\_United States Office of Enforcement EPA Contract No. 68-01-4141 Environmenta | Protec tion Office of General Enforcement May 1978 Agency Washington, DC 20460 SEPA National Emission Standards ‘for Hazardous Air Pollutants Inspection Manual for Vinyl Chloride p | i U.S. DEPOSITORY OCT 10 1978 ''''Re NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS INSPECTION MANUAL for rt Lt VINYL CHLORI DE { EPA Contract No. 68-01-4141 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 ''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. Vi ''TD se VSG US yt 1778 TABLE OF CONTENTS [J ie oa Page ACKNOWLEDGMENT ii LIST OF FIGURES V LIST OF TABLES ix LIST OF INSPECTION FORMS x LIST OF CHEMICAL FORMULAS xi LIST OF ABBREVIATIONS eit 1.0 INTRODUCTION ] 1.1 Background ] 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 ''TABLE OF CONTENTS (Continued) 3.3 Polyvinyl chloride 3.3.1 Suspension polymerization 3.3.2 Emulsion (i.e., dispersion) polymerization 3.3.3 Latex dispersion polymerization 3.3.4 Bulk polymerization 3.3.5 Solvent polymerization 3.4 Clarifying note on the balanced oxychlorination- dehydrochlorination process 3.5 Photographs of equipment 4.0 LEAK DETECTION MONITORING INSTRUMENTATION, RECORDS AND REPORTS 4.1 Leak detection monitoring instrumentation 4.2 Leak detection monitoring recordkeeping 4.3 Routine leak detection and relief discharge recordkeeping 5.0 INSPECTOR SAFETY 6.0 INSPECTION PROCEDURES AND INSPECTION FORMS 6.1 Summary of compliance status 6.2 Checklist 6.3 On review of records 6.4 Pre-test equipment checklist for stack emission test 6.5 Equipment checklist for vinyl chloride concentration in inprocess wastewater, resin, slurry, wet cake and latex samples APPENDIX A: Mean value calculation APPENDIX B: National Emission Standards for Hazardous Air Pollutants - Standard for Vinyl Chloride, October 21, 1976 APPENDIX C: National Emission Standards for Hazardous Air Pollutants - Standard for Vinyl Chloride: Cor- rections and Amendments, June 7, 1977 REFERENCES iv 18 18 ra 26 26 29 36 38 55 55 og 59 60 6] 62 62 62 63 63 86 87 103 109 ''10 TT LIST OF FIGURES Ethylene dichloride process flow diagram using oxychlorination which involves the reaction of oxygen and hydrogen chloride with ethylene. Vinyl chloride monomer process flow diagram using hydrochlorination of acetylene. Vinyl chloride monomer process flow diagram using dehydrochlorination of ethylene dichloride. Polyvinyl chloride process flow diagram using suspension polymerization. Polyvinyl chloride process flow diagram using emulsion (i.e., dispersion) polymerization. Polyvinyl chloride latex process flow diagram using emulsion (i.e., dispersion) polymerization. Polyvinyl chloride process flow diagram using bulk polymerization. Polyvinyl chloride process flow diagram using solvent polymerization. More recent polyvinyl chloride process flow diagram using solvent polymerization. Block diagram of a balanced oxychlorination- dehydrochlorination process. Large capacity VC reactor using the oxychlorination 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. Page 10 13 7 20 24 27 30 32 33 37 40 ''oa bo 3.16 Ss Ae 3.18 3.19 3.20 LIST OF FIGURES (continued) 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. Smal] size PVC reactor with cover removed to clean 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 viny] 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. 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. The top of medium capacity, side-by-side PVC reactors using solvent process. Foreground shows a motor valve for emergency venting through to the VC monomer recovery system. The top of a small capacity PVC stripper vessel used in the suspension, emulsion and latex processes, showing an SRV. A stripper column is shown that removes VC from a PVC-varnish solution resulting from the solvent polymerization process. A typical wastewater stripner column is shown that may be found in EDC, VC and PVC plants. The top of an EDC storage tank is shown with its vent. Cylindrical, side-by-side, above ground VC storage tanks are shown. RD/SRV vents may be seen on pipe rack above tanks. vi 40 4] 4] 42 42 43 43 44 44 ''wo Ww 21 «ee .23 24 oto 26 cy .28 «ed 30 31 32 LIST OF FIGURES (continued ) Spherical, above ground vinyl chloride storage tanks. RD/SRV vents may be seen perched on top of sphere. Underground VC storage tank area. Wash water stripper storage tank. Upper portion of tar storage tank shown with vent. PVC suspension resin rotary dryer and dust col- lector. Drying is accomplished by the application of heat and rotary action. 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 atomiza- tion system is perched at top of dryer. An EDC light ends distillation column is shown with its RD/SRV vent. VCM column condenser and condenser vent motor valve. The top of an EDC light ends column reflex accumulator showing the RD/SRV vent. In the foreground the light ends dryer regeneration liquid knockout vessel is shown in balanced EDC-VC plant. 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 en- compasses the functions of both the light and heavy ends columns. ) Foreground shows the insulated vent piping and motor valve from the reactor refrigerator condenser vessel in a balanced EDC osychlorination plant. vii 45 45 46 46 47 47 48 48 49 49 50 50 ''w . 38 w «oO 4.1 LIST OF FIGURES (continued) Typical RD/SRV assembly with the vents from each connected to a manifold of the vent system. Dual RD/SRV vents mounted at top of spherical vinyl chloride storage tank. Typical pump and double mechanical seal. 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 loading platform shown with pipe rack support for flexible hose VC feed and recovery system in VC plant. Oxychlorination vent scrubber stack. Incinerator and stacks of a PVC plant showing the platform (center stack) on which stack samples are taken to determine VC emission concentration. Schematic diagram of continuous monitoring system for vinyl chloride emissions. viii 51 5] 52 52 53 53 54 58 ''PR -10 11 LIST OF TABLES The potential emission points identified by the keys in Figure 3.1 in the oxychlorination process for ethylene dichloride. Hydrochlorination of acetylene product gases and their boiling point temperatures. The potential emission points identified by the keys in Figure 3.2 in the hydrochlorination of acetylene for vinyl chloride monomer. The potential emission points identified by the keys in Figure 3.3 in the dehydrochlorination of ethylene dichloride for vinyl chloride monomer. The potential emission points identified by the keys in Figure 3.4 in the suspension polymerization process for polyvinyl chloride. The potential emission points identified by the keys in Figure 3.5 in the emulsion (i.e., dispersion) polymerization process for polyvinyl chloride. The potential emission points identified by the keys in Figure 3.6 in the emulsion (i.e., dispersion) polymerization process for polyvinyl chloride latex. The potential emission points identified by the keys in Figure 3.7 in the bulk polymerization process for polyvinyl chloride resin. The potential emission points identified by the keys in Figure 3.8 in the solvent polymerization process for polyvinyl chloride and copolymers. The potential emission points identified by the keys in Figure 3.9 in the solvent polymerization process for polyvinyl chloride and copolymers. Figure number of photographs and corresponding equipment category. ix Page 11 15 19 Ze 20 28 3] 34 35 39 ''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 '' Name Acetylene Chlorine Ethylene Ethylene Dichloride Hydrogen Chloride Oxygen Polyvinyl Chloride Vinyl Chloride Monomer Water LIST OF CHEMICAL FORMULAS Formula HC = CH Cl, CH, = CHo CICH, - CH,C1 HC] 05 + HC = CHCl tz Hoe = CHC] H0 xi ''BOD COD EDC EPA Eq. FR HCL NESHAP PVC KD SOP SRV TSS VAC VC VCM LIST OF ABBREVIATIONS Biological oxygen demand Chemical oxygen demand Ethylene dichloride U.S. Environmental Protection Agency Equation U.S. Federal Register Hydrogen chloride National Emission Standards for Hazardous Air Pollutants Polyvinyl chloride Rupture disc Standard operating procedure Safety relief valve Total suspended solids Vinyl acetate comonomer Vinyl chloride Vinyl chloride monomer xii ''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 n° (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 polyviny] chloride. Final standards (41-FR-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 ''emissions from all known process and fugitive emission sources in 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 FR 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; viny] 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 . . 3 of vinyl chloride for which the reactor capacity is not greater than 0.19 m ''(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 of vinyl chloride for which the reactor capacity is greater than 0.19 m? (50 gal) and less than 4.07 n° (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 viny] chloride alone or in combination with other materials is polymerized. (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. 3 ''“Latex resin" means a resin that is produced by a polymerization process that initiates from free radical catalyst sites and is sold undried. "Bulk resin" means a resin which is produced by a polymerization process in which no water is used. "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. "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. "In vinyl chloride 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. "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. "Run" means the net period of time during which an emission sample is collected. "Ethylene dichloride purification" includes any part of the process of ethylene dichloride production that follows ethylene dichloride formation and in which finished ethylene dichloride is produced. "Vinyl chloride purification" includes any part of the process of vinyl chloride production that follows vinyl chloride formation and in which finished vinyl chloride is produced. 