Document jyQ7XXN9kaQNoEdvenK9ZOdzZ

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 Received EC 12 1977 DEC 9 1977 R. N. wheeler, jo. Mr. R. N. Wheeler, Jr. Union Carbide Corporation P. 0. Box 8004 South Charleston, West Virginia 25303 Dear Mr. Wheeler: Attached you will find a copy of my memorandum to the EPA Regional Offices which you have indicated as containing Union Carbide facilities affected by the vinyl chloride test method requirements. Also attached is a copy of the approved alternate test Method 107 which was sent with the memorandum. Please note that I have slightly modified the applicability statement in order for it to be consistent with the one contained in reference Method 107. You will also find that I deleted the statement in Section 3 regarding adjustment of homopolymer analysis results, as we agreed. I also changed the statement about standard renewal in order to remove any ambiguity. It is my impression that a requirement of standard renewal every three months would not be unduly burdensome, but advise me if you object. I expect to soon prepare a new draft of this method in prepara tion for proposal in the Federal Register along with revised Methods 106 and 107. In the course of this project, your continued assistance would be greatly appreciated. Sincerely yours, 2 Enclosures n m m am ur i m i try Test Support Section Emission Measurement Branch Emission Standards and Engineering Division COLORITE 019219 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY Office of Air Quality Planning and Standards | Research Triangle Park, North Carolina 27711 subject: Alternate Vinyl Chloride Test Methods Resubmitted by date; December 9, 1977 Union Carbide from: William Grimley, Test Support Section Emission Measurement Branch, ESED (MD 19 TO: Director, Surveillance and Analysis Division, Regions II, III, IV, VI, IX In accordance with requests from Regions IV, IX, and Union Carbide, we have reviewed the vinyl chloride test items which Union Carbide has resubmitted for consideration as alternate procedures. This review has been done in collaboration with the Quality Assurance Branch of the Environmental Monitoring and Support Laboratory. The items resubmitted were as follows: 1. Method 106, Section 4.3.2. Alternate chromatographic column Stainless Steel, 6.1 m x 3.2 mm, packed with 20 percent Tergitol -35 on 60/80 mesh Chromasorb W AW. 2. Method 107. Entire method; attached. Based on the,additional supporting information supplied by Union Carbide, both items are now judged acceptable as alternate procedures. Because of widespread interest, the alternate Method 107 (draft copy attached) will, with some refinement, be proposed as such in the Federal Register. Acceptance of the enclosed draft should satisfy Union Carbide's needs for the present. They will be expected to follow the method as it is finally promulgated, of course. For your information, we also expect to propose changes in both Methods 106 and 107 so that it will be possible for the method user to perform a self appraisal to determine acceptance of a particular column as an alternate procedure. This change should greatly reduce the number of requests for alternate procedure approvals. Should you have any questions, please contact me. My FTS phone is 629-5276; commercial phone is 919 541 5276. Enclosure cc: Robert Ajax (MD 13) Richard Biondi (EN 341) Alvin Chun, Region JX Min Clements (,''D 77) Joe Knoll (MD 77) Dames Wu, Region IV Susan Wyatt (MD 13) ti'A form 1330-5 4-7i) COLOR!TE 0X9220 DRAFT Method 107 - Alternate Method - Determination of Vinyl Chloride Content of Inprocess Wastewater, Solvents, Resin-Solvent Solutions, Polyvinyfl Chloride Resin, Resin Slurry, Wet Resin and Latex Samples DEC 9 19 INTRODUCTION Performance of this method should not be attempted by persons unfamili ar with the operation of a gas chromatograph nor by those unfamiliar witt" sampling and analytical laboratory procedures, as there are many detai Is that are beyond the scope of this presentation. 1. Principle and Applicability 1.1 The basis for this method lies in the direct injection of a liquid sample into a chr:natography and the subsequent evaporation of all volatile material into the carrier gas stream of the chroma to- graph, permitting analysis of all volatile material including vi nyl chloride. 