Document RaNz3NqEd30Y4paYEKJKYLJz8

to m m CONFIDENTIAL ROL Correlations 10-10-85 To : From; Date : Subject: J Friend and H. Garrison R D. NeI1ing October 9. 1985 Reactor Opening Loss Emissions Testing r INTRODUCTION require?that PVC R.actor Op.ning Lo. (ROL) . ... be limited to 20 ppm expressed aa pounds vcm par Billion pound* PVC produced (dry weight bsis). The reeulatlon* *ulti!hiiCrrtaJH Procedure* for .assuring ROC eaiealon* which are not itriBninff^ 1,8 Vl88 Poly",rs l"P- CVieta") in-reactor .tea. Proce**. Both the Aberdeen. Mi**. and Okiahoaa City, okla ? h!ve op8r*t,d ln th Pst "nd continue to operate unde^' beeed in 51?? f?r "auring ROL eniaeion*. The equlvalenciei are baaed on following operating procedure* designed to comply with the SO pp. eel*.ion liait .pacified in th* regulation^. SUMMARY A research program to study reactor opening loss emissions has recently been completed by Vista4 The program was designed to study othuBr t currewn. t compliance procedures and to develop improved correlations be U8ed t0 qunntlfy emissions. Special sampling and ln__y i"! : procedures were^iieloped to insure that the reactor opening TMS Pr0V8d t0 b8 8*tP88*V difficult " many sampling attempts were unsuccessful. soiling time during steam stripping variable determining ROL emissions. was identified as The boiling time the critical is the time n^ar thC *nd tl*e 8teaiB stripping processxipssential ly all ,c* h" "*" r"rfrom.t-he '=" ->u ^ /I<tVJ vigorously. ifWv-' the Two correlations were at Aberdeen, at both Aberdeen and form: OadkneladvheoolmonpaeedCfoirty.theonBefoothufortrceoetrnhreeslattwatinoodnalsardrgaerseizeeoxpf raetnhsseciotnors ROL - a exp( -b t ) where: ROL t a and b Reactor Opening Loss, pounds VCM per million pounds PVC produced (dry weight basis) slurry boiling time, minutes Least squares curvefit coeffic ients of experimental data VAB.0001144765 "** confidential 2nd . < ' INTERNAL I w nI f. .--Jr it- <-_ I , .-U'P -IF- L. REVIEW . ISSUE P** ... IT- ... I,. h, . . -- -- 4 * m m CONFIDENTIAL *** ROL ions 10-10-83 The a and b coefficient* were generated by linear least na ysis of forty sample* from six reactors in Oklahoma forty-one samples from seven reactor* in Aberdeen The studied *<,UBtlon eave th best of the deta of rlur squares City and exponential equation forms Figure I showsir, the ROL anVd ub%o,illinn** ttiimm#e data and *exponential curvefit the crr*l*tii>e^e`treasonable J5%!UTlH 'AS'lS^llV V*l :i"v*i\a:Arir lul 5: TM b ourveflt coefficients were obtained ^VisJa ut i lllitlef lux^' * "nd condene.re on the reactors to control the polymer lz"IoIi SDactIonCentrrfIP*Cw concentr*tio'' differs from the reactor vapor vtol tacttmpier ttrllet *** refluxed ste flow. * Condenser .. total y'^ *ln,r fro" the condenser and the reactor were separately, and the emissions were added to obtain the ROL emission*. Analyzing^ he -condenser vapor space Rol and vapor space resuTta sTmTTar To thtat* corr*latln trongly'support the acTuractof`thtdata Hart* tha t,St ",eth0'1* involved. The date sc.tler .1 lenrestiiJ?* timee empheizee the difficulty of obtaining good representative sample* when concentration* are changing quicklv and very -Thu repreeentatl on of M Etllll It reactor opening loe, Missions In conclusion, the research quantifying reactor opening emission* to slurry boiling yielded an improved method of emissions by correlating the finH * DISCUSSION l\I* P*?*?rch Pro*ran consisted of several test runs conducted at both the Oklahoma City plant and the Aberdeen plant. The test run* involved collecting samples of the hot vapors in the reactor and reactoreoa^hther*nd Z* the 8teaM **riPPing process before opening the reactor to the atmosphere to transfer the slurry to blend tanks that'cotlect^^^nr Ab*fdeeft' with ^*ited sampling, h*fl indicated that collecting condensable vapor samples in heated sample bombs# lent--to t h Additional Resting in a controlled environment at researc acilities in Ponca City, Oklahoma concluded that determinations of VOX in a low-pressure steam atmosphere by gas VAB.0001 * * * CQNF i OENTIAL * * * 2nd INTERNAL REVIEW ISSUE Pave 2 CONFIDENTIAL *** rql Correlations 10-10-83 a!