Document KGjpMLrykGLV0vpQLpwXprY9X

COMPLIANCE MANUAL COMPLIANCE WITH VCM EMISSION STANDARD ABERDEEN PVC PLANT r 000115304 dih COMPLIANCE MANUAL ABERDEEN PVC PLANT TABLE OF CONTENTS I. INTRODUCTION II. NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS STANDARD FOR VINYL CHLORIDE III. GENERAL FACILITIES FOR COMPLIANCE IV. SPECIFIC METHODS OF COMPLIANCE V. METHODS OF COMPLIANCE - TYPE I VI. METHODS OF COMPLIANCE - TYPE II VII. METHODS OF COMPLIANCE - TYPE III VIII. TESTING METHODS FOR TYPE III IX. RECORDKEEPING REQUIREMENTS FOR COMPLIANCE X. APPENDIX LEAK DETECTION AND ELIMINATION PLAN DTH 000115305 COMPLIANCE MANUAL ABERDEEN PVC PLANT INTRODUCTION The Aberdeen Plant manufactures polyvinyl chloride (PVC) resin via batch suspension polymerization. Vinyl chloride, a colorless vapor at ambient conditions, has been identified as the cause of serious health problems. The EPA has promulgated specific emission limita tions regarding the chemical. As a user of vinyl chloride, the Aberdeen Plant is subject to com pliance with the EPA's emission standard. Since identification of the associated health problems with vinyl chloride, the plant has expended substantial funds (in excess of $10 MM) to control emission sources and develop emission containment technology. The facilities for containment of vinyl chloride emissions are essentially complete. Proper operation of the facilities will allow the Aberdeen Plant to contain emissions to the extent required by the EPA's regulation. This document is written to describe the emission containment facilities and techniques employed by the plant. Information on facilities and methods of compliance are described as well as specific operating pro cedures that are used. The Compliance Manual is organized into various sections. Section It contains the Emission Standard as it appeared in the Federal Register on October 21, 1976. Section III describes the general containment philosophy and approach used at Aberdeen. Section TV relates to the specific types of approaches used to achieve or demonstrate compliance. Sections V, VI, and VII contain specifics of compliance with each part of the EPA regulation. These sections are used to segregate 1) facili ties which in themselves resxilt in compliance 2) facilities for which calculational methods are needed to show compliance 3) facilities for which emission testing or sampling is needed to prove compliance. For those facilities which require testing, the testing methods and procedures are described in Section VIII. Recordkeeping requirements are described in Section IX. The standard further requires a "Leak Detection and Elimination Plan". Aberdeen developed such a plan and it has been in force since mid-1977. The plan is included in Section X. DTH 000115306 COMPLIANCE; MANUAL ABERDEEN PVC PLANT NATIONAL EMISSION STANDARD FOR HAZARDOUS AIR POLLUTANTS STANDARD FOR VINYL CHLORIDE Attached is the subject document as it appeared in the Federal Register on October 21, 1976. DTH 000115307 THURSDAY, OCTOBER 21, 1976 PART II: ENVIRONMENTAL PROTECTION AGENCY NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS Standard For Vinyl Chloride DTH 000115308 V.' f-0--Protection of Environment are required to be captured and con greatest water usage would be employed CHAPTER I--ENVIRONMENTAL PROTECTION AGENCY SUBCHAPTER C--AIR PROGRAMS , trolled. Hsaath and Environmental Impacts _ EPA prepared a document entitled the and tlmt there would be no recycling of water. There ls no regulation which would require water recycling. Accord ing to SPL the control system utilizing |FRI. BUM ] Quantitative Risk Assessment for Com the most water will not be used gener PART 61--NATIONAL EMISSION STAND munity Exposure to Vinyl Chloride which ally by the Industry and economic fac rARDS FOR HAZARDOUS AIR POLLUTANTS estimates the risk from vinyl chloride tors will cause plants to recycle much Standard for Vinyl Chloride exposure to populations living In the vi of the water. Therefore, according to cinity of vinyl chloride-emitting plants SPI the Impact of the standard on water On December 24, 1975, under section before and after Implementation of con consumption will be negligible. 112 of the Clean Air Act, as amended (42 trols to meet thfstandard. There are no Tlie environmental Impacts of the U.S.C. 1857), the Environmental Protec dose-response data for tire concentra promulgated standard may be summar tion Agency (EPA) added vinyl chloride tions of vinyl chloride found In the am ized as follows: The primary environ to the list of hoz-ardous air pollutants bient air. Therefore, assessments of risk mental Impacts of the standard are ben (40 FTt 50477) and proposed a national at ambient levels of exposure were ex eficial and will consist of vinyl chloride emission standard for It (40 Fit 69532). trapolated from dose-response data from emission reductions of approximately 94 Tire standard covers plants which manu higher levels of exposure using both a percent at ethylene dlchlorlde-vlnyl facture ethylene dlchlortde. vinyl linear model and a log-problt model. chloride plants and 95 percent at poly chloride, nnd/or polyvinyl chloride. Extrapolations made with each of these vinyl chloride plants. Percentage num EPA decided to regulate vinyl chloride models entailed using different sets of bers for both source categories nre based because It has been Implicated as the assumptions. Because different assump on an estimated 90 percent reduction In \ causal agent of angiosarcoma and other tions can be made In extrapolating to fugitive emissions and 1974 emission serious disorders, both carcinogenic and low doses, the health risks are reported levels. noncarclnogenic, In people with occupa tional exposure and In animals with ex1 pcrlmental exposure to vinyl chloride. T* Reasonable extrapolations from these ' : findings cause concern that vinyl chlo[ ride may cause or contribute to the same m\ or similar disorders at present ambient V. air levels. The purpose of the standard Is , to minimize vinyl chloride emissions .~',V from all known process and fugitive T t. emission sources In ethylene dichloride vinyl chloride and polyvinyl chloride plants to the level attainable with best available control technology. This will In ranges. It was estimated that 4.6 million peo ple live within 5 miles of ethylene dlcho- ride-vinyl chloride and polyvinyl chlo ride plants and that the average ex posure around these plants before Instal lation of controls to meet1 the standard Is 17 parks per billion. The exposure levels for uncontrolled planks were cal culated based on estimated 1974 emis sion levels. Using the linear dose-re sponse model EPA found that the rate of Initiation of liver angiosarcoma among people living around uncontrolled The potential secondary environmen tal Impacts of the standard nre either Insignificant or will be minimized with out additional action, except for one ad verse Impact. Hydrogen chloride ls al ready emitted by process equipment at ethylene dlchlorlde-vlnyl chloride plants and by other petrochemical plants In the complexes where ethylene dlchlorldevlnyl chloride plants are typlcnlly lo cated. An Incinerator used to attain the standard at an ethylene dlchlorlde-vlnyl chloride plant could Increase hydrogen chloride emissions by several fold. Typi lmvc the effect of furthering the protec plants is expected to range from less than cally, however, due to the corrosion prob tion of public health by minimizing the one to ten cases of liver angiosarcoma lems which would otherwise occur both health risks to tire people living in tire per year of exposure to vinyl chloride. on plant property and In the community, vicinity of these plants and to any addi- The log-problt model gave predictions plants use scrubbers to control already _ ttonal people who are exposed as a result that are 0.1 to 0.01 times this rate. Tills existing hydrogen chloride emissions |^tof now construction. wide range Ls an Indication of the un Hydrogen chloride emissions resulting * Interested parties participated In the certainties In extrapolation to low doses. frorft control of vinyl chloride emissions /'""''-ulcmaklng by sending comments to EPA. Due to the long latency time observed In arc expected to be controlled for the flic comments have been carefully con cancer cases resulting from vinyl chloride same reason. If even a moderately effi sidered, and where determined by the exposure, Increases Initiated by exposure cient scrubber (98 percent control) were Administrator to be appropriate, changes thLs year will not be diagnosed until the used to control the hydrogen chloride have been made to the regulation as pro 1990's or later. Vinyl chloride ls also es emissions resulting from Incineration of mulgated. timated to produce an equal number of- vinyl chloride emissions, the Increase In Summary or tub Standard prlrnary cancers at other sites, for a total hydrogen chloride emissions from a typ of somewhere between less than one and ical ethylene dlchlorlde-vlnyl chloride In ethylene dlchlorlde-vlnyl chloride twenty cases of cancer per year of ex plant due to the standard would be re plants, the standard limits vinyl chloride posure among residents around planks. duced to 35 percent. However, EPA plans emissions from the ethylene dlchlorlde The number of these eflecls Ls expected to further evaluate the need to control 1 and vinyl chloride formation and puri to be reduced at least In proportion to the hydrogen chloride emissions, since dif fication processes to 10 ppm. For the ox- reduction In the ambient annual average fusion model results Indicate that under ychlorlnatlon process, vinyl chloride vinyl chloride concentration, which ls "worst-case" meteorological conditions, emissions are limited to 0.2 g/kg of ethyl expected to be 5 percent of the uncon the hydrogen chloride emissions from ene dlrhlorlde product. trolled levels after the standard Is Im the process equipment and the Incinera In |>olyvlnyl chloride plants, the stand plemented. tor combined would cause maximum nm- ard limits vinyl chloride emissions from Changes In the standard since pro blcnt concentrations of hydrogen chlo equipment preceding arid'Including the posal do not affect the level of control ride In the vicinity of ethylene dlchlo- stripper in the plant process flow to 10 required. Thus, the environmental Im rlde-vlnyl chloride planks to be In the ppm. Emissions from equipment follow pact of the promulgated standard Ls, same range or somewhat higher than ing the stripper are to be-oontrolled by with one exception, the same as that existing foreign standards and National stripping dispersion, resins to 2000 ppm described In Chapter 8 of Volume I of Academy of Sciences (NARi guidelines and other resins to 400 ppm, or by using the Standard Support and Environmen for public exposure. equivalent controls. Vinyl chloride emis tal Impact Statement. According to data sions from reactor opening are to be re submitted by the Society of Plastics In ` Economic Impact duced to 0.02 g/kg polyvinyl chloride dustry, Inc. (SPI), the Impact on water In accordance with Executive Order product. consumption In the draft environmental 11821 and OMB circular A-107. EPA In both ethylene dlchlorlde-vlnyl Impact statement was overstated. In es carefully evaluated the economic and chloride and polyvinyl chloride plants, timating the impact on water consump Inflationary Impact of the proposed relief valve discharges and manual vent tion, EPA based Its estimates on worst standard and alternative control levels ing of gases are prohibited except under case conditions. That ls, EPA assumed and certified this In the preamble to the emergency conditions. Fugitive emissions that those control systems with the proposed standard. These Impacts are n FEDERAL REGISTER, VOE. 41. NO. 70S--THURSDAY, OCTOBER 21, IV7S DTH 000115309 7 or Vo'ume t of Act. a puM'i hearing was luid on (lie Hie possible exposure patterns, these the Mandctrd Support and Fnrlrorimcn- pro|K>scd standard on February 3, 197G. cases cannot be Ignored In the evaluation fal Impact Statement. Comments on the In Washington, D.C. Presentations were of the potential public health problems. proposed standard have resulted In only made by the Environmental Defense With regard to the alleged overstated one major change In the economic Im Fund, the Society of the Plastics Indus emission levels, the uncontrolled emis pact analysis. EPA estimated that there try, Inc., Dow Chemical Company, Dia sion loveLs reported by EPA were based would be lour plant closures as a result mond Shamrock Corporation, and Air on 1974 data. Tills qualification was of the promulgated standard. Of the four Products and Chemicals, Inc. Copies of stated wherever emission data were pre- plants Identified as possible closure can the comment letters received, the public sented:- EPA recognizes that emissions didates, one has given notice that It no hearing record, and a summary of the have been reduced since that time, and longer produces polyvinyl chloride and comments with EPA's responses are stated this In the preamble to the pro the other three have Indicated that they available for public Inspection and copy posed stnndnrd. EPA decided not to do not Intend to close as a result of the ing at the EPA Public Information Ref gather more recent data on emission standard. erence Unit, Room 2922 (EPA Library), levels, because these emission levels arc The economic Impacts of the promul 401 M Street, SW,, Washington, D.C. In expected to change, and gathering the gated standard may be summarized as addition, copies of the comment sum data would take considerable time both follows: The total capital cost for exist mary and Agency responses may be ob on the part of EPA and on the part of ing plants to meet the standard Is esti tained upon written request from the Industry. Since the purpose of the stand mated to be $198 million, of which $15 Public Information Center (PM-215), ard Is to minimize emissions, these more million Is for ethylene dlehlorlde-vlnyl Environmental Protection Agency, 401 current data would not affect the stand chloride plants and $183 million Is for M Street, SW,, Washington, D.C. 20460 ard Itself. The 1974 emission levels were polyvinyl chloride plants. EPA estimates (specify Standard Supporf and Environ also used In diffusion modeling to project that these plants will have to spend $70 mental Impact Statement, Emission maximum ambient air concentrations million per year to maintain the required Standard for Vinyl Chloride, Volume II). around uncontrolled plants. These maxi emission levels. In addition, the total capital cost for existing plants to meet the EPA's 1983 water effluent guideline Significant Comments and Changes to Tint Proposed Regulation mum air concentrations would probably be lower If 1976 emission levels were used. 17iIr would reduce the relative impact limitations Is expected to be $83 million (1) Dce.ision to list vini/l chloride as a of the standard below that described In and the total annualized operation cost hazardous air pollutant. In general, the the Standard Support and Environmen Is $17 million. The costs to the Industry commentcrs did not contest EPA's deci tal Impact Statement, but would not of meeting the OSHA standard cannot be sion to list vinyl chloride as a hazardous affect the basis of the standard Itself. quantified at this time, but they are ex air pollutant. However, three cotnment- (2) Aptrroach for Regulating Vinyl pected to overlap to some degree with the ers (two companies and one Federal Chloride Under Section 112. Two ap costs to meet EPA's fugitive emission agency) argued that EPA placed undue proaches other than using best avail regulations. Tire costs of meeting the emphasis on factors suggesting that vinyl able control technology were suggested fugitive emission regulations are Included chloride presented a health risk and by the commentcrs for regulating vtnvl in the total costs cited above for meeting Ignored factors suggesting that no sig chloride under section 112. The first was the promulgated regulation. Broken out nificant risk was involved. Under section to ban polyvinyl chloride products for separately, the capital cost of meeting 112, however, EPA could remove vinyl which substitutes arc currently available the fugitive emission regulations Is $37 chloride from the list of hazardous air and to gradually phase out other poly million and the annualized cost Is $25 pollutants only If information were pre vinyl chloride products as substitutes million. sented to EPA that shows that vinyl arc developed. The standard Is not expected to deter chloride Is clearly not a hazardous air In the preamble to the proposed stand construction of new ethylene dlehlorlde- pollutant. As discussed more fully In the ard EPA specified Its reasons lor not set vlnyl chloride plants or most types of comment summary, the commentcrs did ting a zero emission limit for vinyl new polyvinyl chloride plants. For one not provide conclusive evidence that vinyl chloride, as follows: <l> There are bene type of polyvinyl chloride plant (disper chloride Is not a hazardous air pollutant ficial uses of vinyl chloride products for sion process) that represents 13 percent which causes or contributes to death or which desirable substitutes nre not read of the Industry production, the standard serious Illness, nor did they conclusively ily available; (2) there arc potentially would significantly deter the construc prove that the health risk factors em adverse health and environmental Im ,'..1 tion of smaller plants. phasized by EPA were Insignificant. pacts from substitutes which have not It Is est imated that the price of poly Several other commentcrs agreed with been thoroughly studied; (3) there arc a vinyl chloride resins will rise by approxi mately 7.3 pcrce.nt In ord(?r to maintain precontrol profitability and also to re cover the total annualized control casts necessitated by the standard at ethylene dlehlorlde-vlnyl chloride plants and poly vinyl chloride plants. This Increase Is EPA's decision to list vinyl chloride as a hazardous air pollutant, but argued that EPA had overstated the health problem, the emission levels, and the projected ambient air concentrations around un controlled plants. With regard to the al leged overstated health problem, the number of employees, particularly In the fabrication industries, who would be come at least temporarily unemployed: and (4) control technology is available which Is capable of substantially reduc ing emissions of vinyl chloride Into the atmosphere. estimated to translate Into a maximum commentcrs stated, for example, that the EPA agrees that substitutes do exist or consumer price Increase In goods fabri US. worker EPA discussed ns having .could be manufactured for most i*oly- cated from polyvinyl chloride resins of been exposed to vinyl chloride levels low vtnyl chloride uses. However, In general, approximately 3.5 percent Recovery of er than those usually encountered In these substitutes do not have some of the effluent annualized costs plus mainte polyvinyl chloride production has been more desirable characteristics of poly nance of precontrol profitability Is esti dropped from the National Institute of vinyl chloride, such as nonflammability. mated to add approximately 2 percent to Occupational Safety and Health's listing If vinyl chloride and polyvinyl chloride polyvinyl chloride resin prices and result of workers with angiosarcoma. EPA were banned, other substitutes with In an additional maximum consumer agrees that there are questions concern these more desirable characteristics price Increase of 1 perccrit. ing the level of exposure and In some would likely be developed. There Is a risk Public Participation rases the pathology of these cases not that these substitutes would also have Involved directly In polyvinyl chloride adverse health or environmental effects. During the public comment period. 50 and vinyl chloride production. These un Since control measures arc available comment letters on the proposed stand certainties are stated In the appropriate which can reduce vinyl chloride emis ard were received. There were 24 from footnotes of the Scientific and Technical sions by 90 percent or more. It does not Industry; 3 from environmental groups; Assessment Report on Vinyl Chloride and seem prudent to reduce emissions by the 15 from Federal, State, and local agen PolgvinyI Chloride (STAR' where the remaining percentage and take the risk cies; and 8 from Individual citizens. As angiosarcoma cases are listed. However, of introducing new untested chemicals required by section 112(b) (I) (B) of the In spite of these uncertainties, In view of Into the environment ttDERAl REGISTER, VOl. 41, NO }05--THURSDAY, OCTOBER It, 1974 DTH 000115310 / Another Approach suggested by the capacity of no more limn 0.10 m' <50 venllngwill be permitted as a last resort commenters was to base the standard for gal). Reactors In this size range can gen before the relief valve opens. The same each Individual emission point on cost erally be found In a lnlwu-ntory, whereas notification procedures nre required for versus benefit. Several of the fugitive the larger reactors are typically pilot manual venting to the atmosphere ns nio emission sources were named specifically scale facilities. Emissions from laboratory required for relief discharges. os ones for which the costs of control scale equipment are relatively small, and rwere substantially higher than the bene- application of the controls required by , fits. Although EPA did determine a cost- the standard would be exi>enslvc and Im There arc several changes In the nu merical emission limits In the promul gated standard. Except for the standard r benefit ratio for the controls requirepdractical. EPA also decided to exempt re for reactor opening ioss. these chances for a number of emission points, EPA search and development facilities con simply Involve conversion to the Interna does not believe such a ratio Is an appro taining reactors greater than 0.19 m' (50 tional System of Units (SI). There was priate basts on which to set a standard. gal) and no more thnn 4.07 m' (1100 gnl) nn error Involved In the original calcula Section 111 of the Clean Air Act provides In capacity from all parts of the standard tion used to derive the standard for rear- - for the development of standards based except the 10 ppin limit for reactors, tor opening. Correcting this error dou on best control technology (considering strlpiwrs, monomer recovery systems, nnd bles tire allowable emissions. It Ls em costs). Even under section 111, however, mixing, weighing and holding containers. phasized that the change In this stand standards are not based on a fine bal EPA decided not to require these facili ard Is a correction, nnd not a change In ancing of costs versus benefits. Instead, ties to meet other parts of the standard the intent for the degree of control re costs are considered In terms of the af because of the technical problems In quired. fordability of the control technology re volved In doing so. For example, the Tlie pro|>osed standard required the quired to achieve a given emission level standard for reactor opening Is based In Installation of a rupture disc beneath and the economic Impact of possible part on reducing the frequency of open each relief valve to prevent leakage from standards on the Industry In ques ing the reactor. Research and develop the relief valve. A provision has been tion. Unlike section 111, section 112 docs ment reactors have to be opened after added to the promulgated standard so not explicitly provide for consideration every batch for thorough cleaning. Also, that a rupture disc ls not required If of costs, so It would clearly be Inappro stripping tcclmology Is developed Indi the relief