4 ''"Reactor" includes any vessel in which vinyl chloride is partially or totally polymerized into polyvinyl chloride. "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). u Wl Stripper is removed from polyvinyl chloride resin, except bulk resin, in includes any vessel in which residual vinyl chloride slurry form by the use of heat and/or vacuum. In the case of 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. ''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 ''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 chloride 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. ''2.3 POLYVINYL CHLORIDE (PVC) Polyvinyl 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]. ''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 CH = CH, + 1/2 0, + 2HCL——————> CICH, - CH,C1 + H,0. (3-1) é 2 2 2 2 2 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 oxyhydrochlorination process. 9 ''"aua| Aya YILM apLuol yo uaboupAy pue uabAxo $O UOLZDCBU OY} SPALOAUL YOLYM UOLZeULPYOLYDAXO Bulsn weubeLp MO| 4 ssadoud SPlL4OLYydiq aualAy7q «Le aunBLy WwsOdsid ¢—~+ 39VYOLS YVLL 39VYOLS $I SON3 AAV3H W3LSAS AY3A0D3Y 903 0144 @ 1 NWN109 TWAOW3Y uVl SONZ AAV3H SON3 AAW 3H WV31S-— aie él NOILVO YaddINLS ~1Ad, yy 43aLVM HSM 9 BOVYOLS SIS YO YOLOVEY 01-4 2 NWn109 SQN3_1HON eE4 . yOLOVW3u - WOA ONV NOILWNINOTHDAXO WOU4 Y3LYM + N39AX0 S Y3LVM HSVM LN3A WV3LS Yy3LVM B9VYOLS ears 2200%d 903 }\ Hl oNINSINIG NINN TOD HSYMU3LYM NVL 903 " U3LVM LOH aovuois Nowwuvdas P53, 5 oO zany) Q3HSVM j ® 4N3A 301NO1HD N390YNGAH LN3A “914434 N39AXO/XIV 3N3TAHL3 4LN3A 10 ''Table 3.1: The potential emission points identified by the keys in Figure 3.1 in the oxychlorination process for ethylene dichloride. Position Name Key Frequency Reactor Vent ] Intermittent ee continuous oot, bee continuous ens oles Continuous Wash Water Stripper Vent 5 Cont inuous See 6 Continuous cae ie 7 Intermittent Layee, Colum cont nou Finishing Column Vent 9 Cont inuous Light. Ends Purttteation 10 Intermittent Refined EDC Storage 1 Tiycavnt Etant Tank Vent Li ill a Tar-Removed 12 Cont inuous Heavy-Ends Storage Tank Vent 13 Intermittent Tar Storage Tank Vent 14 Intermittent sit sice | eetinsist 11 ''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 ———> HAC = 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 i, lz ''*guajAzsoe 40 UOL}eULYOLYDOupAY BHuLsn wesbetp MOL} Ssad0ud uawouoW apL4oLYyo {AULA *2°E eunbL4 Wws0dSid 0 39VYOLS SON3 AAW3H © LN3A NOILV T1ILSIG ONIGVOT SGN3 AAV3H WOA JOVYOLS WOA ® ©) IN3ZA IN3A ©) LN3A NOILVVLSIG SOGN3 iLHOIN SN3ITAL39V 4yOLOVSY =n Y3SN3GNO9 LN3A | —+l LN3A gindi1 SNigsnyos ® LN3A ( Peousvau SvV9 LN3A 13 ''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 Symbo1 Boiling Point Temperature Acetylene HC = CH - 84°C Hydrogen Chloride HC] ~ 85°C Vinyl Chloride HoC = CHCI - 13°C Ethylene Dichloride CICH, - CH,C] + 83°C The reaction represented in Eq. (3-2) is exothermic. Therefore, the heavy-ends tnat 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 ina 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 Key Frequency Reactor Condenser Vent ] Continuous Scrubber Vent 2 Continuous VCM Condenser Vent 3 : Continuous VCM Storage Vent 4 Continuous Heavy-Ends Storage Vent 5 Intermittent VCM Loading Vent 6 Intermittent rugtive cree | ~ Gace? * 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 Dehydrochlorination of ethylene dichloride 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 CICH, - Cho bT —————> HC = CHC] + HCI. (3-3) In an integrated ethylene dichloride-viny] 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 ''Ivsodsid OL "SPLUOLYSLp aua[Ayza 4o uoLZeULUOLYOUpAYap Bulsn weubeLp MOL} SSad0ud uawoUOW apLuOLYyd [AULA ¥3LVM ONIIO09 4 39vYOLS SON3 AAV3H v 41N3A 39VYOLS a NWN109 SQN3 AAW3H xni434 yaLVM ONIN00D F AN3A 43110834 NAN109 SGNAa LHI u31VM yOLVUVd3aSs 3svild 31LSVM | J) AN3A + AYN3A0934 19H OL G319A934 | "ee aunbl4 a334 203 \ 4 Y3ZINOdvA wails MOLVHOd VAS 4371009 39vYOLS ® 3anuo J G3HSWM 903 OL yazti083y WY3uLS HON|NO 903 ZOVNUNS ONINDVYD Ll W3SN3QNOD TWiLuvd NWn109 HON3NO | <' @ YyOSS3YdNOD baa ‘Lewis N3ONO0D oT 17 ''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 Suspension polymerization The suspension polymerization process is the most common process for polyviny] chloride production [4]. The resin produced is sometimes referred to as suspension resin. Polymerization of viny] 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 to 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 dichloride for vinyl chloride monomer. Position Name Key Frequency Recycling of EDC to Washed Crude Storage ] Intermittent Light-ends Distillation Column Vent Z Intermittent Heavy-ends Distillation Column Vent 3 Intermittent Heavy-ends Storage Vent 4 Intermittent VCM Storage Vent 5 Intermittent Light-ends Column : Waste Water 6 Continuous Quench Column Vent 7 Continuous . Entire Intermittent/ Fugitive Plant Continuous 19 ''“uoLjeztuawAlod uoLtsuadsns Bursn weabetp mols ssad0ud apluolyd [AULAX|Og “pe aunbl4 @)) ONIiddIHS x1ne on] on oe SNIg ONIGTOH sols “09 ©) 4 Longoud YSLVA aisvm Od oe dWwoo 8 ‘QNOD W2A‘93N LN Td N09 uaddIULS LN3A dWNd JOYVHD'S YNVL ONIXIW_ NOILATOS yOLOVSY HOLVS SLN39V BAILOV J9VIYNNS 8 ONIGN3dSNS ASATWLVD YOLVILINI ANVIL LHOISM LN3A ANVIL LHOISM SUNVL JOvuOLS YSWONOWOD SuUVd ANVIL Y3SNWONOW 09 (10U0!}d0) YOLVYOdWAR WOA pKa S39VYOLS WOA ag3zT1Lsia AY3A0I SY WOA YSSNZ0NO9 20 ''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 passed 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 1) 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(2)and(3 Jare 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(4), 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 in the suspension polymerization process for polyvinyl chloride. POSITION NAME KEY FREQUENCY Vinyl Chloride ] Intermittent/Continuous Recovery Vent Vinyl Chloride 2 Intermittent Weighing Tank Vent Comonomer . Weighing Tank Vent : Intermittent Reactor Vent and 4 Intermittent Opening Loss Stripper 5 Intermittent Vent Slurry Blend . Tank Vent 6 Intermittent Centrifuge 7 Intermittent Vent Product Collection 8 Teterrarl shea Vent Silo ; Vent 9 Continuous Waste j Water 10 Continuous Dryer . Bylannc 11 Intermittent Bulk 12 Intermittent Loading a Entire : . Fugitive Plant Intermittent/Continuous 22 ''Keys(5\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 (10) 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 sensitive 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]. Zo ''*UOL}eZLUaWA | Od (uoLsuadsLp **a°L) UOLS[NWe BuLsn weubeLp MO|} SSad0ud apLuoLYyd [AULAALOd vasoval o ‘s Lass eee! SNIS SNIGIOH 7~ ONIddlHS ( D) wang out sous © a 3ZIS y3A0 y3ANG AVudS 1LN3A vaddIULS (0) dWNd 39YVHD 8 ANVL SNIXIN_ NOILNTOS yOLOV3Y HOLVS SLN39V SAILOV 39VAYNNS - ® SNIGN3dSNS ASATVLVD YOLVILINI LOnNdOud ©) «—cG ANVL LHOISM ANVIL LN3A LHOISM "sg'e€ aunBbLly dWOD 8 ‘QNOD WOA_ (934 PN _Jdnos SANVL 39VYOLS YSWONOWOD SuVd ANVIL YSWONOW O90 (10U0}}d0) YOLVYOdWAZ WOA mes 39vYOLS WOA ag3T1LSIG V u3SN30NO9 y WIA YVO ANVIL NOS WOA ANVIL AY¥3A093YN WIA 24 ''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 KEY FREQUENCY Vinyl Chloride ] Intermittent/Continuous Recovery Vent Vinyl Chloride . Weighing Tank Vent 2 Intermittent Comonomer . Weighing Tank Vent 3 Intermittent Reactor Vent and 4 Intermittent Opening Loss Stripper 5 Intermittent Vent Slurry Blend : Tank Vent 6 Intermittent spray Dryer 7 Intermittent Vent Product Collection 8 interniteent Vent Silo 9 Continuous Vent Process 10 Intermittent Water Bulk 11 Intermittent Loading aig 3 Entire a . Fugitive Plant Intermittent/Continuous 2a ''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 is sold and transported in this solution form. The process is identical in almost all ways to the suspension and emulsion processes. It differs in 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; jess 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 ''*uoL}zezLuawd od (uoLsuadstp **a°L) uoLS_nwa Bulsn weubeLp MO|4 Ssad0ud xaze, apLuoLYyd [AULAA|Od “9° auNbL4 ANVL SNIGQ10H NOILVLS SNIGVOT N03 @<«H LONGOud >NWL aNn378 JWOD 8 ‘QNOD WOA 934 of WOOD LN3A @) a YaddI¥LS (3) Sean dWNd 39YVHO 8 YNVL ONIXIN_ NOILNTOS yOLOV3Y HOLVS SLN39V B3AILOV 39VsyNNS. 