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EPA-450/3-73-006-i July 1975 'JU)n&LZ_ Mitt ENGINEERING \ AND COST STUDY OF AIR POLLUTION CONTROL FOR THE PETROCHEMICAL INDUSTRY VOLUME 9: POLYVINYL CHLORIDE MANUFACTURE RECEIVED DEC 4 1975 H.R. GUEST U.S. ENVIRONMENTAL PROTECTION AGENCY Office of Air and Waste Management Office of Air Quality Planning and Standard* Research Triangle Park, North Carolina 27711 ucc 0260S1 EPA-450/3-73-006-1 ENGINEERING AND COST STUDY OF AIR POLLUTION CONTROL FOR THE PETROCHEMICAL INDUSTRY VOLUME 9: POLYVINYL CHLORIDE MANUFACTURE by R.G. Bellamy and W.A. Schwartz Houdry Division Air Products and Chemicals, Inc. P. O. Box 427 Marcus Hook, Pennsylvania 19061 Contract No. 68-02-0255 EPA Project Officer: Leslie Evans Prepared for ENVIRONMENTAL PROTECTION AGENCY Office of Air and Waste Management Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 July 1975 UCC 026052 In-Depth Study of POLYVINYL CHLORIDE PRODUCTION Contract No. 68-02-0255 Prepared For Environmental Protection Agency Research Triangle Park, North Carolina 27711 Prepared By Houdry Division Air Products and Chemicals, Inc. P. 0. Box 427 Marcus Hook, Pennsylvania 19061 Houdry Division A &4kfyotuctL and C6&mea*- ucc 026053 This report is issued by the Environmental Protection Agency to report technical data of interest to a limited number of readers. Copies are available free of charge to Federal employees, current contractors and grantees, and nonprofit organizations - as supplies permit - from the Air Pollution Technical Information Center, Environmental Protection Agency, Research Triangle Park, North Carolina 27711; or, for a fee, from the National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161. This report was furnished to the Environmental Protection Agency by Houdry Division of Air Products and Chemicals, Inc., Marcus Hook,. Pennsylvania 19061, in fulfillment of Contract No. 68-02-0255. The contents of this report are reproduced herein as received from Houdry Division of Air Products and Chemicals, Inc. The opinions, findings, and conclusions expressed are those of the author and not necessarily those of the Environmental Protection Agency. Mention of company or product names is not to be considered as an endorsement by the Environmental Protection Agency. Publication No. EPA-450/3-73-006-i UCC 026054 ii PETROCHEMICAL AIR POLLUTION STUDY INTRODUCTION TO SERIES This document is one of a series prepared for the Environmental Protection Agency (EPA) to assist it in determining those petrochemical processes for which standards should be promul gated. A total of nine petrochemicals produced by 12 distinctly different processes has been selected for this type of in-depth study. These processes are considered to be ones which might warrant standards as a result of their impact on air quality. Ten volumes, entitled Engineering and Cost Study of Air Pollution Control for the Petrochemical Industry (EPA-450/3-73-006a through j) have been prepared. A combination of expert knowledge and an industry survey was used to select these processes. The industry survey has beeir published separately in a series of four volumes entitled Survey Reports on Atmospheric Emissions from the Petrochemical Industry (EPA-450/3-73-005a, b, c and d). The ten volumes of this series report on carbon black, acrylonitrile, ethylene dichloride, phthalic anhydride (two processes in a single volume), formaldehyde (two processes in two volumes), ethylene oxide (two processes in a single volume),high density polyethylene, polyvinyl chloride and vinyl chloride monomer. (JCC 026055 ACKNOWLEDGEMENTS The study reported in this volume, by its nature, relied on the fullest cooperation of the companies engaged in the production of polyvinyl chloride. This was given at a particularly difficult time as all the companies were in the midst of an all out effort to reduce all vinyl chloride monomer emissions to a minimum. Without their information this report could not have been written, we, therefore, list the participating companies to acknowledge their cooperation and assistance. American Chemical Corporation* Borden, Incorporated Continental Oil Company Firestone Plastics Company General Tire & Rubber Company B. F. Goodrich Chemical Company Goodyear Tire & Rubber Company Great American Chemical Corporation Hooker Chemical Corporation Keysor-Century Corporation National Starch & Chemical Company Fantasote Company of New York, Inc. Stauffer Chemical Company Tenneco Chemicals Union Carbide Corporation Uniroyal Chemical Company Universal PVC Resins, Incorporated Air Products and Chemicals, Inc. ^Subsidiary of Stauffer Chemical Company We also acknowledge the help of numerous manufacturers of equipment. UCC 026056 TABLE OF CONTENTS Section I. II. III. 17. V. VI. VII. VIII. IX. X. Title Introduction Chemistry of Polymerization Commercial Processes Commercial Products Plant Emissions National Emission Inventory Industrial Growth Projection Emission Control Devices Model Plant Research and Development Goals Page Number FVC-1 fvc-4 fvc-6 FVC-20 FVC-21 FVC-7^ FVC-75 PVC-70 PVC-86 FVC-93 Figure FV-1 FV-2 FV-3 PV-4 PV-5 PV-6 FV-7 PV-8 Title Page Numb r Polyvinyl Chloride Plant - Suspension Process Polyvinyl Chloride Plant - Dispersion process Polyvinyl Chloride Plant - Bulk Process Polyvinyl Chloride Plant - Solvent Process Suspension Process Total Emissions Dispersion Process Total Emissions Polyvinyl Chloride Resins Yearly Production Location of FVC Manufacturing Plants FVC-7 FVC-9 FVC-10 PVC-12 FVC-71 FVC-73 FVC-76 FVC-77 Table FV-1 FV-2 FV-3 FV-4 PV-5 PV-6 FV-7 PV-8 FV-9 Title Page Number Material Balance - Suspension Process Material Balance - Dispersion Process Material Balance - Bulk Process Material Balance - Solvent process Summary of U.S. Polyvinyl Chloride Plants National Emission Inventory For FVC Manufacture Summary of Fugitive Emissions Statistical Evaluation of FVC Manufac- turer's Emissions for Suspension Process Statistical Evaluation of FVC Manufac- turer's Emissions for Dispersion Process PVC-14 FVC-15 PVC-16 FVC-17 PVC-18 & 19 FVC-22 Thru 63 FVC-67 & 68 PVC-70 FVC-72 ucc 026057 TABLE OF CONTENTS (CONTINUED) Table PV-10 PV-11 PV-12 PV-13 PV-14 PV-15 PV-16 Title Catalog of Emission Control Devices PVC Manufacturing Cost for a Typical Existing 200 MM Lb./Yr. Facility Model Plant I Incorporating Moderate Emission Control Devices Model Plant II Incorporating Extensive Emission Control Devices PVC Manufacturing Cost for a Typical Model I Plant PVC Manufacturing Cost for a Typical Model II Plant Estimate of VCM Emissions from Model Plants Page Number PVC-85 PVC-87 PVC-88 PVC-90 PVC-92 PVC-93 PVC-94 UCC 026058 Introduction polyvinyl chloride (FVC) resins cover a great variety of plastic compounds from the pure homopolymer to an almost endless variety of modifications starting with minor (<10#) amounts of copolymers such as vinylidene chloride, vinyl acetate, ethylene, propylene or an acrylate. The resins themselves are modified with plasticizers, stabilizers, inert fillers and many other additives. (In the case of records and many toys the final product may contain less than 45# FVC and in the case of vinyl asphalt tiles much less than 45#.) Industrial development of FVC resins began some 4o years ago. Production on a full commercial scale began in Germany in 1931 and in the united States in the middle 1930s, aft r the discovery that polyvinyl chloride, when heated in the presence of a suitable high-boiling liquid (a plasticizer), formed a flexible plastic material that resembled rubber or leather. Because plasticized FVC showed itself to be a good insulator, resistant to the weather, and nonflammable, it was put to military uses in World War II. Diversified compounding and processing technology, which developed particularly in the later 1940s and early 1950s, quickly h led to many broad-scale commercial uses. The processing and performance characteristics of FVC r sins can be varied with the molecular weight, which for most commercial FVC resins lies between 50,000 and 120,000. Equally important to the characteristics of the resins is the presence or absence of plasticizer. Most FVC plastics produced in past decades were flexible types, containing plasticizer. While the many processes for plasticized FVC are relatively easy to carry out, the processing of FVC compounds containing essentially no plasticizer (for the production of rigid FVC plastics) Is technically more d manding. The properties of plasticized FVC plastics depend greatly on the exact amounts and chemical types of plasti cizers used; it is common to employ mixtures to achieve th desired properties. Although the great majority of FVC resins used in the various processes to manufacture FVC plastics are homopolymers of vinyl chloride, copolymers are still essential in some processes, where they are used alone or in admixture with homopolymers The most important commercial copolymers of vinyl chlorld are those with vinyl acetate. The higher molecular weight resins with an acetate content of about 2-8# are used for calendering and extrusion, where somewhat faster processing is possible because of their better flow properties compared UCC 026059 FVC-2 with those of conventional homopolymers. Copolymers contain ing over vinyl acetate flow even more readily under the application of heat and pressure and are, therefore, favored in the production of phonograph records. The copolymers also are capable of binding particularly large amounts of mineral fillers and pigments, a capability utilized in the production of vinyl-asbestos floor tile. Because the solubility in esters and ketones of vinyl chloride copolymers with an acetate content of 10-20# is much greater than that of homopolymers, these resins are used in solution coating. The commercial copolymers of vinyl chloride with ethylene and propylene contain 1-8# of ethylene or propylene and are predominantly used in the manufacturing of unplasticized (rigid) PVC products. Such copolymers can be processed raster and have better Impact strength than comparable homopolymers, without any sacrifice in dimensional stability and other Important performance properties. Copolymers of vinyl chloride with vlnylldene chloride are more soluble in solvents than homopolymers and they are good film ~ formers. The few resins of this type that are on the market today are, therefore, mostly used in specialty coatings (In solution and, in some applications. In latex or emulsion form). A few latex FVCs or copolymers of vinyl chloride and ethyl, n-butyl, or 2-ethylhexyl acrylate are used In the production of wall coverings, nonwovens, and house paint. The latexes are 50 percent solid colloidal dispersions in water. Postchlorlnated PVC homopolymer resins have long been in existence but were of little commercial importance until recently. Products made from them have better heat resistance (and higher densities) than products made from ordinary FVC resins. The main application for these resins is in residen tial hot water pipe. In 1973 the production of PVC resins was 4,423,400,000 pounds. As there was a tight supply, this was probably all consumed. Based on production figures since 1962, the growth curve is shown in Figure FV-7 on page PVC-76 and indicates a projection of growth to 1935* However two Important factors have inter jected themselves recently into the picture which may chang this growth projection. One, is the energy crisis which could curtail the supply of ethylene and discourage projected expansions. (This has actually occurred.) Another factor is the recent discovery (January 1974) of the carcinogenic nature of vinyl chloride and the current uncertainty of how OSHA and EPA regulations will effect the profitability of manufacturing PVC resins. In any case, both factors will probably inhibit the growth of PVC, perhaps very drastically. UCC 026060 PVC-3 A third factor that has reduced the demand for PVC resins is the current temporary slump in the building industry. It cannot be overemphasized that the emissions shown in this report are based on data obtained by the reporting plants prior to August 1974. Many, if not all, the plants have made considerable progress in reducing emission since that time so that the emissions shown are those of a transition period and do not reflect current emissions. This is true of fugitive losses as well as known streams as the industry has tightened up their losses in all respects. VJCC 026061 FVC-4 II. Chemistry of Polymerization The polymerization of vinyl chloride can occur in two ways, one in a head-to-tail fashion. CH2CHClCH2CHCl} n or head-to-head or tail-to-tail configuration. ch2chcichcich^} n Research has shown that the head-to-tail position is greatly favored and closely represents the actual polymer. The terminal groups can be saturated, unsaturated or radical fragments from the initiator or solvent, depending on the chain transfer activity of the various groups. Saturated end groups are formed by chain transfer with monomer and polymer and by termination through disproportionation: i/'*'-- CH3J CH2C1j CHC12 Unsaturated chain ends are due to termination by dispro portionation and to chain transfer to monomer: -CH2CHC1CH CHClj -CC1 - CH2; -CH2CHCICH - CH2 Initiator or solvent (chain-transfer agent) fragments, represented by R, can be incorporated in the terminal group: --CH2Rj --CHC1R Due to the high transfer activity of the monomer, about 6056 of the polymer molecules are estimated to have unsaturated end groups. For the same reason, the percentage of chain ends containing initiator fragments is low; the amount of solvent fragments depends upon its transfer activity. Long-chain branching can be caused by the incorporation of the terminal double bond of a polymer molecule into a growing chain: UCC 026062 FVC-5 CH2CHCI. + CHC1 = CH--**->*"--CH2CHC1CHCHC1* or by intermolecular chain transfer to polymer: w*-- CH2CHCI + **--CH2CHC1--'** "> --CH2CH2CI +*^-CH2CCl- I Intramolecular chain transfer (back-biting) leads to the formation of short side chains: --CH2CHCICH2CHCICH2 -> C1HC* CHC1 \/ CH2CHCICH2CCI CHo ucc 026063 PVC-6 III. Commercial Processes Polyvinyl chloride is primarily produced by one of the following four processes. A. Suspension Polymerization Figure PV-1 persents a simplified flow diagram for the suspension process. This process is by far the most common process used to manufacture PVC resins (78% of total capacity). It is likely to remain so for many years although it may gradually decline as bulk polymerization becomes more common and presumably more economic. The precise mechanism of suspension polymerization is still being investigated and there is no accepted theory to explain all the observed phenomena. The general overall process involves the suspension of liquid vinyl chloride (requires pressures of 75 to 300 psig) in a continuous water phase. A free radical catalyst is used to initiate the polymerization reaction. This catalyst is dissolved in the VCM feed. Various suspending agents are used along with continuous agitation to keep VCM droplets small and dispersed. The polymerization occurs in the VCM droplets and proceeds to around 85-90% completion. Efforts are being made, with some success, to drive the reaction to near completion (95-99%) using different initiators. Reactor vessel sizes used in older plants were in the 3000-6000 gallons capacity range. The trend in the last three years has been to go to much larger reactors (15,000 to 35,000 gallons) and to switch from glass lined reactors to stainless steel vessels. The heat of polymerization is removed from the reactor system to maintain the desired operating tempera ture (about 50*C)* After the polymerization reaction has been completed, the batch may be dropped to a stripper tank where the monomer is stripped from the slurry,although some plants strip in the reactor. The effectiveness of the stripping controls the amount of VCM subsequently lost in all equip ment^ downstream of stripper. After being stripped, the slurry is then transferred to a blend tank where it is mixed with other batches of slurry to produce a more uniform product. From the blend tank the slurry is passed through a centrifuge to remove as much water as possible and then into a rotary dryer, the discharge of which is classified and stored in silos. Some companies make only the raw PVC resin and sell to companies UCC 026064 FH3URE , ,PV - I POLYVINYL CHLORIDE PLANT SUSPENSION PROCESS PVC-7 ucc 026065 pvc-8 that compound the resin, while others do some compounding themselves. Compounding consists of making modifications of the raw resin by the addition of plasticizers, anti oxidants, ultraviolet stabilizers, colorants, heat stabilizers, etc. B. Dispersion (Emulsion) Process A simplified flow diagram for a typical dispersion polymerization plant is presented in Figure FV-2. This process is basically very similar to the suspension process in that the batch reactor processes liquid vinyl chloride dispersed in a water system. However, in this case the initiator is soluble in either water or VCM. Water soluble emulsifiers are used in high enough