Document k60Mvmgr5JY9gL8RbGkG0OkqV

\ V\ \' Tenneco Chemicals A Tenneco 0p|T>P3ny Turner Place, P.O. Box 365 Piscataway, New Jersey 08854 (201) 981-5000 October 16, 1978 c, ''v Mr. William Grimley, Test Support Section Emission Measurement Branch, ESED (MD-19) U. S. Environmental Protection Agency Office of Air Quality Planning and Standards Research Triangle Park, North Carolina 27711 RE: Alternate Vinyl Chloride Test Methods Dear Mr. Grimley: We are in receipt of letter of September 21, 1978, which completes the approvals of all the alternate vinyl chloride test methods submitted by Tenneco Chemicals. We have modified paragraphs 5.1.2.1 and 7.3.2 in response to the exception to Method GCF-3.0: Determina tion of Vinyl Chloride from Stationary Sources. A copy of the revised method is attached. Very truly yours TENNECO CHEMICALS, INC. J. P. Sandstedt, Manager Environmental Sciences JPS:eg Att. cc: Mr. Marcus Kantz - EPA Region II Mr. Martin Brittain - EPA Region VI bcc: C. Crain H. Johnson J. W. Kachtick F. W. Kanzler R. Lojewski T. T. Moore R. R. Neugold C. Ibthenbeck D. Scoffield J. T. Sweeney I. B. Wakeman R. Young COLORITE 016997 9 Analytical Procedure Research & Development Department Tenneco Chemicals Alenneco Company Turner Place, P.O. Box 365 Piscataway, New Jersey 08854 (201) 981-5000 Procedure No. GCF-3.0 January 12, 1978 (Revised September 21, 1978) DETERMINATION OF VINYL CHLORIDE FROM STATIONARY SOURCES Alternate Method to EPA Test Method 106 (FR 41:46569, 10/21/77; FR 42: 29008, 6/7/77) INTRODUCTION Performance of this method should not be attempted by persons un familiar with the operation of a gas chromatograph, nor by those who are unfamiliar with source sampling, as there are many details (but are beyond the scope of this presentation. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, a car cinogen . 1. PRINCIPLE AND APPLICABILITY 1.1 A sample of gas is analyzed for vinyl chloride (VCM) by gas chromatography, using a flame ionization detector. 1.2 The method is applicable to the measurement of vinyl chloride (VCM) in stack gases and other sources of atmospheric emis sions from polyvinyl chloride manufacturing processes, except where the VCM is contained in particulate matter. 2. RANGE AND SENSITIVITY The hydrogen flame ionization detector of the Perkin-Elmer Model 3920, and equivalent instruments, is capable of detecting at least 0.2 nanograms of vinyl chloride. The limit of detec tion in bag samples, using a five ml injection, is approxi mately 0.014 ppm (microliters/liter). With proper calibration, the upper limit may be extended as needed. 3. INTERFERENCES Acetaldehyde, which can occur in some vinyl chloride sources, does not interfere with the VCM peak from the columns speci fied in Section 5.3.2. If a resolution of the VCM peak is not This information is furnished without warranty, representation, inducement, or license of any kind, iQCludira<-iBiJkXjAU3T LIMITED TO, THE IMPLIED WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTlCULAFTTUHroSEriSepf * * that it is accurate to the best of Tenneco Chemicals' knowledge or obtained from sources believed by Tenneco Chemicals to be accurate, and Tenneco Chemicals does not assume any legal responsibility for use or reliance upon same. Customers are encouraged to conduct their own tests. Before using any product read its label. COLOR!TE 016998 2- - satisfactory for a particular sample, then chromatograph parameters may be altered provided that the precision and reproducibility of the analysis of the calibration standards are not impaired. If there is reason to believe that inter ferences are occurring from another compound with identical retention time, supplemental confirmation of the VCM peak must be performed by GC-Mass Spectrometry. The GC column used should be identical too, and operated under the con ditions specified in this method. 