8B ONION3SdSNS ASATWLVS YOLVILINI SUNVL S9vy¥OLS YSWONOWOD SYVO MNVL Y3SWONOW O09 (10U0}}d0) YOLVUOdWAZ WOA VO XNVL WONS WOA J9VYOLS WOA g3T1LSIG ANVIL AY3ZA0I3Y ANVIL WOA LHOISM WOA 27 ''Table 3.7: The potential emission points identified by the keys in Fiqure 3.6 in the emulsion (i.e., dispersion) polymerization process for polyvinyl chloride latex. POSITION NAME KEY FREQUENCY | a em vents ] Intermittent/Cont inuous | Welghing Tank Vent : Sienin cene Weighing Tank Vent @ TSerth een re vent and 4 Intermittent Stripper 5 Intermittent rt en 6 Intermittent a Collection 7 Gane nusus Loaeing 8 Continuous Fugitive Entire Intermittent/Continuous Plant 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 develoned 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 ''"UOLZeZLUaWALOd ¥[Nq BuLsn wesbeLp MOL} SSad04d apluolyd [AULAALOg *Z°¢ aunbL4 s193r3u "7,40 3d dOH 4019371109 yOLOV3Y NOILVZINSWA10d SAVIDOLNV isod a ® yO1L90V3Y NOILVZY3WA10d 3d 4Y439NdG3y 3YuNSS3Y¥d Y3WONOW Y3SN30N09 u3SN30NO2 IN3A 2 19A93Y WY > WNNIVA YOSS3YdNOD YOLVILINI N39O0ULIN — 30 ''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 KEY FREQUENCY or. zation 1 Intermittent Post-Polymerization 2 Intermittent Reactor Vent Monomer pouming 3 Continuous a lle Condenser 4 Continuous fressure Reducer 5 Continuous first Bag House 6 Continuous poncnu Bag House 7 Continuous Reject Vent 8 Continuous Fugitive: a | oo 31 ''“UOLJeZLUaWALOd JUaALOS BHULSN weubeLp Moly ssadoud aplLuolyd [AuLAKjod A[4ez “g’g aunbly @)) @)) ONIddIHS ONKdIHS 8 ONIDOVE 8 ONIDOVE Ouls O1IS S9VYOLS S9VYOLS Qy y3i4 YSG0NIN9 SHOLY LINE YSWONOW 09 y31L1I4 ova JONINS Y3WON 39VYOLS YSQNIY : OW Gas LN3A710S @) © a3xiW dN-3 VW 4IN3A10S 32 ''"uoLqezLuawALod YUaALOS BuLsn weubeLp MOL, ssad0ud apLuo_yo [AULAALOd QUuadeu auoW *6°E unbLy zs (|F (le z £ z ¢ i Is 3 = 2 pasy 960101S UsA|OS puD ayoyaoy jAUIA ae oo jUBAIOS Bbuiboyo0g PUD 4,UBAIOS , puo ! S19WOUOW WOA pejohoey Aly & J 4 iy SJONPOIg To pinbi4 Buiks UO!O} rea! kseaorey + Vuenjog ols ait ~<¢ -1d1I90Jg + pores: WA $10}900y) nae uisey +—wWa WOA 2 oar iesuspuo) Pi 33 ''Table 3.9: The potential emission points identified by the keys in Figure 3.8 in the solvent polymerization process for polyvinyl] chloride and copolymers. POSITION NAME KEY FREQUENCY Receiving Tank Vent ] Continuous VCM Storage Vent 2 Continuous Reactor Vent 3 Continuous Flash Evaporator (Stripper) 4 Continuous cone Monomer 5 Continuous Bag Filter 6 Continuous Bag ritterSeneen 7 Continuous Grinder Filter 8 Continuous Grinder Filter-Screen 9 Continuous Storage Silo 10, 11 Continuous Bulk Loading 12, 13 Intermittent Fugitive ue pee! 34 ''Table 3.10: The potential emission points identified by the keys in Figure 3.9 in the solvent polymerization process for polyvinyl chloride and copolymers. POSITION NAME KEY FREQUENCY Reactor ] Continuous Monomer Condenser Lyoy4 Continuous Resin Drying 5 Continuous Silo 6 Continuous Solvent and Vinyl] 7 Continuous Acetate Condenser rene sie | eestor’ 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 ethylene 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 produced 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 HCI] and EDC from the dehydrochlorination to the oxychlorination reactors and EDC refining, respectively. 36 ''HCI EDC OXYCHLORINATION PLANT +———-0, (AIR) yp) EDC OXYCHLORINATION REACTORS ¢——-CH,= CH, . EDC CRUDE EDC REFINNING UNREFINED REFINED EDC EDC y VCM DEHYDROCHLORINATION PLANT VCM EOC DIRECT CHLORINATION PLANT Figure 3.10. Block diagram of a balanced oxychlorination- dehydrochlorination process. a7 ''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 HC] molecule evolves as a by-product. This forms the HC] stream in Figure 3.10. However, in the oxychlorination reaction, governed by Eq. (3-1), two HC] molecules are required for each EDC molecule produced. The HCl 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 is 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. $iq0re Number Equipment Category 3.11 to 3.15 Reactors 3.16 to 3.18 Strippers 3.19 to 3.24 Storage Vessels 3.25 and 3.26 Dryers S.27% tO 3.32 Distillation Vessels 3.33 and 3.34 RD/SRV 3.35 Double Mechanical Seal 3.36 and 3.37 Railroad tank car loading and unloading 3.38 to 3.39 Incinerators 39 ''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 PVC Reactor RD/SRV 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 ''*sassad0ud u0Lzez -Luawk od xaze, pue UOLS|NWa ‘UOLSUadsNsS 3y} UL pasn SL 40}DRaU adh} SLYUL “SSO, BuLUadO 40JDReU PuepuezS “UOLZeZLUaWALOd UOJ PauLNbau aunjeuad SUOLSSLWA YZLM BOUeL{dWOD UL aq 0} Uapuo UL wWazSAS -W3} BY} OF S}Ua}UOD |aY} BSLeU 0} SjUaWaLs KABAODIA BY} OF ,,yUNYZ,, YBNOuYZ seb aplLuolyd LAULA Burzeay ayz aStudwod suoz,Ieeu 40 UOLJUOd UaMO7 1UaA 02 BuLuado ayy yHnouyy padeid st ,yUNuZ JUeYda]],, "uaas aq oste Aew wazsks AUuaAOIIU ApPLUOLYyo *uaddluzs 0} pauuaysueu} pue paAOWed 34am UOL} [AULA 0} pa}yDeuUOD S}UaA [eNuewW puke AYS/dY -NLOS 49ZEM PUL JAd BY} UBAOD HULAOUWAA OF UOLUgG “UNA LeNPLALpuy ‘*SSad0ud ZUaALOS HULSN SudzJaeR9U UuOL}eZLUaWALOd }xXaU UOJ UOLZeUedeud UL UOPDRBU Ued|D 0} JAd ApLs-Aq-apts AzLoeded wntpaw pL’¢e aunbl4 P2AOWAA UBAOD YPLM 4OZDIU JAd SZLS LLeWS ELE aunbl4 40}9e84 DAd jua/ AYS/GY yunay jueyday 4] ''Motor Valve AY . A PVC Reactor Figure 3.15 The top of medium capacity, side-by-side PVC reactors using solvent 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 ''*ssad0ud UOLZeZLUaWALOd JUSALOS *szueld JAd pue JA G9 UL punos aq Aew ZeYZ UMOYS St ay} WOU HULZLNSeA UOLYNLOS YSLUURA-JAd & WOUS JA uwn,od waddiuzs vazemazsem [edLdk, y Ble aunbL4 SaAowed }eY} UMOYS SL UWNLOD Yaddiugs y LE aunbl4 4 UY z 7 4 ~ . pn - . Mm NeW is THis ie is NK | WAM Sis -r a ena ™~ se « uwnjo9 daddys Ja}eM BISEM uwinjog daddisis 43 '' EDC —— Storage Tank Figure 3.19 The top of an EDC storage tank is shown with its vent. RD/SRV Vents vc Storage Tanks 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 ''Vents Figure 3.21 Spherical, above ground vinyl chloride storage 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 ''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 Tar Storage —————- Tank Figure 3.24 Upper portion of tar storage tank shown with vent. 46 ''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. Atomization System Drying Air Delivery Pipe Spray Dryer 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 ''Vent RD/SRV EDC Light Ends Distil- lation Column VCM Column Condensor Figure 3.28 VCM column condenser and condenser vent motor valve. Motor Valve 48 ''*que_d 9A-90F peouel eq UL UMOUS SL |aSS8A ynoYDOUy PLNbL| uoLZerauabau Jakup spua 2y6L| ayy punoubauoy ayy ul og’ aunbL4 “JUPA AYS/GY B42 BuLmoys uoze[Nwndoe xXal[jau uwn[Od spud 7UBL, J9qqg,uR 4o doz su, 62°¢ aunBbL4 a lassan 2 ynoyI0uy, pinbry uoljesauabay AYS/GY soye|NuINDIYy Xa]Joy quan ''*queid uoLrzeuLuo[ YydAxO 9Q3 paoueleg © UL [aSsaA UasuapUod UOzPeUaHLU4JaU 40ZIPIU BY} WOU BALeCA UOJYOW pue BHurdid JUBA paze[NsuL ayy SMOUS PUNOUfeau0y ZE°¢E aunBbl4 Tr 4, PSS adig Ua/A pazejnsu] aAjeA 10, 0/4 (*suwn,od spua Aneay pue YYHL, |yz YyOG JO SUOL}ZOUNY |Yy sassedwoodua FL SHB8YZO UL SLLYM UWNLOD UOLZeLLLISLP Spua ZYbL] ay} $O UOLZOUNJS BY SWUUOJuad UWNLOD HuLYSLULy ayy SUOLZELLePSUL BWOS UT) ‘*dO} BYR UO pazUNOW yUaA S3L pue AYS/GY 84} YzLM UWN| Od Bulystuly JQ] uy jua/ Le°€ aunbly AYS/GY uwinjo9 Burysiury oda 50 ''"yuez afeu0zs aptuolyos [Auta [edtuauds $0 do} 3e pazunow szUuaA AYS/aY Lend ve S,AYS/GY s}ua/n, € ounbLy "wazsks JUaA 9YyZ JO PLOJLUPW e 02 payoaUUOD Yde~a Wors SJUBA B42 YZLM ALquasse AYS/GY LedLdhL EEE aunbL4 —_ Bi S,AYUS/G4Y wa}sAS jua/ jo pjOjiueyy UOWWOD o1 ''*wazshs AUBAODIU 02 payoauu0d SL punoubauo}s ay} UL BSOY AL qLxXda|f AazoweLp Ja_Lews “Hurpeo, JA sof paydezze asoy al qixa,fs YLM UMOUS ARD YUL} PROUL LeU UO SUOLZI9UUOD do] gE'E suNdL4 asOH aiqixal4 wiaysAS Ajaa0o90y4 seg yuey peosey asOH ajqixe|4 Buipeo7 9A ‘Leas LeoLueYydawW a_qnop pue dwnd jed1dhj} GEe*Ee aunbL4 dung bz ''VC Feed and Recovery Flexible Hoses Railroad Tank Car 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 ''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 ''4.9 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) it 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 challanges, 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. 50 ''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 ''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 detector 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-controlled 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. 5/7 '' PUMP > Lu DETECTION PRINT INSTRUMENT OUT DETECTOR it AIR SAMPLE chan —— FLOW a t ) 7 (" Jt . i (- IC _ r > ok of of of of of #1 #2 #3 #n-3 #n-2 #n-1 #n Air Solenoid Tubing Sample Inlet Valve Probe Location 1 Figure 4.1: Schematic diagram of continuous monitoring system for vinyl chloride emissions. 58 ''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 wil] 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. ee ''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 ''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 ''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 ''that results, EDC, VCM and PVC are typically large capacity plants. One plant may cover many acres and extend up 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 is 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 ''"S8D143Q0 LeuolBay Yd 7e ALLJ UO Spuodau wWous a_qe,LeAe aq Kew e7eq Butdaayxpuoday SUBALEM S}S9] UOLSSLWZ R SUOLSSLWG aduelL|dwoy uo syueway = LL» PONsSs]T UaALeM 92eQ Oly SUOLZEIL{ddy UsALeM 6x SpUaWaULNbaYyY BuLuozLUOW Sx "by vad ‘wh uo ‘am Aq wdd uo *[0A Aq wdd SUOLSSLWZ pazeUWLysy Lx “by ued ‘wb uo "3m Aq wdd uo “oA Ag wdd paepueys UuolLsslwy 9x SsuoLze[nbay alqeoiiddy Gy Aduabuawz/*}Lwuazuy/* uo) SUOLSSLWZ JO ADUaNbau4 ts Pa|Le}SU] aq 0} 23K 9OUIYSLXF UT uOL}dLudsag 9ILABQ [OUJU0) UOLSSLWY Cx BILAaG L0u}U0) “Oo auaydsouny éP2}INP B494M ox S80UN0S UOLSSLW bs SNLVLS JIUNOS NOISSIWI WALI YO YSLAWVeVd SSauppy S,WAl4 JINVITdWOD SNOISSIWS J30IMOTIHD TANIA YO4 NOILISdSNI SdVHSIN awey Ss, Wald aweN S,407DedSUT ozeq uoljoadsul (SYS) SALVLS JINVITdW09 40 AYWWWAS 64 ''CHECKLIST NESHAPS INSPECTION FOR VINYL CHLORIDE EMISSIONS COMPLIANCE Inspection Date Inspector's Name GENERAL 1* Firm's name 2* Firm's address 3% Process designation/product identification (check one or more): EDC: [) oxychlorination (] balanced C N~.A. vcM: (J hydrochlorination [] dehydrochlorination [] N.A. PVC: [J suspension (] dispersion C) latex OO N.A. () bulk (1) solution (] 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)] 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: [] unchanging] program controlled g) Data reduction (check one or more) 0 none (J hourly (J shift [J daily [ weekly (J monthly (J other (specify) * Data may be available from records on file at EPA Regional Offices. 