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From: Haidar Alrawi <Haidar.Alrawi@tn.gov> To: Bill Neuffer/RTP/USEPA/US@EPA Cc: John Trimmer <John.Trimmer@tn.

gov> Date: 03/15/2012 02:42 PM Subject: US Nitrogen PSD Application

Mr. Nueffer: Attached, please find the PSD permit application (public version) of the U.S. Nitrogen facility (Midway, TN) in addition to the final determination review document. The PSD BACT analysis for the nitrous oxide (N2O) emissions from the Nitric Acid Plant is discussed starting on page 4-22 of the application. Also, Table 4-7, on page 4-26 lists the proposed control technologies that would be utilized for N2O emissions and the associated destruction efficiences. The BACT determination for the N2O emissions is also discussed on page 5 of the final determination document. The basis of the proposed control technologies (i.e., primary and tertiary) came from the attached October 2010 EPA OAR guidance document " Available and Emerging Technologies for Reducing Greenhouse Gas Emissions from the Nitric Acid Production Industry that you are familiar with. Please let me know if you have any questions, or need additional information. Regards, Haidar Haidar Al-Rawi, P.E., BCEE TN Air Pollution Control (615) 532-0578 (voice) (615) 532-0614 (fax) E-mail: Haidar.Alrawi@tn.gov

US NITROGEN, LLC PREVENTION OF SIGNIFICANT DETERIORATION CONSTRUCTION PERMIT APPLICATION


US NITROGEN, LLC 471 POTTERTOWN ROAD MIDWAY, TENNESSEE
EnSafe Project Number: 0888810409

Prepared for:

25800 Science Park Drive, Suite 300 Cleveland, Ohio 44122

Prepared by:

EnSafe Inc. 220 Athens Way, Suite 410 Nashville, Tennessee 37228 (615) 255-9300 (800) 588-7962 www.ensafe.com August 2011, Revision 1.0

Table of Contents 1.0 2.0 INTRODUCTION ........................................................................................................... 1-1 PROJECT DESCRIPTION ............................................................................................... 2-1 2.1 Site Description ................................................................................................. 2-1 2.2 Proposed Operations ......................................................................................... 2-1 2.2.1 Steam Generating Boiler ......................................................................... 2-1 2.2.2 Ammonia Plant ....................................................................................... 2-6 2.2.3 Nitric Acid Plant ...................................................................................... 2-8 2.2.4 ANSOL Plant......................................................................................... 2-10 2.2.5 Nitric Acid Storage Tank........................................................................ 2-11 2.2.6 ANSOL Storage Tank ............................................................................ 2-11 2.2.7 Cooling Tower ...................................................................................... 2-11 2.2.8 Firewater Pump .................................................................................... 2-11 2.2.9 Flare .................................................................................................... 2-12 2.3 Project Emissions ............................................................................................ 2-12 REGULATORY ANALYSIS ............................................................................................... 3-1 3.1 National Ambient Air Quality Standards............................................................... 3-1 3.2 PSD Requirements ............................................................................................. 3-2 3.2.1 General Requirements ............................................................................ 3-2 3.2.2 Control Technology Review ..................................................................... 3-4 3.2.3 Source Impact Analysis ........................................................................... 3-5 3.2.4 Air Quality Monitoring Requirements ........................................................ 3-6 3.2.5 Source Information/Good Engineering Practice Stack Height ..................... 3-7 3.2.6 Additional Impact Analysis ...................................................................... 3-8 3.3 Nonattainment Rules ......................................................................................... 3-8 3.4 Emission Standards ........................................................................................... 3-8 3.4.1 New Source Performance Standards 40 CFR 60 .................................... 3-8 3.4.2 National Emission Standards for Hazardous Air Pollutants (MACT) 40 CFR 63 .............................................................................................. 3-9 3.4.3 Tennessee Air Permitting Requirements ................................................. 3-10 3.5 Other Requirements ........................................................................................ 3-10 3.5.1 Title V Program .................................................................................... 3-10 3.5.2 Risk Management Program ................................................................... 3-10 3.5.3 General Duty Clause ............................................................................. 3-11 BEST AVAILABLE CONTROL TECHNOLOGY ANALYSIS .................................................... 4-1 4.1 Point Source Emissions ...................................................................................... 4-3 4.1.1 Ammonia Plant Trains 1 and 2 ............................................................ 4-5 4.1.2 Nitric Acid Plant ...................................................................................... 4-7 4.1.3 Steam-Generating Boiler ....................................................................... 4-11 4.1.4 Firewater Pump .................................................................................... 4-13 4.1.5 Flare .................................................................................................... 4-14 4.2 Greenhouse Gases (CO2e) ................................................................................ 4-15 4.2.1 Dilute GHG Emissions Resulting From Combustion .................................. 4-16 4.2.2 Concentrated CO2 Emissions from the Ammonia Plant CO2 Vents ............. 4-18 4.2.3 N2O Emissions from the Nitric Acid Plant ................................................ 4-22 AIR QUALITY ANALYSIS ............................................................................................... 5-1
i

3.0

4.0

5.0

6.0

ADDITIONAL IMPACT ANALYSIS ................................................................................... 6-1 6.1 Growth Analysis ................................................................................................ 6-1 6.2 Soils Analysis .................................................................................................... 6-1 6.3 Vegetation Impacts ........................................................................................... 6-2 Figures

Figure Figure Figure Figure

1 2 3 4

Site Location Map .............................................................................................. 2-2 Proposed Site Map (Topographic) ....................................................................... 2-3 Proposed Site Map............................................................................................. 2-4 Emission Point Locations .................................................................................... 2-5 Tables

Table Table Table Table Table Table Table Table Table Table Table Table Table

1-1 2-1 3-1 3-2 3-3 4-1 4-2 4-3 4-4 4-5 4-6 4-7 6-1

PSD Significance Thresholds Compared to Potential Emissions ............................. 1-2 Projected Annual Emissions.............................................................................. 2-13 NAAQS and PSD Increments and Significance Levels ........................................... 3-2 PSD Significant Emission Rates and Monitoring De Minimis Levels ........................ 3-3 Class I Areas within 300 km of Proposed US Nitrogen Site ................................... 3-6 US Nitrogen Potential Emissions of GHGs ............................................................ 4-3 US Nitrogen Emission Point Sources and Respective Potential Emissions ............... 4-3 Summary of Proposed BACT for Each US Nitrogen Emission Source ...................... 4-4 Financial Comparison of US Nitrogen Ammonia Plant NOX Reduction Options ........ 4-7 Financial Comparison of US Nitrogen Nitric Acid Plant NOX Reduction Options ..... 4-10 Financial Comparison of US Nitrogen Boiler NOX Reduction Options .................... 4-13 Financial Comparison of Nitric Acid Plant N2O Reduction Options ........................ 4-26 Injury Threshold Concentrations for NOX ............................................................. 6-3 Appendices

Appendix Appendix Appendix Appendix Appendix Appendix Appendix

A B C D E F G

Application Forms Emission Calculations Air Dispersion Modeling and Class II Visibility Analysis Correspondence with Federal Land Managers RBLC Search Summary Tables Austin Powder Cost of Capital BACT Financial Analysis Worksheets

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

1.0

INTRODUCTION

US Nitrogen, LLC, a wholly-owned subsidiary of Austin Powder Inc., proposes to construct and operate a facility to manufacture nitric acid, ammonia (NH3), and liquid ammonium nitrate solution (ANSOL). The facility will be located on approximately 400 acres at 471 Pottertown Road, Midway, Greene County, Tennessee, near the intersection of US Highway 11E (Andrew Johnson Highway) and I-81. The approximate Universal Transverse Mercator (UTM) coordinates of the facility are 319,733 meters east and 4,006,685 meters north (UTM Zone 17, NAD 83). The proposed project will result in an increase in air emissions in Greene County, Tennessee, which currently is designated as an attainment or unclassified area for all National Ambient Air Quality Standards (NAAQS). amounts. The federal and state Prevention of Significant Deterioration (PSD) rules require a review of new or modified sources that increase air emissions above certain threshold In addition, nitric acid production is included in the PSD rules as one of 28 source Because categories that have lower thresholds for requiring a PSD construction permit.

the threshold amounts will be exceeded by the proposed project, the project is subject to PSD review under the regulations governing PSD (40 Code of Federal Regulations [CFR] 52.21), and the proposed facility will be classified as a Title V major source of air pollution under 40 CFR 70.2. The proposed project is subject to PSD review for the following pollutants: Nitrogen Oxides (NOX) Greenhouse Gases (GHGs) Emissions of other pollutants are estimated to be below the thresholds triggering PSD review. Table 1-1 summarizes the emissions from the proposed project and identifies which pollutants are subject to PSD review. A more detailed description of project emissions and regulatory applicability is included in Section 3. Greene County is classified as an attainment or unclassified area for all criteria pollutants and is classified as a PSD Class II area. The PSD review has been performed according to the regulations applying to this area designation.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 1-1 PSD Significance Thresholds Compared to Potential Emissions Total Emissions Total Emissions PSD Significant from US Nitrogen Including Potential Emission Rate Sources (TPY) Commercial Facility Criteria Pollutant (TPY) (TPY) Greenhouse Gases (CO2e1) 75,000 197,598 112,188 Particulate Matter (PM) 25 22.63 23.22 PM10 15 10.65 11.11 PM2.5 10 8.15 8.61 Sulfur Dioxide (SO2) 40 0.50 0.50 Nitrogen Oxides (NOX) 40 76.43 76.43 Carbon Monoxide (CO) 100 90.36 87.40 VOCs 40 4.93 4.93 Lead 0.6 Fluorides 3 Sulfuric Acid Mist 7 Hydrogen Sulfide 10 Total Reduced Sulfur 10 Reduced Sulfur Compounds 10

PSD Review Required?

Yes
No No No No

Yes
No No No No No No No No

Note:
1. CO2e = Carbon dioxide equivalents

This application will provide information to support a construction permit approval based on the following demonstrations and analyses of the project: Neither PSD ambient air increments nor NAAQS will be violated. Emissions resulting from operation of the proposed source will not significantly impact any nonattainment area. Best Available Control Technology (BACT) will be applied to each emission unit that will have a significant emission. Economic growth, soils, and vegetation will not be subjected to signifcant adverse impact.

The remainder of the air permit application presents the demonstrations and analyses mentioned above. Section 2 contains a description of the proposed project operations while Section 3 contains an analysis of the applicable regulations. Section 6. Section 4 provides a BACT analysis, and Section 5 presents an analysis of the impact on air quality. The additional impact analysis is contained in The permit application forms, emissions calculations, BACT RACT/BACT/LAER
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Clearinghouse (RBLC) search results, air quality modeling protocol, outputs from air dispersion

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

modeling, meteorological data summaries, receptor set descriptions, pollutant impact plots, BACT financial analysis worksheets, correspondence with the Federal Land Managers, and documentation of Austin Powders cost of capital are included in the appendices. With this application, US Nitrogen provides a detailed demonstration of compliance with all federal and State of Tennessee requirements for air quality protection prior to construction of the proposed new production facility. A construction permit application has been completed and is provided in Appendix A. Therefore, US Nitrogen requests that a construction permit be granted under the PSD provisions of Tennessee Division of Air Pollution Control (TDAPC) Rule 1200-03-09-.01.