4. SAFETY Do not release vinyl chloride to the laboratory atmosphere during preparation of standards. Venting or purging with VCM/air mixtures must be held to a minimum and, when neces sary, the vapor must be routed to the outside air in an approved laboratory hood. Leave hood on at all times when VCM solutions are present. 5. APPARATUS 5.1 Sampling - Figure 1 refers to stack samples. Figure 2 refers to vapor space samples. 5.1.1 Equipment for Stack Samples 5.1.1.1 Probe - Stainless steel, Pyrex glass, or Teflon tubing according to stack temperature, each equipped with a glass wool plug to remove particulate matter. 5.1.1.2 Sampling Line - Teflon 6.4 mm outside diameter for con necting probe to pump, pump to drying tube, and drying tube to sample bag. 5.1.1.3 Aluminized Mylar Bags or Tedlar Bags - 2 liter capacity. 5.1.1.4 Needle Valves (2) for control of flow to sample bag and to activated carbon tube. 5.1.1.5 Charcoal Tube - filled with activated carbon to prevent admission of VCM to atmosphere during sampling operation. 5.1.1.6 Pitot Tube and Manometer - for determining stack flow rate. 5.1.1.7 Flow Meter (0.10 to 1.00 liter/min) for observing sample flow rate. COLOR!TE 016999 .* -3- 5.1.1.8 Pump (400 ml/min) with stainless metal bellow, for filling sample bags from a stack. 5*1.2 Equipment for Vapor Space Samples 5.1.2.1 Vapor samples shall be taken in dedicated sample cylinders or bombs of 150 milliliters minimum capacity. These shall be constructed of Type 304 or 316 stainless steel. The in let shall be fitted with a Nupro "J" series miniature forged body valve or equivalent, and the outlet shall be fitted with a Whitey Co. ball valve No. SS-43M4-S4- The outlet of this valve consists of a V Swagelok fitting which, when equipped with a rubber septum, is used to remove the sample for analysis. 5.1.2.2 5.1.2.3 As required, sample cylinders shall be cleaned with tetrahydrofuran. The cylinder should be immersed in the solvent for a minimum of 24 hours, then rinsed with acetone and dried with air. This procedure shall be undertaken by trained laboratory personnel only. No attempt shall be made to clean inlet and outlet valves; these shall be discarded and replaced. 5.1.2.4 5.1.2.5 Storage of sample bombs within the main plant shall be prohibited. Instead, a storage cabinet or rack shall be provided in the quality control laboratory. Sample bombs shall be capped after cleaning to insure no contamination. Sample cylinder integrity shall be checked periodically by pressure and vacuum tests, and by vapor analysis using a portable leak detector. (Century organic vapor analyzer.) 5.1.3 Unused Samples 5.1.3.1 Unused portions of samples shall be returned to the recovery system. 5.2 Sample Recovery 5.2.1 Syringe - gas tight, Pressure-Lok No. 010035 or equivalent, 5 ml capacity. 5.3 Analysis 5.3.1 Gas Chromatograph - Perkin Elmer Model 3920, or equivalent, equipped with hydrogen flame ionization detector and col umn oven temperature programmer. COLOR!TE 017000  t -4- 5.3.2 5.3.3 5.3.4 5.3.5 5.3.6 5.3. 7 5.3.8 5.3.9 5.4 5.4.1 5.4.2 5.4.3 5.4.4 5.4.5 5.4.6 6. 6.1 6.1.1 Chromatographic Column - Stainless steel, 0.250 inches 10 feet, packed with 15% UCON LB-550X on Anakrom ABS, 60-70 mesh. A 0.25 inches x 5 feet column containing 20% Octoil Son Chromosorb P, 30-60 mesh, acid washed, can be used in place of the UCON column. x Potentiometric Recorder - 1.0 millivolt full scale response with approximately 30 in/hr chart speed. Injection Liners - glass or stainless steel. Integrator - Spectraphysics, Model 6300, or equivalent. Syringe, 10 Microliter - Precision sampling syringe, no. 120022, or equivalent. Filter Drier Assembly - Applied Science Laboratories, 3no. No. 14503, or equivalent. One unit required for each gas cylinder. Soap Film Flow Meter - Applied Science Laboratories, Inc., no. 13000, or equivalent. Regulators - for required gas cylinders. Calibration Volumetric Flasks (5) - 100 ml, glass stoppered Dewar Flask - capacity to hold a 100 ml volumetric flask. Pipettes - volumetric, 10 ml, 5 ml, 2 ml, 1 ml. Analytical