Proposed Rule: Mandatory Reporting of Greenhouse Gas Emissions 

Documentation for October 2009 Site Visit to 3M Cordova, Illinois Regarding Fluorinated Gas PDate:

2 October 2009

Staff Contact Information (Name, email, phone #): Deborah Ottinger, EPA, 343-9149, Ottinger.deborah@epa.gov; Karen Schaffner, RTI, ksschaffner@rti.org; Carrie Richard

Name of Organization (Attach list of all attendees names and emails if possible):

Pat Thornton, Brian Mader, Dana Schnobrich, Tom Herzberg, Char Daehler, Holly Khasi, Kurt Werner, Mike Nash, Paul NMuffat, Mike Parent, Rob Haden, 3M 

Summary 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 flu

The 3M representatives noted the following: The facility has production areas for electrochemical fluorination cells (ECF) (called upstream processes) and for internals processes). The fluorinated gas products are used for a variety of purposes. The facility has a thermal oxidizer that has beeThe facility has been conducting a GHG inventory since 2002 and follows the WRI/WBSCD Greenhouse Gas Protocol. T

developed site-specific emission factor based on emission testing. They estimate emissions based on EF and process activi

To develop EFs for ECF processes, the facility measured fluorinated compounds using EPA Method 320 and EPA Method 

Methods 1 through 4 for flow rate, moisture, etc. and OTM 24 to measure gas flow rates. The facility has online and portabrequire significant calibration and sophisticated analysts to operate properly. The ECF process has significant byproduct gfacility attempted to identify all fluorinated compounds present (some byproducts do not have listed GWPs). The ECF EFapproximately 2 years for 12 processes, for all fluorinated GHG byproducts, requiring significant dollars and instrument timsteady state operations, although they also tested during startups. They assessed the variability in the process during EF degeneral the facility tries to operate the ECF unit as long as possible without shutdown (and associated startup). The facility sampling and analysis as check on the FTIR. Due to the high dynamic range (range of peak sizes) of the samples, an accurdifficult to attain for all constituents; a more realistic target is 20 percent. The emissions profile is a constant and is a functcurrent. The facility also conducted matrix spiking to validate the Method 320 measurements using EPA Method 301 (wheconcentration is added to gas stream and the FTIR must sample and analyze and provide a result that is within 30 percent ofacility did an uncertainty analysis for the concentration measurement (that Method 301 provided), flow measurement (Metfor the process activity measurement for the current. These varied somewhat depending on the compound since some commeasure. The facility also calculated the accuracy and precision for the method and the analytical equipment and also detestandard deviation and relative errors. For downstream batch processes, the facility also developed process-specific EF using calculation methods. The downstreaisolated intermediates and final products and includes flexible batch processes. Batch process in general are not amenable 
testing and it is not feasible to require periodic stream analysis. Approaches or methodology other than the mass-balance a

included in the fluorinated gas rule. The facility currently develops an EF for every process, including every process configuses basic emission calculation from the Pharmaceutical NESHAP, MACT98, EmissionMaster, ASPEN, and other comme

software. Estimates are made for each emission episode. If these emission calculation equations are not appropriate, the famethodologies such as data from bench-scale analysis, representative testing, and maximum flow rates and concentrations. batch processes, chemical engineering calculations are used. Rather than require the same level of monitoring or complian

it would be better to include a tiered approach that accounts for the size of the emissions. For example, use of a tiered apprMON (lb/yr tiered compliance) should be incorporated into the fluorinated gas rule. The MON includes a tiered approach 

continuous processes. In general, the facility does not use AP-42 EF for fluorinated gas processes. For continuous proces

based on stack testing. Emissions from storage tanks (atmospheric) are estimated individually using vapor pressure calculaequipment leaks are estimated using SOCMI EF (EPA 1995 equipment leak protocol document). Monitoring of EL using Etypical for fluorinated gas processes. The facility conducts pressure checks (on reconfiguration of flexible batch equipmen

integrity programs (their engineering specifications are tight for fluorinated gases), and they use welded connections where 

equipment leak emissions. The typical FID monitoring units would not pick up or detect fluorinated organic compounds anThe facility noted that significant data are available from the design phases of product development. The facility reviewed of new product development: (1) conceptual design and development (do significant emission evaluation and characterizincompounds), (2) pilot phase development and process optimization, and (3) manufacturing development (develop an EF). 