concentrations to form micelles which are agglomerates of 20 to 30 emulsified molecules. The initiator either starts a polym r unit from dissolved vinyl chloride or from vinyl chloride picked up by the micelles. In either case the polymer chain reaches its final stage as part of a micelle with theemulsifier molecules clinging to the outside. The partial* _ sizes obtained by dispersion polymerization are much smaller than those obtained by suspension polymerization. For this reason the most commonly employed method for drying is spray drying which ensures maintaining small particle sizes. Approximately 13# of total installed plant capacity is devoted to emulsion process (dispersion) resins. (1) C. Bulk polymerization The commercial method for the bulk polymerization of . . vinyl chloride is the pechiney-St. Gobain two step process ,(2) This process which currently produces about six (6) percent of United States production will probably increase considerably over the next few years if the economics are as favorable as reported by the licensers* Any significant Increase percentage-wise of bulk production would be at the expense of suspension process as the resins from these two processes compete for some of the same markets. A bulk process flow sheet is shown in Figure FV-3* Th process consists of making seed FVC from liquid VCM in an autoclave using very active initiators at 40 to 70 Centigrade (104* to 158F) and at a pressure equivalent t the vapor pressure of VCM at the operating temperature (approximately 70 to 170 psi). Conversion is only 7 to 12#. The suspension of FVC in vinyl chloride liquid is then transferred to a larger autoclave (generally horizontal) along with more liquid VCM and more initiator. The agitator in this autoclave is much more rugged in construction as the polymerization reaction is carried out to 85 to 90# UCC 026066 FIGURE PV-2 POLYVINYL CHLORIDE PLANT DISPERSION PROCESS ucc 026067 FIGURE PV-S FLOW SHEET FOR POLYVINYL CHLORIDE BULK PROCESS PVC-10 ucc 026068 EPA-450/3-73-006-1 ENGINEERING AND COST STUDY OF AIR POLLUTION CONTROL FOR THE PETROCHEMICAL INDUSTRY VOLUME 9: POLYVINYL CHLORIDE MANUFACTURE by R.G. Bellamy and W.A. Schwartz Houdry Division Air Products and Chemicals, Inc. P. O. Box 427 Marcus Hook, Pennsylvania 19061 Contract No. 68-02-0255 EPA Project Officer: Leslie Evans Prepared for ENVIRONMENTAL PROTECTION AGENCY Office of Air and Waste Management Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 July 1975 ucc 026069 i This report is issued by the Environmental Protection Agency to report technical data of interest to a limited number of readers. Copies are available free of charge to Federal employees, current contractors and grantees, and nonprofit organizations - as supplies permit - from the Air Pollution Technical Information Center, Environmental Protection Agency, Research Triangle Park, North Carolina 27711; or, for a fee, from the National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161. This report was furnished to the Environmental Protection Agency by Houdry Division of Air Products and Chemicals, Inc., Marcus Hook, Pennsylvania 19061, in fulfillment of Contract No. 68-02-0255. The contents of this report are reproduced herein as received from Houdry Division of Air Products and Chemicals, Inc. The opinions, findings* and conclusions expressed are those of the author and not necessarily those of the Environmental Protection Agency. Mention of company or product names is not to be considered as an endorsement by the Environmental Protection Agency. Publication No. EPA-450/3-73-006-i u ucc 026070 PVC-11 completion. Temperature is controlled in both reactors by transferrin? heat to or from the jacket and by refluxing part of the vinyl chloride. After the desired yield has been reached the remaining monomer is stripped by vacuum and returned to the monomer recovery system. As there is not water or water vapor involved, it is possible to use a low temperature condenser (-35C) to recover most of the VCM. However, off-setting this particular advantage, is the fact that the autoclave reactor for the final polymerization must be cleaned after every run. The final classification, storage and shipping operations are similar to those employed in the preceeding two processes. It should be noted that since there is no water step there is no VCM carried off in water effluents. D. Solvent Polymerization Only one company manufactures PVC by the solvent process in this country. Most resins produced by this process are copolymers of PVC (75-90%) and polyvinyl acetate (10-25%). The basic process consists of a mixture of the solvent, most generally n-butane, and the comonomers, VCM and VAM, being charged continuously to an autoclave along with the appropriate amount of initiator (0.01 to 0.5%) at 40C (104F). Slurry is continuously drawn off and the PVC filtered from the slurry. The filter cake is dried by flash evaporation and the recovered monomers and solvent returned to the system. The PVC resin is remarkably pure as no emulsifier or suspending agents are required. The resin is used to make high clarity films for use where a water white product is desirable. The cost is higher than other processes and so is limited to those products that justify a higher cost. There is a possibility that solvent polymerization could become more important because of a solvent process used in France employing 100% VCM and producing a resin of much higher syndiotacticity (stereo specificity) suitable for fiber manufacture. This is a low temperature process (-20C or less). A flow sheet for a typical solvent polymerization plant is shown in Figure PV-4. Tables PV-1 thru PV-4 present typical net material balances for the four major processes used to produce PVC. These material balances depict plants without major air emission UCC 026071 PVC-12 ucc 026072 FIGURE PV-4 POLYVINYL CHLORIDE t PVC-13 control devices and in general represent an average of data provided by the plants surveyed in May of 1974. In many cases the survey data was incomplete and the reported flow quantities varied over a wide range. This plus the limited data from the few plants using the dispersion, bulk and solvent polymerization processes has made it difficult to produce firm material balances for these three particular processes. Tables PV-1 thru PV-4 show that feedstock requirements and air emissions of VCM are lowest for the solvent polymerization process whereas the opposite appears to be true for the dispersion process. It should be noted that the solvent process material balance is based on one set of data from only one plant and for this reason may not be truly representative of the process. However, since this is a continuous process it is conceivable that VCM emissions would be lower than for the other three batch type processes. (Continuous processes are easier to control from an emission stand point as there is no hourly or daily opening up of reaction vessels so that emissions are from leaks primarily.) The high feedstock requirements attributed to the disper sion process may help account for the reported 8-104/lb. higher selling price'5) for PVC produced by this process over that for the suspension process. Table PV-5 presents a list of U.S. plants producing PVC. This table also shows published(D capacity figures for these units. UCC 026073 A PVC-14 TABLE PV-1 POLYVINYL CHLORIDE NET MATERIAL BALANCE FOR SUSPENSION PROCESS (TONS/TON OF PVC CAPACITY) ^ /f \ 1* 7" INPUT Vinyl ChlorldeT Monomer (VCM) Comonomer Initiators .. Suspending Agents Surface Active Agents Total Input Stream I.D. on Simplified Polymer Flew Diagram Ingredients 1 0.98-1.05 2 0.01-0.08 3 3 3 1.0598 Other 0.0009 0.0010 0.0003 0.0022 1 " OUTPUT PVC Homopolymer and Co-Polymer Waste Solids and Liquids Fugitive Emissions t-Reactor Vent Stripper or Slurry Tank Vent Monomer Reclaim Vent Condenser Blend Tank. Centrifuge Vent Effluent From Dryer Collectors Fines From Silo Collectors Fines From Baggers Collectors Fines From Bulk Loading Collectors Monomer Storage Safety Valve Vente ; Total Output 4 5 B C D E F 0 a 0 0 A B OO PVC 1.0000 O.OIOO,,. 0.008011) 0.0009 0.0010 jo.0037 VCM 0.0020,-:. 0.0081A1) 0.0014 0.0032 0.0048 0.0042 0.0013 |o.0070 0.0006 1.0275 0.0005 0.0020 ' tSV65V5 S k. (1) Assumed split on total fugitive emissions. VI o'* ucc 026074 i-'Vi V PVC-15 tahle pv-2 POLYVINYL CHLORIDE NET MATERIAL BALANCE FOR DISPERSION PROCESS (TONS/TON OF PVC CAPACITY) INPUT Vinyl Chloride Monomer (VCM) Comonomer Initiators Suspending Agents Surface Active Agents Total Input Stream I.D. on Simplified Polymer Flow Diagram Ingredients Other 1 O.89-I.OO 2 0.01-0.12 3 0.0009 3 0.0020 3 0.0003 1.1039 0.0032 OUTPUT PVC Homopolymer and Co-Polymer Waste Solids and Liquids Fugitive Emissions Reactor Vent (l) Stripper or Slurry Tank Vent Monomer Reclaim Vent Condenser Blend Tank Effluent From Dryer Collectors Fines From Silo Collectors Fines From Baggers Collectors Fines From Bulk Loading Collectors Monomer Storage Safety Valve Vents (1) Total Output 4 5 B C D E a a a a A B PVC .... . 1.0000 0.0200 0.0013 0.0180 0.0020 i0.0053 J o.ooop 1.0475 * - VCM Xr 0.0106 0.0015 0.0123 0.0050 0.0034 ? V0.0241 1 0.0005 0.0022 0.0596 (1) Assumed split based on data received for suspension pr cess. ucc 026075 PVC-16 TABLE PV-3 POLYVINYL CHLORIDE NET MATERIAL BALANCE FOR BULK POLYMERIZATION (TONS/TON OF PVC CAPACITY) INPUT Vinyl Chloride Monomer (VCM) Initiators 'Total Input Stream I.D. on Simplified Polymer Flow Diagram Ingredients Other 1 1.0372 2 0.0009 1.0372 0.0009 OUTPUT PVC Homopolymer Waste Solids and Liquids Fugitive Emissions(2) Reactor Vent (1) Monomer Reclaim Vent Condenser Safety Valve Vents (1) Fines From Silo Collectors Fines From Baggers Collectors Fines From Bulk Loading Collectors Monomer Storage Total Output l B D B a a a A PVC 1.0000 0.0050 0.0047 0.0041 1.0138 VCM 0.0047 0.0008 0.0150 0.0010 j0.0023 0.0005 0.0243 (1) Assumed split based on data received for suspension process* (2) Assumed split to be 50% VCM and 50% PVC. UCC 026076 PVC-17 TABLE PV-4 POLYVINYL CHLORIDE NET MATERIAL BALANCE FOR SOLVENT POLYMERIZATION (TONS/TON OF PVC CAPACITY) INPUT Vinyl Chloride Monomer (VCM) Comonomer Initiators Total Input Stream I.D. on Simplified Polymer Flow Diagram Ingredients Other 1 0.93-1.00 2 0.01-0.08 3 0.0009 1.0169 0.0009 OUTPUT PVC Homopolymer and Co-Polymer Waste Solids and Liquids Fugitive Emissions Reactor Vent (3) Stripper or Slurry Tank Vent Monomer Reclaim Vent Condenser Effluent From Dryer Collectors Fines From Silo Collectors Fines From Baggers Collectors Fines From Bulk Loading Collectors Monomer Storage Safety Valve Vents (3) Total Output 4 5 B C D 0 G G G A B PVC 1.0000 (U1)) VCM - 0.0001 0.0003 0.0050 0.0005 0.0031 > o.oo44(2) J 1.0044 VO.0083 J 0.0001 0.0006 0.0134 (1) No information available. (2) Assumed value. (3) Assumed split based on data received for suspension process. ucc 026077 PVC-18 TABLE PV-5 SUMMARY OF U.S. POLYVINYL CHLORIDE PLANTS Company Location Published Capacity, MM Lbs./Yr. Air Products and Chemicals, Calvert City, Ky. Inc. (Plastics Division) Pensacola, Florida American Chemical Corp. (owned by Stauffer Chemical Company) Long Beach, California Borden Inc. Borden Chemical, Division Illiopolis, Illinois Leominster, Mass. Continental Oil Co. Conoco Plastics Division Aberdeen, Miss. Oklahoma City, Okla. Diamond Shamrock Corp. Diamond Shamrock Chemical Co., Subsidiary Plastics Division Delaware City, Del. Deer Park, Texas Ethyl Corporation Industrial Chemicals Div. Baton Rouge, La. The Firestone Tire & Rubber Co., Firecstone Plastics Co. Division Perryville, Maryland Pottstown, Pa. The General Tire & Rubber Co., Chemical/ Plastics Division Ashtabula, Ohio Point Pleasant, W. Va. The B.F. Goodrich Co. B.F. Goodrich Chemical Co., Division Long Beach, Calif. Henry, Illinois Louisville, Kentucky Avon Lake, Ohio Pedricktown, N.J. The Goodyear Tire & Rubber Co., Chemical Division Plaquemine, Louisiana Niagara Falls, N.Y. Great American Chemical Corporation Fitchburg, Mass. 150 50 150 140 180 285 240' 100 270 180 230 270 125 50 140 140 340 140 170 100 100 40 ucc 026078 PVC-19 Company TABLE FV- 5 SUMMARY OP U.S . POLYVINYL CHLORIDE PLANTS (1) (CONTINUED) Location Published Capacity, MM Lbs.Aear Keysor-Century Corp. Saugus, Calif. Monsanto Company, Monsanto Polymers 8c Petrochemicals Company Springfield, Mass. National Starch & Chemical Corporation Meredosla, Illinois Occidental Petroleum Corp . Burlington, N.J. Hooker Chemical Corp., Hicksville, N.Y. Subsidiary Ruco Division Olin Corporation, Assonet, Mass. Thompson Plastics Co. Div Fantasote Company Passaic, N.J. Point Pleasant, W. Va. Roblntech Painesville, Ohio Stauffer Chemical Co. Plastics Division Delaware City, Del. Tenneco Chemicals, Inc. (A major component of Tenneco Inc.), Tenneco Plastics Division Burlington, N.J. Flemlngton, N.J. Union Carbide Corp. Texas City, Texas Chemicals & Plastics Div. South Charleston, W. Va. Uniroyal, Inc., Uniroyal Chemical Division Falnesville, Ohio 35 70 10 180 15 150 60 ` 90 aso 175 165 70 240 160 140 TOTAL CAPACITY 5,400 UCC 026079 PVC-20 IV. Commercial Products PVC resins are compounded into a wider variety of products than most any other plastic. They range from emulsions and caulks to clear films and rigid structural shapes. PVC resins are used to make both flexible and rigid foams with a wide range of density. They have one big advantage over most foams as they are generally rated "self-extinguishing" in fire ratings while other foams need considerable "doctoring". The chemical inertness of PVC makes it an excellent material for pipe and exterior building forms and coatings (on steel and aluminum). It can be made flexible as leather or as rigid as glass. It can be made clear or most any color desired. Compounded PVC resins are converted to end products by several processes. Extrusion is used to produce both rigid extrusions (e.g., pipe and conduit, siding and window sashes) and flexible extrusions (e.g., electrical wire insulation, garden hose, and packaging film). Rigid vinyl sheets are generally produced on calendars which produce more than eight million pounds per year of film and sheet products. Dispersions or plastisols are used for fabric coating (either on knife machines, roller coaters, or casting machines), and in the production of low-cost type of vinyl floor tile in which plastisol is cast on a felt base. Plastisols are also used in rotational molding (e.g., for toys and traffic cones) and in the dipping and hot-spraying of tool handles and appliance parts. The use of compression molding for PVC resins is restricted to the production of phonograph records. Injection molding of rigid PVC has been developed largely in the 1960s and is mostly employed in the production of pipe fittings, and to a much smaller extent in the production of parts for communications equipment, business machines and toys. A complex and still emerging technology in the processing of compounded PVC resins is the blow-molding of containers. UCC 026080 PVC-21 V. Plant Emissions Table PV-6 shows individual plant capacity figures and emission data for most of the major U.S. plants producing PVC. Emissions from these plants are as follows: A. Continuous Air Emission 1. VCM Recovery System Inerts Vent (Source Area D) The VCM recovery system is where all the VCM vapors drawn off the stripper (and at times from the reactor) are compressed and condensed to recover most of the unreacted monomer for recycling to the polymerization reaction. This is a major emission stream for most plants, not because of total stream volume which is low, but because of high concentration of vinyl chloride. It results from the necessity to purge inerts from the monomer recovery system. Emissions can be reduced by condensing under pressure and low tempera ture cooling (10 to -30F). It can be even more effectively reduced by using a vent scrubber or carbon adsorber. The reported vent streams in this category are shown as source area D in Figures PV-1 through PV-4and Tables PV-1 through PV-6. Losses range from 0.0001 to 0.01 lbs. VCM/lb. product. 