess Wastewater and Reactor Opening Loss. The responses require the
inspector, in most cases, to actually view and verify. In the case of
instrumentation, there is provision for the inspector to determine the
accuracy of the instrumentation and/or system calibration. It is strongly
recommended that a calibration be performed on one or more monitoring
points of the leak detection monitoring system. In doing so, the inspector
automatically checks the integrity of those monitoring points.
It may be more practical for the plant's personnel to provide the
responses to No. 23 rather than the inspector. However, the inspector
should be present during the time the sample is being prepared and data
obtained. '
It is strongly recommended that the inspector observe in its entirety
the plant's procedure to determine the reactor opening loss.
6.3 ON REVIEW OF RECORDS
Due to the maturity of the PVC industry and the economic environment
62
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that results, EDC, VCM and PVC are typically large capacity plants. One
plant may cover many acres and extend tip to 100 to 200 feet above ground
level as well as below ground level. It may be physically Impossible for
an Inspector to inspect all parts of a plant in person. It is strongly
recommended that the central point of the inspector's focus be placed on
the records that the plant is required to maintain, and particularly
the leak detection monitoring system. Therefore, the review and assessment
of the plant's records-is an important aspect of every inspection. The
Items in the form provided for the review of records 1s designed to
elucidate compliance at the major or potential emission points.
6.4 PRE-TEST EQUIPMENT CHECKLIST FOR STACK EMISSION TEST
The stack emission test required in the Standard, Test Method 106,
is very clear and precise on the equipment and apparatus to perform
the test. This form is designed to ensure that both inspector and
plant personnel are reminded of the entire equipment and apparatus list
required. It also serves to document alternative or equivalent
equipment or procedures.
6.5 EQUIPMENT CHECKLIST FOR VINYL CHLORIDE CONCENTRATION IN INPROCESS
WASTEWATER, RESIN, SLURRY, WET CAKE AND LATEX SAMPLES
Test Method 107 is also clear and precise on the equipment and
apparatus required to analyze samples in a head space analyzer. This
form is designed to aid the inspector and plant personnel in conducting
analytical tests that conform with the Standard.
63
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SUMMARY OF COMPLIANCE STATUS (SCS) Inspection Date_
Inspector's Name_
Firm's Name
NESHAPS INSPECTION FOR VINYL CHLORIDE EMISSIONS COMPLIANCE
Firm's Address
PARAMETER OR ITEM
*1 Emission Sources
*2 Where ducted?
Atmosphere or Control Device
*3 Emission Control Device
Description
In Existence
Date to be Installed
*4 Frequency of Emissions
Cont. /Intermit. /Emergency
*5 Applicable Regulations
*6 Emission Standard
ppm by vol. or ppm by wt.
or gm. per Kg.
*7 Estimated Emissions
ppm by vol. or ppm by wt.
or gm. per Kg.
*8 Monitoring Requirements
*9 Waiver Applications
*10 Date Waiver Issued
*11 Remarks on Compliance
Emissions & Emission Tests
Waivers
Recordkeeping
EMISSION SOURCE STATUS
* Data may be available from records on file at EPA Regional Offices.
-------
CHECKLIST
NESHAPS INSPECTION FOR VINYL CHLORIDE EMISSIONS COMPLIANCE
Inspection Date
Inspector's Name
GENERAL
1* Firm's name
2* Finn's address
3* Process designation/product identification (check one or more):
EDC: n oxych 1 orination Q balanced d N.A.
VCM: D hydrochlorination Q dehydrochlorination Q N.A.
PVC: D suspension Q dispersion Q latex D N.A.
D bulk Q solution Q copolymer
4. Rated and average annual reactor/cracking capacity
EDC: Design* ; Normal Max* ; Actual
VCM: Design* ; Normal Max* ; Actual
PVC: Design* ; Normal Max* ; Actual
LEAK DETECTION MONITORING SYSTEM
5*. Permanent leak detection monitoring system [61.65(8){i)J
a) Total number of points monitored:
b) Number of measuring instruments: ; Type(s)
c) Time interval to cycle all points:
d) Definition of a Leak:
e) Lower detection limit (LDL) of instrument
f) Measurement sequence:Q unchanging Q program controlled
g) Data reduction (check one or more)
D none D hourly Q shift Q daily Q weekly Q monthly
Q other (specify)
* Data may be available from records on file at EPA Regional Offices.
65
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6. Calibration of leak detection monitoring system [61.65(8)(111)]:
a) List Instruments and data from monitor points which
were tested for calibration. (Attach sheets If more
space is required.)
Date &
Time
Location
in Plant
Instrum.
Iden.
Cal. VCM
Concen .
Instrum. VCN
Concen .
Percent
Deviation
Action
Required
b) Calibration method used (check one or more)
D None
Q Paragraph 61.65(8)(111)(A) - Test Method 106 - 5.2.1, 5.2.3
D Paragraph 61.65(8)(111)(B)
D Other
STACK EMISSION MONITORING SYSTEM
7* Emission (I.e., stack) monitoring system
a) List emission (i.e., stack) sources
Location
in
Plant
Ducted
Processes
Continuous
or Sampling,
Other
Number of
Monitoring
Points
h) |nwer Detection 1 1m1t (LF)L) of instrument _
66
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8. Calbratlon of emission monitoring system:
a) List instruments and data from monitor points which were
tested for calibration.
Date &
Time
Location
in Plant
Instrum.
Iden.
Cal. VCM
Concen .
Instrum. VCM
Concen .
r
Percent
Deviation
Action
Required
PORTABLE INSTRUMENT
9. Calibration of portable hydrocarbon detector(s):
a) List instrument(s) which were tested for calibration
Date &
Time
Location
in Plant
Instrum.
Iden.
Cal. VCM
Concen .
i
Instrum. VCM
Concen.
Percent
Deviation
Action
Required
b) Calibration method used (check one or more)
D None
Q Paragraph 6l.65(7)(ii1)(A) - Test Method 106-5.2.1, 5.2.3
D Paragraph 61.65(7)(111}(B)
Q Other
67
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LEAK DETECTION AND ELIMINATION
10* Leak detection and elimination process [61.65(8)1
a) What 1s the frequency of the "Leak Detection Patrol"?_
b) Check typical points and equipment which are required to be routinely
checked for leaks by the "Leak Detection Patrol" in the following:
P reactor
Q cracking
furnace
D stripper
D EDC purification
P recovery system
P mixing
P weighing
D holding tank
n separation tank
P blending tank
D storage - raw
D storage - finished
P Others:"
n storage - heavy
Q storage - water
D light ends col.
P heavy ends col.
n wastewater col.
n water wash col.
Q water quench col
Q wash water
stripper
D dryer
n condensers
D RD/SRV
D control devices
D pumps
Q compressors
Q agitator(s)
D loading
Q unloading
D flanges
D valves
D filter strainers
P centrifuges
P holding bins
P silos
c) What is the average elasped time between the determination of a
leak by personnel of the "Leak Detection Patrol" and the plant's
personnel taking corrective action for the purpose of eliminating
the leak?
Small leaks:
Large leaks:
d) What is the average elapsed time between the monitoring system
alarm becoming activated and the plant's personnel taking
corrective action for the purpose of eliminating the leak?
Small leaks: ___
Large leaks:
DISCHARGES TO THE ATMOSPHERE
11. List any SRV's which do not use RD's or vent to recovery
system or to gas hold tank.
Location in Plant
Comments
68
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12. If a pressure gage 1s located between rupture disc (RD) and safety relief
valve (SRV), list points in the plant where the gage indicates a higher than
normal pressure, typically 0 to 5 psig. (Note: While in common use in plants,
a pressure gage between RD and SRV 1s not a requirement of the Standard.)
Identify those RD/SRV points which are in PVC plants by check (/} in column 3.
RD/SRV
Identification
Location
In Plant
PVC
Service
Inspector's
Comments
13? List vents, other than emergency types, which are vented to the atmosphere
and not connected to a recovery system, and which are suspected of having
had short and/or long periods of emissions exceeding the limits specified
in Sections 61.62, 61.63, 61.64 and 61.65.
Vent
Identification
Location
In Plant
Location of Nearest
Monitoring Point(s)
FUGITIVE EMISSIONS
14. Investigate and witness the plant's standard operating procedure [61.65(c)l
for fugitive emission sources [61.65(b){1), (b}(2), (b)(5), (b)(6) and
(b)(7)j and list any possible deficiencies.
Pertinent Fugitive
Emission Source
Location
In Plant
Possible
Deficiency
69
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15. Are plant personnel following the established standard operating procedures?
n Yes D No
16. If the response to the above Is "NO", 11st pertinent fugitive emission
source, location In plant and action required where the established standard
operating procedure 1s not being followed.
Pertinent Fugitive
Emission Source
Location
In Plant
— - -
Action
Required
17* List equipment, location in plant, identification in the process of
any pump, compressor and agitator which 1s not equipped as seal-less
or with a double mechanical seal or double outboard seal, and
does not duct emissions through a control system, or maintain
proper pressurization between seals or equivalent.
Equi pment
Location
In Plant
Identification
In Process
Inspector's
Comments
18* Incoming raw material received by:
D pipeline Q Truck Q Rail
19* Finished product material shipped by:
D Pipeline Q Truck D
70
D Barge
Q Barge
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REACTORS AND FURNACES
20? Give the number of reactors for each capacity.
EDC: Capacity Number
PVC: Capacity
Number
VCM (Hydrochlorination):
Ca pac i ty.
Number
21? Give the number of cracking furnaces.
VCM(dehydrochlorination): Capacity
Number
CONTROL DEVICES
22* List control devices, location in plant, major entering streams, major
exiting streams, vent location.
Control
Device
Location
In Plant
Major
Entering Streams
Major
Exiting Streams
Vent
Location
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STACK EMISSIONS
23. List plant's performance specifications of stack emission continuous
monitoring Instrumentation:
a) Stack identification ;
b) Mean value, __^ , calculated from a series of absolute
measurements made by using the equipment specifications and
procedure of reference Test Method 106 (see APPENDIX A);
c) Number of measurements used to calculate the mean value ;
d) Accuracy, percent of the mean value;
e) Calibration error, percent of each calibration
gas mixture value;
f) Zero drift (2 hr.), percent of calibration span;
g) Zero drift (24 hr.), percent of calibration span;
h) Calibration drift (2 hr.), percent of calibration span;
i) Calibration drift (24 hr.), percent of calibration span;
j) Response time, (Time required from the insertion
of a known vinyl chloride concentration gas sample into the
stack and the stack instrument indicating a value 95% of the
known vinyl chloride concentration).
24. If more than one stack was tested, and if the other test data were
significantly different from the above data, use attach sheets to provide
the information obtained from other stack tests.
25. Were the stack emission tests made under conditions of maximum production
rate?
D Yes Q No
If the response is No, give the percent of maximum production rate under
which the stack emission tests were made: percent.
26. Were all stack samples analyzed within 24 hours? D Yes Q No
If the response is No, give elapsed time, to the nearest hour, from
taking sample to its being analyzed: hours.
72
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27* List deviations or substitutes from reference Test Method 106 equipments
materials and procedures which are required in conducting the stack
emission test.
Equipment/Materials/Procedure
Identification
Deviation or Substitutes
From Test Method 106
Inspector's
Comments
INPROCESS WASTEWATER
28. Identify any inprocess wastewater stream and location in plant which is
mixed with another water stream prior to the reduction of vinyl chloride
concentration to 10 ppm or less.
Inprocess Wastewater
Stream Identification
Location
In Plant
,
Identification
of Process Step
Inspector's
Comments
REACTOR OPENING LOSS
29. Briefly describe the plant's procedure to determine the emission due to
opening the reactor.
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ON REVIEW OF RECORDS
NESHAPS INSPECTION FOR VINYL CHLORIDE EMISSIONS COMPLIANCE
Review Date
Reviewer's Name
Firm's Name
Firm's Address
EMISSION (STACK)
1. Review of hourly Dyes Dno average from continuous stack emission.
2t Number of stack emissions (continuous emissions for 1 hour or more) which
exceeded limits specified in Sections 61.62, 61.63 and 61.64:
Were there additional emissions which were not properly and accurately
reported in the appropriate Semi-annual Report?
D Yes DNo
If the response to No. 3 is Yes, list date, time, emission point
location, duration, estimated integrated emission! and the cause or
causes of emission. (Attach sheets if more space is required.)
Date &
Time
Location
In Plant
Duration
Est. Integrated
Emission
Cause or
Causes
Action
Taken
LEAK DETECTION SYSTEM
5. Review of (check one or more) Qhourly D shift Qdaily Q weekly
Qmonthly average from leak detection system.
Data may be available from records on file at EPA Regional Offices.
74
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6. Number of times one or more monitoring points Indicated emission levels
exceeded the value for the leak definition (See CHECKLIST 5 (d):
7. List date, time, monitoring point location, duration, estimated integrated
emission and the cause or causes of emission of those leaks in No. 6.
(Attach sheets if more space is required.)
Date &
Time
Location
In Plant
Duration
Est. Integrated
Emission
t
Cause or
Causes
Action
Taken
ATMOSPHERIC DISCHARGES
8* List information of emergency discharges to the atmosphere.
Date &
Time
Location
in Plant
-
Duration
Est. Integrated
Emission
Cause or
Causes
Inspector's
Comments
75
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9. Determine from plant records whether temperature, pressure, flow
rate(s) and/or other process variables and/or If equipment failures
(I.e., reduced flow rate of cooling water, defective temperature
controller, etc.) gave rise to the necessity of the emergency dlscharge(s)
from PVC reactors. List the date, time, location in plant and the con-
dition(s) which appear to have produced the need for an emergency discharge(s).
Date &
Time
Location
In Plant
Conditions
10.. List the dates and time when similar or equivalent conditions existed
as in No. 12 and for which an emergency discharge was not reported.
Date &
Time
Location
In Plant
Conditions
76
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11.
Review the leak detection records of those monitoring points nearest
the location(s) and down stream in No. 13 on those dates and times
where conditions existed which appear to give rise to the necessity
of emergency discharge. List date, time, location in plant and the
emission levels of the nearest monitoring points.
Date &
Time
Location
In Plant
Emission Level of Monitoring Points
f e
12. List the date, time, location in plant from the tabulation in No. 14
where the owner/operator appears not to be in compliance with the
NESHAPS vinyl chloride standard and its amendments.
Date &
Time
Location
In Plant
Inspector's Comments
77
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REACTOR OPENING LOSS
13t Review analytical records of vinyl chloride concentration 1n
reactor vapor space to determine "reactor opening loss" of
reactor (and stripper where applicable), prepolymeHzatlon
and post polymerization vessels. List date, vessel identi-
fication, and batch identification where emissions exceeded
standard.
Date
Vessel
Identification
Batch
Identification
Inspector's Comments
RESIN. SLURRY, WET CAKE AND LATEX SAMPLING
Review analytical records of vinyl chloride concentration in polyvinyl
chloride resin, slurry, wet cake and latex to determine the weighed
average residual vinyl chloride concentration in all grades of poly-
vinyl chloride resin processed through the stripping operation on each
calendar day. List date, vessel identification, and batch identifi-
cation where emissions exceeded standard.
Date
Vessel
Identification
Batch
Identification
Inspector's Comments
78
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RECORDKEEPING
15. Review and assess the recordkeeping as required in the standard in
the listing below, and comment on each with respect to completeness,
form and ease of reference.
Record
%
Stack emission monitoring
Leak detection monitoring
Leaks detected by "Leak
Detection Patrol"
Stack emission tests
Reactor opening emissions
Inprocess waste water
emissions
Resin, slurry, wet cake
and latex emissions
Inspector's Comments
79
-------
PRE-TEST
EQUIPMENT CHECKLIST FOR STACK EMISSION TEST
(TEST METHOD 106)
NESHAPS INSPECTION FOR VINYL CHLORIDE EMISSIONS COMPLIANCE
Pre-Test Meeting Date
Inspector's Name
Firm's Name
Finn's Address .
1. Probe
, a) Is probe made of stainless steel, pyrex glass, or teflon tubing?
b) What is temperature of stack?
c) Does probe have glass wool plug? Q Yes Q No
2. Sample line
a) Is sample line made of teflon? Q Yes Q No
b) Is a new unused piece used for each series of bag samples? O Yes Q No
3. Quick connects
a) Are 2 male and 2 female connects used? Q Yes D No
b) Are they made of stainless steel? Q Yes Q No
c) Does the pair for the bag have ball checks? Q Yes Q No
d) Are they assembled as required? Q Yes Q No
4. Rigid container
a) Is container leak proof? Q Yes O No D Unknown
b) Does it have a cover to protect contents from sunlight? Q Yes O No
5. Sampling bags
a) What material are bags made of? _____
b) Are bags of 100 liter capacity? Q Yes Q No Q Unknown
80
-------
6. Needle valve
Will needle valve allow proper adjustment of sample flow? D Yes Q No
7. Vacuum pump
a) Is pump of the leak-free type? Q Yes Q No
b) Does pump have a minimum capacity of 2 liters per minute? Q Yes Q No
8. Charcoal tube
Does a charcoal tube follow pump to prevent admission of vinyl chloride
to atmosphere? Q Yes Q No
9. Flow meter
Does the flow meter have a capability of measuring flow range from 0.10
to 1.00 liter per minute? Q Y*s D No
10. Pi tot tube and manometer
a) What type of pi tot tube is used?
b) Is pitot tube attached to probe? Q Yes D No
c) Will an inclined manometer be used? Q Yes D No
11. List substitutes for equipment and materials required in Test Method 106 in
conducting stack emission tests.
