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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 38 39 40 41 42 43 44 45 In the United States, the majority of ammonia is produced using a natural gas feedstock; however, one synthetic ammonia production plant located in Kansas is producing ammonia from petroleum coke feedstock. In some U.S. plants, some of the CO 2 produced by the process is captured and used to produce urea rather than being emitted to the atmosphere. There are approximately 13 companies operating 26 ammonia producing facilities in 17 states. More than 55 percent of domestic ammonia production capacity is concentrated in the states of Louisiana (29 percent), Oklahoma (20 percent), and Texas (6 percent) (USGS 2016). There are five principal process steps in synthetic ammonia production from natural gas feedstock. The primary reforming step converts methane (CH 4) to CO 2, carbon monoxide (CO), and H 2 in the presence of a catalyst. Only 30 to 40 percent of the CH 4 feedstock to the primary reformer is converted to CO and CO 2 in this step of the process. The secondary reforming step converts the remaining CH 4 feedstock to CO and CO 2. The CO in the process gas from the secondary reforming step (representing approximately 15 percent of the process gas) is converted to CO 2 in the presence of a catalyst, water, and air in the shift conversion step. Carbon dioxide is removed from the process gas by the shift conversion process, and the hydrogen gas is combined with the nitrogen (N 2) gas in the process gas during the ammonia synthesis step to produce ammonia. The CO 2 is included in a waste gas stream with other process impurities and is absorbed by a scrubber solution. In regenerating the scrubber solution, CO 2 is released from the solution. The conversion process for conventional steam reforming of CH 4, including the primary and secondary reforming and the shift conversion processes, is approximately as follows: 0.88CH 4 + 1.26Air + 1.24H 2 O → 0.88CO 2 + N 2 + 3H 2 N 2 + 3H 2 → 2NH 3 To produce synthetic ammonia from petroleum coke, the petroleum coke is gasified and converted to CO 2 and H 2. These gases are separated, and the H 2 is used as a feedstock to the ammonia production process, where it is reacted with N 2 to form ammonia. Not all of the CO 2 produced during the production of ammonia is emitted directly to the atmosphere. Some of the ammonia and some of the CO 2 produced by the synthetic ammonia process are used as raw materials in the production of urea [CO(NH 2) 2], which has a variety of agricultural and industrial applications. The chemical reaction that produces urea is: 2NH 3 + CO 2 → NH 2 COONH 4 → CO(NH 2 ) 2 + H 2 O Only the CO 2 emitted directly to the atmosphere from the synthetic ammonia production process is accounted for in determining emissions from ammonia production. The CO 2 that is captured during the ammonia production process and used to produce urea does not contribute to the CO 2 emission estimates for ammonia production presented in this section. Instead, CO 2 emissions resulting from the consumption of urea are attributed to the urea consumption or urea application source category (under the assumption that the carbon stored in the urea during its manufacture is released into the environment during its consumption or application). Emissions of CO 2 resulting from agricultural applications of urea are accounted for in the Agriculture chapter. Previously, these emission estimates from the agricultural application of urea were accounted for in the Cropland Remaining Cropland section of the Land Use, Land Use Change, and Forestry chapter. Emissions of CO 2 resulting from non-agricultural applications of urea (e.g., use as a feedstock in chemical production processes) are accounted for in the Urea Consumption for Non- Agricultural Purposes section of this chapter. Total emissions of CO 2 from ammonia production in 2015 were 10.8 MMT CO 2 Eq. (10,799 kt), and are summarized in Table 4-18 and Table 4-19. Ammonia production relies on natural gas as both a feedstock and a fuel, and as such, market fluctuations and volatility in natural gas prices affect the production of ammonia. Since 1990, emissions from ammonia production have decreased by 17 percent. Emissions in 2015 have increased by approximately 12 percent from the 2014 levels. Table 4-18: CO2 Emissions from Ammonia Production (MMT CO2 Eq.) Source 1990 2005 2011 2012 2013 2014 2015 Ammonia Production 13.0 9.2 9.3 9.4 10.0 9.6 10.8 Total 13.0 9.2 9.3 9.4 10.0 9.6 10.8 4-22 DRAFT Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990–2015