2. Dryer Stacks and Miscellaneous Solid Handling Vents (Source Area G) The dryer vent is continuous but the amount of VCM emission varies widely from plant to plant. If the stripping of VCM at the strippers is done effectively then the emission at the dryer stack is less. However if the stripping is done poorly over 20% of the total emission can occur here. It is a difficult stream to control with add on devices because the volume of air (13,000 to 25,000 ACFM per 5,000-10,000 pounds per hour of dry PVC product) is large, the concentration of VCM low (less than 0.1%) and the air is at 150F with a high moisture content. These figures are typical for rotary dryers which are used in most suspension type plants. Losses range from 0.0005 to 0.006 lbs. VCM/lb. product. Spray dryer exhaust gas flow is similar to that of a rotary dryer except the stream is generally larger, hotter and more nearly saturated with moisture. Spray dryers are generally used in dispersion plants although a few are also used in suspension plants. After the PVC solids are dried, they are most often transported in the plant via pneumatic conveying systems. The air conveying streams are not laden with moisture and are at ambient temperatures but their volumes are very high and the VCM concentration much lower than in the dryer stream (0-15 PPM VCM). UCC 026081 TABLE FV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE PVC-22 Plant Code Number: A-l Plant Capacity, Million Lbs.Ar.: Process: Suspension 95 Source Area Description Type Of Control Device Control Catalog I.D. No. Emissions Lbs/Lb Prod. Tons Ar. VCM FVC VCM FVC A RR Car Unloading A Barge Unloading A Transfer Pumps, Valves, Etc D&H Reactor Vacuum System (1) B Reactor VentilatingSystem D Recovery System E Slurry Tanks G Dust Collector G Silos Total Loss To Water Systems (2) Reactors Strainers Slurry Tanks Centrifuges (3) (3) .0003 .0006 .0007 .0605 .0008 .0027 .0112 .0055 .001 .0833 14.25 28.5 33.25 2873.75 38.0 128.25 c 532.0 5X10-5 261.25 4.6X10-8 47.5 5.46-5 3956.75 2.37 0.22 2.59 1.85X10-8 1.85X10-8 1.85X10-9 1.5X10-5 8.79X10-J 8.79X10-4 8.79X10-5 0.7125 Notes 1.5X10-5 0.714 (1) Loss very high here. Have Just installed improvements that should reduce VCM emissions by one-third. This would bring it down to about`.04 lbs.Ab. prod, which is still high. This also includes fugitive losses. (2) Loss to water systems so low that they have Insignificant impact on total VCM loss. (3) Standard vacuum, compression and condensing system used to recover VCM for economic reasons. o rcn 52 ooo O CO TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MAHUFACTURE (CONTINUED) Plant Code Number: A-2 Plant Capacity, Million Lbs.Ar.: Process: Suspension 38.4 Source Area Description Type Of Emission Control Device Control Device Catalog I.D.No. Lb s */Lb . Prod. VCM FVC Tons/Yr. VCM FVC A RR Car Unloading A Transfer Pumps, Valves, Etc. D Reactor Vacuum System (1) B Reactor Ventilation System D Recovery System E Slurry Tanks G Dust Collector G Silos Total Loss To Water Systems Reactor Strainers Slurry Tank Centrifuge1 (2) (2) .0003 .0009 .026 .0013 .0027 .0112 .0055 .001 8.76 26.28 759.2 & 327.04 5X10-5 160.6 4.5X10- 29.2 5.5X10-5 1427.88 1.46 0.13 1.59 1.95X10-8 1.95X10-8 1.95X10- 1.53X10-5 Notes (1) This 1b main point of VCM emission. They are looking for improvements to reduce the loss. Could also stand improvements in slurry tank vent losses. Fugitive emissions included here. (2) Standard vacuum, compression and condensing system used to recover VCM for economic reasons. ! PVC-23 oT ' on 3CO TABLE Pff-6 NATIONAL EMISSIONS INVENTORY FOR PTC MANUFACTURE (CONTINUED) Plant Code Number: A-3 Plant Capacity, Million Lbs.Ar.: Process: Suspension 175 Source Area . Description B Upset Losses Avg. on Cent* Basis Di Recovery System Condenser Vent (1 l>2 Recovery System Condenser Vent (1 E Tank Vent Gi Dryer Vent G2 Silo Vents H Fugitive Total * No PVC loss data are given. Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs./Lb. Prod. Tona/Yr. VCM FVC VCM __ FVC .0006 .0075 .0003 .0025 .0035 .0002 .0088 (4) * 52.56 657.0 26.28 219.0 306.6 17.52 770.00 .0234 2040.96 Notes: (1) Major emission control device Is monomer recovery system (vacuum stripper) which was ius+ installed in May 1974. It is not clear if above emission figure is before or after thif device was Installed. (Presumably "after") . (2) Considering installation of gas holder for collection of emissions at Dr and possiblv b and E followed by a scrubber system. Gi and G2 emissions would be reduced with improved vacuum system at Di. F BU (4) Assumed^0% 'vcm** 5^mpyession and condensing system used to recover VCM for economic reasons. PVC-24 ucc 026084 ! TABLE FV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: A-4 Plant Capacity, Million Lbs. Ar.: 120 Process: Suspension Source' Area Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs * /Lb i. Prod. TonsAr. VCM PVC VCM PVC G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector G Dust Collector E Blend Tank Vent E Blend Tank Vent E Blend Tank Vent , * C Slurry Tank Vent 13' Total .00021t1) .00026 .00006 .00018 .00032 .00001 .00017 .00003 .00008 .00010 .00038 .00048 .00004 .00036 .00005 .00001 .00004 .00489 .00026 .00036 .00033 .00021 .00489 .01196*12 *3 .00176 12.6 19.3 0.7 23.4 22.3 299.3 22.3 20.2 12.6 299.3 732.0 15.7 3.7 11.0 10.2 1.8 5.1 5.8 29.6 2.6 2.9 0.4 2.6 16.1 <0 0 Kin) 107.5 Notes or\>j O cgCnD o (1) All losses are confuted from total throughput (120 M/year). (2) No fugitive losses are estimated or even Implied which could explain the low total emission. (3) No VCM recovery system vent losses given, they could be included in this emission loss. TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: A-5 Plant Capacity, Million Lbs.Ar.: 75 Process: Suspension Source Area Description Type Of Emission Control Device Control Device Catalog I.D.No. Emissions Lbs ./Lb. Prod. Tons/yr. VCM PVC VCM PVC G Exhaust From Dust Collector P Centrifuge VCM In Resin D Vent Condenser E Slurry Tank Vent B Reactor Vent E Blow Down Tank Vent B Reactor Cleaning F Slurry Filtration Total (2) (1) .00400 .000003 .00009 .00090 .00600 .00005 .000003 .0000008 .00030 .00006 .010957 .000450 150.0 33.8 225.2 i.9 410.9 3.4 11.9 2.3 17.0 Notes: (1) Standard vacuum( compression and condensing system used to recover VCM for economic reasons. (2) No fugitive losses given and report admits that losses given are only a part of total losses. PVC-26 <=> <Oo0o0>) oO t TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FTC MANUFACTURE (CONTINUED) Plant Code Number: a-6 Plant Capacity, Million Lbs./Vr.j Pr cesa: Suspension 75 Source * Area B B D D E 0 D B B H Description Reactor Safety Valves(3) Reactor Jets Stripper Jets Recovery Condenser Vent Blend Tank Vent Dryer Vents Purification Condenser Vent Reactor Exhaust System Reactor Purge System Fugitive(4) Total Type Of Emission Control Device Control Device Catalog I.D.No. {3) VCD-1&2 * Emissions Lbs./Lb. Prod. Tons/Yr. VCM PVC(1) VCM FVC(l) .0032 .0003 .0015 .0015 .0018 .0144 .0020 .0019 7.45X10-6 .00015 .0091(2) .0091 .02145 .0235 120.0 11.25 56.25 56.25 67.5 75.0 71.25 0.28 5.63 341.3 804.7 540.0 0. 341.3 881.3 PVC-27 Notes (1) Total PTC loss from material balance and known losses Is .0308 lbs./lb. prod, or 1155* tons per year. (2) Considerable improvement is envisioned here when they switch to much larger reactors. Their estimate is about a 40 to 50% total drop in VCM emissions. (3) Extra cooling used to condense VCM vapors beyond normal system. This is an emission control device to control emissions as well as for economic reasons. (4) Assumed 50% VCM, 50% PVC. TABLE FV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: a-7 Plant Capacity, Million Lbs./fr.: Process: Suspension 135 Source Area D E D D Q G G G B H Description Recovery Condenser Vent Blend Tank Vent Blower Reactor Jets Stripper Jets Dryer Discharge (3) Silos Bagging Machine Bulk Loading Safety Valves Fugitive Total Type Of Emission Control Device (4) Control Device Catalog I.D. No. VCD-1&2 Emissions Lbs./Lb . Prod. Tons/fr. VCM PVC VCM FVC .0015(2) .0060 .OO67 .0018 .0009 - - .0040 .0089(5) (1) - - .0063 .00055 .00022 .00034 .0089 101.25 405.0 452.25 121.5 60.75 - -- 270.0 600.75 (1) 425.25 37.125 14.85 22.95 600.75 .0297 .01631 2011.5 1100.925 OtaO> C{>-4) 9C0D Notes: . (1) (2) (3) (4) (5) Biown losses plus fugitive losses from material balance Indicate 0.0389 lbs./lb. pvc prod or a total of 2626 tons of solid loss per year. * Now equipment on order (delivery late 1974) to improve efficiency from 99.536 to 99 9i This will reduce total VCM loss to .0003 at this point. Considerable improvement will result from installation of new type cyclones of 99 Q* efficiency as compared to present 99.556. Equipment is on site and will be installed shortly. <nI rGoO In addition to standard vacuum, compression and condensing system a two-stage low temperature condensing system is used (40F water and 0F freon or glycol). This is an emission on control device as well as an economic device. Assumed 50% VCM, 50% PVC. t 1 J TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PTC MANUFACTURE (CONTINUED) Plant Coda Number: a-8 t1) Plant Capacity, Million X&s./Yr.: 225 Process: Suspension Source Area Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs * A*b . Prod. Tons/Yr. VCM PVC VCM FVC B Safety Relief Devices D Reactor Evacuator E Blending Tanks D Recovery System Vent (3) G Cyclones & Bag Filters - Solid St Liquid Hastes H Fugitive (2) Total VCD-2 .0024 .0043 .0054 .0041 .0027 .0134(4) .0012 .0047 .0141 .0134 .0323 .0334 270.0 483.75 607.5 461.25 303.75 1507.5 135.0 528.75 1586.25 1507.5 3633.75 3757.5 PVC-29 Notes: (1) All plants at location have a standard section covering control devices. Only parts of this section apply to each individual plant. (2) The only indication that fugitive emissions are being reduced is in the standard section on control devices that says an organic vapor detection device is being used to locate VCM leaks. It is stated that it can detect VCM levels below odors detection but does not indicate how sensitive it is. (3) Standard vacuum, compression and condensation system used to recover VCM for economic reasons. 0c rao> f=; 0O CO to (4) Assumed 50% VCM, 50% PVC. i TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED)" Plant Code Number: a-9 Plant Capacity, Million Lbs.ArX75 Process: Suspension Source Area Description B Safety Relief Devices B Reactor Evacuator E Blending Tanks D Recovery System Vent G Cyclones & Bag Filters U Fugitive (2) Total Type Of Control Emission Device Control Catalog Device fi^ I.D.No. (3) VCD-2 Emissions Lb s /Lb Prod. TonsAr. VCM PVC VCM PVC .0012 .0072 .0048 .0003 .0071 . .0077(4) .0001 .0015 .0077 .0283 .0093 104.7 636.4 420.5 30.2 626.8 673.8 2492.4 7.4 131.4 673.8 1 812.6 PVC-3 0 Notes; (1) All plants at location have a standard section covering control devices. Only Darts of this section apply to each individual plant. JF (2) The only indication that 'fugitive emissions are being reduced Is in the standard section on control devices that says an organic vapor detection device 13 being used to locate VCM leaks. It is stated that It can detect VCM'levels below odors detection but does not indicate how sensitive it is. (3) Xn addition to standard vacuum compression and condensing system, low temperature (4) cond nslng is used which makes Assumed 50% VCM, 50% PVC. this an emission control device as well as an economic one. I TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Numbert A-10 Plant Capacity* Million Lbs.Ar.: 120 Process : Suspension Source Area B B E D Q H Description Safety Relief Devices Reactor Evacuators Blend Tank Recovery System Vent Cyclone & Bag Filters Solid & Liquid Losses Fugitive (2) Total Type Of Control Emission Device Control Catalog Pevlce(l) I.D. No. (4) VCD-3 Emissions Lbst/Lb Prod. Tons/Yr. VCM PVC VCM PVC .0016 .0009 .0067 .0053 .0087 .0002 .0013 .0053 .0053 .0275 (3)5),. 0275 .0553 .0350 98.6 412.2 325.9 535.2 12.3 325.4 1650.0 3359.6 55.2 79.7 325.4 1650.0 2110.3 PVC-31 C otoO Notes (1) All plants at location have a standard section covering control devices. Only parts of this section apply to each individual plant. (2) The only indication that fugitive emissions are being reduced is in the standard section on control devices that says an organic vapor detection device is being used to locate VCM leaks. It is stated that it can detect VCM levels below odors detection but does not indicate how sensitive it is. 3) High fugitive emission. !4) Standard vacuum, compression and condensing system used to recover VCM for economic reasons. (5) Assumed 50% VCM, 50% PVC. ! TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number; A-ll Plant Capacity, Million Lbs.Ar.: Pr ceaa; Suspension 80 Source Area B B E D 0 H Description Safety Devices Reactor Evacuations Blend Tanks Recovery Condenser Vent Cyclones & Bag Filters Solid & Liquid Losses Fugitive (2) Total Type of Control Emission Device Control Catalog Device; H I.D. No. (3) Emissions Lbs /Lb * Prod. Tons AT. VCM PVC VCM PVC .0043 .0024 .0012 .0052 .0052 .0090 .0061(4) .0006 .0024 .0090 .0061 164.25 92.0 45.6 197.5 200.2 344.7 233.5 22.3 90.7 344.7 233.5 .0334 .0181 1277.8 691.2 Not 8 ooC>O 2O ro (1) All plants at location have a standard section covering control devices. Only parts of this section apply to each individual plant. (2) The only Indication that fugitive emissions are being reduced is In the standard section on control devices that says an organic vapor detection device is being used to locate VCM leaks. It is stated that it can detect VCM levels below odors detection but does not indicate how sensitive it is. (3) Standard vacuum, compression and condensing system used to recover VCM for economic reasons. (4) Assumed 50% VCM, 50% PVC. i PVC-32 1 TABLE PV-6 RATIONAL EMISSIONS INVENTORY FOR FTC MANUFACTURE (CONTINUED) Plant Code Number: A-1S Plant Capacity, Million Lbs./5fr.: Process: Suspensicm 113 Source * Area Description B Safety Relief Devices B Reactor Evacuators E Blending Tanks D Recovery Condenser Vent (3) G Cyclone & Bag Filters - Solid & Liquid Losses H Fugitive (2) Total Type Of Emission Control Device Control Device Catalog I.D. No. VCD-2 Emissions Lbs./Lb . Prod. Tons/5fr. VCM PVC VCM PVC .0004 .0022 .0060 .0007 .0093 .0046 .0052 (4) .0002 .0012 .0046 .0052 .0284 .0112 23.6 124.8 337.3 41.2 525.6 261.5 294.1 1608.1 11.8 64.8 ^ 261.5 < 294.1 632.2 P V C -33 m0. s d Notes: (1) All plants at location have a standard section covering control devices. Only parts of this section apply to each individual plant. (2) The only Indication that fugitive emissions are being reduced is in the standard section on control devices that says an organic vapor detection device is being used to locate VCM leaks. It is stated .that it can detect VCM levels below odors detection but does not indicate how sensitive it is. (3) Standard vacuum, compression and condensation system used to recover VCM for economic reasons. (4) Assumed 50% VCM, 50% PVC. TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number; A-13^) Plant Capacity, Million Lbs./Yr.: 42 Pr cess; Suspension Source Area D G H Description Recovery System Vent Bag Filters Fugitive Total Type of Emission Control Device Control r*t Catalog I.D. No. Emissions Lbs./Lb . Prod. VCM PVC Tons Ar. VCM PVC .00203 .0002 .0086(2} * .0086 42.9 4.2 181.7 181.7 .01083 .0086 228.8 181.7 * No data are given Tor FVC losses. Fugitive loss noted Is assumed. PVC-34 Notes (1) No emission devices No mention of type. Installed at this plant now but all being considered for future.' (2) Assumed 50% VCM, 50% PVC. TABLE fvt-6 RATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: A-l4 Plant Capacity, Million Lba./Yr.: 130 Process: Suspension Source Area Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs * /Lb Prod. Tons/Yr. VCM PVC VCM PVC NO SATISFACTORY DATA PVC-3S ucc 026095 t TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Cod Number: a-15 f1) Plant Capacity, Million Lbs./fr.t 175 Process: Suspension Source Area Description Type of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs/Lb* Prod. Tons/Yr. VCM PVC VCM PVC D Recovery System Vent (2) G Primary Dust Collector G Primary Dust Collector G Secondary Dust Collector G Secondary Dust Collector G Silo Collectors G Bag Filters G Bag Filters G Bag Filters G Bog Filters G Bag Filters G Bag Filters A Transfer System A Transfer System B Vacuum Jet Steam D Recycle on VCM Recovery System G Conveying Losses - Transfer Losses G Emission from Hood Over Callender - Transfer Losses to Trucks & RR Cars H Building Emissions H Fugitive .001086 .00395 .00528 .000049 .000049 .000025 .000025 .000049 .000049 .002122 .003800 .000035 .000429 .000573 .000429 .000573 .00100 .000213 .000068 .000213 .000049 .000053 .000034 .000018 .000049 .000049 .001135 - .000667(3).000667 .0 .6 .0 *3 4.3 2.2 2.2 .3 4.3 185.7 332.5 3.1 99.3 58.3 37.5 50.1 37.5 50.1 87.5 18.6 5.9 18.6 4.3 4.6 3.0 1.6 4.3 58.3 Total .018320 .004417 1603.1 386.2 Notes: (1) Data are complete and coverage of control devices excellent. Should discuss as exemplary report (2) Lower vacuum used than normal, no data are given for condensing conditions but the low emission indicates that some cooling or chilling is involved. <rO-=J>) c y2=i (3) Assumed 50% VCM, 50% PVC. oO CD CD Ve-DAd TABLE FV-6 NATIONAL EMISSIONS IHVEHTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: A-l6 Plant Capacity, Million Lbs.Ar.: Process: Suspension 4p Source Area B C C E D G H Description Type Of Emission Control Device Reactor Vents Stripper Vents During Evacuation'2 > Stripper VentU) Slurry Storage Vent Recovery System Bag Filters Fugitive Total Control Device Catalog I.D. No. VCD-3 Emissions 03 S /Lb . Prod. VCM FVC Tons/yr. VCM FVC .0056 .0018 NA NA , . .0008U) .0046 .0070 (3) * .0070 112.0 36.0 16.0 92.0 140.0 140.0 .0198 .0070 396.0 140.0 * No data for FVC losses are given. PVC-37 o C> CO ow Notes: (^) This VGM loss is low compared to most recovery system losses. May be due to use of scrubber system. (2) Slurry tank (actually blend tank) is air evacuated continuously to keep concentration of VCH vapors low. (3) Assumed 50% VCM, 501 PVC.