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2.0

PROJECT DESCRIPTION

US Nitrogen proposes to build and operate a nitric acid, NH3, and ANSOL production facility at this location for the purpose of vertical supply chain integration with other Austin Powder locations throughout the United States. US Nitrogens parent company, Austin Powder, operates similar facilities throughout the world, meeting recognized environmental, safety, and pollution control requirements. The ANSOL produced here will be combined offsite with other substances under certain conditions as an ingredient in explosives. However, explosives will not be manufactured at this location. 2.1 Site Description A site locality map (Figure 1) and a topographic map

The proposed US Nitrogen facility will be constructed on approximately 400-acre site near Midway, Greene County, Tennessee. (Figure 2) provide details of the location and property boundaries of the proposed site. A site plan with site boundaries (Figure 3) and an emissions point location map (Figure 4) are included. The northern end of the area is adjacent to Pottertown Road in the Pottertown community. The area extends to the west and south adjacent to the Southern Rail line and includes most of West Seven Springs Road. The site is adjacent to the DTR Tennessee facility, Forest Road, and US Highway 11E (Andrew Johnson Highway) at the northwest corner of the proposed site. 2.2 Proposed Operations

The proposed operations are based on standard best practices commonly found in facilities producing nitric acid, NH3, and ANSOL primarily using natural gas cracking and steam. Facility processes and equipment are described in the following sections. 2.2.1 Steam Generating Boiler US Nitrogen proposes to install a natural gas-fired boiler that will be used to provide the steam needed to operate the various processes and equipment at the facility. use only natural gas as fuel. The boiler will have a maximum heat input capacity of 130 Million British Thermal Units per hour (MMBtu/hr) and will

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

DWAY

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

Figure 4

Emission Point Locations


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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

2.2.2 Ammonia Plant The NH3 plant will consist of two trains, capable of producing a total of 200 tons of synthetic NH3 per day, or 68,000 tons per year. Synthetic ammonia refers to NH3 that has been synthesized from natural gas. The natural gas molecules are reduced to carbon and hydrogen. The hydrogen is then purified and reacted with nitrogen, which is obtained from the air, at a molar ratio of 3 to 1. The gas is then compressed and condensed to a liquid. The process of reducing the natural gas molecules to carbon and hydrogen is called the catalytic steam reforming method. this method: (1) (2) (3) (4) (5) (6) Natural gas desulfurization Catalytic steam reforming CO shift Carbon Dioxide (CO2) removal Methanation NH3 synthesis Six steps are required to produce synthetic NH3 using

The first, third, fourth, and fifth steps remove impurities such as sulfur, CO, CO2, and water from the feedstock, hydrogen, and synthesis gas streams. manufactured and nitrogen (air) is introduced. the synthetic gas. 2.2.2.1 Natural Gas Desulfurization In the second step, hydrogen is The sixth step produces anhydrous NH3 from

In this step of the NH3 synthesis process, sulfur contained in the natural gas feedstock is removed using zinc oxide. 2.2.2.2 After Catalytic Steam Reforming the natural gas feed is mixed automatically with steam in

desulfurization,

the Steam-Feed Preheater, and the mixture is sent to the primary reformer. The reformer uses indirect heating fired on natural gas. The process stream passes downward through the catalyst filled tubes in the reforming furnace, producing a gas containing hydrogen, CO, CO2, steam, and methane. The partially reformed gas then flows to the Secondary Reformer, where it is combined with preheated, compressed air in a specially designed mixer to form a final synthesis gas having a hydrogen-to-nitrogen ration of 3 to 1. This process step is an exothermic reaction that does not require an external source of heat. The gas leaving the secondary reformer is then quenched with
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

process condensate.

Below the combustion chamber is a catalyst bed in which the remaining

methane, approximately 70%, is converted to hydrogen and carbon oxides (CO and CO2). 2.2.2.3 Carbon Monoxide Shift

CO is formed as a byproduct in the catalytic steam reforming process as described above. Most of the CO and water contained in the hot synthesis gas stream are converted to CO2 and hydrogen in the CO Converter in the presence of a conversion catalyst. Unreacted steam is condensed and separated from the synthesis gas in the Knockout Drum. 2.2.2.4 Carbon Dioxide Removal There, the CO2 is removed from the gas by The MDEA solution is regenerated in

After the CO shift, the CO2 is removed from the process gas by cooling the gas and sending it through the CO2 Absorber, an absorption tower. absorption in methyl diethanolamine (MDEA) solution.

the Amine Regenerator and recirculated through the CO2 Absorber in a continuous cycle. Initially, the CO2 gas (approximately 91% pure) will be captured and vented to the atmosphere. At a later date, efforts will be made to capture this CO2 for commercial use at another facility. 2.2.2.5 Methanation

Upon leaving the CO2 absorber, the synthesis gas consists primarily of uncombined hydrogen and nitrogen with residual amounts of CO2 and CO. The final purification of the reformed gas takes place by reheating the gas and passing it through the Methanator. In the Methanator, the carbon oxides contained in the gas are catalytically converted to methane and water. The purified synthesis gas is cooled; the water vapor condensed and separated, and flows to the compressor Knockout Drum. 2.2.2.6 Ammonia Synthesis

In this final step, the hydrogen and nitrogen-rich synthesis gas is converted to NH3. The process is not 100% efficient, and some of the unconverted synthesis gas leaving this step is mixed with incoming raw synthesis gas and recycled back through the process. The plant contains one multi-service reciprocating Compressor. The Compressor has four services: NH3 synthesis gas, NH3 recycle gas, process air, and refrigeration NH3. The Compressor is of horizontal-opposed configuration and is driven by an electric motor coupled to the compressor shaft. Lubrication of the frame is provided by a frame driven oil pump. A water-cooled oil cooler and an oil filter are included in the frame lubricating system.
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After methanation, the synthesis gas is compressed and joined by the recycled synthesis gas and passed through the Gas Filter to remove entrained compressor oil and water. the unconverted synthesis gas and sent to the separator. Any NH3 in the synthesis gas, which is condensed at this point in the process, is separated from The gas from the filter then passes through the shell side of the Loop Heat Exchanger. The gas is cooled in the Loop Heat Exchanger and then flows through the Secondary Ammonia Condenser, where it is further cooled, thereby condensing a large portion of the NH3 present in the gas. Cooling takes place by evaporation of refrigerant NH3 in a closed-system. The NH3-synthesis gas mixture flows to the Secondary Ammonia Separator, where the liquid NH3 is separated before the gas passes through the tube side of the Loop Heat Exchanger. The unconverted synthesis gas flows to the Ammonia Converter, where the gas stream is preheated by a heat exchanger in the Converter and flows downward through the catalyst bed. The converter uses an iron oxide catalyst to react hydrogen and nitrogen to form NH3. NH3 in the gas leaving the Converter passes to the Primary Ammonia Condenser, where water cooling reduces the temperature of the gas stream and thereby condenses a portion of the product NH3. From the Primary Ammonia Condenser, the NH3-synthesis gas mixture flows to the Primary Ammonia Separator where the liquid NH3 is separated. The synthesis gas is returned as recycled gas to the Compressor, except for a small quantity which is purged to control the quantity of inert gases (methane and argon) in the system. Ammonia sent to the separator is flashed to remove impurities from the liquid. The NH3-rich flashed vapor then undergoes pressure reduction to be condensed in a chiller, where anhydrous NH3 flows to the Battery Limits and is stored as a liquid until it is used to produce nitric acid, ANSOL, and/or sold commercially. 2.2.3 Nitric Acid Plant The nitric acid plant will have the capacity to produce up to 500 tons per day of weak nitric acid. Weak nitric acid can have concentrations ranging from 30 to 70 percent nitric acid. To produce nitric acid, US Nitrogen will utilize a high-temperature catalytic oxidation process using the NH3 produced in the process described previously in Section 2.2.2. three steps: (1) (2) (3) NH3 oxidation, Nitric oxide oxidation, and Absorption.
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This process will consist of

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

2.2.3.1

Ammonia Oxidation

In this process, the NH3 is mixed with ambient air, heated, and then passed over a platinum catalyst, where the NH3 is oxidized to nitric acid. The raw materials required for production of nitric acid are atmospheric air and NH3. These raw materials are combined at elevated temperature and pressure and passed over a platinum-containing catalyst, where the NH3 reacts with oxygen in the air. The resultant process gas is passed through the heat exchanger train where the major portion of this reaction energy is recovered as heat. 2.2.3.2 Nitric Oxide Oxidation Under these conditions, the nitric oxide formed during the NH3 A portion of

The nitric oxide rich gas stream is first cooled in a waste heat recovery boiler and then further cooled in a cooler condenser. oxidation step is further oxidized to nitrogen dioxide and nitrogen tetroxide. power for the air compressor by driving a hot gas expander. 2.2.3.3 Absorption

the reaction energy recovered in the heat exchanger train is used to reheat the tail gas to provide

The final step sends the nitrogen dioxide and nitrogen tetroxide mixture from the condensation step to the bottom of an absorption tower, where it flows countercurrent to water introduced at the top of the tower. Nitric acid is formed by contact of the nitrogen dioxide and tetroxide with water and is removed at the bottom of the absorption tower. The bottom absorption tray produces acid at the product concentration, which then flows into the bleacher section. In the bleacher, the product acid contacts a counter-current flow of bleach air which strips the remaining dissolved NOX from the acid. The stream of clear, bleached acid is then allowed to flow under pressure to storage. The heat produced in the oxidation and absorption reactions is removed by cooling water passing through coils on the trays in the lower section of the column. Tail gas, now reduced in NOX content to approximately 1,000 parts per million (ppm) by volume, leaves the absorber and flows to the tail gas reheating system. Tail gas first enters the bleach air cooler before entering the shell side of the tail gas heater. The tail gas is preheated sufficiently to avoid process gas condensation in the tail gas heater and then enters the tail gas heater. The tail gas is heated to approximately 600F in the tail gas heater. It then flows to the expander gas heater where it is further heated to 1200F after being fed to the steam superheater. Tail gas from the hot gas expander then flows to the NOX emission control system.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