Balance - capable of weighing to + 0.001 g. Syringe, 10 microliter - see section 5.3.6. Vials - SKC no. 226-02-100, development vials with teflon lined septum caps for storage of standard solutions. REAGENTS Analysis Hydrogen Gas - zero grade COLORITE 017001 I 0 -5- 6.1.2 Helium Gas - zero grade 6.1.3 Air - zero grade 6.1.4 Tetrahydrofuran (THF) - Baker analyzed reagent no. 3 3-9450, or equivalent. Five microliters of THF, when injected into the gas chromatograph operated as specified in Section 7.3, must not show any peak eluting at the retention time shown by the VCM in the standards or samples. 6.2 Calibration 6.2.1 Vinyl Chloride - approved sample bomb containing liquid monomer. Must have grounding cable. The commercial material assaying more than 99.9% is satisfactory. 7. PROCEDURES 7.1 Stack Sampling 7.1.1 Stack or Duct Sampling - Assemble the sample train as in Figure 1, GCF-3.0 making sure that all connections are tight. Perform a bag lead check as in section 7.4. 7.1.1.1 Sample Point - to be located at least two stack or duct diameters downstream and one half diameter upstream from any flow disturbance such as a bend, expansion, contraction or visible flame. For a rectangular cross section, an equivalent diameter is to be determined as follows: Equivalent Diameter - 2 x (length) x (width) length + width Place the end of the probe at the centroid of the cross section. 7.1.1.2 Sampling - Start the pump with the needle valve adjusted to provide a flow of 0.4 liter per minute through the flow meter, activated carbon tube and to the atmosphere. After approximately three times the volume of the sampling system has been allowed to flow through, open the valve to the sample bag and throttle the valve to the activated carbon tube. Control the flow to the sample container at 400 ml/min filling the sampling bag for a period of 5 minutes. Measure the flow rate within the stack by use of the pitot tube and manometer. When the sampling has been completed, close the valve to the sample bag and cut off the pump. Place the bag, properly identified, in an area where it is not exposed to direct sunlight. Repeat the sampling program by taking 5 samples evenly spaced over a one hour period. In calculating the average VCM content, weigh the value obtained on each sample in accordance with the stack flow rate measured during the time the sample was taken. COLORITE 017002 a 6- - 7.1.1.3 Pump leak checks - Before and after each use the pump must be checked for leaks by shutting off the inlet with the pump running. The rotameter should drop to zero if the pump is leak free. 7.1.2 Sample Storage - Sample bags must be kept out of sunlight. Analyze within an eight hour period after collection of sample. 7.2 Vapor Space Sampling 7.2.1 Sampling Technique 7.2.1.1 Inspect vessel to be sampled and all associated piping. Check that sample connections are properly fitted with valves and appropriate connections. For reactors, sample connections shall consist of a k or 3/8 inch O.D. thermocouple connector, or equal, attached to a base valve appropriate for the sample nozzle. Sample tubes of a length sufficient to reach 5" from the dished bottom, midway into the reactor and 5" below the dished head shall be fitted with a ball valve and half coupling or quick-disconnect. For tanks, pipes, etc. sample connections shall be fitted with ball valves and quick-disconnects. 7.2.1.2 Use premarked sample containers; label to include: DateTime_____________________________ VesselSample Location Batch/Lot No. Internal TemperaturePressure Operator Sample cylinders shall be constructed of Type 304 or 316 stainless steel and be fitted with appropriate valves and quick-disconnect fittings. 7.2.1.3 Where appropriate, cool to below 100F. 7.2.1.4 Complete VCM purge procedure (SOP) 3-5 psig nitrogen pressure should be locked on vessel. 