` t oc rcoon X O CmD TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number; A-17-1, A-17-2, A-17-3 f1) Plant Capacity, Million Lbp./Yr.; 125 Process; Suspension Source Area Description Type Of Emission Control Device A RR Car Unloading A Storage Vent A Charge Line Filter B Reactor B Reactor Vent & Fouling D Recovery System, Seal Water D Recovery System Tank Vent D Recovery System Drain E Blend Tank Vent & Drain P Cyclones & Bag Filters D Recovery System Vent (2) D . Recovery System Degassing (2) f 3) Total Control Device Catalog I.D. No. VCD-9 Emissions Lb s Aib * Prod. Tons/Yr. VCM PVC VCM PVC .0002 * 12.5 .0001 .0002 6.75 12.5 .00474 296.25 .0042 262.5 .0004 25.0 .0001 6.75 .0001 6.75 .0004 25.0 .00425 265.6 .00066 41.25 .00544 340.0 .02079 1300.9 * pvc data not determined for this composite tabulation. Notes ft This is a composite tabulation of three (3) suspension systems at one plant. These recovery system losses were noted for only one of the suspension systems (A-17-2). The losses for that system (A-17-2) are inordinantly high while the losses for the other two systems (A-17-1 and A-17-3) are low. Normal vacuum, compression and condensation system used for economic reasons. (3) No fugitive losses noted. TABLE FV-6 NATIONAL EMISSIONS INVEMTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: A-l8 ( ^ Plant Capacity, Million Lbs. Ar.: 117 Process: Suspension S urceArea Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs/Lb . Prod. Tons Ar. VCM FVC VCM FVC D&H Monomer Recovery Vent & Fugitive(12)3 G Bag Filters (3) B Reactor Vent E Blend Tank Vent C Stripper F Centrifuge Sampling Total .01407 .01134 .00250 .00350 - - - .03141 .00100 .00353 .00087 .00102 .00048 .00020 .00710 823.1 663.4 146.3 204.8 -- - 0 1837.6 58.5 206.5 50,9 59.7 28.1 11.7 415.4 Notes (1) This is a composite tabulation of two (2) suspension systems at one plant. (2) Fugitive emissions are included with monomer recovery system losses as the material balance for the whole process is made here. (3) High loss here indicates high VCM content of slurry to centrifuge and dryer. PVC-39 ucc 026099 t TABLE PV-6 RATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: a-19 Plant Capacity, Million Lbs./Yr : 82 Process: Suspension Source Area Description Type Of Emission Control Device D&H Monomer Recovery Vent & Fugitivet1) a Bag Filters B Reactor E Blend Tank C Stripper F Centrifuge - Sampling Total Control Device Catalog I.D. No. Emissions Lbs /Lb . Prod. VCM FVC Tons/fr. VCM FVC .03.9 .0080 .0025 .0035 - - -- .0010 .0055 .0015 .0008 .0007 .0002 779.0 345.1 107.8 151.0 - -- mw 43.1 237.2 64.7 34.5 30.2 8.2 .0330 .009? 1382.9 417.9 Notes: fl) Fugitive emissions are Included with monomer recovery system losses as the material balance for the whole process is made here. TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Numbert A-20 Plant Capacity, Million Lbs.Ar.: 223 Process: Suspension Source Area D B B E G P G G G H Description Monomer Recovery Vent Reactor Vent Reactor Effluent, Water Stream Slurry Tank Vent (1) Dryer Vent Centrifuge, Water Stream Bag Filters (2) Bag Filters Bag Filters Fugitive Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lb s ^Lb . Prod. TonsAr. VCM FVC VCM FVC .00119 .00311 .00032 .00681 133*9 -- .. 349.9 .00319(3) 36.0 .00010 766.1 .01317 .00149 - - .00037. 1481.6 .00081(3) 167.6 .00037 -- .00001 .00001 - .00541(4) .00541 608.6 -- 358.9(3) 11.3 91.1(3) 41.6 1.1 1.1 608.6 .03150 .01027 3543.7 1155.3 P V C -41 0C ro 2o Not s: (1) Improved degassing system proposed which should help to reduce VCM loss, a slurry tank vent and also from dryer vent. In fact all downstream VCM emissions from the slurry tank. (2) No VCM emissions are indicated for bag filters and so are probably reflected in fugitive emission* (3) Not a potential air emission, therefore excluded from total. (4) Assumed 50% VCM, 50% PVC. i TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PTC MANUFACTURE (CONTINUED) Plant Code Number: A-21 Plant Capacity, Million Lbs.Ar.: 115 Process: Suspension Source Area A B C D E G P F Description RR Car Unloading Reactor Vent Stripper Vent (4) Monomer Recovery Slurry Vent Dryer Centrifuge Sifter Total1 Type Of Emission Control Device Control Device Catalog I.D. No. VCD-4&10 VCD-4 VCD-1,2&4 VCD-4 Emissions Lbs # /Lb . Prod. Tons/Yr. VCM FVC VCM FVC :SI(2&3) : .0040 .0001 .0005 .0030 - .0010 - .0020 .0035 .0005 .0040 60.0 120.0 235.6 8.8 27.6 180.0 * - 60.0 120.0 210.0 30.0 240.0 .0106 .0110 632.0 660.0 <=> d c-o*n OO ro Notes: (1) VCM emissions have been shown by areas and include fugitive losses. 2) This plant has a gas holder for miscellaneous VCM vapors and contains them extremely well. (3) They are going to a solvent cleaning system which will eliminate normal opening and closing (3-6 batches) of reactor to one or two per year. (4) This loss is due to losses inherent in the evacuation system. TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) PVC-43 Plant Code Number: A-22 Plant Capacity, Million Lbs./Vr.i 108.6 Process: Suspension Source Area A H A B B D H H H C D H 0 G G G G G E G E F G gC G rag G o G^ H Notes: Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs Aib . Prod. Tons/Tr. VCM FVC VCM PVC RR Car Unloading Emission From Storage Building Transfer Pump Reactor Vent Reactor Vacuum System VCM Recovery Condenser Polymerization Building Vents Storage Tank Vent Building Vent Fan Reactor Safety Valve & Rupture Disc Condenser Vent Building Vent Bag Filters Bag Filters Bag Filters Apron Dryers Apron Dryers Bag Filters Slurry Tank Vent(l) Rotary Dryer Slurry Tank (i> Centrifuge Bag House Dryer Bag House Bag House Bag House Fugitive .000080 .000066 .000722 -- * .000200 .012258 .001661 .001252 .000099 .000795 .004302 .000676 - - -- .000784 .000042 .000042 .000009 .000649 .000157 - .001770 .000127 .001610 .000907 .001641 .000062 .000102 - -- .000079 .000039 - .000579 .001282 .000343 .000171 .000090 .000039 .000016 .000520 .005363(21'.005363 4.34 3.58 39.21 10.86 665.76 90.21 68.00 5.38 43.18 233.65 36.66 42.58 2.28 2.28 0.49 96.13 6.90 87.44 49.26 89.13 3.37 2.12 31.45 18.63 4.89 0.87 291.28 Total i (1) These so-called "slurry tanks" are actually blend tanks. .035534 .008362 1929.93 (2) Assumed 50% VCM, 50% PVC. 1 35.25 - 8.53 ' 5.54 4.29 * 69.63 9.29 2.12 28.24 291.28 454.17 TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: A-23 Plant Capacity, Million Lbs.Ar.: 233 Process: Suspension Source Area A D D A D D A E E a a G G G H Description VCM Receiver, Fresh VCM Receiver, Recovered (1) VCM Receiver, Mixed VCM Receiver, Fresh VCM Receiver, Recovered (1) VCM Receiver, Mixed Strainer Blend Tank Blend Tank Bag Filters Resin Silos . Resin Silos Resin Silos Exhaust From Compounding Lines Fugitive Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lb s t /Lb * Prod. TonsAr. VCM PVC VCM PVC .00003 .00005 .00005 .00015 .00007 .00030 .00020 .00044 .00388 ,01399<2) .00002 .00001 .00001 .000015 .01012(4) .02936 # 3.9 * 5.7 6.1 17.1 8.8 35.9 23.7 52.6 1 459.9^. 1659.6(2) 2.7 1.3 0.9 1.8 1200.7 3480.7 Notes ssoB No data are given for FVC losses. (1) New refrigerated condenser system to be Installed this year will reduce these losses about 85#. (2) Ineffective stripping of VCM from latex causes high VCM emission here. Also makes fugitive losses greater. (3) Emission control.procedure section Identical for both plants A-23 and a-24. (4) Assumed 50% VCM, 50% PVC. 1 TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: a-24 Plant Capacity, Million Lbs.Ar.: 220 Process; Suspension Source Area Description Type Of Emission Control Device Control Device Catalog IJD. No. Emissions Lbs./Lb. Prod. Tons/fr. VCM FVC VCM PVC D Recovery System Vents B Reactor Dump Screen C Slurry Tank Vent (3) B Reactor Cleaning Exhauster (1) G Dryer Exhaust (1) G Silos H Fugitive Total .000005 .001022 .002492 .002250 .005388 .000103 .006255(4) .017515 * 0.4 113.9 275.9 245.3 595.7 11.4 6B8.5 1931.1 PVC-45 * No data are given for FVC losses. Notes: (1) Less losses here than sister plant (A-23) perhaps due to higher temperature used to ' eliminate VCM from latex. (2) Emission control procedure section identical for A-23 and A-24. (3) Continuous exhauster on both slurry and blend tanks to prevent VCM buildup In vapor space. (4) Assumed 50% VCM, 50% PVC. TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: a-25 Plant Capacity, Million Lba.Ar.: 120 Process: Suspension Source Area B B D B H E F G G G Description Reactor Fouling Course Material & Lost Batches VCM Recovery Vent (1) Spillage Process Leaks Slurry Tank Vent Centrifuge Dryer Spillage Dryer Exhaust RR Car Spillage Total Type of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs * /Lb . Prod. Tons Ar. VCM PVC VCM PVC .000015 .000022 .013432 .000003 .000650 .000204 .000058 .000029 .003351 .000001 .002657 .004015 - .000650 - -- .000752 .026025 .000767 .002227 0.9 1.3 805.9 0.2 39.0 12.3 3.5 1.8 201.0 0.1 159.4 245.9 39.0 45.1 1561.5 46.0 133.6 .017765 .037093 1066.0 2225.5 Notes: (1) The loss at this point is 75% of total loss noted. Sg 20CT>o I TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: A-26 Plant Capacity, Million Lbs.Ar.: 175 Process: Suspension Source Area B D C E G G H H Description Reactor Vents VCM Recovery System (1) Stripper Vents(2) Slurry Vent Dryer Product Transfer Reactor Room Vents, Fugitive Misc. Fugitive (Matl. Balance) Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs Aib . Prod. Tons/fr. VCM* FVC* VCM* FVC* .0012 .0013 .0048 .0042 .0058 .0025 .0017 .0042 - .0011 .0001 105.1 113.9 420.5 367.9 508.1 219.0 148.9 367.2 -- 96.4 8.8 - .0257 .0012 2250.6 105.2 PVC-47 "Emissions to air only. Notes; (1) We have no information regarding systen used but as emission is very low, system must be considered excellent. (2) Exhauster reducing VCM vapor accumulation in vapor space. 2o r I TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: a-27 Plant Capacity, HillIon Lbs.Ar.: 220 Proceae: Suspension Source Area B D C E G 6 H H Description Reactor Vents VCM Recovery System (1) Stripper Vents (2) Slurry Vents Dryer Product Transfer Reactor Room Vents, Fugitive Hisc. Fugitive (Material Balance) Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs./Lb . Prod. TonsAr. VCM* FVC* VCM* FVC* .00119 .00150 .00154 .00561 .00711 .00158 .00170 .00520 .00115 .00012 !31.9 166.2 170.7 621.7 787.9 m 587.3 127.4 13.3 .02553 .00127 2830.0 140.7 * Emissions to air only. PVC-48 Notes: (1) We have no information considered excellent. on' system used but as the emission is very low, system must be (2) Exhauster reducing VCM vapor accumulation In vapor space. o CO I TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: A-28 Plant Capacity, Million Lbs.A**.: Process: Suspension 23 Source Area B C C G H Description Reactor Vents Stripper Clean Out (2) Stripper Operation (3) Bag Filters Fugitive Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs /Lb Prod. Tons/yr. VCM PVC VCM PVC .0017 .0016 .0199 .0030 .0105 * lg.5 18.4 228.8 3^.5 120.7 421.9 PVC-49 ucc 026109 * No loss data for PVC are given.1 Notes: (1) Overall loss is high due mainly to high loss from stripping operation and fugitive losses. From brief description of process it appears that vacuum and condensing equipment is minimal. (2) Evacuation to keep VCM vapor concentration low. (3) Includes VCM recovery system. TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: b-1 Plant Capacity, Million Lbs.Ar.: 40 Process: Dispersion Source Area B B D B E 0 a H Description Operating Upset Reactor Vent Recovery System Vent (4) Filter Cleaning Blend Tank Vents Dryer Filter Cleaning Dryer Vent(2) Fugitive Losses(3) To Sewer To Landfill To Landfill TOTAL Type Of Emission Control Device Control Catalog I.D. No. . VCD-2 Emissions Lb s /Lb . Prod. Tons Ar. VCM FVC VCM FVC .00300 .00060 .00469 .00020 .00500 .00005 .01774 .01000 .04128 .00320 DO 020(2) .10000 .05290 .10000 .25612 57.8 12.0 93.7 4.0 99.9 1.0 354.8 199.7 822.9 65.7 4.4 2001.7 1055.6 2001.7 5129.1 Notes: (1} These losses seem unusually high. (2) These losses are very high and indicate a poor stripping system or lack of heat In final VCM removal cycle. (3) Fugitive losses somewhat high. (*) Along with normal vacuum and compression system, a low temperature Brine cooling system is used to keep emission at this point low. PVC-50 orcon O o o 1 TABLE FV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: B-2 Plant Capacity, Million Lbs./iTr.: 7.7 Process: Dispersion Source Area B B E Description Reactor Blowdown Reactor Evacuation Hold Tank Displacement TOTAL Type Of Emission Control Device Control Device Catalog I.D. No. , Emissions Lbs /Lb Prod. Tons/fr. VCM PVC VCM PVC .00205 .00068 .00011 .00284 * -- -- 7.9 2.6 0.4 10.9 * No data on product loss are given. Notes; (l) Material balance closed without any report of fugitive emissions. (2) Total emissions extremely low but all products are sold as liquid latlces so no drying is Involved which may account for such low emissions. PVC-51 oC CP O t J PVC-52 TABLE FV-6 RATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Humbert b-3 Plant Capacity, Million Lba./Vr.t 27 Process: Dispersion Source Area B C E D a H Description Reactor Vent Stripper Vent Slurry Storage Vent (4) Recovery System Vent Bag Filters Fugitive TOTAL Type Of Emission Control Device Control Device Catalog I.D.No. VCD-3 Emissions Lbs/Lb Prod. TonB/ifr. VCM FVC VCM FVC .0056(1) .0018 .0015 .0008^ .0350(2) .0116f3) .0563 * 75.6 24.3 20.3 10.8 472.5 1^6.6 760.1 No data are given for FVC losses. Notes !1) This figure does not agree with #/tlr figures even allowing for hours in operation. 2) Loss of VCM through bag filters Is extremely high. Indicating poor stripping of VCM In stripper. (3) Fugitive emission somewhat high and no mention is made of how calculated. (4) Continuous air evacuation from blend tank (here called slurry tank) to keep VCM vapor concentration from building up. 2o8 ro 1 TABLE FV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: B-4 .. Plant Capacity, Million Lbs./Vr.: 40 I1) Process: Dispersion1 * 3 Source Area D&H B C G G G Description Recovery System and Fugitive Reactor Vent Slurry Tank Vent (3) Bag Filter From Dryer Micropulveriser Bag Filters-Silos-Shipping Sampling TOTAL Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lb s /Lb 4. Prod. Tons/fr. VCM FVC VCM FVC .0246(2) .0025 .0002 .0094 -- -- .0367 -- .0050 .0195 .0018 .0050 .0018 .0026 .0357 492.0 50.0 4.0 188.0 -- ---- -- 734.0 -- 100.0 390.0 36.0 100.0 36.0 52.0 714.0 a n< ULJl Notes; (1) Based on 350 Day/fr. 2) Based on a material balance. While heat and vacuum are used in this recovery system the loss is very high, perhaps refrigerated cooling would help. (3) Change over losses only. ucc 026113 i oc tcon 0 -a TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: B-5 Plant Capacity, Million Lbs.Ar.: u Process: Dispersion Source Area A A A B D B C E E a B Description Tank Car Unloading VCM Storage Vent Charge Filter Reactor Vent and Waste Seal Water Accumulated Vapor Latex Transfer Screen(4) Blow and Blend Tanks Blend Tank Heel Bag House Degassing Jet Kisc. Spillage, Waste, Etc. TOTAL1 Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs./Lb . Prod. Tons/fr. VCM PVC VCM PVC .0003 .0001 .0003 .0060 .0005 .0001 .0574 .0039 -- .0536 .0395 -- .1610(1) -- -- .0129 -- -- .0753 .0001 .0026 .0008 -- .0222 1.4 0.7 1.4 32.q 2.8 0.7 315.7 21.8 294.7 217.5 -- .1137(2) 889.6 . -- __ 69.5 __ 4l4.0 0.7 14.0 5.6 <n Ol 122.0 625.8 Notes; (1) This is an abnormally high VCM loss. (21 Very high PVC loss. (3) Combining the two losses Indicates that about one-quarter (25jfi+) of the initially charged VCM is loss to. atmosphere and solid waste. Although this Is a small /i.v is. hard to believe such high losses. (4) Evidently there is no VCM recovery system used. i TABLE PV-6 NATIONAL EMISSIONS IHVEHTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: B-6 Plant Capacity, Million Lbs.Ar.: 3.5 Process: Dispersion Source Area A A A B D C E G B Description Tank Car Unloading VCM Storage Charge Filter Reactor Seal Water Latex Screen and Blew Tank Blend Tank Bag House Reactor Degassing Jet Solid and Liquid Wastes TOTAL Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs /Lb Prod. Tons/Yr. VCM FVC VCM FVC .0003 .0001 .0003 .0066 .0007 .0914 .0042 .0871 .0716 -- .2623 0m mm -- -- .0238 -- .0001 .0885 .0011 -- .0287 .1422 0.5 0.3 0.5 11.4 1.2 158.7 7.3 151.1 124.3 -- 455.3 -- -- 41.2 -- 0.3 153.5 2.0 -- 49.8 246.8 PVC-55 Notes: This plant is the same as B-5 only this operation is a co-polymer dispersion rather than a homo-polymer dispersion. Losses are abnormally high even for a small operation. The emission figures indicate that close to one million pounds of VCM is loss to the air to produce three and a half million pounds of FVC. Same notes apply as B-5 TABLE FV-6 NATIONAL EMISSIONS IHVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: b-7 Plant Capacity, Million Lba.Ar.; 24 Proceas: Dispersion <i) Source Area Description Type Of Emission Control Device Control Catalog I.D. No. Emissions Lbs*/tb Prod. TonsAt . VCM PVC VCM PVC A Storage Tank Vent D Scrubber Vent H Fugitive C Flash Pot Vents (2) C Dryer Exhaust Total VCD-3 .0007 .0021 .0009 .0112 .0008 .0157 * 8.8 26.3 10.8 134.9 io.i 190.9 * No product losses reported. Notes (1) This is a unique product and can be considered a dispersion process. (2) Atmospheric vent to stack. PVC-56 ucc 026116 t TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: B-a Plant Capacity, Million Lbs. Ar.: 26 Process: Dispersion Source Area B C C E D G H Description Reactor Vent Stripper Clean Out Stripper Operation Slurry Vent Recovery System Bag Filters Fugitive (4) (5) Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs *Aib Prod. Tons/Yr. VCM PVC VCM PVC .0074 0035m .loeiW .0024 .o8 ,0313(2) .0127 * 96.2 45.5 1379.3 31.2 10.4 406.9 165.1 .1642(3) 2134.6 ' * No data for PVC losses are given. PVC-57 Notes (1) Very high VCM loss (see E-2). (2) Higher loss than most plants. (3) Hard to believe that l/6th of total vinyl chloride is emission to atmosphere. (4) Evacuation to keep VCM vapor concentration low. 5) No VCM recovery. Just vacuum Jet steam evacuation. aro\>> O -* O i TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: B-9 Plant Capacity, Million Lbs.Ar.: 15 Process; Dispersion Source Area Description Type Of Emission Control Device Control Catalog I.D. No. Emissions LbS /Lb Prod. Tons Ar. VCM PVC VCM PVC H Fugitive (1) 0436 * 327.1 Total 0436 327.1 * No solid PVC waste data are given. Notes; (1) All emissions are considered fugitive . Indicated figure (0.0436) obtained from ov rail material balance (4.1g VCM emission: 4.1/94.0 .0436 lbs. VCM emission per pound of product produced). Only latlces made no drying systems Involved. PVC-58 O c~ co O to 00 I TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: B-10 ^ Plant Capacity, Million Lbs. Ar.: Process: Dispersion 15 Source Area Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs./Lb. Prod.