The majority of the compression power required for the plant is extracted from the heated tail gas in the hot gas expander. The tail gas is discharged from the expander, flows through the NOX emission control system and into the economizer to preheat boiler feedwater. The tail gas then exhausts to the atmosphere through the stack. 2.2.4 ANSOL Plant The ANSOL plant will have the capacity to produce a maximum of 420 tons of ANSOL per day, or 130,000 tons per year. ANSOL is produced by the neutralization of nitric acid with NH3. The resulting aqueous ammonium nitrate solution will be sent to various Austin Nitrogen facilities for further processing, or sold as a raw material to customers. ANSOL (84 % by weight) is produced in the neutralizer by the reaction between NH3 vapor and nitric acid. The NH3 required for the reaction is provided by vaporizing liquid NH3. Nitric acid is supplied from the battery limits to the neutralizer. a sparger system in the bottom of the neutralizer. The NH3 is mixed with the nitric acid by The NH3 flow to the neutralizer is flow

ratio-controlled to the nitric acid flow to obtain the proper reaction. A smaller amount of acid is added to the neutralizer based on the pH of the neutralizer mixture and is used for fine control. Product ANSOL overflows from the neutralizer to the ANSOL surge tank where it is then pumped to the storage tanks. The heat of reaction generated in the neutralizer boils off steam, which passes overhead into the ammonium nitrate scrubber along with a small amount of unreacted NH3. The steam is used to vaporize the NH3 feed. The function of the ammonium nitrate scrubber is to condense enough steam to control the ammonium nitrate concentration of the scrubber and consequently the neutralizer and to remove the unreacted NH3 in the rising gases. Dilute ammonium nitrate is externally cooled in the circulated ANSOL cooler, and upon recirculation to the scrubber packing, condenses water from the stream for concentration control and neutralizes the unreacted NH3 in the gas stream. A small amount of nitric acid is added to the ammonium nitrate scrubber to Dilute maintain the acid-rich conditions necessary for neutralization of the unreacted NH3. ammonium nitrate formed in the scrubber overflows back to the neutralizer. The overhead gases from the ammonium nitrate scrubber, which are now primarily water, are fed to the vent scrubber for removal of remaining traces of NH3 and entrained ammonium nitrate. The vent scrubber is circulated with process condensate that is externally cooled in the circulated condensate cooler. The cooled, circulated, process condensate condenses a portion of the water in
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

the overhead gases in the packed bed section. The amount of water condensed is controlled to provide the absorber feedwater required for the nitric acid plant. 2.2.5 Nitric Acid Storage Tank US Nitrogen will install one nitric acid storage tank capable of storing 1,667 tons of weak nitric acid (60%). The tank will have an estimated capacity of 500,000 gallons. The vents from the nitric acid tank will be piped to the NOX emission control system at the nitric acid plant under vacuum. Approximately every 90 days the NOX emission control system will be shut down for approximately 24 hours. During that time, the ANSOL production process will continue running, which will pull nitric acid from the tank, while no additional nitric acid is added. 2.2.6 ANSOL Storage Tank US Nitrogen will install one ANSOL storage tank capable of storing 2,956 tons, on an 84% basis. The tank will have an estimated capacity of 700,000 gallons. The ANSOL tank will be heated with steam to maintain a temperature at or above 170F. ANSOL will start to solidify or crystallize to ammonium nitrate at or below temperatures of 168F. 2.2.7 Cooling Tower Cooling water will be used in various places throughout the plant for process cooling needs. The cooling tower will utilize a wet, mechanical induced-draft design, incorporating two or three cells. As the cooling water is used in the process, it is heated. The warm cooling water is pumped to the cooling tower, where the heat is rejected to the atmosphere. The cooling water is pumped to the top of the cooling tower cell and flows over a series of louvers or baffles as gravity pulls it to the basin. As air is forced through the louvers by mechanical fans, a portion of the warm water evaporates, effectively cooling the remaining water supply. and mist. During this process, some minute amounts of water become entrained in the airflow and leave the cooling tower in the form of drift Since a cooling tower tends to concentrate dissolved solids (within set design parameters), this entrained water becomes a source of particulate matter (PM) emissions. The cooling tower will have three cells and serve the design heat duty with a recirculating cooling water flow rate of 45,000 gallons per minute. The drift rate will not exceed 0.0005%. 2.2.8 Firewater Pump US Nitrogen will install a diesel-powered emergency firewater pump to provide fire-fighting capability. The diesel engine, which will be rated at approximately 400 horsepower (hp), will be routinely tested, as required by Federal, state, and local fire codes.
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The engine will be

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

Tier II-compliant to meet required emissions standards under 40 CFR 60, Subpart IIII, for stationary compression ignition internal combustion engines. 2.2.9 Flare A flare stack will be installed primarily to mitigate CO emissions during NH3 unit startup and to combust vent gas during safety relief. Normal emissions from the flare will be no more than those associated with operation of the 5 MMBtu/hr flare pilots and purge gas. 2.3 Project Emissions Calculations

Table 2-1 below summarizes the projected annual emissions from this project. supporting projected annual emissions are contained in Appendix B.

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Table 2-1 Projected Annual Emissions (TPY) Source Description Cooling Tower Firewater Pump Boiler Flare Plant Road
1

PM 0.59 0.01 3.19 0.00 7.97 7.97 1.45 1.45 22.63

PM10 0.46 0.01 3.19 0.00 2.12 1.97 1.45 1.45 10.65

PM2.5 0.46 0.01 3.19 0.00 0.23 1.36 1.45 1.45 8.15

SO2 0.04 0.25 0.01 0.10 0.10 0.50

NOX 0.13 4.28 2.32 54.80 7.45 7.45 76.43

VOC 0.05 2.31 0.47 1.05 1.05 4.93

CO 0.11 17.14 2.71 30.66 4.54 30.66 4.54 90.36

CO2 24 50,061 2,848 22,380 45,394 22,380 45,394 188,481

CH4 0.001 0.944 0.053 0.422 0.422 1.842

N2O 0.000 0.094 0.006 29.100 0.042 0.042 29.284

CO2e 24 50,110 2,851 9,021 22,402 45,394 22,402 45,394 197,598

NH3 144.5 1.75 1.75 148

Nitric Acid Plant ANSOL Plant Ammonia Train 1 Flue Gas Ammonia Train 1 CO2 Vent Ammonia Train 2 Flue Gas Ammonia Train 2 CO2 Vent Total US Nitrogen Emissions:

Emissions from Potential Commercial Facility Non-Condensable Gas Vent Cooling Tower Total Project Emissions Including Potential Facility2: 0.59 23.22 0.46 11.11 0.46 8.61 0.50 76.43 4.93 6.12 87.40 5,305 102,998 3.440 5.282 29.284 5,378 112,188 148

Note:
1. 2.

3.

Emissions include truck traffic from proposed commercial facility, which would share the same entrance road. The US Nitrogen ammonia plant CO2 vents would be routed to the proposed commercial facility, therefore, Total Project Emissions = Total US Nitrogen Emissions Ammonia Train CO2 Vents + Emissions from Potential Commercial Facility. CO2e = Carbon dioxide equivalents

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3.0

REGULATORY ANALYSIS

The proposed US Nitrogen facility will be subject to both federal and State of Tennessee air quality regulations. These regulations impose permitting requirements and specific standards for expected air emissions. include: NAAQS established by the United States Environmental Protection Agency (EPA) for specific criteria pollutants (40 CFR 50) New Source Review to determine if the facility meets the requirements of the PSD regulations (40 CFR 52.21) New Source Performance Standards (NSPS) which impose emission standards on new facilities (40 CFR 60) Hazardous Air Pollutant (HAP) regulations for specific categories and subcategories of HAPs (40 CFR 63) Tennessee Air Pollution Control Regulations. The standards and regulations that apply to the proposed US Nitrogen facility

Detailed discussions of these regulations as they pertain to the proposed US Nitrogen facility are provided in the following sections. 3.1 National Ambient Air Quality Standards The EPA has promulgated standards for six criteria pollutants:

The Clean Air Act (CAA) Amendments of 1970 mandated that the EPA establish NAAQS to protect the public health and welfare. PM less than or equal to 10 microns in size (PM10) and less than or equal to 2.5 microns in size (PM2.5), SO2, CO, ozone (O3), NO2, and lead (Pb). The primary NAAQS are promulgated to protect the public health, and the secondary NAAQS are promulgated to protect the public welfare from any known or anticipated adverse effects associated with the presence of pollutants in the ambient air. Areas in violation of the NAAQS are designated as nonattainment areas and new sources to be located in or near these areas may be subject to more stringent air permitting requirements. Table 3-1.
3-1

The existing applicable NAAQS are presented in

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 3-1 NAAQS and PSD Increments and Significance Levels (g/m3, unless otherwise noted)[1,2] NAAQS Pollutant and Time Period PM10 Annual Arithmetic Mean 24-Hour Average PM2.5 Annual Arithmetic Mean 24-Hour, 98th Percentile SO2 Annual Arithmetic Mean 24-Hour Average 3-Hour Average 1-Hour Average NO2 Annual Arithmetic Mean 1-Hour Average CO 8-Hour Average 1-Hour Average O3 8-Hour Average (2008 standard)3 8-Hour Average (1997 Standard) 1-Hour Average Pb Rolling 3-Month Average Quarterly Primary 150 15.0 35 80 365 196 100 188 10,000 40,000 0.075 ppm 0.08 ppm 0.12 ppm 0.15 1.5 Secondary 150 15.0 35 1,300 100 0.075 ppm 0.08 ppm 0.12 ppm 0.15 Class I Increment 4 8 1 2 2 5 25 2.5 PSD Class II Increment 17 30 4 9 20 91 512 25

Significance Levels 1 5 0.30 1.2 1 5 25 7.84 1 7.52 500 2,000

Notes:
1. 2. 3.

NAAQS Sources: 40 CFR Part 50 and TAPCR 1200-03-03-.03(1)(a);PSD Class Increments and Significance Level Sources: 40 CFR Part 52.21(c) and TAPCR 1200-03-09-.01(m) g/m3 denotes microgram per cubic meter The 2008 ozone standard is currently under reconsideration by EPA and has not yet taken effect

3.2

PSD Requirements

3.2.1 General Requirements Under federal and State of Tennessee PSD review requirements, all major new or modified sources of air pollutants regulated under the CAA must be reviewed and a pre-construction permit issued. Tennessees State Implementation Plan (SIP), which contains PSD regulations, has been approved by EPA, and EPA has granted PSD approval authority to the TDAPC. A major facility is defined as any one of 28 named source categories that have the potential to emit 100 tons per year (TPY) or more or any other stationary facility that has the potential to emit 250 TPY or more of any pollutant regulated under the CAA.
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Potential to emit means

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

the capability, at maximum design capacity, to emit a pollutant after the application of control equipment. A major modification is defined under PSD regulations as a change at an existing major facility that increases emissions by greater than significant amounts. PSD significant emission rates are shown in Table 3-2.
Table 3-2 PSD Significant Emission Rates and Monitoring De Minimis Levels [1] De Minimis Ambient Levels Concentration PSD Significant (g/m3)[2] Pollutant Emission Rate (TPY) Averaging Time PM 25 10 24-Hour PM10 15 10 24-Hour PM2.5 10 SO2 40 13 24-Hour NOX 40 14 Annual CO 100 575 8-Hour Ozone (VOCs or NOX) 40 Pb 0.6 0.1 3-Month Fluorides 3 0.25 24-Hour Sulfuric Acid Mist 7 Hydrogen Sulfide (H2S) 10 0.2 1-Hour Total Reduced Sulfur (including H2S) 10 10 1-Hour Reduced Sulfur Compounds (including H2S) 10 10 1-Hour Greenhouse Gases (CO2e)[3] 75,000

Notes:
1. 2. 3.

Source: 40 CFR 52.21 g/m3 = microgram per cubic meter CO2e = Carbon dioxide equivalents

EPA has promulgated regulations that define certain increases above ambient air quality baseline concentrations for NO2 and CO as constituting significant deterioration. The EPA class designations and allowable PSD increments are presented in Table 3-1. The State of Tennessee adopted the EPA class designations and allowable PSD increments for NO2 and CO increments. HAPs previously regulated under the National Emission Standards for Hazardous Air Pollutants (NESHAP) program are exempt from federal PSD applicability because the HAPs are now regulated under Title III of the CAA Amendments of 1990. PSD review is used to determine whether significant air quality deterioration will result from the new or modified facility. Federal PSD requirements are contained in 40 CFR 52.21, The State of Tennessee has adopted
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Prevention of Significant Deterioration of Air Quality.

