To: Alexis McKittrick, Mausami Desai

From: Natalie Tang Date: 1/29/2015 RE: Strong Nitric Acid Facilities in the U.S

Summary El Dorado Chemical Company produces both weak (53% -63% concentration) and concentrated (strong) nitric acid (98% or greater concentrations). This facility does not use the Uhde process to produce concentrated nitric acid. Instead, it uses a chemic al dehydrating method using the NACSAC® process. This method is not known to produce additional N 2 O emissions on top of the production of the weak nitric acid feedstock. Weak nitric acid production is covered by the GHGRP, thus associated emissions from strong nitric acid production at El Dorado Che mical Company should already be included under Subpart V of the GHGRP.

There is currently one other known strong nitric ac id producer also using the NACSAC® process in the United States with the possibility of two other str ong nitric acid plants at existing facilities becom ing operational as early as the end of 2015. The latte r two plants are being designed and built by ThyssenKrupp Uhde and therefore will use the Uhde p rocess for nitric acid production. All three of the se facilities currently report to GHGRP.

Background Weak nitric acid production is defined as having a 30% to 70% strength in a solution as defined by the Greenhouse Gas Reporting Program (GHGRP). 1 Based on the 2010 Best Available Control Technolo gy (BACT) paper published by EPA, it is produced by a three-step high-temperature catalytic ammonia oxidation process:

4 NH 3 + 5 O 2  4 NO + 6 H 2 O (Reaction 1)

2 NO + O 2  2 NO 2 (Reaction 2)

3 NO 2 + H 2 O  2 HNO 3 + NO (Reaction 3)

Strong nitric acid is defined as nitric acid of 95% to 99% concentration. It can be produced in two wa ys: 2

1) Uhde process (direct strong process or DSN), produc ed directly from ammonia 2) Dehydrating, bleaching, condensing, and absorption of weak nitric acid

According to the 2010 BACT paper, El Dorado Chemica l Company is the only strong nitric acid plant in the United States and uses the strong direct proces s and there are no known US plants utilizing the second method. 3

El Dorado Chemical Company LSB industries, the parent company of El Dorado Che mical Company, defines their nitric acid commercial blends as “aqueous solution up to 89%” and also off er concentrated nitric acid, described as “aqueous solution up to 99% concentration.” 4 However, El Dorado Chemical Company suffered majo r damage to their DSN 98% concentrated nitric acid plant during an explosion on May 15, 2012. It was determined that repairs to this plant were not feasible and th at that a new plant would be required. 5According to El Dorado Chemical Company’s Arkansas Draft Air Permit, the company uses a Nitric Acid

Concentration and Sulfuric Acid Concentration (NACS AC) process that “concentrates weak nitric acid (56%-65% strength) to strong nitric acid (greater t han 98% strength) by extracting water from the weak nitric acid with sulfuric acid. 6 Based on this description and on NACSAC process f low diagram from the manufacturer 7 , El Dorado Chemical Company no longer uses the Uhd e process and instead uses a chemical dehydrating method to produce concentrated nitric acid.

The secondary production of high strength acid from weak is not known to result in additional N2O
emissions 8 . Thus, any emissions during production of strong nitric acid occur in the production of the weak nitric acid feedstock, which is covered by Sub part V of the GHGRP.

Their permit also confirms that they also produce n itric acid at concentrations of 56%-65%.

Uncertainties

• Only a draft of the Air Permit was available online . Further research indicates that the permit was awarded in 2013 after which construction on the expansion could commence. 9 From the draft air permit an expansion is only mentioned for a second D.M. Weatherly Nitric Acid Plant, however, conflicting information is found in news s ources regarding components of the expansion. 10 It is unclear if the NACSAC® is currently operati ng or is still being constructed.

• El Dorado Chemical Company’s permit suggests that t hey only produce weak nitric acid at 56% to 65% concentrations and strong nitric acid at 98% or above concentrations. However, their company website advertises that they are able to pr oduce commercial nitric acid blends as “aqueous solution up to 89%” and it is unclear how they are achieving nitric acid concentrations greater than 65% but less than 98% and emissions fr om production of these concentrations may not be reported to GHGRP.

Other Strong Nitric Acid Plants in the U.S. Another GHGRP reporting facility, Radford Army Ammu nition Plant (GHGRP ID: 1001818) also uses the NACSAC method to produce strong nitric acid. 11 This plant has been in operation from 2010. Emis sions from strong nitric acid production should already b e reported to the GHGRP.

ThyseenKrupp Uhde is the manufacturer of the equipm ent that uses the Uhde process to produce nitric acid and offers four types of equipment 12 :

Process Product
Uhde medium

- pressure process Produces one type of nitric acid with a max. concen tration of 65% or two types of acid with different concentr ations, e.g. 60% nitric acid and 65% nitric acid Uhde high

- pressure process Produces one type of nitric acid up to 67% o r two or more acids with different concentrations
Uhde dual

- pressure process Nitric acid concentrations of more than 68% can be achieved with two or more product streams of differ ent concentrations. “external streams of weak nitric a cid can be processed if required” Uhde azeotropic nitric acid process (extended dual pressure process) “Nitric Acid with elevated concentrations of 68%” N o weak acid co-productionThyssenKrupp Uhde has been selected by CF Industrie s to provide engineering and supply services to

their Donaldsonville (GHGRP ID: 1002301) and Port N eal (GHGRP ID: 1006005) fertilizer producing facilities. The new plants are scheduled to come o n stream in 2016. 13 14 It is not clear what concentration of nitric acid that these plants will be producing using the Uhde process.