valve ls tied Into a process line priate to consider costs to a greater ex vidually for each resin In research and or recovery system. In tills case, any tent under section 112 than would be development equipment. Therefore, at leakage from the relief valve would be done under section 111. As discussed In tainment of the stripping limitations In contained. the preamble to the proposed standard the research and development equipment The regulation for obtaining vinyl for vinyl chloride, EPA believes costs would not always be possible. The 4.07 chloride samples lias been changed to nn may bo considered under section 112, but m' (1100 gal) figure was selected as an operating procedure. The promised only to a very limited extent; l.e., to upper cut-off point because there ere no standard stated that there were to be assure that the costs of control technol commercial reactors smaller than this. no emissions from taking the samples. ogy are not grossly disproportionate to (4) Emission lirnifs. The only major Several commenters pointed out that Ihc the amount of emission reduction change In the emission limits between use of the word "no" would make tills achieved. In comparison with other proposal and promulgation Is the addi regulation Impractical to enforce. There emission points, the costs of controlling the fugitive emission sources mentioned tion of a provision for emergency manual venting of vinyl chloride from reactors fore. the promulgated standard specifies the operating procedure which EPA orig by the commenters are relatively small to the atmosphere. The proposed stand inally Intended to be used to control compared with the amount of emission ard prohibited all manual venting to the this source. Tills revision Is only a change reduction achieved. atmosphere. In the preamble to the pro In wording nnd does not represent a Several commenters recommended W' ''adding to the regulation a provision for posed standard, EPA Invited interested persons to comment on whether permit change In the level of the standard. Tlie regulation for taking samples has ''""''excess emissions during startup, shut ting manual venting to the atmosphere also" been revised to apply only to sam down, and malfunction. EPA considered couid result In overall lower emissions. ples containing at least 10 percent by this comment, and decided that tills There are several methods available for weight vinyl chloride. Tills ls consistent additlpn Is not necessary for the vinyl preventing relief discharges from reac with the other parts of the standard chloride standard. Startup and shutdown tors. one of which Is manual venting of which apply to equipment- "tn vinyl of tlie process has essentially no effect part of the reactor contents for purposes chloride service." "In vinyl chloride serv on emissions to the atmosphere for poly of cooling and reduction In pressure ice" distinguishes between situations vinyl chloride production, and technology within the reactor. The higher the tem where vinyl chloride Is clearly Involved exists to avoid excess emissions during perature and pressure within the reac and situations where vinyl chloride Is a startup and shutdown at ethylene dl- tor, the greater the amount of vinyl minor component or contaminant, and chloridcvinyl chloride plants. We do not chloride which has to be removed to as defined in promulgated 161.01(1) believe plants should be allowed to emit bring the reactor under control. Manual means that a piece of equipment con excess emissions during malfunctions, venting can be done at a lower pressure tains or contacts either a liquid that ls and therefore are requiring them to shut than the pressure required to open the at least 10 percent by weight vinyl chlo down Immediately. relief valve. For this reason manual vent ride or a Ras that Ls at least 10 percent (3) Selection o/ source categories. In ing can result In lower emissions than by volume vinyl chloride. the preamble to the proposed standard would occur by allowing the reactor to The proposed standard required a vinyl EPA recognized that some small research discharge through the relief valve. Fur chloride monitoring system for continu and development facilities may exist thermore. a manual vent valve Is under ously measuring vinyl chloride levels both where the emissions of vinyl chloride are the control of an operator and can be within the plant (for leak detection) and insignificant and coverlng-thesc facilities closed. A relief valve may become clogged within stacks. Tlie proposed standard did undcT the standard would bc.unnecessary with resin and not close. The result not outline required specifications for tlie and Inappropriate. However, EPA did not would be loss of all the reactor contents. monitoring system, except that It was to have sufficient information available to The contents of a reactor can be man analyze the samples with gas chromatog clearly define which facilities should be ually vented to a gasholder or other hold raphy, or if all hydrocarbons were as excluded from the standard, and ing vessel. However, In some cases, such, sumed to be vinyl chloride, with infrared encouraged Interested parties to submit as during severe weather conditions, sev spectrophotometry, flame Ion detection, such Information during the comment eral reactors may be out of control at or equivalent. It required that each plant period. Based on the Information .sub one time. There would be Insufficient submit a description of Its monitoring mitted, EPA decided to exempt poly vinyl chloride reactors and associated equipment from applicability of all parts holding capacity under these conditions to manually vent the contents of all Uie reactors to a gasholder. Therefore, when system to EPA, so that EPA could deter mine whether It was acceptable or not Comments were received Indicating a need for EPA to specify some criteria for of the standard If the reactors are used all other measures to prevent relief valve judging the acceptability at monitoring In research and development and have a discharges have been exhausted, manual systems. The accuracy at Uvt monitor FEOERAl REGISTER, VOl. 41, NO. 205- THURSDAY, OCTOtll -> DTH 0000001115311 liMv' Ini; system would lie related to U\c fre (g)(3) (in, and 61.70(f) (2) <n so that made the same as for other resins and quency of calibration. Therefore, EPA measurement of the vinyl chloride levels others requested thnt they be made less lias Included In the promulgated stand In the resins Is to be made Immediately stringent. EPA decided not to make the ard requirements for the frequency of after stripping Is completed rather than standard for stripping dispersion resins calibration and procedures to be carried as the resin Is being transferred out of the same as for other resins because there out in the calibration of the monitoring the stripper. Tills allows a plant to carry Is sufficient evidence to Indicate thnt Instruments. out operations in a stripper after strip these resins are more difficult lo strip T he. portable hydrocarbon detector re ping has been completed but before It Is than other resins. With regard to mak quired by the proposed standard was re transferred out of the stripper. Tills Is ing the stripping levels for dispersion quired to have a sensitivity of 5 ppm. consistent with the original Intent of the resins less stringent, only one of the eight Comments were received indicating that standard. manufacturers of dispersion resins spe Instruments In tills sensitivity range are The regulation for loading and unload cifically commented that the dispersion delicate and require continuing mainte ing lines In 5 61.65(b)(1) has been re resin standard should be made less nance. The portable hydrocarbon detec vised to clarify that It applies only to stringent. Only two of several grades of tor Is required for leak detection and for lines that are disconnected alter each dispersion resins made by this company measuring vinyl chloride concentrations loading or unloading operation. Perma cannot meet the 2,000 ppm limit. The Inside the equipment before opening It. nently installed pipelines that arc opened proposed standard takes Into considera A 5 ppm sensitivity Is not needed In Infrequently for Inspection or mainte tion that some resins are more difficult either case, and the required sensitivity nance, for example, are covered by the to strip than others by providing for has been changed to 10 ppm In the pro opening of equipment regulation rather averaging among different resins. mulgated standard. than the loading and unloading line (5' Testing, reporting, and record The proposed standard contained a regulation. keeping. There are several relatively single regulation for compressors. The The regulation for Inproeess waste- minor changes In the testing, reporting, promulgated standard has separate regu water In the proposed standard could and recordkeeping requirements. A pro lations for rotating and reciprocating have been misinterpreted to require In vision has been added to 5 61 67 which compressors. This is consistent with hav dividual treatment of wastewater requires that stack pas samples taken ing separato regulations for rotating and streams. Section 61.65(b) (9) (1) of the with Test Method 106 are to be analyzed reciprocating pumps In both the pro promulgated standard clarifies that within 24 hours. This Is consistent with posed and promulgated standards. wastewater streams thnt are required to the requirements In the pro|y->srd Test Section 61.66 of the proposed standard be treated (l.e.. those containing greater Method 106. The promulgated standard provided for the use of equivalent meth than 10 ppm vinyl chloride) can be com nlso specifies that In averaging the re ods of control which have been approved bined to be treated. However, waste- sults of the three runs required by Test by ETA. The promulgated standard re water streams that contain greater than Method 106, a time-weighted average Is quires that the plant owner or operator 10 ppm vinyl chloride cannot be com to be used. submit a request for determination of bined with wastewater streams that con One eommentcr requested that the equivalency within 30 days of tire pro tain less than 10 ppm vinyl chloride be oxygen content and moisture content be mulgation date if the alternative control fore treatment: le., dilution cannot be specified for the 10 ppm concentration method Is Intended as the Initial means used to meet the standard. standards. T7ie proposed standard speci of control. The purpose of this Is to pro The commenters recommended several fied that the vinyl chloride concentration vide time for EPA to evaluate the method changes In the emission limits which ls to be corrected to 10 percent oxygen before the plant has to be In compliance have not been Incorporated Into the (wet basis) If combustion Is used as the Tor existing sources, 00 days after the promulgated standard. Thrse are dis control measure. In the promulgated promulgation dale). EPA also suggests cussed In the following paragraphs. standard, this requirement has been ex that this request for determination of It was recommended that the require panded to all control measures equivalency be accompanied by a re ment for double mechanical seal* on A provision has been added to the quest for waiver of compliance pursuant pumps, compressors, and agitators be re promulgated standard which states that to section 112(c) (1) (B) (11) of the Act. moved because the single seals currently If a reactor Is also used as a stripper, the Tire request for a waiver for compliance used on this equipment have small emis reactor opening emissions may be deter should provide for the case where EPA sions and arc more reliable than double mined Immediately following the strip determines that a method Is not equiv mechanical seals. EPA Is aware that each ping operation. If a reactor Is also used alent and the plant needs to purchase fugitive emission source, such as one as a stripper, the resin ls In the reactor other equipment. In no case will the pump, taken by Itself causes relatively when It Is opened. This means that vinyl waiver ol compliance be extended beyond small emissions. Fugitive emissions con chloride In the resin which has already two years from the date of promulga sidered as a whole are a significant been stripped to acceptable levels ran tion. source of emissions, however, and the In escape from the resin and become part There are several wording clarifica tent of the standard Is to reduce these. of the reactor opening loss. It Is EPAs tions which have been made In the pro mulgated standard. The definition for Double mechanical seal pumps are com monly used In the Industry for emission Intent that once a resin has been stripped to the required levels, that additional "In vinyl chloride service" (5 60.61(1)) reduction. Sealless pumps or equivalent controls are not required. Under the new has been clarified by stating that It systems are available as options to double provision, vinyl chloride escaping from means equipment that contacts vinyl mechanical seals. the resin after It has been stripped to clilorlde as well os equipment that con The commenters recommended In acceptable levels Ls not counted as part tains vlnyi chloride. This would Include creasing the averaging time for the 10 of the reactor opening loss. such equipment'as agitators. ppm limits and the emission limits for A section requiring continuous moni Words have-been added In 55 61.62, 6163, and 61.64 to clarify that the 10 ppm emission limits do not have to be met when equipment has already been opened In compliance with the regula tion for opening ol equipment. Equip ment that has met the opening of equipment regulation con-contain more than 10 ppm vinyl chloride and would be In violation of the standard If this statement were not included. The requirements for stripping poly reactor opening and stripping to 30 days. Some of the commenters apparently thought that the 10 ppm limits had to be met on an Instantaneous basts. However, since the performance test for determin ing compliance consists of three runs for a minimum of an hour each, the aver aging time for the 10 ppm limit Ls at least three hours. Increasing the averaging time to 30 days lor nny of the emission limits would permit higher peak emis sion levels. EPA has determined that this ls neither desirable nor necessary. toring of stack emissions has been added to the promulgated standard. The con tinuous monitoring of stock emissions was required In the proposed standard. The addition of a specific paragraph for emission monitoring serves only to clarify the requirement. The standard has been revised so thnt the Initial report requires a "description" rather than a "detailed description" of the equipment used to control fugitive emissions. Several commenters pointed out that a detailed description would vinyl chloride resins to specified levels Some commenters requested that the contain proprietary Information. EI'A have been revised In 55 61.64(e), 61.67 stripping levels for dispersion resins be agrees that a detailed description In the FEDERAL REGISTER, VOl. 41, NO. 305--THURSDAY, OCTOBER 31, 1976 DTH 000115312 ^ . - <. umicrc-wary. II ivtldl- In section 8.4 ol Tost Method 106 the (2) Vinyl clilorldo by any process, , v, Ucwil Information It needed. EPA can requirement lor an automatic Integrator and/or ' '/h' obtain It tinder tecllon 114 of the Act and ha* been replaced with a requirement for (31 One or more polymers containing . the plant can request confidential treat- a disc Integrator or planlmeter for meas any fraction of polymerized vinyl chlo mtQt In accordance with 40 CFH Part 2 uring peak area. This change Is In re ride. for tnformaUoc It believes to , be sponse to a comment which states that (b) This subpart docs not apply Us proprietary. automatic Integrators are unnecessarily equipment used In research and develop The propoeed ttAndard required that elaborate and expensive. ment If the renctor used to polymerize > . a aemlannual report be nbmltted erery A new section 6.6 has been added to the vinyl chloride processed In the equip 160 dayt. The promulgated standard Test Method 10$ which requires deter ment lias a capacity of no more thnn tpeclflea date* for the submittal of the mination of the water vapor content of 0.19 m* (50 gal). report*. It also tpeclflea that the flrtt the sampling bag by measuring tlie am fe) Sections of this subpart other than emlannual report doea not hare to bo bient temperature and pressure near the i 61.64(a) (1), (b), (c), and (d) do not submitted until at least nix months alter bag. The vinyl chloride concentration of apply to equipment used In research and the Initial rcj>ort 1* submitted. the bag can then be reported on a dry development if the reactor used to po Hie ttandard 1ms been rcvLscd to elim basis. A provision for checking the rigid lymerize the vinyl chloride processed In inate the requirement to record the cause container for leaks has been added to the equipment has a capacity of greater ol any leak detected by the vinyl chlo section 7.4 of Test Method 108. than 0.19 m* (50 gal) and no more than ride detector, the action token to repair the leak, and the amount of time re quired to repair the leak; EPA Is con cerned only that leaks are detected and The only change In Test Method 107 Is the provision In Section 5.3.2 for use of Carbopak C as well as Cnrbopak A. 4 07 m'(1100 gal). fifil.ftl Definition*. Terms used In this subpart arc defined repaired. That this has been done can be established by looking at the strip chart record of measurements made by the vinyl chloride detector. These records are Atmioanr: Section 112 of the Clean Air Act mi added by sec. 4(a) of Pub. L. D1 604, 84 Stat. 1686 (43 U.S.C. 1867c-7; Section 114 of the Clean Air Act. as added by see. 4(a) of Pub. L. 01-604, 84 Stat. 1687, and amended hi the Act. in subpart A of this part, or In this section as follows: (a) "Ethylene dlchlorlde plant" In cludes any plant which produces ethjl- still required for the portable hydrocar by Pub. L. 03-319, sec. 6(a)(4), 88 Stat. 259 ene dlchlorlde by renctlon of oxygen and bon detector however. (42 use. 1867C-0); Section 301(a) of the hydrogen chloride with ethylene. Several commentators recommended Clean Air Act, aa amended by sec. 16(c)(2) <b> "Vinyl clilorlde plant" Includes that the companies be allowed an extra two weeks to submit to EPA data from of rub. U 01-SO4. 84 Stat. i71S (43 U.SC. 1857g(a)). nny plant which produces vinyl chloride by nny process. the Initial performance test They also recommended that they submit the data by regular mall rather than registered mall. EPA has not adopted either of these recommendations. A source Is supposed to be In compliance with the standard within 90 days of the promulgation of the standard. The standard requires that the emission tests be done within the 00 day period, and permits an extra 30 days for determination of results. Tlie purpose of using registered mall Is to document the fact that emission data nave been sent and received. Tills way f the results are lost tn the mall, there 111 be no question that they were sent. (6) Test method. Test Method 106 has been changed to recognize that on a gas chromatograph equipped with a Chrom- osorb 102 column, acetaldehyde may Interfere wit-h the vinyl chloride peak. When a sample Is expected to contain acetaldehyde, a secondary column as de scribed In section 4.3.2 must be employed. Mass spectroscopy or another absolute analytical technique Is required to con' firm the vinyl chloride peak obtained with the gas chromatograph, only If peak resolution with, tlie secondary column Is not successful. In section 4.1.4. aluminized Mylar bags can be substituted lor Tedlar bags. EPA now has data to allow this substitution, provided that the samples- are analyzed within 24 hours of collection. In section 5.1.3 of Tost- Method 106 the requirement to use "oxygen gas" has been replaced with "oxygen gas or air, as required by the detector." Several eommentors stated that most gas chromato graphs are designed to use hydrogen and air for their flame detectors. When used In this way, they are capable of detect ing 0.5 ppm vinyl chloride In air. This Is Dated: October 12. 1976. John Quari.es, Acting Administrator. Part 61 of Chapter I, Title 40 of the Code of Federal Regulations Is amended as follows: The table of sections for Part 61 Is amended by adding a list of sections for new Subport F and Part 61 Is amended by adding a new Subpart F reading as follows: Subpart F---National Emission Standard for Vinyl Chlorlda Sec 61.60 Applicability. 61.81 Definitions. 61.62 Emission standard for ethylene dl- chlorlde plants. 61.63 Emission standard for vinyl chloride plants. 61.64 Emission standard for polyvinyl chlo ride plants. 61.65 Emission standard for ethylene dl- chlorlde, vinyl chloride and poly vinyl chloride plants. 61.66 Equivalent equipment and procedures. 61.67 Emission testa. 61 68 Emission monitoring. 61.60 Initial report. 61.70 Semiannual report. 81.71 Recordkeeping. Attthorttt: Section 113 of the Clean Air Act as added by eec. 4(a) of Pub. L. 01-60-t, 84 Stat. 1685 (42 U3.C. 1857C-7): section 114 of the Clean Air Act, as added by sec. 4(a) of Pub. L. 91-004, B4 Stat. 1687, and amended by Pub. L. 03-319, sec. 6(a) (4). 88 Stat. 250 (43 U.S.C. 1857c 9); section 301(a) of the Clean Air Act, as amended by see. 16(c) (3) of Pub L. 01-604. 84 Stat. 1713 (42 08.0. 1857g (a)). Subpart F--National Emission Standard for Vinyl Chloride ' 6 61.60 Applicability. (a) This subpart applies to planta which produce: <c> "Polyvinyl chloride plant" Includes any plant where vinyl clilorlde alone or in combination with other materials Is polymerized. (d> "Slip gauge" means a gauge which has a probe that moves through the gas/ liquid interlace In a storage or trnnsfer vessel and Indicates the level of vinyl chloride In the vessel by the physical state of the material the gauge dis charges. <e> "Type of Tcsln" means the broad classification of resin referring to the basio manufacturing process for produc ing that resin. Including, but not limited to, the suspension, dispersion, latex, bulk, and solution processes. tf> "Grade of resin" means the sub division of resin classification which de scribes It as a unique resin, l.e., the most exact description of a resin with no fur ther subdivision. fg) "Dispersion resin" means a resin manufactured In such away as to form fluid dispersions when dispersed In a plasticizer or plastlclzer/dlluent mix tures. (hi "hatex resin" means a resin which Is produced by a polymerization process which Initiates from free Tadleal catalyst sites and Is sold undried. <1> "Bulk resin* 'means a resin which Ls produced by a polymerization process in which no water ls used. <J) "Inprocess wastewater" means any water which, during manufacturing or processing, conies Into direct contact with vinyl chloride or polyvinyl chloride or results from the production or use of any raw material. Intermediate product, finished product, by-product, or waste product containing vinyl chloride or polyvinyl chloride but which has not been discharged to a wastewater treat ment process or discharged untreated as sensitive enough for monitoring tlie 10 (1) Ethylene dlchlorlde by reaction of wastewater. ppm emission limits stipulated tn the oxygen and hydrogen chloride with (k' "Wastewater treatment process" standard. ethylene, Includes any process which modiflea FEDERAL REGISTER, VOL 41, NO. 105--THURSDAY, OCTOBER 21, 197* DTH 000115313 I ' characteristics such as BOD. COD, TSS. 61.fill I ini-Mim vlanilanl for *in?l stripper (or the reactor If the plant has and pH. usually for the purpose of meet rliloriili- plnnl*. no stripper) In the plant process flow Is ing diluent guidelines Rnd standards; It An owner or operator of a vinyl chlo not to exceed 10 ppm, except as provided docs not Include any process the purpose ride plant shall comply with the require In 6 61.65(a). This requirement does not of which Is to remove vinyl chloride from ments of this section and 5 61.65. apply to equipment that has been water to meet requirements of this (a) Vinyl chloride formation and puri opened, is out of operation, and met the subpart. fication: 11)0 concentration of vinyl requirement In 6 61.65(b) (6) (1) before (1) "In vinyl chloride service" means chloride In all exhaust puses discharged being opened. that a piece of equipment contains or to the atmosphere from any equipment <d> Monomer recovery system. The contacts either a liquid that Is at least used In vinyl chloride fonnnllnn and/or concentration of vinyl chloride In all ex 10 percent by weight vinyl chloride or a purification Is not to exceed 10 ppm. ex haust gases discharged to the atmos gas that Is at least 10 percent by volume vinyl chloride. <mi "Standard operating procedure" means a formal written procedure offi cially adopted by the plant owner or cept ns provided In 5 61.65(a). This re phere from each monomer recovery sys quirement does not npply to equipment- tem Is not to exceed 10 ppm. except ns that has been opened. Is out of operation, provided In 5 61.65(a). Tills requirement and met the requirement In 5 61.65<b> does not apply to equipment that has (6) (1) before being opened. been opened. Is out of operation, and met operator and available on a routine basis to those persons responsible for carrying out the procedure. (n) "Run" means the net period of time during which an emission sample Is collected. (o) "Ethylene dichlorlde purification" Includes any part of the process of ethyl ene dichlorlde production which follows ethylene dichlorlde formation and In which finished ethylene dichlorlde Is produced. (p) "Vinyl rhlorldc purification" In cludes any part of the process of vinyl chloride production which follows vinyl chloride formation and In which finished vinyl chloride Is produced. fn> "Reactor" Includes any vessel In which vinyl chloride Is partially or totally polymerized Into polyvinyl chloride. 