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

PSD regulations in TAPCR 1200-03-09-.01(4). Major new facilities and major modifications are required to undergo the following analysis related to PSD for each pollutant emitted in significant amounts Control technology review Source impact analysis Air quality analysis (monitoring) Source information Additional impact analyses

In addition to these analyses, a new facility must also be reviewed with respect to Good Engineering Practice (GEP) stack height regulations. these requirements are presented in the following sections. The projected emissions from this proposed project are estimated to exceed the significant emission rates for multiple pollutants, as summarized in Table 1-1. is required. 3.2.2 Control Technology Review PSD regulations concerning control technology review require that all applicable federal and state emission standards be met, and that BACT be applied to control emissions of subject pollutants from the source. The BACT requirements are applicable to pollutants that exceed the PSD-significance level if the facility is a new source that qualifies as a major PSD source, or to all regulated pollutants for which the increase in emissions from the facility or modification exceeds the significant emission rates listed in Table 3.2. Basically, major sources must install the most effective emission controls considered technically feasible by the permitting authority, taking into consideration environmental, energy, and economic impacts. The requirement for BACT was contained in the PSD requirements prescribed by Therefore, PSD review Discussions concerning each of

the CAA Amendments of 1977.

The premise behind the BACT requirement was that it would

optimize the consumption of the available PSD air quality increments and thereby maximize the potential for future economic growth without significantly degrading air quality. Guidelines for the evaluation of BACT can be found in EPAs Guidelines for Determining Best Available Control Technology (EPA, 1978) and the PSD Workshop Manual (EPA, 1980). These guidelines were established by EPA to provide a consistent approach to BACT and to ensure that the impacts of alternative emission control systems are measured by the same set of parameters. In addition, through implementation of these guidelines, BACT in one area may not be identical to BACT in
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

another area. According to EPA (1980), BACT analyses for the same types of emissions unit and the same pollutants in different locations or situations may determine that different control strategies should be applied to the different sites, depending on site-specific factors. Therefore, BACT analyses must be conducted on a case-by-case basis. Further discussion of BACT, including a full BACT analysis for all applicable pollutants, can be found in Section 4. 3.2.3 Source Impact Analysis All PSD applicants must conduct air quality analyses to assess the ambient impacts associated with construction and operation of the facility. A separate air quality analysis must be submitted for each regulated pollutant for which the applicant proposes to emit in a significant amount from a new or modified major source. The main purpose of the analysis is to demonstrate that the new emissions from the source, in conjunction with related emissions from other sources, will not cause or contribute to a violation of any applicable NAAQS or PSD increment. Additional studies are performed to evaluate effects on visibility and soils and vegetation. The PSD regulations specifically provide for the use of atmospheric dispersion models in performing analyses, estimating baseline and future air quality levels, and determining compliance with NAAQS and allowable PSD increments. the impact analysis. consultation and prior approval. Designated EPA models normally must be used in performing Guidance for the use and application of dispersion models is The source impact Specific applications for other than EPA approved models require EPAs

presented in 40 CFR 51, Appendix W Guideline on Air Quality Models.

analysis for criteria pollutants to address compliance with the NAAQS and PSD increments may be limited to the new or modified source if the net increase in impacts as a result of the new or modified source is below significance levels, as presented in Table 3.1. NAAQS and PSD increments. Class I areas are pristine areas (e.g., National Parks and Wilderness Areas) that have been designated by Congress and are afforded a greater degree of air quality protection. There are six Class I areas located within 300 kilometers (km) of the facility. Table 3-3 lists the Class I areas within 300 km of the site of the proposed US Nitrogen facility and their relative distances from the proposed facility location. As is demonstrated in Section 5 and Appendix C, the proposed US Nitrogen facility will be in compliance with all applicable

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 3-3 Class I Areas within 300 km of Proposed US Nitrogen Site Class I Area Managed By Distance from US Nitrogen (km) Great Smoky Mountains NP National Park Service 47 Shining Rock US Forest Service 85 Linville Gorge US Forest Service 102 Joyce Kilmer - Slickrock US Forest Service 116 Cohutta US Forest Service 187 Mammoth Cave NP National Park Service 288

US Nitrogen consulted with the Federal Land Managers (FLMs) responsible for the Class I areas within 300 km of the proposed US Nitrogen site regarding the need for modeling analyses to assess the impacts of emissions from this source on Class I visibility and air quality related values (AQRV). The FLMs for the National Park Service and the Forest Service each indicated that the increase in emissions due to this proposed project would likely result in no adverse impacts to any AQRVs at their respective Class I areas. Therefore, additional impact analysis is not required at this time. Copies of correspondence with the FLMs are included in Appendix D. There are several receptors at the Great Smoky Mountain National Park that are located less than 50 km from the proposed site. The FLMs requested a near-field impacts and visibility analysis for these receptors. The Class I analysis documented in Section 5 and Appendix C demonstrate impacts less than the Class I significant impact levels and no adverse effects on visibility. 3.2.4 Air Quality Monitoring Requirements In some circumstances, an application for a PSD permit must contain an analysis of continuous ambient air quality data in the area affected by the proposed major stationary facility or major modification. For a new major facility, the affected pollutants are those that the facility potentially would emit in significant amounts. For a major modification, the pollutants are those for which the new emissions increase exceeds the significant emission rate. However, if the predicted ambient impact (i.e., the modeled concentration for the applicable averaging time, caused by the proposed significant emission increase) is below the prescribed significant monitoring value, the applicant can be exempt from this data requirement. Where required, ambient air monitoring for a period of up to one year is generally appropriate to satisfy the PSD monitoring requirements. A minimum of four months of data is required. Existing data from the vicinity of the proposed source may be used if the data meet certain quality assurance requirements, otherwise, additional data may be needed. Guidance on designing a PSD monitoring network is provided in EPAs Ambient Monitoring Guidelines for Prevention of

Significant Deterioration (EPA, 1987a).


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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

As described in the air modeling report in Appendix C, NO2 impacts from the facility are less than the de minimis levels presented in Table 3-2; thus, air monitoring is not required. 3.2.5 Source Information/Good Engineering Practice Stack Height Source information must be provided to adequately describe the proposed project. General process descriptions for the proposed operations at the new US Nitrogen Facility are presented in Section 2. The 1977 CAA Amendments require that the degree of emission limitation required for control of any pollutant not be affected by a stack height that exceeds GEP or any dispersion technique. On July 8, 1985, EPA promulgated final stack height regulations (EPA, 1985a). Identical regulations have been adopted by Tennessee (TDAPC Rule 1200-03-24). the highest of: 1. 2. 65 meters (213 feet); or A height established by applying the formula: Hg = H + 1.5L Where Hg is the GEP stack height, H is the height of the structure or nearby structure, and L is the lesser dimension (height or projected width) of nearby structure(s); or 3. A height demonstrated by a fluid model or field study. GEP stack height is defined as

Nearby is defined as a distance up to five times the lesser of the height or width dimensions of a structure or terrain feature, but not greater than 0.8 km. Although GEP stack height regulations require that the stack height used in modeling for determining compliance with NAAQS and PSD increments not exceed the GEP stack height, the actual stack height may be greater. The stack height regulations also allow increased GEP stack height beyond that resulting from the above formula in cases where plume impaction occurs. Plume impaction is defined as concentrations measured or predicted to occur when the plume interacts with the elevated terrain. Elevated terrain is defined as terrain that exceeds the height calculated by the GEP stack height formula.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

3.2.6 Additional Impact Analysis In addition to air quality impact analyses, federal and TDAPC PSD regulations require analyses of the impairment to visibility and the impacts on soils and vegetation that would occur as a result of the proposed source [40 CFR 52.21(o)]. These analyses are to be conducted primarily for PSD Class I areas. Impacts as a result of general commercial, residential, industrial, and other growth associated with the source also must be addressed and are discussed in Section 6. These analyses are required for each pollutant emitted in significant amounts. 3.3 Nonattainment Rules

Based on the current nonattainment provisions, all major new facilities and modifications to existing major facilities located in a nonattainment area must undergo nonattainment review. A new major facility is required to undergo this review if the proposed pieces of equipment have the potential to emit 100 TPY or more of the nonattainment pollutant. A major modification at a major facility is required to undergo review if it results in a significant net emission increase of 40 TPY or more of the nonattainment pollutant or if the modification is major (i.e., 100 TPY or more). The proposed US Nitrogen site is located in Greene County, which is classified as an attainment/unclassified area for all criteria pollutants. Therefore, nonattainment requirements are not applicable. 3.4 Emission Standards

3.4.1 New Source Performance Standards 40 CFR 60 The NSPS are a set of national emissions standards that apply to specific categories of new sources. As stated in the CAA Amendments of 1977, these standards shall reflect the degree of emission limitation and the percentage reduction achievable through application of the best technological system of continuous emissions reduction the Administrator determines has been adequately demonstrated. applicable requirements. A review of 40 CFR 60 was performed to identify potentially

40 CFR 60, Subpart A General Provisions.


this part (40 CFR 60).

Subpart A specifies notification, recordkeeping,

performance testing, and monitoring requirements. This subpart applies to all sources subject to

40 CFR 60, Subpart IIII Standards of Performance for Stationary Compression Ignition Internal Combustion Engines. This subpart applies to owners and operators of stationary compression
ignition (CI) internal combustion engines (ICE) that commence construction after July 11, 2005.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

The proposed firewater pump engine will be subject to Subpart IIII. This engine is subject to the emission standards listed in Table 4 of this subpart.

40 CFR 60, Subpart Db Standards of Performance for Industrial-Commercial-Institutional Steam This subpart applies to each steam generating unit that commences Generating Units.
construction, modification, or reconstruction after June 19, 1984, and that has a heat input capacity of greater than 100 MMBtu/hr. The proposed steam generating boiler will have a maximum heat input capacity of 130 MMBtu/hr.

40 CFR 60, Subpart G Standards of Performance for Nitric Acid Plants. This subpart applies to
each nitric acid production unit that begins construction or modification after August 17, 1971. This process will be subject a NOX emission limitation and continuous emissions monitoring requirements. 3.4.2 National Emission Standards for Hazardous Air Pollutants (MACT) 40 CFR 63 The EPA has promulgated emissions standards for HAPs for various industrial categories. These NESHAPs that resulted from the 1990 CAA Amendments are based on the use of Maximum Achievable Control Technology (MACT). The adopted standards are contained in 40 CFR 63. Affected sources are required to apply MACT for the promulgated industrial category or to obtain a case-by-case MACT determination from the applicable regulatory authority after submitting a MACT analysis. year of a combination of HAPs. The proposed US Nitrogen facility will be an area source of HAP emissions, emitting less than 10 tons per year of each individual HAP and less than 25 tons per

40 CFR 63, Subpart A General Provisions.


this part (40 CFR 63).