65 ''6. Calibration of leak detection monitoring system [61.65(8)(iii)]: 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. VCM Concen. Percent Deviation Action Required b) Calibration method used (check one or more) C) None (] Paragraph 61.65(8)(iii)(A) - Test Method 106 - 5.2.1, 5.2.3 [) Paragraph 61.65(8)(iii)(B) (1 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 b) Lower Detection Limit (LDL) of instrument ''8. Calbration of emission monitoring system: a) List instruments and data from monitor points which were tested for calibration. Date & Location Instrum. | Cal. VCM | Instrum. VCM | Percent Action Time in Plant Iden. Concen. Concen. Deviation | Required PORTABLE INSTRUMENT 9. Calibration of portable hydrocarbon detector(s): a) List instrument(s) which were tested for calibration Date & Location Instrum. | Cal. VCM | Instrum. VCM | Percent Action Time in Flant Iden. Concen. Concen. Deviation | Required b) Calibration method used (check one or more) L) None (J Paragraph 61.65(7)(iii)(A) - Test Method 106-5.2.1, 5.2.3 (J Paragraph 61.65(7)(iii)(B) ( Other 67 ''LEAK DETECTION AND ELIMINATION 10* Leak detection and elimination process [61.65(8)] a) What is 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: (J storage - finished (0 Others: (] reactor (] storage - heavy (J control devices (] cracking (0 storage - water (J pumps furnace 0) light ends col. (1 compressors C) stripper (J heavy ends col. O agitator(s) () EDC purification CO wastewater col. O loading CJ recovery system (] water wash col. 00 unloading DO mixing (0 water quench col. () flanges O weighing (J wash water (1) valves DD holding tank stripper Cl filter sératners (J separation tank (J dryer ri) cenbvifuses (J blending tank (0 condensers CO holding bins [] storage - raw [J RD/SRV C] 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 ''12. If a pressure gage is 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 is not a requirement of the Standard.) Identify those RD/SRV points which are in PVC plants by check (/) in column 3. RD/SRV Location PVC Inspector's Identification In Plant Service 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 Location Location of Nearest Identification In Plant Monitoring Point(s) FUGITIVE EMISSIONS 14. Investigate and witness the plant's standard operating procedure [61.65(c)] for fugitive emission sources [61.65(b)(1), (b)(2), (b)(5), (b)(6) and (b)(7)4 and list any possible deficiencies. Pertinent Fugitive Location Possible Emission Source In Plant Deficiency 69 ''15. Are plant personnel following the established standard operating procedures? O Yes ( No 16. If the response to the above is "NO", list pertinent fugitive emission source, location in plant and action required where the established standard operating procedure is not being followed. Pertinent Fugitive Location Action Emission Source In Plant Required 17* List equipment, location in plant, identification in the process of any pump, compressor and agitator which is 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. _ Location Identification Inspector's Equipment In Plant In Process Comments 18% Incoming raw material received by: (J Pipeline (1) Truck — Rail C1) Barge 19* Finished product material shipped by: (J Pipeline ( Truck C) Rail () Barge 70 '' REACTORS AND FURNACES 20* Give the number of reactors for each capacity. EDC: Capacity Number PVC: Capacity Number VCM (Hydrochlorination) : Capacity 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 Location Major Major Vent Device In Plant Entering Streams Exiting Streams Location 71 ''STACK EMISSIONS rae 24. 25s 26. 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) . 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. Were the stack emission tests made under conditions of maximum production rate? OJ Yes 0 No If the response is No, give the percent of maximum production rate under which the stack emission tests were made: percent. Were all stack samples analyzed within 24 hours? Oo Yes [J No If the response is No, give elapsed time, to the nearest hour, from taking sample to its being analyzed: hours. 72 ''27* List deviations or substitutes from reference Test Method 106 equipments materials and procedures which are required in conducting the stack emission test. Identification Equipment/Materials/Procedure 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. ya ''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 Clyes Ono average from continuous stack emission. 2* Number of stack emissions (continuous emissions for 1 hour or more) which exceeded limits specified in Sections 61.62, 61.63 and 61.64: 3. Were there additional emissions which were not properly and accurately reported in the appropriate Semi-annual Report? (1) Yes [No 4. 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 & Location uration Est. Integrated Cause or Action Time In Plant Emission Causes Taken LEAK DETECTION SYSTEM 5. Review of (check one or more) [Jhourly ([Jshift [daily CJ weekly Cimonthly average from leak detection system. * Data may be available from records on file at EPA Regional Offices. 74 '' 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 & Location Guration Est. Integrated Cause or Action Time In Plant Emission Causes Taken ATMOSPHERIC DISCHARGES 8* List information of emergency discharges to the atmosphere. Time Date & |Location Est. Integrated Duration Emission in Plant Cause or Causes Inspector's Comments 75 ''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 discharge(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 & Location Time 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 & Location eae Time In Plant Conditions 76 '' 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 & Location Time In Plant Emission Level of Monitoring Points 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 & Location Time In Plant Inspector's Comments 77 ''REACTOR OPENING LOSS 13* Review analytical records of vinyl chloride concentration in reactor vapor space to determine "reactor opening loss" of reactor (and stripper where applicable), prepolymerization and post polymerization vessels. List date, vessel identi- fication, and batch identification where emissions exceeded standard. Date Vessel Batch Inspector's Comments Identification Identification RESIN, SLURRY, WET CAKE AND LATEX SAMPLING 14* Review analytical records of vinyl chloride concentration in polyviny] 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 Batch Identification | Identification Inspector's Comments '' 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 _ Inspector's Comments 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 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 Firm'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? (] Yes [) No 2. Sample line a) Is sample line made of teflon? C) Yes 0) No b) Is a new unused piece used for each series of bag samples? [] Yes [] No 3. Quick connects a) Are 2 male and 2 female connects used? [J] Yes [J No b) Are they made of stainless steel? [J Yes (J No c) Does the pair for the bag have ball checks? [J Yes (J No d) Are they assembled as required? [] Yes [] No 4. Rigid container a) Is container leak proof? () Yes [] No’ {J Unknown b) Does it have a cover to protect contents from sunlight? (] Yes (J No 5. Sampling bags a) What material are bags made of? b) Are bags of 100 liter capacity? (J Yes [J No (J Unknown 80 '' 10. 11. Needle valve Will needle valve allow proper adjustment of sample flow? [J Yes (J No Vacuum pump a) Is pump of the leak-free type? J) Yes () No b) Does pump have a minimum capacity of 2 liters per minute? (J Yes) No Charcoal tube Does a charcoal tube follow pump to prevent admission of vinyl chloride to atmosphere? [[] Yes [J No Flow meter Does the flow meter have a capability of measuring flow range from 0.10 to 1.00 liter per minute? [J Yes [J No Pitot tube and manometer a) What type of pitot tube is used? b) Is pitot tube attached to probe? [J Yes LJ No c) Will an inclined manometer be used? [J Yes (J) No List substitutes for equipment and materials required in Test Method 106 in conducting stack emission tests. Equipment/Materials j ' Identification Substitute Inspector's Comments 81 ''12. 13. 14. Is plant in compliance with Test Method 106? O Yes [) No If the response is No, list action items which must be completed prior to Test date in order to conduct stack emission tests: Action Item 1: 2: 3: Test Date: 82 ''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 (20z) capacity? Ol Yes (J No b) Do the bottles have waxed lined screw on top? O Yes ([(] No c) Do the bottles have electrical tape or equivalent to prevent loosening of bottle tops? Ol Yes (J No 2. Vials a) Are vials of 50 ml capacity? [1] Yes (J) No b) Are they equipped with sealed Teflon faced Tuf-Bond discs for water samples? (0 Yes ({] No c) Are they equipped with seals and caps, Perkin-Elmer Corporation No. 105-0118 or equivalent? O Yes (9 No~ [J Unknown 3. Analytical balance a) Is it capable of weighing reproducibility to + 0.001 gram? Ol Yes () No- [J Unknown 83 ''> N oO b) What is the weighing span in the region of weight that is used in Test Method 107? Syringe a) Is its capacity 100 uz? () Yes [J No (J Unknown b) Is the model Precision Series "A" No. 010025 or equivalent? [1 Yes (J No [J Unknown Vial Sealer a) Is the Model, Perkin-Elmer No. 105-0106 or equivalent? O) Yes (© No [J Unknown Gas Chromatograph a) Is the Model, Perkin-Elmer Model F-40 head space analyzer No. 104-0001 or equivalent? O) Yes (©) No [ Unknown b) List substitutes used for the following: 2m x 3.2 mm stainless steel column; contains [4% carbowax on carbopak A (or Carbopak B) Perkin-Elmer No. 105-0133 or equivalent: Thermometer a) Range 0 to 100°C, with accuracy + 0.1°C, Perkin-Elmer No. 105-0109 or equivalent. 