Limitations of the Definition of Weak Nitric Acid a nd Strong Nitric Acid Commercial use nitric acid usually has a strength o f 53%- 68%, although can have concentrations up to 99%. During this research, nitric acid was most co mmonly available in concentrations of 68%, 72%, and 98%. Concentrations of 98% and higher appear to pr oduced using chemical dehydration of weak nitric acid, however, it is unclear how concentrations bet ween 68% and 97% are produced. More research should be considered if concentrations above 68% an d between 97% are being produced in the United States or, on the other hand, available for distrib ution only. As mentioned in the background section of this document, the GHGRP defines weak nitric acid a s having concentrations between 30% - 70% and OAQPS defines strong nitric acid as having a concen tration of 95% - 99%. Current definitions of weak and strong nitric acid do not cover all the concent rations that are produced.

1 Office of Air, U.S. Environmental Protection Agenc y. “40 CFR Part 98: Mandatory Reporting of Greenhou se Gases,” §98.220. http://www.ecfr.gov/cgi-bin/text-idx?tpl=/ecfrbrows e/Title40/40cfr98_main_02.tpl January 28,
2015.

2 Office of Air Quality Planning and Standards (OAQP S), U.S. Environmental Agency. “Available and Emerg ing Technologies for Reducing Greenhouse Gas Emissions from the Nitric Acid Production Industry,” U.S. Environmental Protection Agency, December 2010, p.7

. http://www.epa.gov/nsr/ghgdocs/nitricacid.pdf January 28, 2015.

3 OAQPS, p.6-7.

4 LSB Industries.” What Our Products Are Used For,”2 012, LSB Industries. http://www.lsbindustries.com/chemical?phpMyAdmin=bd 47d61ca5ff3d7349b86f5ab8f66958 January 28, 2015.

5 Magnolia Reporter, “El Dorado Chemical will build new nitric acid plant, replacing facility lost to e xplosion,” July 12, 2012. http://www.magnoliareporter.com/news_and_business/l ocal_business/article_034649e2-cbf4-11e1- 913f-001a4bcf887a.html February 3, 2015.

6 Arkansas Department of Environmental Quality, Draf t Operating Air Permit. Permit No. 0573-AOP-R16, Va lid between November 24 2010 and November 23, 2015. http://www.adeq.state.ar.us/ftproot/Pub/WebDatabase s/PermitsOnline/AirDrafts/0573-AOP-R16.pdf January 26,
2015.

7 Plinke, “Nitric Acid,” brochure, http://www.plinke.de/fileadmin/user_upload/pdf/Flye r/PLINKE_HNO3_08- 2012.pdf February 2, 2015.

8 OAQPS,p. 7.

9 Magnolia Reporter, “LSB Industries gets air qualit y permit for El Dorado construction,” November 22, 2013. http://www.magnoliareporter.com/news_and_business/l ocal_business/article_d2c20e5a-533d-11e3-ae0f0019bb2963f4.html February 2, 2015.

10 Magnolia Reporter, “LSB Industries will build new $120 million nitric acid plant in El Dorado,” Decem ber 2, 2102. http://www.magnoliareporter.com/news_and_business/l ocal_business/article_433f8472-3e6e-11e2-9e1a001a4bcf887a.html February 3, 2015.

11 Case, Joy, “Radford AAP celebrates new nitric-sulfu ric acid facility” U.S. Army, October 12, 2010. http://www.army.mil/article/46470/Radford_AAP_celeb rates_new_nitric_sulfuric_acid_facility/ February 3, 2015.

12 ThyssenKrupp Uhde, “Nitric Acid,” brochure. http://www.thyssenkrupp-industrialsolutions.com/fileadmin/documents/brochures/uhde_br ochures_pdf_en_4.pdf January 26, 2015.

13 CHEManager, “ThyssenKrupp Uhde Wins Contract for F ertilizer Plants in USA, November 12, 2012. http://www.chemanager-online.com/en/news-opinions/h eadlines/thyssenkrupp-uhde-wins-contract-fertilizer

plants-usa February 3, 2015.14 ThyssenKrupp Uhde, “ThyssenKrupp receives mega-ord er for fertilizer plants in the US exceeding 1 bill ion

euros,” press release, November 2, 2012. http://www.thyssenkrupp.com/en/presse/art_detail.ht ml&eid=TKBase_1351847416160_1211657050 February 3,
2015.

All from N 2 O emissions nitric acid production are associated w ith weak nitric acid, which is sold commercially and used as feedstock for concentrated nitric acid.