61.61 Emission slnmlnril for piilninjl rliloriile plant*. An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of this section and 5 61.65. (a) Reactor: The following require ments apply to reactors: (1) The concentration of vinyl rhlorirlc In all exhaust gases discharged to the atmosphere from each reactor is not to exceed 10 ppm, except as provided In paragraph (a) (2) of this section nnd 6 61.65(a). (2) The reactor opening loss from each reactor Is not to exceed 0.02 g vinyl chloride/Kg (0.00002 lb vinyl chloride/ lb) of polyvinyl chloride product., with the product determined on a dry solids basis. This requirement applies to any vessel which is used ns a reactor or ns the requirement In 6 61.65(b) (6) (I) be fore being opened. <e) Sources following the strippcr(s) : The following requirements apply to emissions of vinyl chloride to the at mosphere from the combination of ail sources following the stripper(s) tor the reactor(s) If the plant has no strlpper(s)] In the plant process (low In cluding but not limited to, centrifuges, concentrators, blend tanks, fitters, dry ers, conveyor air discharges, baggers, storage containers, and Inproccss waste water: (1) In polyvinyl chloride plants tiring stripping technology to control vinyl chloride emissions, the weighted avem-e residual vinyl chloride concentration In nil grades of polyvinyl chloride resin processed through the stripping opera tion on each calendar day. measured cri "Reactor opening loss" means the both a reactor nnd a stripper. Tn Ihc immediately after the stripping opera emissions of vinyl chloride occurring bulk process, the product means the tion Is completed, may not exceed: when a reactor Is vented to the atmos gross product of prepolymerlzntlon nnd <i) 2000 ppm for polyvinyl chloride phere for any purpose other than an postpolymerization. dispersion resins, excluding latex resltis; emergency relief discharge as defined In (3) Manual vent valve discharge: Ex (il) 400 ppm for all oilier polyvinyl 5 61 65(a). cept for an emergency manual vent valve chloride resins. Including la'cx resins, (s) "Stripper" includes any vessel in discharge, (here Is to be no discharge to nvernged separately for each type of res which residual vinyl chloride Is removed the atmosphere from any manual vent in; or from polyvinyl chloride resin, except valve on rt polyvinyl chloride reactor in (2) In polyvinyl rhloridc plants con bulk resin, in the slurry form by the use vinyl chloride service. An emergency trolling vinyl chloride emissions with of heat and/or vacuum. In the case of manual vent valve discharge means a technology other than stripping or In bulk resin, stripper includes any vessel discharge to the atmosphere which could addition to stripping, emissions of vinyl which is used to remove resldunl vinyl not have been avoided by taking meas chloride to the atmosphere may not chloride from polyvinyl chloride resin ures to prevent the discharge. Within 10 exceed: Immediately following the polymeriza days of any discharge to the atmosphere (I)2 g/kg (0.002 lb/lb) product from tion step In the plant process flow. from any manual vent valve, the owner the strlpper(s) tor rcaetor(s) If the 61.62 l,!iiii**in Mnmliiril for clliyli-iic ilitliloriilr plants. or operator of the source from which the plant lias no strlppcr(s)] for dispersion discharge occurs shall submit to the Ad- ' polyvinyl chloride resins, excluding latex minlstrator a report In writing contain resins, with the product determined on a An owner or operator of an ethylene ing Information on the source, nature dry solids basis; dichlorlde plant shall comply with the requirements of this section and 5 61.65. (a) Ethylene dichlorlde purification: .The concentration of vinyl chloride in all exhaust gpscs discharged to the at mosphere from any equipment used In and cause of the discharge, the dale and time of the discharge, the approximate total vinyl chloride loss during the dis charge, the method used for determining the vinyl chloride loss, the action that was taken to prevent the discharge, nnd measures adopted to prevent luture dis (II) 0.4 g/kg (0.0004 lb,lb) product from the strippers Tor reactor(s) If the plant has no strlpper(s)l for nil other polyvinyl chloride resins. Including latex resins. with the product dctennlncd on a dry solids basis. ethylene dichlorlde purification Is not charges. 61.6.3 Knii*siiin *l:inilarif fur a Ili* 1.-tie- . to exceed 10 pfim, except ns provided In 5 61.65(a).' This requirement does not npply to equipment that has been (b) Stripper: The concentration of vinyl chloride In all exhaust gases dis charged to the atmosphere from each stripper Is not to exceed 10 ppm. except ilirlilnriili-, a'mil rMiiridi- nnd pnlji ill* I rliloriile |d:ml*. An owner or operator of an ethylene dichlorlde, vinyl chloride, and/or poly opened, Is out of operation, and met the as provided In 5 61.65(a). Tills require vinyl chloride plant shall comply with requirement In 5 61.65(b) before being ment docs not apply to equipment thnt the requirements of tills section. opened. ' has been opened, Is out of operation, nnd (a) Relief valve discharge: Except for (b) Oxychlorinatlon reactor; Except met the requirement In | 61.65(b) (6) (1) an emergency relief discharge, there Is as provided In 5 61.65(a), emissions of before being opened. to be no discharge to the atmosphere vinyl chloride to the atmosphere from each oxychlorinatlon reactor are not to exceed 0.2 g/kg the 100 percent ethylene (c) Mixing, weighing, nnd holding containers: The concentration of vinyl chloride In all exhaust gases discharged to the atmosphere from each mixing, from any relief valve on any equipment In vinyl chloride service. An emergency Tellet discharge means a discharge which could not hnve been avoided by taking dichlorlde product from the oxychlorl- weighing, or holding container in vinyl measures to prevent the discharge. With . nation process. chloride service which precedes the in 10 days of any relief valve discharge. FEDERAL REGISTER, VOL 41, NO. 205--THURSDAY, OCTOBER 21, l?7A DTH 000115314 \ the o-.', nrr or operator of llic source from system from which the concentration of ride is to be reduced so that the equip which the relief valve discharge occurs vinyl chloride In the exhaust gases does ment contains no more than 2.0 percent shall submit to the Administrator a re not exceed 10 ppm; or equivalent ns by volume vinyl chloride or 0.0050 m' (25 port in writing containing Information provided in 5 61.66. gal) of vinyl chloride, whichever Is on the source, nature and cause of tire (ill) Rotating, compressor: Vinyl larger, at standard temperature and discharge, the date and time of the dls- chloride emissions from seals on all ro pressure; and charge, the approximate total vinyl chlo r ride loss during the discharge, the mctliod used for determining the vinyl chlo ride loss, tire action that was token to tating compressors In vinyl chloride service arc to be minimized by Installing compressors with double mechanical scnls, or equivalent as provided In 8 61.66. <li' Any vinyl chloride removed from the equipment In accordance with para graph (b)(6) (I) of this section Ls to be ducted through a control system from prevent the discharge, and measures If double mechanical seals are used, vinyl which the concentration of vinyl chlo adopted to prevent future discharges. chlorjde emissions from the seals are to ride In the exhaust gnses does not. exceed (b) Fugitive emission sources: .be minimized by maintaining the pres 10 ppm, or equivalent its provided In (li loading and unloading lines: Vinyl sure between the two seals so that, any 8 61 66. chloride emissions from loading and un leak that occurs is Into the compressor; 7) Samples: Unused portions of sam loading lines which are opened to the by ducting any vinyl chloride between ples containing at. least 10 percent by atmosphere after each loading or un the two seals through a control system weight, vinyl chloride nre to be returned loading operation are to be minimized from which the concentration of vinyl to the process, and sampling technique: as follows: chloride In the exhaust gases does not m e to be such that sample containers In (1) After each loading or unloading exceed f 0 ppm; or equivalent as provided vinyl chloride service are purged Into a operation and before opening a loading In 8 61.66. closed process system. ojr unloading line to tile atmosphere, the (Iv) Reciprocating compressors: Vinyl fR> Leak detection and elimination: quantity of vinyl chloride In all ports of chloride emissions from seals on all re Vinyl chloride emissions due to leaks each loading or unloading line that are ciprocating compressors In vinyl rlilorlde from equipment In vinyl chloride service to be opened to the atmosphere is to be service are to be minimized by Installing me to be minimized by Instituting and reduced so that the parts combined con double outboard seals, or equivalent as implementing a formal leak detection tain no greater than 0.0038 m' (0.13 ft') provided In 8 61.66. If double outboard and elimination program. The owner or of vinyl chloride, at standard tempera seals are used, vinyl chloride emissions operator shall submit a description of ture and pressure; and from the seals are to be minimized by the program to tbe Administrator for (11) Any vinyl chloride removed fiom maintaining the pressure between the approval. The program Is to he sub a loading or unloading line in accord two seals so that any leak Hint occurs Is mitted within 45 days of the effective ance with paragraph (b)(l'(i) of this Into the compressor; by ducting any date ol these regulations, unless n waiver section Is to be ducted through a control vinyl clrlorldc between the two seals ot compliance ls granted under 8 61.11 system from which the concentration of through a control system from which the Jf a waiver of compliance is granted, the vinyl chloride In the exhaust gases does concentration of vinyl chloride In the program Ls to be submitted on a date not exceed 10 ppm, or equivalent as pro exhaust gases docs not exceed 10 ppm; srheduled by the Administrator. Ap vided In { 61.66. or equivalent as provided In 8 61.66. proval of a program will be granted by (2) Slip gauges: During loading or un (v) Agitator: Vinyl chloride emissions the Administrator provided he finds: loading operations, the vinyl chloride from seals on nil agitators In vinyl chlo <!' It Includes a reliable and accurate emissions from each slip gauge In vinyl ride service are to be minimized by In vinyl chloride monitoring system for de chloride service are to be minimized by stalling agitators with double mechani tection of major leaks and identification ducting any vinyl chloride discharged cal seals, or equivalent as provided in of the general area of the plant where a from the slip gauge through a control 8 61,66. If double mechanical seals arc leak Is located. A vinyl chloride monitor rsystem from which the concentration of used, viiiyl chloride emissions from the ing system means a device wlilrli obtains vinyl chloride In the exhaust gases does seals are to be minimized by maintaining air samples from one or more points on not exceed 10 ppm, or equivalent as pro the pressure between the two seals so n continuous sequential basis and ana vided In } 61.66. that any leak that occurs Is Into the agi lyzes Hie samples with gas chromatog (3). Leakage from pump, compressor, tated vessel; by ducting any vinyl clilo- raphy or. If tbe owner or operator as and agitator seals: ride between the two seals through a sumes that all hydrocarbons measured (1) Rotating pumps: Vinyl chloride control system from which the concen arc vinyl chloride, with Infrared spectro emissions from seals on all rotating tration of vinyl chloride In the. exhaust photometry flame Ion detection, or an pumps In vinyl chloride service are to be gases does not exceed 10 ppm; or equiva equivalent or alternative method. minimized by Installing sealless pumps, lent as provided In 8 61.66. Mi' It Includes a reliable and accurate pumps with double mechanical seals, or (4) Leakage from relief valves: Vinyl portable liydroeaibon detector to bo used equivalent as provided In S 61.66. If chloride emissions due to leakage from routinely to find small leaks and to pin - double mechanical seals are used, vinyl each relief valve on equipment in vinyl point the major leaks Indicated by the chloride emission from the seals are to chloride service are to be minimized by vinyl rlilorlde monitoring system. A be minimized by maintaining the pres Installing a rupture disk between the portable hydrocarbon detector means a sure between the two seals so that any equipment and the relief valve, by con device which measures hydrocarbons leak that occurs Is Into the pump: by necting the relief valve discharge to a willi a sensitivity of at least 10 ppm ducting any vinyl chloride between the process line or recovery system, or equiv mid is of such design and size that It ran two seals through a. control system from alent as provided In 8 61.66. be used to measure emissions from local which tire concentration- of vinyl chlo (5' Manual venting of gases: Except ized points. ride In the exhaust gases does not ex as provided In 161.64(a)(3). all gases < lit' R provides for nri arreplable cali ceed 10 ppm; or equivalent as provided which are manunlly vented from equip bration and maintenance schedule for In 5 61.66. ment in vinyl chloride service are to be the vinyl chloride monitoring system and (ID Reciprocating pumps: Vinyl chlo ducted through a control system from portable hydrocarbon detector. For the ride emissions from seals on all recipro which the concentration of vinyl chloride cating pumps tn vinyl chloride service In the exhaust gases does not exceed 10 are to be minimized by Installing double ppm; or equivalent as provided In 8 61.66. outboard seals, or equivalent as provided (6) Opening of equipment; Vinyl In i 61.66. If double outboard seals Are chloride emissions from opening of vinyl chloride monitoring system, a dally span eherk ls to be conducted with a concentration of vinyl chloride equal to the concentration defined as a leak ac used, vinyl chloride emissions from the equipment (Including loading or unload cording to paragraph (b) (8) (vl) of this seals are to be minimized by maintaining the pressure between the two seals so ing lines that arc not opened to the at mosphere after each loading or unload ing operation) are to be minimized as that any leak that occurs Is Into the follows: section. Tire calibration Is to be done with either: (Ai A calibration gas mixture pre pump; by ducting any vinyl chloride be- (1) Before opening any equipment for pared from the gnsea specified In sections k. tween the two 6eals through a control any reason, the quantity of vinyl chlo 5.2.1 and 5.3.3 of Test Method 100, or FEOESAl REGISTER, VOL. 41, NO. 205--THURSDAY, OCIORER 21. 1976 DTH 000115315 i Hi A callbinlion rns cylinder contain vinyl chloride In equipment ^4.75 m* of emission test results and other data ing the appropriate concentration of 01250 Bnl In volume for which an mis needed to determine emissions. vinyl chloride. If a calibration gas cylin der is used, the analysis must be trace able to the National Bureau of Stand ards nr to a gravimcti ically calibrated sion limit is prescribed In 9 61.65(b)(6) (1) prior to opening the equipment and using Test Method 106, n portable hydro (g) Unless otherwise specified, lire owner or operntor shall use test Test Methods In Appendix B to tills part for each test ns required by paragraph; vinyl chloride permeation tube carbon detector, or an equivalent or al (g)(l>, (g> <2>, <gM3>, (g) < 4', and i ivi The location and number of points ternative method. Tire method of meas (gi`5) of tills section, unless nn equiva to be monitored and tho frequency of urement Is to meet the requirements in lent method or an alternative method monitoring provided lor in the program are acceptable when they are compared 9 61.67(g) (5) (1) (A) or (gi 05' (H <B>. has been approved by tire Administrator If the Administrator finds reasonable with the number of pieces of equipment | fil.fjfi F.quHnlrnl vipiipmcid ami pro- grounds to dispute lire results nblninrd In vinyl chloride service and the size Rnd recliirr". by nn equivalent or alternative method, physical layout of tire plant. 'v) It contains an acceptable plan of action to be taken when a leak is de tected. (vtl It contains a definition of leak Upon written application from an own er or operator, the Administrator may approve use of equipment or procedures which have been demonstrated to his he may require the use of a reference method If tire results of the refeicnre and equivalent or altei native methods do not agree, the results oblninrd by tire reference method prevail, nnd the Ad which is acceptable when compared with satisfaction to be equivalent In terms of ministrator may notify the owner or the background concentrations of vinyl reducing vinyl chloride emissions to the operator that approval of the method chloride In the areas of the plant to be monitored by the vinyl chloride monitor ing system. Measurements of background concentrations of vinyl chloride In the areas of the plant to be monitored by the vinyl chloride monitoring system are to be included with the description of the program. The definition of leak for a given plant may vary among the differ ent areas within the plant and Is also to change over time as background con centrations In the plant are reduced. (9) Inproccss wastewater: Vinyl chlo atmosphere to those prescribed for com pliance with a specific .paragraph of this subpart. For an existing source, any re quest for rising an equivalent method as the initial measure of control Is to be submitted to the Administrator within 30 days of the effective date. For a new source, any request for using an equiva lent method Is lo be submitted to the Administrator villi the application for approval of construction or modification required by 9 61.07. previously considered to be equivalent or alternative Is wilhdrnwn 'll Test Method 106 Is to be used to determine tire vinyl chloride emissions from any source for which nn emission limit is prescribed in 55 61.62<n> or (bi 5 61.63'a', or 5 5 61.64m' (1>, (b\ 'o', or < (11. or from any control system to which reactor emissions are required to be ducted in 5 61.64'n' <2' or to which tunl- live emissions are required to be durted in 55 R1.65 (b> (li <lt' . <b'<2>, ibX5i. (b'(6 > Mi', or (b) < 9 > i li'. ride emissions to the atmosphere from 61.67 l'.miiiiim U-U. < 1 * For each run. one sample is to be Inproccss wastewater are to be reduced as follows: (1) The concentration of vinyl chlo ride In each lnprocess wastewater stream containing greater than 10 ppm vinyl chloride measured immediately as it leaves a piece of equipment and before being mixed with any oilier inproccss wnstewater stream Is to be reduced to no more than 10 ppm by weight before being mixed with any other inprocess wastewa ter stream which contains less than 10 ppm vinyl chloride: before being exposed lo the atmosphere, before being dis charged to a wastewater treatment proc ess: or before being discharged untreated as a wastewater. The paragraph does (a) Unless a waiver of emission testing Is obtained under 9 61.13. the owner or operator of a source to which this sub part applies shall test emissions from the source, (1) Within 90 days of the effecllve date In the case of qn existing source or a new source which has an initial startup date preceding the effective dale, or (21 Within 90 days of startup In,the case of a new source. Initial startup of which occurs after the effective date. (b) The owner or operator shall pro vide the Administrator at least 30 days prior notice of an emission test to afford the Administrator the opportunity to have an observer present during the test. collected. The sampling site Is to tie nt least two stack or duct diameters down stream and one half diameter upstrenm from any flow disturbance such as iv bend, expansion, contraction, or visible flame. For a rectangular cross section an equivalent diameter Is to be determined from the following equation: f li'iigMi I 1 w idi li) rqiiivnli-iit ditiincli r - 2 length I width Tire sampling point in tire duct, is lo be at the centroid of the cross section. The sample Is to be extracted at a rnte proportional to the gRS velocity at the sampling point. Tire sample is to Ire taken over a minimum of one hour, nnd apply to water which Is used to displace vinyl chloride from equipment before It (c) Any emission test Is to be con ducted while the equipment being tested Is to contain a minimum volume of 50 liters corrected to standard conditions. Is opened to the atmosphere In accord ance with 9 61.64(a) (21 or paragraph (b) (6) of this section, but does not apply to water which Is used to wash out equip ment after the equipment has already been opened to the atmosphere In ac cordance with 5 61.64(a)(2) or para- . graph (b) (6) of this section. is operating at the maximum production rate at which the equipment will bo op erated and under other relevant condi tions ns may be specified by the Adminis trator based on representative perform ance of the source. (d) Each emission test Is to consist of three runs. For the purpose of deter (lt> For gas streams containing more Ilian 10 percent oxygen, tho concentra tion of vinyle chloride ns determined by Test Method 106 Is to be corrected to 10 percent oxygen for determination of emissions by using the following equa tion: <11) Any vinyl chloride removed from mining emissions, the average of results the inprocess wastewater in accordance with paragraph (b) (9) (i) of this section of all runs Is to apply. The average Is to be computed on a time weighted basis, * r r( * jp o 11.,1,-,r1i-i nl 11, Is to be ducted through a control system (e) All samples arc to be analyzed from which the_ concentration of vinyl within 24 hours, and vinyl chloride emis ^*fc(rtri*ctrd) *'r ''`"''"'nlrvilnn of \\ny\ th'inid.