0 Yes 0 No Sample Tray Thermostat System a) Perkin-Elmer No. 105-0103 or equivalent. 1 Yes (J No Septa a) Sandwich type, for automatic dosing, 13 mm, Perkin-Elmer No. 105-1008 or equivalent. [] Yes () No 84 ''10. Integrator - Recorder a) Hewlett-Packard Model 3380A or equivalent. [] Yes({J No 11. Filter dryer assembly a) Perkin-Elmer No. 2230117 or equivalent. OO Yes) No 12. Soap Film Flowmeter a) Hewlett-Packard No. 0101-0113 or equivalent. O Yes (OO No 85 ''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 r-1 Diy, (A-1) i=1 where X. = The jth absolute measurement obtained from reference Test Method 106, ‘n > = Sum of the n- absolute measurements, i=] 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 Il: ENVIRONMENTAL PROTECTION AGENCY NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS Standard For Vinyl Chloride federal register CO 0O ''46560 Title 40—Protection of Environment TER I—ENVIRONMENTAL PROTECTION AGENCY SUBCHAPTER C—AIR PROGRAMS [FRL 618-1] PART 61—NATIONAL EMISSION STAND- ARDS FOR HAZARDOUS AIR POLLUTANTS Standard for Vinyl Chloride On December 24, 1975, under section 112 of the Clean Air Act, as amended (42 U.8.C. 1857), the Environmental Protec- tion Agency (EPA) added vinyl chloride to the list of hazardous air pollutants _ (40 FR 59477) and proposed a national - emission standard for it (40 FR 59532). The standard covers plants which manu- facture ethylene dichloride, vinyl chloride, and/or polyvinyl chloride. EPA decided to regulate vinyl chloride because it has been implicated as the causal agent of angiosarcoma and other serious disorders, both carcinogenic and noncarcinogenic, 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 from all known process and fugitive emission sources in ethylene dichloride- vinyl chloride and polyvinyl chloride plants to the level attainable with best available control technology. This will have the effect of furthering the protec- tion of public health by minimizing the health risks to the people living in the vicinity of these plants and to any addi- tional people who are exposed as a result of new construction. Interested parties participated in the rulemaking by sending comments to EPA. The comments have been carefully con- sidered, and where determined by the Administrator to be appropriate, changes have been made to the regulation as pro- mulgated. : SUMMARY OF THE STANDARD In ethylene dichloride-vinyl chloride plants, the standard limits vinyl chloride emissions from the ethylene dichloride and vinyl chloride formation and puri- fication processes to 10 ppm. For the ox- ychlorination process, vinyl chloride emissions are limited to 0.2 g/kg of ethyl- ene dichloride product. In polyvinyl chloride plants, the stand- ard limits vinyl chloride emissions from equipment preceding and including the stripper in the plant process flow to 10 ppm. Emissions from equipment follow- ing the stripper are to be controlled by stripping dispersion resins to 2000 ppm and other resins to 400 ppm, or by using equivalent controls. Vinyl chloride emis- sions from reactor opening are to be re- duced to 0.02 g/kg polyvinyl chloride product. In both ethylene dichloride-vinyl ’ chloride and polyvinyl chloride plants, relief valve discharges and manual vent- ing of gases are prohibited except under emergency conditions. Fugitive emissions RULES AND REGULATIONS are required to be captured and con- trolled. HEALTH AND ENVIRONMENTAL IMPACTS EPA prepared a document entitled the Quantitative Risk Assessment for Com- munity Exposure to Vinyl Chloride which estimates the risk from vinyl chloride exposure to populations living in the vi- cinity of vinyl chloride-emitting plants before and after implementation of con- trols to meet the standard. There are no dose-response data for the concentra- tions of vinyl chloride found in the am- bient air. Therefore, assessments of risk at ambient levels of exposure were ex- trapolated from dose-response data from higher levels of exposure using both a linear model and a log-probit model. Extrapolations made with each of these models entailed using different sets of assumptions. Because different assump- tions can be made in extrapolating to low doses, the health risks are reported in ranges. It was estimated that 4.6 million peo- ple live within 5 miles of ethylene dicho- ride-vinyl chloride and polyvinyl chlo- ride plants and that the average ex- posure around these plants before instal- lation of controls to meet the standard is 17 parts per billion. The exposure levels for uncontrolled plants were cal- culated based on estimated 1974 emis- sion levels. Using the linear dose-re- sponse model, EPA found that the rate of initiation of liver angiosarcoma among people living around uncontrolled plants is expected to range from less than one to ten cases of liver angiosarcoma per year of exposure to vinyl chloride. The log-probit model gave predictions that are 0.1 to 0.01 times this rate. This wide range is an indication of the un- certainties in extrapolation to low doses. Due to the long latency time observed in cancer cases resulting from vinyl chloride exposure, increases initiated by exposure this year will not be diagnosed until the 1990’s or later. Vinyl chloride is also es- timated to produce an equal number of primary cancers at other sites, for a total of somewhere between less than one and twenty cases of cancer per year of ex- posure among residents around plants. The number of these effects is expected to be reduced at least in proportion to the reduction in the ambient annual average vinyl chloride concentration, which is expected to be 5 percent of the uncon- trolled levels after the standard is im- plemented. Changes in 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 6 of Volume I of the Standard Support and Environmen- tal Impact Statement. According to data submitted by the Society of Plastics In- dustry, Inc. (SPI), 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. That is, EPA assumed ‘that those control systems with the greatest water usage would be employed and that there would be no recycling of water. There is no regulation which would require water recycling. Accord- ing to SPI, the control system utilizing the most water will not be used gener- ally by the industry and economic fac- tors will cause plants to recycle much of the water. Therefore, according to SPI the impact of the standard on water consumption will be negligible. 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 will consist of vinyl] chloride emission reductions of approximately 94 percent at ethylene dichloride-vinyl chloride plants and 95 percent at poly- vinyl chloride plants. Percentage num- bers for both source categories are based on an estimated 90 percent reduction in fugitive emissions and 1974 emission levels. The potential secondary environmen- tal impacts of the standard are either insignificant or will be minimized with- out additional action, except for one ad- verse impact. Hydrogen chloride is al- ready emitted by process equipment at ethylene dichloride-vinyl chloride plants and by other petrochemical plants in the complexes where ethylene dichloride- vinyl chloride plants are typically lo- cated. An incinerator used to attain the standard at an ethylene dichloride-vinyl chloride plant could increase hydrogen chloride emissions by several fold. Typi- cally, however, due to the corrosion prob- lems which would otherwise occur both on plant property and in the community, plants use scrubbers to control already existing hydrogen chloride emissions. Hydrogen chloride emissions resulting from control of vinyl chloride emissions are expected to be controlled for the same reason. If even a moderately effi- cient scrubber (98 percent control) were used to control the hydrogen chloride emissions resulting from incineration of vinyl chloride emissions, the increase in hydrogen chloride emissions from a typ- ical ethylene dichloride-vinyl chloride plant due to the standard would be re- duced to 35 percent. However, EPA plans to further evaluate the need to control hydrogen chloride emissions, since dif- fusion model results indicate that under “worst-case” meteorological conditions. the hydrogen chloride emissions from the process equipment and the incinera- tor combined would cause maximum am- bient concentrations of hydrogen chlo- ride in the vicinity of ethylene dichlo- ride-vinyl chloride plants to be in the same range or somewhat higher than existing foreign standards and National Academy of Sciences (NAS) guidelines for public exposure. EcONOMIC IMPACT In accordance with Executive Order 11821 and OMB circular A-107, EPA carefully evaluated the economic and inflationary impact of the proposed standard and alternative control levels and certified this in the preamble to the proposed standard. These impacts are FEDERAL REGISTER, VOL. 41, NO. 205—THURSDAY, OCTOBER 21, 1976 89 ''discussed in Chapter 7 of Volume I of the Standard Support and Environmen- tal Impact Statement. Comments on the proposed standard have resulted in only one major change in the economic im- pact analysis. EPA estimated that there would be four plant closures as a result of the promulgated standard. Of the four plants identified as possible closure can- didates, one has given notice that it no longer produces polyvinyl chloride and the other three have indicated that they do not intend to close as a result of