Equipment/Material s
Identification
Substitute
Inspector's Comments
81
-------
12. Is plant 1n compliance with Test Method 106? D Yes D No
13. If the response 1s No, 11st action Items which must be completed prior
to Test date 1n order to conduct stack emission tests:
Action Item 1:
2:
3:
14. Test Date:
82
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EQUIPMENT CHECKLIST FOR VINYL
CHLORIDE IN INPROCESS WASTEWATER,
RESIN, SLURRY, WET CAKE AND LATEX SAMPLES
(TEST METHOD 107)
NESHAPS INSPECTION FOR VINYL CHLORIDE EMISSIONS COMPLIANCE
Inspection Date
Inspector's Name_
Firm's Name
Firm's Address
1. Sample bottles
a) Are the sample bottles of 60 ml (2oz) capacity?
D Yes Q No
b) Do the bottles have waxed lined screw on top?
D Yes D No
c) Do the bottles have electrical tape or equwalent to prevent
loosening of bottle tops?
D Yes D No
2. Vials
a) Are vials of 50 ml capacity?
D Yes D No
b) Are they equipped with sealed Teflon faced Tuf-Bond discs for
water samples?
D Yes D No
c) Are they equipped with seals and caps, Perkin-Elmer Corporation
No. 105-0118 or equivalent?
D Yes Q No D Unknown
3. Analytical balance
a) Is It capable of weighing reproduclblllty to + 0.001 gram?
D Yes D No Q Unknown
83
-------
b) What 1s the weighing span 1n the region of weight that 1s used
1n Test Method 107?
4. Syringe
a) Is Its capacity TOO yi? Q Yes O No Q Unknown
b) Is the model Precision Series "A" No. 010025 or equivalent?
D Yes Q No D Unknown
5. Vial Sealer
a) Is the Model, Perkin-Elmer No, 105-0106 or equivalent?
D Yes D No D Unknown
6. Gas Chromatograph
a) Is the Model, Perkin-Elmer Model F-40 head space analyzer
No. 104-0001 or equivalent?
Q Yes D No D Unknown
b) List substitutes used for the following:
2 m x 3.2 mm stainless steel column;
contains 0.4% carbowax on carbopak A (or Carbopak B)
Perkin-Elmer No. 105-0133 or equivalent:
7. Thermometer
a) Range 0 to 100°C, with accuracy + 0.1°C, Perkin-Elmer No. 105-0109
or equivalent.
D Yes D No
8. Sample Tray Thermostat System
a) Perkin-Elmer No. 105-0103 or equivalent.
D Yes D No
9. Septa
a) Sandwich type, for automatic dosing, 13 mm, Perkin-Elmer No. 105-1008
or equivalent.
Q Yes D No
84
-------
10. Integrator - Recorder
a) Hewlett-Packard Model 3380A or equivalent. Q YesQ No
11. Filter dryer assembly
a) Perkin-Elmer No. 2230117 or equivalent. Q YesQ No
12. Soap Film Flowmeter
a) Hewlett-Packard No. 0101-0113 or equivalent.
D Yes D No
85
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APPENDIX A: MEAN VALUE CALCULATION
The mean value calculated from the reference method (Test Method 106)
test data measurements Is used as a norm to assess the stack emission
continuous monitoring Instrumentation.
The mean value of the data set Is calculated according to the
following expression
n
*-lT I] x.
1=1 1
where
X.; = The 1—absolute measurement obtained from reference Test
1 Method 106,
n
£ = Sum of the n- absolute measurements,
1=1
n = Number of absolute measurements,
X~ = Mean value.
86
-------
APPENDIX B
NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR
POLLUTANTS
Standard For Vinyl Chloride
87
-------
THURSDAY, OCTOBER 21,1976
PART II:
ENVIRONMENTAL
PROTECTION
AGENCY
NATIONAL EMISSION
STANDARDS FOR
HAZARDOUS AIR
POLLUTANTS
Standard For Vloyl Chloride
88
-------
46640
TW*4O—Protection of Enviiwmwm
CHAPTER I—ENVIRONMENTAL
PROTECTION AGENCY
[rat, eta-n
PART 62—NATIONAL EMISSION STAND-
ARDS FOR HAZARDOUS AIR POLLUTANTS
Standard for Vinyl eWorld*
On December 24. 1075, under section
US of the Clem Air Act. a* amended (42
VAC. 1857). the Environmental Protec-
tion Agency (EPA) added vinyl eWorld*
to toe Hit of hasardou* air pollutant*
v(40 PR 6*477) and proposed • national
•mission standard for It (40 PR 59533).
The standard coven plants which manu-
facture ethylene dlchlortde, vinyl
chloride, and/or polyvlnyl chloride.
EPA decided to regulate vinyl chloride
because it has been Implicated as the
fauna! agent of aTiglfHiarK<*mn and other
serious disorders, both carcinogenic and
noncarcthogenic. In people with occupa-
tional exposure and in animals with ex-
perimental exposure to vinyl chloride.
Reasonable extrapolations from these
findings cause concern that vinyl chlo-
ride may cause or contribute to the same
or similar disorders at present ambient
air levels. The purpose of the standard is
to minimize vinyl chloride emissions
tram all known process and fugitive
emission sources in ethylene dlchlortde-
vlnyl chloride and polyvlnyl chloride
plants to the level attainable with best
available control technology. This wffl
have the effect of furthering the protec-
tion of public health by ™«"t™«« average
vinyl chloride concentration, which is
expected to be 5 percent of the uncon-
trolled levels after the standard Is im-
plemented.
Changes m the standard since pro-
posal do not affect the level of control
required. Thus, the environmental Im-
pact of the promulgated standard is.
with one exception, the same as that
described in Chapter 0 of Volume I of
the Standard, support and Xnvtro*mtn~
tal Impact Statement. According to data
submitted by the Society of Plastics In-
dustry, inc. (SPD. the Impact on water
consumption In the draft environmental
Impact statement was overstated. In es-
timating the Impact on water consump-
tion. EPA based its estimates on worst
case conditions. The* to. EPA assumed
that those control systems with the
greatest water usage would be employed
and that there would be no reeycBn*
of water There is no regulation which
would require water recycling. Accord-
Ing to 8PX the control system "**""*"g
the most water win not be used gener-
ally by the industry and economic fac-
tors win cause plants to recycle much
of the water. Therefore, according to
SPI the impact of the standard on water
consumption wffl be Ti«gHgtM»
The environmental impacts of the
promulgated standard may be summar-
ized as follows: The primary environ-
mental impacts of the standard are ben-
eficial and wfll consist of vinyl chloride
emission reductions of approximately 04
percent at ethylene dlchloride-vinyl
chloride plants and 96 percent at poly-
vinyl chloride plants. Percentage num-
bers for both source categories are based
on an estimated 90 percent reduction m
fugitive emissions and 1974 emission
levels.
The potential secondary environmen-
tal impacts of the standard an either
insignificant or wfll be **'*M*'*'*
-------
•UUS AND REGULATIONS
485€1
fa Chapter T of Voiumeof
ActnMiit. Comments OB ttw
propoMd standard have resulted to only
one major change In the economic tan-
pMt analysfc. SPA estimated that there
would be four plant closures u a matt
of the promulgated standard. Of the 1 our
plants Identified M possible elotara can-
didate* on* has given notice that it no
loafer produce! polyvmyl chloride and
the other three have Indicated that they
do not Intend to cloee a* a result of the
standard.
The economic impact* of the promul-
gated standard ™*y be summarised aa
follows: The total capital cost for exist-
ing plants to meet the standard Is esti-
mated to be $19$ mffllon, of which $15
mifflon is for ethylene dlchtorlde-vmyl
chloride plants and $185 mffllon is for
polyrlnyl chloride plants. EPA estimates
that these plants will hare to spend $70
million per year to maintain the required
emission levels. In addition, the total
capital cost for existing plants to meet
the EPA's 1983 water effluent guideline
limitations Is expected to be $83 million
and the total finTWf1l*f1 operation cost
Is $1? million. The costs to the industry
of meeting the OSHA standard cannot be
quantified at this time, but they are ex-
pected to overlap to some degree with the
costs to meet EPA,'s fugitive emission
regulations. The costs of meeting the
fugitive emission regulations are Included
m the total costs cited above for meeting
the promulgated regulation. Broken out
separately, the capital cost of meeting
the fugitive emission regulations is $37
mffllon and the annualteed cost is $85
The standard is not expected to deter
construction of new ethylene dtebloride-
vlnyl chloride plants or most types of
new polyrlnyl chloride plants. For one
type of polyvlnyl chloride plant (disper-
sion process) that represents 13 percent
of the Industry production, the standard
would significantly deter the construc-
tion of smaller plants.
It Is estimated that the price of poly-
vinyl chloride resins wffl rise by approxi-
mately 7.3 percent in order to »"»«"ttdn
preeontrol profitability and also to re-
cover the total """»i|i"d control costs
necessitated by the standard at ethylene
dlchloride-vinyl chloride plants and poly-
vinyl chloride plants. This increase is
estimated to translate into a mMtnuupi
consumer price increase in goods fabri-
cated from polyvlnyl chloride resins of
approximately 3.5 percent Recovery of
effluent «my«ii«fd costs plus mahxte-
nance of preeontrol profitability is esti-
mated to add approximately 2 percent to
polyvlnyl chloride resin prices and resuH
m an additional ""ftxlmiim consumer
price Increase of 1 percent
PUILIC PAITICIPATXOV
During the public comment period. 50
comment letters on the proposed stand-
ard were received. There were 24 from
industry; 3 from environmental groups;
IS from Federal. State, and local agen-
cies; and I from Individual citizens. Ae
required by section 112(b) (1) (B) of the
Act, a public hearing was held on the
proposed standard on February 3. 1076.
in Washington. D.C. Presentations were
made by the Environmental Defense
Fund, the Society of the Plastics Indus-
try, me, Dow Chemical Company, Dia-
mond Shamrock Corporation, and Atr
Products and chemicals, inc. Copies of
the comment letters received, the public
hearing record, and a summary of the
comments with EPA's responses are
available for public inspection and copy-
ing at the BPA Public Information Ref-
erence Unit Room 2922 (EPA Library).
401 M Street 8W, Washington. D.C. m
addition, copies of the comment sum-
mary and Agency responses may be ob-
tained upon written request from the
Public Information Center (PM-215).
Environmental Protection Agency. 401
M Street SW, Washington. D.C. 20460
(specify Standard Support and Environ-
mental Impact Statement. Emission
Standard tor Vinyl Chloride, Volume I/).
SlGKOTCAHT COMCXNW AMD CHAIfGZS TO
TH1 PtOPOSKD RxaULATIDir
(1) Decision to list vinyl chloride at a
hazardous air pollutant. In general, the
commenters did not contest EPA's deci-
sion to list vinyl chloride as a hazardous
air pollutant However, three comment-
ers (two companies and one Federal
agency) argued that EPA placed undue
emphasis on factors suggesting that vinyl
chloride presented a health risk and
ignored factors suggesting that no sig-
nificant risk was Involved. Under section
112, however, EPA could remove vinyl
chloride from the' list of hazardous air
pollutants only If information were pre-
sented to EPA that shows that vinyl
chloride Is clearly not a hazardous air
pollutant As discussed more fully In the
comment summary, the commenters did
not provide conclusive evidence that vinyl
chloride Is not a hazardous air pollutant
which causes or contributes to death or
serious Illness, nor did they conclusively
prove that the health risk factors em-
phasized by EPA were Insignificant
Several other commenters agreed with
EPA's decision to list vinyl chloride as a
hazardous air pollutant but argued that
EPA had overstated the health problem.
the emission levels, and the projected
ambient air concentrations around un-
controlled plants. With regard to the al-
leged overstated health problem, the
commenters stated, for example, that the
UJ3. worker EPA discussed as bavins-
been exposed to vinyl chloride levels low-
er than those usually, encountered in
polyvlnyl chloride production has been
dropped from the National Institute of
Occupational Safety and Health's listing
of workers with angiosarcoma. XPA
agrees that there are questions concern-
ing the level of exposure and in some
cases the pathology of these cases not
involved directly In polyvlnyl chloride
and vinyl chloride production. These un-
certainties are stated In the appropriate
footnotes of the Scientific and Technical
Assessment Report on Vinyl Chloride and
Polyvinvl Chloride (STAR) when the
angiosarcoma cases an listed. However.
In spite of these uncertainties. In view of
the possible exposun patterns.
cases cannot be ignored m the evamation
of the potential publfc health problems.
With regard to the alleged overstated
emission levels, the uncontrolled f*n1t-
sioa levels reported by EPA wen based
on 1974 data. This «pmll«tgMter waa
stated wherever emission data wen pre-
sented. EPA recognizes that **•" <•*•»•
have been reduced since that time, and
stated this in the preamble to the pro-
posed standard. EPA decided not to
gather more recent data on emission
levels, because these emission levels am
expected to change, and gathering the
data would take considerable tune both
on the part of EPA and on the part of
Industry. Since the purpose of the stand-
ard is to minimize emissions, these man
current data would not affect the stand-
ard Itself. The 1974 emission levels were
also used In diffusion modeling to project
nutTitnum ambient *alr concentrations
around uncontrolled plants. These maxi-
mum air concentrations would orobably
be tower if 1976 emission levels-were used.
This would reduce the relative impact
of the standard below that described in
the Standard Support and Snvironmen-
tal Impact Statement, but would not
affect the baste of the standard itself.
(2) Approach for Regulattna Vinyl
Chloride Under Section 112. Two ap-
proaches other than using best avail-
able control technology wen suggested
by the commenters for regulating vinyl
chloride under section 112. The first was
to ban polyvlnyl chloride products for
which substitutes an currently available
and to gradually phase out other poly-
vinyl, chloride products as substitutes
an developed.
In the preamble to the proposed stand-
ard EPA specified its reasons for not set-
ting a zero emission limit for vinyl
chloride. M follows: (l) Then are-bene-
fldal uses of vinyl chloride products for
which desirable substitutes an not read-
ily available; (2) then an potentially
adverse health and environmental im-
pacts from substitutes which have not
been thoroughly studied; (3) then ana
number of employees, particularly in tha
fabrication Industries, who would be-
come at least temporarily unemployed;
and (4) control technology Is available
which is capable of substantially reduc-
ing emissions of vinyl chloride into the
atmosphere. .
EPA agrees that substitutes do exist or
could be manufactured for most poly-
vlnyl chloride uses. However, In general.
these substitutes do not have some of the
man desirable characteristics of poly-
vinyl chloride such as nftnftatnTnaMlHTi
If vinyl chloride and polyvlnyl chloride
wen banned, other substitutes with
these more desirable characteristics
would likely be developed. Then to a risk
that these substitutes would also havw
adverse health or environmental effects.
Bine* control measures an available
which can reduce' vinyl chloride emis-
sions by M percent or more, it does not
seem prudent to reduce emlssions-by tat
remaining percentage and take the risk
of introducing new untested chemirali
mto the environment
ffDIIAL HfOlSTtl, VOl. 41. HO JOS—TMU*S»AV. OCTOIfS. II. W4
90
-------
46562
Another approach suggested by the
eommenters was to base the standard for
each individual emission point on cost
venma benefit Several of the fugitive
emission amines were named specifically
as onee for which the costs of control
were substantially higher than the bene-
fits. Although EPA did determine a cost-
benefit ratio for the controls required
for a number of emission points, EPA
does not believe such a ratio Is an appro-
priate basis on which to set a standard.
Section 111 of the Clean Air Act provides
for the development of standards based
on best control technology (considering
costs) . Even under section 111, however,
standards are not based on a fine bal-
ancing of costs versus benefits. Instead.
costs are considered In terms of the af-
fordabfllty of the control technology re-
quired to achieve a given emission level
and the . economic Impact of possible
standards on the Industry In ques-
tion. Unlike section 111, section 112 does
not explicitly provide for consideration
of costs, so It would clearly be Inappro-
priate to consider costs to a greater ex-
tent tinder section 113 than would be
dona under section 111. As discussed in
the preamble to the proposed standard
for vinyl chloride, SPA believes costs
may be considered under section 119, but
only to a very limited extent; I.e., to
assure that the costs of control technol-
ogy an not grossly disproportionate to
the amount of emission reduction
achieved. In comparison with other
•m<««fa»n points, the costs of controlling
the fugitive emission sources mentioned
by the commenters are relatively small
compared with the amount of emission
Several commenters recommended
adding to the regulation a provision for
excess emUslmis during startup, shut-
down. and ™*i*muHin«i. EPA considered
this comment, and decided that this
addition to not necessary for the vinyl
chloride standard. Startup and shutdown
of the process has essentially no effect
on «mi««in«Mi to the atmosphere for poly-
vlnjrl chloride production, and technology
exists to avoid excess emissions during
startup and shutdown at ethylene dl-
ehloridevtnyl chloride plants. We do not
believe plants should be allowed to emit
excess emissions during malfunctions,
and therefore are requiring them to shut
down
(S) Selection of source categories. In
the preamble to the proposed standard
EPA recognized that some small research
and development facilities may exist
when the emissions of vinyl chloride an
inrfg«Mi««i«t and covering these faculties
under the standard would be unnecessary
and Inappropriate. However. EPA did not
have sufficient Information available to
dearly define which facilities should be
excluded from the standard, and
encouraged Interested parties to submit
such information during the comment
period. Based on the Information sub-
mitted. EPA decided to exempt poly-
vinyl chloride reactors and associated
equipment from applicability of afl parts
of the standard tf the reactors an used
la research and development and have a
•WES AND REGULATIONS
capacity of no more than 0.19 m" <60
gal). Reactors in this sto range can gen-
erally be found In a laboratory, whereas
the larger reactors an typteaDy pOot
scale faculties. Emissions from laboratory
scale equipment an relatively small, and
application of the controls required by
the standard would be expensive and Im-
practical. EPA also decided to exempt re-
search and development faculties con-
taining reactors greater than 0.10 m* (60
gal) and no more than 4.07 m* (1100 gal)
in capacity from all parts of the standard
except the 10 ppm limit for reactors,
strippers, monomer recovery systems, and
mixing, weighing and holding containers.