1.2 This procedure is suitable for determining the vinyl chloride content of inprocess wastewater, solvents, rfisin solvent solutions PVC resin, wet cake slurries, latex and fabricated resin samples, The column employed has been shown to resolve vinyl chloride from othe r materials such as acetaldehyde, acetone and vinyl acetate. Howeve|r, if a resolution of the vinyl chloride peak i$ not satisfactory for a particular sample, then chromatograph parameters may be altered pr o- vided that the precision and reproducibility of the analysis of vi nyl chloride cylinder standards are not impaired; If there is reaso; to a i c' o 'sent S'. <>i t'"* sa; s], .. 1 / ' Ct. j.i identical reteiif.Oi ' - f * 1 ,, , ',.7 1 :on c' , a iS Chin- . .,n ur Vi'. . y s 't i snc.i as WiiU : : per: : s . COLOR!TE 019221 2, Range and Sensitivity The lower limit of detection of vinyl chloride in dry PVC resin is 0,2 ppm. For resin solutions, latexes and wet resin this limit rises inversely as the nonvolatile (resin) content decreases. With proper calibration the upper limit may be extended as needed. 3. Precision and Reproducibility A comparison of precision and reproducibility between the alternative method and Method 107 using a suspension resin homopolymer sample showed the alternative method had a standard deviation of 0.95 percent at the 340 ppm level and yielded mean results ten percent higher than Method 107. Method 107 in the same test had a standard deviation of 1.89 percent. A standard sample of latex containing 181.8 ppm vinyl chloride analyzed ten times by the alternative method showed a standard deviation of 7.5 percent and a mean error of 0.21 percent. A sample of vinyl chloride copolymer resin solution was analyzed ten times by the alternative method and showed a standard deviation of 6.6 percent at a level of 35 ppm. The i..crease in standard deviation on the latex and the resin solu tion samples is due to the correction of the analysis from a gross basis to a contained dry solids basis. Both the latex and resin solution samples contained acetaldehyde along with other monomers and solvents. COLOR!TE 019222 ` t 4. Safety Do not release vinyl chloride to the laboratory atmos phere during preparation of standards, vjenting or purging with ; VCM/air mixtures must be minimized land when necessary must be routed to the outside air,. Vinyl chloride, even 'at lov ppm levels, ^ must never be vented inside the laboratory. ` 5, Apparatus 5.1 Sampling 5.1.1 Bottles - Sixteen-ounce wide mouth with p olyethylene lined screw caps. 5.1.2 Vials - 51 ml Hypo- vi a lr.J sealed with 7efl on faced Tuf-Bcnd discs or equivalent for water sam pies. 5.2 Sample Recovery 5.2.1 Vials - 20 ml with poiycone screw caps. 5.2.2 Analytical balance - Capable of weighing to t -0,01 gv ram. 5.2.3 Syringe - 50 microliter with removable net -die. 5.2.4 Frittedglass sparger fine. 5.2.5 Aluminum welching dishes. 5.2. 5 b-;,,r.pi .-a L-.' 11 a;; ' o e * iect isampl a solution, \ , [ *1 ' T t' ' \ * - > Chromasorb W Ah 00/50 mesh. 1 ,, .. , ! V'ticn ar tvth? "-'t, rvi worTr i n -''.vth-: fn, nnt r.onstitu'c*1* on arsArent COLOR!TE 01922 S f { i :| l f ;i *l 'i 1 ` j 5.3.3 Valeo Instrument Six Pdrt Rotary Valve for column back flush. 5.3.4 Septa for H.p. chromatqgraph injection pert. 5.3.5 Injection port liners - H.P., chromatograph 5.3.6 Regulators for requiredj gas cylinders. 5.3.7 Soap film flow meter Hewlett Packard No. 0101-0113 :\ or equivalent. 5.4 Calibration 5.4.1 Analytical Balance capable of weighing to -0.1 mg. 5.4.2 Erlenmyer Flask with glass stopper 125 ml 5.4.3 Pipets 0.1, 0.5, 1, 5 ahd 10 ml. 5.4.4 Volumetric Flasks - 10 ml and 100 ml. Reagents 6.1 Analysis 6.1.1 Hydrogen gas - zero grade 6.1.2 Nitrogen gas - zero graejo 5.1.3 Air - zero grade 6.1.4 Tetrahydrofuran - reagent grade Analyze the tetrahydrofuran (THF) by injecting 1C microliters into the prepared gas chromatograph. Compare the chromatogram vri to thnr shown on the next page. T f the chrom v.o-p.v a is - u:nro rn'>l- A, tv ,, TEIF should V COLORITE 019224 determine if the THF is acceptable for use. If the scan is comparable to B, the THF should be accebtable for use in the analysis. interfering peaK de toe to r response 6.2.1 vinyl chloride 99.9+%-.For preparation of standard solutions. Procedure 7.1 Sampling 7.1.1 Sampling Other Than Water - Allow the liq uid or dried resin to flow from a tap on the tank, s iio or pipeline until the tap has been purged. Fill a wide-mouth pint bottle and immediately tightly c ap the bottle. Place an identifying label on each bottle and record the date, time, sample location and material on the A \ . 