the standard. The economic impacts of the promul- gated standard may be summarized as follows: The total capital cost for exist- ing plants to meet the standard is esti- mated to be $198 million, of which $15 million is for ethylene dichloride-vinyl chloride plants and $183 million is for polyvinyl chloride plants. EPA estimates that these plants will have 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 annualized operation cost is $17 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 in the total costs cited above for meeting the promulgated regulation. Broken out separately, the capital cost of meeting the fugitive emission regulations is $37 million and the annualized cost is $25 million. The standard is not expected to deter construction of new ethylene dichloride- vinyl chloride plants or most types of new polyvinyl chloride plants. For one type of polyvinyl 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 will rise by approxi- mately 7.3 percent in order to maintain precontrol profitability and also to re- cover the total annualized control costs necessitated by the standard at ethylene dichloride-viny] chloride plants and poly- vinyl chloride plants. This increase is estimated to translate into a maximum consumer price increase in goods fabri- cated from polyvinyl chloride resins of approximately 3.5 percent. Recovery of effluent annualized costs plus mainte- nance of precontrol profitability is esti- mated to add approximately 2 percent to polyvinyl chloride resin prices and result in an additional maximum consumer price increase of 1 percent. PUBLIC PARTICIPATION During the public comment period, 50 comment letters on the proposed stand- ard were received. There were 24 from industry; 3 from environmental groups; 15 from Federal, State, and local agen- cies; and 8 from individual citizens. As required by section 112(b) (1) (B) of the RULES AND REGULATIONS Act, a public hearing was held on the proposed standard on February 3, 1976, in Washington, D.C. Presentations were made by the Environmental Defense Fund, the Society of the Plastics Indus~- try, Inc., Dow Chemical Company, Dia- mond Shamrock Corporation, and Air 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 EPA Public Information Ref- erence Unit, Room 2922 (EPA Library), 401 M Street, SW., Washington, D.C. In 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 for Vinyl Chloride, Volume II). SIGNIFICANT COMMENTS AND CHANGES TO THE PROPOSED REGULATION (1) Decision to list vinyl chloride as 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 U.S. worker EPA discussed as having been exposed to vinyl chloride levels low- er than those usually. encountered in polyvinyl chloride production has been dropped from the National Institute of Occupational Safety and Health’s listing of workers with angiosarcoma. EPA agrees that there are questions concern- ing the level of exposure and in some cases the pathology of these cases not involved directly in polyvinyl 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 Polyvinyl Chloride (STAR) where the angiosarcoma cases are listed. However, in spite of these uncertainties, in view of 46561 the possible exposure patterns, these cases cannot be ignored in the evaluation of the potential public health problems. With regard to the alleged overstated emission levels, the uncontrolled emis- sion levels reported by EPA were based on 1974 data. This qualification was stated wherever emission data were pre- sented. EPA recognizes that emissions 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 are expected to change, and gathering the data would take considerable time both on the part of EPA and on the part of industry. Since the purpose of the stand- ard is to minimize emissions, these more current data would not affect the stand- ard itself. The 1974 emission levels were also used in diffusion modeling to project maximum ambient air concentrations around uncontrolled plants. These maxi- mum air concentrations would ably be lower if 1976 emission levels Were used. This would reduce the relative impact of the standard below that described in the Standard Support and Environmen- tal Impact Statement, but would not affect the basis of the standard itself. (2) Approach for Regulating Vinyl Chloride Under Section 112. Two ap- proaches other than using best avail- able control technology were suggested by the commenters for regulating vinyl chloride under section 112. The first was to ban polyvinyl chloride products for which substitutes are currently available and to gradually phase out other poly- vinyl_chloride products as substitutes are developed. In the preamble to the proposed stand- ard EPA specified its reasons for not set- ting a zero emission limit for vinyl chloride, as follows: (1) There a ne- ficial uses of vinyl chloride products for which desirable substitutes are not read- lly available; (2) there are potentially adverse health and environmental im- pacts from substitutes which have not been thoroughly studied; ¢3) there are a number of employees, particularly in the 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. Z EPA agrees that substitutes do exist or could be manufactured for most poly- vinyl chloride uses. However, in general, these substitutes do not have some of the more desirable characteristics of poly- vinyl chloride, such as nonflammability. If vinyl chloride and polyvinyl chloride were banned, other substitutes with these more desirable characteristics would likely be developed. There is a risk that these substitutes would also have adverse health or environmental effects. Since control measures are available which can reduce’ vinyl chloride emis- sions by 90 percent or more, tt does not seem prudent to reduce emissions-by the remaining percentage and take the risk of introducing new untested chemicals into the environment. FEDERAL REGISTER, VOL. 41, NO. 205-——THURSBAY, OCTOBER 21, 1976 90 ''46562 Another approach suggested by the commenters was to base the standard for each individual emission point on cost versus benefit. Several of the fugitive emission sources were named specifically as ones 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- fordability 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 under section 112 than would be done under section 111. As discussed in the preamble to the proposed standard for vinyl chloride, EPA believes costs may be considered under section 112, but only to a very limited extent; ie., to assure that the costs of control technol- ogy are not grossly disproportionate to the amount emission reduction achieved. In comparison with other emission points, the costs of controlling the fugitive emission sources mentioned by the commenters are relatively small compared with the amount of emission reduction achieved. Several commenters recommended adding to the regulation a provision for excess emissions during startup, shut- down, and malfunction. EPA considered this comment, and decided that this addition is not necessary for the vinyl chloride standard. Startup and shutdown of the process has essentially no effect on emissions to the atmosphere for poly- vinyl chloride production, and technology exists to avoid excess emissions during startup and shutdown at ethylene di- chlorideviny] chloride plants. We do not believe plants should be allowed to emit excess emissions during malfunctions, and therefore are requiring them to shut down immediately. . (3) Selection of source categories. In the preamble to the proposed standard EPA recognized that some small research and development facilities may exist where the emissions of vinyl chloride are insignificant and covering these facilities under the standard would be unnecessary and inappropriate. However, EPA did not have sufficient information available to clearly define which facilities should be excluded from the standard, and encouraged interested parties to submit such information during the comment . Based on the information sub- mitted, EPA decided to exempt poly- vinyl chloride reactors and associated equipment from applicability of all parts of the standard if the reactors are used in research and development and have a RULES AND REGULATIONS capacity of no more than 0.19 m* (50 gal). Reactors in this size range can gen- erally be found in a laboratory, whereas the larger reactors are typically pilot scale facilities. Emissions from laboratory scale equipment are 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 facilities con- taining reactors greater than 0.19 m* (50 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 there are no commercial reactors smaller than this. (4) Emisston limits. 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. There are 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 pressure within the reactor. The higher the tem- perature and pressure 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 pressure than the pressure 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 severe weather conditions, sev- eral reactors may be out of control at one time. There 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 before the relief valve opens. The same notification procedures are required for manual venting to the atmosphere as are required for relief discharges. There are several changes in 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 (SI). There was an error involved in the original calcula- tion used to derive the standard for reac- tor opening. Correcting this error dou- bles the allowable emissions. 