EPA decided not to require these facili-
ties to meet other parts of the standard
because of the technical problems In-
volved in doing so. For example, the
standard for reactor opening Is based In
part on reducing the frequency of open-
ing the reactor. Research and develop-
ment reactors have to be opened after
every batch for thorough cleaning. Also,
stripping technology Is developed Indi-
vidually for each resin In research and
development equipment. Therefore, at-
tainment of the stripping limitations In
the research and development equipment
would not always be possible. The 4.07
m* (1100 gal) figure was selected as an
upper cut-off point because then an no
commercial reactors smaller than this.
(4) Emitsitm Umits. The only major
change In the emission limits between
proposal and promulgation Is the addi-
tion of a provision for emergency manual
venting of vinyl chloride from reactors
to the atmosphere. The proposed stand-
ard prohibited all manual venting to the
atmosphere. In the preamble to the pro-
posed standard, EPA Invited Interested
persons to comment on whether permit-
ting manual venting to the atmosphere
could result in overall lower emissions.
Then an several methods available for
preventing relief discharges from reac-
tors, one of which Is manual venting of
part of the reactor contents for purposes
of cooling and reduction In pressun
within the reactor. The higher the tern-
peratun and pressun within the reac-
tor, the greater the amount of vinyl
chloride which has to be removed to
bring the reactor under control. Manual
venting can be done at a lower pressun
than the pressun required to open the
relief valve. For this reason manual vent-
Ing can result In lower emissions than
would occur by allowing the reactor to
discharge through the relief valve. Fur-
thermore, a manual vent valve is under
the control of an operator and can be
closed. A relief valve may become clogged
with resin and not close. The result
would be loss of all the reactor contents.
The contents of a reactor can be man-
ually .vented to a gasholder or other hold-
ing vessel. However, In some cases, such
as during seven weather conditions, sev-
eral reactors may be out of control at
one time. Then would be Insufficient
holding capacity under these conditions
to manually vent the contents of all the
reactors to a gasholder. Therefore, when
all other measures to prevent relief valve
discharges have been exhausted, manual
venting will be permitted as a last resort
befon the relief valve opens. The same
notification procedures an required for
manual venting to the atmosphere as art
required for relief discharges.
Then are several changes to the nu-
merical emission limits in the promul-
gated standard. Except for the standard
for reactor opening loss, these changes
simply involve conversion to the Interna-
tional System of Units (81). There wa«
an error Involved In the original calcula-
tion used to derive the standard for reac-
tor opening. Correcting this error dou-
bles the allowable fminntoruL- It Is em-
phasized that the change In this stand-
ard Is a correction, and not a change In
the Intent for the degree of control re-
quired.
The proposed standard required the
installation of a rupture disc beneath
each relief valve to prevent leakage from
the relief valve. A provision has been
added to the promulgated standard so
that a rupture disc Is not required if
the relief valve is tied Into a process line
or recovery system. In this ease, any
leakage from the relief valve would be
contained.
The regulation for obtaining vinyl
chloride samples has been changed to an
operating procedure. The proposed
standard stated that then wen to be
no emissions from taking the samples.
Several commenters pointed out that the
use of the word "no" would make this
regulation Impractical to enforce. There-
fore, the promulgated standard specifies
the operating procedure which EPA orig-
inally Intended to be used to control
this source. This revision is only a change
In wording and does not represent a
change In the level of the standard.
The regulation for taking samples has
also been revised to apply only to sam-
ples containing at least 10 percent by
weight vinyl chloride. This Is consistent
with the other parts of the standard
which apply to equipment "in vmyl
chloride service." "In vinyl chloride serv-
ice"
means that a piece of equipment con-
tains or contacts either a liquid that te-
at least 10 percent by weight vmyl chlo-
ride or a gas that is at least 10 percent
by volume vinyl chloride.
The proposed standard required a vinyl
chloride monitoring system for continu-
ously measuring vinyl chloride levels both
within the plant (for leak detection) and
within stacks. The proposed standard did
not outline required specifications for the
monitoring system, except that it was to
analyse the samples with gas chromatog-
raphy. or if all hydrocarbons wen as-
sumed to be vinyl chloride, with infrared
spectrophotometry. .flame ton detection.
or equivalent R required that each plant
submit a description of its monitoring
system to EPA. so that EPA could deter-
mine whether it was acceptable or not
Comments wen received
need for EPA to specify some
Judging the acceptability of
systems. The accuracy of the monttor-
3g a
a for
MOttM MOISTM, VOl. «> NO JOS—tMU«»*Y. OCTOSII 11. 1*7*
91
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•ULES AND REGULATIONS
4656S
tag system would be related to the fre-
quency of calibration. Therefore, EPA
has Included in the promulgated stand-
ard requirements for the frequency of
calibration and procedures to be carried
out In the calibration of the monitoring
Instruments.
The portable hydrocarbon detector re-
quired by tile proposed standard was re-
quired to have a sensitivity of 5 ppm.
Comments were received Indicating that
Instruments m this sensitivity range are
delicate and require continuing mainte-
nance. The portable hydrocarbon detec-
tor to required for leak detection and for
measuring vmyl chloride concentrations
inside the equipment before opening it
A 5 ppm sensitivity to not needed in
either case, and the requkwd sensitivity
has been changed to 10 ppm in the pro-
mulgated standard.
The proposed standard contained a
single regulation for compressors. The
promulgated standard has separate regu-
lations for rotating and reciprocating
compressors. This Is consistent with hav-
ing separate regulations for rotating and
reciprocating pumps in both the pro-
posed and promulgated standards.
Section 61.66 of the proposed standard
provided jor the use of equivalent meth-
ods of control which have been approved
by EPA. The promulgated standard re-
quires that tiie plant owner or operator
submit a request for determination of
equivalency wtthin SO days of the pro-
mulgation date if the alternative control
method to intended ae the initial means
of control. The purpose of this to to pro-
vide time for EPA to evaluate the method
(for existing sources. 90 days after the
promulgation data). EPA atoo suggest*
that this request for determination of
equivalency be accompanied by a re-
quest for waiver of ftmnpllafirft pursuant
to section Il2(c) UHB) (tt) of the Act
The request fora waiver for T»""t
should provide for the ease where EPA
determines that a method to not equtv-
alent and the plant needs to rfnrrhisir
other equipment. In no ease wffl the
waiver of oompHanoe be extended bejpnd
two years from the date of promulga-
tion.
There are several wording clarifica-
tions which have been made in the pro-
mulgated standard. The definition for
"in vmyl chloride service" (160.61(1))
has been clarified by stating that tt
means equipment that contacts vinyl
chloride as well as oqutomoni that con-
tains vinyl chloride. This would Include
such equipment as agitators.
Words have been added m || 61.63.
61.63, and 61.64 to clarify that the 10
ppm emtorion limits do not have to be
met when equipment has already been
opened m compliance with the regula-
tion for opening of equipment Equip-
ment that has met the opening of
equipment regulation can contain more
than 10 ppm vinyl chloride and would be
in violation of the standard If thto
statement were not Included.
The requirements for stripping pdy-
vtnyl chloride reams to specified levels
have been revised m ||61.64(e), 61JT
has been re-
vised to clarify that it applies only to
lines that are disconnected after each
loading or unloading operation. Perma-
nently installed pipelines that are opened
Infrequently for Inspection or mainte-
nance, for example, are covered by the
opening of equipment regulation rather
than the loading and unloading line
regulation.
The regulation for inprocess waste-
water in the proposed standard could
have been misinterpreted to require In-
dividual treatment of wastowater
streams. Section 61.6B(b> (»> (» of the
promulgated standard clarifies that
wastowater streams that are required to
be treated (te, those containing greater
than 10 ppm vmyl chloride) can be com-
bined to be treated. However, waste-
water streams that contain greater than
10 ppm vinyl chloride cannot be com-
bined with wastewater streams that con-
tain less than 10 ppm vinyl chloride be-
fore treatment; Le« dQntlon cannot be
used to meet the standard.
The commenters recommended several
changes in O** tunlirtmi limits which
have not been incorporated Into the
promulgated standard. These are dis-
cussed in the following paragraphs.
It was recommended that the require-
ment for double mechanical seals on
pumps, compressors, and agitators be re-
moved because the single seals currently
used on this equipment have small emis-
sions and are more reliable than double
mechanical seals. EPA to aware that each
fugitive «••««••«««» source, such as on*
pump, taken by itself causes relatively
fmsjll *"i*^fffff^y» Pugltifft emissions con-
sidered M a whole an a slgnhVant
source of ftf «•**«•«•. however, and the In-
tent of the standard to to reduce these.
Double mechanical seal pumps are com-
monly used in the Industry for emission
reduction. Seauess pumps or equivalent
systems are available as options to double
mechanical seals.
The commenters refomm«Ti«1<*1 In-
creasing the averaging time for the 10
ppm limits and the emission limits for
reactor opening and stripping to SO days.
Bu»mf of **** commenters apparently
thought that the 10 ppm limits had to be
met on an Instantaneous basto. However.
since the performance test for determin-
ing compliance consists of three runs for
* minimum of an hour each, the aver-
aging time for the 10 ppm limit to at least
three hours. Increasing the averaging
time to SO days for any of the emission
limits would permit higher peak emis-
sion tevelr EPA hu determined that thto
to neither desirable nor necessary.
Borne commenters requested that the
stripping levels for dispersion resins be
made the same as for other resins and
others requested that they be made less
stringent EPA decided not to make the
standard for stripping dispersion resins
the same as for other resins because there
to sufficient evidence to Indicate that
these resins are more difficult to strip
than other resins. With regard to mak-
ing the stripping levels for dispersion
resins less stringent, only one of the eight
manufacturers of dispersion resins spe-
cifically commented that the dispersion
resin standard should be made toss
stringent. Only two of several grades of
dispersion resins made by this company
cannot meet the 2.000 ppm limit. The
proposed standard takes Into consldera->
tton that some resins are more difficult
to strip than others by providing for
averaging among different resins.
(5) Tnttitff. reporting, and ncard-
ketftng. There are several relatively
minor changes in the testing, report
and recordkeeping requirements. A pro-
vision hat been added to 161.67 which
requires that stack gas samples taken
with Test Method 106 are to be enabled
within 34 hours. This to consistent with
the requirements in the proposed Test
Method 106. The promulgated standard
attt> specifies that in averaging the re-
sults of the three runs required by Test
Method 166. a time-weighted average to
to be used.
One eommenter requested that the
oxygen content and moisture content be
specified for the 10 ppm concentration
standards. The proposed standard speci-
fied that the vmyl chloride concentration
to to be corrected to 10 percent oxygen
(wet basto) tf combustion to used M the
control measure. In the promulgated
standard, this requirement has been ex-
panded to an control measures.
A provision has been added to the
promulgated standard which states that
tf a reactor to also used as a stripper, the
reactor n««««»g emissions may be deter-
mined Immediately following the strip-
ping operation. If a reactor to also used
M a stripper, the resin to m the reactor
when H to opened. This means that vinyl
chloride m Che resto which has already
been stripped to acceptable levels can
escape from the resin and become part
of the reactor opening loss. It to EPA's
mtont that once a resm has been stripped
to the required levels, that additional
controls are not required. Under Mxnew
provision, vinyl chloride escaping from
the resin after it has been stopped to
acceptable levels to not counted M part
of the reactor opening loss.
A set tton requiring continuous moni-
toring of stack emissions has been added
to the promulgated standard. The con-
tinuous monitoring of stack imitosliif"
was required In the proposed standard.
The addition of a specific paragraph for
clarify the requirement.
The standard has been revised so that
the initial report requires a -description'*
rattier than a -detailed description'' of
the equipment used to control ~
out that a detailed
contain proprietary
that a detailed description m
FtDtKAl IfeiStfl, VOL 41. NO. JOS—THUISOAV, OCTOMJ 11. 1*7«
92
-------
IB unnecessary. If addl-
tnformaaon to needed. BPA earn
obtain It under section 114 of the Aet s*MI
ttM plant eaa request eonfldenttal treat-
ment in accordance with 40 CPU Part 3
for information it believes to be
imBI*SiU»y.
Tfce proposed standard required that
-a semiannual report be submitted every
180 days. The promulgated standard
specifies dates for the submittal of the
reports. B also specifies that the first
semiannual report does not have to be
submitted nntfl at least six months after
t>m initial report to submitted.
The standard has been revised to eUm-
Inato the requirement to record the cause
of any leak detected by the vinyl chlo-
ride detector, the action taken to repair
ttM leak, and the amount of time re-
quired to repair the leak. EPA ta con-
cerned only that leaks are detected and
repaired. That this has been done can be
established by looking at the strip chart
record of measurements made by the
vinyl chloride detector. These records are
•tin required for the7 portable hydrocar-
bon detector however.
Several commentators recommended
that ttM companies be allowed an extra
two weeks to submit to EPA data from
the Initial performance test They ate
recommended that they submit the data
by regular mafl rather than registered
mafl. EPA has not adopted either of these
reeommendations. A source to supposed
to be to onmpllMW with the standard
90 days of ***** promulgation of
the standard. The standard requires that
the emission teats be done within the
'•0 day period, and permits an extra SO
days for determination of results. The
purpose of using registered mafl Is to
document the fact that emission data
have been sent and received. This way
if-the results are lost In the mafl. there
wfll be no Question that they were sent
(6) rest method. Teat Method 108 has
been changed to recognise that on a gas
chromatograph equipped with a Chrom-
osorb 103 column, aeetaldehyde may
Interfere with the vinyl chloride peak.
When a sample' la expected to contain
aeetaldehyde. a secondary column as de-
scribed In section 4J.3 must be employed.
llasa spectroscopy or another absolute
analytical technique is required to con-
firm the vinyl chloride peak obtained
with the gas ehromatograph. only tf peak
resolution with the secondary column la
not successful."
Si section 4.1.4, alumtniied Mylar bags
can be substituted for Tedlar bags. EPA
now has data to allow this substitution,
provided that the samples are analysed
within 34 hours of collection.
In section 5.1.S of Test Method 106
the requirement to use "oxygen gas" has
been replaced with "oxygen gas or air. as
required by the detector." Several corn-
mentors stated that most gaa chromato-
graphs are designed to use hydrogen and
air for their flame detectors. When used
in thle way. they are capable of detect-
ing 0 J ppm vinyl chloride to air. Tills Is
sensitive enough for monitoring the 10
limits stipulated in the
•UUS AND MOUUTiONS
In section e.4 of Test »*«*>»~1 106 the
requirement for an automatic integrator
has been replaced with a requirement for
a disc Integrator or plantmeter for meas-
uring peak area. This change Is ta re-
sponse to a comment which states that
automatic Integrators are unnecessarily
elaborate and expensive.
A new section 6.6 has been added to
Test Method KM which requires deter-
mination of the water vapor content of
the sampling bag by measuring the am-
bient temperature and pressure near the
bag. The vinyl chloride concentration of
the bag can then be reported on a dry
basis. A provision for checking the rigid
container for leaks bis been added to
section 7.4 of Test Method 100.
The only change in Test Method 107 Is
the provision in Section 5.3.3 for use of
Carbopak C as wen as Carbopak A.
ABTHOUTT: Section 111 of the Clean Air
Act ae added by eeo. 4 (ft) at Pub. L. M-eM.
M Stat 18M (49 UAO. 18570-7; Section 114
of the Clean Air Act, M added by we. 4(a)
of Pob. 1*81-804.8* Stat. 1687. and amended
by Pub. L. 88-818. MO. 6(e) (4). M Stat. 380
(49 U.S.C. 1M70-0); Section Ml (a) or tbe
Clean Air Act, M amended by eec. U(e)'(9)
of Pub. u ti-eoi. at Stat mi One or more polymers •~**~*~t
any fraction of polymailsed vmyl •ehlo-
rlde.
(b) This subpart does not apply to
equipment used m research and develop-
ment if the reactor used to polymeriae
the vinyl chloride processed m the equip-
ment has a capacity of no more than
0.19m'(60 gab.
(e) Sections of this subpart other than
|6l.«4(a)(l). "Type of resin" means the broad
classification of resin referring to the
basic manufacturing process for produc-
ing that resm, including, but not limited
to. the suspension, dispersion, latex, bulk.
and solution processes.
"Latex resin" means a ream which
to produced by a polymerisation process
which Initiates from free radical catalyst
sites and to sold undrted.
(t) "Bulk resin'-means a resin which
ta produced by a polymerisation process
in which no water to used.
(J) "Xnprocess wastewater" means any
water which, during manufacturing or
processing, comes Into direct contact
with vinyl chloride or polyvmyl chloride
or results from the production or use of
any raw material, intermediate product
finished product by-product
product wmtamlng vinyl chloride
polyvmyl chloride but which has i
been discharged to a ' __._
ment process or discharged untreated as)
wastewater.
(k) "Wastewater treatment
includes any process which
FtDfMl mum. VOL 41. NO MS-THUM0AY, OCIOBU 11. 1«74
-------
RUUS AND RfOULATIONS
characteristics such M BOD, COD. TS8.
and pH. usually tor the purpose at meet-
ing ettient guManaes and standards; it
doe* not tnotade-any process the purpose
of which to to remove vinyl chloride from
water to meet requirement of thto
•ubpart.
