Proposed Rule: Mandatory Reporting of Greenhouse Gas EmissionsDocumentation for October 2009 Site Visit to 3M Cordova, IllinoisRegarding Fluorinated Gas ProductionDate:2October 2009Staff Contact Information (Name, email, phone #):Deborah Ottinger, EPA, 343-9149,Ottinger.deborah@epa.gov; Karen Schaffner, RTI,ksschaffner@rti.org; Carrie Richardson, RTIName of Organization (Attach list of all attendees namesand emails if possible):Pat Thornton, Brian Mader, Dana Schnobrich, Tom Herzberg, Char Daehler, Holly Khasi, Kurt Werner, Mike Nash, Paul Narog, Ken Ramm, JeffMuffat, Mike Parent, Rob Haden, 3MSummary of Discussion(e.g., applicability, reporting requirements, etc.):The purpose of the site visit was to discuss emission estimation techniques and analytical methods available to measure fluorinated gas emissions.The 3M representatives noted the following:The facility has production areas for electrochemical fluorination cells (ECF) (called upstream processes) andfor internals (called downstreamprocesses). The fluorinated gas products are used fora variety of purposes. The facility has a thermal oxidizer that has been online since 2004.The facility has been conducting a GHG inventory since 2002 and follows the WRI/WBSCD Greenhouse Gas Protocol. The facility hasdeveloped site-specific emission factor based on emissiontesting. They estimate emissions based on EF and process activity data.To develop EFs for ECF processes, the facility measuredfluorinated compounds using EPA Method 320 and EPA Method TO15,along with EPAMethods 1 through 4 for flow rate, moisture, etc. and OTM 24to measure gas flow rates. The facility has online and portable FTIR; FTIR unitsrequire significant calibration and sophisticated analysts to operate properly. The ECF process has significantbyproduct generation and thefacility attempted to identify all fluorinated compounds present (some byproducts do not have listed GWPs). The ECF EFs were developed overapproximately 2 years for 12 processes, for all fluorinated GHG byproducts, requiring significant dollars and instrument time. EF were based onsteady state operations, although they also tested duringstartups. They assessed the variability in the process during EF development and ingeneral the facility tries to operate the ECF unit as longas possible without shutdown (and associated startup). The facility also conducted GC/MSsampling and analysis as check on the FTIR. Due to the high dynamic range (range of peak sizes) of the samples,an accuracy of 5 percent isdifficult to attain for all constituents; a more realistic target is 20 percent. The emissions profile is a constant and is a function of the processcurrent. The facility also conducted matrix spiking tovalidate the Method 320 measurements using EPA Method 301 (where a knownconcentration is added to gas stream and the FTIR must sample and analyze and provide a result that is within 30 percent of the known). Thefacility did an uncertainty analysis for the concentration measurement (that Method 301 provided), flow measurement (Method 1 through 4), andfor the process activity measurement for the current. These varied somewhat depending on the compound since some compounds are harder tomeasure. The facility also calculated the accuracy and precision for the method and the analytical equipment andalso determined the overallstandard deviation and relative errors.For downstream batch processes, the facility also developed process-specific EF using calculation methods. The downstream area producesisolated intermediates and final products and includesflexible batch processes. Batch process in general are not amenable to traditional sourcetesting and it is not feasible to require periodicstream analysis.Approaches or methodologyother than the mass-balance approachshould beincluded in the fluorinated gas rule. The facility currently develops an EF for every process, including every process configuration. The facilityuses basic emission calculation from the Pharmaceutical NESHAP, MACT98, EmissionMaster, ASPEN, and other commercially availablesoftware. Estimates are made for each emission episode. If these emission calculation equations are not appropriate, the facility uses alternativemethodologies such as data from bench-scale analysis, representative testing, and maximum flow rates and concentrations. For the majority of thebatch processes, chemical engineering calculations are used.Rather than require the same level of monitoring or compliance for all process vents,it would be better to include a tiered approach that accounts for the size of the emissions. For example, use ofa tiered approach similar to theMON (lb/yr tiered compliance) should be incorporated intothe fluorinated gas rule. The MON includes a tiered approach for both batch andcontinuous processes. In general, the facility does not useAP-42 EF for fluorinated gas processes. For continuous processes, EF are typicallybased on stack testing. Emissions from storage tanks (atmospheric) are estimated individually using vapor pressurecalculations. Emissions fromequipment leaks are estimated using SOCMI EF (EPA 1995 equipment leak protocol document). Monitoring of EL using EPAMethod 21 is nottypical for fluorinated gas processes. The facilityconducts pressure checks (on reconfiguration of flexible batchequipment), conducts mechanicalintegrity programs (their engineering specifications are tight for fluorinated gases), and they use welded connectionswhere possible to reduceequipment leak emissions. The typical FID monitoring units would not pick up or detect fluorinated organic compounds anyway.The facility noted that significant data are availablefrom the design phases of product development. The facility reviewed their three main phasesof new product development: (1) conceptual design and development(do significant emission evaluation and characterizing of emissions andcompounds), (2) pilot phase development and process