Subpart A specifies notification, recordkeeping,

performance testing, and monitoring requirements. This subpart applies to all sources subject to

40 CFR 63, Subpart ZZZZ National Emissions Standards for Hazardous Air Pollutants for Stationary Reciprocating Internal Combustion Engines. As a new stationary RICE located at an area
source of HAPs, per 63.6590(c)(1), the firewater pump engine must meet the requirements of Subpart ZZZZ by meeting the requirements of 40 CFR 60, Subpart IIII for compression ignition engines. Therefore, as discussed earlier, this engine is subject to the requirements of 40 CFR 60,

Subpart IIII Standards of Performance for Stationary Compression Ignition Internal Combustion Engines.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

40 CFR 63, Subpart JJJJJJ National Emission Standards for Hazardous Air Pollutants for Industrial, Commercial, and Institutional Boilers Area Sources. Per 63.11195(e), gas-fired boilers,
as defined in 63.11237, are not subject to any requirements of Subpart JJJJJJ. 3.4.3 Tennessee Air Permitting Requirements The TDAPC regulations require any new source to obtain an air permit prior to construction. Major new sources must meet the appropriate PSD and/or nonattainment requirements as discussed previously. Required permits and approvals for air pollution sources include NSR for nonattainment areas, PSD, NSPS, NESHAP, construction permits, and operating permits. The requirements for construction permits are contained in TDAPC Rule 1200-03-09-.01. 3.5 Other Requirements

3.5.1 Title V Program The 1990 CAA Amendments also established a federally-mandated air operating permit program. The program requires the states to adopt regulations consistent with the CAA and the implementing regulations promulgated by EPA in 40 CFR 70. The program applies to Title V or Part 70 sources that include major stationary sources of air pollutants. The State of Tennessee has adopted the requirements of 40 CFR 70 in TDAPC Rule 1200-03-09-.02 which specify that all affected sources have a Title V permit to operate. The projected emissions from this proposed project are estimated to exceed the thresholds for Title V applicability. 3.5.2 Risk Management Program The 1990 CAA Amendments required both the EPA to issue regulations which would help prevent accidental releases of hazardous chemicals. EPA was required to address the consequences of accidental releases beyond a facility's property. The EPA met their obligation with the promulgation of 40 CFR 68, Accidental Release Prevention Requirements: Risk Management Programs Under

the Clean Air Action Section 112(r)(7) in June 1996. The rule applies to all stationary sources that
have a regulated substance present in a process in more than the listed threshold quantity. If the threshold quantity for a regulated substance is exceeded, then the facility would need to develop a risk management plan. The NH3 to be used at this facility will be anhydrous (100%) NH3 which is above the regulated NH3 solution level of 20 percent aqueous NH3 solution. Thus, the facility is required to prepare a risk management plan.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

3.5.3 General Duty Clause The facility is also subject to the general duty clause under Section 112(r)(I) of the CAA. The general duty clause directs owners and operators of stationary sources to identify hazards that may result from accidental releases, to design and maintain a safe facility, and to minimize the consequences of releases when they occur. The general duty clause applies to all stationary sources that have any "extremely hazardous substance" that are not limited to the list of regulated substances under Section 112(r) or under Occupational Safety and Health Administrations regulations.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.0

BEST AVAILABLE CONTROL TECHNOLOGY ANALYSIS

The PSD regulations require new and modified major stationary sources to apply BACT to each emission unit which is subject to regulation under the CAA and which has the potential to emit air pollutants in significant amounts as defined by 40 CFR 52.21(b)(23)(i) and TAPCR 1200-03-09-.01(4)(b)(24). in attainment areas. regulated pollutants. BACT is essentially an emission limitation based on the maximum degree of reduction for each pollutant, on a case-by-case basis, taking into account technical feasibility, energy, environmental, and economic impacts. In no event can the application of BACT result in the emission of any pollutant which would exceed the emissions allowed by an applicable NSPS or NESHAP. The BACT is defined in the CAA as a numerical emission limit. The numerical limit can be based on the application of air pollution control equipment, specific production processes, methods, systems or techniques, or fuel cleaning or combustion techniques. The PSD regulations are applicable to sources located

Greene County is classified as attainment or unclassified for all

Applicability
The US Nitrogen facility is a major stationary source. The pollutants subject to review under the PSD regulations, and for which BACT analysis is required are shown in Table 1-1.

BACT Analysis Approach


Under the PSD program, newly constructed and modified major stationary sources in areas which are in attainment of the NAAQS must implement BACT. Economic as well as energy and environmental impacts are considered in a BACT analysis. The top-down BACT approach requires that a source not only consider the most stringent emission limits previously approved, but it also must evaluate all demonstrated and potentially applicable technologies, including innovative controls and lower polluting processes. These technologies and emission limits are identified through a review of EPAs RACT/BACT/LAER Clearinghouse (RBLC), Federal/State/Local new source review permits, technical journals and reports, and other sources (See Appendix E for RBLC searches). If the proposed BACT is equivalent to the most stringent emission limit, no further However, if the most stringent emission limit is not selected, additional analysis is necessary. analyses are required. Once the most stringent emission limit has been identified, its technical feasibility must be determined. A technology that is available and is applicable to the source under review is A control technique is considered available if it has reached
4-1

considered technically feasible.

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

the licensing and commercial sales stage of development.

In general, a control option is

considered applicable if it has been, or is soon to be, developed on the same or similar source type. If the control technique is technically feasible, that control is considered to be BACT unless economic, energy, or environmental impacts preclude its use. Therefore, if the chosen technology is not applicable or is technically or economically infeasible for the source in question, the next most stringent emission limits are evaluated. The process continues until an emission level cannot be eliminated.

Impact Analysis of Control Alternatives


When the most stringent technically feasible emission limitation is not selected as BACT, justification must be provided in terms of adverse environmental, energy, or economic impacts. The net environmental impact is the first analysis performed for each alternative. Both beneficial impacts and adverse impacts should be included in the analysis, including air pollutants not currently regulated under the CAA. Therefore, an analysis of unregulated air pollutants and their potential impact is required as part of the BACT analysis. The second analysis involves energy impacts. The direct energy impacts of the control alternatives are estimated in terms of energy consumption (Btu, barrels of oil, kWh, etc.) availability in subsequent years. The third analysis involves evaluating the economic impacts of control alternatives with primary consideration to the cost effectiveness (dollars per ton of pollutant removed) for each option. The analysis generally includes an estimate of capital annualized costs for each alternative based on vendor quotes and established EPA cost-estimating procedures. For the purposes of these economic impact analyses, a capital recovery rate of 15% was used which deviates from the guidance provided in the EPA Cost Control Manual. This rate was used to more accurately reflect the actual weighted cost of capital to US Nitrogen from both debt and equity sources, plus an allowance for the considerable risk associated with the construction and operation of this facility. (See Appendix F for a detailed analysis of US Nitrogens cost of capital.) In addition, the impacts of relying on scarce fuels must be considered because of the possibility of a change in

Enforceability
An emission limit must be proposed for each emission unit subject to BACT and the emission limit must be federally enforceable. That is, the emission limit must be short-term and specific such that regulatory agency personnel can determine compliance at any time.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

GHG BACT Analysis


As of January 2, 2011, new EPA rules regulating GHG emissions from large facilities came into effect. The new rules modify certain permitting requirements under the Federal CAA, including PSD, to require that regulated facilities include GHG emissions in their permits. EPAs new rules now provide that any facility that triggers PSD requirements for pollutants other than GHGs also will be subject to PSD requirements, including BACT, for GHGs if the new or modified source increases emissions by more than 75,000 TPY of CO2e. A summary of GHG pollutants for US Nitrogen is given in Table 4-1. Total GHG potential emissions exceed 75,000 TPY.
Table 4-1 US Nitrogen Potential Emissions of GHGs (TPY) Pollutant Emissions (TPY) CO2e (TPY) CO2 188,481.6 188,481.6 CH4 1.84 38.7 N2O 29.3 9,078.0

4.1

Point Source Emissions

As stated earlier (See Section 1.0.), point sources at the US Nitrogen facility which emit NOX and GHGs were considered in the BACT analysis. For simplicity and clarity, all GHGs are considered together in this BACT analysis and are handled separately from the NOX emissions (See Section 4.2.). A summary of the individual emission point sources is shown in Table 4-2. While this section includes a brief description of the processes that result in the emissions being addressed in the BACT analysis, Section 2.2 provides a detailed description of all facility processes.
Table 4-2 US Nitrogen Emission Point Sources and Respective Potential Emissions (TPY) Source Description NOX CO2 CH4 N2O Ammonia Plant Train 1 Flue Gas 7.5 22,380.0 0.422 0.042 Ammonia Plant Train 1 CO2 Vent 45,394.3 Ammonia Plant Train 2 Flue Gas 7.5 22,380.0 0.422 0.042 Ammonia Plant Train 2 CO2 Vent 45,394.3 Nitric Acid Plant 54.8 29.1 Steam-Generating Boiler 4.3 50,061.1 0.944 0.094 Firewater Pump 0.1 23.9 0.001 0.000 Flare 2.3 2,848.0 0.053 0.006

A summary of the proposed BACT for each NOX and GHG point source is shown in Table 4-3.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 4-3 Summary of Proposed BACT for Each US Nitrogen Emission Source Control Technologies Considered In Descending Order of Reduction SCR Ammonia Plant Flue LNB SNCR SCR Nitric Acid Plant NOX Steam Boiler NSCR Extended absorption SCR plus LNB plus FGR ULNB plus FGR LNB and FGR Firewater Pump Flare GHG From Combustion Sources Concentrated CO2 Diesel engine design in accordance with 40 CFR 60, Subpart IIII Maintain high combustion efficiency by complying with 40 CFR 60.18 CCS Energy and process efficiency CCS Process efficiency Tertiary controls Catalytic Decomposition Tertiary controls NSCR Primary controls 3.2 g/kWh 1.1 lbs/hr None None 3.0 g/hp-h 3.1 lbs/hr during SU, 0.49 lbs/hr during NO Various Comply with 40 CFR 60, Subpart IIII Comply with 40 CFR 60.18 0.01 lbs/MMBtu LNB 0.01 lbs/MMBtu UNLB plus FGR 0.524 lbs NOX/T HNO3 SCR 0.6 lbs NOX/T HNO3 Extended absorption plus SCR 0.41 lbs NOX/T NH3 LNB 0.41 lbs NOX/T NH3 SCR Lowest RBLC Emission Rate Control Technology Associated With Lowest RBLC Rate Emission Rate Proposed As BACT Control Technology Proposed As BACT

Pollutant

Emission Source

Comments SCR and LNB are technically feasible. Chose lowest RBLC rate using SCR. Estimated cost $4,546/T NOX removed. All technologies are technically feasible. Chose combination of extended absorption and SCR to achieve a 99% reduction. Estimated cost $231/T NOX removed. All technologies are technically feasible. Chose lowest RBLC rate using ULNB plus FGR. Estimated cost $2,649/T NOX removed. Chose compliance with 40 CFR 60, Subpart IIII as BACT Rates based on AP-42 factors for combustion of flare gas (SU) and natural gas (NO). Chose compliance with 40 CFR 60.18 as BACT. CCS not commercially available for these sources. Chose energy and process efficiencies as BACT. CCS transport costs for geologic sequestration alone estimated to be $115/T CO2. Terrestrial sequestration not commercially available. Chose process efficiencies as BACT.