U) "in vinyl chloride service" means
that a piece of equipment contain* or
contacts either a liquid that to at toast
10 percent by weight vinyl chloride or a
gas *»«•* k at lent 10 percent by yolume
vinyl chloride. .
(m> "Standard operating procedure
mean* a formal written procedure offi-
cially adopted by the plant owner or
operator and available on a routine bath
to thoM persona responsible for -carrying
out the procedure.
"Elhylene dicbloride purification*
includes any pert of the process of ethyl-
ene «M»M«gM« production which follows
ethylene dichloride formation and hi
which finished ethytene dichloride la
produced.
(p) "Vinyl chloride purlflcattoc" In-
chides any part of the process of vinyl
chloride production which foQows vinyl
chloride formation and to which finished
vtnyl chloride Is produced.
"Stripper" Includes any vessel In
which residual vinyl chloride is removed
from polyvlnyl chloride resin, except
bulk resin, in the slurry form by the use
of beat and/or vacuum. In the case of
bulk resin, stripper Includes any vessel
which to used to remove residual vinyl
chloride from polyvlnyl cmortde resin
Immediately following the polymerisa-
tion step in the plant procees flow.
B 61.62 Emission •un£>rd for jethylene
" dkblorMe plant*.
An owner or operator of an ethylene
dfrfai^rtdit plant shall comply with the
requirements of this section and 1 61.M.
(a) Ethylen* dichloride purification:
The concentration of vinyl chloride in
an exhaust gases discharged to the at-
mosphere from any equipment used m
ethylene dichloride purification to not
to exceed 10 ppm, except as provided la
|el.65. This requirement does not
apply to equipment that has been
opened, vls out of operation, and met the
requirement In f 61.66 (b> before being
opened.
(b) Oxychlorinatton reactor: Except
as provided in |61.66(a), emissions of
vlsyl chloride to- the atmosphere from
each oxychlorinatlon reactor are not to
exceed 0 2 g/kg the 100 percent ethylene
dichloride product from the oxychlori-
natlon process. „
An owner or operator of a vinyl chlo-
ride plant shall complywith the require-
ments of this section and 16148.
(a) Vtayl chloride formation and puri-
fication: The coneentratton of vtayl
chloride ta an exhapst gases discharged,
•O «DB ftCDSQesDuiW IPOin WQy OQRugMlMttnt
used In vinyl chloride formation and/or
purification is not to exceed 10 ppm, ex-
cept M provided In {61.6B(a). This re-
quirement does not apply to equipment
that has been opened, to out of operation.
and met the requirement -In 161.68 (b)
(6) (1) before being opened.
§ 61.64 Eminfon standard for pdrvinyl
chloride plants.
An owner or operator of a polyvfayl
chloride plant shall comply with the re-
quirements of thto section and 161.66.
(a) Reactor: The following require-
ments 'apply to reactors:
(1) The concentration of vlnyl~cnlo-
ride in an exhaust gases discharged to
the atmosphere from each reactor to not
to exceed 10 ppm. except as provided in
paragraph (a)(2) of thto section and'
( 61.66(a>.
(2) The reactor opening toss from each
reactor to not to exceed 0.03 g vinyl
chloride/Kg (0.00009 Ih vinyl chloride/
tt» of polyvlnyl chloride product,- with
the product determined on a dry solids
basis. Thto requirement applies to any
vessel which to used as a reactor or as
both a reactor and a stripper. In the
-bulk process, the product means the
gross product of prepolymertoatton and
postoolymerixatlon.
(8) Manual vent.vajve discharge: Ex-
cept for an emergency manual vent valve
discharge, there to to be no discharge to
the atmosphere from any «""*^ml vent
valve on a polyvlnyl chloride reactor In
vinyl chloride service. An emergency
manual vent valve discharge means a
discharge to the atmosphere whlchxoukt
not have been avoided by taking meas-
ures to prevent the discharge. Within 10
days of any discharge to the atmosphere
from any manual vent valve, the owner
or operator of the source from which the
discharge occurs shall submit to the Ad-
ministrator a report in writing contain-
ing information on the source, nature
and cause of the discharge, the date and
time of the discharge, the approximate
total vinyl chloride Joes during the dis-
charge, the method used for determining
the vinyl chloride loss, the action that
was taken to prevent the discharge, and
measures adopted to prevent future dis-
charges.
(b) Stripper: The -concentration of
vinyl chloride In all exhaust gases dis-
charged to the atmosphere from each
stripper to not to exceed 10 ppm. except
as provided to |«1.66(a). Thto require-
ment does not apply to equipment that
has been opened, to out of operation, and
met the requirement in 161.66(b) (6) (I)
before being opened.
(e) Mixing, weighing, and holding
containers: The concentration of vtayl
chloride la all exhaust gases discharged
to the atmosphere from each mixing,
weighing, or holding container in vtayl
chloride service which precedes the
stripper (or the reactor * the plant baa
no stripper) In the plant jaouiss flow to
not to exceed 10 ppm. except ae provided
In 1 61.66(a). Thto requirement doesta**
A*M»9^ AUK A^HatB^^k^MMA 64*^4 %^^M l^^MB
apply to equipment VBM ns» IMBB
opened; to out of operation, and met fee
requirement ta |6L68(6)tt> before
being opened.
. Thto requirement
does not apply to equipment that has
i*\mm opened, to out of operation, and met
the requirement; ta I ei.66(b) (6) (0 be-
fore being opened.
(e) Sources following the stripperd) :
The following requlremente apply to
»mi«rinn. Of vinyl chloride to the at-
mosphere from the combination of a*
sources following the stripper(s) (or the
reactor(s) If the plant has no ttrtp-
per(s)l ta the plant process now in-
cluding but not limited to. osntrifugae,
concentrators, blend tanks, fitters, dry>.
era, conveyor air discharges, baggers.
storage containers, and luprocess i
water:
(1) In polyvlnyl chloride plants i
Stripping t«n»tnwil/igy to
chloride «mfarin»i«1 the weighted average
residual vtayl chloride concentratioa g*
all grades, of poiyvtayl chloride resin
processed through the stripping operaA
tlon on each calendar day, measures!
after
tlon to completed, may not exceed:
(1) 2000 ppm for pc&vtayTchtorld*
dispersion resins, excluding latex reataa;
(11) 400 ppm for all other polyvtayl
chloride resins, Inclndhig latex reenM,
averaged separately for each type of res-
in; or
(2) In polyvtayl chloride plante eon»
trolling vinyl chloride «*••*••*•'•" with
technology other than strtpptag or ta
addition to stripping, emissions of vtayl
chloride to the atmosphere may not
exceed: '
(1)2 g/kg (0.002 lb/n» product from
. the stripper(s) [or reactor(s) If- the
plant has1 no strtpper(s) 1 for dispersion ,
polyvlnyl chloride reataa, excluding latex
resins, with the product determined on •
dry solids basto;
(tt) 0.4 g/kg (0.0004 Ib/Tb) product
from the strippers [or reaetor(s) if the
plant has no stripper (s)] for an other
polyvtayl chloride resins, including latex
resins, with the product determined on
a dry solids basto.
§ 61.65 EmiMfen. tlandwd /or ethrlew
diehloride, vinyl chloride and poly
vinyl chloride pUnU.
An owner or operator of an ethylene
dichloride. vinyl chloride, and/or poly-
vtayl chloride plant than comply with.
the requirements of thto section.
(a) Relief valve discharge: Except for
an emergency relief dtocharge. there ta
to be no discharge to the atmosphere
from any relief valve on any equipment
relief discharge means a discharge whloh
could not have been avoided by taktag
measures to prevent the dtoeharge.'Wtth-
ta 10 days of any relief valve discharge,
raoiiAi KWISTH, vot. 41. NO. aos
94
-THIMSOAV, OCT06H II, l»7«
-------
46666
(he owner or operator of the source from
which the relief valve discharge occur*
•ban submit to the Administrator a re-
port in writing containing information
on the source, nature and cause of the
discharge, the date and time of the dis-
charge, the approximate total vinyl chlo-
ride loss during the discharge, the meth-
od need for determining the vinyl chlo-
ride loss, the action that was taken to
prevent the discharge, and measures
adopted to prevent future discharges.
(b> Fugitive emission sources:
(1) loading and unloading lines: Vinyl
chloride emissions from loading and un-
loading lines which are opened to the
atmosphere after each loading or un-
loading operation are to be minimized
as follows:
(1) After each loading or unloading
operation and before opening a loading
or unloading line to the atmosphere, the
quantity of vinyl chloride in all parts of
each loading or unloading line that are
to be opened to the atmosphere is to be
reduced so that the parts combined con-
tain no greater than 0.0038 m1 (0.13 ff)
of vinyl chloride, at standard tempera-
ture and pressure; and
(tt) Any vinyl chloride removed from
a loading or unloading line in accord-
ance with paragraph (b) (1) of this
section is to be ducted through a control
system from which the concentration of
vinyl chloride in the exhaust gases does
not exceed 10 ppm, or equivalent as pro-
vided in 161.64.
(3) Slip gauges: During loading or un-
loading operations, the vinyl chloride
ami««intMi from each slip gauge in vinyl
chloride service are to be minimized by
ducting any vinyl chloride discharged
from the slip gauge through a control
system from which the concentration of
vinyl chloride in the exhaust gases does
not exceed 10 ppm, or equivalent as pro-
vided in 161.66.
(3) Leakage from pump, compressor,
and agitator seals:
(1) Rotating pumps: Vinyl chloride
emissions from seals on all rotating
pumps In vinyl chloride service are to be
minimised by fri«*«iHTiy sealless pumps,
pumps with double mechanical seals, or
equivalent as provided in 161.66. If
doable mechanical seals are used, vinyl
chloride emission from the seals are to
be minimized by maintaining the pres-
sure between the two seals so that any
leak that occurs is into the pump; by
ducting any vinyl chloride between the
two nf»ln through a control system from
which the concentration of vinyl chlo-
ride In the exhaust gases does not ex-
ceed 10 ppm: or equivalent as provided
in 161.86.
(11) Reciprocating pumps: Vinyl chlo-
ride emissions from seals on all recipro-
cating pumps m vinyl chloride service
are to be minimised by Imrtfrllfog double
outboard seals, or equivalent as provided
m | $1.66. If double outboard seals are
mod, vinyl chloride emissions from the
seals are to be minimized by maintaining
(he pressure between the two seals so
that any leak that occurs Is Into the
pump; by ducting any vinyl chloride be-
tween fee two seals through a control
tUUS AND IEGULATIONS
system from which the concentration of
vinyl chloride in the exhaust gases does
not exceed 10 ppm; or equivalent as
provided in } 61.66.
Oil) Rotating compressor: Vinyl
chloride emissions from seals on an ro-
tating compressors in vinyl chloride
service are to be »«»nlmlged by »»«»-»fHng
compressors with double mechanical
seals, or equivalent as provided in 161.66.
If double mechanical seals are used, vinyl
chloride emissions from the seals are to
be minimised by maintaining the pres-
sure between the two seals so that any
leak that occurs is Into the compressor:
by ducting any vinyl chloride between
the two seals through a control system
from which the concentration of vinyl
chloride in the exhaust gases does not
exceed 10 ppm; or equivalent as provided
in i 61.66.
(Iv) Reciprocating compressors: Vinyl
chloride emissions from seals on all re-
ciprocating compressors in vinyl chloride
service are to be minimized by Installing
double outboard seals, or equivalent as
provided in { 61.66. If double outboard
seals are used, vinyl chloride emissions
from the seals are to be minimized by
maintaining the pressure between the
two seals so that any leak that occurs is
into the compressor; by ducting any
vinyl chloride between the two seals
through a control system from which the
concentration of vinyl chloride in the
exhaust gases does not exceed 10 ppm;
or equivalent as provided In { 61.66.'
(v) Agitator: Vinyl chloride emissions
from seals on all agitators in vinyl chlo-
ride service are to be minimized by in-
stalling agitators with,double, mechani-
cal seals, or equivalent as provided in
161.66. If double mechanical seals are
used, vinyl chloride emissions from the
seals are to be minimized by maintaining
the pressure between the two seals so
that any leak that occurs is into the agi-
tated vessel; by ducting any vinyl chlo-
ride between the two seals through a
control system from which the concen-
tration of vinyl chloride in the exhaust
gases does not exceed 10 ppm; or equiva-
lent as provided in 161.66.
(4) Leakage from relief valves: Vinyl
chloride emissions due to leakage from
each relief valve on equipment in vinyl
chloride service are to be minimized by
Installing a rupture disk between the
equipment and the relief valve, by con-
necting the relief valve discharge to a
process line or recovery system, or equiv-
alent as provided in 161.66.
(S> Manual venting of gases: Except
as provided in i 61.64. all gases
which are manually vented from equip-
ment in vinyl chloride service are to be
ducted through a control system from
which the concentration of vinyl chloride
in the exhaust gases does not exceed 10
ppm: or equivalent as provided in 9 61.66.
(6> Opening of equipment: Vinyl
chloride emissions from opening of
equipment (including loading or unload-
ing lines that are not opened to the at-
mosphere after each loading or unload-
ing operation) are to be minimized as
(I) Before opening any equipment for
any reason, the quantity of vinyl chlo-
ride Is to be reduced so that the equip-
ment contains no more **»•»» 3.0 percent
by volume vinyl chloride or 0.0950 m' (25
gal) of vinyl chloride, whichever Is
larger, at standard temperature and
pressure; and
(II) Any vinyl chloride removed from
the equipment in accordance with para-
graph (b) (6) (1) of this section Is to be
ducted through a control system from
which the concentration of vinyl chlo-
ride in the exhaust gases does not exceed
10 ppm, or equivalent as provided in
; 61.66.
<7> Samples: Unused portions of sam-
ples containing at least 10 percent by
weight vinyl chloride are to be returned
to the process, and sampling techniques
are to be such that sample containers in
vinyl chloride service are purged into a
closed process system.
<8* Leak detection and elimination:
Vinyl chloride emissions due to leaks
from equipment in vinyl chloride service
are to be minimized by instituting and
implementing a formal leak detection
and elimination program. The owner or
operator shall submit a description of
the program to the Administrator for
approval. "Hie program is to be sub-
mitted within 45 days of the effective
date of these regulations, unless a waiver
of compliance is granted under 161.11.
II a waiver of compliance is granted, the
program is to be submitted on a date
scheduled by the Administrator. Ap-
proval of a program will be granted by
the Administrator provided he finds:
(i> It Includes a reliable and accurate
vinyl chloride monitoring system for de-
tection of major leaks and identification
of the general area of the plant where a
leak is located. A vinyl chloride monitor-
ing system means a device which obtains
air samples from one or more points on
a continuous sequential basis and ana-
lyzes the samples with gas chromatog-
raphy or, if the owner or operator as-
sumes that all hydrocarbons measured
are vinyl chloride, with infrared spectro-
photometry flame ion detection, or an
equivalent or alternative method.
(ii> It includes a reliable and accurate
portable hydrocarbon detector to be used
routinely to find small leaks and to pin-
point the major leaks indicated by the
vinyl chloride monitoring system. A
portable hydrocarbon detector means a
device which measures hydrocarbons
with a sensitivity of at least 10 ppm
and is of such design and size that it can
be used to measure emissions from local-
ized points.
(ill > It provides for an acceptable cali-
bration and maintenance schedule for
the vinyl chloride monitoring system and
portable hydrocarbon detector, for the
vinyl chloride monitoring system, a daily
span check Is to be conducted with a
concentration of vinyl chloride equal to
the concentration defined as a leak ac-
cording to paragraph (b) (8) (vt) of this
section. The calibration Is to be done
with either:
(A* A calibration gas mixture pre-
pared from the gases specified In secttaos
5.3.1 and 5.3.3 of Test Method 106. or
MOUAl IMIfTI*. VOL 41. NO. lOS-IHlWSOAV. OCIOSil II. W6
95
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RULES AND MGUUTIONS
46587
(B) A calibration gas cylinder contain-
ing the appropriate concentration of
vinyl chloride. It a calibration ga* cylin-
der is used, the analysis moat be trace-
able to the National Bureau of Stand-
ards or to a gravimetrically calibrated
vinyl chloride permeation tube.
dv) The location and number of points
to be monitored and the frequency of
monitoring provided for in the •program
are acceptable when they are compared
with the number of pieces of equipment
in vinyl chloride service and the size and
physical layout of the plant.
(v) It contains an acceptable plan of
action to be taken when a leak is de-
tected.
(vl) It contains a definition of leak
which Is acceptable when compared with
the background concentrations of vinyl
chloride in the areas of the plant to be
monitored by the vinyl chloride monitor-
ing system. Measurements of background
concentrations of vinyl chloride in the
areas of the plant to be monitored by the
vinyl chloride monitoring system are to
be included with the description of the
program. The definition of leak for a
given plant may vary among the differ-
ent areas within the plant and Is also to
change over time as background con-
centrations in the plant are reduced.
(9) Inprocesswastewater: Vinyl chlo-
ride «into«ton« to the atmosphere from
inprocess wastewater are to be reduced
as follows:
(D The concentration of vinyl chlo-
ride In each inprocess wastewater stream
containing greater than 10 ppm vinyl
chloride measured immediately as it
leaves a piece of equipment and before
being mixed with any other inprocess
wastewater stream Is tobe reduced to no
more than 10 ppm by weight before being
mixed with any other inprocess wastewa-
ter stream which contains less than 10
ppm vinyl chloride; before being exposed
to the atmosphere, before being dis-
charged to a wastewater treatment proc-
ess ; or before being discharged untreated
as a wastewater. The paragraph does
apply to water which Is used to displace
vinyl chloride from equipment before It
is opened to the atmosphere In accord-
ance with |61.M(a)<2) or paragraph
(b) (6) of this section, but does not apply
to water which is used to wash out equip-
ment after the equipment has already
been opened to the atmosphere in ac-
cordance with I6l.64(a><2) or para-
graph (b) (6) of this section.