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 case, 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 there were 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 vinyl chloride service.” “In vinyl chloride serv- ice” distinguishes between situations where vinyl chloride is clearly involved and situations where vinyl chloride is a minor component or contaminant, and as defined in promulgated § 61.61(1) means that a piece of equipment con- tains or contacts either a liquid that is at least 10 percent by weight vinyl chlo- ride or a gas that is at least 10 percent by volume vinyl chloride. : The proposed standard required a viny) 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 analyze the samples with gas chromatog- raphy, or if all hydrocarbons were as- sumed to be vinyl chloride, with infrared spectrophotometry, flame ion detection, or equivalent. It required that each plant submit a description of tts monitoring system to EPA, so that EPA could deter- mine whether it was acceptable or not. Comments were received indicating a need for EPA to specify some criteria for judging the acceptability of monitoring systems. The accuracy of the monitor- FEDERAL REGISTER, VOL. 41. NO. 205—THURSDAY, OCTOBER 21, 1976 91 ''ing 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 the proposed standard was re- quired to have a sensitivity of 5 ppm. Comments were received indicating that instruments in this sensitivity range are delicate and require continuing mainte- nance. The portable hydrocarbon detec- tor is required for leak detection and for measuring vinyl chloride concentrations inside the equipment before opening it. A 5 ppm sensitivity is not needed in either case, and the required 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 havy- ing separate regulations for rotating and reciprocating pumps in both the pro- posed and promulgated standards. Section 61.66 of the proposed standard provided for the use of equivalent meth- ods of control which have been approved by EPA. The promulgated standard re- quires that the plant owner or operator submit a request for determination of equivalency within 30 days of the pro- mulgation date if the alternative control method is intended as the initial means of control. The purpose of this is to pro- vide time for EPA to evaluate the method before the plant has to be in compliance (for existing sources, 90 days after the promulgation date). EPA also suggests that this request for determination of equivalency be accompanied by a re- quest for waiver of compliance pursuant to section 112(c) (1) (B) (if) of the Act. The request fora waiver for compliance should provide for the case where EPA determines that a method is not equiv- alent and the plant needs to purchase other equipment. In no case will the waiver of compliance be extended two years from the date of prom - There are several wording clarifica- tions which have been made in the pro- mulgated standard. The definition for “in vinyl chloride service” (§ 60.61(1)) has been clarified by stating that it means equipment that contacts vinyl chloride as well as that con- tains vinyl chloride. This would include such equipment as agitators. Words have been added in §§ 61.62, 61.63, and 61.64 to clarify that the 10 ppm emission limits do not have to be met when equipment has already been 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 viny! chloride and would be in violation of the standard if this statement were not included. The requirements for stripping poly- vinyl chloride resins to specified levels have been revised in $§ 61.64(e), 61.67 RULES AND REGULATIONS (g) (3) (1), and 61.70(c) (2) (1) so that measurement of the vinyl chloride levels in the resins is to be made immediately after stripping is completed rather than as the resin is being transferred out of the stripper. This allows a plant to carry out operations in a stripper after strip- ping has been completed but before it is transferred out of the stripper. This 1s consistent with the original intent of the standard. The regulation for loading and unload- ing lines in § 61.65(b)(1) 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 wastewater streams. Section 61.65(b) (9) (1) of the promulgated standard clarifies that wastewater streams that are required to be treated (Le., those containing greater than 10 ppm vinyl 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., dilution cannot be used to meet the standard. The commenters recommended several 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 is aware that each fugitive emission source, such as one pump, taken by itself causes relatively small emissions. Fugitive emissions con- sidered as a whole are a significant source of emissions, however, and the in- tent of the standard is to reduce these. Double mechanical seal pumps are com- monly used in the industry for emission reduction. Sealless pumps or equivalent systems are available as options to double mechanical seals. The commenters recommended in- creasing the averaging time for the 10 ppm limits and the emission limits for reactor opening and stripping to 30 days. Some of the commenters apparently thought that the 10 ppm limits had to be met on an instantaneous basis. 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 is at least three hours. Increasing the averaging time to 30 days for any of the emission limits would permit higher peak emis- sion levels. EPA has determined that this is neither desirable nor necessary. Some commenters requested that the stripping levels for dispersion resins be 46563 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 is 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 less 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 considera tion that some resins are more difficult to strip than others by providing for averaging among different resins. (5) Testing, reporting, and record- keeping. There are several relatively minor changes in the testing, reporting, and recordkeeping requirements. A pro- vision has been added to § 61.67 which requires that stack gas samples taken with Test Method 106 are to be analyzed within 24 hours. This is consistent with the requirements in the proposed Test Method 106. The promulgated standard alsd specifies that in averaging the re- sults of the three runs required by Test Method 166, a time-weighted average is to be used. One commenter requested that the oxygen content and moisture content be specified for the 10 ppm concentration standards. The proposed standard speci- fied that the vinyl chloride concentration is to be corrected to 10 percent oxygen (wet basis) if combustion ts used as the control measure. In the promulgated standard, this requirement has been ex- panded to all control measures. A provision has been added to the promulgated standard which states that if a reactor is also used as a stripper, the reactor opening emissions may be deter- mined tmmediately following the strip- ping operation. If a reactor is also used as a stripper, the resin is in the reactor when it is opened. This means that vinyl chloride in the resin which has already been stripped to acceptable levels can escape from the resin and become part of the reactor opening loss. It is EPA’s intent that once a resin has been stripped to the required levels, that additional - controls are not required. Under the new provision, vinyl chloride escaping from the resin after it has been stripped to acceptable levels is not counted as part of the reactor opening loss. A section requiring continuous moni- toring of stack emissions has been added to the promulgated standard. The con- tinuous monitoring of stack emissions was required in the proposed standard. The addition of a specific paragraph for emission monitoring serves only to clarify the requirement, The standard has been revised so that the initial report requires a “description” rather than a “detailed description” of the equipment used to control fugitive emissions. Several commenters pointed out that a detailed description would contain proprietary information. EPA agrees that a detailed description in the FEDERAL REGISTER, VOL. 41, NO. 205—THURSDAY, OCTOBER 21, 1976 92 ''specifies dates for the submittal of the reports. It also specifies that the first semiannual report does not have to be submitted until at least six months after the initial report is submitted. The standard has been revised to elim- inate the requirement to record the cause of any leak detected by the vinyl chlo- ride detector, the action taken to repair established by looking at the strip chart record of measurements made by vinyl chloride detector. These records are still required for the portable hydrocar- bon detector however. Several commentators recommended by regular mail. EPA has not adopted either of these reeommendations. A source is supposed to be in compliance with the standard within 90 days of the promulgation of the standard. The standard requires that the emission tests be done within the °90 day period, and permits an extra 30 days for determination of results. The purpose of using registered mail is to document the fact that emission data have been sent and received. This way if the results are lost in the mail, there will be no question that they were sent. (6) Test method. Test Method 106 has been changed to recognize that on a gas chromatograph equipped with a Chrom- osorb 102 column, acetaldehyde may interfere with the vinyl chloride peak. When a sample is expected to contain acetaldehyde, a secondary column as de- scribed in section 4.3.2 must be employed. Mass spectroscopy or another absolute analytical technique is required to con- firm the vinyl chloride peak obtained with the gas chromatograph, only if