1 Table 4-19: CO2 Emissions from Ammonia Production (kt) Source 1990 2005 2011 2012 2013 2014 2015 Ammonia Production 13,047 9,196 9,292 9,377 9,962 9,619 10,799 Total 13,047 9,196 9,292 9,377 9,962 9.619 10,799 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 39 40 41 42 43 44 Methodology Carbon dioxide emissions from production of synthetic ammonia from natural gas feedstock is based on the 2006 IPCC Guidelines (IPCC 2006) Tier 1 and 2 method. A country-specific emission factor is developed and applied to national ammonia production to estimate emissions. The method uses a CO 2 emission factor published by the European Fertilizer Manufacturers Association (EFMA) that is based on natural gas-based ammonia production technologies that are similar to those employed in the United States. This CO 2 emission factor of 1.2 metric tons CO 2/metric ton NH 3 (EFMA 2000a) is applied to the percent of total annual domestic ammonia production from natural gas feedstock. Emissions of CO 2 from ammonia production are then adjusted to account for the use of some of the CO 2 produced from ammonia production as a raw material in the production of urea. The CO 2 emissions reported for ammonia production are reduced by a factor of 0.733 multiplied by total annual domestic urea production. This corresponds to a stoichiometric CO 2/urea factor of 44/60, assuming complete conversion of ammonia (NH 3) and CO 2 to urea (IPCC 2006; EFMA 2000b). All synthetic ammonia production and subsequent urea production are assumed to be from the same process— conventional catalytic reforming of natural gas feedstock, with the exception of ammonia production from petroleum coke feedstock at one plant located in Kansas. Annual ammonia and urea production are shown in Table 4-20. The CO 2 emission factor for production of ammonia from petroleum coke is based on plant-specific data, wherein all carbon contained in the petroleum coke feedstock that is not used for urea production is assumed to be emitted to the atmosphere as CO 2 (Bark 2004). Ammonia and urea are assumed to be manufactured in the same manufacturing complex, as both the raw materials needed for urea production are produced by the ammonia production process. The CO 2 emission factor of 3.57 metric tons CO 2/metric ton NH 3 for the petroleum coke feedstock process (Bark 2004) is applied to the percent of total annual domestic ammonia production from petroleum coke feedstock. The emission factor of 1.2 metric ton CO 2/metric ton NH 3 for production of ammonia from natural gas feedstock was taken from the EFMA Best Available Techniques publication, Production of Ammonia (EFMA 2000a). The EFMA reported an emission factor range of 1.15 to 1.30 metric ton CO 2/metric ton NH 3, with 1.2 metric ton CO 2/metric ton NH 3 as a typical value (EFMA 2000a). Technologies (e.g., catalytic reforming process, etc.) associated with this factor are found to closely resemble those employed in the United States for use of natural gas as a feedstock. The EFMA reference also indicates that more than 99 percent of the CH 4 feedstock to the catalytic reforming process is ultimately converted to CO 2. As noted earlier, emissions from fuels consumed for energy purposes during the production of ammonia are accounted for in the Energy chapter. The total ammonia production data for 2011 through 2015 were obtained from American Chemistry Council (2016). For years before 2011, ammonia production data (see Table 4-20) were obtained from Coffeyville Resources (Coffeyville 2005, 2006, 2007a, 2007b, 2009, 2010, 2011, and 2012) and the Census Bureau of the U.S. Department of Commerce (U.S. Census Bureau 1991 through 1994, 1998 through 2011) as reported in Current Industrial Reports Fertilizer Materials and Related Products annual and quarterly reports. Urea-ammonia nitrate production from petroleum coke for years through 2011 was obtained from Coffeyville Resources (Coffeyville 2005, 2006, 2007a, 2007b, 2009, 2010, 2011, and 2012), and from CVR Energy, Inc. Annual Report (CVR 2012 ,2014, 2015, and 2016) for 2012, 2013, 2014, and 2015. Urea production data for 1990 through 2008 were obtained from the Minerals Yearbook: Nitrogen (USGS 1994 through 2009). Urea production data for 2009 through 2010 were obtained from the U.S. Census Bureau (U.S. Census Bureau 2010 and 2011). The U.S. Census Bureau ceased collection of urea production statistics, and urea production data for 2011, 2012, 2013 and 2014 were obtained from the Minerals Yearbook: Nitrogen (USGS 2015, 2016). USGS urea production data for 2015 was not yet published and so 2014 data were used as a proxy for 2014. Industrial Processes and Product Use 4-23

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    Cement Production 33.3 45.9 32.0 35

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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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    New Mexico 70,608 52,250 12.0 0.263

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    C Storage Factor, Proportion of Ini

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    1 Table 7-2: Emissions from Waste (

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    2013 321 10,536 2014 323 10,613 201

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    1 2 3 4 5 6 7 8 9 10 EF i = emissio

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    a Miscellaneous includes TSDFs (Tre

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    Enteric Fermentation NC NC + NC + (

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