Any vinyl chloride removed from
the inprocess wastewater In accordance
with paragraph (b) (0) (1) of this section
ts to be ducted through a control system
from which the concentration of vinyl
chloride in the exhaust gases does not
exceed 10 ppm, or equivalent as provided
in 101.06.
(c) The requirements in paragraphs
O»U>. 0»<2>, (b)(5), 0»<0>.
and (b) CO) of this section are to be In-
corporated into a standard operating
procedure, anr made available upon re-
quest for inspection by the Administra-
tor. The standard operating procedure is
to include provisions for measuring the
vinyl chloride in equipment ^4.75 m*
01250 gal in volume for which an mis-
sion limit is prescribed In I «l.W(b>(0)
(1) prior to opening the equipment and
using Test Method 100. a portable hydro-
carbon detector, or an equivalent or al-
ternative method. The method of meas-
urement Is to meet the requirements In
1 61.67fg> <5> (1) (A) or «5> (i) (B).
§ 61.66 Equivalent equipment and pro-
cedure*.
Upon written application from an own-
er or operator, the Administrator may
approve use of equipment or procedures
which have been demonstrated to his
satisfaction to be equivalent in terms of
reducing vinyl chloride emissions to the
atmosphere to those prescribed for com-
pliance with a specific paragraph of this
subpart For an existing source, any re-
quest for using an equivalent method as
the initial measure of control to to be
submitted to the Administrator within
30 days of the effective date. For a new
source, any request for using an equiva-
lent method is to be submitted to the,
Administrator with the application fojr
approval of construction or modification
required by 101.07.
§ 61.67 Eminion test*.
(a) Unless a waiver of emission testing
is obtained under 101.13. the owner or
operator of a source to which this sub-
part applies shall tost emissions from
the source.
<1> Within 90 days of the effective date
In the case of an existing source or a
new source which has an initial startup
date preceding the effective date, or
<2> Within 90 days of startup In the
case of a new source, initial startup of
which occurs after the effective date.
(b) The owner or operator shall pro-
vide the Administrator at least 30 days
prior notice of an emission test to afford
the Administrator the opportunity to
have an observer present during the test.
Any emission test Is to be con-
ducted while the equipment being tested
is operating at the maximum production
rate at which the equipment will be op-
erated and under other relevant condi-
tions as may be specified by the Adminis-
trator based on representative perform-
ance of the source.
(d) Each emission test is to consist
of three runs. For the puspose of deter-
mining emissions, the average of results
of all runs Is to apply. The average is to
be computed on a time weighted basis.
(e> AH samples are to be analyzed
within 24 hours, and vinyl chloride emis-
sions are to be determined within 30 days
after the emission test. The owner or
operator shall report the determinations
to the Administrator by a registered
letter dispatched before the close of the
next business day following the deter-
mination.
(2). , (g><4>. and
(g) (8) of this section, unless an equiva-
lent method or an alternative method
has been approved by the Administrator.
If the Administrator, finds reasonable
grounds to dispute the results obtained
by an equivalent or alternative method,
he may require -the use of a reference
method. If the results of the reference
and equivalent or alternative methods
do not agree, the results obtained by the
reference method prevail, and the Ad-
ministrator may notify the owner or
operator that approval of the method
previously considered to be equivalent or
alternative is withdrawn.
(1) Test Method 100 is to be used to
determine the vinyl chloride emissions
from any source for which an emission
limit is prescribed in If 61.02 (a) or (b)
I 61.63, or || 61.64(a) (1). (b), (c), or
(d) , or from any control system to which
reactor emissions are required to be
..ducted in 1 61.64(a> (2) or to which fugi-
tive emissions are required to be ducted
in If 61.65. , For each run. one sample is to be
collected. The sampling site is to be at
least two stack or duct diameters down-
stream and one half diameter upstream
from any flow disturbance such as a
bend, expansion, contraction, or visible
flame. For a rectangular cross section an
equivalent diameter is to be determined
from the following equation:
The sampling point in the duct is to
be at the centrold of the cross section.
The sample is to be extracted at a rate
proportional to the gas velocity at the
sampling point. The sample is to be
taken over a minimum of one hour, and
is to contain a "tiiMimifit volume of 50
liters corrected to standard conditions.
For gas streams containing more
than 10 percent oxygen, the concentra-
tion of vinyle chloride as determined by
Test Method 106 is to be corrected to 10
percent oxygen for determination of
emissions by using the following equa-
tion:
rt ,,,,„«. .,.,,-.=r» r
10. ft
whim:
O,
~Tlu> coucMitnUon of rinyl cliluridr In
t rlnrl c
t Mctaod DM.
chloride a
C.-TbTaonemtnUoa ot
mminnMl by Tat .
a>«-P«neot oireto la the unMtat air M
ttaodftrd oondlttottt.
10.0-Pmaat oxjwa la lot unblral alf «t
M*ndMd /wodlUoof, mlnu tot 10
DUMnt oiyifu towhleb ttM
ttda tl brinf nud*.
Percrni Oi-Ptra
.
traint oyito to th»
7
the
Appttdli A.a( Put to otthli chapter"
(Ill) For those yHtflwi sources where
ission limit is prescribed in terms
of mass rather than concentration, mass
KOEMl MOUTH, VOl. 41.
NO. JOS—THUISOAV. OCTOMI 11. !«?«
96
-------
46568
emissions in kg/100 kg product an to
be determined by using the foQowtng
equation:
rIC» (2.80) Q 10-1 [HOOl
Z
Cii-kf vinyl chloride/100 kg product.
C»-The ooDoeotnttoo of vinyl ebloride as measured
by Tia$ Method 10ft.
SJO»Denslty of vinyl chloride at one atmosphere and
90*C IB kc/m>.
«-Vohm»trlc flow rate IB m'/hr ae determined by where:
Befsrenoe Method t of Appendii A to Part 90
of this chapter.
10-'-Conversion factor for ppm.
Z-Prodoctloc rate (kg/hi).
Test kfethod 107 is to be used to
when:
CM ^kf vinyl chloride/100 kg product.
C«-tne concentration of vinyl chloride as measured
by Test Method 107.
K-water flow rate ID 1/hr. determined In accordance
with a method which has been submitted to
and approved by the Administrator.
Ur-<- Conversion lector for .Ppm.
Z-Prodnctlon ml* (kg/STddermliied In accord-
ance with a method which hu been submitted
and approved by the Administrator.
(5) The reactor opening loss for which
an emission limit Is prescribed in 1 61.64
(a) (2) Is to be determined. The number
of reactors for which the determination
Is to be made to to be specified by the
Administrator for each Individual plant
at the time of the determination based
on the plant's operation. For a reactor
IULES AND REGULATIONS
that is also used as a stripper, the deter*
minatlon may be made immediately fol-
lowing the stripping operation.
<1> Except as provided in paragraph
(gXBXli) of this section, the reactor
opening loss is to be determined using
the following equation:
W (2.60) (10-') (C6)
yz
(2)
determine the concentration of vinyl
chloride in each Inprocess wastewater
stream (or which an emission limit is
prescribed in I 6l.65(b) (9) (l> .
<3) Where a stripping operation is
used to attain the emission limit in 1 61.-
64 (e). emissions, are to be determined
using Test Method 107 as follows:
(1) The number of strippers and sam-
ples and the types and grades of resin to
be sampled are to be determined by the
Administrator for each individual plant
at the time of the test based on the
plant's operation.
(11) Each sample Is to be taken Imme-
diately following the stripping operation.
(Ill) The corresponding quantity of
material processed by each stripper Is to
be determined on a dry solids basis and
by a method submitted to and approved
by the Administrator.
(iv) At the prior request of the Ad-
ministrator, the owner or operator shall
provide duplicates of the samples re-
quired In paragraph (g) (3) (i> of this
section.
(4) Where control technology other
than or in addition to a stripping opera-
tion is used to attain the emission limit
In 1 61.64 , emissions are to be deter-
mined as follows:
(1) Test Method 106 is to be used to
determine atmospheric emissions from
all of the process equipment simultane-
ously. The requirements of paragraph
(g) (1) of this section are to be met.
(11) Test Method 107 is to be used to
determine the concentration of vinyl
chloride in each Inprocess wastewater
stream subject to the emission limit pre-
scribed m | ei.M(e). The mass of vinyl
chloride in kg/ 100 kg product in each
In process wastewater stream la to be de-
termined by using the following equa-
tion:
-[C, R 10-1 H001
Ok( vinyl chloride emissions/kg product.
r-CapachyorU>ereactorlnin>. '
2.eo-DensUy of vinyl chloride at one atmosphere and
10-< > Conversion factor for ppm.
CS-ppm by volume vinyl chloride as determined by
Teat Method 106 or a portable hydrocarbon
detector which measures hydrocarbons
with a sensitivity of at least 10 ppm.
y=Number of batches since the reactor was last
opened to the atmosphere.
Z=Average kg of poly vinyl chloride produced per
batch In the number of batches since the rf actor
was last opened to the atmosphere.
(A) If Method 106 is used to deter-
mine the concentration of vinyl chloride
and (b), i 61.63(a).
and §61.64(aXl>, (b), (c).and (d).and
for any control system to which reactor
emission are required to be ducted in
5 61.65, ,
(b) The vinyl chloride monitoring sys-
tem(s) used to meet the requirement m
paragraph (a) of this section is to be a
device which obtains air sampels from
one or more point** on a continuous
sequential basis and analyzes the samples
with gas chromotography or, if the owner
or operator assumes that all hydrocar-
bons measured are vinyl chloride, with
infrared spectrophotometry, flame ton
detection, or an equivalent or alterna-
tive method. The vinyl chloride monitor-
ing system used to meet the requirement*
in i &1.65(b) (8) (l) may be wed to meet
the requirements of this section.
(c) A dally span check Is to be con-
ducted for each vinyle chloride monitor-
Ing system used. For all of the emission
sources listed in paragraph 'a> of this
section, except the one for which an emis-
sion limit is prescribed in 5 6l42(b) . the
dally span check Is to be conducted with
a concentration of vinyl chloride equal
to 10 ppm. For the emission source for
which an emission limit is prescribed in
i 6l.62(b), the daily span check is to be
conducted with a concentration of vinyl
chloride which Is determined to be
determined to be equivalent to the emis-
sion limit for that source based on the
emission test required by |67.67. The
calibration is to be done with either:
(1) A calibration gas mixture pre-
pared from the gases specified in sections
5.2.1 and 5.2.3 of Test Method 106, or
(2) A calibration gas cylinder con-
taining the appropriate concentration of
vinyl chloride. If a calibration gas
cylinder is used, the analysis must be
traceable to the National Bureau of
Standards or to a gravimetrically cali-
brated vinyl chloride permeation tube.
§ 61.69 Initial report.
(a) An owner or operator of any
source to which this subpart applies shall
submit a statement In writing notifying
the Administrator that the equipment
and procedural specifications in Si 61.6S
(b)(6), (b)<7>, and (b)(8) are being
implemented.
(b) (1) In the case of an existing
source or a new source which has an
initial startup date preceding the effec-
tive date, the statement is to be submit-
ted within 90 days of the effective date.
unless a waiver of compliance is granted
under i 61.11, along with the informa-
tion required under § 61.10. If a waiver
of compliance is granted, the statement
is to be submitted on a date scheduled
by the Administrator.
(2) In the case of a new source which
did not have an initial startup date pre-
ceding the effective date, the statement
is to be submitted within 90 days of the
initial startup date.
(c) The statement is to contain the
following information:
(I) A list of the equipment installed ,
for compliance,
(2) A description of the physical and
functional characteristics of each piece
of equipment.
(3) A description of the methods
which have been Incorporated into the
standard operating procedures for meas-
uring or calculating the pminninroe fop
which emission limits are prescribed in
{{61.65 (b) UXD and is to be determined. The number
source to which this subpart applies shall
submit to the Administrator on Septem-
FfOERAl IICISTEP, VCL. 41, NO
205—THURSDAY, OCTOBER 31,
97
1976
-------
•UUS AND MOUIATIONS
46509
tMr 16 and March IB at each year a report
in writing containing *n« Information
required by this section. The flnt semi-
annual report to to be submitted follow-
in(l) m the ease of an existing source
or » new source which hM an Initial
startup date preceding the effective date,
the first report Is to be submitted within
ISO dan of the effective date, unless a
waiver of compliance Is granted under
161.11. If a waiver of compliance Is
granted, the flnt report ta to be sub-
mitted bn a date scheduled by the Ad-
(2) In the case of a new source which
did not have an initial startup date pre-
ceding the effective date, the flnt report
Is to be submitted within 180 days of the
initial startup date.
(c) Unless otherwise specified, the
owner or operator shall use the Test
Methods in Appendix B to this part to
conduct •™i*«*«i« tests as required by
paragraphs . i 61.63,
or II 01.64(a) (1), (b), (c), or (d>. or for
any control system to which reactor
•miMtona «re required to be ducted m
I 6l.64(a) (3) or to which fugitive emis-
sions are required to be ducted in 161.66
(bXlXtt), (b)(3), If continuous stripping to used.
one representative sample of polyvinyl
chloride resin ta to be taken for each
grade of resin processed or at Intervals
of • hours for MfhJ^* °* re>m whlcl1
quent The sample to to be taken as the
ream flows out of the stripper and Iden-
tified by resin type and grade and the
date and time the sample was taken.
The corresponding quantity of material
processed by each stripper over the time
period represented by the sample during
the eight hour period, to to be recorded
and identified by resin type and grade
and the date and time It represents.
(ill) The quantity of material proc-
essed by the stripper to to be determined
on a dry solids basis and by a method
submitted to and approved by the Ad-
ministrator.
(iv) At the prior request of the Ad-
ministrator, the owner or operator shall
provide duplicates of the samples re-
quired In paragraphs (O(2X1) and (c)
(2) (11) of this section.
, (v) The report to the Administrator by
the owner or operator to to include the
vinyl chloride content found In all the
samples required In paragraphs (e) (3)
(i) and (c) <2)(II) of this section, aver-
aged separately for each type of resin.
over «"y>h calendar day and weighted ac-
cording to the quantity of each grade of
resin processed by the stripper(s) that
calendar day, according to the following
equation:
Ar,-
^-24-hour »T
,-TnS°o7
Ntfn;
'
on eftntT, !•*••§
Mtaovwlhilfrhoei
lf, . :.m warn • It tetat
tyjw ptodond darb* tb» *•
M-CononSSSao of rtnjl ohlocld* In go* auopto at
.
**.. OL A, kad OV
aTcndM
,
*f rerta produced darlns
(vl> The owner or operator shall re-
tain at the source and make available
for Inspection by the Administrator for
a minimum of 3 yean records of aO data
needed to furnish the information re-
quired by paragraph (e) (3) (v) of this
section: The records are to contain the
following Information:
(A) The vinyl chloride content found
In all the samples required In paragraphs
(c) (3) (1) and (c) (3) (It) of this section.
Identified by the resin type and grade
and the time and date of the sample, and
(B) The corresponding quantity of
polyvinyl chloride resin processed by the
stripper(s), identified by the resin type
and grade and the time and date it
represents.
<3) The owner or operator shall In-
clude In the report a record of the emis-
sions from each reactor opening for
which an emission limit ta prescribed In
161.64 (a) (3). Emissions are to be deter-
mined in accordance with 161.67(g) (6).
except that emissions for each reactor
an to be determined. For a reactor that ta
also used as a stripper, the determination
may be made Immediately following the.
stripping operation.
161.71 Reeordkeeping.
(a) The owner or operator of any
source to which this subpart applies shall
retain the following Information at the
source and make it available for inspec-
tion by the Administrator for a mini-
mum of two yean;
(1) A record of the leaks detected by
the vinyl chloride monitoring system, as
required by I 61.6S(b) (8), including the
concentrations of vinyl chloride as
measured, analysed, and recorded by the
vinyl chloride detector, the location of
each measurement and the date and ap-
proximate time of each measurement.
(2) A record of the leaks detected
during routine monitoring with the
portable hydrocarbon detector and the
action taken to repair the leaks, as re-
quired by I 6l.65(b) (8), including a
brief statement explaining the location
and cause of each teak detected with
the portable hydrocarbon detector, the
date and time of the leak and any action
taken to eliminate that leak measured in
accordance with 161.68.
(3) For the relief discharges from
reactors subject to the provisions of
|61.65(»>, a dally operating record for
each reactor, Including pressures and
temperatures.
3. Appendix B is amended by adding
Test Methods 106 and 107 as follows:
109—DBWMINATIOIt Or VUfTL
OLOUDS VBOK STATIONABY SOU»CBS
xirrsoDucnoN
Performance of this method should not b»
•ttftmptrl by persons unfamiliar with th»
operation of a gas chromatograph. nor by
than who ar» unfamiliar with source sam-
pling, as there are many details that are
beyond the scope of this presentation. Car*
must be exercised to prevent exposure of
..«»rn..B personnel to vinyl chloride, a ear-
olBogexi.
1. Principle and Applicability.
l.l An integrated bag sample of stack gas
containing vinyl chloride (ehloroethylsne)
is subjected to ehromatographle analysis.
using a flam* lonlcatlon detector.
1.3 The method Is applicable to the meas-
urement of vinyl chloride In stack gases from
etbyleae dtchlorlde. vinyl chloride and poly-
vinyl chloride manufacturing processes, ex-
cept when the vinyl chloride Is contained la
paniculate matter.
a. flange and Bensitlvlty.