7.2.1.5 Connect sample apparatus at sample tap. The inlet should be connected to the vessel; the outlet should be connected to an auxiliary vacuum supply, recovery header or directed COLORITE 017003  -7- to VCM emission control equipment. During this step, both inlet and outlet valves should be closed. Attach grounding cable to sample cylinder. 7.2.1.6 Open valves on sample cylinder. Open valve on vessel to be sampled. 7.2.1.7 Purge gas through sample cylinder for two minutes. Close sample cylinder valve; close inlet valve. Close sample nozzle valves. 7.2.1.8 Disconnect sample cylinder and place silicone rubber septum in Swagelok fitting on outlet valve. 7.2.1.9 Repeat steps 5-8 for sample duplication, as required. 7.3 ANALYSIS 7.3.1 Preparation of Gas Chromatograph - install the chromatographic column and condition overnight at 150C. Do not connect the exit end of the column to the detector while conditioning. 7.3.1.1 Flow Rate Adjustment - Adjust the flow rates as follows; a. Helium Carrier Gas - set cylinder regulator at 60 psig. Adjust chromatograph regulator for a flow rate of 30 - 40 ml/min as measured with a bubble flow meter. Use 60 ml/min for the Octol S column. b. Burner Air Supply - set cylinder regulator at 60 prig. c. Hydrogen Supply - set cylinder regulator at 30 psig. Optimize flow rates for b and c with the chromato graph regulators following instrument instruction manual. Record the flow rates obtained. 7.3.1.2 Temperature Adjustments - set temperatures as follow:. : a. Column oven - 55C b. Injector block -120C c. Detector - 200C 7.3.1.3 Ignition of flame ionization detector - follow instrument manual directions. 7.3.1.4 .Electrometer Range - use setting of 1 or 10, as required. COLORITE 017004  -8- 7.3.2 7.4 8. 8.1 8.1.1 Operating the Chromatograph - allow the baseline to stabilize and condition the column at the start of each day by injecting 5 microliters of the 150 ppm standard. Immediately after elution of the VCM peak, program the column oven at maximum rate to 150C to purge the solvent. Hold eight minutes at 150C and cool to 55C at maximum rate in preparation for the sample. When the baseline stabilizes insert the needle of the 5 ml. syringe into the bag, and slowly flush the syringe twice before taking the 5 ml. sample. For cylinder samples, open the globe valve and insert the syringe needle through the septum and the valve into the cylinder. Flush and sample as above. Record the integrated area and retention time of the VCM peak and the temperature of the sample. Repeat injection until two consecutive peaks do not differ in area by more than 5%. Use the average of these two for the calcu lation of VCM concentration in the gas sample. Bag Leak checks - sample bags must be checked for leaks prior to and after each use by connecting a water mano meter and pressurizing to 10 cm H2O. Allow to stand for 10 minutes. Any displacement shown by the manometer indi cates a leak. Bags which have been used previously should also be checked for residual VCM content before use. Zero grade nitrogen or other zero grade gases such as helium should be used to pressure the bag and the gas analyzed for VCM content. Bags checked in this manner must be flushed with VCM free gas until a value of less than 0.1 ppm VCM is obtained. Bag flushing should be vented to an approved exhaust hood or through an activated carbon trap. CALIBRATION Calibration is to be performed each eight-hour period when the instrument is used. Each day, prior to running samples, the column should be conditioned by running previous days 150 ppm standard. Preparation of Standards - standards containing VCM in the range of 15 to 150 ppm (wt/vol) are prepared in THF as described below. With the 5 ml gas sample specified in Section 7.3.2, these standards will correspond to approxi mately 6, 12 and 60 ppm of VCM in gas samples. Stock Solution - approximately 3% (wt/volume). All opera tions must be carried out in a well ventilated hood. Add about 75 ml of THF (see section 6.1.4) to a 100 ml volume tric flask, stopper and weigh to + 1 mg. Cool the THF by immersing the flask in a Dewar flask containing dry ice and acetone. Add approximately 3 grams of liquid monomer from the bottom valve of a vertically mounted sample bomb (fig.3). Make certain that the bomb is properly grounded. COLOR!TE 017005  * -9- Stopper the flask, invert it gently to mix the contents, and allow it to warm slowly to room temperature. Reweigh the flask to + 1 mg and calculate the weight of added VCM. Fill the flask to the mark with THF as quickly as possible and mix gently by repeatedly inverting the flask. 