^urUJ-*r#?!l analyaa* of ample taken in heated gas bonba were was blended ever a wide r.^ee of kiewi 5?2'Mllon pflaudler reactor at various temperatures hmiditi*. yCN concntratlon* and sanpled , . kowyeittiufts , Xl U III 4 <1 1 t 1 C 8 , and DrSIBUPlB T >i * . deterniJim#tn? compared directly to EPA Methodflr-~f or both accuracy and precision. aily equivalent in dsttflIahaoaetekrmrogehapenabacrletoscmudmdcpi2uulpalotnorirrsnasittncea1gynso1dJtbfieoo*teahnceftmehnhehranhctrniieeccp.oacasr-nlooi-iyttbegaslppprneliiusnyeri.msonoisonecsppiagsedillssed.to.uvathrfnfecrreaaIioornsyuSemmtssxpueMcltedrirtteoehhtecrteeimleballeyetlehRdRcleysette.hiaVafsneiCvdmen.gMaaeipfrfrdlaclcfciinhidcohcgMnti^tuadauynstenldhdytynsa,ost0Dprtfaeermeblsettvllhheseceee'aal'o,wrvudpcvasetmhaaiproedmpoenoUntrpsartlressis"wkab*m.eearipnen^lgdeAs department, the plants collected ccoorrpooorraatte* PPrrohcnesosss the samples and pn-j _ _ A Engineering data from the __ _ . Department, reactors samples in the lab, and evaluated the results v nt and from analyzed the the Despite elaborate precautions, a substantial percenters of the He^"SiI.id ^ollect re unsuccsssful. Many times the 2?sam Jh '* f 11,ut*d tln available near the "d of analval^ fnJI'mnf1 ?BVarlably a bad.sample would cause a high caused hv ... *" **10j*i This was due to sample condensation .??!?..! ill tracmg difficulties or by VCM .volution from nozzli The nartleiacS h ""ft or fro" PVC fouling in th. sample ""iV . T?e Prtial condensation of the steam in the sample lnflat*d th* concentration of VCM in the sample. Occasslonally, a leaking sample line connection allowed air to snter tha !!!d ! *y! " "bUa *he sa"Pie "* being collected thus diluting not no^Jh,! r ca"fne th -n-lyai* to come out low. It is clearly collect representative hot vapor samples for ROL k!rVV*ry batch ln a pvc Plant. Too many conditions and aamole or "a*onabl* c"troi can occur that prev.nt obtaining a sample or that causa a non-representative sample to be caught Tha currant steam stripping procedures at Aberdeen and Oklahoma City st#ef*tr? ? v*ry similar, though some minor differences exist. The steam stripping process consists of a slurry heating period, a hold period, and a cool down period. The heating period involves adding s earn irectly to the reactor slurry while removing VCM vapors to a recovery system. The process is characterized by a constantly increasing slurry temperature and an essentially constant low vapor space temperature. When most of the VCM is vaporized and recovered e reactor pressure begins to drop to the vapor pressure of water and the water in the slurry begins to boil. The vapor space temperature rapidly rises and approaches the slurry temperature. The boiling is maintained for a specified time period. Then cooling water flow to the condenser is 3 *r te d, st,e m flow to the reactor is stopped, and the slurry n 1 1 n-wtvif fiiiwtj ? r a g s trmparsture Then s lurryrblend^tank0633 ** stopped and slurry is transferred to a VAB.0001144767 * ft ft CONFIDENTIAL * i ii 2nd INTERNAL REVIEW ISSUE fJ 'j- I '.n- Page 3 * CONFIDENTIAL *** ROL Correlations 10-10-85 A <5 plants Some of the variables Investigated Included the nsxlaua th* ^a"ed tner;iUr* ^*ched- th cooling "t^r f"w before dumS and* *t8a" fl?" waa stopped, the final temperature defined a. the elapsed time from when the"apor .!. " pPo!"J ItIII III V#POr *pac* t8P^atui. reached l2o ""t* investigated and high ROl emissions were anticipated the s^Sm continued until normal .tripping parL^r*:^ obtained ""Pl*8 and Special ROL sampling procedures and sampling systems were devmlnn.fi ? instruments, and vacuum gauges to allow two sample, to be' ^ In a*"pl* *>ombs simultaneously. The sample bombawere ied^ce thecae V" `S* h0t b* With aapl" downward to conSictid thro,,^ C condenaar nozzle. The second bomb was a rSac^or ` " 88para?a at ^aced and insulated sample line to lter?