- In Mm Mh in it iv;e4, rrrrf'* tM to 1(> per. percent oxyfun. chloride In the exhaust gases does not sions are to be determined within 30 days exceed 10 ppm, or equivalent as provided after the emission test, lire owner or CTh% conrrnWuUnn of vinyl rhWldr rvi nmwnrM by T*vt Method tort. 20.9-I>re<nt oivsti tn the Ambient nlr nt In 9 61.60. operator shall report the determinations Mnndnrd rondtUnn*. (c) Tho requirements in paragraphs to the Administrator by a registered 10.9-|We*nt oxygen In tho nml<iMd oir nt sUncHrd condition*, mh>u ihn to (b)(1), (b)(2), (b)(6), (b)(6). (b)(7) letter dispatched before the close of the portent oxyc*n to which then>rn''- and (b) (8) of tills section are to be In next business day following the deter lion IS brine mnrto. rcfccnt Ot* Percent niyeon In tho Mhiu*l cm w corporated into a standard operating mination. HiNuntrM by Ueferone* Method 5 In procedure, anr made available upon re (f) The owner or opera lor shall retain Appendix A of Putt on of this rhnpter. quest for Inspection by the Administra at the plant and make available, upon dll' For those emission sources where tor. Tho standard operating procedure Is request, for Inspection by the Adminis the emission limit Is prescribed In terms to Include provisions for measuring the trator, for a minimum of 2 years records of mass rather than concentration, mas* FEDERAL REGISTER, VOL. 41, NO. 10S--THURSDAY, OCTOER 2). 1476 DTH 000115316 emissions In kg/100 kg product are to that Is also used as a stripper, tlie deter detection, or an equivalent or alterna be determined by using the following mination may be made Immediately fol tive method. The vinyl chloride monitor equation: lowing the stripping o|>ernUon. ing system used to meet the requirements | !C> (2.00) Q IQ *] HOP] Z r<>: *-kR Inyl chlorMtVIOO kg product i-Tl* ronfcntratlon of rJnyi chloride M monsured bjr Tart Method 100. ^.60-*Pen.<Ur of vinyl chloride el one fttmoophvr* end aPC In kg/m1. <^Volumetrlc flow rot* In mVhr os determined hy Reference Method 2 of AppendU A to Port CO of this chnnlor. 1 10-*Onrenflon fiwtcr ft'T ppm. /-Production rat* (kg/hr). (2) Test Method 107 Is to be used to determine the concentration of vinyl (D Except as provided In paragraph (g)(5)(il) of this section, the reactor opening loss is to be determined using the following equation: W (2.60) (10* ') (Cb) %h'rr: ' YZ C*kg thiyl chloride fjnlsflous/kg product. H Capacity of the reactor In nr*. 2.fi0D*Mly of tiny! ehlorldo at one atmosphere and 20" Cln k*/m#. 1a0>^~Cppomnvehrysivoonlufamcetovr finoryrl*pcmhl.oride a* determined by Tost Molhod ion or a porlaldc hydroeiuNtn In I 61.65(b) (8) (1) may be used to meet the requirements of this section. (c) A datly span check Is to be eonducted for each vinyle chloride monitor ing system used. For all of the emission sources listed In paragraph (a> of this section, except tire one for which an emis sion limit Is prescribed In 5 61.62(b), the dally span check Is to be conducted with a concentration ol vinyl chloride equal to 10 ppm. For the emission source lor which an emission limit Is prescribed In 5 61.62(b), the dally span check Is to be chloride In each Inproecss wastewater stream for which an emission limit Is prescribed in | 61.65(b) (9) (1). (3> Where a stripping operation Is used to attain the emission limit In | 61.- detector which measure* hydrocarbon* with a arnnUlvlty of at leaat 10 ppm. "Numher of hatch** since th* reactor wv Ivt 0|>ene<l to the atmosphere. '"Avocoao kg ol polyvinyl eWorld* produced per --baten In the number of batches sine* the reactor was last opened to the atmosphere. conducted with a concentration of vinyl chloride which Is determined to be determined to be equivalent to the emis sion limit for tiint source based on the emission test required by 5 67.67. The 64(e). emissions are to be determined 'calibration Is to be done with either: using Test Method 107 as follows: (A) If'Method 10G is used to deter (1) A calibration gas mixture pre (1) The number of strippers and sam mine the concentration of vinyl chloride pared from the gases specified in sections ples and the types and grades of resin to (Cb), the sample is to be withdrawn at 5.2.1 and 5.2.3 of Test Method 106, or be sampled are to be determined by the a constant rate with a probe of sufllcient (2> A calibration gas cylinder con Administrator for each Individual plant length to reach the vessel bottom from taining the appropriate concentration of at the time of the test based on the the manhole. Samples are to be taken vinyl chloride. If a calibration gas plant's operation. for 5 minutes within 6 inches of the ves cylinder Is used, the analysis must be (ID Each sample Is to be taken Imme sel bottom, 5 minutes near the vessel traceable to the National Bureau ol diately following the stripping operation. center, and 5 minutes near the vessel top. Standards or to a gravimctrlcally cali (Ill) The corresponding quantity of (B) If a portable hydrocarbon dctcc- ` brated vinyl chloride permeation lube. material processed by each stripper Is to tor Is used to determine the concentra 61.6') Initial report. be determined on a dry solids basis and by a method submitted to and approved by the Administrator. (Iv) At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re quired in paragraph (g) (3) (1) of this section. 00^(4) Where control technology other r ^an or In addition to a stripping opera- n Is used to attain the emission limit { 61.64(e), emissions are to be deter mined as follows: (D Test Method 106 Is to be used to determine atmospheric emissions from nil of the process equipment simultane ously. The requirements of paragraph (g) (1) of this section are to be met. (ID Test Method 107 Is to be used to determine the concentration of vinyl chloride In each lnprocess wastewater stream subject to the emission limit pre scribed In i 61.64(e). The mass of vinyl tion of vinyl chloride (Cb), a probe of sufficient length to reach the vessel bot tom from the manhole Is to be used to make the measurements. One measure ment will be made within 6 inches of the vessel bottom, one near the vessel center and one near the vessel top. Measure ments arc to be made at each location until the reading is stabilized. All hydro carbons measured are to be assumed to be vinyl chloride. (C) The production rate of polyvinyl chloride (Z) Is to be determined by a method submitted to and approved by tire Administrator. (ID A calculation based on the number of evacuations, the vacuum involved, and the volume of gas in the reactor is hereby approved by the Administrator as an al ternative method for determining reac tor opening loss for postpolymerlzallon reactors hi the manufacture of bulk resins. (a) An owner or operator of any source to which tills subpart applies shall submit a statement In writing notifying the Administrator that the equipment and procedural specifications In {} CI.65 (b)(1). (b)(2), (b)(3), (b)(4), (b)(5), <b)(G', (b)(7), and (b)(8) are being Implemented. (b)(1) In the case of an existing source or a new source which has an initial startup date preceding the effee- tlve date, the statement Is to be submit ted within 90 days of the effective date, unless a waiver of compliance is granted under J 61.11. along with the Informa tion required under 61.10. If a waiver of compliance Is granted, the statement Is to be submitted on a date scheduled by the Administrator. (2) In the case of a new source which did not have an Initial startup date pre ceding the effective date, the statement is to be submitted within 90 days of the chloride In kg/100 kg product in each g (.1.611 Kivii-iM>n in (mil ori n Initial startup date. In process wastewater stream is to be de termined by using the following equa tion: Cpx~ ic t n vo Z 'i jiooi llorr1 ,,. Cm vinyl rlilnrhWlOO kg prclud. < 4-Uip concentration of tiny! chWrt'd* fw mctwUT*d ; hy Tost MMhod 1H7. \ RwWftfcr flow rnlMn t/hr, determined In accordant* r with a method which ho* been submitted to I and approved by the Administrator. : 10 Conversion fartor for ppin. ( /-Production rate (kR/hO determined hi accord \ ance with a method which liw been submitted and approved by tti* Administrator. (5) The reactor opening loss for which (a) A vinyle chloride monitoring sys tem Is to be used to monitor on a con tinuous basis the emissions from the sources for which emission limits arc pre scribed in 5 61.62(a) and (b). $ 61.63(a). and I 61.64(a) (1); (b), (c). and (d), and for any control system to which reactor emission are required to be ducted in 5 61.65(b)(1)(H). and (b)(2), (b)(5), (b) (6) (ID , and (b) <9) (ID . (b) The vinyl chloride monitoring system(s) used to meet the requirement In paragraph (a) of this section Is to be a device which obtains air sampcls from (c) The statement Is to contain the following Information: (1) A list of the equipment Installed for compliance, (2) A description of the physical and functional characteristics of each piece of equipment. <3) A description of the methods which have been Incorporated Into the standard operating procedures for meas uring or calculating the emtsslons for which emission limits are prescribed In 55 61.65 (b) (1) (1) and (b)(6) (I). (4) A statement that each piece of equipment Is Installed and that each an emission limit Is prescribed In | 61.64 one or more points on a continuous piece of equipment and each procedure (a) (2) Is to be determined. The numher sequential basis and analyzes the samples is being used. of reactors for which the determination is to be made Is to be specified by the Administrator for each individual plant at the time of the determination based with gas chromotography or, If the owner or operator assumes that all hydrocar bons measured are vinyl chloride, with 61.70 Srniiiinmutl report. (a) (2) Is to be determined. The number source to which this subpart applies shall the plant's operation. For a reactor infrared spectrophotometry, flame Ion submit to the Administrator on Septem- FEDERAt REGISTER, VCl. 4), NO. 205--THURSDAY, OCTOBER 21, 1726 DTH 000115317 I \ r* i . . ... < i' . c' r,t vrnr a uT'or*. of 8 hours fo: each grade of resin which may be made immediately following the In writing containing the Information Is being processed. whichever Is more fre stripping oi>cratlon. required hi- this section. The first scml- quent. The sample Is to be taken as the nnnual report Is to he submitted follow resin flows out of tire stripper and Iden S bl.71 Jircordkeopine. ing the first full 6 month reporting period tified by resin type and grade and the (a) Tire owner or operator nl any after the initial report Is submitted. date and time the sample was taken. source to which this subpart applies shnll <b)(1) In the case of an existing source The corresponding quantity of material retain the following Information at the or a new source which has an Initial processed by each stripper over the time source and make It available lor inspec startup date preceding the effective date, period represented by the sample during tion. by the Administrator for a mini the first report Is to be submitted within the eight hour period. Is to be recorded mum of two years: 180 days of the effective date, unless a and Identified by resin type and grade (1) A record of the leaks detected In- waiver of compliance Is granted under and the date and time It represents. the vinyl chloride monitoring system, a; 5 61.11. If a waiver of compliance Is (Ill) The quantity of material proc required by 5 61.65'b) 18'. Including the granted, the first report Is to be sub- essed by the stripper ts to be determined concentrations of vinyl chloride ns milted on a date scheduled by the Ad on a dry solids basts and by a method mensuml, analysed, and recorded by the ministrator, submitted to and approved by the Ad vinyl chloride detector, the location of (21 In the case of a new source which ministrator. each measurement and the date and ap did not have an Initial startup date pre (Iv) At the prior request of the Ad proximate time of each measurement ceding the effective date, the first report ministrator, the owner or operator shall (2) A record of the leaks detectrd is to be submitted within 180 days of the provide duplicates of the samples re during routine monitoring with the Initial startup date. quired in paragraphs (c)(2) (1) and (c) portable hydrocarbon detector and the (c) Unless otherwise specified, the owner or operator shall use the Test Methods In Appendix B to this part to conduct emission tests as required by paragraphs (c)(2) and (c)(3) of this section, unless an equivalent or an alter native method has been approved by the Administrator. If the Administrator finds reasonable grounds to dispute the results obtained by an equivalent or al ternative method, he may require the use of a reference method. If the results of the reference and equivalent or alterna tive methods do not ngree, the results obtained by the reference method pre (2) (it) of tilts section. (v) The report to the Administrator by the owner or operator Is to Include the vinyl chloride content found In all the samples required In paragraphs (c) (2) (l) and (c)(2)(H) of this section, aver aged separately for each type of resin, over each calendar day ntid w eighted ac cording to the quantity of each grade of resin processed by the stripper's) that calendar day, according to the following equation: S Po,M0i action taken to repnlr the leaks, as re quired by }61.65(b'(8). Including a brief statement explaining the location and rausc of each leak detected with the portable hydrocarbon detector, thr date and time of the leak and any action taken to eliminate that lenk measured In accordance with 5 61 68. (3) For the relief discharges from reactors subject to (hr provisions of 5 61.65(a), a dally operating lerord loi each reactor, including pressures and temperatures. 2. Appendix B Is amended bv adding Test Methods 106 and 107 as follows vail, and the Administrator may notify AT'--<i7r~ Mkthoo 100--DrtrnMiNAiioN rn Vinti. the owner or operator that approval of CmOMPt rsoxt PTATmmnr Smi-scis the method previously considered to be equivalent or alternative is withdrawn. (1) Tire owner or operator shnll In clude in the report a record of any emis sions which averaged over any hour period (commencing on the hour) are Poi^ox \ " \-Pambta9 q7( A nvrrnpn concentration of Ijrr* T, rarln Hi ppm. Q*Totnl production of typo T, r*ln om th* 24-hoar period, In Vj*. lNTSODVf t|ON Performance of lids method should not i>a Attempted by person. uufamlltnr wllh th" operation of A gas chromatograph. nor hv those who are unfamiliar with source 'smpllnp. ni there are many del ills (ha* am in excess of the emission limits pre scribed in 55 61.62(a) or (b>, 5 61.63(a), or 55 61.64(a) (1), (b), (c), or (d), or lor any control system to which reactor emissions are required to be ducted In 5 61.64(a) (2) or to which fugitive emis sions are required to be ducted in 61.65 7\v*Typn of rr.h; )** 1,?, . . m whore ra ts ^ot*l mitii'M't <>( rcMn typo# prMncM ihiriflf lhf> hour period. A/*=Conrri)lfM|nn of vlnjl chloride In on" ?ntnpU* o( grail* (?, rrrin. In ppm. Production of grn<l* 0\ rc<ln reprinted by tho sample, In fcg. 01= (trade of rrrin, e g.. Ou 01, nnd Ou nTotikl numbtr of grade* of nta produced during tho 24-hour period. beyond the scope of Ihls presrnta'lon. Care moat be exercised (o prevent exposure of sampling personnel to vinyl chloride, a car cinogen. 1. Principle and Applicability. 1.1 An Integrated hnR sample of slack gin containing vinyl chloride (rhloroethylcne) Is subjected to chromatographic analysis, (b) (1) (11), (b) (2), (b) (5), (b) (6) (ill, or (b) (9) (11). The emissions are to be meas ured in accordance with i 61.68. <2* In polyvinyl chloride plants for which a stripping operation is used to attain the emisison level prescribed in 5 61.64(e), the owner or operator shall include In the report a record of the vinyl chloride content In the polyvinyl chloride resin. Test Method 107 Is to be Used to determine vinyl clUoride content as follows: _ . (vl) The owner or operator shall re tain at the source and make available for inspection by the Administrator for a minimum of 2 years records of nil data needed to furnish the Information re quired by paragraph (c)(2) (v) of tills section: The records are to contain the following information: (A) Tile vinyl chloride content found In all tlie samples required in paragraphs (g) (2) (1) and (c) (2) (111 of this section, Identified by the resin type and grade using A name Ionization detector. 1.9The method Is applicable to the meas urement of vinyl chloride In slack gases from ethylene dlehlorlde, vinyl chloride and poly vinyl chloride manufacturing processes, ex cept where the vinyl chloride Is contained In particulate mnttrr. 2. Range and Sensitivity. The lower limit of detection will vary ac cording to the chromatograph used. Values reported Include 1 x 10 T mg and 4 y. 10 ' mg. 3. Interferences Acetaldehyde, which can occur in some (1) If batch stripping is used, one rep and the time and date of the sample, and vinyl chloride sources, will Inlertcre with the resentative sample of polyvinyl chloride (B) The corresponding quantity of vinyl chloride peak from the Chromosnrb |f)2 resin is to be taken from each batch of each grade of resin Immediately follow ing the completion of the stripping, and grade and the date and time the batch Is completed. The corresponding quantity of material processed In each stripper batch Is to be recorded and Iden tified by resin type and grade and the date and time the batch Is completed. (if) If continuous stripping Is used, one representative sample of polyvinyl polyvinyl chloride resin processed by the stripper(s), identified by the resin type and grade and the time and date it represents. (3) The owner or operator shall in clude In the report a record of the emis sions from each reactor opening for which an emission limit Is prescribed In 5 61.64(a) (2). Emissions arc to be deter mined In accordance with J 61.67(g) (5), except that emissions for each reactor column. See sections 4.3 2 and 6.4. Tf resolu tion of the vinyl chloride peak Is still not satisfactory for a particular sample, then chromatograph parameters can he further altered with prior approval of the Admin istrator. If alteration of the chromatograph parameters falls to resolre the vinyl chloride peak, then supplemental confirmation of the vinyl chloride peak through an absolute analytical technique, such m maw spectro scopy, must be performed. 4. Apparatus. 4.1 Sampling (Figure 11. chloride resin Is to be taken for each are to be determined. For a reactor that is 4.1 1 Probe--Stainless steel. Tyre* glass, grade of resin processed or at intervals also used as a stripper, the determination or Teflon tubing according to stack temper- FEDERAl REGISTER, VOl. 41, NO. 205--THURSDAY. OCTOBER 31. 19X6 DTH 000115318 . >. - vv, 7,p'.ug t / .3 Flow meter D -iumctcr type. 0 to ami the attenuator setting Reeord the lab to remove pnrllciMntc mailer. 10(0 ml/mln range accurate to :! 1%. to oratory pressure. From the rhart, relerl (he 4.1 3 Sample line--Teflon, 6.4 mm cnIrH* meter nitrogen In preparation of standard j>eak having the retention time correspond diameter, of sufficient length to connect gas mixtures. ing to vinyl chloride, as determined In Bce- probe to bag. A new unused piece Is employed 4.4.6 Stop watch--Of known accuracy, to tlon 7 2. Measure the peak area. Am. by use for each series of bag samples that constitutes time gas flow In preparation of standard gas of 11-, and a disc Integrator or a planlmder. an emission test. mixtures. Measure the peak height. H., Record A- and 4 1.3 Male (2) and femalo (2) stainless steel quick-connects. with ball checks (one pair without) located as shown In Figure 1. 6. Reagents. It Is necessary that all rea gents be of chromatographic grade. 6.1 Analysis. the rclrntlon time. Repeat the Injection at least two times or until two consecutive vinyl chlortde peaks do not vary In area more than 414 Tedlnr bags, 100 liter capacity--To contain sample. Teflon bags are not accept able. Aluminized Mylar bags may be used, 8.1.1 Helium gas or nitrogen gas- Zero grade, for chromatographic carrier gas. 6 1.2 Hydrogen gas--Zero grade. 6%. The average value lor these two areas v/lll bo vised to compute the bag concentra tion. provided that the samples are analyzed 5 1.3 Oxygen gas, or Air, as required by Compare the ratio of H, to A- for the vinyl within 24 hours of collection. the detector--Zero grade. chloride sample with the same ratio for the 4.1 5 Rigid, leakproof containers for 4.1.4, 6 2 Calibration. standard peak which Ls closest In height. As with covering to protect contents front sun 5.2.1 Vinyl chloride, POP ) C --For prep n guideline, If these ratios dlflcr by more light. aration ol standard gas mixtures. than 10%. the vinyl chloride peak may not 4.1.8 Needle valve--To adjust sample flow 6.2.2 Calibration cylinders (3), optional-- be pure (possibly acetaldehyde Ls present) rate. One each of 60, 10 and 5 ppm vinyl chloride and the secondary column should be em 4.1.7 Pump--Leak-free. Minimum capac In nitrogen with certified analysis. Analysis ployed (see Section 4 3 21. ity 3 liters per minute. must be traceable to N13S (National Bureau 6.5 Measure the ambient temperature nnd 4.1.8 Charcoal tube--To prevent admis of Standards) or to a gravlmetrlcaHy cali barometric pressure near tbe bag. (Assume sion of vinyl chloride to atmosphere In vicin brated vinyl chloride permeation tube. the relative humidity to be mo percent ! ity of samplers. 5.2.3 Nitrogen gas--Zero grade, for prep From a water saturation vapor pressure table, 4.1.9 Flow meter--For observing sample aration of standard gas mixtures. determine the record and water vapor con flow rate: capable of measuring a flow range 6. Procedure. tent of the bag. from 0.10 to 1.00 liter per minute. 6.1 Sampling. Assemble the sample train 7. Calibration and Standards. 4.1.10 Connecting tubing--Teflon, 6.4 mm outsldo diameter, to assemble sample train as In Figure 106-1. Terform a bag leak check according to Section 7.4. Observe that all 7.1 Preparation of vinyl chloride standard pas mixtures. Evacuate a sixteen-inch square (Figure 1). connections between the bag and the probe Tedlnr bag that has passed a leak check 4.1.11 Pitot tube--Type S (or equivalent), are tight. Place the end of the probe at the (described In Section 7 4) and meler In 5 0 attached to the probe so that the sampling centroid of the stack and start the pump liters o( nitrogen. While the bag Is filling, use flow rate can be regulated proportional to with the needle valve adjusted to yield a the 0 5 mt syringe to Inject 260rl of (in.P 1 % the stack gas velocity. flow of 0.5 1pm. After a period of lime suffi vinyl chlortde through the wall of tbe bag. 4 2 Sample recovery. cient to purge the line several times has Upon withdrawing the syringe needle, im 4.2.1 Tubing--Teflon, 6 4 mm outside elapsed, connect the vacuum line to the mediately cover the resulting hole with a diameter, to connect bag to gas chromato bag and evacuate the bag until the rotam piece of adhesive tape. This gives a (v-n-en- graph sample loop. A new unused piece Is eter Indicates no flow. Then reposition the trntlon of 50 ppm of vinyl chloride In a like employed for each series of bag samples that sample and vacuum lines and begin the ac manner use the other syringe to prepare dilu constitutes an emission test, and la to be dis tual aampllng, keeping the rate proportional tions having 10 and 6 ppm vinyl chloride carded upon conclusion of analysis of those to the stack velocity. Direct the gas exiting concentrations. Place each bag on a smooth bags. the rotameter away from sampling personnel. surface and alternately depress opposite 4 3 Analysis. At the end of the sample period, shut oil the sides of the bag 60 times to further mix the 4.3.1 Gas chromatograph--With flame pump, disconnect the sample line lrom the gases. Ionization detector, potentlometrlc strip) chart recorder and 1.0 to 6.0 ml heated sam pling loop In automatic sample valve. 