HM lower limit of detection will vary ac-
cording to the chromatograph used. Values
reported include 1 x 10-' mg and 4 x 10-'
mg.
3. Interferences.
Aeetaldehyde, which can occur In some
vinyl chloride sources, wUl Interfere with the
vinyl chloride peak from the Chromosorb 102
column. See sections 4.8.2 and 9.4. U resolu-
tion of the vinyl chloride peak Is still not
satisfactory for a particular sample, then
chromatograph parameters can be further
altered with prior approval of th* Admin-
istrator. If alteration of the chromatograph
parameters falls to resolve the vinyl chloride
peak, then supplemental confirmation of th»
vinyl chloride peak tfarouf h an absolute
analytical technique, such as mass spectro-
scopy, must be performed.
4. Apparatus.
4.1 •imping (Figure 1).
4.1.1 Probe—Stainless steel, Pyrex glass.
or Teflon tubing according to stack temper-
nOflAl IMISTII, VOL 41. NO. 105—TMUtSOAY, OCTOHI II, 197*
98
-------
46570
RULES AND REGULATIONS
ature. each equipped with a glass wool plug
to remove partteulate matter.
4.14 Sample line—Teflon, e.4 mm outside
diameter, or sufficient length to connect
probe to bag. A new unused place 1* employed
for each series of bag samples that constitute*
«n emission test.
4.1.* Male (3) and female (3) (Ulnlees
•teal quick-connects, with ball check! (one
pair without) located as shown la Figure 1.
4.1.4 Tedlar bags, 100 liter capacity—To
contain sample. Teflon bags are not accept-
able. Alumlnlzed Mylar bags may be used.
provided that the samples are analyzed
within 34 hours of collection.
4.1.8 Rigid leakproof containers for 4.1.4.
with covering to protect contents from sun-
light.
4.1.8 Needle valve—To adjust sample flow
rate.
4.1.7 Pump—Leak-free. Minimum capac-
ity 3 liters per minute.
4.1.8 Charcoal tube—To prevent admis-
sion of vinyl chloride to atmosphere In vicin-
ity of samplers.
4.1.9 Flow meter—For observing sample
flow rate; capable of measuring a flow range
from 0.10 to 1.00 liter per minute.
4.1.10 Connecting tubing—Teflon, 8.4 mm
outside diameter, to assemble sample train
(Figure 1).
4.1.11 Pilot tube—Type B (or equivalent),
attached to the probe so that the sampling
flow rate can be regulated proportional to
the stack ga* velocity.
4.3 Sample recovery.
4.3.1 Tubing—Teflon, 6.4 mm outside
diameter, to connect bag to gas ehromato-
graph sample loop. A new unused piece Is
employed for each aeries of bag samples that,-
constitutes an emission test, and Is to be dis-
carded upon conclusion of analysis of those
bags.
44 Analysis.
4.3.1 Oas ehromatograph—With flame
lonlzatlon detector, potentlometrlc strip
chart recorder and 1« to 6.0 ml heated sam-
pling loop In automatic •ample' valve.
444 Chromatographle column—Stainless
utoel. 3.0 x 8-3 mm, containing 80/100 mesh
Chxomoeorb 103. A secondary oolum of OK
8P-M. SO* on 80/80 mesh AW Chromoaorb
P, stainless steel. J.O m X 34 mm. will be
required if aceteJdehyde is present, if used.
the 8P-06 column k» placed after the Chromo-
aorb 109 ~J"""» The combined columns
should then be operated at 110X3.
444 Flow meters (3)—Rotemeter type,
0 to 100 ml/mln capacity, with flow control
valves.
4.8.4 das regulators—For required gal
cylinders.
440 Thermometer—Accurate to one de-
gree centigrade, to measure temperature of
heated sample loop at time of sample injec-
tion.
4.8.8 Barometer—Accurate to 5 nun Hg, to
measure atmospheric pressure around gas
chromatograpb during sample analysis.
44.7 pump—Leak-free. Minimum capac-
ity 100 ml/mln.
4.4 Calibration.
4.4J Tubing—Teflon, 8.4 mm outside
diameter, esparate pieces marked for each
calibration concentration.
444 Tedlar bags—BUteen-lnch equate
•He. separate bag marked for each calibra-
tion concentration.
4.44 Syrlnge-04 ml. gastight.
I 4.4.4 ejlinge—80jO.BJa« tight.
1 > Mention of trade names on specific prod-
•net* does not constitute endorsement by the
Environmental Protection Agency.
4.4.5 Flow meter—Rotameter type, 0 to
1000 ml/mln range accurate to ±1%. to
meter nitrogen In preparation of standard
gas mixtures.
4.44 Stop watch—Of known accuracy, to
time gas flow In preparation of standard gas
mixtures.
B. Reagents. It Is necessary that all rea-
gents be of Chromatographle grade.
5.1 Analysis.
5.1.1 Helium gas or nitrogen gas—Zero
grade, for Chromatographle carrier gas.
5.1.3 Hydrogen gas—Zero grade.
6.1.8 Oxygen gas. or Air. as required by
the detector—Zero grade.
6.3 Calibration.
6.3.1 Vinyl chloride, M.9+%—For prep-
aration of standard gas mixtures.
6.2.3 Calibration cylinders (3), optional—
One each of 50, 10 and 5 ppm vinyl chloride
In nitrogen with certified analysis. Analysis
must be traceable to NB8 (National Bureau
of Standards) or to a gravlmetrlcally cali-
brated vinyl chloride permeation tube.
6.34 Nitrogen KM—Zero grade, for prep-
aration of standard gas mixtures.
6. Procedure.
6.1 Sampling. Assemble the sample train
u-ln Figure 106-1. Perform a bag leak check
according to Section 7.4. Observe that all
connections between the bag and the probe
are tight. Place the end of the probe at the
centrold of the stack and start the pump
with the needle valve adjusted to yield1 a
flow of 04 1pm. After a period of time suffi-
cient to purge the line several times has
elapsed, connect the vacuum line to the
bag and evacuate the bag until the rotam-
eter Indicates no flow. Then reposition the
•ample and vacuum lines and begin the ac-
tual sampling, keeping the rate proportional
to the stack velocity. Direct the gas exiting
the rotameter away from sampling personnel.
At the end of the sample period, shut off the
pump, disconnect the sample line from the
bag, and disconnect the vacuum line from
the bag container. Protect the bag container
from sunlight.
64 Sample storage. Sample bags must be
kept out of direct sunlight. When at all pos-
sible, analysis Is to be performed within 34
hours of sample collection.
63 Sample recovery. With a piece of Tef-
lon tubing identified for that bag, connect a
bag Inlet valve to the gas chromatograph
sample valve. Switch the valve to withdraw
gas from the bag through the sample loop.
Plumb the equipment so the sample gas
passes from the sample valve to the leak-free
pump, and then to a charcoal tube, followed
by a 0-100 ml/mln rotameter with flow con-
trol valve.
6 4 Analysis. Set the column temperature
to 100* C the detector temperature to 150*
C, and the sample loop temperature to 70* C.
When optimum hydrogen and oxygen flow
rates have been determined verify and main-
tain these flow rates during all chromato-
craph operations. Using zero helium or
nitrogen M the carrier gas, establish a flow
rate In the range consistent with the manu-
facturer'* requirements for satisfactory de-
tector operation. A flow rate of approxi-
mately 40 ml/mln should produce adequate
separations. Observe the base line periodi-
cally and determine that the noise level has
stabilized and that base line drift has ceased.
Purge the sample loop for thirty "condi.at
• th» nts of 100 ml/mln, then activate the
sample valve. Record the injection time (the
position of the pen on the chart at the time
of sample Injection), the sample number, the
•ample loop temperature, the column tem-
perature, carrier gas flow rate, chart speed
and the attenuator setting. Record the lab-
oratory pressure. From the chart, select the
peak having the retention time correspond-
ing to vinyl chloride, as determined In Sec-
tion 74. Measure the peak area. A., by use
of H». and a disc Integrator or a planlmeter.
Measure the peak height. H.. Record A. and
the retention time. Repeat the injection at
least two times or until two consecutive vinyl
chloride peaks do not vary In area more than
5%. The average value for these two areas
will be used to compute the bag concentra-
tion.
Compare the ratio of H« to A. for the vinyl
chloride sample with the same ratio for the
standard peak which is closest in height. As
a guideline. If these ratios differ by more
than 10%, the vinyl chloride peak may not
be pure (possibly acetaldehyde la present)
and the' secondary column should be em-
ployed (see Section 44.2).
6.6 Measure the ambient temperature and
barometric pressure ne&r the bag. (Assume
the relative humidity to be 100 percent.)
From a water saturation vapor pressure table,
determine the record and water vapor eon-
tent of the bag.
7. Calibration and Standards.
7.1 Preparation of vinyl chloride standard
gas mixtures. Evacuate a slxteen-lnch square
Tedlar bag that has passed a leak check
(described In Section 7.4) and meter In 6.0
liters of nitrogen. While the bag is filling, use
the 0.6 ml syringe to Inject 360*1 of M3 + <*
vinyl chloride through the wall of the bag.
Upon withdrawing the syringe needle. Im-
mediately cover the resulting hole with a
piece of adhesive tape. This gives a concen-
tration of 60 ppm of vinyl chloride. In a like
manner use the other syringe to prepare dilu-
tions having 10 and 5 ppm vinyl chloride
concentrations. Place each bag* on a smooth
surface and alternately depress opposite
sides of the bag 60 times to further "»'•» the
gases.
74 Determination of vinyl chloride re-
tention time. This section can be performed
simultaneously with Section 74. Establish
chromatognph conditions Identical with
those in Section 64. above. Set attenuator
to X 1 position. Flush the «««»riit«g loop
with zero helium or nitrogen and activate
the sample valve. Record the injection time,
the sample loop temperature, the column
temperature, the carrier gas flow rate, the
chart speed and the attenuator setting.
Record pnars and detector responses that
occur In the absence of vinyl chloride. Main-
tain conditions. With the equipment plumb-
Ing arranged Identically to Section 64. flush
the sample loop for SO seconds at the rate of
100 ml/mln with one of the vinyl chloride
calibration mixtures and activate the campl*
valve. Record the Injection time. Select the
peak that corresponds to vinyl chloride.
Measure the distance on the chart from the
Injection time to the time at which the peak
maximum occurs. This quantity, divided by
the chart speed, is defined as the retention
time. Record.
74 Preparation of ehromatograph cali-
bration curve. Make a gas Chromatographle
measurement of each standard gas mixture
(described In Section 7.1) using nomliUone
Identical with those listed In Section «4
above. Flush the sampling loop for 30 seconds
at the rate of 100 ml/mln with each standard
gas mixture and activate the •ample varr*.
Record C.. the concentrations of vinyl chlo-
ride Injected, the attenuator setting, chart
•peed, peak area, sample loop temperature.
column temperature, carrier gas flow rate.
and retention time. Becord the laboratory
pressure, calculate AH the peak ana multt-
FEDHAl KGISTU. VOL 41. NO. 20;
i_IMU«SDAY. OCI08II 31. 1t74
99
-------
ROIIS AND REGULATIONS
46571
pUed by the attenuator setting. Bepeat until
two injection MM* are within 6*. then plot
those potato vs O.. When the other concen-
trations have been plotted. draw a smooth
curve through the potato. Peifotm ealfbra-
Uon dally, or before and after Melt set or
bag Tfnr1*^ whichever to more frequent.
7.4 Bag teak checks. Wbito performance
of thto section to required subsequent to bag
me. tt to atoo advised that it ba performed
prior to bag nee. After each nee, make sure
a bag did not develop leak* a* follow*. To leak
check, connect a water manometer and pres-
enrtte the bag to ft-10 em H,O (3-4 in H.O).
Allow to atand for 10 minutes. Any d'Tp™*1*-
ment In the water manometer Indlcatee a
leak. Abo check the rigid container for leak*
in ^**" itiftTirffr
(Non: An alternative leak check method
to to pressurise the bag to 6-10 em H.O or
3-4 In. B.O and allow to etand overnight.
A deflated bag Indicates a leak.) For each
•ample bag in ito rigid container, place a
rotameter m-une betaesn the bag and the
pump inlet Evaeuaxe the bag. Failure of the
rotameter to regtoter aero flow when the bag
appeare to be empty indlcatee a leak.
8. Calculations.
1.1 Determine the sample peak area ai
follow.:
Equation 106-1
8j vinyl chloride concentrations, From
the calibration enure described in Section
TJ. above, select the value of O. the* eor-
to Ar tbe sample peak area, Cal-
b as follows:
C.P,T<
Msw*Ut-l.
Ucrmoa 107 — DanaMtWATioM or Vnm CHLO-
X.-Tbt ample peak ana.
' —i inoinidrt ptet area.
EquaUon 106-9
When:
B»>-Th» water vepor content ot Ibe bee Mmbtt, at
snatTHd.
Ci-Tba emMBgauon «f vinyl eWorld* la the beg
P.-Tffeoneente»2lo of vinyl ebMdt Indtotted by
'JSe'Etentarr
'Uffff. mm Hf.
leap tempenton OB On
snle at tte ttoe ef aoslysli, *K.
Pf-Tbe tebontorj pnsnn st Uae of analysto, i
IVoTbe nlenne* tonptntur*. Hie aample leop
hmpmton neonbd during eaUbmaooT'K^
ft. References.
1. Brown. D. W, Loj. B. W. and Stephen-
son. 1C. B. "Vinyl Chloride Monitoring Hear
the B. P. Ooodrloh Chemical Company m
Lontovul*, Kentucky." Region IV, TJB. Envi-
ronmental Protection Agency, Surveillance
and Analysis Division, Athens, Georgia. June
34, 1974.
X "Evaluation of A Collection and Analy-
tical Procedure for Vinyl Chloride In Air.*
by O. D. Clayton and Associate:
IS. 1974. SPA Contract Ho. 6*-oa-140t, Task
Order Ho. a. EPA Beport oM. 76-VCU-l.
S. "BtandardUatton of Stationary Source
k liethod for Vinyl Chloride," by isM-
i nwtttnta, 1970. SPA Contract
Ho. W-U-IOM.-'nMk Order Ho. 7.
i am Vom CHLOBIDI CommiT o*
PoLTvnm. CBLOUM Beam, SI.VIBT. War
C***, *tra LACK SAMTLS*
nrrmoDucnon
Performance of this method should not be
attempted by JIIIKITIII «•>**»*<>•«» witn tlie
operation of a gas enromatograpn. nor by
those who are imf*miii» with sampling, as
there are many details that are beyond the
scope of this presentation. Car* must be
exercised to prevent exposure of sampling
personnel to vinyl chloride, a carcinogen.
1. Principle and Applicability.
1.1 The basis for this method relates to
the vapor equilibrium which to established
between BVCK. PVO. resin, water, and air
in a closed system. It has been demonstrated
that the BVCM in a PVC resin will equili-
brate in a closed vessel quite rapidly, pro-
vided that the temperature of the PVO resin
to maintained above the glass transition
temperature of that specific resin.
1.3 Tnto procedure to suitable for deter-
mining the vinyl ehlorlde ip«*«5y»«ff> (VOM)
content of inproces* wastewater samples.
and the residual vinyl chloride monomer
(BVCM) content of polyvlnyl chloride (PVO)
resins, wet cake, slurry, and latex samples.
tt cannot be used for polymer In fused form,
such as sheet or cubes. If a resolution of the
vinyl chloride peak to not satisfactory for a
particular sample, then chromatograpb
parameters may be altered with prior ap-
proval of the Administrator. If there to rea-
son to believe that some other hydrocarbon
with an identical retention tune to present
in the sample, then supplemental confirma-
tion of the vinyl ehlorlde peak through an
absolute analytical technique, such as mass
speetroscopy, should be performed.
*. Range and Sensitivity.
The lower limit of detection of vinyl Ohio.
ride wffl vary according to the ehrometo-
graph used. Values reported Include 1X10-*
mg and 4X 10" mg. With proper ealibrattoa.
the upper limit may be extended as needed.
3. Precision and Beprodudbnity.
An interlaboratory comparison between
seven laboratories of three resin samples.
each split Into three parts, yielded a standard
deviation of 2.63% for a sample with a mean
of 3.09 ppm. 4.18% for a sample with a mean
of IM ppm, and 0.99% for a sample with a
mean of 02.60 ppm.
4. Safety.
Do not release vinyl chloride to the labora-
tory atmosphere during preparation of stand-
ards. Venting or purging with VOM/atr mix-
tures must be held to a minimum VJben
they are required, the vapor must be routed
to outside air. Vinyl ehlorlde. even at tow
ppm levels, must never be vented Inside the
laboratory. After vials have been analysed,
the pressure within the vial moat be vented
prior to removal from the instrument turn-
table. Vials must be vented Into an activated
charcoal tube using a hypodermic needle to
prevent release of vinyl chloride into the
laboratory atmosphere. The charcoal must
be replaced prior to vinyl chloride break-
through.
S. Apparatus.
6.1 Hampllngi
5.1.1 Bottle*— «0 ml (9 OB), with waxed
lined screw on tops, for PVO samples.
6.1 J Vlsls IK) ml Hypo-vials.' sealed with
Teflon faced Tuf-Bond discs for water sam-
ples.
6.1J Electrical tape— or equivalent, to
prevent loosening of bottle tope.
6 .9 Sscnplo reoovory.
6J.1 Vlato— with seals and caps. Perkln-
Bmer Corporation Ho. 106-0118. or equiva-
lent.