optimization, and (3) manufacturing development (develop an EF). Phase3 includes“management of change”. These data should be allowed todetermine emissions from processes.The facility has an emissions data management systemthat estimates emissions based on the process-specific EFs, and the process activity data,sums the emissions over every fluorinated GHG compound and every vent, and creates the emissions reports and alerts. Each combination ofprocess code, burden center, equipment, vent, and compound would have a separate EF. Process weights for batch processes are recorded on thelast day of the batch process. The facility does track yields for the downstream processes, and they focus on changes in yield that are more than0.5 percent. The emissions inventory is developed by summing the emissions vents and determining the percent of batches and vents that werevented to the thermal oxidizer (for batch processes, operators manually track this, while for continuous processes, tracking is more automated).Multiple processes are vented to the thermal oxidizer including the ECF processes, batch processes, and the fractionation columns. Each ECF cellsystem is vented into the thermal oxidizer, and multiple vents/cells are sent simultaneously. The vent streams have high heating value. Thethermal oxidizer vents to a quench system to cool the stream prior to the caustic scrubber (where HF is removed). Mostof the vent lines areoperated at negative pressure to reduce emission lossesfrom ducts. The thermal oxidizer is down for approximately3 weeks every two years formaintenance; the process continues to operate during the thermal oxidizer maintenance downtime. Most continuousprocess vents are vented tothe thermal oxidizer, and the facility is working to captureand vent batch vents to the thermal oxidizer (with focus ontop-emitting processes). Ifthe thermal oxidizer is down for some reason and the processmust run, the vents are sent to scrubbers.The facility determined the DE of the thermal oxidizer usingFTIR and GC/MS at the inlet and outlet for each fluorinated GHG compound, andalso conducted EPA Methods 1 through 4 and OTM 24. The outlet concentrations were nondetectables for every fluorinatedGHG compoundexcept CF4. The facility also tried concentrating methods at theoutlet to see if they could measure compounds but could not.To estimate the DEwhere nondetects were found, the facility used the detection limit for the outlet concentration since the rule text didspecifically state that half ofthe detection limit could be used (they could not determine99.99 percent because they were using the detection limit values, although this likelyunderestimates the DE, and overestimates the emissions).The facility provided specific comments on the mass approachin the original proposed rule. The facility tried to apply the mass balance approachto their largest process onsite, using a simplified byproduct profile (the analysis would be more complicated/worsewith all byproducts), and usingEPA recommended errors. They attempted to estimate the error of analysis and to estimate the propagated error.3M provided severalobservations on the mass balance approach: does not account for accumulation of intermediates, byproducts, and products;does not account formultiple products from 1 intermediate; does not account for multi-step synthesis with long batch times; there is a common element problem whenmultiple raw materials containing the same element are used (i.e., 2 raw materials with F); problem with reactions that have multiple consumptionpaths for a raw material; assumes a short time constant for the process, no significant inventory ; and has a large analytical burden (especially forbatch processes).The analytical burden of the mass balance approach is significant as it requires frequent, detailed analysis ofstreams sent to the destruction device.The rule should allow facilities to balance the economic impact with the accuracy needed and not dictate the frequencyand precision required ofthe analysis. The daily sampling and analysis does not account for EHS consideration, i.e., hazards to operators. The facility noted that multipleanalytical methods will be required to meet the accuracyand to speciated the compounds. No single method will workfor 3M, where there aremulti-phase streams and a large number of components in streams. With NMR analysis, the facility gets theresults in a week or in a month (thisanalytical method could be done on an irregular basis as acheck on the compounds and concentrations). The mass balance will require multipleGC, LCP, IC, and LC, and NMR to analyze all the streams at their facility; the approach would cost the facility $50 million in methoddevelopment and $50 to 70 million in capital to purchase analytical equipment. The approach unfortunately treats all streams as if it was a finalproduct. While the flow measurement could be conducted on adaily basis, requiring daily compositions for all streams is extremely burdensome,as there are many daily samples to calculate.[Additional information is contained in the Confidential Addendum to the site visit containing additional notes.]Written Comments Provided?Did they also submit to Docket?NoDate sent to EPA-CCDNone

# EPA Docket No. EPA-HQ-OAR-2009-0927

The following information is located in the confidential ity files of the Director, Climate

Change Division, U. S. Environmental Protection Agency, Wa shington DC. This information is

confidential pending final determination by the Administrator and is not available for public

inspection.

Site Visit Notes from 3M Cordova IL, D. Ottinger, U.S . EPA, and K. Schaffner and C.

Richardson, RTI International. Dated October 2, 2009.

The notes contain additional information about the 3M fluorinated gas production

processes and the facility’s experience with emission estimation for fluorinated GHG. The

confidential material is comprised of 14 pages of notes.