4 3.2 Chromatographic column--Stainless slcel, 2.0 X 3.2 mm, containing 80/100 mesh Chromosorb 102, A secondary colum of OB SF-98, 20% on 60/80 mesh AW Chromosorb F, stnlnlesB steel, 2.0 m X 3 2 mm. will be required If seetaldehydo Is present. If used, hag. and disconnect the vacuum line from the bag container. Protect the bag container from sunlight. 6 2 Sample storage. Sample bags must he kept out of direct sunlight, When at all pos sible, analysis Is to be performed within 24 hours of sample collection. 6.3 Sample recovery. With a piece of Tef lon tubing Identified for that bag. connect a 72 Determination of vinyl chloride rrtenllon time. This section can be performed simultaneously with Section 7.3 Establish chromatograph conditions Identical with those In Section 0.3, above. Pet attenuator tot X 1 position. Flush the samplln R loop with zero helium or nitrogen and activate the sample valve. Record the Injection time, the sample loop temperature, the column the SP-B6 column Is placed after the Chromosorb 102 column. The combined columns should then be operated at 110'C. 4.3 3 Flow meters (2)--Rotameter type, 0 to 100 ml/mln capacity, with flow control valves. 4.3.4 Gas regulators--For required gas cylinders. bag Inlet valve to the gas chromatograph sample valve. Switch the valve to withdraw gas from the hag through the sample loop. Plumb the equipment so the sample gas passes from the sample valve to the leak-free pump, and then to a charcoal tube, followed by a 0-100 ml/mln rotameter with flow con trol valve. temperature, the carrier gas flow rate, tbe chart speed and the attenuator setting Record peaks and detector responses that oernr In the absence of vinyl chloride. Main tain renditions With the equipment plumb ing arranged Identically to Section 0 3, (lush the sample loop for 30 seconds at the rate of 100 ml/mln with one of the vinyl chloride 4.3 6 Thermometer--Accurate to one de 6.4 Analysis. Set the column temperature calibration mixtures and activate the sample gree centigrade, to measure temperature of heated sample loop at time of sample Injec tion. 4.3.6 Barometer--Accurate to 5 mm Hg, to measure atmospheric pressure around gas chromatograph during sample analysis. 4.3.7 pump--Leak-free. Minimum capac ity 100 ml/mln. ~ 4 4 Calibration. 4.4.1 Tubing--Teflon,-6.4 mm outside diameter, separate pieces marked for each calibration concentration.-- 4 4.2 Tedlnr bags--Sixteen-Inch square sire, separate bag marked for each calibra tion concentration. 4 4 3 Syringe--0.6 ml, gas tight. j 4.4.4 Syringe--60M. gas tight. to 100* C the detector temperature to 160* C. and the sample loop temperature to 70" C. When optimum hydrogen and oxygen now rates have been determined verify nnd main tain these flow rates during all chromato graph operations. Using zero helium or nitrogen as the carrier gas, establish a flow rate in the range consistent with the manu facturer's requirements for satisfactory de tector operation. A flow rate of approxi mately 40 ml/mln ahould produce adequate separations. Observe the base line periodi cally and deterihlnc that the noise level has stabilized and that base line drift has ceased. Purge the sample loop for thirty seconds at the rate of 100 ml/mln, then activate the sample valve. Record the Injection time (the position of the pen on the chart at the time valve. Record the Injection time. Select the peak that corresponds to vinyl chloride. Measure the distance on the chart from the Injection time to the time at which the peak maximum occurs. This quantity, divided by the chart speed, ls deflned as the retention time Record. 73 Preparation of chromatograph cali bration curve. Make a gns chromatographic measurement of each standard gas mixture (described In Section 7.1) using conditions Identical with those listed In Section 6.3 above. Flush the sampling loop for 30 seconds at the rate of 100 ml/mln with each standard gas mixture and activate the sample valve. Rcrord C,. the concentrations of vinyl chlo ride Injected, the attenuator setting, chart Sliced, peak area, sample loop temperature, 1 ' Mention of trade names on specific prod of sample Injection), the sample number, the column temperature, carrier gas flow rale, ucts does not constitute endorsement by the sample loop temperature, tbe column tem and retention time. Record the laboratory Environmental Protection Agency. 1 perature, carrier gas flow rate, chart speed pressure. Calculate A,, the peak area multl- 1 DTH 000115319 FEDERAL REGISTER, VOL 41, NO. 305--THURSDAY, 0C105ER 21, 1976 .v..'.onua`.nr reftrig, Repeat until two Injection Areas are within 8%. then plot t.hrwa points v C,. When the other concrnIration* irnrn been plotted, draw a smooth curve through the point* Perform calibra tion dally, or before and after each act of line namplra, whichever I* more frequent. 7.4 hap leak checks. While performance of this flection la required subsequent to bag use, it l* also advised that It be performed prior to bap use. Alter each use, make sure a bng did not develop leaka as follows. To leak cheek, connect a water manometer and pres surize the bag to 6-10 cm H,0 (3-4 In H.O). Allow to stand for 10 minutes. Any displace ment In the water manometer Indicates a leak. Also check the rigid container for leaks In this manner. (Not*: An alternative Irak check method Is to pressurise the bag to 6-10 cm 11,0 or 2-4 In. n.O and allow to stand overnight. A deflated bag Indicates a leak.) For each sample bag in Its rigid container, place a rotameter In-line between the bag and the pump Inlet. Evacuate the bag. Failure of the rotameter to register zero flow when the bag appears to be empty Indicates a leak. 8. Calculations. 8.1 Determine the sample peak area as follows: *4* ^ Sstis ( trrU mui r*uf le frCuct *n ut csttlnw Sansrflt Vf tb bTficMattl rrttacIlM Rcntr. A,= AmA/ where: A ,*3 be rnmple peak srea. A.-Th measured peak area. Air.The attenuation factor. Equation 106--1 Mrrnoo 107--Dettiimination or Vintl Culonu Content or iNraoctss Wastxwate* Samples; and Vintl Chi-obip* Content or Poltvtntl Cin-osios Resin, Surasr, Wet Cars, and Latex Samples mg and 4v 10 ' mg. With proper calibration, the upper limit may be extended as needed. 3 Precision and Reproducibility. An Interlaboratory comparison between seven laboratories of three resin samples, 8.2 Vinyl chloride concentrations, rrona the calibration curve described In Section INTRODUCTION Performance of this method should not be each split Into three parts, yielded a standard deviation of 2 63% for a sample with s mean of 3 09 ppm. 4.16% for a sample with a mean 13, above, select the value of C, that cor responds to A, the'sample peak area. Cal culate C, as follows: attempted by pernona unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with sampling, as of 168 ppm. and 6.39% for a sample with a mean of 62.66 ppm. 4 Safety. ,, _ there are many details that are beyond the IVo not release rlnyl chloride to the labora scope of this presentation. Care must be tory atmosphere during preparation of stand ` "7\7\(r-r~) exercised to prevent exposure of sampling ards. Vcnttng or purging with VCM. air mix Equation 106-3 Wlirre: Pwi-'The vftlrr vnpor conlret of the bog gamble, M annlyred. C"Th eoneentrstlon of vinyl chloride la the hog sample In rpm. C.The conccntrallon of vinyl chloride Indicated by tbe gas chromatograph, In ppm. F.-The reference pressure, the laboratory pressure recorded during callbmllon, mm llg. Ti --The sample loop temperature on the absolute scale et the time of analysis, 'K. r.'sThr laboratory prwsure at time of analysis, mm H*. F.The reference temperature, the eample loop temperature recorded during calibration, *K' personnel to vinyl chloride, a carcinogen. 1. Principle and Applicability. 1.1 The basis for this method relates to the vapor equilibrium which Is established between RVCM, PVC. resin, water, and air In a closed system. It has been demonstrated that the RVCM In a PVC ream will equili brate In a closed vessel quite rapidly, pro vided that the temperature of the PVC resin Is maintained above ths glass transition temperature of that spcctllc resin. 12 This procedure Is suitable for deter mining the vinyl chloride monomer (VCM) content of tnproccss wastewater samples, tures must be held to a minimum. When they are required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels. mut never be vented Inside ths laboratory. After vials have been analyzed, the pressure within the vial must be vented prior to removal from the Instrument turn table Vials must be vented Into an activated charcoal tube using a hypodermic needle to prevent release of vinyl chloride Into ths laboratory atmosphere. The charcoal must be replaced prior to vinyl chloride break through. 6. Apparatus. 6.1 Sampling. 9 References 1. Brown, D. W., boy, E. W. and Stephen son. M. H. "Vinyl Chloride Monitoring Near ths B. P. Ooodrlch Chemical Company In Louisville, Kentucky." Region IV, UJB. Envi ronmental Protection Agency, Surveillance and Analysis Division, Athens, Georgia, June 34. 1974. 2. "Evaluation of A Collection and Analy tical ProceduralTM: Vinyl Chloride In Air," by G. D. Claytoq.and Associates, December 13, 1974. EPA Contract No. 68-02-1408, Task Order No. 3, EPA Report oN. 76-VCD-l. and the residual vinyl chloride monomer (RVCM) content of polyvinyl chlortde (TVC) resin*, wet cake, slurry, and latex samples. It cannot be used for polymer In fused form, auch as sheet or cubes. If a resolution of ths vinyl chloride peak la not satisfactory for a particular sample, then chromatograph parameters may be altered with prior ap proval of the Administrator, ff there Is rea son to believe that some other hydrocarbon with an Identical retention time Is present In the ssmple, then supplemental confirma tion of the vinyl chloride peak through an absolute analytical technique, auch as mass spectroscopy, should be performed. 6.1.1 Bottles--00 ml (3 oz), with waxed lined screw on tops, for PVC samples. 6.1 J Vials--60 ml Hypo-vlala.' scaled with Teflon faced Tuf-Bond discs for water sam ple*. 5.12 Electrical tape--or equivalent, to prevent loosening of bottle tops. 6.2 Sample recovery. 5.3.1 Vlala--With seals and cap*. PerklnElmcr Corporation No. 106-0118, or equiva lent. 62.1 Analytical balance--Capable et weighing to *0.001 gram. 53.1. Syringe, 100 al --Precision Series "A" No. 010026, or equivalent. 3. "Standardization of Stationary Source 2. Range and Sensitivity. Emission Method for Vinyl Chloride," by Mid west Research Institute, 1976. EPA Contract No. 68 -03-1098, Task Order No. 7. The lower limit of detection of vinyl chlo ride will vary according to the chromato graph used. Values reported Include I X I0-* 1 Mention of trad* names on speclflc prod ucts doe* not constitute endorsement by Use Environmental Protection Agency. DTH 000115320 y. FE0ERAI REGISTER, VOL 41, NO. 70S--IHURSOAT. OCTOBER 11, 197* ; c V" .'.'mrir 50. :C"V- 010(1 or equlvalentS3 Analyals. B.3.1 Om chromatograph--Perkln-Elmer Corporation Model P 40 bead-space lur- wn"ng ami weighing, u*'ng a 100 ^1 syringe. In the ease of dl*|>orrlon resin*, the cup cannot be used. The sample is Instead weighed approximately In an aluminum dish, transferred to the tared vial and weighed tor- Ignite the detector according to the manufacturer's Instruction*. 75.1 4 Amplifier balance--.Balance the amplifier according to the manufacturer's Instruction*. lyzer, No. 104-0001, or equivalent. accurately in the vial. The sample la then 755 Programming the chromatograph-- 5.3,3 Chromatographic column--Staln- placed In the Perkln-Elmer head space ana Program the chromatograph as follows: less steel, 3 mx35 mm, containing 0.4% lyzer (or equivalent) and conditioned for one rCarlxm-ax 1B00 on Carbopak A, Perkln-Elmer hour at 90'C. Corporation No, 106-0133, or equivalent. Not*: Borne aluminum vial caps have a ,*`^*'arbopJc C can bo used In place of Carbopockenter section which must be removed prior a. I--Dosing time--The normal netting Is 1 second*. b. A--Analysis time--The normal setting h 8 minutes. Certain types of sample* con to placing Into sample tray. If not removed, tain high bolting materials which can cause 5.3.3 Thermometer--0 to 100* C, accurate serious damage to the Injection needle will Interference wtlh the vinyl chloride peak on to 0.1* C, Perkln-Elmer No. 105-0109 or occur. subsequent analyses. In these eases the equivalent. 755 Suspension reeln slurry and wet cake analysts time must be adjusted to eliminate 6.3.4. Sample tray thermostat system-- samples--Slurry must be Ottered using a the Interference. An automated backflush Perkln-Elmer No. 105-0103. or equivalent. small Buchner funnel with vacuum to yield system ran also be used to solve this prob 5.3.5 Septa--Sandwich type, for auto- wet cake. The Altering process must bo con lem. matte dosing, 13 mm, Perkln-Elmer No. 105- tinued only as long as a steady stream of c. R--Flushing--The normal setting is 0 2 1008, or equivalent. water Is exiting from the funnel. Excessive minute*. 5.3.8 Integrator - recorder -- Hewlett - filtration time could result In some loss of d. W--Stabilization time--The nomal set Packard Model 33B0A, or equivalent. VCM. The wet cake sample (0.10 to 4.5 grams) ting Is 0 2 minute*. 5.3.7 Filter drier assembly (3)--Perkln- Is added to a tared vial (Including septum e. X--Number of analyses per sample--The Elmer No. 2230117, or equivalent. and aluminum cap) and Immediately sealed. normal setting Is 1. 8.3.8 Soap film flowmeter--Hewlett Pack Sample weight la then determined to 3 deci 7.3.3 Preparation of sample turntable--Be ard No. 0101-0113, or equlralent. mal places. The sample la then placed In the fore placing any sample Into turntable, be 6.4 Calibration. Perkln-Elmer head space analyzer (or equiva certain that the center section of the alu 5.4.1 Regulators--for required gaa cyln- lent) and conditioned for one hour at OO'C. minum cap has been removed. The numbered ders. A sample of wet cake Is used to determine sample bottles should be placed in the cor 8. Reagents. TS (total solids). This Is required for calcu responding numbered positions In the turn 6.1 Analysis. lating the RVCM. table. Insert samnle* In the following order: 6.1.1 Hydrogen gas--zero grade. 7.2.3 Dispersion resin slurry samples.-- Positions 1 A 2--Old 2000 ppm standard* 6.1.3 Nitrogen gas--zerograde. 6.15 Air--zerograde. This material should not be Altered. 8ample for conditioning. These are necessary only must be thoroughly mixed. U6lng a tared siteri the analyzer has not been used for 24 6 2 Calibration. vial (Including septum end aluminum cap) hours or longer. 6.2.1 Standard cylinders (4)--one each add approximately 8 drops (0 25 to 0 35 rtxdtlon 3--60 ppm standard, freshly pre- of 50. 500, 2000, and 4000 ppm vinyl chloride grams) of slurry or latex using a medicine pared. In nitrogen, with certified analysis. 7. Procedure. 7.1 Sampling. 7.1.1 PVC sampling--Allow the resin or slurry to flow from a tap on the tank or silo until the tap line has been well purged. Ex tend n 60 ml sample bottle under the tap. Oil. end Immediately tightly cap the bottle. Wrap electrical tape around the cap end bottle to prevent the top from loosening. Place an Identifying label on each bottle, and record the date, time, and sample location both on the bottles and In a log book. dropper. This should be done immediately after mixing. Seal the vial as soon as possible. Determine sample weight accurate to 0 001 grama. Total sample weight must not exceed 0.60 grams. Condition the vial for one hour at 90"C In the analyzer. Determine the TS on tho slurry sample (Section 7.3.5). 7.2.4 Inprocess wastewater samples-- Using a tared rial (Including septum and aluminum cap) quickly add approximately 1 cc of water using a medicine dropper. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 gram. Con dition the vial for two hours at B0*C In the Position 4--500 ppm standard, freshly prepared. Position 5--2000 ppm standard, freshly prepared. Position 6--4000 ppm standard, freshly pre pared. rosltlnn 7--Sample No. 7 (This Is the first sample of the day. but Is given as 7 to be con- alstent with the turntable and the integrator printout.) After all samples have been positioned. In sert the second not of 60, 600, 2000. and 4000 ppm standards. Sample*. Including *(nnd- ard.e must Ire conditioned In the hath of ..o'"* 7.1.2 Water sampling--Prior to use, the analyzer. 90* C for 1 hour (not to exceed 5 hours). 3 ml vials (without the discs) must be 7.3 Analysis. 7 3 4 Start chromatograph program - capped with aluminum foil end muffled at 7.3 1 Preparation of gas chromatograph-- When all sample*. Including standards, have 400 "C for at least one hour to destroy or Install the chromatographic column and con been conditioned at 90* C for 1 hour, start remove any organic matter that could In dition overnight at 160"C. Do not connect the the analysis program according to the manu terfere with analysis. At the sampling loca exit end of the column to the detector while facturers' Instructions. These Instructions tion fill the Tlals bubble-free, to overflowing conditioning. must be carefully followed when atartlng an that a convex meniscus forms at the top. 75.1.1 Flow rate adjustments--Adjust The excess water Is displaced as the sealing Aow rales as follows: disc Is carefully placed, Teflon side down, on a. Nitrogen carrier gas--Set regulator on the opening of the vlel. Place the aluminum cylinder to read 60 pslg. Set regulator on seal over the disc and the neck of the vial chromatograph to 15 kg/em*. Normal Aowa and crimp Into place. Affix an Identifying at this pressure should be 25 to 40 ec/mtnute. label on the bottle, and record the date, time, Check with bubble Aow meter. and sample location both on the vials and b. Burner air supply--Set regulator on cyl In a log book. All snmplee must be kept re inder to read 50 pslg. Set regulator on frigerated until analyzed. chromatograph to supply air to burner at a 7.3 Sample recovery. Samples must be run rate between 250 and 300 cc/mlnute. Check within 24 hours. with bubble flowmeter. 7.2 1 Resin samples--The weight of the resin used must be between 0.1 and 4-6 grams. An exact weight must be obtained (0.001 gram) for each sample. In the case of sus pension resins a volumetric xup can be pre pared which will hold the required amount of sample. The sample bottle Is opened, and the cup volume of resin Is added to the tared sample vial (including septum and alumi num cap). The vial Is Immediately sealed and the exact sample weight Is then obtained. Report this value on the data sheet as It Is required for calculation of RVCM. In the case of relatively dry resin samples (water 3. Hydrogen supply--Set regulator on cyl inder to read 30 pslg. Set regulator on chromatograph to supply approximately 35-4-6 cc/mlnute. Optimize hydrogen flow to yield the most sensitive detector response without extinguishing the flame. Check flow with bubble meter and record this flow 75.15 Temperature adjustments--Set temperatures as follows: a. Oven (chromatographic column), 50* C. b. Dosing line, 140* C. e. Injection block. 140* C. d. Sample chamber, water temperature, content <0.3 weight %), 100 B1 of distilled 90* C + 1.0* C. water must be Injected Into the rial, after 75.1.3 Ignition of flame Ionization detec and stopping program to prevent damage to tho dosing assembly. 7.3.5 Determination of total solids (TS!. For wet cake, slurry, resin solution, and PVC latex samples, determine TS for each aamplc by accurately weighing approxim ately 3 to 4 gram* of sample In an aluminum pan before and after placing In a draft oven (105 to 110* C). Samples must be dried to constant weight. After first weighing re turn tho pan to tho oven for a short pe riod of time and then rcwelgh to verify com plete dryness. TS is then cslculated as tho flnAl sample weight divided by Initial sam ple weight. 8. Calibration. Calibration 1* to be performed each eighthour period when the instrument Is used. Each day. prior to running sample*, the col umn should be conditioned by running two of the previous days 2000 ppm standards. 8.1 Preparation of Standards. Calibration standards are prepared by fill ing the vials with tho vinyl chlorlde/nltrogen standards, rapidly seating the septum and sealing with the aluminum cap. Use a stainless steel line lrom the cylinder to the vial. Do not use rubber or tygon tubing. Tho aample lino from the cylinder must be I | I j .I [ ' ( I | 1 ' j j , j r FEDERAL REGISTER, VOL 41, NO. 303--THURSDAY, OCTOBER 21, 1976 DTH 000115321 to tilling vials. After purging, rulin'* the (V" rate to approximately 600-1000 cc/mln Place *nrl of tubing iDto vial (ncAr bottom) and after one minute slowly remove tubing. Place septum In vIM as soon as possible to mini mize mining air with sample. After the stand ard vial* ere sealed, Inject 100^,1 of distilled water. 8.3 Preparation of chromatograph calibra tion curve. Prepare two BO ppm, two BOO ppm. two 2000 ppm. and two 4000 ppm atandard sample* Run the calibration samples In exactly the same manner as regular samples. Plot A., the Integrator area counts for each standard sample vs C,. the concentration of vinyl chloride In each standard anmple. Draw a line of best fit through the points. 8. Calculations. 8.1 Response factor. From the calibration curve described In Section 8.3. above, select the value of C. that corresponds to A. for each sample. Com pute the response factor, Rt, for each sample, as follows: R/ = ~ Equation 107-1 V/ 9 2 Residual vinyl chloride monomer con centration, or vinyl chloride monomer con centration. Calculate C... as follows: r\. +*t0 Equation 107-2 C.fs^roiippMtratlon of vinyl chlorlrit In tb* wtmplo, In ppm. r** laboratory atmosphere prawira, mna 1?j. Ti - Rfvim temperature *K. Af,*MoU>*nKr wight of VCM (02.6>. !'* Volume of vapor phtue (vial volume less wmpte volume). m fWHpht o( wvmpl*. crams, corwtant (62,300). Kltrnry'a l^aw conytant f>c Vf'M In I'Ve at *rO, for VCM In \ m (approximate) wastewater sample at 90*C, K 3=5.0X10"* T*-= Equilibration temperature, *K. U the following renditions are mot, Equation 107-7 aa be ptmplinrd u follow*: I. 1*1-22* O (296* K). 1 Ti-W* O (3*3* K). t P.-750 mm llg. where V*-*Vlal volume, co fJM)j $. Sample contain* lea than 0J% waten ;--i! (< 197X10 '+ 6.988X10 Equation 107-3 The (ollnwlns K^nr-rsl smiattnn out be wwd lor ear wroplo whlrh rnnulne VCM, I'VC nd/ot srwtw. C A.r. n,ri x I k,i rs) r, { x.(i - ts) r,] where: TV-ToUlaoW'lSr Nob*: K, imwt <foU'rmlnM. Equation 107-4 Rcflulta calculated unlnf? Equation 107-4 represent concentration baaed on the total sample. To obtain results based on dry PVC oontenfe, divide by T3. For a t ee (approximate) wastewater sample, Equation I07-4 can be simplified to the followlnf: c,,,~ til ~'+{2,0MX10",)J Equation 107-5 10. References 1 Residual Vinyl Chloride Monomer Con tent of Tolyvlnyl Chloride Resina and Wet Cake Samples, B F. Cloodrleh Chemical Co. Standard Test Procedure No. 100B-T. B. F. Goodrich Technical Center, Avon Lake, Ohio. January 30, 1975. 2. Berms, A. R , "The Solubility of Vinyl Chloride In Polyvinyl Chloride." ACS-DIvlslon of Polymer Chemistry, Polymer Pre prints fS (3): 197, 1974. 