S.3J Analytical balance— Capable of
weighing to ±0.001 ,
6.SJ. Syringe. 100
-A- Ho. 010098, o
or equivalent.
nets does not conetttBte <
Bnvtaonmental Protection Agency.
bytko
IDEtAt MGISTfa., VOL 41. NO. 105—THUISOAIf, OCTOMi tl. 1*7*
100
-------
46572
8.3.4 Tial SeaMr. Perkln-Elmer No. 106-
0106 or *qutval*nt.
63 Analysis.
84.1 Oas chromatograph—Perkln-Elmer
Corporation Had*! F-10 heed-*pae* ana-
lyser. Ho. 104-0001, or equivalent.
6.3.3 OhNtnatographlc column—Attain-
less steel. • mX34 mm, o""***^"*; Ov4*
Carbowax 1600 on Oarbopak A. Perktn-Euner
Corporation Ho. 106-0183. or equivalent.
Oarbopak o can be used In place of Oarbopak
844 Thermometer—0 to 100* C, accurate
to :t0.1* C. Perkln-Elmer No. 108-0100 or
equivalent.
64.4. Sample tray thermostat system—
Farkin-EJxoar Ho. 108-4108, or equivalent.
544 Septa—Sandwich type, for auto-
matic dosing, 13 mm, Perkln-Klmer Ho. 106-
1008. or equivalent.
64.6 Integrator - recorder — Hewlett -
Packard Model 3380A. or equivalent.
64.7 niter drier assembly (»)—Perkln-
Bmer Ho. 3330117. or equivalent.
644 Boap film flowmeter—Hewlett Pack-
aid No. 0101-OU3. or equivalent.
8.4 Calibration.
8.4.1 Regulator*—for required gas eyin-
ders.
6. Reagents.
6.1 Analysts.
6.1.1 Hydrogen gas—aero grade.
6.14 Nitrogen gas—•ero grade.
6.3 Calibration.
6.3.1 SUndard cylinders (4>—on* each
of 60, 800, 3000. and 4000 ppm vinyl chloride
tn nitrogen, with eertMed analyst*.
7. Procedure.
7.1 Sampling.
7J.I PTO *ampllng—Allow toe resin or
•lurry to flow from a tap on the tank or *Ho
until the tap line hai been well purged. Ex-
tend a 60 ml sample bottle under the tap, flu.
and immediately tightly cap the bottle. Wrap
electrical tape around the cap and bottle to
prevent toe top from toosenlng. Place an
Identifying label on each bottle, and record
the date. time, and •ample location both on
the bottle* and In a log book.
7.1.3 Water lampllng—Prior to us*, the
60 ml vial* (without the discs) muat be
capped with aluminum foil and muffled at
400*O for at toast one hour to destroy or
remove any organic matter that could In-
terfere with analysis. At the sampling loca-
tion fill the vial* bubble-free, to overflowing
eo that a convex meniscus forma at the top.
The ezoeee water I* displaced a* the eeaUng
disc I* carefully placed. Teflon aid* down, on
the opening of the vlaL Place the aluminum
aval over the disc and the neck of the vial
and crimp into place. Affix an Identifying
label on the bottle, and record the date, time.
and sample location both on the vial* and
In a log book. All sample* mutt be kept re-
frigerated until analysed.
7.3 Sample recovery. Sample* must be run
within 34 hours.-
7.2.1 Resin sample*—Th* weight of the
resin used must be between 0.1 and 4.8 grams.
An exact weight must be obtained (±0.001
gram) for each sample. In the ease of sus-
pension resins a volumetric cup can be pre-
pared which will hold the required amount
of sample. The sample bottle Is opened, and
the cup volume of resin Is added to the tared
sampl* vial (including septum and alumi-
num cap). The vial Is Immediately sealed
and the exact sample weight is then obtained.
Report tfata value on the data sheet as It Is
required for calculation of BVCM. In th*
•as* of relatively dry ream aamplee (water
•ontent <04 weight *). 100 .1 of distilled
wator must be injected into tte vial, after
tttUB AND tfOOlATlONS
sealing and weighing, using a 100 J syringe.
In th* case of dispersion resins, the cup
cannot be and. Th* sampl* I* Inrtrairt
weighed approximately In an aluminum dish,
transferred to the ta «d vW and weighed
accurately in the vtaL Th* Mmpl* is then
placed In the P*rkln>Zlm*r head space ana-
lyser (or equivalent) and conditioned for on*
hour at M*O.
HOTS: Bom* aluminum vial caps have a
center section which must be removed prior
to placing into sample tray. If not removed.
serious damage to the injection needle will
occur.
7.2.3 Suspension resin slurry and wet cake
samples—Slurry most be filtered using a
small Buehner funnel with vacuum to yield
wet cake. The filtering process must be con-
tinued only as long as a steady stream of
water Is exiting from the funnel. Excessive
filtration time could result In some lots of
VCM. The wet cake sample (O.io to 4.8 grams)
Is added to a tared vial (Including septum
and aluminum cap) and Immediately sealed.
Sample weight la then determined to 3 deci-
mal places. The sample Is then placed In the
Parkin -Klmer head space analyser (or equiva-
lent) and conditioned for one hour at 80*C.
A sample of wet cake u used to determine
T3 (total solids). This la required for calcu-
lating the BVCM.
7.3.3 Dispersion resin slurry samples.—
This mateiiaT should not be filtered. Sampl*
must be thoroughly mixed. Oilng a tared
vial (Including septum and aluminum cap)
add approximately 8 drops (0.36 to 0.38
grams) of slurry or latex .using a medicine
dropper. This should be done immediately
after mixing. -Seal the vial as soon aa possible.
Determine sampl* weight accurate to 0.001
grams. Total sample weight muat not exceed
0.60 grama. Condition the vial for one hour
at PO-C In the analyzer. Determine the TB
on the Uurry sample (Section 7.3.6) .
7.2.4 Inprocees wastewater samples—
Using a tared vial (Including septum and
aluminum cap) quickly add approximately
I cc of water using a medicine dropper. Seal
the via! as soon as possible. Determine
sample weight accurate to 0.001 gram. Con-
dition the vial for two hours at SO'C In th*
analyzer.
7.3 Analysis.
7 J.I Preparation, of gas chromatograph —
Install th* ehrotnatographle column and con-
dition overnight at IBO'C. Do not connect the
exit end of the column to the detector while
tor—Ignite tbe d*t*etor according to th*
manufacturer* instructions.
7J.1A AmpHflar Delano* Bslsnrsj «*•
amplifier according to th* uianufacuuat's
7.3.1.1 Flow rate adjustments — Adjust
flow rates as follows:
a. Nitrogen carrier gaa — Set regulator on
cylinder to read 60 pslg. Set regulator on
chromatograph to 14 kg/cm*. Normal flows
at this pressure should be 36 to 40 ce/mlnute.
Check with bubble flow meter.
b. Burner air supply — Set regulator on cyl-
inder to read 80 pslg. Set regulator on
chromatograph to supply air to burner at a
rate between 350 and 300 ec/mlnuto. Check
with bubble flowmeter.
3. Hydrogen supply— Set regulator on cyl-
inder to read to pslg. Bet regulator on
chromatograph to supply approximately
M-t-t ce/mlnute. Optimize hydrogen flow to
yield the most sensitive detector response
without extinguishing the flame. Check flow
with bubble meter and record this flow
7.3.1.3 Temperature adjustments— Set
temperature* as follows:
a. Oven (ehromatographle column), SO*
C.
b. Daunt line. 1*0' C.
e. injection block. 140* C.
d. Sample chamber, water temperature,
•0* O±lJf C.
7.3.1.3 Ignition of flame tonlzatton detec-
7.3.3 Programming th* ehromatograpB—
Program th* chromatograph as follows:
a. I—Dosing time—The normal setting Is
3 seconds.
b. A—Analysis time—The normal setting
Is • minutes. Certain types of sample* eon-
tain high boiling materials which can cause
Interference wtlh th* vinyl chloride peak on
subsequent analyses. In these cases tb*
analysis tun* must be adjusted to *"mtriitT
the Interference. An automated backflosh
system can also be used to solve this prob-
lem.
e. B—Flushing—The normal setting Is 0.3
minutes.
d. W—Stabilisation time—The nomal set-
ting Is 0.3 minutes.
e. X—Number of analyses per sample—Th*
normal setting is 1.
732 Preparation of .sample turntable—Be-
fore placing any sample into tumtabl*. be
certain that the center section of the alu-
minum cap has been removed. The numbered
sample bottles should be placed In the cor-
responding numbered positions In the turn-
table. Insert samcles In the followlna order:
Positions 1 * 3—Old 3000 ppm standards
for conditioning. These are necessary only
after the analyzer has not been used for 34
hours or longer.
Position 3—50 ppm standard, freshly pre-
pared.
Position 4—600 ppm standard, freshly pre-
pared.
Position 6—3000 ppm standard, freshly
prepared. /
Position 6—4000 ppm standard. fresh"* pre-
pared.
Position 7—Sample Ho. 7 (This Is tb* first
sample of the day. but Is given aa 7 to be con-
sistent with the turntable and the Integrator
printout.)
After all samples have been positioned. In-
sert the second set of 60. 600. 3000. and 4000
ppm standards. Samples. Including stand-
ards must be conditioned In the bath of
90' C for l hour (not to exceed 8 hours).
74.4 Start chromatograph program-
When all samples. Including standards, have
been conditioned at BO* C for 1 hour, start
the analysis program according to the manu-
facturers' Instructions. Thee* Instructions
must be carefully followed when starting
and stopping program to prevent damage to
the dosing assembly.
7.3.6 Determination of total solids (TS).
For wet cake, slurry, resin solution, and
PVC latex samples, determine TS for each
sample by accurately weighing approxim-
ately 3 to 4 grama of sample In an aluminum
pan before and after placing In a draft
oven (105 to 110' C). Samples must b* dried
to constant weight. After first weighing re-
turn the pan to the oven for a short pe-
riod of time and then rewelgh to verify com-
plete dryneas. TS Is then calculated a* tb*
final sample weight divided by initial sam-
ple weight.
0. Calibration.
Calibration si to be performed each eight-
hour period when the Instrument Is used.
Each day. prior to running sample*, th* col-
umn should b* conditioned by running two
of the previous days 3000 ppm standards.
8.1 Preparation of Btsnlarlt
Calibration standards are prepared by fin-
ing the vials with th* vinyl chloride/nitro-
gen standards, rapidly seating th* a*ptoxa
and sealing with th* aluminum cap. Use a
stainless steel one from th* cylinder to th*
vial. Do not use rubber or tygon tubing. Th*
sample line from the cylinder
HOttM HOISTtt, VOL 41, NO. 1M—THUISDAY, OCTOIEt 11 j 1976
101
-------
AND MOMATIONS 46671
, (mto hood) for aararal mmut
•X vtaav Aftor purglnc. reduce tha flow
rato to •pptnilm* My »00-1000 ee/mln. Flao*
aad of tabmff into vml (aaar bottom) and
mar oaa mttuto alowly remove tublnf. Flao*
aaptam la vial aa aooa aa poatlbl* to mlni-
I air with eemple. Aftar th* ctand
ard vlala ara aaatod. tnjaot 100*1 of <
watar.
•J Preparation of cbromatograph oaUbra- Equatloa 107-1
tton curt*.
Prepare two 80 ppm. two 800 ppm. two 9000
ppm. aad two 4000 ppm etandard i
Boa tha calibration aample* la exactly tha _ A,Pm.
•am* manner a* regular samplea. Plot
tha Integrator area count* lot <
tlfet CKMaUNvOwXatttOBL flf
ehlohda la each etaadard'aampla. Draw
Una of bait At through the potato
J. Oatertaaoaa. Equation 107-4
V*l naHvODaW M*OV)ff« avfaaVwl*
From th* calibration curre deeerlbad la
tb* vata* of O.
i to A. for each aampl*. Oom-
Datethereeponaefactor.B,.foreaob•ample. Barolt* caKralated nrtng »
-------
APPENDIX C
NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR
POLLUTANTS
Standard for Vinyl Chloride:
Corrections and Amendments
103
-------
RULES AND REGULATIONS 29005
IPRL 740-71
PART 61—NATIONAL EMISSION STAND-
ARDS FOR HAZARDOUS AIR POLLUTANTS
Standard for Vinyl Chloride; Corrections
and Amendments
AGENCY: Environmental Protection
Agency.
ACTION: Final rule.
SUMMARY: These amendments are be-
ing made to the vinyl chloride standard
which was promulgated unjler the au-
thority of the Clean. Air Act on October
21. 1976. The standard contains some
typographical errors and needs clarifica-
tion in some parts. These amendments
are intended to correct the typographical
errors and clarify the standard.
EFFECTIVE DATE: June 7,1977.
FOB FURTHER INFORMATION CON-
TACT:
Don R. Goodwin. Emission Standards
and Engineering Division. Environ-
mental Protection Agency. Research
Triangle Park. North Carolina 27711.
telephone 919-688-8146, ext. 271.
SUPPLEMENTARY INFORMATION:
On October 21.1976. under section 112 of
the Clean Air Act. as amended (42 UJ3.C.
1857), the Environmental Protection
Agency (EPA) promulgated a national
emission standard for vinyl chloride (41
FR 46560). The standard covers plants
which manufacture ethylene dtehlorlde.
vinyl chloride, and/or polyvinyl chloride.
Since that time, it has become apparent
that a few sections of the standard and
Test Methods 106 and 107 are unclear.
The purpose of the amendments being
made at this time is to clarify these sec-
tions and to correct typographical errors.
These corrections are in addition to those
published on December 3, 1976 (41 FR
53017). The Administrator finds that
FEDCtAl IECISTER, VOl. 42, NO. 10»—.TUESDAY, JUNE 1,
104
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29006
RULES AND REGULATIONS
good cause exists for omitting prior
notice and public comment on these
amendments as unnecessary and for
making them immediately effective be-
cause they simply clarify and correct the
existing regulations and impose no ad-
ditional substantive requirements.
The most significant amendment In-
volves clarification of the requirements
for certification of the analysis of gas
cylinders which may be used to calibrate
testing and monitoring equipment. The
standard, as promulgated on October 21.
1076. requires that an analysis of the gas
used for calibration purposes, "• * * be
traceable to the National Bureau of
Standards or to a gravlmetrtcally cali-
brated permeation tube." Comments
were received indicating that the term
"traceable" was unclear.
These amendments require that the
composition of gas cylinders which may
be used for calibration of testing and
monitoring equipment be certified by the
gas manufacturer. The certified compo-
sition must have been determined by di-
rect analysis of the gas contained in each
calibration cylinder using an analytical
procedure the manufacturer had cali-
brated on the day the analysis was per-
formed. Calibration of the analytical
procedure was to have been done using
gases for which the concentrations have
been verified: (1) By comparison with a
calibrated vinyl chloride permeation
tube. (2) by comparison with a gas mix-
ture prepared in acordance with the pro-
cedure described in J 7.1 of Test Method
106 and using 99.9 percent vinyl chloride,
or (3) by direct analysis by the National
Bureau of Standards. These amendments
are being made to 5! 81.65(b)(8)(ill)
'and 61.68(c), which contain the moni-
toring requirements, and to || 5.2 and 6.2
of Test Methods 106 and 107. respec-
tively.
There are several other changes in
wording for clarification purposes. For
example, 161.60 is being amended
to clarify that the testing, reporting, and
recordkeeplng requirements apply to re-
search and development equipment sub-
ject to (I 61.64 (a) (1), (b), (c). and (d),
and definitions for standard temperature
and pressure are being added to S 61.61.
The phrase "in vinyl chloride service" is
being added to I61.65(b)
Mi) to clarify that conducting a series
of three runs is not necessary when Test
Method 107 Is being used to determine
emissions. A change is being made in
t61.67(g)(l)(lll) rwhich was originally
promulgated as i 61.67rg) (I) (11) 1 to es-
tablish that the concentration emission
limits for gas streams are to be de-
termined on a dry basis. Similarly. word-
Ing is being added to « 61.70 (2) (v) to
establish that vinyl chloride concentra-
tions in polyvlnyl chloride resin are to
be determined on a dry weight basis. An
additional change to this same section is
being made to clarify that a sample from
each batch of resin Is to be measured for
its vinyl chloride content. Section 61.71
(a) is being changed to correct typo-
graphical errors and to clarify that daily
operating records for polyvlnyl chloride
reactors are required to be kept whether
a relief valve discharges or not.
Section 4.3.2 of Test Method 106 is
being revised to allow the option of using
Poropak T as the column packing in-
stead of OE SF-96 in a secondary gas
chromatographic column If acetaldehyde
Is present. This packing has also been
shown to produce adequate separation
of vinyl chloride and acetaldehyde. Sec-
tion 61.67 (e) of the regulation and S 6.2
of Test Method 106 are being amended
to include a limit on the amount of time
a test sample can be kept before it is
analyzed for vinyl chloride. Section 1.2
of Test Method 107 is being amended to
clarify that chromatograph parameters
can be altered if the precision and re-
produclbility of analysis of vinyl chloride
cylinder standards Is not impaired. Sec-
tion 5.3.2 of Test Method 107 is being
amended to allow the use of a pair of
Poropak Q columns if methanol or ac-
etaldehyde is present in the sample. Also
in Test Method 107 a clarification for the
term K» has been added to I 9.2.
The remaining changes are corrections
of typographical errors or .are self-
explanatory.
These amendments are issued under
the authority of section 112 of the Clean
Air Act, sec. 4 of Pub. L. 91-604. 84
Stat. 1685 (42 U.8.C. 1857C-7) and sec-
tion 301 (a) of the Clean Air Act sec. 2 of
Pub. L. No. 90-148. 81 Stat. 504. as
amended by sec. (15) (c) <2) of Pub. L.