(^) Tons/fr, VCM* FVC* VCM* FVC* C Stripper Vents G - Plastic System Vent B Reactor Room Vents H Mlsc. Fugitive (Material Balance) Total .02314 .00030 .00220 .00220 .02784 (3) 173.6 2.2 16.5 16.5 208.7 (3) * Air emissions only.1 Notes 1) This unit makes latices only. 2) Product averages 83$.FVC,figures based on total pounds of product. 3) No FVC losses to atmosphere. PVC-59 o r- 05 O -* O <0 TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: C-l Plant Capacity, Million Lbs./Yr.; 32 Process: Bulk Source Area B B D G H H Description Safety & Relief Valvest1) Reactor Vents Recovery System Vent (2) Bag Filters Scrap & Haste Fugitive Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs s flSty Prod. TonsAr. VCM FVC VCM PVC .002784 mm .OO7865 - .002000 .002784 .000716 .006446 .003973(3). 003973 .017338 .013203 45.1 127.5 32.4 11.6 64.4 281.0 45.1 103.6 64.4 213.1 PVC-60 Notes: (1) No values given, assumed to be negligible. (2) Emission high considering they used refrigerated cooling for the vent condenser. However, no conditions are given. (3) Assumed 50% VCM, 50% PVC. TABLE FV-6 NATIONAL EMISSIONS INVENTORY FOR PVC MANUFACTURE (CONTINUED) Plant Code Number: C-2 Plant Capacity* Million Lbs.Ar.: 1Q5 Process: Bulk Source Area D D D G B B Description Recovery System Pump Ventt1) Recovery System Tank Vent Recovery System Pump Seal Hater Bag Filters Reactor Vents Reactor Cleanings Spillage & Scrap Fugitive Total Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs /Lb i. Prod. Tons/fr. VCM PVC VCM PVC .01502 .00184 - .00029 - .00018 .00104 < - .01168 - .00083 .00823(2) .00823 .02660 .02074 788.4 96.4 15.3 9.6 54.8 - 431.9 1396.4 613.2 43.8 431.9 1088.9 on<n1s\ Notes (l)Recovery system has high emission losses. Improvement In condensing and degassing system ' . might help and is proposed for near future. (2)Assumed 50% VCM, 50% PVC. TABLE Pff-6 NATIONAL EMISSIONS INVENTORY FOR PTC MANUFACTURE (CONTINUED) Plant Code Number: c-3 Plant Capacity, Million Lbs./fr.: 163 Pr cess: Bulk Source Area D A D A B D B 0 0 G G G G G H B Description Type Of Emission Control Device Recovery System Vent Storage Vent Recovery System - Caustic Scrubber Transfer Filter First Stage Reactor Vent Transfer Filter Vacuum System on Reactors Bag Filters Before Screening Bag Filters to Silos Bag Filters to Screen Powder Blender Silos Bagging Hopper RR Car Loading Fugitive Emergency Venting Control Device Catalog I.D. No. VCD-2 Total Emissions Lbs,/Lb. Prod. Tons/fr. VCM PVC VCM FVC .001564 .000068 .000052 .000016 .000008 .000026 .000104 .001669 .001251 .002034 .000991 .000417 .001043 .001043 .000417 .000010 .000209 .000005 .000502 .000005 .000104 .002529(3 .002529 .000443 131.4 U 1.3 0.7 2.2 l40.2 105.1 83.2 35.0 87.6 0.9 0.4 0.4 212.4 37.2 8.8 170.8 87.6 35.0 47*i lie * 212.4 * .010097 .006942 848.1 584.7 PVC-62 ucc 026122 Not St (1) This plant seems to be an exemplary one with excellent emission controls. (2) Assumed 50% VCM, 501 PVC. t TABLE PV-6 NATIONAL EMISSIONS INVENTORY FOR FVC MANUFACTURE (CONTINUED) Plant Code Number: D-l Plant Capacity, Million Lbs.Ar.: 24 Process: Solvent Sourc Area Description Type Of Emission Control Device Control Device Catalog I.D. No. Emissions Lbs a Alb a Prod. TonB/fr. VCM FVC VCM FVC . TM2ro oO A D F A B C C G G G - G D D D D D D D D D D D D D H Notes: Solution Storage VCM Vent Scrubber Centrifuge Solid Feed Tank Precipitation Tank Slurry Tank (2) Slurry Tank Drying Stages Drying Stages Drying Stages Vacuum Transfer Bin Storage Crude Solvent Storage Crude Solvent Storage Crude Solvent Storage Extractor VCD-3 .000001 .000074 .000014 .000028 .001130 .000282 .000212 .006532 - .001765 - - .001388 .000245 .000011 - g g(U 3 CwO w 3 0.9 0.2 0.3 13.6 3.4 2.5 78.4 21.2 -- - 16.7 2.9 0.1 - - Extract Storage Vinyl Acetate Still Vinyl Acetate Storage Solvent Still Solvent Storage Aldehyde Column Non-Solvent Still Non-Solvent Storage Fugitive - .000706 .000035 .000060 - .000056 - - .000247 n* 0 - 8.5 0.4 0.7 0.7 - 3.0 Total .012786 153.5 (1) Low emissions but there Is no other solvent process to compare with it to indicate If this is normal for this type process. (2) Atmospheric v nts to keep tanks at atmospheric pressure. 1 PVC-64 Particulate PVC emissions ar also associated with these vent streams. However, with cyclones and bag filters the particulate emissions are relatively small in amount (approximately 0.004 lbs./lb. of product). 3. Centrifuge Vent (Source Area F) In many cases there is a centrifuge vent associated with the suspension process. The magnitude of the VCM emission in this vent depends on the efficiency of upstream stripping. Reported values range between 0.00001 and 0.004 lbs. of VCM/lb. of PVC product. 4. Blend Tank (Source Area E) The blend tank emissions vary widely from plant to plant and depend markedly on the efficiency of the stripping operation. The volume is very low and it can be tied into the stripping system in order to eliminate any direct emission to the outside air. Blend tank emissions are only associated with the suspension and dispersion type processes and in these plants the reported VCM losses vary between 0.0001 and 0.007.lbs./lb. of PVC product. B. Intermittent Air Emissions 1. Unloading and Charging Facilities (Source Area A) There is a certain amount of VCM emission at virtually all unloading facilities. Most plants unload under pressure and most vapors are kept enclosed, but there is always some emission plus losses at pumps, valves, meters, etc. The same is true for weigh tanks, meters and pumps used to charge reactors. None of these emissions are controlled other than using good practices consistent with handling of a toxic liquified gas. Reported VCM losses from these sources range from 0.0004 - 0.001 lbs./lb. of PVC product. 2. Reactors (Source Area B) There are several possible emission streams from the reactors. During operation, if a run-away reaction occurs, it is generally stopped by releasing the pressure and venting to stacks (one company uses a gas holder). This vent contains a high concentration of VCM but only lasts for 5 to 15 minutes and occurs infrequently. Several companies are working on (may have it worked out by now) a "short stopping reaction" that would mak "blow down" unnecessary. UCC 026124 PVC-65 A more frequent reactor emission occurs when the vessel is purged and during cleaning. Normally after the polymerization reaction is completed and the batch is removed, VCM vapors are pulled from the reactors by a vacuum system and a new charge is added. However, the reactors must be cleaned periodically (every two to six batches). This means each reactor is opened every one to three days for about three hours for cleaning. This causes emissions which are normally kept down by pulling a vacuum on the reactor and compressing and condensing the removed vapors. During the actual cleaning operation, a substantial air stream is blown through the vessel to help protect the worker(s) in the reactor from VCM exposure. The amount of VCM in the vented air stream is very low (5 to 50 ppm) and would present the same problems of emission control as do the dryer and conveying air systems. New improved methods of cleaning reactors such as water jet or solvent cleaning systems greatly reduce these emissions or a water purge can be used to push the VCM remaining after the reaction is over to the recovery system. Total reported VCM emissions from the reactors normally varies between 0.001-0.01 lbs./lb. of PVC product, with the lowest values (0.001-0.003 lbs./lb. associated with the bulk and solvent polymerization processes. If no equipment is provided to recover VCM from the reactor vent the VCM emissions can be as high as 0.04-0.08 lbs./lb. of PVC product. 3. Safety Valves (Included in Source Area B) Occasionally a run-away condition in the reactor can cause the relief valves to open resulting in VCM emissions. Most of the surveyed plants did not report emissions from this source. However, the few plants that did report these losses showed VCM emission figures of 0.0004-0.004 lbs./lb. of PVC product. Since these emissions are for a short period on a very infrequent basis they represent a rather large instantaneous rate. 4. Strippers (Source Area G) The emissions from a stripper are generally completely contained in the overall vacuum, compression, condensation cycle of the VCM recovery system and present no particular problem. However in some plants the stripper is opened to the atmosphere following the vacuum step in order to repressure the vessel and dump the batch to the blend tank. This can result in some VCM emission. In plants employing a monomer recovery system the reported VCM emissions associated with the stripping operation vary between zero and 0.005 lbs./lb. of PVC. If no recovery UCC 026125 PVC-66 system is used these losses can be as high as 0.1 lbs./lb. of PVC. All but one of the few plants that do not have monomer recovery systems are small capacity units (3-11 million PPY PVC). C. Fugitive Emissions It has been assumed that "Fugitive Emissions" cover all air emissions that are not diverted to a simple vent or stack from the equipment itself. They are caused by leaks at pumps, flanges, filters, strainers, seals, etc., and can be reduced greatly by "good housekeeping". It would be possible to eliminate pump packing or seal leakage by the use of "canned pumps" at some expense in old plants but with less expense in new units. The principal problem with "fugitive emissions" is to keep them low at all times. These emissions can be reasonably under control one minute and suddenly increase greatly. Only good maintenance, with the accent on preventive maintenance, can keep fugitive emissions at a reasonable low level. Table PV-7 lists all the reported fugitive VCM emissions for the various PVC plants. The only truly meaningful "fugitive emission" is one that is arrived at from a material balance after accounting for all known emissions and discharges. It is difficult to be certain that all wastes (solid, liquid and dissolved) have been included in the overall material balance. If some of these losses are omitted, the reported fugitive air emissions are high. It is also difficult to determine the exact composition of these air emissions. In most of the survey reports these losses are shown as VCM. Based upon the "snow field" appearance around the plants undoubtedly some of these emissions are particulate PVC. For this study an arbitrary assumption has been made that material balance losses are 50% VCM and 50% PVC waste. This was assumed by the producers of Plants A-6 through A-13 and considered reasonable by several other manufacturers. While the reported fugitive emissions (VCM) for the individual plants vary over a wide range. Table PV-7 shows that the average VCM fugitive emission for the suspension, dispersion and bulk processes are similar (0.005-0.01 lbs./ lb. of PVC). As might be expected, fugitive emissions for the solvent process appear to be much lower (0.00025 lbs./lb. of PVC). UCC 026126 TABLE FV-7 SUMMARY OP FUGITIVE EMISSIONS Plant Method Determined Suspension Process A-l A-2 A-3 A-4 A-5 A-6 A-7 A-o A-9 A-10 A-ll A-12 A-13 A-l4 A-15 A-16 A-17 A-l8 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-2 8 Quantity not specified separately Quantity not specified separately Material balance No indicated fugitive loss, but there is material balance No fugitive losses reported - no material balance By difference - assumed 5056 VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. By difference - assumed 50% VCM, 50% PVC, By Mfgr. No emission data given Close check on all emissions Close check on all emissions No specific value given Quantity not specified separately Quantity not specified separately Unidentified losses from material balance Quantity not specified separately Fugitive emissions are "guesstimate" Fugitive by material balance Fugitive by material balance 0 _ Process leaks (method not given) Material balance r*O Material balance vj Material balance Subtotal Wt . Average Note: (1) Assumed to be 50% VCM and 50% PVC. VCM Emissions Lb/Lb of Prod. Tons/Yr mm - 0.0088d> -- 0.0091 0.0089 0.0134 0.0077 0.0275 0.0061 0.0052 0.0086 0.0018 0.0070 (!) _ 0.0054 (!) -- 0.0083 0.0101 O.OO63 0.0006 0.0059 0.0069 0.0105 0.0081 - 770.0 -- 341.3 600.7 1,507.5 673.8 1,650.0 233.5 294.1 181.7 157.6 i4o.o * 608.6 450.4 1,200.7 688.5 39.0 516.1 775.7 120.7 10,949.9 TABLE PV-7 SUMMARY OF FUGITIVE EMISSIONS (CONTINUED) Plant Method Determined Dispersion Process VCM Emissions Lb/Lbs of Prod Tons/Yr PVC-68 ucc 026128 B-l B-2 B-3 B-4 B-5 B-6 B-7 B-8 B~9 B-10 Material balance None reported - produce liquid latex only Method not specified Quantity not specified separately Not specified Not specified Unusual product and process Material balance All emissions considered fugitive - no effective control device Material balance, manufacture latices only Subtotal Wt. Average Bulk Process C-l Material balance C-2 Material balance C-3 Material balance Solvent Process Subtotal Wt. Average D-l Material balance Total VCM Emissions . Wt. Average Emissions1 ' 0.0100 0.0116 199.7 - 0.0009 0.0127 0.0436 0.0022 0.0119 0.0047(1) 0.0082(1) 0.0025(1) 0.0047 10.8 165.1 327.1 16.5 875.8 76.0 431.9 212.4 720.3 0.00025 0.0079 3.1 12,549.1 Notes: (1) All fugitive emissions have been considered 50% VCM and 50% PVC waste. (2) For all plants listing fugitive emissions. PVC-69 Total reported air emissions for the various PVC plants vary over a wide range. Part of this variation can be explained by the differences in processing schemes and the amount of emission control equipment employed. However, there are many apparent inconsistencies in the data. These are possibly caused by not including all sources of emission in the survey reports and also distributing material balance losses to the incorrect source. It is usually difficult to ascertain average emission rates for batch type processes especially if there are many vent streams involved and some of these represent large volume flow rates with variable low concentration emissions. Table PV-8 and Figure PV-5 show the distribution of reported total VCM emissions in the various suspension type PVC plants. Table PV-9 and Figure PV-6 show the same information for the dispersion type plants. The statistical data shown in these tables and curves is completely random and merely indicates the wide variations from plant to plant at this time. Since we are not at all certain that all emissions have been reported and we know that some plants have admittedly only reported a part of their emissions, we cannot even obtain a reliable average or mean. D. Solid and Liquid Waste These waste products arise from such operations as vessel cleaning, screening and spillage. The solid material is disposed of via landfill or contract haulage. These losses normally are between 0.001 to 0.03 lbs. of PVC per lb. of PVC product with the associated VCM losses about one-tenth of these values. E. Waste Water Process waste water arises from sources such as centrifuging and VCM stripping. Only a few plants reported information regarding waste water. The VCM emissions associated with this water reject range from 0.00001 to 0.001 lbs./lb. PVC. UCC 026129 * P V C -70 ucc 026130 TABLE PV-8 STATISTICAL EVALUATION OF PVC MFGR'S EMISSIONS FOR SUSPENSION PLANTS Code No. Total VCM Emission Rank No. Rank No. Code