^nLrtZleVwat bef0ra collecting each samp^ror^cJ dirt ! caused by resin buildup in the nozzle. Air powered rmnnhil* ?*rC,?nnC*ed tQ the sample bomb outlets. The eductors were The saLiin^ in8d20 C? 22 in' H ` vacuUBI using plant process air. condenser through the sample bomb, the^Suc^r.^^hi^d^ctor reactor then blocked in. temperatures and pressures for the boibs biock2dt?ner' and !aTpie bomb were raad and recorded, then the lab Th^hofhi ^ pe"yd f*-on ** hot box. and transported to the for VCM concentration with a gas chromatograph. y ROL emissions were calculated based on analyzed sample bomb VCM concentrations, measured reactor vapor space volume, and reactor batch size. The sample bomb concentration was used to calculate the quantity of VCM m the sample bomb. The quantity of VCM in the reactor was then calculated by adjusting the sample bomb quantity for temperature, pressure, and reactor vapor apace volume. The vapo space volume was measured by cooling a reactor to ambient temperature *ll** gripping, opening the reactor and measuring the slurry level, then adjusting for slurry density at the higher temperature. e the for the accuracy of the vapor volume determinations was checked by addine volumes of all the materials charged to the reactor and adjusting the volume change caused by converting VCM to PVC and by removing unreacted VCM faxing the steam stripping VAB.0001144768 MB * CONFIDENTIAL * * * 2nd INTERNAL REVIEW ISSUE Page 4 * w m CONFIDENTIAL * * * ROL Correlations 10-10*85 The Okl^ggng City reactor hatch size# (weight of PVC produced oer batch) Wrr determined by dividing the test run period production bv D^odue^on!?1* nUmber f batches produced. The Oklahoma City plant hltorie*l"ro*d mu 1 *1Phe reactor VCM charge quantity *$r'the hlatorical conversion factor to PVC for each grade Sf ream produced The ROL emission data was correlated to many of the parameters .m**ea+sured during a. the t est runs. Boiling time was identified as the * ih**^a icant variable determining ROL emissions. The ROL data was "f linear, exponential, logarithmic, and data beat di*cu"d ln the summary, the exponential model fit the conclusions The conclusions from this emissions are as follows: extensive study of reactor opening loss Correlations have been developed that relate Reactor Opening Loss to the slurry boiling time during the steam stripping process. The correlations are based on extensive data from both plants and Jgjg reactor size>~ The Aberdeen Expansion reactors must be correlated separately from the other Aberdeen and Oklahoma City reactors because the vapor space volumes and the batch sizes are much larger than the other reactors. "L&yt --- TheROL data obtained during the test runs was accurate and ^--C.e P re seated--the actual Reactor Opening Loss emissions. Several separate correlations confirmed the consistency of the data. Previous testing in a controlled environment had concluded that hot bomb sampling and GC analysis yielded results that were comparable with EPA Test Method 106 in both precision and accuracy. Sampling low pressure condensable vapor atmospheres for composition analysis is extremely difficult and is not practical to do on every batch produced in a PVC plant. Too many conditions and factors beyond reasonable control can occur that prevent obtaining a sample or that cause a nonrepresentative sample to be caught. *** CONFIDENTIAL *** 2nd *i * INTERNAL REVIEW r ` . H. .+ 4k - t .S I - j--* . .1 T I ISSUE VAB.0001144769 Page 5 , **,