3. Bcrens, A. R, "Tire Diffusion of Vinyl Chloride In Polyvinyl Chloride." AOS-Dlvlslon of Polymer Chemistry, Polymer Pre prints IS (3): 203. 1974. 4. Bcrens, A. R.. I., B. Crider. C. J. Tom*nek and J. M. Whitney, Analysts for Vinyl Chloride In FVC Powders by Head-Space Oas Chromatography." to be published. |FR Doc 70-30849 Filed 10-20-7fl;8:46 am] DTH 000115322 FCDERAl RtOItTER. VOL 41, NO SOS--THURSDAY, OCTOBER 11, 1*7* f J* '/S> COMPLIANCE MANUAL ABERDEEN PVC PLANT HI. GENERAL FACILITIES FOR COMPLIANCE The vinyl chloride emission standard, as included in Section II, has a number of specific requirements. The general approach to achieving compliance has been: 1. Containment at the source. Typical of such items would be rupture disks, sample recirculation and double mechanical seals. 2. Collection and combination of all process vents and exhaust gases with final treatment via incineration. This was required by the need to reduce vapor exhaust streams to less than 10 ppm. 3. Collection of in-process wastewater with subsequent vacuum-steam stripping. This was required to achieve the in-process wastewater 10 ppm limitation. 4. Resin slurry steam stripping to a vacuum pump-compressor system to achieve the 400 ppm limitation. 5. Definition of specific operating conditions to achieve compliance on reactor opening loss and equipment opening. Steam purging to a vacuum system is used. Attached Figure I describes the various specific areas used by the plant to achieve compliance. The lines with arrows indicate the direction of vinyl chloride containing vapor or liquid streams. DTH 000115323 COMPLIANCE MANUAL ABERDEEN PVC PLANT SPECIFIC METHODS OF COMPLIANCE The emission standard required substantial process modifications and development of various operating techniques. To simplify the discussion of specific modifications and procedures which will be employed to achieve and maintain compliance we have divided the specific process requirements into three types. Sections V, VI and VII contain specifics of each of these types. Type I - The standard included requirements for specific physical modifica tions. The installation of these modifications results in com pliance. Such items would include containment of exhaust vents, installation of rupture disks, installation of double mechanical seals, definition of operating procedures, collection of process wastewater, sample recirculation, prevention of relief valve discharges and an in force leak detection and elimination plan. Other than definition of these items, their appropriate installation and periodic inspection to assure proper operation, no other comliance efforts are involved. Type II - ? This type of requirement allows the specification of a specific operating technique with a proof via calculation as a route to indicating compliance. Essentially this involves purging or evacuation calculations to show that the operating method used is satisfactory to assure compliance is being achieved. This type is applicable to: 1) Reactor Opening Loss - Where the operating method used can be shown to purge the reactor vapor space. 2) Unloading Line Discharges During Disconnect - Where the line volume and the final line pressure is used to calculate the loss per disconnect. Thus a specific pressure or less results in achieving compliance. 3) Equipment Opening - Where the vessel volume, the steam purge quantity and time, and the final vessel pressure can be used to show a purging technique at which compliance is achieved. Type II compliance utilizes theoretical evacuation and purging equations with an appropriate, conservative, efficiency factor to indicate a compliance condition. DTH 000115324 SPECIFIC METHODS OF COMPLIANCE (Cont.) Type III - This type of requirement demands periodic sampling to show maintenance of compliance. Sampling, analysis and data recording are outlined within the emission standard. This type includes: 1) Analysis of final vent exhausts to the atmosphere. This must be less than 10 ppm. 2) Analysis of reactor slurry residuals VCM content which must be less than 400 ppm. 3) Analysis of inprocess wastewater which must be less thir 10 ppm. Attached is a Table which describes the type category into which each of the various standard requirements fall. DTH 000115325 o8- z XX m UJ o Q XX X SPECIFIC METHODS OF COMPLIANCE DTH 0 0 0 1 1 5 3 2 6 UJ a. X X 8- 03 a>-. X XXXXXXXXX XXX XX H CO pp V) u c 3 <D o ci 3 H X bO 3 p X 3 O ci w H cj 3 CL CO a bee p CL rH d 0 rH a > 3 P tu cl CL, rtC UJ rto< x 3 UJ o a: xz UJ c c +rt ocj <H to P dP co <D 4-1 to 0u <33 Cl P 0) 0 X o U 3 X O z x Cl/Ll , be cl x be bfl Ci to O bCUJ C C H C *H C 0 o X E -h 6 Q- Cl X 4E-1 tao <4-11 TH3 U0 aH, *aH S < 10 -H <0 Q Xo 8- O to c/J Cl (-4 to 4-1 4-1 CJ m w oH be i--i j p rt h > P to to Ci XbO 00 ce oe 40 0 P X Tl o <D X CL 3 UJ 0 0 3 c O UJ O 0 s oi O o 3 > Cl H H O pp 0 - Ci to to U o o i--4 cl, be 0 P 3 -p- p d CL, c E CD 4) 3 o U 3 H *r4 o P-8 CL H d ' d 3 Ci X p to to to CD CD d 4-> -H o H 3 CD DC DC w s s a CO DC be 3 be H c Ci rH 3 Ci CO CO rH d c to p CD c be eo to o 3 d rH rH a33 CD o P CL^ ao CO CO d CL to H 0 05 CO CO to rH P X V) p 3 h *5: to iH Ci be 3 CO 0 Ci o H rH d o d CD to rH a 3 P to d H CO to bO rt rH B 0) CO (0 X rH 0 Cl J3 V5 UJ CO 0 0 to X c m u o to rt O CO x to *H O -H S tO Q aj rH to P P CD rH CL o CL be ci B to B 3 0 3 to O Cl in Cl (D o pP UJ o 0o0 3 to H P Cl c, P 3 be bO 4J C rt cl 3 CLi d 3 C ttJ rt s e rj 3 X H H rH 0 H 0 O <D 0 ID 0 to DC X 3 3 3 C P CJ 3c CL bC CL bo *"4 (D .*-4 H Oh e 0 c d r> --H rJ iH 3 rH CL 40 o tH UP C<Ov d bO bo m d ci UJ CD 0) 0 o <D CL, CL p H p o O H P 3 oo a> p P (D 0 tn E o rt O Cl P CL Li-. to be >3c bO o bC <j r*4 r4 Cl p o 3 o > 3 3 Oi P to to 3 (D CD 0 0 p M tp "d a rt rH p P. rH fc E 0 a CJ to P CD d rt O H o o ,--I rH r-H --4 H Cl 40 a. h d CJ 40 o d CL, CL --H O3d 3 H H CL Pdc 3 3 3 E rt CLX 0 CD 3 C ctJ DC CD z or. 0 o C QCCD d cr cr rt 0 3 X CL s: UJ UJ in 03 PH tU ctirtrtXCJT3000 s: UHJ tOtOtO0vO00vOvO vOvDvOvOvOvOvO'OvO rH /--> rH P 4<--\ e--\ <--\ iH *H iH V_8 e--n rH '--t v,_/ l---\ e---s r--v /--> N ID ' vO 'cO_/ f-. V--* 00 V--' 05 W 05 V--/ . /--% 1---N r-v ,__, Cr_O> VX_)/ X XL--I-< X'_/ VX-- 'X--> OCJ in LO m in LD LO LO LO vO vD vO VC VC vO vO vO i--L r-H rH rH rH i--H r--1 rH vO vO vO vO vO vO vO COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I As previously indicated, Type I systems are physical modifications and/or plant practices which, in themselves, result in achieving compliance. As shown on Table 2 these items are: l( Collection of reactor, recovery, unloading line, equipment opening, manual vent and wastewater stripping exhaust gases. 2. Installation of pump and compressor and agitator double mechanical seals. 3. Installation of rupture disks under relief valves. 4. Prevention of any but emergency relief valve discharges. 5. Sample recirculation requirements. 6. An in force leak detection and elimination program. 7. Associated operating procedures for each area. On the following pages each specific area of the compliance is described. The emission sources, method of compliance and compliance procedure is defined. DTH 000115327 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: S 61.64 (a) (1) The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each reactor is not to exceed 10 ppm, except as provided in paragraph (a) (2) of this section and 61.65 (a). Problem: The reaction process in Aberdeen utilizes condenser cooling for maintaining reactor temperature control, for resin residual reduction during steam stripping and for reactor vapor space purging for opening loss compliance. The catalyst used generates inert gases such as C02. These inerts must be purged from the condenser or they will blanket the tubes and prevent effective cooling for control. Emission Sources : The emission sources are the eight PVC reactors. Method of Compliance Previously these inert gases, with associated vinyl chloride, were vented to the atmosphere directly above the respective reactors. Procedures have now been instituted so the inert gases are vented into the recovery system. This procedure precludes emissions from the reactors and thus results in achieving compliance. Compliance Procedure : Upon determining a need to vent the condenser of a reactor: (1) Place mode selector into the "Emergency" position. (2) Open the reactor condenser valve. (3) Open the reactor recovery valve. (4) Observe the recovery system pressure indicator. (5) When pressure indication exceeds 20 to 30 psig, close the reactor recovery valve and reactor condenser valve. (6) Return the reactor to the "Polymerization" mode. DTH 000115328 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHOD OF COMPLIANCE - TYPE I Item: 61.64 (a) (3) Manual vent valve discharge: Except for an emergency manual vent valve discharge, there is to be no discharge to the atmosphere from any manual vent valve on a polyvinyl chloride reactor in vinyl chloride service. Problem: The Aberdeen Plant formerly operated 60, small (2200 gallon), PVC reactors. These small reactors periodically required manual venting to maintain control. Emission Sources : The sources were the sixty small PVC reactors. Method Of Compliance: The plant has shut down all of these reactors. They all have been physically removed from the plant. The plant now operates only large reactors. These polymerization reactors employ improved cooling technology which does not require any manual venting. Compliance Procedure : No manual vent valve emissions occur as no manual venting is required. DTH 000115329 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: I 61.64 (d) Monomer recovery system. The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each monomer recovery system is not to exceed 10 ppm except as provided in 61.65 (a). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in I 61.65 (b) (6) (i) before being opened. Problem: Periodically, inert gases containing vinyl chloride accumulate in the recovery systems. This increases the system pressure and prevents acceptable recovery rates. Emission Sources : The Plant operates three recovery systems: (1) Module No. 1 Recovery System (2) Module No. 2 Recovery System (5) Emission Recovery System * Method Of Compliance : Vent equalization lines have been installed for each recovery monomer receivers. Thus the pressure buildup can be controlled by venting from these receivers to the vent gas incinerator. Compliance Procedure : The equalization lines are installed and all valves remain open. No specific procedure is involved. DTH 000115330 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: 61.65 (a) Relief valve discharge: Except for an emergency relief discharge, there is to be no discharge to the atmosphere from any relief valve on any equipment in vinyl chloride service. Problem: As required to meet operating safety codes (ASME ft others) equipment in vinyl chloride service are all equipped with appropriate relief valves. Attached Table 3 lists the equipment at Aberdeen in vinyl chloride service with safety relief valves. Emission Sources : See attached Table 3 for a listing of equipment in vinyl chloride service with safety relief valves. Method Of Compliance : The relief valves will discharge only in case of an emergency. Compliance Procedure : None. DTH 000115331 TABU- 3 EQUIPMENT IN VINYL CHLORIDE SERVICE WITH SAFETY RELIEF VALVES ABERDEEN PVC PLANT Conoco Vess. No. Description No. of Relief Valves 43-001 89-201 89-202 89-305 VCM Sphere East Storage Bullet West Storage Bullet Tank Farm K. 0. Drum 2 2 2 1 45-731 45-732 45-734 45-735 D-300 Reactor D-400 Reactor D-500 Reactor D-600 Reactor 2 2 O 2 45-011 45-012 45-013 45-027 45-028 45-017 45-018 55-008 55-009 45-005 64-691 64-008 64-009 Middle RVCM Receiver South RVCM Receiver Charge Receiver North K. 0. Scrubber South K. O. Scrubber North Seal Water Separator South Seal Water Separator North RVCM Condenser South RVCM Condenser RVCM Collect Tank RVCM Filter North Charge Filter South Charge Filter 1 1 1 1 1 1 1 1 1 1 1 1 1 45-741 45-742 45-743 45-744 D-741 Reactor D-742 Reactor D-743 Reactor D-744 Reactor 2 2 2 2 45-317 89-520 45-745 '45-761 45-760 45-763 45-762 45-764 55-338 55-337 East RVCM Receiver West RVCM Receiver Charge Receiver North K. 0. Scrubber South K. 0. Scrubber North Seal Water Separator South Seal Water Separator RVCM Collect Tank East RVCM Condenser West RVCM Condenser 1 1 1 1 1 1 1 1 1 1 45-026 45-308 45-342 T-701 Inlet Tank T-702 Vac, Pump Disch. Tank T-703 Comp. Discharge Tank 1 1 1 DTH 000115332 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: I 61.65 (b) (1) (ii) Any vinyl chloride removed from a loading or unloading line in accordance with paragraph (b) (1) (i) of this section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in 61.66 Problem: To meet the requirement of I 61.65 (b) (1) (i) the line connections from the railcars must be evacuated. The vapors evacuated are required to be contained. Emission Sources: These would be each of the three lines at each of the un loading spots if containment facilities were not in place. Method of Compliance: During the evacuation procedure on the unloading lines the vapors are pulled by the emission recovery system. As this system ultimately discharges to the recovered monomer receivers in Module No. 1, any emission would occur at that point. As indicated, this sovirce is directed to the incinerator which reduces the VCM content to less than 10 ppm. Compliance Procedure: When the unloading of railcars is complete: 1. Turn off and isolate the unloading compressors. 2. Close the valves on the railcars. 3. Close the valves on the unloading lines. 4. Via the local switch, open the actuated valves into the recovery header to the emission recovery system. 5. Observe the line pressure. 6. When line pressure is reduced to the required amount, close the evacuation valves and proceed to disconnect the lines. DTH 000115333 COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: S 61.65 (b) (2) Slip gauges: During loading or unloading operations, the vinyl chloride emissions from each slip gauge in vinyl chloride service are to be minimized by ducting any vinyl chloride discharge from the slip gauge through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in i 61.66. Problem: Previously slip gauges were used to determine the liquid level in VCM railcars. Emission Sources : Vinyl chloride railcars as received by the plant. Method Of Compliance: All slip gauges have been replaced with totally enclosed, float type, level indicators. These devices are used only during loading of VCM cars, a procedure not applicable at the Aberdeen plant. During unloading, the appearance of vapor in the unloading line sight glass indicates the railcar is empty of liquid vinyl chloride. All three liquid vinyl chloride lines have been equipped with sight glasses to detect the change from liquid to vapor. Compliance Procedure : As slip gauges are not used in Aberdeen, no specific procedure is involved. DTH 000115334 r c COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: 61.65 (b) (3) (i) Rotating Pumps: Vinyl chloride emissions from seals on all rotating pumps in vinyl chloride service arc to be minimized by installing sealless pumps, pumps with double mechanical seals, or equivalent as provided in s 61.66. If double mechanical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the pump; by ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as pro vided in 61.66. Problem: The plant has fifteen pumps in vinyl chloride service. All of these pumps are centrifugal, rotating, pumps. Previously, these pumps were equipped with single mechanical seals. Emission Sources: Attached is a list of rotating pumps in vinyl chloride service (see Table 4) . Method of Compliance: Eleven of the process pumps in vinyl chloride service are located in the Module No. 1 or Module No. 2 reactor areas. These pumps have each been equipped with double mechanical seals. The seal ing fluid is high pressure water. This high pressure water insures that any leak of the seal results in water entering the process rather than an emission of vinyl chloride. The remaining four pumps are located in the vinyl chloride un loading area. These pumps are also equipped with double mechanical seals. The sealing fluid is an oil which is contained in a small reservoir above the pump. Circulation is via Thermosyphon action. The reservoir is vented to a recovery system such that a seal failure does not result in an emission of vinyl chloride. Compliance Procedure: The seals in question do not require a specific operating procedure. To insure against seal leakage periodic inspections are desirable. The plant has developed an inspection check list which is attached. Inspections with the completion of the check list are done once per week by process engineering personnel. DTH 000115335 TABU- 4 r CHECKLIST - ROTATING PUMPS IN VINYL, CHLORIDE SERVICE ABERDEEN PVC PLANT Conoco No. 72-217 72-218 72-126 72-270 72-044 72-045 72-869 72-001 72-002 72-876 72-875 72-878 72-877 72-884 72-883 Description Seal Fluid East Bullet Pump West Bullet Pump North Sphere Pump South Sphere Pump East Charge Pump West Charge Pump RVCM Pump East Col. Tk. Pump West Col. Tk. Pump East Charge Pump West Charge Pump East RVCM Pump West RVCM Pump East Col. Tk. Pump West Col. Tk. Pump Seal Fluid Press. Seal Fluid Seal Fluid Flow Level Any Leakage r DTH 000115336 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE -TYPE I Item: 61.65 (b) (3) (ii) Problem: Reciprocating Pumps: Vinyl chloride emissions from seals on all reciprocating pumps in vinyl chloride service are to be minimized by installing double outboard seals, or equivalent as provided in 61.66. The plant does not use reciprocating pumps in vinyl chloride service. Emission Sources: None Method of Compliance: None required. Compliance Procedure: None required. VTH 000115337 compliance manual ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: S 61.65 (b) (3) (iii) Rotating Compressors: Vinyl chloride emissions from seals on all rotating compressors in vinyl chloride service are to be minimized by installing compressors with double mechanical seals, or equivalent as provided in 61.66. If double mechanical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the com pressor; by ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equiv alent as provided in 61.66. Problem: The plant has thirteen centrifugal, rotating compressors in vinyl chloride service. Previously, these compressors were equipped with single mechanical seals. Emission Sources: Attached is a list of rotating compressors in vinyl chloride service (see Table 5). Method of Compliance All of the rotating compressors in vinyl chloride service are now equipped with double mechanical seals. The sealing fluid is high pressure water. This high pressure water insures that any leak of the seal results in water entering the process rather than an emission of vinyl chloride. Compliance Procedure: The seals in question do not require a specific operating pro cedure. To insure against seal leakage, periodic inspections are conducted. A check list for this inspection has been developed and is attached. Inspections are done once per week by process engineering personnel. DTH 000115338 tabu; 5 CHECKLIST - ROTATING COMPRESSORS IN VINYL CHLORIDE SERVICE ABERDEEN PVC PLANT Conoco No. 72-711 72-712 72-792 72-709 72-710 72-752 72-753 72-751 72-904 72-903 72-712 72-902 72-901 Description Seal Fluid East Compressor West Compressor North Compressor East Vac. Pump West Vac. Pump East E.R. Compressor West E.R. Compressor E.R. Vac. Pump Middle Compressor South Compressor North Compressor North Vac. Pump South Vac. Pump Seal Fluid Press. Seal Fluid Seal Fluid Any Flow Level Leakage DTH 000115339 COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: 1 61.65 (b) (3) (iv) Reciprocating Compressors: Vinyl chloride emissions from seals on all reciprocating compressors in vinyl chloride service are to be minimized by installing double outboard seals, or equivalent as provided in 61.66. If double outboard seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the compressor; by ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided in 61.66. Problem: The plant utilizes reciprocating compressors for unloading vinyl chloride railcars. These are piston type compressor machines. Emission Sources: The unloading area contains four reciprocating compressors. Method of Compliance: The piston type compressors contain packing type seals. The space between the seals essentially vents into the crankcase head. Some of the compressors contain two sets of packing seals while some contain three packing type seals. In any case, leakage through the first, or process side seal, is vented into the crankcase head. The crankcase head is vented into the emission recovery system,thus any leakage through the seals is vented through a control system. As the exhaust gases from the emission recovery system are routed to the re covered monomer receivers in Module No. 1 and these receivers are vented to the incinerator, the regulation requirements are met. Compliance Procedure: No specific compliance procedure is involved. Periodic operation checks will be made weekly by process engineering personnel. DTH 000115340 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: 61.65 (b) (3) (v) Agitator: Vinyl chloride emissions from seals on all agitators in vinyl chloride service are to be minimized by installing agitators with double mechanical seals, or equivalent as provided in 61.66. If double mechan ical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the agitated vessel, by ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided in i 61.66. Problem: Previously, the plant operated as many as 60 small (2200 gallon) PVC polymerization reactors. These reactors were equipped with single mechanical seals on the agitators. The plant also had larger reactors equipped with double mechanical seals. Emission Sources: The sources were the 60 small reactors with the single mechanical seals and the large reactors with the double mechanical seals. Method of Compliance : The plant has shut down all sixty of the small polymerization reactors. These have been removed from the plant and scrapped. The plant now operates only eight large (18-20,000 gallon) reactors. Each agitator on these reactors is equipped with a double mechanical seal. High pressure sealing fluid is used to insure any leak is into the process rather than emitted to the atmosphere. Compliance Procedure: The double mechanical seals in question do not require a specific operating procedure. To insure against leakage, periodic inspection is necessary. This inspection is done by operating personnel on each batch on each reactor. An additional inspection is done by engineering personnel once per week. The attached check list is used for the engineering inspection. DTH 000115341 Conoco No. 51-031 51-032 51-185 51-186 51-101 51-102 51-103 51-104 TABU- 6 CHECKLIST - AGITATORS IN VINYL CHLORIDE SERVICE ABERDEEN PVC PLANT Description D-300 Agitator D-400 Agitator D-SOO Agitator D-600 Agitator D-741 Agitator D-742 Agitator D-743 Agitator D-744 Agitator Seal Fluid Seal Fluid Press. Seal Fluid Flow Seal Fluid Any Level Leakage? 