No. Total VCM Emission A-l A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 .0833 .0489 .0234 .01196 .01096 .02145 .0297 .0323 .0283 .0553 .0334 .0284 .01083 -- .01832 .0198 .02079 .03141 .0330 .03150 .0106 .03553 .02936 .01752 .01777 .0257 .02553 .0367 27 25 11 4 3 10 17 20 14 26 22 15 2 ---- 7 8 9 18 21 19 1 23 16 5 6 13 12 24 1 A-21 2 A-l 3 3 A-5 4 A-4 5 A-24 6 A-25 7 A-15 8 A-16 9 A-17 10 A-6 11 A-3 12 A-27 13 A-2 6 -- -- 14 A-9 15 A-12 16 A-23 17 A-7 18 A-18 19 A-20 20 A-8 21 A-19 22 A-ll 23 A-22 24 A-28 25 A-2 26 A-10 27 A-l .0106 .01083 .01096 .01196 .01752 .01777 .01832 .0198 .02079 .02145 .0234 .02553 .0257 -- .0283 .0284 .02936 .0297 .03141 .03150 .0323 .0330 .0334 .03553 .0367 .0489 .0553 .0833 Notes: .77173 (1) X2 - VCM emissions squared; used to calculate t variance and standard deviation. (2) Percentile used to space data correctly on Probability of Occurrence Curve. ,<1> X2 .00011236 .00011729 .00012012 .00014304 .00030695 .00031577 .00033562 .00039204 .00043222 .00046010 .00054756 .00065178 .00066049 -- .00080089 .00080656 .00086201 .00088209 .00098659 .00099225 .00104329 .00108900 .00111556 .00126238 .00134689 .00239121 .00305809 .00693889 .02817105 Mean Variance Std. Dev Percentile (21 3.57 7.14 10.71 14.29 17.86 21.43 25.00 28.57 32.14 35.71 39.29 42.86 46.43 -- 50.00 53.57 57.14 60.71 64.29 67.86 71.43 75.00 78.57 82.14 85.71 89.29 92.86 96.43 0.02858 0.00023512 0.01533 TABLE PV-9 STATISTICAL EVALUATION OF PVC MFGR'S EMISSIONS FOR DISPERSION TYPE PLANTS Code No. B-l B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 8-iO Total Emissions 0.04128 0.00284 0.0563 0.0367 0.1610 0.2623 0.0157 0.1642 0.0436 0.02784 Rank No. 5 1 7 4 8 10 2 9 6 3 Rank NO. 1 2 3 4 5 6 7 8 9 10 Code No. B-2 B-7 B-10 B-4 B-l B-9 B-3 B-5 B-8 B-6 Total Emissions 0.00284 0.0157 0.02784 0.0367 0.04128 0.0436 0.0563 0.1610 0.1642 0.2623 0.81176 X2 .00000807 .00024649 .00077507 .00134689 .00170404 .00190096 .00316969 .02592100 .02696164 .06880129 .13083513 Percen tile 9.091 18.182 27.273 36.364 45.455 54.545 63.636 72.727 81.818 90.909 Mean * 0.08118 Variance * 0.00721552 Std. Dev. 0.0849 Note: If we eliminate B-5, 6 and 8 because of abnormally high values, the statistical numbers are: Mean Variance Std. Dev 0.03163 0.00035655 0.01888 P V C -72 ucc 026132 i PVC-73 o3 V0 a_ Sllx*' IM XN30H3d 'SN0ISSIW3 WDA TYXOl UCC 026133 PVC-74 VI. National Emission Inventory Based upon the emissions shown in Table PV-6, total approximate VCM air emissions from the surveyed PVC manufacturing plants (approximately 4.0 billion Lbs/Yr PVC capacity) are as follows: Process VCM Emissions______ T/T of PVC T7YR Suspension Dispersion Bulk Solvent 0.0280 0.0625 0.0166 0.0128 0.0288 48/599.6 6,534.1 2,525.5 153.5 " 57,812.7 a1 i7 Based on an estimated 4.9 billion Lbs/Yr PVC production rate in the U.S. during 1974, the total VCM emissions from PVC manufacturer are estimated to be approximately 70,000 Tons/Yr. It should be noted that most PVC plants are run at near maximum capacity throughout the year which tends to stabilize emissions. However, because of higher cooling water and air temperatures during the summer months, VCM emissions are somewhat higher at that time of the year. } vN 0 ? > 3 v > / ^ \J UN ucc 028134 PVC-75 VII. Industry Growth Potential The growth of polyvinyl chloride has been fairly steady over the past three decades. The main process used was the dispersion (emulsion) method until the 1950's when the suspension process became predominant. The solvent process has been in existence for a long time (started in the 1930's) but is currently used by only one company so it is unlikely to expand much. The newest commercial process is the bulk process and it will probably expand far more than the suspension process if it proves to be more economic (as claimed by its licensor) and if VCM emissions can be more easily controlled. Figure PV-7 indicates the growth rate of PVC (all processes) from 1962 to date (3) (1973 last production figure(4) and projects future growth to 1985. As noted on the figure, the growth rate has been 11.8% from 1962 through 1973. A diminished growth rate of 4.9% is projected to 1985. There are several factors that lead one to believe the growth of PVC will slow down significantly. One is the "energy crisis" which could limit the raw material availability, another is the drastic slow down in domestic construction, and the third is the discovery of the carcinogenic nature of vinyl chloride monomer. This last factor has stopped its use as a container material for liquor, food stuffs, etc. It probably has curtailed its use (film form) as a food wrap and could well injure its saleability in other areas. Another factor that is impossible to evaluate at this writing is the future manufacture of PVC with the new OSHA Standard (January 1, 1975). No company would build a new plant if they thought they could not meet the OSHA Standard and most now feel they could not. Figure PV-8 shows the location of existing PVC manufacturing plants. UCC 026135 SEM I-LO G ARITHM IC 359-51 FVC-7 7 ucc 026137 i Jf ca/< */ Figure PV-8 i Location of FVC Manufacturing Plants PVC-78 VIII. Emission Control Devices Any device used to reduce emissions significantly and is not used for any other reasons (primarily economic) is considered an Emission Control Device. In other words, it can not be profitable or it would be considered a necessary adjunct to the process. In the case of the commercial production of polyvinyl chloride resin there are a remarkably few devices that can be considered truly Emission Control Devices under this definition. However, there are some devices that are used for economic reasons that can be made far more effective than the economics of the process would dictate and such refinements could properly be called Emission Control Devices. This is because the producer is primarily trying to reduce the emission of VCM to a minimum (1 ppm in the working environment). In addition to devices, there are a number of procedures (real and possible) that are in their entirety an Emission Control Device even though it is a process procedure rather than a specific piece of equipment. In fact in the case of reducing VCM emission to a minimal value, these procedures are more important than the usual control devices. We will first list equipment and then procedures including known and used methods as well as projected devices and procedures. A.1 Control Devices VCD-1 - Improved Stripping The stripping of VCM from the latex in the suspension and dispersion processes is the most important proce dure in respect to all subsequent downstream emissions. Whatever VCM is not removed here will, in all probability, wind up as an air emission. Most plants have a vacuum system and then compress and condense the VCM vapors to make a substantial recovery of unreacted VCM. Ideally the vacuum pulled should equal the vapor pressure of the water at the temperature used for the polymerization. This would normally be about 25" vacuum (5n Hg absolute pressure) at 135F. Actual operating pressure is slightly higher in order to minimize foaming. The difference between using a vacuum of 25" Hg vs. 15" Hg vacuum means a reduction of VCM of about 0.0028 lbs VCM/lb product downstream from the stripper. This is with normal cooling water of about 80F. This does not necessarily reduce the total VCM emissions to the air unless adequate cooling and compression or absorption is used to collect the VCM from this vacuum system. UCC 026138 PVC-79 The vapors from the vacuum pump are compressed to about 75 psig, and condensed (85F or lower) before being vented. This type of high vacuum (>20" vac.) system is employed by plants A-15, A-18, A-19 and A-22. Probably other plants, which provided insuf ficient details of their vacuum system, also use this type of low pressure evacuation. A system suitable for a 200 million pound per year plant, capable of pulling 25" vacuum and compressing to 75 psig can be bought for about $200,000 to $225,000. Installed cost with necessary condenser would be about $750,000. (This is about twice the amount spent for the average system normally used up to now which pull 10" to 15" Hg vacuum.) Power requirement for the low pressure vacuum pump and compressor would be 80 KWH/hr. Approximately 35 GPM of cooling water is required for the condenser. VCD-2 - Refrigeration for Vacuum Recovery System In order to increase VCM recovery from the vacuum system some manufacturers (A-6, A-22 and C-3) copl the net vent streams to -15 to -30F. VCM emission loss (at 25" vac.) without refrigeration would be 0.005 lbs. of VCM/lb. PVC. Cooling the vent to -30F recovers approximately 80% of this material. For a 200 million pounds per year PVC plant a 5 ton refrigera tion unit would be required. This would cost about $70,000 (installed). Power requirements for this unit would be about 15 KWH/hr. VCD-3 - VCM Recovery System Vent Scrubber Another effective way to minimize emissions from the VCM recovery system is to pass the compressed vent gases (inerts and VCM vapors) through a scrubber using a liquid having good solvency for VCM and that can be separated from the VCM. This is done at several plants (A-16, A-28, B-3, B-7 and D-l) with resulting low emission losses from this source, see Table PV-10. For a 200 million pounds per year plant, typical feed to the scrubber would be about 115 lbs./hr. of VCM. Assuming compression and water cooling is used ahead of the scrubber for VCM recovery, the scrubber feed will be available at 75 psig and 85F and contain a maximum of 70 mol.% VCM (on an instantaneous basis, average composition 10% or less). A 20 ft. by 12 inch diameter packed tower should be able to obtain 96% recovery of VCM from this vent stream. Based on an average emission UCC 026139 PVC-80 rate of 0.005 lbs. of VCM/lb. PVC product for a plant without a scrubber approximately one million pounds of VCM will be recovered (at 10$/lb. equivalent to $100,000 per year). The installed investment cost for the scrubber-stripper system and associated pumps and heat exchangers would be approximately $125,000. Utility requirements for the model plant size scrubber would be 5 KWH/hr., 500 lbs./hr. of 400-600 psig steam and 40 GPM of cooling water. VCD-4 - Gas Holder Only one plant is using a gas holder at this time (A-21) and it is interesting to note that it has the lowest total VCM emission of any of the plants where the data can be considered reasonably complete (0.0106 lbs. of VCM/lb. of PVC product). This particular plant vents relief valves and rupture disks from compressors, reactors, strippers, etc.; reactor purge lines, miscell aneous vents from weigh tanks, storage tanks, pumps, condensers, knockout pots, etc.; vacuum pump discharge from stripping tank, and manual reactor vents into the gas holder. The vapors from the gas holder are compressed, chilled and condensed VCM is returned to VCM storage. It is estimated that the installed cost for the gas holder and associated compression and heat exchange system for a 200 million pound PVC plant would be approximately $950,000. Utility requirements would consist of 40 KWH/hr., and 25 GPM of cooling water. In some cases, safety regulations may prevent sending pressure relief valve vents to the gas holder. In these plants, it would be desirable to provide separate pressure control instrumentation for automatic venting to the gas holder when pressure increases to somewhat below the relief valve set pressure. In this way prsssure upsets can be handled without opening the safety valves. VCD-5 - Carbon Adsorption The use of activated carbon has been demonstrated experimentally as a way to reduce VCM emissions. It certainly could be used on the outlet vent of the VCM recovery system where the concentrations are high (over 10% VCM) and possibly prove to be reasonably economic in this service. How effective it would be on the outlet of a rotary dryer is conjecture, as the outlet temperature ranges from 140 to 160F and the VCM concentration is less than 0.1% with air volumes of 13,000 to 25,000 ACFM per 5,000-10,000 pounds per hour of dry PVC product. The economics would represent UCC 026140 PVC-81 a direct added cost as the recovery value of the VCM would be significant. Also, the excess amount of water vapor would limit the adsorption capacity severely. To adsorb 50 ppm of vinyl chloride vapors from a dry air stream of 18,000 ACFM at 150 F and atmospheric pressure requires about 1,200 cubic feet (19 tons) of activated carbon for an 8-hour adsorption cycle.(a) This assumes half of the carbon is in service while the remainder is being regenerated. The regeneration would probably be done with steam at elevated pressure (50 psig) followed by effluent cooling (to 100F) for VCM condensation and recovery (60 lbs./8-hr. cycle). As indicated, the above carbon requirements are based on processing a dry vent stream. A dryer vent of this magnitude would contain about 16,000 lbs. of water per 8-hour period. This water will undoubtedly increase the amount of activated carbon required. There is some question as to how many times the activated carbon can be regenerated. Experimentally it has been regenerated at least fifteen times without any loss in adsorptive capacity.(7) However, because of the large volume of activated carbon involved it is important to know the ultimate life of this material. Because of uncertainties as to the amount of carbon involved and ultimate carbon life it is difficult to develop meaningful economics for this form of emission control device at this time. VCD-6 - Thermal Incineration Thermal incineration of the vent stream from a VCM recovery system is impractical compared to other devices as there is nothing to offset the high investment and fuel requirement. Other devices recover VCM for reuse and thereby partially pay for the increased investment and operating cost. The fuel value of the incinerated VCM streams is negligible. The incineration of the air from a rotary dryer containing 15 to 100 ppm of VCM is possible albeit costly. Fuel requirement is large as the VCM contributes an insigni ficant amount of combustible and the air is fairly well saturated with water vapor. In addition, a large scrubber system may be required to remove the small amount of hydrogen chloride formed. The equation for the reaction is: 2 CH2:CH Cl + 5 02 --------- 4 C02 + 2 H20 + 2 H Cl (a) Calculated based on published data of Calgon Corp.(7) UCC 026141 PVC-82 In order to conserve energy it would be necessary to employ feed-effluent heat exchange or generate steam with the incinerator effluent. Commercial incinerators with high heat recovery (75-80%) will have an installed cost of 10-15 dollars per cubic foot per minute of feed gas. Therefore, the incineration of the combined vent streams from a 200 million pound per year capacity plant (200,000 SCFM) would take a minimum capital investment of $3,000,000 and consume about 95 million Btu/hr. of fuel (based on 85% heat recovery) and approximately 365 KWH/hr. would be required for induced draft fans. It should be noted that there is some doubt if the VCM will be completely burned in the incinerator. At the very low concentration of VCM involved combustion efficiency could be low. VCD-7 - Catalytic Incineration It is possible to catalytically incinerate to similar levels obtained with a thermal unit. The catalytic facility would operate at lower temperature (800-1000 versus 1800F) and therefore require less heat recovery and consume less fuel. The somewhat lower initial investment and fuel saving would be offset by catalyst replacement costs and the danger of catalyst fouling and poisoning. VCD-8 - Canned Pumps An important source of fugitive emissions is from pump glands and seals on liquid VCM pumps. This source could be eliminated by the use of canned pumps. In a new plant they would increase the capital cost of pumps about 35%. In an established plant, it would be a direct cost increase. They normally reduce maintenance costs but when they go "bad" the pump must be replaced so on an overall maintenance cost basis the canned pump represents little or no advantage. Canned pumps could be installed systematically in a preventive maintenance program and reduce pump emission to "zero". Incre mental cost for installing canned pumps in a new 200 million pound per year PVC plant would be approximately $10,000. Replacing pumps in the same size existing plant would cost about $30,000. UCC 026142 PVC-83 B. Procedures VCD-9 - Solvent Cleaning One of the principal sources of intermittent emissions is from the opening and closing of the reactors. A method to reduce this emission is to solvent clean the reactors. There are several solvents that are very efficient, such as tetrahydrofuran, dimethyl formamide, and ethylene dichloride. The use of any of these solvents does introduce a possible emission problem but since they are all liquids at normal temperatures, these emissions are much easier to contain and control than VCM. One company (A-17) does use a solvent system and the following economics have been given, all converted to a 200 million pound per year plant. Capital