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DRAFT Inventory of U.S Greenhouse Gas Emissions and Sinks

2017_complete_report

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 4.8 Adipic Acid Production (IPCC Source Category 2B3) Adipic acid is produced through a two-stage process during which nitrous oxide (N 2O) is generated in the second stage. Emissions from fuels consumed for energy purposes during the production of adipic acid are accounted for in the Energy chapter. The first stage of manufacturing usually involves the oxidation of cyclohexane to form a cyclohexanone/ cyclohexanol mixture. The second stage involves oxidizing this mixture with nitric acid to produce adipic acid. Nitrous oxide is generated as a byproduct of the nitric acid oxidation stage and is emitted in the waste gas stream (Thiemens and Trogler 1991). The second stage is represented by the following chemical reaction: (CH 2 ) 5 CO(cyclohexanone) + (CH 2 ) 5 CHOH(cyclohexanol) + wHNO 3 → HOOC(CH 2 ) 4 COOH(adipic acid) + xN 2 O + yH 2 O Process emissions from the production of adipic acid vary with the types of technologies and level of emission controls employed by a facility. In 1990, two major adipic acid-producing plants had N 2O abatement technologies in place and, as of 1998, three major adipic acid production facilities had control systems in place (Reimer et al. 1999). One small plant, which last operated in April 2006 and represented approximately two percent of production, did not control for N 2O (VA DEQ 2009; ICIS 2007; VA DEQ 2006). In 2014, catalytic reduction, non-selective catalytic reduction (NSCR) and thermal reduction abatement technologies were applied as N 2O abatement measures at adipic acid facilities (EPA 2016). Worldwide, only a few adipic acid plants exist. The United States, Europe, and China are the major producers. In 2015, the United States had two companies with a total of three adipic acid production facilities (two in Texas and one in Florida), all of which were operational (EPA 2016). The United States accounts for the largest share of global adipic acid production capacity (30 percent), followed by the European Union (29 percent) and China (22 percent) (SEI 2010). Adipic acid is a white crystalline solid used in the manufacture of synthetic fibers, plastics, coatings, urethane foams, elastomers, and synthetic lubricants. Commercially, it is the most important of the aliphatic dicarboxylic acids, which are used to manufacture polyesters. Eighty-four percent of all adipic acid produced in the United States is used in the production of nylon 6,6; 9 percent is used in the production of polyester polyols; 4 percent is used in the production of plasticizers; and the remaining 4 percent is accounted for by other uses, including unsaturated polyester resins and food applications (ICIS 2007). Food grade adipic acid is used to provide some foods with a “tangy” flavor (Thiemens and Trogler 1991). Nitrous oxide emissions from adipic acid production were estimated to be 4.3 MMT CO 2 Eq. (14 kt N 2O) in 2015 (see Table 4-29). National adipic acid production has increased by approximately 40 percent over the period of 1990 through 2015, to approximately 1,055,000 metric tons (ACC 2016). Over the period 1990 through 2015, emissions have been reduced by 72 percent due to both the widespread installation of pollution control measures in the late 1990s and plant idling in the late 2000s. In April 2006, the smallest of the four facilities ceased production of adipic acid (VA DEQ 2009); furthermore, one of the major adipic acid production facilities was not operational in 2009 or 2010 (Desai 2010). All three remaining facilities were in operation in 2015. Very little information on annual trends in the activity data exist for adipic acid. Table 4-29: N2O Emissions from Adipic Acid Production (MMT CO2 Eq. and kt N2O) Year MMT CO2 Eq. kt N2O 1990 15.2 51 2005 7.1 24 2011 10.2 34 2012 5.5 19 2013 3.9 13 2014 5.4 18 4-32 DRAFT Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990–2015

2015 4.3 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 Methodology Emissions are estimated using both Tier 2 and Tier 3 methods consistent with the 2006 IPCC Guidelines. Due to confidential business information, plant names are not provided in this section. Therefore, the four adipic acidproducing facilities will be referred to as Plants 1 through 4. Plant 4 was closed in April 2006. Overall, as noted above, the three plants that are currently operating facilities use abatement equipment. Plants 1 and 2 employ catalytic destruction and Plant 3 employs thermal destruction. 2010 through 2015 All emission estimates for 2010 through 2015 were obtained through analysis of EPA’s GHGRP data (EPA 2014 through 2016), which is consistent with the 2006 IPCC Guidelines Tier 3 method. Facility-level greenhouse gas emissions data were obtained from the GHGRP for the years 2010 through 2015 (EPA 2014 through 2016) and aggregated to national N 2O emissions. Consistent with IPCC Tier 3 methods, all adipic acid production facilities are required to calculate emissions using a facility-specific emission factor developed through annual performance testing under typical operating conditions or by directly measuring N 2O emissions using monitoring equipment. 24 More information on the calculation, monitoring and QA/QC methods for process N 2O emissions applicable to adipic acid production facilities under Subpart E can be found in the electronic code of federal regulations. 25 EPA verifies annual facility-level GHGRP reports through a multi-step process (e.g. combination of electronic checks and manual reviews) to identify potential errors and ensure that data submitted to EPA are accurate, complete, and consistent. 26 1990 through 2009 For years prior to EPA’s GHGRP reporting, for both Plants 1 and 2, 1990 to 2009 emission estimates were obtained directly from the plant engineer and account for reductions due to control systems in place at these plants during the time series. These prior estimates are considered confidential business information and hence are not published (Desai 2010). These estimates were based on continuous process monitoring equipment installed at the two facilities. In 2009 and 2010, no adipic acid production occurred at Plant 1 per reporting to EPA’s GHGRP (EPA 2012; Desai 2011b). For the Plant 4, 1990 through 2009 N 2O emissions were estimated using the following Tier 2 equation from the 2006 IPCC Guidelines until shutdown of the plant in 2006: E aa = Q aa × EF aa × (1 − [DF × UF]) where, E aa = N 2O emissions from adipic acid production, metric tons Q aa = Quantity of adipic acid produced, metric tons EF aa = Emission factor, metric ton N 2O/metric ton adipic acid produced DF = N 2O destruction factor UF = Abatement system utility factor The adipic acid production is multiplied by an emission factor (i.e., N 2O emitted per unit of adipic acid produced), which has been estimated, based on experiments that the reaction stoichiometry for N 2O production in the preparation of adipic acid, to be approximately 0.3 metric tons of N 2O per metric ton of product (IPCC 2006). The “N 2O destruction factor” in the equation represents the percentage of N 2O emissions that are destroyed by the 24 Facilities must use standard methods, either EPA Method 320 or ASTM D6348-03 and must follow associated QA/QC procedures consistent during these performance test consistent with category-specific QC of direct emission measurements. 25 See . 26 See . Industrial Processes and Product Use 4-33

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    Total 1,862.5 2,441.6 2,197.3 2,059

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    Total Emissions 6,366.7 7,315.6 6,7

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    Coal b 1,653.7 1,596.3 1,809.1 -3%

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    Activity 1990 2005 2011 2012 2013 2

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    2013 321 10,536 2014 323 10,613 201

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    1 2 Table 7-16: Approach 2 Quantita

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    a Miscellaneous includes TSDFs (Tre

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    Enteric Fermentation NC NC + NC + (

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