All Combustion Sources Ammonia Plant CO2 vent

NA

NA

Energy and process efficiency

NA

NA

90,788.6 TPY CO2e

Process efficiency

N2O

Nitric Acid Plant

NA

NA

29.1 TPY N2O 9021 TPY CO2e

Primary plus tertiary control (catalytic decomposition)

Chose primary plus tertiary (catalytic decomposition) controls as BACT. Estimated cost $1.18/T CO2e.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.1.1 Ammonia Plant Trains 1 and 2 4.1.1.1 Process Description The Ammonia Plant will consist of two trains, capable of producing a total of 200 tons of synthetic NH3 per day (100 tons per train), or 68,000 tons per year. Synthetic NH3 refers to NH3 that has been synthesized from natural gas. The natural gas molecules are reduced to carbon and hydrogen. The hydrogen is then purified and reacted with nitrogen, which is obtained from the air, at a molar ratio of 3:1. The gas is then compressed and condensed to a liquid. The process of reducing the natural gas molecules to carbon and hydrogen is called the catalytic steam reforming method. this method: (1) (2) (3) (4) (5) (6) Natural gas desulfurization Catalytic steam reforming CO shift CO2 removal Methanation NH3 synthesis Six steps are required to produce synthetic NH3 using

The first, third, fourth, and fifth steps remove impurities such as sulfur, CO, CO2, and water from the feedstock, hydrogen, and synthesis gas streams. manufactured and nitrogen (air) is introduced. the synthetic gas. 4.1.1.2 Flue Gas The flue gas leaving the primary reformer is controlled at In the second step, hydrogen is The sixth step produces anhydrous NH3 from

The reaction in the primary reformer is highly endothermic; therefore, external heat must be added by the combustion of natural gas. approximately 1950F. It is cooled in an air preheater coil, waste heat boiler and the economizer before being exhausted to the atmosphere at 425F. 4.1.1.2.1 Flue Gas NOX Emissions These include, in descending order of removal efficiency,

There are three control technologies/methods available for reducing the NOX content of flue gas emissions from ammonia plants. Reduction (SNCR).
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(1) Selective Catalytic Reduction (SCR), (2) low-NOX burners (LNB), and (3) Selective Non-catalytic

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

LNBs minimize the formation of NOX by controlling the quantities and the way in which fuel and air are introduced and mixed in the reformer. LNBs have the smallest impact on operating costs. SNCR and SCR are fundamentally similar, in that they use an NH3-containing reagent to react with the NOX produced in the reformer to convert the NOX to nitrogen and water. SNCR accomplishes this at higher temperatures (1700F-2000F) in the upper reformer region, while SCR operates at lower temperatures (about 700F) and hence, needs a catalyst to produce the desired reaction between NH3 and NOX. SCR technology is capable of achieving much larger reductions in NOX emissions, up to 90 percent, compared to 30 to 60 percent reductions achievable by SNCR. While the difference between the SNCR and SCR may seem minor, they result in significant differences in performance. In the case of SNCR, the reaction occurs in a somewhat uncontrolled fashion (e.g., the existing upper reformer becomes the NOX control reaction vessel, which is not what it was originally designed to be) while in the SCR case, a dedicated reactor and the reaction-promoting catalyst ensure a highly controlled, efficient reaction. Because of the uncontrolled manner in which the mixing of the flue gas and NH3 occurs in the upper part of the reformer and the need to achieve higher removal efficiencies to match the lowest emission rate found in the RBLC search, SNCR was not considered technically feasible. The results of a RBLC search using keywords ammonia, reformer and fertilizer identified three similar sources (See Appendix E for the details of the search). The lowest limit identified in the RBLC for NH3 reformers was 11.93 lbs/hr for a 700 ton per day (TPD) plant, or 0.41 lbs NOX/ton of NH3 (TNH3). The control method specified for this source is LNB and good combustion practices. 4.1.1.2.1.1 Economic Analysis

The economic impact of using SCR and LNB to reduce ammonia plant flue gas NOX emissions was evaluated by determining the cost per ton of NOX removed for each technology. Detailed Financial Analysis Worksheets are included in Appendix G, while Table 4-4 summarizes the results of the analysis. The US Nitrogen facility will make use of existing ammonia and nitric acid plant equipment which are being re-located to the Greene County facility, including existing primary reformers for each train. In order to achieve an emission rate in the range of the lowest rate identified during the RBLC search using LNB, the reformers would need to rebuilt, thus significantly increasing costs.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 4-4 Financial Comparison of US Nitrogen Ammonia Plant NOX Reduction Options 1,2 LNB SCR Inlet NOX (TPY) 52.3 52.3 Outlet NOX (TPY) 19.7 7.5 Reduction Efficiency (%) 62 86 NOX Reduced (TPY) 32.6 44.8 Total Capital Investment ($) $5,759,1003 $538,403 Capital Recovery Cost ($/yr) $920,0823 $86,016 O&M Annual Expense ($/y) $172,773 $117,627 Total Annual Cost ($) $1,092,855 $203,643 Cost Of NOX Removed ($/T) $33,523 $4,546

Notes:
1. 2.

3.

See Appendix G, Tables G-1 and G-2 for detailed financial analysis worksheets. All costs, except the cost of each ton of NOX removed, and all emissions are per Ammonia Plant train, therefore each must be multiplied times two for the entire Ammonia Plant. Reflects the cost to rebuild the primary reformer to accommodate new LNBs.

4.1.1.2.1.2

Energy Impacts

SCRs normally consume electrical energy, however, in the case of an SCR on the US Nitrogen Ammonia Plant, the NH3 can be mixed in an existing fan from the primary reformer, thus requiring no additional electricity. Use of LNBs can result in some relatively minor reductions in efficiency. 4.1.1.2.1.3 Environmental Impacts NH3 is

SCRs consume NH3 and unreacted NH3 will be emitted to the atmosphere (NH3 slip).

a precursor to the formation of PM10 and PM2.5 in the atmosphere. LNBs do not result in the direct emission of additional air pollutants and result in very minor indirect emissions. LNBs require no reagents like NH3. 4.1.1.2.1.4 Proposed BACT

Because the use of LNB would require the re-building of the reformers, thus increasing capital costs considerably, an emission limit of 1.71 lbs/hr or 0.41 lbs NOX/TNH3 using SCR is proposed as BACT. This limit would apply to Ammonia Plant Trains 1 and 2. 4.1.2 Nitric Acid Plant 4.1.2.1 Process Description The nitric acid plant will have the capacity to produce up to 500 tons per day of weak nitric acid. Weak nitric acid can have concentrations ranging from 30 to 70 percent nitric acid. To produce nitric acid, US Nitrogen will utilize a high-temperature catalytic oxidation process using the NH3 produced in the process described previously. This process will consist of three steps:
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

(1) (2) (3)

Ammonia oxidation, Nitric oxide oxidation, and Absorption.

4.1.2.1.1 Ammonia Oxidation In this process, the NH3 is mixed with ambient air, heated, and then passed over a platinum catalyst, where the NH3 is oxidized to nitric acid. production of nitric acid are atmospheric air and NH3. The raw materials required for These raw materials are combined at

elevated temperature and pressure and passed over a platinum-containing catalyst, where the NH3 reacts with oxygen in the air. The resultant process gas is passed through the heat exchanger train where the major portion of this reaction energy is recovered as heat. 4.1.2.1.2 Nitric Oxide Oxidation Under these conditions, the nitric oxide formed during the NH3 A portion of

The nitric oxide rich gas stream is first cooled in a waste heat recovery boiler and then further cooled in a cooler condenser. oxidation step is further oxidized to nitrogen dioxide and nitrogen tetroxide. power for the air compressor by driving a hot gas expander. 4.1.2.1.3 Absorption

the reaction energy recovered in the heat exchanger train is used to reheat the tail gas to provide

The final step sends the nitrogen dioxide and nitrogen tetroxide mixture from the condensation step to the bottom of an absorption tower, where it flows countercurrent to water introduced at the top of the tower. Nitric acid is formed by contact of the nitrogen dioxide and tetroxide with water and is removed at the bottom of the absorption tower. The bottom absorption tray produces acid at the product concentration which then flows into the bleacher section. In the bleacher, the product acid contacts a counter-current flow of bleach air which strips the remaining dissolved NOX from the acid. The stream of clear, bleached acid is then allowed to flow under pressure to storage. 4.1.2.2 Nitric Acid Plant Stack NOX Emissions

There are three control technologies/methods available for reducing the NOX content of stack emissions from nitric acid plants. These include, in descending order of removal efficiency, (1) SCR, (2) nonselective catalytic reduction (NSCR), and (3) extended absorption. All are considered technically feasible for use at the US Nitrogen facility.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

Extended absorption reduces NOX emissions by increasing the efficiency of the existing process absorption tower or adding absorption tower height. In the catalytic reduction process, tail gases from the absorption tower are heated to ignition temperature, mixed with fuel (natural gas, NH3, hydrogen, propane, butane, or naphtha) and passed over a catalyst bed. In the presence of the catalyst, the fuels are oxidized and the NOX is reduced to nitrogen gas. There are two types of catalytic reduction used in nitric acid plants NSCR and SCR. With NSCR systems, free oxygen in the tail gas must be eliminated by adding a fuel (usually natural gas) and, after completing this step, to provide for the reaction with the NOX, in the presence of a catalyst, to produce a tail gas with a reduced NOX concentration. The catalysts used in NSCR usually contain platinum or palladium. These noble metals are deposited on either alumina pellets or honeycomb type of substrate. With NSCR systems, most of the hydrocarbons from the natural gas are converted to CO2 and CO, resulting in additional emissions of 6,000-7,000 ppm CO2 and 300-400 ppm of CO, as well as some unburned hydrocarbons. With SCR systems, oxygen is not consumed before the NOX is reduced, and the NOX in the tail gas is selectively reduced in the presence of a catalyst. The SCR system can be installed on either side of the hot tail gas expander. The location depends on the temperature of the tail gas as it enters the expander. A small quantity of NH3 is mixed with the tail gas in a static mixer prior to being fed over the catalyst. nitrogen. In the reactor, tail gas flows through the catalyst where NOX is reduced to The tail gas leaves the reactor with a reduced NOX concentration of 33-150 ppm,

depending on the NOX concentration at the inlet to the SCR, the amount of catalyst, and the reaction time. For nitric acid plants the inlet NOX concentration can range from 1,000-3,000 ppm depending on the extent to which NOX is reduced in the absorption tower. SCR systems are easier to operate than NSCR systems and they begin reducing NOX during plant startup much earlier than NSCR. Although there are some additional emissions of NH3 (known as slip) with SCR operation, there are no increases in emissions of CO2, CO, or unburned hydrocarbons. The results of a RBLC search of nitric acid plants identified eleven similar sources (See Appendix E for the details of the search.). The lowest emission limit identified in the RBLC was 0.524 lbs NOX/ton of 100% acid produced (T100%
Acid).

The control method specified is SCR.