7.1.2 r Sampling Frio,, fc u: a, the 50 ni ijvoo- COLORITE 019225 bubble-free to overflowing so that a convex menilscus forms at the top. The excess i/ater is displaced as the sealing disc is carefully placed, Teflon-side down on the opening of the vial. Place the aluminum seal over the disc and neck of the vial and crimp into place, Affix an identifying label on the vial and record the date, time and sample location'on the label. All samples must be kept refrigerated until analyzed, 7.2 Sample Recovery. hours. Samples must be run within twenty-four 7.2.1 Resin Samples : Weigh nine grams of tetrahydrofuran to the nearest 0.01 gram in a tared 20 ml vial. Add one gram of resin to the tared vial containing the tetrahydrofuran. Close the vial tightly with the screw cap and shake or other wise agitata the vial until complete solution or the "resin is obtained; This may take several minutes to several hours depending on the nature of the resin. 7.2.2 Suspension resin slurry and wet resin samples Slurry must be filtered using aj small Buchner funinel with vacuum to yield a wot. r^sin sample. The filterin g proceo be C'",i nuccl .illy u long a-;, a sl.aa.dv r t of v/afur ting fro/1 Ilia ;:u;: = ' ` 1 , dxcossi r ; L:ilt ration COLORITE 01922(5 the seme as the resin sample. A sample of the wet resin is used to determine total solids. This is re quired for calculating the RVCK. (Section 7.3.51 7.2.3 Latex and Resin Solvent Solutions - Samples must be thoroughly mixed. Accurately weigh one gram of the latex or resin-solvent solution into a 20 mi vial containing nine grams of THF as for the resin samples (7.2.1). Cap and shake until complete solution is effected. Determine the total solids of the latex or resin solution sample. (Section 7.3.5) 7.2.4 l'nprocoss waste wv. tor, solvents and non-viscous liquid samples. No preparation of these samples is required. The neat samples are injected directly into the gas chromatograph. Analysis 7.3.1 Preparation of gar. chromatograph. Install the chre '-.tosraohi; condition overnight ivl ' w * 'Do not connect tha exit end of the column to the while conditioning. 7.3.1.1 Flow rate adjustments - Adjust the flow COLORXTE 019227 b. Burner air supply. Set regulator on the cylinder at 40 ps^g. Bet regulator on the chromatograph to supply air to the burner to yield a flow rate of 250 to 300 cc per minute using the flow meter. c. Hydrogen. Set regulator on cylinder to read GO psig. Sot regulator on the chromatograph to supply 30 to 40 cc per iminute using the flow meter. Optimize hydrogen flow to yield the most sensitive detector response without extinguishing the flame. Chock flow hth flow meter and record th.ijs flow, d. nitrogen back flush gas. Set regulator on the chromatograph using the soap film flow meter to yield ;> flow rate of 40 cc per minute, 7.3.1.2 Temperature adjustments. inUr -^ ^- ,, ' 1 r>-. i Set temperatures a. Oven (chromatographic column) 7Cf"C "injection pint - 100C c. Detector - 300C 7.3.1.3 Ignition of flame ionization detector. Igr.-a the ^ 'tecinr according to the manufacturer A' '" ' ; ^ , 'c ".Di l/i : ,\ COLOR!TE 019228 7,3.2 Chromatographic Analyses a, Sample* injection. Remove needle from fifty micro liter syringe. Open sample vlai ar.d draw fifty microliters of THF-sanpla solution into the syringe, Recap sample v ial. Attach needle to the syringe ana bolding the syringe vertically die npr jst, ojret: i.e.: more ; Liters chr.n.gr a rr z . ue. ... 7 jv-'c .j c': r ystern. b. Bach r;;c'.r r. 1. - "t; I .rr ' rotes have clapped uf to ~anp a ; u " : I. i \ -,] *;; t ; p Jc: v- -A'--, ! u... . *i v rs , *; * l f*'u! > pi -, ' _ \ l^V\ U l IT r'l . V \ , .v ` c . /' f. , t\;. -3.3 Chrov i tzrap > a ri:-.-. Sop flu-". tv-_Pac::v oftor f,: ;o. COLOR!TE 019229 1 4 7.3.5 Determination of Total Solids (T.S,.) For wet resir., resin solution and DVC latex samples, deter- mine the T.S. tor each sample by accurately weighing approxi- mately three-to five-grams of sample into a tared all uninum The procedure is as follows: Water is the ,<vjnr volatile component. Tare the vc , yb irr* a i-sn anti odd thrua-to 1 a;' j of sac,ole to the di; n. 