“management of change”. These data should be allowed to determine emissions from processes. The facility has an emissions data management system that estimates emissions based on the process-specific EFs, and the 

sums the emissions over every fluorinated GHG compound and every vent, and creates the emissions reports and alerts. Ea

process code, burden center, equipment, vent, and compound would have a separate EF. Process weights for batch processlast day of the batch process. The facility does track yields for the downstream processes, and they focus on changes in yie0.5 percent. The emissions inventory is developed by summing the emissions vents and determining the percent of batches vented to the thermal oxidizer (for batch processes, operators manually track this, while for continuous processes, tracking Multiple processes are vented to the thermal oxidizer including the ECF processes, batch processes, and the fractionation csystem is vented into the thermal oxidizer, and multiple vents/cells are sent simultaneously. The vent streams have high hethermal oxidizer vents to a quench system to cool the stream prior to the caustic scrubber (where HF is removed). Most of operated at negative pressure to reduce emission losses from ducts. The thermal oxidizer is down for approximately 3 weemaintenance; the process continues to operate during the thermal oxidizer maintenance downtime. Most continuous procesthe thermal oxidizer, and the facility is working to capture and vent batch vents to the thermal oxidizer (with focus on top-ethe thermal oxidizer is down for some reason and the process must run, the vents are sent to scrubbers. The facility determined the DE of the thermal oxidizer using FTIR and GC/MS at the inlet and outlet for each fluorinated G
also conducted EPA Methods 1 through 4 and OTM 24. The outlet concentrations were nondetectables for every fluorinate

except CF4. The facility also tried concentrating methods at the outlet to see if they could measure compounds but could nwhere nondetects were found, the facility used the detection limit for the outlet concentration since the rule text did specificthe detection limit could be used (they could not determine 99.99 percent because they were using the detection limit valueunderestimates the DE, and overestimates the emissions). The facility provided specific comments on the mass approach in the original proposed rule. The facility tried to apply the to their largest process onsite, using a simplified byproduct profile (the analysis would be more complicated/worse with all 

EPA recommended errors. They attempted to estimate the error of analysis and to estimate the propagated error. 3M proviobservations on the mass balance approach: does not account for accumulation of intermediates, byproducts, and products

multiple products from 1 intermediate; does not account for multi-step synthesis with long batch times; there is a common 

multiple raw materials containing the same element are used (i.e., 2 raw materials with F); problem with reactions that have paths for a raw material; assumes a short time constant for the process, no significant inventory ; and has a large analytical batch processes). The analytical burden of the mass balance approach is significant as it requires frequent, detailed analysis of streams sent to The rule should allow facilities to balance the economic impact with the accuracy needed and not dictate the frequency and the analysis. The daily sampling and analysis does not account for EHS consideration, i.e., hazards to operators. The facil

analytical methods will be required to meet the accuracy and to speciated the compounds. No single method will work for 

multi-phase streams and a large number of components in streams. With NMR analysis, the facility gets the results in a we

analytical method could be done on an irregular basis as a check on the compounds and concentrations). The mass balance 

GC, LCP, IC, and LC, and NMR to analyze all the streams at their facility; the approach would cost the facility $50 million development and $50 to 70 million in capital to purchase analytical equipment. The approach unfortunately treats all streamproduct. While the flow measurement could be conducted on a daily basis, requiring daily compositions for all streams is e

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?No Date sent to EPA- CCDNone 
EPA Docket No. EPA-HQ-OAR-2009-0927 

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

Change Division, U. S. Environmental Protection Agency, Washington 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.