91-604. 84 Stat. 1713 <42 U.8.C. 1857g
(a)). The amendments to 11161.67 and
61.68 are also Issued under the author-
ity of section 114 of the Clean Air Act,
as added by sec. 4 (a) of Pub. L. 91-604.
84 Stat. 1687 and amended by Pub. L.
93-319. sec. 6(a) (4). 88 Stat. 259 '42
U.S.C. 1857C-9).
NOR: The Environmental Protection
Agency has determined that thin document
does not contain a major proposal requiring
preparation of an Economic Impact Analy-
sis under Executive Orders 11831 and 11940
and OMB Circular A-107.
Dated: May 26.1977.
EDWARD F. TUBRK.
Acting Assistant Administrator
for Air and Waste Management.
Part 61 of Chapter I. Title 40 of the
Code of Federal Regulations is amended
as follows:
1. fit i 61.60. paragraph is.
amended as follows:
§ 61.60 Applicability.
• « • • •
(c) Sections of this subpart other than
{1)61.61; 61.64 (a)(l), (b), «c).and (d):
61.67; 61.68; 61.69; 61.70: and 61 71 • • V
2. In §61.61 paragraphs ft) and
are added as follows:
§ 61.61 Definition..
U) "Standard temperature" means a
temperature of 20' C <69* P>.
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HIKES AND REGULATIONS
29007
(S*cs 113 »nd 30I(a). Clean Air Act (49
U3C 18S7C-7 and 1M7((») ).)
5. Section 61.67 to amended by deleting
and reserving paragraph (d), revising
paragraphs (e). (gHlHIl) and (gXl)
(ffl>. and by adding paragraph (gXl)
(iv) as follows:
| 61.67 Emission tens.
» • • • •
(d) [Reserved]
(e> When at aU possible, each sample
is to be analysed within 24 hours, but in
no case in excess of 72 hours of sample
collection. Vinyl chloride emissions are
to be determined within SO days after the
emission test. The owner or operator
shall report the determinations to the
Administrator by a registered letter dis-
patched before the close of the next busi-
ness day following the determination.
(!)••*
(11) Each emission test to to consist of
three runs. For the purpose of determin-
ing «ni«n««"M. the average of results of
all runs to fb apply. The average to to be
computed on a time weighted basis.
(iU> For gas streams containing more
than 10 percent oxygen the concentra-
tion of vinyl chloride as determined by
Test Method 106 to to be corrected to 10
percent oxygen (dry basto) for determi-
nation of emissions by using the follow-
ing equation:
10.9
6. Section 61.68 to amended by revis-
ing paragraphs (c) <1> and (2) as fol-
lows:
8 61.68 EmUilon monitoring.
(1) A calibration gas mixture pre-
pared from the gases specified in sections
6.2.1 and 5.2.2 of Test Method 106 and
in accordance with section 7.1 of Test
Method 106. or
(2) A calibration gas cylinder stand-
ard containing the appropriate concen-
tration of vinyl chloride. The gas com-
position of tho calibration gas cylinder
standard to to have been certified by the
manufacturer. The manufacturer must
have recommended a maximum shelf
life for each cylinder so that the concen-
tration does not change greater than
±6 percent from the certified value. The
date of gas cylinder preparation, certified
vinyl chloride concentration and recom-
mended maximum shelf life must nave
been affixed to the cylinder before ship-
ment from the manufacturer to the
buyer. If a gas chromatograph to used as
the vinyl chloride monitoring system.
these gas mixtures may he directly used
to prepare a chromatograph calibration
curve as described in section 7.3 of Test
Method 106. The requirements in sec-
tions S.2.3.1 and 6.2.3.2 of Test Method
106 for certification of cylinder stand-
ards and for establishment BP^ verlfica-
"•'-"•—«—* 20.«-percentO,
where:
C» ,„„.«.«)=The concentration of vinyl
chloride in the exhaust gases, corrected
to 10-percent oxygen.
C»= The concentration of vinyl chloride
as measured by Test Method 106.
20.9=Percent oxygen in the ambient
air at standard conditions.
10.9= Percent oxygen in the ambient
air at standard conditions, minus the
10.0-percent oxygen to which the
correction is being made.
Percent Oj= Percent nxygen in the
exhaust gas an measured by Refer-
ence Method 3 in Appendix A of
Part 60 of this chapter.
dv> For those emission sources where
the emission limit to prescribed in terms
of mass rather than concentration, mass
emissions in kg/100 kg product are to be
determined by using the following equa-
tion:
where:
f»x=kg vinyl chloride/100 kg prod-
uct.
C»=The concentration of vinyl chlo-
ride as measured by Test
Method 106.
2.00- Density of vinyl chloride at one
atmosphere and 20" C in
kg/m».
Q— Volumetric flow rate in m'/hr a*
determined by Reference
Method 2 of Appendix A to
Part 60 of this chapter.
10—=- Convention factor for ppm.
7 = Production rate (kg/hr).
tion of calibration standards are to be
followed.
are amended as follows.
§ 61.70 Semiannual report.
• • • • •
(O • • *
(2) • • •
(1) If batch stripping to used, one rep-
resentative sample of polyvlnyl chloride
resin to to be taken from each batch of
each grade of resin Immediately follow-
ing the completion of the stripping op-
eration, and identified by resin type and
grade and the date and time the batch
to completed. The corresponding quan-
tity of material processed In each strip-
per batch to to be recorded and identi-
fied by resin type and grade and the
date and time the batch to completed.
• • • • •
(v) The report to the Administrator
by the owner or operator to to Include
the vinyl chloride content found in each
sample required by paragraphs (c)(2»
<1> and (c> (2) (11) of this section, aver-
aged separately for each type of ream,
over each calendar day MM! weighted
according to the quantity of each grade
of resin processed by the strlpper(s)
that calendar day, according to the fol-
lowing equation:
ATl-
where:
A=24-hour average concentration of
type TI resin in ppm (dry
weight basto).
0=Total production of type 7,
resin over the 24-hour period,
in kg.
T,=Type of resin; i=l,2 . . . m
where m to total number of
resin types produced during
the 24-hour period.
M= Concentration of vinyl chloride
in one sample of grade C.
.' resin, in ppm.
P= Production of grade <7< resin
' represented by the sample, in
kg.
(/i= Grade of resin; e.g., GI, <7* and
Ot.
i. = Total number of grades of resin
produced during the 24-hour
period.
• • • • •
8. Section 61.71 to amended by correct-
ing paragraphs (a) (2) and (a) (3). and
by adding paragraph t» that tort
(3) A record of emissions
in accordance with 161.68.
(4) A daily operating record for each
polyvlnyl chloride reactor, g
pressures and temperatures. •
9. Section 1.1 of Test Method ips
to corrected as follows:
,1.1 An, Integrated bag sample of stack
gas ~«««*««««"f- vinyl chloride (chloroetbene)
to subjected to chfomatogfaphio analysis, w-
Ing a flame lonlaatlon detector.
10. Section 3 of Test Method lot to
corrected as follows:
8. fttter/ereiwe*. Aeeteldehyds. which oaa
occur In eome vinyl chloride aouroas. win In-
terfere with the vinyl chloride . ~ ~
the Chromaeorb 100* column. Bee
4.3.2 and 6.4. If resolution of ta* rmyl
chloride peak to atui not satisfactory for a
particular cample, then ehromatogranh pa-
rameters can be further altered with prior
approval of the Administrator. If alteration
of the chromatograph paramatsn fans to
resolve the vinyl chloride peak, than sup-
plemental confirmation of the vinyl chloride
peak through an absolute analyttesl
nique. meh as mass epoctraoopy. mast w»
performed.
11. Section 4.1 of Teat Method 106 to
corrected as follows:
4.1 SompHftf (Figure 106-1).
12. Section 4.14 of Test Method 106 to
corrected as follows:
4.14 Uale (9) and female (9) atalnl*as%
steel quick-connect*, with ball checks (on*
pair without) located aa shown In Figure
106-1.
HOflUt UOISTII, Vd. 4J, NO. 1O«—TUUOAT. JUNI 7, 1«77
"106
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29008
RULES AND REGULATIONS
13. Section 4.1.10 of Test Method 108 is
corrected as follows:
4.1.10 Connecting tubing. Teflon. ••*
mm outside diameter, to aaaemble sample
trmln (Figure 108-1).
14. Section 4.3.2 of Teat Method 106 Is
amended aa follows:
4.34 diTometographlc column, stainless
steel. 2 mx3.3 mm. containing 80/100 mesh
Chromasorb 103. A secondary column of OE
SF-98,20 percent on 80/80 mesh AW Chroma-
•orb P. stainless steel. 2 mx34 mm or Pora-
pak T. 80/100 mesh, stainless steel. I mx34
mm Is required if acetaldehyde la present. If
used, a secondary column la placed after the
Chromasorb 103 column. The combined
columns should then be operated at 130* C.
15. Section 5.9 of Test Method 106 Is
revised as follows:
6.3 Calibration. Use one of the following
options: either 6.3.1 and 6.3.3. or 6.3.8.
84.1 Vinyl chloride. 99.9+ percent. Pur*
vinyl chloride gas certified by the manufac-
turer to contain a minimum of 99.9 percent
vinyl chloride for use In the preparation of
standard gas mixture* In Section 7.1. U the
gas manufacturer maintains a bulk cylinder
supply of 99.0+ percent vinyl chloride, the
certification analysis may have been per-
formed on this supply rather than on each
gas cylinder prepared from this bulk supply.
The date of gu cylinder preparation and the
certified analysis must have been affixed to
the cylinder before shipment from the gas
manufacturer to the buyer.
633 Nitrogen gat. Zero grade, for prepa-
ration of standard go* mixture*.
64.3 Cylinder standard* (3). das mix-
ture standards (60, 10, and 8 ppm vinyl
chloride in nitrogen cylinders) for which the
gas composition lias been certified by the
manufacturer. The manufacturer must have
recommended a maximum shelf life for each
cylinder so that the concentration does not
change greater than ±6 percent from the
certified value. The date of gas cylinder prep-
aration, certified vinyl chloride concentra-
tion and recommended maximum shelf life
must have been affixed to the cylinder before
shipment from the gas manufacturer to the
buyer. These gas mixture standards may be
directly used to prepare a chromatograph
calibration curve as described in section 7.3.
6.3.3.1 Cylinder standards certification.
The concentration of vinyl chloride in nitro-
gen In each cylinder must have been certified
by the manufacturer by a direct analysis of
each cylinder using an analytical procedure
that the manufacturer had calibrated on ttie
day of cylinder analysis. The calibration of
the analytical procedure shall, as a minimum,
have utilized a three-point calibration curve.
It I* recommended that the'manufacturer
maintain two calibration standards and use
these standards in the following way: (1) a
high concentration standard (between 60 and
100 ppm) for preparation of a calibration
curve by an appropriate dilution technique;
(3) a low concentration standard (between
6 and 10 ppm) for verification of the dilution
technique used.
6.3.3.2 Establishment and twH/tefltton a/
calibration standards. The concentration of
each calibration standard must have been
established by the manufacturer using
reliable procedures. Additionally, each
calibration standard must have been veri-
fied by the manufacturer by one of the
following procedures, and the agreement
between the initially determined concen-
tration value and the verification concen-
tration value must be within ± 6 percent:
(1) verification value determined by com-
parison with a calibrated vinyl chloride
permeation tube. (3) verification value
determined by comparison with a gas mix-
ture prepared in accordance with the pro-
cedure described In section 7.1 and using
99.94- percent vtnyle chloride, or (3) verifi-
cation value obtained by having the
calibration standard analyzed by the Na-
tional Bureau of Standards. All calibration
standards must be renewed on s time
interval consistent with the shelf life of
the cylinder standards sold.
16. Section 6.2 of Test Method 106 is
•amended as follows:
6.3 Sample storage. Sample bags must be
kept out of direct sunlight. When at ill
possible analysis Is to be performed a lib in
24 hours, but in no case In excess of 73
hours of sample collection.
17. Section 7.1 of Test Method 106 is
•amended as follows:
7.1 Preparation o/ vinyl chloride stand-
ard fas mixture*. Evacuate a slxteen-inch
square Tedlar bag that has passed a leak
check (described In Section 7.4) and meter
In 8 liters of nitrogen. While the bag is
filling, use the 0.6 ml syringe to inject
350*1 of 99.9+ percent vinyl chloride
through the wall of the bag. Upon with-
drawing the syringe needle. Immediately
cover the resulting hole with a piece of
adhesive tape. The bag now contains a
vinyl chloride concentration of 80 ppm. In
a like manner use the other syringe to
prepare gas mixtures having 10 and 5 ppm
vinyl chloride concentrations. Place each
bag on a smooth surface and alternately
depress opposite sides of the bag 60 times
to further mix the gases. These gas mixture
standards may be used for 10 days from the
date of preparation, after which time prep-
aration of new gas mixtures I* required.
(CAtrnoM.—Contamination may be a prob-
lem when a bag Is reused if the new gas
mixture standard contains a lower con-
centration than the previous gas mixture
standard did.)
18. Section 7.3 of Test Method 106 is
amended as follows:
7.3 Preparation o/ cnromatoeraph eaW-
bration curve. Hake a gas chromatographlc
measurement of each gas mixture standard
(described In section 644 or 7.1) using con-
ditions identical with those listed in sections
6.3 and 8.4. Plush the sampling loop for 30
seconds at the rate of 100 ml/mln with each
standard gas mixture and activate the sam-
ple valve. Record C«, the concentration of
vinyl chloride Injected, the attenuator set-
ting, chart speed, peak area, sample loop
temperature, column temperature, ^carrier
gas flow rate, and retention time. Record the
laboratory pressure. Calculate A,, the peak
area multiplied by the attenuator setting.
Repeat until two Injection areas are within
8 percent, then plot these points v. C<. When
the other concentrations have been plotted,
draw a smooth curve through the points.
Perform calibration dally, or before and after
each set of bag samples, whichever is more
frequent.
19. Section 1.2 of Test Method 107 is
amended as follows:
14 This procedure is suitable tor deter-
mining the vinyl chorlde monomer (VCM)
content of Inprocess wastewater samples, and
the residual vinyl chloride monomer
(RVCM) content of polyvlny] chloride
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RULES AND REGULATIONS
29009
23. Section 7J^.d. of Test Method 107
to corrected u follows:
d. W—StaMMMtton tim«. Hie normal set-
ting la 03 minute*.
23. Section 9.2 of Test Method 107 to
corrected as follows:
93 Residual vinyl chloride monomer con-
centration, or vinyl chloride monomer con-
centration.
Calculate C,,t as follows:
where:
C,..
Equation 107-2
Concentration of vinyl chloride
in the sample, in ppm.
Pt— Laboratory atmosphere pre—
sure, mm Eg.
Tt= Room temperature, *K.
Af.= Molecular weight of VCM
(62.5).
I',-* Volume of vapor phase (vial
volume less sample volume).
m ,= Weight of sample, grama.
R.= On- constant (62,360 (ec-mm-
niole-degreos Kelvin)!
K = Henry's Low constant. For
VCM in PVC at 90* C,
K=<6.;>2X10-«=jr». For
VCM in 1 cc (approximate)
wa«lewnt*r sample at 90° C,
K=5.0X10-*= K...
TV = Equilibration temperature, °K.
If the following conditions are met,
Equation 107-2 can be simplified as
follows:
1. Ti=22sC <295'K)
2. r,=W)e C (363° K)
3. P.=750 mm Hg.
4-K-=r'-n
where
l",= Vial volume, cc (23.5).
5..Sample contains less than 0.5 percent
water.
Equation 107-3
The following general equation cnn be used for any sample which contains VCM,
PVC and water.
Equation 107-4
where:
rS=Total solids.
NOTE: K* must be determined for sam-
ples with a vapor volume to liquid volume
ratio other than 22.5 to 1. This ratio can
be obtained by adjusting the sample weight
through giving consideration to the total
solids and density of the PVC.
Results calculated using Equation 107-4
represent concentration based on the total
sample. To obtain results based on dry
PVC content, divide by TS.
For a 1-cc wastewater sample (that is,
22.5 to 1 vapor volume to liquid volume
ratio), Km is 5.0X10-'. Thuu, Equation
107-4 can be simplified to the following:
A.
~
+ (2.066X 10-') 1 Equation 107-5
(Sees. 112 and 301 (a) of the Clean Air Act, 42 U.S.C. 18»7c-7 and 1857g(a).)
(FR DOC.77-1682B Piled «-»-77:8:4S an|
FfOfXAl MOISTM, VOL. 42, NO. lOt—TUUOAY, JUNI 7, 1»77
108
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REFERENCES
1. National Emission Standards for Hazardous Air Pollutants: Standard
for Vinyl Chloride, Environmental Protection Agency, Federal Register,
Vol. 41, No. 205, Thursday, October 21, 1976.
2. Scientific and Technical Assessment Report on Vinyl Chloride and
Polyvinyl Chloride, Environmental Protection Agency, EPA-600/6-75-004,
June 1975.
3. Standard Support and Environmental Impact Statement, Volume 2:
Promulgated Emission Standard for Vinyl Chloride, Environmental
Protection Agency, EPA-450/2-75-0096, September 1976.
A. Standard Support and Environmental Impact Statement: Emission
Standard for Vinyl Chloride, Environmental Protection Agency,
EPA-450/2-75-009, October 1975.
5. Speciality Vinyl Chloride Resin Processes Effects of Governmental
Regulations, R. N. Wheeler, Jr., Union Carbide Corporation, South
Charleston, West Virginia 25303, September 1, 1976.
6. Vinyl Chloride - An Assessment of Emissions Control Techniques and
Costs, B. H. Carpenter, Environmental Protection Agency, EPA-650/2-74-097,
September 1974.
* in.
109
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