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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

A review of the permit for the facility for which this emission limit was set revealed the following information. The permit addresses two nitric acid plants Plant 7 and Plant 9. Both plants existed at the time of the issuance of the permit. The limit of 0.524 lbs NOX/T100% while a limit of 0.6 lbs NOX/T100%
Acid Acid

was set for Plant 7

was set for Plant 9. Plant 7 was equipped with SCR while
Acid)

Plant 9, at the time of the issuance of the permit, employed hydrogen peroxide injection. The permit states that the limit for Plant 7 (0.524 lbs NOX/T100% the emission rate for Plant 9 (0.6 lbs NOX/T100% of evidence that SCR can routinely achieve that rate. 4.1.2.2.1 Economic Analysis
Acid)

was set based on the fact that

the SCR currently operating at Plant 7 was achieving that emission rate. The permit states that was set based on the preponderance

The economic impact of using NSCR and SCR to reduce NOX emissions from the nitric acid plant stack beyond the reductions achieved by the existing extended absorption tower was evaluated by determining the cost per ton of NOX removed for each. Detailed Financial Analysis Worksheets are included in Appendix G, while Table 4-5 summarizes the results of the analysis. Note that because NSCR reduces both NOX and N2O, for the purposes of the financial analysis, the costs of the NSCR have been split 80% for NOX reductions and 20% for N2O reductions. This split is based on the fact that incoming NOX concentrations to the NSCR would be approximately 2,000 ppm while incoming N2O concentrations would be approximately 500 ppm.
Table 4-5 Financial Comparison of US Nitrogen Nitric Acid Plant NOX Reduction Options1 NSCR2 SCR Inlet NOX (TPY) 1,643.9 1,842.9 Outlet NOX (TPY) 82.6 54.8 Reduction Efficiency (%) 95 97 NOX Reduced (TPY) 1,561.3 1,788.1 Capital Recovery Cost ($) $1,519,840 $943,939 Annualized Capital Investment ($/yr) $242,812 $150,805 O&M Annual Expense ($/y) $671,390 $263,224 Total Annual Cost ($) $914,202 $414,029 Cost Of NOX Removed ($/T) $586 $232

Notes:
1. 2.

See Appendix G, Tables G-3 and G-4 for detailed financial analysis worksheets. Applied 80% of NSCR costs to the reduction of NOX and 20% to the reduction of N2O.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.1.1.2.2.2

Energy Impacts

Both NSCRs and SCRs consume electrical energy. In the case of the NSCR, additional electrical usage is estimated to be 30 megawatt hours per year (MWh/yr) while additional electrical usage for the SCR is estimated to be 44 MWh/yr. In addition, the NSCR would consume an estimated 92.9 MMscf/yr (94,758 MMBtu/yr) of natural gas. 4.1.1.2.2.3 Environmental Impacts

Both NSCRs and SCRs consume resources NH3 or natural gas. With an SCR unreacted NH3 would be emitted to the atmosphere (NH3 slip). NH3 is a precursor to the formation of PM10 and PM2.5 in the atmosphere. The additional electrical usage of both NSCR and SCR will result in the indirect emission of NOX, SO2, and CO2 from the generation of electricity. As stated earlier, with the NSCR system, most of the hydrocarbons from the natural gas are converted to CO2 and CO, resulting in additional emissions of 6,000-7,000 ppm CO2 and 300-400 ppm of CO, as well as some= unburned hydrocarbons. As noted earlier, NSCR reduces both NOX and N2O. 4.1.1.2.2.4 Proposed BACT

As stated earlier, the US Nitrogen facility will make use of existing ammonia and nitric acid plant equipment which are being re-located to the Greene County facility. The existing nitric acid plant absorption tower is designed to reduce NOX emissions to 1,500-2,000 ppm, which is about 1,500 ppm lower than the concentration emitted from an absorption tower designed for commercial purposes only, with no reduction for NOX control purposes. Therefore, extended absorption, at no additional cost to the facility, will initially reduce NOX emissions by about 50%. Based on this analysis an emission limit of 12.5 lb/hr or 0.6 lbs NOX/T100%
Acid

using a combination of

extended absorption and SCR is proposed as BACT. The extended absorption will reduce the NOX concentration from about 3,000 ppm to about 1,500 ppm, while the SCR will reduce the concentration from about 1,500 ppm to 33 ppm. This will result in an overall NOX reduction of approximately 99%. 4.1.3 Steam-Generating Boiler 4.1.3.1 Process Description The boiler will have US Nitrogen proposes to install a natural gas-fired boiler that will be used to provide the steam needed to operate the various processes and equipment at the facility. a maximum heat input capacity of 130 MMBtu/hr and will use only natural gas as fuel.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.1.3.2

Boiler NOX Emissions

There are three possible control technologies for reducing NOX emissions from natural gas-fired boilers in the 100200 MMBtu/hr range. These include, in descending order of removal efficiency, (1) SCR with LNB and flue gas recirculation (FGR), (2) ultra-low-NOX burners (ULNB) with FGR, and (3) LNB with FGR. All are considered technically feasible for use at the US Nitrogen facility. LNBs and ULNBs minimize the formation of NOX by controlling the quantities and the way in which fuel and air are introduced and mixed in the boiler. operating costs. With an SCR, a small quantity of NH3 is mixed with the boiler exhaust gas in a static mixer prior to being fed over the catalyst. In the reactor, the NH3/exhaust gas mixture flows through the catalyst where NOX is reduced to nitrogen. The results of a RBLC search for 100-200 MMBtu/hr, natural gas-fired boilers identified eighteen similar sources (See Appendix E for the details of the search.). The lowest emission limit identified in the RBLC was 1.8 lbs/hr for a 175 MMBtu/hr boiler. Although no control method is specified in the RBLC, a review of the Preliminary Determination Summary for the permit associated with this emission limit indicates the applicant proposed to use LNB to meet the emission limitation. Further investigation revealed that the 1.8 lbs/hr emission limit is equivalent, in that case, to 0.01 lb/MMBtu or 9 ppmv NOX, dry, corrected to 3% oxygen, averaged over three hours, which was designed to be consistent with State of Texas BACT guidance. 4.1.3.2.1 Economic Analysis LNBs have the smallest impact on

The economic impact of using SCR plus LNB and FGR, ULNB plus FGR, and LNB plus FGR to reduce boiler NOX emissions was evaluated by determining the cost per ton of NOX removed for each technology. Detailed Financial Analysis Worksheets are included in Appendix G, while Table 4-6 summarizes the results of the analysis.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 4-6 Financial Comparison of US Nitrogen Boiler NOX Reduction Options1 LNB + FGR ULNB + FGR SCR+LNB+FGR Inlet NOX (TPY) 47.8 47.8 47.8 Outlet NOX (TPY) 14.3 4.3 1.4 Reduction Efficiency (%) 70 91 97 NOX Reduced (TPY) 33.5 43.5 46.4 Total Capital Investment ($) $337,325 $607,185 $1,462,846 Capital Recovery Cost ($/yr) $53,892 $97,005 $233,706 O&M Annual Expense ($/y) $10,120 $18,216 $162,227 Total Annual Cost ($) $64,011 $115,220 $395,934 Cost Of NOX Removed ($/T) $1,911 $2,649 $8,533

Note:
1.

See Appendix G, Tables G-5 through G-7 for detailed financial worksheets.

4.1.3.2.2

Energy Impacts In the case of an SCR on the boiler, this usage is estimated to be

SCRs consume energy. approximately 44 MWh/yr. 4.1.3.2.3

Environmental Impacts

SCRs consume NH3. With an SCR, un-reacted NH3 would be emitted to the atmosphere (NH3 slip). NH3 is a precursor to the formation of PM10 and PM2.5 in the atmosphere. The additional electrical usage will result in the indirect emission of NOX, SO2, and CO2 from the generation of electricity. 4.1.3.2.4 Proposed BACT

Based on this analysis, a NOX emission limit of 0.01 lb/MMBtu (1.3 lb/hr) using ULNB in combination with FGR is proposed as BACT. The SCR plus LNB and FGR option is considered an unacceptable alternative for BACT since the incremental cost ($96,798/T) of the small additional NOX reduction (2.9 T/yr) is unreasonably high, there is additional consumption of resources (NH3) and electrical energy, there are both direct (NH3) and indirect (NOX, SO2, and CO2) emission of additional air pollutants, and the ULNB plus FGR option can achieve an emission rate equal to the lowest rate in the RBLC. 4.1.4 Firewater Pump 4.1.4.1 Process Description US Nitrogen will install a diesel-powered emergency firewater pump to provide fire-fighting capability. The diesel engine, which will be rated at approximately 400 hp, will be routinely tested, as required by Federal, state, and local fire codes. The engine will be Tier II-compliant to meet required emissions standards under 40 CFR 60, Subpart IIII, for stationary compression ignition internal combustion engines.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.1.4.2

Pump NOX Emissions

As mentioned above, the firewater diesel engine will be subject to 40 CFR 60 Subpart IIII (NSPS). The emission standard for stationary fire pump engines (Table 4 to Subpart IIII of Part 60

Emission Standards for Stationary Fire Pump Engines) is 3.0 grams per hp-hour (g/hp-h) or
4.0 grams per kilowatt-hour (g/kW-h). The results of a RBLC search for diesel powered firewater pumps identified thirty-three similar sources (See Appendix E for the details of the search.). The lowest emission limit identified in the RBLC was 3.2 g/kW-h or 1.58 lbs/hr for a 300 hp diesel engine. The control method listed in the RBLC is none. 4.1.4.3 Proposed BACT

Complying with 40 CFR 60 Subpart IIII (3.0 g/hp-hr) is proposed as BACT. 4.1.5 Flare 4.1.5.1 Process Description A flare stack will be installed primarily to mitigate CO emissions during ammonia plant startup and to combust vent gas during safety relief. Normal emissions from the flare will be no more than those associated with operation of the 5 MMBtu/hr flare pilots and purge gas. It is assumed that only one ammonia plant will start up at any given time. The flare burner is a smokeless flare with no PM emissions. Startup will occur a maximum of three times per year for 36 hours per event. The emissions from the vents last approximately 12 hours per event. During startup, the maximum heat input, including the heat value of the natural gas as well as the gases from the ammonia plant, is expected to be 45.6 MMBtu/hr. 4.1.5.2 Flare NOX Emissions

The only control technology/method available for the control NOX emissions from flares is to maintain a high (at least 98%) combustion efficiency. 40 CFR 60.18 specifies the requirements for achieving and maintaining this efficiency. the US Nitrogen facility. The results of a RBLC search using the keywords flare and ammonia identified only one similar source (See Appendix E for the details of the search.). The emission limit identified in the RBLC was 1.1 lbs/hr. No control method is specified in the RBLC. This is considered technically feasible for

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

The EPA AP-42 NOX emission factor for flares is 0.068 lb/MMBtu and the AP-42 NOX emission factor for uncontrolled combustion of natural gas is 100 lbs/106 standard cubic feet (scf) of natural gas. Based on the maximum heat input during startup of 45.6 MMBtu/hr, the proposed NOX emission rate during the 36 hours per year of startup is 3.1 lbs/hr. During normal operations the emission rate will be 0.49 lbs/hr. 4.1.5.3 Proposed BACT

Operating the flare in compliance with 40 CFR 60.18 with an emission limit during startup of 3.1 lbs/hr and an emission limit during normal operations of 0.49 lb/hr is proposed as BACT. 4.2 Greenhouse Gases (CO2e) These GHG emissions fall into

Table 4-1 summarizes the GHG emissions from the US Nitrogen facility while Table 4-2 provides the details of the emissions for each emission source. The three categories are: Relatively dilute GHG emissions resulting from combustion Concentrated CO2 emissions (greater than 90% CO2) from the ammonia plant CO2 vents N2O emissions from the nitric acid plant three categories, and for simplicity, were addressed in this analysis in those three categories.