peak resolution with the secondary column is not successful.” In section 4.1.4, aluminized Mylar bags can be substituted for Tedlar bags. EPA now has data to allow this substitution, provided that the samples are analyzed within 24 hours of collection. In section 5.1.3 of Test Method 106 the requirement to use “oxygen gas” has been replaced with ‘“‘oxygen gas or air, as required by the detector.” Several com- mentors stated that most gas chromato- graphs are designed to use hydrogen and air for their flame detectors. When used in this way, they are capable of detect- ing 0.5 ppm vinyl chloride in air. This is sensitive enough for monitoring the 10 ppm emission limits stipulated in the standard. RULES AND REGULATIONS In section 6.4 of Test Method 106 the requirement for an automatic integrator has been replaced with a requirement for & disc integrator or planimeter for meas- uring peak area. This change is in re- sponse to a comment which states that automatic integrators are unnecessarily elaborate and expensive. A new section 6.5 has been added to _ Test Method 106 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 has been added to section 7.4 of Test Method 106. The only change in Test Method 107 is the provision in Section 5.3.2 for use of Carbopak C as well as Carbopak A. AUTHORITY: Section 112 of the Clean Air Act as added by sec. 4(a) of Pub. L. 91-604, 84 Stat. 1685 (42 U.S.C. 18570-7; 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. 98-819, sec. 6(a) (4), 88 Stat. 259 (42 U.S.C. 1857c-9); Section 301(a) of the Clean Air Act, as amended by sec. 15(c) (2) of Pub. L. 91-604, 84 Stat. 1718 (42 U.S.C. 1857g (a) ). Dated: October 12, 1976. JOHN QUARLES, Acting Administrator. Part 61 of Chapter I, Title 40 of the Code of Federal Regulations is amended as follows: The table of sections for Part 61 is amended by adding a list of sections for new Subpart F and Part 61 1s amended by adding a new Subpart F reading as follows: Subpart Fates Seen Standard for Vinyl Bec. 61.60 61.61 61.62 Applicability. Definitions. Emission standard for ethylene di- chloride plants. Emission standard for vinyl chloride plants. Emission standard for polyvinyl chlo- ride plants. Emission standard for ethylene di- chloride, vinyl chloride and poly- vinyl chloride plants. Equivalent equipment and procedures. Emission tests. Emission monitoring. Initial report. 61.70 Semiannual report. 61.71 Recordkeeping. AvTHorIrr: Section 112 of the Clean Air Act as added by e#ec. 4(a) of Pub. L. 91-604, 84 Stat. 1685 (42 U.S.C. 18570-7); 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. 250 (42 U.8.C. 1857c-9); section 301(a) of the Clean Air Act, as amended by sec. 15(c) (2) of Pub. L. 91-604, 84 Stat. 1713 (42 U.8.C. 1857g(a)). Subpart F—National Emission Standard . for Vinyl Chloride § 61.60 Applicability. (a) This subpart applies to plants which produce: (1) Ethylene dichloride by reaction of oxygen and hydrogen chloride with ethylene, 61.63 61.64 61.65 61.66 61.67 61.68 61.69 (2) Vinyl chloride by any process, and/or (3) One or more polymers containing “ fraction of polymerized vinyl -chlo- e. (b) This subpart does not apply to equipment used in research and develop- ment if the reactor used to polymerize the vinyl chloride processed in the equip- ment has a capacity of no more than 0.19 m* (50 gal): (c) Sections of this subpart other than § 61.64(a) (1), (b), (c), and (d) do not apply to equipment used in research and development if the reactor used to po- lymerize the vinyl chloride processed in the equipment has a capacity of greater than 0.19 m* (50 gal) and no more than 4.07 m® (1100 gal). § 61.61 Definitions. Terms used in this subpart are defined in the Act, in subpart A of this part, or in this section as follows: (a) “Ethylene dichloride plant” in- cludes any plant which produces ethyl- ene 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 polymerized. (d) “Slip gauge” means a gauge which 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 dis- charges. (e) “Type of resin” means the broad classification of resin referring to the basic manufacturing process for produc- ing that resin, including, but not limited to, the suspension, dispersion, latex, bulk, and solution processes. (f) “Grade of resin” means the sub- division of resin classification which de- scribes it as a unique resin, 1.e., the most exact description of a resin with no fur- ther subdivision. (g) “Dispersion resin” means a resin manufactured in such away as to form fluid dispersions when dispersed in a plasticizer or plasticizer/diluent mix- tures. (h) “Latex resin” means a resin which is produced by a polymerization process which 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 treat- ment process or discharged untreated as wastewater. (k) “Wastewater treatment process” fncludes any process which modifies FEOERAL REGISTER, VOL. 41, NO. 205—THURSDAY, OCTOBER 21, 1976 o3 ''characteristics such as BOD, COD, TSS, and pH, usually for the purpose of meet- ing effluent guidelines and standards; it does not include any process the p' of which is to remove vinyl chloride from water to meet requirements of this subpart. (1) “In vinyl chloride 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” means @ formal written procedure offi- cially adopted by the plant owner 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 dichloride purification” includes any part of the process of ethyl- ene dichloride production which follows ethylene dichloride formation and in which. finished. ethylene dichloride is produced. (p) “Vinyl chloride purification” in- cludes any part of the process of vinyl chloride production which follows vinyl chloride formation and in which finished vinyl chloritle is produced. ’ (q) “Reactor” includes any vessel in which viny] 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 atmos- phere for any purpose other than an emergency relief discharge as defined in § 61.65(a). . (s) “Stripper” includes any vessel in which residual]. vinyl chloride is removed from polyvinyl chloride resin, except bulk resin, in the slurry form by the use of heat and/or vacuum. In the nye bulk resin, stripper includes any which is used to remove residual vinyl chloride from polyvinyl] chioride resin immediately following the polymeriza- tion step in the plant process flow. 61.62 Emission standard for ethylene ' dichloride plants. An owner or operator of an ethylene dichloride plant shall comply with the requirements of this section and § 61.65. (a) Ethyl dichloride purification: The concentration of vinyl chloride in all exhaust gases discharged to the at- mosphere from any equipment used in ethylene dichloride purification is not to exceed 10 ppm, except as provided in § 61.65(a). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in § 61.65(b) before being opened. (b) Oxychlorination reactor: Except as provided in § 61.65(a), emissions of vifty] chloride tothe atmosphere from each oxychlorination reactor are not to exceed 0.2 g/kg the 100 percent ethylene dichloride product from the oxychlori- nation process. v RULES AND REGULATIONS § 61.63 Emission standard for vinyl chloride plants. An owner or operator of a vinyl chlo- ride plant shall comply-with the require- ments of this section and § 61.65. (a) Vinyl chloride formation and puri- fication: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from any equipment’ used in vinyl chloride formation and/or purification is not to exceed 10 ppm, ex- cept as provided in § 61.65(a). This re- quirement does not apply to equipment _ that has been opened, is out of operation, and met the requirement ‘in § 61.65(b) (6) (i) before being opened. ; § 61.64 Emission standard for polyvinyl chloride plants. ‘ An owner or operator of a polyvinyl chioride plant shall comply with the re- quirements of this section and § 61.65. (a) Reactor: The following require- ments apply to reactors: (1) The concentration of vinyl thlo- ride in all exhaust gases discharged to the atmosphere from each reactor is not to exceed 10 ppm, except as provided in Paragraph (a)(2) of tnis section and’ § 61.65 (a). (2) The reactor opening loss from each reactor is not to exceed 0.02 g vinyl chloride/Kg (0.00002 Ib vinyl chloride/ lb) of polyvinyl chloride product, ‘with the product determined on a dry solids basis. This requirement applies to any vessel which is used as a reactor or as, both a reactor and a stripper. In the -bulk process, the product means the gross product of prepolymerization and postpolymerization. (3) Manual vent. valve discharge: Ex- cept for an emergency manual vent valve discharge, there is to be no discharge to the atmosphere from any manual vent valve on a polyvinyl chloride reactor in vinyl chloride service. An emergency manual vent valve discharge means a discharge to the atmosphere which could 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 Joss 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 is not to exceed 10 ppm, except as provided in § 61.65(a). This re- ment does not apply to equipment that has been opened, is out of operation, and met the requirement in § 61.65(b) (6) (i) before being opened. (c) Méaxing, wefghing, and holding containers: The concentration of vinyl chloride in all exhaust gases d to the atmosphere from each mixing, weighing, or holding container in vinyl chloride service which precedes the . the stripper (s) Cor reactor(s) if the dispersion 46565 stripper (or the reactor if the plant has no stripper) in the plant process flow is hot to exceed 10 ppm, except as provided in § 61.65(a). This requirement does not apply to equipment opened, is out of operation, requirement in § 61.65