'Weigh to the nearest milligram. b. Volatile solvent is the major volatile component. n . ortio" of if',': sn-pf .> a 3a n! ..-.crew cap i ll aw i u **..!._* 1. Q T awtii ato ly . 1 ' ; .-.al to tap nearest ;.i1 liyran - > n sj ci p r. ' o vial an..; 1 an; f;or n ; :\ co f vo-gram part-on of the 'P ^n f - ~ ' '..n, i-'u:; '.`.ighir.y; dish. Recap the v j a 1 and g:'i l.t che nj<.\ v, at 1 i y fh;: vJ. al v/oight lo -d "if ' --.-mol - :-lt. -to v^ig'-irwr pan a;: a o.30C ov-:n Ci.i; ;v.v ' . v: Ft':'1'' ant afi.ov to cool to re. ' ^7yr-\ :: 'J -o'- ' -,o t at .'.a the r.3ar?:-t 3 , i. of,'*, r . i. r. in Vt.'gh .<, .. -1 an the alumina Vi ` 1 t, arter heating dlviiod by not weight of Simple add >-- V the pan originally time-- 100. 1 i i i j COLOR!TE 01923G i 1j | a. Prepare a one percent by weight solution of vinyl chloride in tefrahydrofurtn by bubbling vinyl chloride gas frprn a cylinder into a t.arod 125 ml glass stoppered flash containing Tit-', 71'.e approximate -,v rant of vi yyl chloride shoulc\ be ;ui. VJ) , ) . .o > , one on the i tc" oe carrieu out in a laboratory hos4. Adjust the vinj -1 chloric :low rron '.la oyLinear sc :.hat the v,i.nyi chloride solves 'cor. tr , p : - c : y ' n '-he 7b ' in' La not bio /n to t*! ; v* 1 ' SV 'b ia'i ah" soictic: : u. cry "'a 'V c.r.t Welch a' r; -1 r>?ve..l flesh it: r r .1. . ; Cl. O . .> ".v-'i res t , h i ' :j c lut vr ' J , b i ft: sol';.'1.! ta > n a L 00 :' 1 a] re O' to ciio .ad, wi; a : art. swj rl u! unemo i. ...as- S. Oil'-.: ryi r t' -i forc.lv . cans soi.u-- >'lg ' rhv tyc-ix.-'l c s 1 i.brrnh ion cervv-, COLOR!TE 019231 100 75 L i' IG U P.E TYPICAL GAS CHROMATOGRAPHIC FO'.I PPM VIKYl* CHLQRIDft VS .Kb* l* * RAK/DRO* U-A< 0j. / / / J t- 'J COLORITE 019232 y. Calcuinfci.ona. 9.1 Response factor. rrcn the calibration .--.v.-v/e described in Section 8.1 select tne value of Co that corresponds to He for each sarmpie, Compute t he raspor.sc- f 11r , Rf . for each aamnie as revs; nc Residual c.' orj.ao ronoter eoncootractor; c 'TfcUruiC i/Or.CU r;-r* '/Jli/V. ' r ' . h n m ro- c r.: .c r* '-t \\: o, .' j * x ^., 2 v "'or r'.* ( ; * ' \ / ; .v j ^ ^ COLORITE 019233 SCOPE OF BURLINGTON EPA COMPLIANCE PROJECT / 1. INCINERATION SYSTEM - (Gas streams above 10 ppm) One incinerator with a caustic scrubber supplied as a package unit from Trane, Caustic storage tanks with pH control system are also required. Quench water for the incinerator to be cooling tower overflow stream which will be diverted to mix box with high salt concentration, MAJOR STREAMS Vent Condenser Discharge Water Stripper Vents (2) Vessel Entry as required 2. WATER STRIPPER SYSTEM - (Process water above 10 ppm) A continuous steam stripping column with a Nash vacuum pump to control vacuum. Unit includes a new feed storage tank and feedbottoms exchanger, and automatic filtration system. J MAJOR STREAMS Foam K. 0. Pots Fume Scrubber water Barometric Sumps Ho & Co 3. SLURRY PUMP PROJECT-(Eliminate nitrogen for stripp&rs) One homopolymer and one copolymer transfer pump with inter connecting piping. 4. VESSEL ENTRY - (Less than 2 Vol % VCM to open) Provide piping and tie-ins to sources of nitrogen or steam and tie vessels into existing recovery systems. 5* DISPERSION TOWER STEAMING - (Less than 2600 ppm) Provide steam piping into top of each dispersion tower with provisions to steam during stripper-tower recovery. 6. COPOLYMER REACTOR RECOVERY - (Less than 2300 ppm) Method not as yet selected. Alternatives: 1. Steam reactor and install jet cleaning system, 2. Water spray alone or with jet cleaning system COLORITE 019234 A SCOPE OF BURLINGTON EPA COMPLIANCE PROJECT PAGE ~2 7. DISPERSION STRIPPING SYSTEMS Met+iod^not determined. Best guess is ^"direct steam heating system for each stripper. What, if any, recovery equipment will be required has not been determined. Additional projects that will require justification by Manufacturing Dept.: 1. / 2. ' 3. 4. 5. Spare Vent Condenser Spare Brine System Additional Ho/Co Compressor capability Additional Plastisol Compressor capability Well Water quality improvement COLORITE 019235