000115342 dth COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: S 61.65 (b) (4) Leakage from relief valves: Vinyl chloride emissions due to leakage from each relief valve on equipment in vinyl chloride service are to be minimized by installing a rupture disk between the equipment and relief valve discharge to a process line or recovery system, or equivalent as provided in 61.66. Problem: Per ASME and other code requirements, pressure vessels in vinyl chloride service are equipped with relief valves. Emission Sources: The emission sources are the pressure vessels in vinyl chloride service. Attached is Table 7 which lists the vessels subject to this part of the regulation. Method of Compliance : The vessels listed are equipped with rupture disks located between the equipment of the relief valves. On some equipment, specifically the VCM filters, the dis charge of the relief valve is routed back into a pressure vessel. Compliance Procedure: The rupture disks do not require a specific operating procedure. To insure against malfunctions, periodic inspections are made of all rupture disks in vinyl chloride service. A check list for this inspection has been developed and is attached. The inspections are conducted weekly by process engineering personnel. DTH 000115343 TABU- 7 VCM SERVICE SV/RD VESSEL CHECKLIST ABERDEEN PVC PLANT Date Inspector Vessel No. Vessel Design Is B1. Val. R.D. Press. R.D. Design Press. Temp. Lock. Open? Ga. Read. Press. Temp. Action I. Area 1 - VCM Unloading Area 93-001 89-201 89-202 45-305 VCM Sph ere No. 1 VCM Sphere No. 2 East Bullet No.l East Bullet No.2 West Bullet No.l West Bullet No.2 Tank Farm K.O. Drum 100 125 100 125 200 650 200 650 200 650 200 650 150 366 II. Area 2 - Module No. 1. PVC Reactors 45-731 45-732 45-734 45-735 D-300R D-300R D-300R D-300C D-400R D-400R D-400C D-500R D-500R D-500C D-600R D-600R D-600C RD1 RD2 SV SV RD SV SV RD SV SV RD SV SV 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 N. A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. III. Area 3 - Module No. 2 PVC Reactors 45-741 45-742 45-743 45-744 D-701R D-701R D-701C D-702R D-702R D-702C D-703R D-703R D-703C D-704R D-704R D-704C RD SV SV RD SV SV RD SV SV RD SV SV 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. N.A. DTH 000115344 TABLE 7 (Contd.l VCM SERVICE SV/RD VESSEL CHECKLIST ABERDEEN PVC PLANT Date Inspector________ __________ Vessel No. Vessel Design Is B1. Val. R.D. Press. R.D. Design Press. Temp. Lock Open? Ga. Read. Press. Temp. Actioi IV. Area 3 - Module No. 1 Charge Recovery 45-010 45-011 45-012 45-013 45-027 45-028 45-017 45-018 45-005 64-691 64-008 64-009 45-026 45-308 45-342 55-008 55-009 North RVCM Receiv. Midd. RVCM Receiv. South RVCM Receiv. Fresh VCM Receiv. North K.O. Scrubb. South K.O. Scrubb. North Seal Sep. South Seal Sep. RVCM Coll. Tank RVCM Filter North Chg. Filter South Chg. Filter F..R. Inlet Tank E.R. Inter. Tank ` E.R. Outlet Tank N. RVCM Cond. S. RVCM Cond. 150 150 150 150 150 150 150 150 150 300 300 300 150 150 150 150 150 150 150 150 150 150 150 300 300 400 650 150 150 350 140 140 400 400 V. Area - Module No. 2 Charge Recovery 45-317 89-520 45-745 45-761 45-760 45-763 45-762 45-764 55-338 55-337 East RVCM Receiv. West RVCM Receiv. Fresh VCM Receiv. North K.O. Scrubb. South K.O. Scrubb. North Seal Sep. South Seal Sep. RVCM Coll. Tank E. RVCM Cond. W. RVCM Cond. 150 150 150 150 150 150 150 300 150 300 150 300 150 300 150 160 150 400 150 400 N.I.S. - Not in service at time of inspection DTH 000115345 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: 61.65 (b) (5) Manual venting of gases: Except as provided in 61.64 (a) (3), all gases which are manually vented from equipment in vinyl chloride service are to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided in i 61.66. Problem: Equipment in vinyl chloride service is listed in Table 3. Emission Sources: If manual venting were to occur, then the emissions sources would be equipment listed in Table 3, Method of Compliance : Manual venting is prohibited by our operating procedures until equipment has been evacuated or purged as described for com pliance in i 61.65 (b) (6) (i). Compliance Procedure: Vessels are not manually vented until'procedures relative to 61.65 (b) (6) (i). Normal operat ing procedures do not involve manual venting. Refer to compliance procedures for 61.65 (b) (6) (i) for details of equipment opening procedures. DTH 000115346 r COMPLIANCCEI; MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: 61.65 (b) (6) (ii) Any vinyl chloride removed from the equipment in accordance with paragraph (b) (6) (i) of this section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in 61.66. Problem: Section 61.65 (b) (6) (i) calls for reducing the vinyl chloride in equipment in vinyl chloride service to no more than 2.0 percent by volume vinyl chloride. Emission Souces: Table 3 contains a list of equipment in vinyl chloride service. If emissions were to occur in violation of this part of the regulation, they would occur from equipment listed on Table 3. Methods of Compliance: Prior to opening any equipment in vinyl chloride service specific evacuation and purging procedures are employed. The procedure results in compliance with 61.65 (b) (6) (i). During the procedures, all exhaust gases are routed through one of the three monomer recovery systems. No discharges occur from the vessels themselves. Any emissions, should they occur, would ultimately be from the recovered monomer receiver in Module No. 1. As emissions from this source are incinerated, this procedure results in compliance with this section of the regulation. Compliance Procedure: Specific procedures to meet this requirement involve first pulling a vacuum on the designated equipment and then purging for a finite period with steam while the prescribed recovery system continues to pull a vacuum. Specifics of the purging techniques are described under 61.65 fb) (6) (i) in Section VI. r DTH 000115347 COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: 61.65 (b) (7) Samples: Unused portions of samples containing at least 10 percent by weight vinyl chloride are to be returned to the process, and sampling techniques are to be such that sample containers in vinyl chloride service are purged into a closed process system. Problem: The plant does not routinely sample any vinyl chloride streams. We rely upon analyses given to us by our VCM suppliers. Emission Sources: Very infrequent sampling of recovered monomer is possible. A specific evacuation method for the sampling bomb is available for this purpose. Not applicable. Method of Compliance: A connection is available at the inlet to the emission recovery system. Following analysis the sample bomb (container) with the unused portion of the sample is attached to the connection and a vacuum is pulled. This results in hecirculating the unused portion of the sample and achieving compliance with the regulation. Compliance Procedure: For recirculation of usused portion of sample: 1. Attach container to the connection just south of T-701 in the emission recovery system. 2. Open valves and pull a vacuum and container. 3. Shut valves and disconnect container. For sampling: 1. Attach container to sampling connection at point. 2. Open valves and fill container. This may take several minutes. 3. Do not purge through container to the atmosphere as this is prohibited. 4. Close valves, disconnect sample container and take it im mediately to the laboratory for analysis. r DTH 000115348 r COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: 61.65 (b) (8) Leak detection and elimination: Vinyl chloride emissions due to leaks from equipment in vinyl chloride service are to be minimized by instituting and implementing a formal leak detection and elimination program. Problem: A leak detection and elimination program must be formalized, approved by the EPA, and implemented to meet the requirement of this section. Emission Sources: The potential emission sources are the equipment and piping in vinyl chloride service. The applicable plant areas arc: 1. Railcar Unloading Area 2. Module No. 1 Reactor Area 3. Module No. 2 Reactor Area 4. Vent Gas Incinerator Area Methods of Comp 1 i ance: A formalized "Leak Detection Program" was submitted to the EPA on May 9, 1977. The EPA subsequently reviewed and approved the plan as accceptable. The plan has been in operation since August, 1977. Compliance Procedure: Refer to Section X which contains the Leak Detection and Elimination program approved by the EPA and in force in the plant. DTH 000115349 O COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE I Item: S 61.65 (b) (9) (ii) Any vinyl chloride removed from the in-process wastewater in accordance with paragraph (b) (91 (i) of this section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in 61.66. Problem: Paragraph (b) (9) (i) calls for the stripping of in-process wastewater to 10 ppm. The exhaust gases which accrue from the stripping operation must be contained. Emission Sources: If no controls were installed, the emissions would be from the wastewater stripping units. Method of Compliance :The exhaust gases from the in-process wastewater stripping process are ducted into one of three recovery systems. These systems exhaust to the RVCM receivers, any emissions from which are ultimately incinerated. Compliance Procedure: The in-process wastewater strippers are connected to the recovery systems. The specific procedure employed to strip in-process wastewater is described in Section VII. DTH 000115350 r r COMPLIANCE MANUAL ABERDEEN PVC PLANT V. METHODS OF COMPLIANCE - TYPE I Item: 5 61.65 (c) The requirements in paragraphs (b) (1), (b) (2), (b) (5), (b) (6), (b) (7) and (b) (8) of this section are to be incorporated into a standard operating procedure, and made available upon request for inspection by the Administrator. The standard operating procedure is to include provisions for measuring the vinyl chloride in equipment greater than 1250 gallons in volume for which an emission limit is pre scribed in 61.65 (b) (6) (i) prior to opening the equip ment and using Test Method 106, a portable hydrocarbon detector or an equivalent or alternative method. The method of measurement is to meet the requirements in 61.67 (g) (5) (i) (A) or (g) (5) (i) (B) . Problem: Operating procedures need to be defined for: 1) Unloading line disconnect 2) Slip gauges 3) Manual venting of gases 4) Opening of equipment 5) Sample recirculation 6) Leak detection and elimination Emission Sources: The emission sources would be the vinyl chloride containing equipment involved in these operations. Method of Compliance: Standard operating procedures are defined. indicated in each specific section. These are Compliance Procedure: See the procedures described under each particular paragraph DTH 000115351 r COMPLIANCH MANUAL r ABERDEEN PVC PLANT VI. METHODS OF COMPLIANCE - TYPE II Type II systems involve the utilization of particular operating pro cedures which can be shown to achieve compliance. The proof of being in compliance involves the use of the operating procedure and a calculational method which shows the procedure reaches the desired con dition. This type of compliance is applicable to three requirements within the standard. 1) Reactor Opening Loss 2) Unloading Line Discharges During Disconnect 3) Equipment Opening On the following pages is the description of the emission problems, a definition of the operating procedure and an associated calculation showing that the operating proceudre, when used, will result in compliance. r DTH 000115352 r COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE II Item: 61.64 (a) (2) The reactor opening loss from each reactor is not to exceed 0.02 g. vinyl chloride/Kg (.00002 lh. vinyl chloride/Lb.j of polyvinyl chloride product, with the product determined on a dry solids basis. This requirement applies to any vessel which is used as a reactor or as both a reactor and a stripper. Problem: Following reactor recovery, the solution is transferred to PVC blend tanks prior to drying. The reactor is rinsed with water. During this rinse, air enters the reactor as it does during dump equalization. The air which contains some VCM is subsequently removed via steam jet evacuation prior to the next batch being charged. The exhaust from the steam jet constitutes the "reactor opening loss" as it does contain some vinyl chloride. Emission Sources: The emission sources are the eight PVC reactors in Module No. 1 and Module No. 2. The actual point of emission is the exhaust from the steam jet evacuation discharge. Method of Compliance: Compliance on this area is an adjunct to reactor steam stripping procedures in use. The plant utilizes reactors for resin slurry stripping thus avoiding emissions from multiple vessels. Additionally, our reactors are equipped with direct mounted, reflux condensers. This allows refluxing of a considerable volume of vapor through the reactor vapor space. Steam rates into the reactor and reflux rates at the end of recovery are specifically controlled to insure maximum purge through the vapor space. This purge volume can be calculated to show that the reactor opening condition prescribed by the EPA is being achieved. Attached is a description of conditions which occur at the end of. the recovery process. Purging calculations are also included which on a very conservative basis indicate sufficient purging occurs to meet the reactor opening condition. As steam vapor is used as the purge media, a serious sample problem exists. As of now we have been totally unable to sample an atmosphere of essentially 100% steam at a slight negative pressure. The method proposed by the EPA is not adaptable to this condition. We are continuing to work with Method of Compliance: (Cont.) vendors to obtain a device capable of analyzing the atmos phere within the reactor. Upon obtaining a suitable device when one is developed, we are confident we will be able to demonstrate compliance by analytical as well as calculationa1. methods. Compliance Procedure: The Federal Government requires us to reduce the VCM content of reactor slurry to a 400 ppm level before transfer of the slurry from the reactor to the blend tanks. In addition, we must also meet a requirement for reduction of VCM in the vapor space above the slurry in each reactor. To meet the requirements of the government we steam strip each reactor batch prior to transfer to the blend tanks. It is most important that we properly and uniformly strip each batch so we can meet the government's requirements. The following steam stripping procedure is to be used on every batch processed. Any variations in the procedure or any associated problems in the operation of the recovery system should be brought to the attention of the shift supervisor. Recovery Procedure: (To be precisely followed for all products) 1. Kill reaction at conditions described on product formula sheet. 2. Start compressors and begin recovery. 3. Set temperature set point to 200F and start steam into the reactor. 4. Wait until vacuum pumps come on. 5. Reset temperature set point to 230F. 6. When reactor temperature reaches 215F, turn emergency cooling water on the condenser. 7. Leave both steam and cooling water on during the next 10 minutes and continue recovering. 8. Evacuate dump valve during last five minutes of recovery. 9. ' Shut off steam, emergency cooling water and recovery system. 10. Dump reactor. 11. Sample slurry 5 to 10 minutes after start of dump. 12. During recovery the back pressure controller is to be set at 6". DTH 000115354 r REACTOR OPENING LOSS COMPLIANCE ABERDEEN PVC PLANT 1. The reactor is used as a stripper in our process. Operating procedures result in achieving both the 400 ppm slurry level and reactor opening loss requirements. 2. During the stripping process, the reactor slurry is heated to 200F and brought to a boiling condition at this temperature. The boiling is induced by the vacuum pump-compressor system. The reactor slurry temperature is subsequently raised to 215F. During this period, boiling and thus purging of the vapor space continues to occur. While boiling at this point results in purging the vapor space with steam, this factor is not used in the re actor opening loss compliance calculation. .3. When boiling at 215F is developed, specific operating procedures are used to maximize purging for 10 minutes. These conditions are: 1. Full reflux cooling on the condenser. 2. Maximum steam rate into the reactor. Steam rates are measured and typically are 17,000 to 23,000 pounds per hour. The base purge calculation rate used is 15,000 pounds per hour which is the lowest steam purge rate ever observed. 4. This base purge rate results in a vapor displacement volume of 67,000 cubic feet per batch. This is the calculated steam vapor emitted from the slurry surface at the operating conditions used. 5. The amount of liquid material in the reactor occupies 70% of total volume. A conservative assumption used in our calculation is that the purge vapor displacement applies to the entire reactor volume rather than the 30% which is the actual vapor space volume. 6. At the initiation of the purging condition at 215F, the VCM content of the vapor space is probably about 5% or less. Again, for the calculation, a conservative assumption is made that the VCM content is 100%. 7. To determine the total volume of gas flow required to reduce the vapor from 100% to the less than 2500 ppm required, the "Classical Mixing Equation" is used. This equation is: - Q/V t C = CG e where: C = Final vapor concentration (.002500 for 2500 ppm) C0= Initial vapor concentration (1.0 for 100%) 0 = Flow rate, cubic feet hour V = Volume to be purged (2523 cubic feet for Module No. 2975 cubic feet for Module No. 2 reactors) t = Period of time for purging (10 minutes) 1 reactors and DTH 000115355 8. Resolution of the classical mixing equation yields: r Required Purge Volume Tn Module No. 1 = 15115 cu. ft. Required Purge Volume In Module No. 2 = 17823 cu. ft. 9. Even with the various conservative assumptions made in 2, 3, 5, and 6, the actual purge volume is 4.43 or 3.76 greater than required. 10. Specific values related to this calculation are attached. DTH 000115356 REACTOR OPENING LOSS CALCULATION DATA DTH 000115357 OJ o 5 w (J D Q o s ooo ora o oo * s O 00 VO p- o OJ vo o CO o o LT\ o vo rH O On o o CTN On CVI UA O r-i i--1 OJ t-- o * vo o -4l/A OJ o o ooo o o (--1 o o o r> UA r\ on ir\ OJ CO t-- --l vo vo CO OJ CO * t-- rH OJ o oo o QO O LT\ VO On On -=t CO OJ OJ b-- o vo o CM OJ o ON f--1 o t-- o o M O l/MA OJ H CO LTN OJ CO " OJ OJ rH LTN rH h- o o o o o rH o o OJ o o LTN r- o o LTN oi co rH vo vo OJ LTN iH--I * on LTs tn ij to r> 3 JJ . o p cd P PQ u o <D a. p CJ oJ U o Cl o Dm CJ s po cd > > Cm ft d> 0) <y bD bl) bO cd cd hu (L> a) OJ > >> <! < c XJ o p o cd > pq Dm x! o <D p i--l cd o hJ pq s A rQ P rQ tJ xi l-D r> r r< c cc o oo rH H *rH CO CO CO to to to H H H Bag W M pq <U CJ OJ rH rH rH ) > (tf cd cd *>> ouo rH rH rH H rH H <3 Oh P rx, Eh o3 -P C in <u i--I o S >o CO O <D Jm H o cn rjj p PM CJ H o Jh O cd 3 > CJ CJ P K Jh cd Jh uo to oi p CD to CM O P o CJ Cm B <u cd o Eh CM EH P c dJ s H P cr1 W bD C rH X H c o P A, O P S rH cH cd cd to to P CQ CJ H rH to TJ Bu p4 IP Vv, (U rH p EP o r> to dJ cd u rH H a o' P (U dj a cd OJ cd >o rH rH pp CO p r rH OJ p C3 tn 0 > p H (p > 1--1 dJ cd < ps H p C r O rH O > rH CJ o <* o <D d> p <Vh > rH P P cd raH c H dO OJ bO o cj (P Eh o dJ U PH cd Jh a Ch 9 bO bO < CO Dm d) rH ft Cl C H rH <u g c. > ft rH <D rH bO bO bO ro O Cm >M dJ CM P o' H O (2 (2 9 CM P CO ct) > dJ cc 1 rH CM on -4- LTN VO t- 0O On O H CM m -p- tr\ VD *H H i--I i--t i--I i--I t-- QO i--| i--I COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE II Item: 61.65 (b) (1) (i) Problem: Emission Sources: After each loading or unloading operation and before opening a loading or unloading line to the atmosphere, the quantity of vinyl chloride in all parts of each loading or unloading line that are to be opened to the atmosphere is to be re duced so that the parts combined contain no greater than 0.13 cu. ft. of vinyl chloride, at standard temperature and pressure. The Aberdeen plant unloads vinyl chloride railcars. Un loading is via reciprocating compressors which pressure vapor into the car and thus, liquid out of the railcar. When the liquid is completely unloaded, the reciprocating compressors are reversed. Vapors are pulled off the com pressors. To achieve compliance the vapor must be suf ficiently removed so that the volume exposed to the atmos phere upon disconnect is within compliance. The emission sources are the unloading lines connected at the railcars. Method of Compliance Compliance Procedure: The unloading lines are connected to a vacuum system. Upon completion of unloading the railcar valves are shut, the compressors are stopped. The lines are then pulled down via the emission recovery system to a specific vacuum such that compliance is achieved. 1. When railcar is unloaded, reverse the compressors and pull the cars to a 10 psig pressure. 2. Close valves on railcar. 3. Shutoff and isolate the compressors. .4. Return to railcar and actuated the valves for pull down to the emission recovery system. 5. Wait until pressure is reduced to less than 6.0 inches of vacuum. 6. Close block valve on unloading line. DTH 000115358 7. Shut actuated valve to emission recovery system. 8. Line may now be disconnected. RAILCAR UNLOADING LINE COMPLIANCE n -AB-E-R-D-E-E-N--P-VC--P-L-A-N-T 1. The volume of the unloading hose was determined to be 1.2 gallons or 0.16 cu. ft. 2. To achieve compliance the pressure in the line must be reduced so the 0.16 cu. ft. contains less than 0.13 cu. ft. of vinyl chloride at standard conditions. 3. The required evacuation pressure is P,, = F 0.13 X 760 016 = 6*17., MM Hg = 24.3 In Hg 4. This is equivalent to a 5.6 in. Hg vacuum. 5. Compliance is achieved if the vacuum in the line is 5.6 in.IIg or more. r DTH 000115359 COMPLIANCE MANUAL ABERDEEN PVC PLANT METHODS OF COMPLIANCE - TYPE II Item: 61.65 (b) (6) (i) Before opening any equipment for any reason, the quantity of vinyl chloride is to be reduced so that the equipment contains no more than 2.0 percent by volume vinyl chloride or 25 gallons of vinyl chloride, whichever is larger at standard temperature and pressure. Problem: Periodically equipment must be opened for inspection, repairs or various other maintenance functions. The standard requires purging and/or evacuation to reduce the vinyl chloride content before opening. Emission Sources: The potential emission sources would be the vessels in vinyl chloride service that could exceed the emission limitation. Attached Table 8 indicates these vessels. Method of Compliance Each of the vessels indicated on Table 8 has been equipped with a steam purge line. The line is designed with an orifice which allows purging with steam at a rate c5f 35 SCEM. These vessels are also tied into the recovery systems. Upon a maintenance requirement the vessel is first evacuated to a vacuum with the recovery system. Steam is then injected into the vessel at a rate of 35 SCFM. The steam purges these vessels to the recovery system. After a prescribed amount of time the vinyl chloride content is reduced to the appropriate level. Table 8 indicates the volume of each of the vessels and the required purging time to achieve compliance. Attached also is the calculational method used to determine the purging time needed to achieve compliance. Compliance Procedure: 1. Isolate the vessel involved from the process by closing the appropriate valves. 2. Line up the vessel to a recovery system. 3. Start recovery system and pull vessel to a vacuum pressure. 4.' Open steam line into vessel. Inject steam while continuing to pull with the recovery system. 5. Continue recovering and injecting steam until time required has elapsed. 6. If desired, continue purging for additional time to insure the complete removal of vapors. DTH 000115360 r Compliance Procedure: 7. Vessel may now be opened, (Cont.) a) Shut off steam. b) Close line to recovery system. c) Equalize pressure to atmosphere. d) Open vessel. 