Investment $300,000 Solvent Purified Loss 1% (99% Eff.) 1.253 x 8.34 x 6 x 104 @ 9-l/2/Lb. 6 x 106 Gals/Yr. 6 x 104 Gals/Yr. ' 6.27 x 10s Lbs/Yr. $59,600/Yr. Utilities 50 PSIG Steam Cooling Water Electricity 3.762 x 106 Lbs/Yr. 12.0 x 106 Gals/Yr. 2.5 x 103 KWH/Yr. Chemical & Misc. Supplies $2,500/Yr. Labor 7% of Battery Limits Capital Investment $11,200/Yr. Plant A-17 uses the solvent system to clean the reactors after every three or four batches. In addition to reactor cleaning, the solvent should be considered for cleaning pipes, pumps, vessels, etc. As with reactor cleaning, the major problem is associated with separation of the solvent from the PVC resin. VCD-10 - Water Purge of Reactors A method used (in conjunction with a gas holder) to reduce VCM emissions from reactors is to thoroughly purge all the VCM vapors to the gas holder by filling the reactor with water. The water is recycled so that there is no VCM loss to water after the initial charge. This purging is only done in preparation for cleaning the reactor (every 3 to 6 batches). UCC 026143 PVC-84 Cost for the water purge system should be less than $200,000 for the model size plant. VCD-11 - Leak Detection In order to detect and eliminate leaks as soon as they occur, it is necessary to continuously monitor specific areas for VCM vapors. In a 200 million pounds per year PVC plant, four or five ten-point monitors are required to provide reasonable coverage. These monitors (chromatographs) cost about $20,000 per unit installed. The associated alarm and signal system costs another $30,000 and a data processing system another $40,000 to $90,000. This brings the equipment cost up to $150,000 to $200,000. To follow up on alarms, the part time services of a man and portable VCM detector ($5,000) is required. The system more often than not requires the full time assistance of a pipe fitter to minimize leakage. In addition, the full time services of an instrument man is necessary to keep the chromatographs in operation. To monitor battery limits and off site VCM concentrations requires personnel and equipment, but the cost varies markedly and indeterminantly due to wide differences in frequency of testing and number of locations tested. UCC 026144 TABLE PV-10 CATALOG OF EMISSION CONTROL DEVICES * Plant No. A-6 A-7 A-8 A-9 A-10 A-10 A-12 A-l6 A-17 A-21 A-21 A-21 B-7 C-l D-l Device No. VCD-1&2 VCD-1&2 VCD-2 VCD-2 VCD-2 VCD-3 VCD-2 VCD-3 VCD-9 VCD-1&2 VCD-4 VCD-9 VCD-3 VCD-2 VCD-2&3 LbS. VCM/Hr. In Out 1009 4620 4l6 - 65 - - - - 13 iS 7 122 - 9.5 - 53.8 2.0 27.4 - 29.0 74 Eff .56 99.3 99.5 75 - 75 85 96 - - - - 99.2 - - Remarks -30F cooling Conditions not given Conditions not given Conditions not given -70F cooling EDC scrubbing medium Conditions not given 30 plate col. 13'V 34" high 70 psig Use EDC as solvent, closed system No conditions or rates given except discharge No conditions or rates given except discharge No conditions or rates given except discharge No conditions or medium given No temp, given for refrigeration unit Cooled to 14F, acetone is scrubbing medium FVC-85 ucc 026145 Note: * Most of the respondents are in the process or have plans to reduce VCM emissions. We have only listed those that were in actual service at the time the reports were made. i PVC-86 ix. Model Plant It should be noted here that most PVC plants have undoubtedly done much to reduce fugitive losses during the past year. This also applies to many procedures where far more care is now exercised to minimize VCM emissions. This takes time and the results are certainly not completely reflected in the emissions reported as of June or July of 1974. For this reason our Model Plant "set up" may indicate higher input VCM content to certain devices or higher fugitive losses than are actually the case today. Table PV-11 presents economics for a typical existing 200 million pound per year PVC plant without VCM emission control devices. Table PV-12 provides incremental investment, utility and manpower requirements for the same size plant with a moderate amount of emission control equipment. This facility (Model Plant I) employs the following devices and procedures to reduce VCM emissions. 1. VCD-1 Improved Stripping 2. VCD-2 Refrigeration of VCM Recovery System Vent 3. VCD-8 Canned Pumps 4. VCD-11 Leak Detection Program The best way to reduce VCM losses downstream from the stripper (or the reactor if stripping is done there) is to strip the latex as thoroughly as possible of residual VCM. As the polymerization goes to about 95% completion at best, it is economical to recover most of the VCM. It is possible to recover 99% of the VCM if a vacuum of about 25" Hg (5 in. Hg absolute) can be pulled on the latex and the vapors are compressed and chilled (-30F) under pressure (70 psig) and care has been taken to minimize leaks into the system. This is not easy to do even with the proper vacuum-compression equipment due to foaming problems. This is particularly true of dispersion latices as they foam far more readily than suspension latices. Considerable work ie being done on this problem and our Model Plant devices assume considerable success in this area. The low temperature refrigeration is necessary so that the inerts that must be vented from the system can be discharged with a minimum VCM loss. The vacuum system should be flexible enough so that it can be used to evacuate VCM vapors from other vessels such as reactors, blend tanks, etc., whenever necessary to minimize VCM emissions to the air. The replacement of all pumps handling liquid VCM with canned pumps should reduce variable fugitive emissions which occur with some frequency due to packing or seal failures on regular centrifugal pumps. ucc 026146 FVC-87 TABLE FV-11 PVC MANUFACTURING COST FOR A TYPICAL EXISTING 200 MM LB./YR. FACILITY Direct Manufacturing Cost Raw Material Vinyl Chloride <3 10^/Lb. Vinyl Acetate @ 19$S/Eb. Additives 22-1/2^/Lb. Initiator @ $1.65/Lb. Labor @ 20 X 5.65 X 8/Shift Maintenance (5# of Invest.) Utilities Indirect Manufacturing Cost Plant Overhead (110# Labor) Laboratory (25# Labor) Fixed Manufacturing Cost Depreciation (10 Yr. Straight Line) Insurance & Property Tax (2.3# Invest) Total Manufacturing Cost General Expenses Administration (3# of Mfg. Cost) Sales (1# of Mfg. Cost) Research (2.5# of Mfg. Cost) Finance (6# of Investment) Total Cost Product Value, FVC Profit Before Taxes Profit After Taxes (52%) R0I (NPAT X 100/Plant Investment) ^/Lb. pvc $/Yr. 10.10 0.75 0.90 0.17 0.49 0.55 0.40 13.36 0.54 0.12 0,66 - 1.10 0.25 1.35 15.37 30,740,000 0.46 0.15 0.38 ~0P.d6M6M 1T65 17.02 34,040,000 24.00 48,000,000 6.98 13,960,000 3.35 6,700,000 30.4# UCC 026147 PVC-88 TABLE PV-12 200 MM LBS/YEAR PLANT MODEL PLANT I INCORPORATING MODERATE EMISSION CONTROL DEVICES Capital Increase for Emission Control Devices VCD-1 High Vacuum and Compr. for Max. VCM stripping VCD-2 Refrigeration on Condenser to -30*F VCD-8 Substitute Canned Pumps VCD-11 Monitoring for VCM Emissions Total Capital Investment Increase $ 750,000 70.000 10.000 175,000 $1,005,000 Increase in Operating Cost and Energy Requirements Control Device VCD-1 VCD-2 VCD-8 VCD-11 Total GPM Cooling Water 35 __ 35 Electric Power KWH/HR. 80 15 __ 95 Labor 2-1/2 Men/Shift Annual Cost 2.5x5.65x8760 * $125,000 UCC 026148 PVC-89 Table PV-13 presents incremental economic factors for a facility (Model Plant XI) which includes extensive VCM emission control equipment. This plant incorporates the same control devices as Model Plant I except the refrigera tion unit is replaced with a lean oil scrubber on the VCM recovery system vent, in addition it includes the use of a gas holder (VCD-4) and solvent cleaning of reactors. The use of a scrubber to control VCM emissions from a VCM recovery system has proven effective in several plants (A-10, A-16, B-3, B-7, and D-l) and ensures a very low VCM emission to the atmosphere. (Less than .0010 lbs VCM/lb product) Only one plant (A-21) reported using a gas holder (VCD-4). It is interesting to note that this particular plant has the lowest VCM emission of all the suspension plants that have given reasonably complete emission data. They also use a water purge for reactors (VCD-10). All controllable emissions (to vents, stacks, etc.) are sent to the gas holder. They are then compressed and sent to the VCM recovery system. (Resulting atmospheric vent contains less than 0.005 lbs VCM/lb product.) Only one plant (A-17) reported the use of solvent cleaning of reactors (VCD-9) as standard procedure. Several plants are experimenting or trying to develop a workable system but are having difficulty separating the solvent from the polymer efficiently and economically. This cleaning system could significantly reduce sporadic VCM emissions caused by frequent openings and cleanings of many reactors. (Less than .002 lbs VCM/lb product emitted with control device.) The model plants as presented do not include any devices to handle VCM emissions from dryers or downstream processing areas. The use of activated carbon is a possibility but it remains to be proven if it is practical. It might well be of value for dispersion plants where it is difficult to strip the latices effectively at the strippers. However roost dispersion plants use spray dryers which means an effluent air stream with more moisture content, higher temperatures and large volumes. All of which increase the quantity of activated carbon requirement. It is also not clear as to how to handle the effluent from the adsorber during regeneration. Incineration has not been used in the model plants because of the large fuel requirement and the fact that emissions, such as HC1, S02 and MOx* not now emanating from PVC plant, would be formed in significant amounts. Scrubbing of the large volume air streams with low VCM content has not been considered. There are no data available to indicate that an equilibrium condition exists favorable for a significant reduction of VCM by scrubbing; not to mention the tremendous size of equipment involved with its incumbent high cost. UCC 026149 PVC-90 TABLE PV-13 200 MM LBS./YEAR PVC PLANT MODEL PLANT XI INCORPORATING EXTENSIVE EMISSION CONTROL DEVICES Capital Increase for Emission Control Devices VCD-1 High Vacuum and Compr. for Max. VCM Stripping VCD-3 Scrubber for VCM Recovery System Vent VCD-4 Gas Holder VCD-8 Substituting Canned Pumps VCD-9 Solvent Cleaning of Reactors VCD-11 Monitoring for VCM Emissions Total Capital Investment Increase $ 750,000 125.000 950.000 10,000 300.000 175.000 $2,310,000 Increase in Operating Cost and Energy Requirements Control Device VCD-1 VCD-3 VCD-4 VCD-8 VCD-9 VCD-11 Total Steam Lbs/Hr Cooling Water GPM Electric Power KWH/Hr Chemicals $/Yr 35 500 40 25 500 15 80 5 40 1 62,100 1000 115 126 62,100 Labor 3 Men/Shift Annual Cost 3x5. 65 x 8760 = $150,000 UCC 026150 PVC-91 Tables PV-14 and PV-15 present economics for the Model I and Model II plants. Table PV-16 presents an estimate of VCK emissions from the suspension PVC process incorporating the emission control devices employed in the model plants. The reduction in emissions shown for the Model II plant can be readily accomplished with present technology. Any substantial further reduction in VCM emissions will require additional research and process development effort. ucc 026151 PVC-92 TABLE PV-14 PVC MANUFACTURING COST FOR A TYPICAL MODEL I PLANT, 200 MM LBS./YR. PRODUCTION Direct Manufacturing Cost C/Lb. PVC Raw Materials Vinyl Chloride @ 10$/Lb. Vinyl Acetate @ 19$/Lb. Additives @ 22^C/Lb. Initiators @ $1.65/Lb. Labor @ 22\ x 5.65 x 8/Shift Maintenance (5% of Investment) Utilities _ 10.10 0.75 0.90 0.17 0.55 0.58 0.41 13.46 Indirect Manufacturing Cost Plant Overhead (110% Labor) Laboratory (25% Labor) 0.61 0.14 HTTF Fixed Manufacturing Cost Depreciation (10 Yr. Straight Line) Insurance & Property Tax (2.3% Investment) 1.15 0.26 1.41 Total Manufacturing Cost 15.62 General Expenses Administration (3% Mfg. Cost) Sales (1% Mfg. Cost) Research (2.5% Mfg. Cost) Finance (6% of Investment) 0.47 0.16 0.39 0.69 "T77T Total Cost 17.33 $/Yr. 31,240,000 34,660,000 Product Value PVC Profit Before Taxes Profit After Taxes (52%) ROI (NPAT x 100/Plant Investment) 24.00 6.67 3.20 48,000,000 13,340,000 6,400,000 27.8% UCC 026152 PVC-93 TABLE PV-15 PVC MANUFACTURING COST FOR A TYPICAL MODEL II PLANT, 200 MM LBS./YR, PRODUCTION Direct Manufacturing Cost $/Lb. PVC Raw Materials Vinyl Chloride @ lOC/Lb. Vinyl Acetate @ 19C/Lb. Additives @ 22Js<:/Lb. Initiators @ $1.65/Lb. Miscellaneous Chemicals Labor @ 23 x 5.65 x 8/Shift Maintenance (5% of Investment) Utilities 10.10 0.75 0.90 0.17 0.03 0.56 0.61 0.42 IT34 Indirect Manufacturing Cost Plant Overhead (110% Labor) Laboratory (25% Labor) 0.62 0.15 0.78 Fixed Manufacturing Cost Depreciation (10 Yr. Straight Line) Insurance & Property Tax (2.3% Investment) 1.22 0.28 1.50 Total Manufacturing Cost 15.82 General Expenses Administration (3% Mfg. Cost) Sales (1% Mfg. Cost) Research (2.5% Mfg. Cost) Finance (6% of Investment) 0.47 0.16 0.40 0.73 "TT7F Total Cost 17.58 $/Yr. 31,640,000 35,160,000 Product Value PVC Profit Before Taxes Profit After Taxes (52%) ROI (NPAT x 100/Plant Investment) 24.00 6.42 3.08 48,000,000 12,840,000 6,160,000 25.3% ucc 026153 PVC-94 TABLE FVC-16 ESTIMATE OF VCM EMISSIONS FROM MODEL PLANTS (SUSPENSION) VCM EMISSIONS, TONS/TON OF VCM Source Area Fugitive Total Plant without Control Devices .0030 .0030 .0032 .0048 .0042 .0013 .0070 .0080 .0345 Model Plant I .0015 .0020 .0010 .0015 .0015 .0002 .0030 .0050 .0157 Model Plant II .0005 .0005 .0010 .0003 .0005 .0002 .0010 .0030 .0070 Ci w o n w > UCC 026154 PVC-95 X. Research and Development Goals Technological research and development will be concerned with reducing vinyl chloride emissions to very low values as compared with the current emission level. One of the major sources of emissions is the vent to remove inerts from the VCM recovery system. More development should be done on an economical system for scrubbing this vent stream with a liquid from which vcm can be easily stripped and liauified for reuse. Another important emission source is the reactor, not during polymerization, but when it is being cleaned. All reactors in the suspension and dispersion process tend to build up PVC on the walls and agitator. Most plants still clean by hand, a few of the newer plants (or reactors) are equipped with water jet lances for self cleaning but even these must be mechanically cleaned at times. This means that whenever a reactor is cleaned, it is open and there is some VCM emission regardless of the care taken. A good solvent cleaning system is desirable. There are several solvents that work well (dimethyl formamide, tetrahydrofuran-) . The problem has been to separate the solvent from the dis- solved PVC economically. The development of an economical system would certainly be a big aid towards the reduction of ambient VCM emissions. One of the difficulties associated with efficient stripping of VCM from the latex is the tendency of latices to foam. Dispersion latices are particularly bad because of their high soap content. The most obvious approach is the addition of foam breakers (silicones, alcohols, etc.). Another approach is the use of mechanical foam breaking devices incorporated into the stripper. Any improvement in this area could result in a marked reduction of VCM emissions downstream of the stripper. Also, there are a number of heat exchangers (falling film, wiped film, multiple effect, etc.) that might make efficient and economically feasible, the removal of 99+% of the VCM from the latex if it were possible to keep the latex from coagulating. Both areas of study, heat exchange devices and stable emulsions, under rigorous conditions are ones that could result in significant reductions of downstream emissions, plus a reduction in the VCM content of the product PVC resin. UCC 026155 PVC-96 REFERENCES 1. "FVC Chemical Profile", Chemical Marketing Reporter, May 20, 1974. 2. Albright, L. F., "Processes for Major Addition - Type Plastics and Their Monomers", McGraw Hill, Inc,, New York, N.Y., 1974. 3. "Chemical Economics Handbook", Stanford Research Institute, September 1972 and September 1973. 4. U.S. Tarriff Commission, March 6, 1974. 5. "Current Prices of Chemicals and Related Materials", Chemical Marketing Reporter, November 11, 1974. 6. Private communications with Roy F. Weston, Inc., Consulting Engineers, West Chester, Pennsylvania. 