8.1.2 Stock Solution - approximately 0.15% (wt/volume). Accurately dilute 8.1.1 by pipetting 5 ml into a 100 ml volumetric flask partially filled with THF and diluting to the mark with THF. 8.1.3 Calibration Standards - prepare three calibration standards by accurately pipetting 1, 2 and 10 ml of solution 8.1.2 into 100 ml volumetric flasks partially filled with THF. Dilute to the mark and mix each flask thoroughly by repeated inversion. Using the original weight of VCM in 8.1.1, cal culate the concentration of each calibration standard. For reproducibility of standard preparation see Table I. 8.1.4 Storage of Standards - transfer the calibration standards to SKC development vials and store under refrigeration. For calibration, remove fresh vials from the refrigerator and allow them to warm to room temperature before use- Stan dards prepared in this manner have been found stable for periods of 3 to 4 weeks (Table ID . 8.1.5 Disposal of THF Solutions - in a well ventilated hood, trans fer VCM stock solutions and spent calibration standards to a beaker containing several grams of Ionol. Allow the con tents to evaporate to dryness. 8.2 Preparation of Calibration Curve - run the calibration stan dards in duplicate from 8.1.3 in exactly the same manner as the column conditioning, using 5 microliter injections. Plot the integrator area counts for each standard vs. the con centration of VCM in that standard. Draw a line of best fit through the points. 9. CALCULATIONS 9.1 Response Factor - calculate the response factor (FR) from the slope of the calibration curve in integrator area counts per microgram of VCM. 9.2 Residual Vinyl Chloride Content - calculate the vinyl chloride content of bag samples as follows: COLORXTE 017006 GCF-3.0 FIGURE 2 SCHEMATIC ASSEMBLIES FOR VCM VAFOR SPACE SAMPLING COLORITE 017007 -10- , . _ Integration area x 1000 ml x 22.41 x TUK (ppmj - Fr x 5 ml sample x 62.50 x 273K VCM (ppm) = Microliters/liter, or ppm Vol/Vol Where FR = Response factor in counts/microgram T K = Temperature, in degrees K, of gas sample at time of analysis. /jg COLOR!TE 017008 TAELE I REPRODUCIBILITY OF STANDARD PREPARATION ppm (v/t./vol.) Response, &s prepared area/ppm ppm (wt./vol.) Response, as prepared area/ppm 3.82 42.87 62.24 104.5 120.9 98.0 101.5 108.5 107-6 110.0 124.9 225.6 259-6 337-8 382.8 111.4 109.3 111.8 105-5 112.5 Average Response, area/ppm = 107-6 Average Deviation = 3-57 Standard Deviation = 4.71 TABLE II STABILITY OF STANDARD SOLUTIONS Age, Days 0 3 6 7 9 11 14 16 20 23 104,5 ppm Response 107.6 - 101.6 102.1 - 110.5 - - 105.4 107.4 107.2 120.9 p?ai Response 110.0 107.0 105.9 - 112.1 - - 109.0 94.4 - 62.6 ppm Response 103.5 108.3 97-5 - 107.1 - - 90.4 - 104.3 pp. Response 109.7 102.6 105*5 106.7 - 101.7 - - - COLORITE 017009 GCF-3.0 TABLE III COMPARISON OF VCM-AIR SAMPLING CONTAINERS Storage Time 0 hours 24 hours 48 hours 120 hours VCM Analysis (ppm) Tedlar Bag 100 liters Tedlar Bag 2 liters Stainl Steel Cy 17.2 18.3 17.7 18.9 18.6 17.8 19.1 18.6 17.8 19.0 18.8 18.0 All containers filled from cylinder containing 18.3 ppm of VCM in nitrogen. COLORITE 017010 GCF-3.0 FIGURE 1 SAMPLING TRAIN Metering Valve I To Atmosphere 4 NOTE: Following assembly all connections must be checked for leaks while sample is being pumped through the system to the atmosphere. COLORXTE 017011 GCF-3.0 m COLORITE 017012 FIGURE 2 SCHEMATIC ASSEMBLIES FOR VCM VAPOR SPACE SAMPLING GCF-3.0 Fig. 3 COLOR!TE 017013