8. When opening the tank farm storage vessels or any of the VCM receivers use a portable hydrocarbon detector to measure VCM content upon opening. r DTH 000115361 r TABLE .8 EQUIPMENT OPENING COMPLIANCE ABERDEEN PVC PLANT Conoco No. Description Volume, Gallons Required Purging T ime Recommended Purging Time 43-001 89-201 89-202 89-305 VCM Sphere East Storage Bullet West Storage Bullet Tank Farm K.O. Drum 700,000 60,000 60,000 456 2 days 16 hrs. 5 hrs. 25 min. 5 hrs. 25 min. 3 min. 5 days 12 hrs. 12 hrs. 10 min. 45-011 45-012 45-013 45-027 45-028 45-017 45-018 55-008 55-009 45-005 64-691 64-008 64-009 45-317 89-520 45-745 45-761 45-760 45-763 45-762 45-764 55-338 55-337 Middle RVCM Receiver South RVCM Receiver Charge Receiver North K.O. Scrubber South K.O. Scrubber North Seal Water Separator South Seal Water Separator North RVCM Condenser South RVCM Condenser RVCM Collect Tank RVCM Filtei North Charge Filter South Charge Filter East RVCM Receiver West RVCM Receiver Charge Receiver North K.O. Scrubber South K.O. Scrubber North Seal Water Separator South Seal Water Separator RVCM Collect Tank East RVCM Condenser West RVCM Condenser RVCM Filter North Charge Filter South Charge Filter 7,390 7,390 7,390 590 590 128 128 124 124 560 25 40 40 7,390 7,390 8,000 700 700 200 200 560 124 124 25 40 40 40 min. 40 min. 40 min. 3 min. 3 min. i min. i min. i min. i min. 3 min. 1 min. 1 min. 1 min. 60 min. 60 min. 60 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 40 min. 40 min. 43 min. 4 min. 4 min. 2 min. 2 min. 3 min. 1 min. 1 min. 1 min. 1 min. 1 min. 60 min. 60 min. 60 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 10 min. 45-026 45-308 45-342 r-701 Inlet Tank T-702 Vac. Pump Disch. Tank T-703 Comp. Discharge Tank 566 456 456 3 min. 3 min. 3 min. 10 min. 10 min. 10 min. DTH 000115362 r r r EQUIPMENT OPENING COMPLIANCE ABERDEEN PVC PLANT 1. The required purging time was determined from the vessel volume, purge flow rate and the initial and final vinyl chloride concentrations. 2. The mixing equation is: C -- Cq g -Q/V t Where: C = Final vapor concentration (.02 for 2-) C0 = Initial vapor concentration (1.0 for 100) Q = Flow rate, cubic feet hour (2100 SCF1I) V = Volume to be purged t = Period of time required for purging 3. Consider the RVCM receivers which have a volume of 7390 gallons of 988 cubic feet. 4. Plugging in the values to the mixing equation - Q/988 t .02 = 1.0 e - lm .02 = Q/988 t 3.91 = Q/988 t t = 3.91 x 988 5 psig = , 2100 x 14.7 psig U,D^ nours t ^ 40 minutes DTH 000115363 COMPLIANCE MANUAL ABERDEEN PVC PLANT VII. METHODS OF COMPLIANCE - TYPE III As indicated previously, this type of compliance demands periodic sampling to show maintenance of compliance. Sampling, analysis and data recording requirements are outlined in the standard. This type of compliance includes: 1) Analysis of final vent exhausts to the atmosphere. This must be less than 10 ppm. 2) Analysis of reactor slurry residuals VCM content which must be less than 400 ppm. 3) Analysis of inprocess wastewater which must be less than 10 ppm. On the following pages in the description of the emission problems, is a definition of the operating procedure, sampling method and frequency which are applicable to compliance. DTH 000115364 r S~'!' COMPLIANCE MANUAL ABERDEEN PVC PLANT VII. METHODS OF COMPLIANCE - TYPE III Item: 61.64 (e) Mixing, weighing, and holding containers: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each mixing, weighing, or holding container in vinyl chloride service which precedes the stripping (or the reactor if the plant has no stripper) in the plant process flow is not to exceed 10 ppm, except as provided in 61.65 (a). Problem: Any manual vents, inerts collection, etc. are collected and routed to the recovered VCM receivers in module No. 2. These exhausts are collected from: Reactors Manual Vent Valve Discharges Monomer Recovery System Exhausts Unloading Lines Reciprocating Compressor Seals Rotating Pump Seals Manual Vent Exhausts Equipment Opening Exhaust Gases Sample Recirculation Inprocess Wastewater Stripping Eventually these exhausts pressure up the recovered VCM receivers and must be vented off. The concentration of the vent stream as it exits to the atmosphere must be less than 10 ppm to meet the standard requirements. Emission Sources: The emission source would be the vent stream from the receiver if no further treatment were required. This vent is now directed to the incinerators. Thus the point of emission is now the vent exiting the incinerator. Method-of Compliance: The receiver vent is first routed to a refrigeration system. The refrigeration system reduces the vinyl chloride content of the vent stream. DTH 000115365 The-stream then flows to the vent gas incinerator. This incinerator operates at 2200F. The vinyl chloride is burned in the incinerator, a process which reduces its content to less than 10 ppm. r The vapor stream, following thermal treatment, is routed through a water scrubber to remove HCL and chlorine. It eventually discharges from the vent stack. Compliance Procedure: The vent gas incinerator is kept in a ready mode at all times. Natural gas is used to keep the equipment ready to receive vinyl chloride. Upon a buildup in pressure in the recovered receivers the operator will: 1. Press "high fire" switch on the control panel. 2. This will slowly begin to vent vapor into the incinerator fire box. 3. The operator will continue to vent in this manner until the pressure drops off. 4. When ready the operator will press the "low fire" button on the control panel. 5. This will slowly decrease the vapor vent gas flow to the incinerator. DTH 000115366 INCIN'ERA JCRUBBER DATA LOCI Date U4-~4J fH VxtI {M/) u u: uLU oX COT) uu c c, c UJ Q-- uo h- oX ^ o (Tl I o II o Li, I--d)* Lr. >x d) ^ --H (-1 1 d> KH D. Li Cu X --< co O3 ><u O' a> o So t- oo rLOi oi 0 1I n n x _oo o d> u- cr3 v-' Oil *--( rOj H o oLA II 4J --O< A_) D -Cu T I-2 (F ire b o x = 2100-2500) TISH-5A (R e fra c to ry = 2100-2500) TISH-3B ( R e fr a c to r y = 2100-2500) ________ A larm s? TG-2 (L iq u id 0 u tle t-9 0 -1 5 0 ) PI-1 (Scrub. P re s s .=1.5 to 7 .0 ") O ther i F I-2 (Stm . Flow= 0) F I-5 (T o ta l H20=80-90) F I-4 (St Scrub. H20=30-50) DTH 0 0 0 1 1 5 3 6 7 r COMPLIANCE MANUAL ABERDEEN PVC PLANT r c VII. METHODS OF COMPLIANCE - TYPE III Item: 61.64 (e) (1) (ii) Sources following the stripper: The following requirements apply to emissions of vinyl chloride to the atmosphere from the combination of all sources following the stripper (or the reactors if the plant has no stripper) in the plant process flow including but not limited to, centrifuges, concentrators, blend tanks, filters, dryers, conveyor air discharges, baggers, storage containers, and improcess wastewater. In polyvinyl chloride plants using stripping technology to control vinyl chloride emissions, the weighed residual average in all grades of polyvinyl chloride resin processed through the stripping operation on each calender day, measured immediately after the stripping operation is completed, may not exceed 400 ppm for polyvinyl chloride resin averaged separately for each type of resin. Problem: The Aberdeen Plant produces only one type of resin, this is by the suspension process: The Aberdeen Plant utilizes stripping technology. The reactors are used as the stripping vessels. The standard requires stripping to a level of 400 ppm of less. Emission Sources: The regulation states the concentration of vinyl chloride in resin as it exits the stripper must be less than 400 ppm. Method of Compliance: Compliance is achieved through steam stripping in the reactor vessels following completion of reaction. The plant utilizes reactors for resin slurry stripping thus avoiding emissions from multiple vessels. The reactors are equipped with direct mounted, reflux condensers. This allows refluxing of considerable material which substantially improves stripping efficiency. Attached is the condidions used for the stripping recovery process. Compliance Procedure: The Federal Government requires us to reduce the VCM content of reactor slurry to a 400 ppm level before transfer of the slurry from the reactor to the blend tanks. In addition, we must also meet a requirement for reduction of VCM in the vapor space above the slurry in each reactor. typtt DTH 000115368 To meet the requirements of the government we steam strip each reactor batch prior to transfer to the blend tanks. It is most important that we properly and uniformly strip each batch so we can meet the government's requirements. r Compliance Procedure: The following steam stripping procedure is to be used on every (Cont.) batch processed. Any variations in the procedure or any associated problems in the operation of the recovery system should be brought to the attention of the shift supervisor. Recovery Procedure: (To be precisely followed for all products] 1. Kill reaction at conditions described on product formula sheet. 2. Start compressors and begin recovery. 3. Set temperature set point to 200F and start steam into the reactor. 4. Wait until vacuum pumps come on. 5. Reset temperature set point to 230F. 6. When reactor temperature reaches 215F, turn emergency cooling water on the condenser. 7. Leave both steam and cooling water on during the next 10 minutes and continue recovering. 8. Evacuate dump valve during last five minutes of recovery. 9. Shut off steam, emergency cooling water and recovery system. 10. Dump reactor. 11. Sample slurry 5 to 10 minutes after start of dump. 12. During recovery the back pressure controller is to be set at 6". DTH 000115369 c r COMPLIANCE MANUAL ABERDEEN PVC PLANT VII. METHODS OF COMPLIANCE - TYPE III Item: 61.65 (b) (9) (i) The concentration of vinyl chloride in each inproccss wastewater stream containing greater than 10 ppm vinyl chloride measured immediately as it leaves a piece of equipment and before being mixed with any other inprocess wastewater stream is to be reduced to no more than 10 ppm by weight before being mixed with any other inprocess wastewater stream which contains less than 10 ppm vinyl chloride; before being exposed to the atmosphere, before being discharged untreated as a wastewater. Problem: Water accumulates in the recovery system during the stripping and recovery process. This water collects in the: K.O. Scrubbers (5) Seal Water Separators (6) RVCM Receivers (4) Additionally water is used for vapor displacement on some equip r ment. This water is exposed to VCM vapor and, in untreated form, contains in excess of 10 ppm vinyl chloride. Emission Sources: The process piping allows drainage to one of two process water stripping tanks. These vessels accumulate this water. Periodically the water is steam stripped at a vacuum to a recovery system. The wastewater is then pumped out of the stripper. The emission point is at the discharge of the pump, prior to entering the sewer system. Method of Compliance: When a sufficient amount of water is collected, the water is steam stripped at a vacuum. The stripping operation reduces the vinyl chloride content to 10 ppm. Compliance Procedure: 1. Line up tank to recovery system. 2. Start recovery system and pull down to a vacuum. 3. Begin to inject steam at maximum rate. 4. Inject steam at maximum rate to reach a water temperature of 200F. 5. Continue to inject steam for 45 minutes. Allow temperature to rise to 230F. 6. With steam injection and recovery continuing, pump out tank. 7. When tank is empty, shut off steam, recovery system and pump. 8. Utilize vapor steam injection on top of tank as a pump assist if needed. 9. Sampling is to be done at pump discharge as is necessary to monitor compliance. DTH 000115370 r COMPLIANCE MANUAL ABERDEEN PVC PLANT VIII. TESTING METHODS FOR TYPE III The Emission Standard requires, in some instances, sampling for compliance as well as for on going process emission monitoring. This sampling is specific for: 1. Exhaust emissions to the atmosphere which must be less than 10 ppm. 2. Slurry VCM residual level following stripping, which must be less than 400 ppm. 3. Inprocess wastewater discharge, which must be less than 10 ppm. A. Sampling Information 1. Exhaust Emissions to the Atmosphere Which Must Be Less Than 10 PPM. This sample will be obtained from the exhaust stack of the incinerators. Sampling for compliance will be by method 106. Sampling and analysis will be in precise accordance with method 106 as far as we can determine. r Following the emission test for compliance, the plant will conduct emission tests on a periodic basis to assdre compliance is being maintained. For such testing we propose the following schedule: a) Process sampling and analysis via a gas bag sample - 1 per week. b) Process sampling and analysis via method 106 - 1 per quarter. 2. Slurry VCM Residual Level Following Stripping Which Must Be Less Than 400 PPM. Following the stripping operation, the reactor product slurry is pumped to the Dryer area. Sampling of this stream will be at the discharge of the transfer pump to the blend tank area. "For compliance testing, three samples of each batch will be obtained. In accordance with the standard, the average value of the three samples will be used to determine compliance. Sampling equipment will be as described in the Federal Register. The three samples will be taken after 5 minutes, 10 minutes, and 15 minutes after the staTt of the slurry transfer operation. This will insure the sampling is representative of the batch. We suggest for compliance testing that a total of eight reactor batches r be analyzed, one from each of the plant's reactor-strippers. DTH 000115371 c A. Sampling Information 2. (Cont.} Following the testing for compliance verification the plant will conduct further testing on a periodic basis to insure compliance is being maintained. We suggest this be done on three reactorbatches per week. Sampling on these three batches will be as discussed above. 3. Inprocess Wastewater Discharge, Which Must Be Less Than 10 PPM. This sample will be obtained from the discharge of the process wastewater stripper following wastewater stripping. This sample is obtained prior to mixing with other wastewater and entrance into the wastewater treatment system. For compliance testing we suggest obtaining three samples from each batch stripped, the three samples being obtained to insure a representative analysis. We further suggest a total of six stripping batches be analyzed. Following the testing for compliance verification, the plant will conduct further testing on a periodic basis to insure compliance is being maintained. We suggest this be done on two stripped batches per week. Sampling will be as discussed above. 9 B. Analytical Information 1. Method 106 This analysis is applicable to emissions from the vent gas incinerator. We have reviewed the method described in the Federal Register. To date our analyses have been via gas bag analysis. We are building a sampling device to meet the Federal Register's description. This device will be used for the initial emission testing and periodically thereafter for emission monitoring. As far as we are able to determine our emission testing for compliance verification will meet all the requirements of method 106 as described in the Federal Register. 2. Method. 107 This method is applicable for determining the vinyl chloride content of reactor slurry, and inprocess wastewater. DTH 000115372 DETERMINATION OF VINYL CHLORIDE CONTENT OF IN-PROCESS WASTEWATER SAMPLES AND POLYVINYL Cl I LORI OF. SLURRY SCOPE This method is designed to measure the residual vinyl chloride (RVCM) in PVC slurry samples and in waste water. It was taken from EPA Method 107. METHOD OUTLINE The slurry is filtered and a sample of the wet cake is scaled in a vial (for samples of water transfer 1 gm. to the vial). A separate sample of the wet cake is taken for a % solids measurement. The sample in the vial is heated to 90C to drive the VCM into the headspace. A sample of the headspace is injected into a chromatograph. The vinyl peak is compared to a standard and the RVCM in ppm by weight is calculated. APPARATUS 1. Perkin-Elmer F-42 automatic headspace gas chromatograph equipped with a Fill and back flush attachment. 2. Columns - precolumn 1/8" X 24" carbopac analytical 1/8" X 36" Phenylisocyanate/ durapac. 3. Recorder, 1 MV range. 4. Integrator or similar device to measure peak area (SP-4000 Data Processor is used). 5. Oven - Natural draft set at 100C. 6. Vials and seals for F-42 (PE 105-0118). 7. Seal crimper for above vials. 8. Syringe, 100 pi gas-tight. 9. Thermometer accurate to 0.2 at 90C. REAGENTS 1. Vinyl chloride 99+%. 2. Standard Gas Cylinders, 50 ppm, 500 ppm, 5000 ppm. NBS certified gas b.lcnds of VCM in nitrogen. 3. Gases for F-42, zero grade air, nitrogen, hydrogen. 4. Nitrogen for VC1 blends - 99+% purity. jypjj 000115373 Analytical Information 2. (Cont.) The plant uses equipment essentially identical to the method described in the Federal Register. There are minor differences in the calculational procedure which have no effect on the calculated result. Attached is a detailed description of the analysis and a Table 9 which specifically indicates the differences in calculation. We propose to use this method both for verification of compliance and for ongoing process monitoring. DTH 000115374 PROCEDURE 1. The Perkin-Elmer F-42 Chromatograph must be preset to operating conditions to resolve the VQI. 2. The circulating bath temperature should be at 90+^ 0.4C. 3. Take the slurry sample and filter using vacuum and a buchner funnel for 15 seconds (until the water just quits coming off in a steady stream). 4. Take a preweighed vial and add a plug of the wet cake (about 1.5g). Cap vial and weight back to nearest mg. Put another plug of wet cake into a tared dish and reweigh. 5. Dry the sample in the dish at 100C for 45 minutes and reweigh. 6. Record in a notebook the sample identification weight, and total solids content of wet cake. 7. Seal the vial containing the sample and put it into the F-42 tray - note its position in the notebook. 8. Prepare 3 standards by filling the vials with the VCM in nitrogen standards and rapidly seating the septum. The first standard is to be 50-60 ppm, the second is 500 ppm, and the third should match the highest reading expected. If gas blends are not available in the range required, then lab blends can be made from nitrogen and pure VC1 as per Method 107. 9. The F-42 tray is loaded with the three standards fir^t followed by the samples. The F-42 can be started after 1 hour of equilibration*time. 10. For water samples transfer 1 gm. of sample to a pre-weighed vial. Rcwcigh the vial.to Nearest mg and seal. Treat as above. 11. Water samples are to be equilibrated for 2 hours rather than one hour. This can be done by being sure the water samples are the last samples in the tray. CALCULATION (TS) Solids Fraction = dry resin wt. wet resin wt. Convert the' three standards to ppm based on resin using the following equation: C RVCM A -P Tj MV RW + K (TS) T2 + K (1-TS) PW Where the following values are assumed: C RVCM Concentration of VCM on an as is basis in resin or water. DTH 000115375 CALCULATION (Cont.) A = PPM, VCM in Vapor P = Lab Pressure (760) Tj= Lab Temperature (295K) V = Volume of Vial (23.0cc) R " Gas Constant (6.236 X 10^) W = Sample wt. (1.0 g) TS = Solids Fraction (0.65) Kp = Henry's Constant for Polymer(6.52 X 10" ') Kw = Henry's Constant forWater (5.0X 10~ ) T2 = Water Bath Temperature (363K) M = Mole Weight of VCM (62.5) SIMPLIFIED FOR CONSTANT FACTORS Crvcm = A X 0.065 This factor is not altered unless lab temperature changes by more than +_ 5C or lab pressure does not vary more than + 10mm. The for each standard is calculated and entered in the data processor as the standard concentration. The data processor then does the following calcu lations using external standard method: Rf = Area Std. CRVCM Where: PPM, RVCM of (Resin $ Slurry) = Area Sample r x (sFTTfsT SIV = the weight of the wet cake (gm) or water sample (SW X TS) = Weight of dry resin (gm). PPM, RVCM of water sample = Area Sample Rf X SW NOTES: 1. The conditions for the F-42 with the specified columns are as follows: (a) . Injecto-r Temperature 150C (b) Oven Temperature 80 (c) Detector Temperature 150 (d) Needle Temperature 150 (e) Hydrogen Pressure 2.1ATM (f) Air Pressure 2.6 (g) Fcreflush Pressure 1.9 (h) Backflush Pressure 1.8 ( Adjusted to give minimum baseline shift in backflush) DTH 000115376 (i) Dosing Time (j) Analysis Time 00 Backflush Time (1) Stabilization Time (m) Detector Range 3 see. 0.9 min 3.2 min 2 min. 1 PREPARED BY: APPROVED BY: AZj'-//2Jr Original Issue 11/1/77 DTH 000115377 tabli: y POINTS OF DIFFERENCES BETWEEN EPA METHOD 107 AND RVCM ANALYSIS AT ABERDEEN* PLANT EPA METHOD 107 Use 2 M X 3.2 MM column of 0.4% carbowax 1500 on carbopac C or equivalent. Samples must be run within 24 hours. Add 100 N1 water to bottle containing standard gas blends. CALCULATION Calculate each sample by the following equation: CRVCM (1-TS) T + Kp (TS) T2 + Kw Crvcm = VCM in dry resin. A = Area of VCM Peak R = Response Factor = Area Std. PPM, VCM Vapor Std. P = Laboratory Pressure T^ = Laboratory Temperature M = Mole Weight of VCM (62.5) V - Volume of Vial VaporSpace W = Sample Weight R = Gas Constant (62,360) , Kp = Henry's Constant'Polymer (6.52 X 10 ) Kw = Henry's Constant Water (5.0 X 10 ) T2 = Water Bath Temperature (363K) TS = Total Solids O ABERDEEN Initially used the specified column but found some interference peaks. Changed to a column previously found to resolve the VCM. It is a 1/8" X 36" column packed with durapac Phenylisocyanate. Samples are run daily except on week ends. Samples from 7:00 a.m. Friday to 7:00 a.m. Monday are all run on Monday. Water was tried but no difference could be seen so for labor consider ations, the practice was dropped. CALCULATION Method was simplified by considering everything constant except area of peak, response factor, sample wt. , and total solids. Aberdeen constant values are listed below. The maximum possible error, as a result of these assumption, is +_ 3.0% relative. P = 760 Tj = 22C (295K) M = 62.5 V - 23.0 R = 62360 Kp = 6.52 X 10"b Kw = 5.0 X 10~b T2 = 90C (363K) The equation reduces to: CRVCM = DTH 000115378 The 0.065 constant is not changed unless lab temperature varies by more than +_ 5C and pressure remains within + 10 mm. COMPLIANCE MANUAL ABERDEEN PVC PLANT IX. RECORDKEEPING REQUIREMENTS FOR COMPLIANCE The plant will maintain emission records to insure maintenance of compliance and to enable emissions to be determined. 1. The operating records of each reactor batch including pressure and temperature charts. These will be used to: a) Insure operating conditions required for reactor opening loss are being employed. b) Insure operating conditions required for slurry stripping are being employed. c) Insure that no relief discharges are occurring from the reactors. 2. Emission monitoring results for slurry stripping on the three weekly test batches. 3. Emission monitoring results for inprocess wastewater stripping on the two weekly test batches. 4. Emission monitoring results for the vent gas incinerator exhaust gases. 5. Vent Gas Incinerator Daily operating log sheet. 6. a) Reactor Agitator Seal Check List b) Rotating Pump Seal Check List c.) Rotating Compressor Seal Check List d) Vessel Rupture Disk Check List 7. Hydrocarbon Detection results from opening: a) VCM Sphere (1) b) VCM Bullets (2) c)~ Charge Receivers (2) d) ~RVCM Receivers (4) (These vessels exceed 1250 gallons) 8. Leak Detection data as described in Section X. DTH 000115379 This information will be kept in an organized fashion and will be available for inspection by the Administrator for a minimum of two years. This data will be used for submittal of the semiannual report. We suggest the initial submittal be on March 15, 1979. COMPLIANCE MANUAL ABERDEEN PVC PLANT X. APPENDIX Leak Detection and Elimination Plan This plan was previously submitted to the LPA on May 9, 1977 DTH 000115380 DTH 000115381 torn is lU O&/0/A/AL. oetcwmoK 04C ** i ABERDEEN f/queEZ EXC, .F.LAN.Z V/NYL CHUOR/Q& J&Mtt No. MHM DTH 000115382 DTH 000115383