7. "Controlling Vinyl Chloride Emissions with Granular Activated Carbon", Bulletin 23-200, Calgon Corporation, Pittsburgh, Pennsylvania, 1974. U UCC 026156 APPENDIX I BASIS OF THE STUDY I. Industry Survey The study which led to this document was undertaken to obtain information about selected production processes that are practiced in the Petrochemical Industry. The objective of the study was to provide data for the EPA to use in the fulfillment of their obligations under the Clean Air Amendments of 1970. The information obtained during the study includes industry descriptions, air emission control problems, sources of air emissions, statistics on quantities and types of emissions and descriptions of emission control devices currently in use. The principal source for these data was an Industry Questionnaire but it was supplemented by plant visits, literature searches, in-house back ground knowledge and direct support from the Manufacturing Chemists Association. More than 200 petrochemicals are currently produced in the United States, and many of these by two or more different processes. It was obvious that the most Immediate need was to study the largest tonnage, fastest growth processes that produce the most pollution. Consequently, the following 32 chemicals (as produced by a total of 41 different processes) were selected for study: Acetaldehyde (two processes) Acetic Acid (three processes) Acetic Anhydride Acrylonitrile Adipic Acid Adiponitrlie (two processes) Carbon Black Carbon Disulfide Cyclohexanone Ethylene Ethylene Dichloride (two processes) Ethylene Oxide (two processes) Formaldehyde (two processes) Glycerol Hydrogen Cyanide Maleic Anhydride Nylon 6 Nylon 6,6 "Oxo" Alcohols and Aldehydes Phenol Phthalic Anhydride (two processes) Polyethylene (high density) Polyethylene (low density) Polypropylene Polystyrene Polyvinyl Chloride Styrene Styrene - Butadiene Rubber Terephthalic Acid (1) Toluene Di-isocyanate (2) Vinyl Acetate (two processes) Vinyl Chloride (1) Includes dimethyl terephthalate. (2) Include* nathylenediphenyl and polymethylene polyphenyl isocyanates. The Industry Questionnaire, which was used as the main source of information, was the result of cooperative efforts between the EPA, Air Products and the EPA's Industry Advisory Comnittee. After receiving approval from the Office of Management and Budget, the questionnaire was sent to selected producers of most of the chemicals listed above. The data obtained from the returned questionnaires formed the basis for what have been named "Survey Reports". These have been separately published in four volumes, numbered EPA-450/3-73-005a, b, c, and d and entitled "Survey Reports on Atmospheric Emissions from the Petrochemical Industry - Volumes I, II, III, and IV. UCC 026157 1-2 The purpose of the survey reports was to screen the various petrochemical processes into the "more11 and "less - significantly polluting processes". Obviously, significance of pollution is a term which is difficult if not impossible to define because value judgements are involved. Recognizing this difficulty, a quantitative method for Significant Emission Index (SEX) was developed. This procedure is discussed and illustrated in Appendix Il^of this report. Each survey report includes the calculation of an SEI foe the petrochemical that is the subject of the report. These SEI's have been incorporated into the Emission Sumnary Table that constitutes part of this Appendix (Table X). This table can be used as an aid when establishing priorities in the work required to set standards for emission controls on new stationary sources of air pollution in accordance with the terms of the Clean Air Amendments of 1970. The completed survey reports constitute a preliminary data bank on each of the processes studied. In addition to the SEX calculation, each report includes a general introductory discussion of the process, a process description (including chemical reactions), a simplified process flow diagram, as well as heat and material balances. More pertinent to the air pollution study, each report lists and discusses the sources of air emissions (including odors and fugitive emissions) and the types of air pollution control equipment employed. Xn tabular form, each reports summarizes the emission data (amount, composition, temperature, and frequency); the sampling and analytical techniques; stack numbers and dimensions; and emission control device data (types, sizes,' capital and operating costs, and efficiencies). .~ Calculation of efficiency on a pollution control device is not necessarily a simple and straight-forward procedure. Consequently, two rating techniques were developed for each type of device, as follows: 1. For flares, incinerators, and boilers a Completeness of Combustion Rating (CCR) and Significance of Emission Reduction Rating (SERR) were used. 2. For scrubbers and dust removal equipment, a Specific Pollutant Efficiency (SB) and a SERR were used. 4 The bases for these ratings and example calculations are included in Appendix III of this report. II. In-Denth Studies The original performance concept was to select a number of petrochemical processes as "significant polluters", on the basis of data contained in completed questionnaires. These processes were then to be studied "in-depth". However, the overall time schedule was such that the EFA requested an initial selection of three processes on the basis that they would probably turn out to be "significant polluters". The processes selected in this manner were: 1. The Furnace Process for producing Carbon Black. 2. The Sohio Process for producing Acrylonitrile. 3. The Oxychlorination Process for producing 1,2 Diehloroethane (Ethylene Dichloride) from Ethylene. ucc 026158 TABLE I onssidis sumwf ISTIKHTED <*> CUggStfr AI, tHlSSTfMC IM US.lYMI F|i l of 3 ^rdrocarbooa Fertlculetee Oxldee of Nltroeen fulfur Oxldee Carbon Monoxide Total Total Velfthti Acetaldehyde vU Ethftta* VU EttMMi AetU Acid vU Nttlmal vie Buteee tfU AetaMM Acttlc Anhydride vie Acetic Acid Acrylonitrile (*) Adipic Acid Adlywltrlle vie Butedleoe via Adipic acid Csrh-io glach Cerh'M fit mlfide Cycl-ibexeaoee HIM :hyl Tereyfathelete (4TM) Btliy lene Ctby^eoe Bichloride vie Oxychloride*lea *1* Diract Cblarination Ethy .ene Oxide Foteuldehyde vie Silver Cetelyet vie Iren Oxide Cetelyet Clycnrol vie Eplcblerohydtln Hyd*"Ee* Cyanide Oirect preceee Iecc;*eaetee Kele:c Anhydride Nylon 6 Nylon 1,6 Ore )*rocoeo nieoul , rhthiUc anhydria* via O-Xylan* via Naphthalaon Nl|h Denelty poiyetby let* Lou ivnalty folyatbylana Foljrj ropy lene Pelyttyreae foljrviayl Chloride Styrtne Styrine-Butedite lubber Vinyl Acetete vie Acetylene vie Bthyleee Vinyl Chloride Total* 1U 0 0 40 6.1 3.1 in 0 11.2 0 156 0.15 70 91 15 95.1 29 5.9 21.1 25.7 lb 0.5 1.1 36 0 0 5.25 26.2 0.1 0 79 75 17.5 20 42 4*3 9.6 5.3 0 17.6 1.217.6 0 0 0 0 0 0 0 0.2 6.7 0.5 ol 0.3 0 1.6 0.2 0*4 0 0 0 0 0 0 0.0 0 1.5 5.5 OoOl 0 Sal 1.9 2.1 1*4 0*1 0.4 12 0.07 lob 0 0 0.6 49.1 0 0 0.01 0.04 0 0 5.S 29.6 50.5 0.06 4.9 0.1 0 0.1 0.2 0 0 0.3 0 0 0 0.61 0 0 0 0 0.07 0 0.1 0 0 0 0 0 0 0.14 0 0 TB 0 94.2 0 0 0 0 0 0 0 0 0 0 21.6 4.3 0 1.0 2.0 0 0 0.1 0 0 0 0 0.02 0 0 0 0 0 2*4 0 0 0 0 1.2 0 '0 0.9 0 0 0 33.9 0 27 0 14 1.3 5.5 19b 0.14 0 0 1,070 0 77.5 55 0.2 21.9 0 0 107.2 24.9 0 0 eb 240 0 0 19.3 0 43.b 45 0 0 0 0 0 0 0 0 0 0 4,852,4 i.t 27 0.01 54 7.6 4.4 3B5 30 44.4 0.54 4,0b0 3.1 144 144.5 17.6 117.3 29 4b.2 131 50.4 lb 0.91 44 294 1.5 3.5 24.4 24.3 31.7 47 41.3 74.4 37.4 21.b 74 4.5 12 5.3 TB 18.2 6,225.9 <*> 44 27 l 3,215 490 253 13.000 1.190 3,200 10 17,544 120 5,700 7,4b0 1.240 7,450 2,300 4^440 1,955 2,070 | *240 54 231 2.950 90 330 440 1,940 422 4 100 ij'700 1,460 110,220 IMt Imucu nuaberi in b<4 on lui than loot eorvey. Alt bMtd on engineering judgaewat of ben currant control. (2) lituatt future plan:* will employ boat currant control lcchnlquea. (!) IicMw oat bane, Include* Hj* and oil volatile organic*. (0) Inc lode* non-volatll* organic* and Inorganic*. IS) Knighting factors ueed era: hydrocarbon* - $0, particulate* - 60, NO, - 60, SO, - 20, and CO - 1. lb) Inferred to olaavhoro In this atody aa "Significant Bgtaslon Irvin." or "SPI". (7) total* ar* not equal acroaa and dovn duo to rounding. ' f (11 tolaatona haaod no vtoet la non aa obaalat* cat a Ly at. Sea lapoct No. EF6-4S0/1- 73-006 b for up-to-date lafornation. Probably baa up to lOi |ov blaa ucc 026159 TA1LE 1 passim twrnir ri(> I of i *10 missions IN mo. M* LBS. ftEAR WlPlrtfM (J> UrUcuUf (*> Q.t* .1 mtroaan juUtir 0.1*.. Carbon Moooaide Total tot.t lf*l.btd ictul4ib|it vii IthyltM vll IlkUttl Autk Acid via Mtthenot via Ruteae via iciulklqiia Acetic iiAfirlk via ietiie Ac14 Acrylonitrile (9) Adipic Ac14 Adipoeitrile via totadicoe via Adipic Acid Carton Hack Carbon Dioulftde Cyciotosaeoae Dlaathyl TareytotoUte (*TPA) Sthyleoa ttbjrUae Dicklorlde via CfcycblerUatloo IthyUnt Ostde via Direct CUtriutlo roraldefeydo via Silver Catalyat via Ire* OaUa Catalyst Clycarol via Bplcklarohydrlft %4ropa Cyaaid* Direct Itacaaa Iaocyaaataa Malaic Anhydride Nyloa b Nylon 4,6 0*o frocaa* Ptit belie Anhydride via O-Ryleae via Nitktkaltii U|b Density Poly*thy leo* Lev Density tolyatbyleae Peiypropyloaa Polystyrene Pelyvioyl Chloride Styraaa Styreae-Ru tedlean Rubber Vinyl Acetate via Acetyl**# via Itbylaoa Viayl Chloride 01.2 0 0 12.2 0.72 m 0 io.i 0 66 0.06 17.1 72.4 i*. 110 14.1 11.0 U.l 17.* 1.0 0 1.1 11 0 0 2.46 u.l 0.2 0 210 262 152 20 52 i.i 1.65 6.5 0 0 0.1* 6.4 0.5 2.2 0.07 0 1.1 0.1 0.1 0 0 0 0 0 0 0.7 0 i.i i.i 0.01 0 11.1 0 6.2 5 0.5 0.1* 10 0.05 0.11 0 0 0 0 00.06 0 0 0.5 n.i *7.1 0.06 1.0 0.01 0 0.07 0.1 0 0 0.11 0 0 0 0 0 0 0 0 0.05 0 0.4 0 0 0 0 0 0 0.1 0 0 n 0 0 0 0 0 0 0 0 0 Q 0 6.9 1.1 0 0.86 i.i 0 0 0.01 0 0 0 0 0.02 0 0 0 0 0 06.C 0 0 0 1.13 0 0 00 .11 0 0 0 0 0 2.5 1.62 10* 0.09 0 0 1.590 0 85.1 41.* 0.1 25 0 0 **.7 17.0 0 0 28651 0 0 16.2 0 111 O 0 0 0 0 0 0 0 0 0 __ a_ 1.2 0 0.06 0 16.7 2.15 596 J9.5 62.6 0.56 1,670 1.26 162 118,7 77 126 .i 23 i.i 36.6 6.9 0 87 272 2,2 5,3 IS.2 21,1 126 0 216 267 152,5 21.47 63 i. 2,36 4.5 T* _ 17,1 ** 0 2 0 980 60 11,000 779 3,010 30 7,200 30 6,260 6,060 1,410 8,800 2,740 1,410 1,250 i,**i 700 0 225 2,720 m its 125 1,706 1,100 0 17.200 21.200 12,190 1,640 6,840 225 170 360 TR 1.170 Total* ,1*7.1 li, 70,1 40.5 1.100 4,151.* 114,111 O(2)) la i w 1001 .utvey, *11 biM* a. wtinurltt, Jud,u.iat of best current cootrel. csatr.l t*chal,u... Probably hat up to UR 1<m biaa. (2) Kactudee nathane, include* HjS aad all volet11 > arowlc. (4) Include* noo'volatile argaaiaa aad Inorpenlc*. (S> toifhtloc factor* used era; hydrocarbon* SO i particulate* * M. NO. - *0, *0_ - *0, M4 CO <*) Referred to elsewhere ie chi* study aa "Slgnif_._c_u__t toUalw larfu" ,, "til". (7) Total* are aot ofval acroaa aad down 4w to couadloe. < <m stoat 1 of 2. uco 026160 Aceteldofayde via BilqrttM via Ethanol Acc:ic Ac14 vie Mathnnel via lutaw via Acetaldehyde Ace :1c Anhydride via Acetic Ac14 Acryloaltrll* (t) Adipic Acid MitwaUriU via BulaAlaaa vl* Mific Ac 14 Carton Hack Cert*oa DleuMlde Pinttbyl Taraphtlulate (*TM) Itt) 1.0. Itbyleae Dlcbleclde via Ouychlorlaatlea Itbyleae daMc via PItact Cblartaatli rerealdehyde via (liver Catalyet via Iraa OvMe Catalyst Clycerel via lrlclloh)dtli Priitin Cyeelde Plract Procter lUtflHIW Keltic Anhydride My lot a Mylot 4.4 Ova Praceee Hktotl Ihthlllc Anhydride via O-tyItot via Naphthalene Hl(h OtatIcy Polyethylene Low >ttally falyethylaee Pvlyitoyyltoa Valyatyvaaa Poly 11ay l chloride llyr-tot Icyrwaa-liilotitot ItMtr VIay. Acetate via Acetyleae via Ithylene Viay'.. Chloride Tot ala Badaalone (*), TAtLl 1 passions smamr |fl > tM 1.1 2? O.M M 22 ID.* wo so ut.t lal i.lM 4,3 210 IAS 94 253 AS 120 tn.T S 25 0.1 (ID) 115 3AA A.T 10*0 43 4A 1<A 47 ] 30 190 43 137 1.4 14 M TA 45 10,101 ( Total Uelehted (5) bv IMO 102 il 3 3,215 1,470 313 1D.00D 1,970 4.110 AQ 14.140 150 11.960 11,500 1.410 14,450 5.060 >,510 1,105 3,515 2,000 M U0> 45* 5,410 184 650 7A5 3,660 1,522 160 23,600 11.400 15,140 1,10 10,540 610 1,040 70S TA 1.4)0 144,410 <7> h| 3 of 3 tec lotted (Mar o( Men Plant. mn - i*80) A 0 6 0 3 i 5 7 4 3 ii t 10 10 IS 40 it 1 0 10 4 10 10 A ii A 0 ii 41 n ii IS 9 4 1 4 10 1*1 Lb#,/Tear 1,140 96V 600 1,020 175 1,705 1,145 1,630 635 220 3,000 871 1,900 2,965 22,245 6,650 5,593 4,1*1 5,914 mi* 245 412 1,009 359 406 1,511 1,727 2,363 720 603 2.315 5,269 1,160 3,500 4,375 5,953 4,464 206 1,220 5,400 2,4*0 4M 1,200' 500 2,015 2,100 1.10O () 1.100 945 550 5,000 (0> 1,100 3,600 5,900 40,000 8.150 () 11.540 4,000 <9> 4,000 1.510 {() 320 202 2,120 720 1.500 3,000 3.000 4,200 1,900 (9) 529 0,500 21,100 5,800 4,700 9,000 lOpOQQ 5,230 356 2,200 13,000 !> (1) O) |4) (S) (*) (7) (t) (*) '10) * "" auafcara arc hated oo lata thee 1001 aurvty. All bated oa totlottrlay, judpaneat of Matt currant control, Accuacc future plant# will Mfloy btit current control technique#. bclulti MthMf! include* HjS and alt volatile org*tca. Include# no*-volatile or|Mlc end Inorganic*. Nii|htln| factor# ued ore: faydroearhoa# - $0, paniculate* - A0, M0X - AO, S0_ - 20, and CO - 1, lefarred to cleeuhere in thl# study a# **ignifloa*t teleaion Index*1 or "SCI*1. Total# ere not equal ccroe# end down due to rounding. H 1995. I See eheet 1 of 1 Jue to anticipated future chut down of necglnai plant*. probably hat up to 10?. low blat. ucc 026161 1-6 In order to obtain data on these processes, the operators and/or licensors of each vere approached directly by Air Products' personnel. This, of course, was a slow and tedious method of data collection because mass mailing techniques could not be used, nor could the request for data be identified as an "Official EPA Requirement". Yet, by the time that OMB approval was given for use of the Industry Questionnaire, a substantial volume of data pertaining to each process had already been received. The value of this procedure is indicated by the fact that first drafts of thes three reports had already been submitted to the EPA, and reviewed by the Industry Advisory Committee, prior to the completion of many of the survey reports. In addition, because of timing requirements, the EPA decided that four additional chemicals be "nominated" for in-depth study. These were phthalic anhydride, formaldehyde, ethylene oxide and high density polyethylene. Consequently, five additional in-depth studies were undertaken, as follows: 1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride. 2. Air Oxidation of Methanol in a Methanol Rich Process to produce Formaldehyde over a Sliver Catalyst. (Also, the subject of a survey report.) 3. Air Oxidation of Methanol in a Methanol-Lean Process to produce Formaldehyde over an Iron Oxide Catalyst. 4. Direct Oxidation of Ethylene to produce Ethylene Oxide. 3. Low pressure catalytic polymerization of Ethylene. The primary data source for these was the Industry Questionnaire, although SEI rankings had not been completed by the time the choices were made. In addition separate "In-Depth" studies were made on Polyvinyl Chloride (PVC) and Vinyl Chloride Monomer (VCM) using data obtained from a separate survey made in the summer of 1974. ucc 026162 1. REPORT NO. EPA-450/3-73-006-1 TECHNICAL REPORT DATA IPlease read Instructions on the reverse before completing) 3. RECIPIENT'S ACCESSION NO, 4. TITLE AND SUBTITLE Engineering and Cost Study of Air Pollution Control for the Petrochemical Industry, Volume 9: Polyvinyl Chloride Manufacture 7. AUTHORIS) 5. REPORT DATE July 1975 a. PERFORMING ORGANIZATION CODE B. PERFORMING ORGANIZATION REPORT NO R. G. Bellamy, W. A. Schwartz 9. PERFORMING ORGANIZATION NAME AND AOORESS Houdry Division/Air Products and Chemicals, Inc. P. 0. Box 427 Marcus Hook, Pennsylvania 19061 12. SPONSORING AGENCY NAME AND ADDRESS EPA, Office of Air Quality Planning & Standards Industrial Studies Branch Research Triangle Park, N.C. 27711 10. PROGRAM ELEMENT NO. 11. CONTRACT/GRANT NO. 68-02-0255 13. TYPE OF REPORT AND PERIOD COVERED Final Report 14. SPONSORING AGENCY CODE IS. SUPPLEMENTARY NOTES IS. ABSTRACT This document is one of a series prepared for the Environmental Protection Agency (EPA) to assist It in determining those petrochemical processes for which standards should be promulgated. A total of nine petrochemicals produced by twelve distinctly different processes has been selected for this type of In-depth study. Ten volumes, entitled Engineering and Cost Study of Air Pollution Control for the Petrochemical Industry (EPA-45Q/3-73-tit)fea through .1) have been prepared. A combination of expert knowledge and an Industry survey was used to select these processes. The Industry survey has been published separately in a series of four volumes entitled Survey Reports on Atmospheric Emissions from the Petrochemical Industry (EPA-450/3-73-005a, b, c, and d). This volume covers the manufacture of polyvinyl chloride. Included Is a process and Industry description, an engineering description of available emission control systems and the cost of these systems. 17. a. DESCRIPTORS Air Pollution* Polyvinyl ChTorlde Vinyl Chloride Chiorohydrocarbons 13- DISTRIBUTION STATEMENT EPA Farm 2330-1 (9-73) KEY WORDS AND DOCUMENT ANALYSIS b.IDENTIFIERS/OPEN ENDED TERMS c. cosati Field/Group Petrochemical Industry Polymer Manufacture 19. SECURITY CLASS (This Report) Unclassified 20. SECURITY CLASS (Thispage) __ Unclassified 7A 7B 7C 11G 13B 13H 21. NO. OF PAGES 22. PRICE ..... ucc 026163 INSTRUCTIONS 1. 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FA Form 222*1 (9-72) (Reversal AL UCC ENVIRONMENTAL PROTECTION AGENCY Technical Publications Branch Office of Administration Research Triangle Park, North Carolina 27711 OFFICIAL BUSINESS AN EQUAL OPPORTUNITY EMPLOYER POSTAGE ANO FEES PAID ENVIRONMENTAL PROTECTION AGENCY EPA 335 Return this sheet it you do NOT wish to receive this material or if change ot address is needed^!]. {Indicate change, including ZIP code.) PUBLICATION NO. EPA-450/3-73-006-i