The relatively dilute GHG emissions resulting from combustion include emissions from the following: Ammonia Plant, Train 1 flue gas Ammonia Plant, Train 2 flue gas Steam-Generating Boiler Firewater Pump Flare

Because little information was available in the RBLC for GHG emissions at the time of this analysis, two recent documents issued by EPA were used as the primary source of information on control technologies for the US Nitrogen GHG emissions. Those two documents are: Available and

Emerging Technologies for Reducing Greenhouse Gas Emissions from Industrial, Commercial, and Institutional Boilers, USEPA, Research Triangle Park, October 2010 and Available and Emerging Technologies for Reducing Greenhouse Gas Emissions from the Nitric Acid Production Industry,
USEPA, Research Triangle Park, December 2010.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.2.1 Dilute GHG Emissions Resulting From Combustion For this category of emission sources there are two control technologies/methods available for reducing GHG emissions and they are, in descending order of control efficiency, (1) carbon capture and sequestration (CCS) and (2) energy/process efficiency methods. the commercial level for any of these types of sources. 4.2.1.1 Ammonia Plant, Trains 1 and 2 Flue Gas CCS was not considered technically feasible for any of these emission sources since it has not been demonstrated at

The flue gas streams from each train are the same. As discussed in Section 4.1.1.2, the emissions from the flue result primarily from the combustion of natural gas. Natural gas is the fuel option that results in the lowest amount of CO2 being formed during combustion. The natural gas combustion process will be optimized for maximum fuel efficiency to the extent practicable. The proposed GHG BACT emission limits per train are as follows (See Appendix B for a detailed description of the basis for these limits.): CO2 CH4 N2O 22,380.0 TPY 0.422 TPY 0.042 TPY

4.2.1.2

Steam-Generating Boiler The boiler is expected to operate at

As discussed in Section 4.1.3, the steam-generating boiler will be a 130 MMBtu/hr natural gas-fired boiler. The boiler will provide steam for plant processes. natural gas per year. The boiler will burn only natural gas, the fuel option with the lowest CO2 emission rate, and be designed with ULNB plus FGR for NOX control (See Section 4.1.3.), the latest instrumentation and controls for controlling efficiency, and insulation to minimize energy leakage. The boiler will be operated with a thermal efficiency of 81% or greater. The proposed GHG BACT emission limits are as follows (See Appendix B for a detailed description of the basis for these limits.): CO2 CH4 50,061.1 TPY 0.944 TPY
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75% capacity and will be limited to a maximum use of 840 million standard cubic feet (MMscf) of

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

N2O

0.094 TPY

4.2.1.3

Firewater Pump It may run for any number of hours during an actual

As discussed in Section 4.1.4, the fire water pump is a 400 hp diesel engine. It will be run no more than one hour per week for testing. emergency. The maximum number of normal operating hours per year is expected be no more than 100. The diesel engine will be designed for energy efficient operation. The proposed GHG BACT emission limits are as follows (See Appendix B for a detailed description of the basis for these limits.): CO2 CH4 N2O 23.9 TPY 0.001 TPY 0.000 TPY

4.2.1.4

Flare

As discussed in Section 4.1.5, the flare is used to control emissions from startup vents during ammonia plant startup, as well as NH3 releases during upsets. It is assumed that only one train of the ammonia plant will start up at any given time. The flare burner size is 5 MMBtu/hr and is an energy efficient, smokeless flare (no PM emissions). Ammonia plant startup will occur a maximum of three times per year for 36 hours per event. During startup, the maximum heat input, including the heat value of the pilot natural gas as well as the gases from the plant, is expected to be 45.6 MMBtu/hr. As also described in Section 4.1.5, the flare will be designed and will operate in accordance with 40 CFR 60.18. The requirements in 40 CFR 60.18 are intended to result in a combustion efficiency of 98% or higher to ensure that the flare serves its purpose of reducing emissions of CO, NH3, and other components in the gases flowing to the flare. Maximizing the combustion efficiency of the flare maximizes the amount of CO2 and other GHGs produced by the flare. During normal operations, only natural gas, the fuel option with the lowest CO2 emission rate, will be combusted. BACT is proposed to be energy efficient combustion in accordance with 40 CFR 60.18 with proposed GHG BACT emission limits as follows (See Appendix B for a detailed description of the basis for these limits.):

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

Normal Operations
CO2 CH4 N2O 2,559.8 TPY 0.048 TPY 0.005 TPY

Startup
CO2 CH4 N2O 287.8 TPY 0.005 TPY 0.001 TPY

4.2.2 Concentrated CO2 Emissions from the Ammonia Plant CO2 Vents The concentrated CO2 emissions are emitted from the CO2 vents at the Ammonia Plant Trains 1 and 2. CO2 emissions result from NH3 synthesis after the CO shift. The CO2 is removed from the process gas by cooling the gas and sending it through the CO2 Absorber, an absorption tower. There, the CO2 is removed from the gas by absorption in MDEA solution. The MDEA solution is regenerated in the Amine Regenerator and re-circulated through the CO2 Absorber in a continuous cycle. Initially, the CO2 gas will be captured and vented to the atmosphere. At a later date, efforts will be made to capture this CO2 for commercial use at another facility. The concentration of CO2 in this gas stream is approximately 91 percent. There are two control technologies/methods available for reducing the content of GHGs in the CO2 vents. They are, in descending order of removal efficiency, (1) CCS and (2) energy/process The fact that the CO2 concentration in the vents is high makes CCS Process (i.e., combustion in the primary reformers) efficiency methods.

a potentially technically feasible option. technically feasible. 4.2.2.1

efficiency methods that minimize the formation of CO, and thus, CO2, are also considered

Carbon Capture and Sequestration

CCS involves capturing CO2, transporting it, as necessary, and permanently storing it instead of releasing it into the atmosphere. 4.2.2.1.1 Capture

Isolation of relatively pure CO2 is technically feasible since the existing gas stream has a CO2 concentration of 91%. Some additional concentration of the CO2, as well as the removal of water, will be required, which is also technically feasible.
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.2.2.1.2

Transportation

Long-term carbon storage is possible only in a very limited number of sites in the southeastern US and the US Nitrogen site is not a suitable storage location. Accordingly, the captured CO2 must be transported to a suitable storage site in order to achieve any environmental benefit. Pipelines are the most common method for transporting large quantities of CO2 over long distances. Approximately 3,600 miles of CO2 pipeline operate today in the United States. These pipelines generally carry CO2 from naturally-occurring underground reservoirs, natural gas processing facilities, NH3 manufacturing plants, and large coal gasification projects to oil fields. Pipeline transportation of CO2 is typically accomplished with CO2 that is compressed to pressures of 1,200 to 2,000 pounds per square inch. This compression requires high levels of energy consumption. In addition, water must be eliminated from CO2 pipeline systems, as the presence of water results in formation of carbonic acid, which is extremely corrosive to carbon steel pipe. The primary compressor stations are located at the CO2 source and at the storage site with booster compressors located as needed along the pipeline. In overall construction, CO2 pipelines are similar to natural gas pipelines, requiring the same attention to design, monitoring for leaks, and protection against overpressure, especially in populated areas. All of these technical issues can be addressed through modern pipeline construction and maintenance practices; therefore, transporting the CO2 from the CO2 vents at the US Nitrogen facility is considered technically feasible. 4.2.2.1.3 Storage

There are several options for permanent storage of CO2. They include gaseous storage in various geological formations (including saline formations, exhausted oil and gas fields, and un-mineable coal seams), liquid storage in the ocean, and terrestrial sequestration. Liquid storage in the ocean was not considered in this analysis since the US Nitrogen facility location is at least 300 miles from the ocean. 4.2.2.1.3.1 Geologic Formations

The geologic formations considered appropriate for CO2 storage are layers of porous rock deep underground that are capped by a layer or multiple layers of non-porous rock above them. In this application, a well is drilled down into the porous rock and pressurized CO2 is injected into it. Under high pressure, CO2 turns to liquid and can move through a formation as a fluid. Once injected, the liquid CO2 tends to be buoyant and will flow upward until it encounters a barrier of non-porous rock, which can trap the CO2 and prevent further upward migration.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

The degree to which a specific underground formation is amenable to CO2 storage can be difficult to determine. Research is being performed today which is aimed at developing the ability to characterize a formation before CO2 injection in order to predict its CO2 storage capacity. Discussed below are the geologic formations that have some potential for application to the US Nitrogen facility. 4.2.2.1.3.1.1 Depleted Oil and Gas Reservoirs In general, they are

These are formations that held crude oil and natural gas at some time.

characterized by a layer of porous rock with a layer of non-porous rock which forms a dome. This dome offers great potential to trap CO2 and makes these formations excellent storage opportunities. As a value-added benefit, CO2 injected into a depleting oil reservoir can enable recovery of additional oil and gas, because when it is injected into a depleted oil bearing formation, the CO2 dissolves in the trapped oil and reduces its viscosity. This improves the ability of oil to move through the pores in the rock and flow with a pressure differential toward a recovery well. It is estimated that 50 to 90 billion metric tons of storage potential exists in mature oil and gas reservoirs identified by the Regional Carbon Sequestration Partnerships (RCSPs). and four Canadian provinces. Formed by the US Department of Energy in 2003, the seven Partnerships span 40 states, three Indian nations, According to the Southeast Regional Carbon Sequestration Partnership (SERCSP), there are no known oil or gas reservoirs providing CO2 sequestration opportunities within the immediate vicinity of the US Nitrogen facility in Greene County, Tennessee, but there may be some potential storage capacity in southwestern Virginia, approximately 100 miles from the facility. Although no extensive investigation has been undertaken, these oil fields potentially provide a storage opportunity that can be considered technically feasible. 4.2.2.1.3.1.2 Un-Mineable Coal Seams

Un-mineable coal seams are those that are too deep or too thin to be mined economically. All coals have varying amounts of CH4 adsorbed onto pore surfaces, and wells can be drilled into un-mineable coal beds to recover this coal bed CH4 (CBM). Initial CBM recovery methods, dewatering and depressurization, leave an appreciable amount of CBM in the reservoir. Additional CBM recovery can be achieved by sweeping the coal bed with nitrogen or CO2, which preferentially adsorbs onto the surface of the coal, releasing the CH4. It is estimated that 150 to 200 billion metric tons of CO2 sequestration potential exists in un-mineable coal seams identified by the RCSPs. According to SERCSP, none of these seams are in the vicinity of the US Nitrogen facility, but there may be some potential storage capacity in un-mineable seams of the central Appalachian coal basin of southwestern Virginia, approximately 100 miles from the facility.
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Although no extensive

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

investigation

has

been

undertaken,

these

un-mineable

coal

seams

potentially

provide

a sequestration opportunity that can be considered technically feasible. 4.2.2.1.3.1.3 Saline Formations

Saline formations are layers of porous rock that are saturated with brine. They are much more commonplace than coal seams or oil and gas bearing rock, and represent an enormous potential for CO2 storage capacity. The RCSPs estimate a range of 3,300 to 12,000 billion metric tons of sequestration potential in saline formations. However, much less is known about saline formations than is known about crude oil reservoirs and coal seams, and there is a greater amount of uncertainty associated with their ability to store CO2. Saline formations contain minerals that could react with injected CO2 to form solid carbonates. The carbonate reactions have the potential to be both a positive and a negative. They can increase permanence but they also may plug up the formation in the immediate vicinity of an injection well. Additional research is required to better understand these potential obstacles and how best to overcome them. Such saline formations do not exist in the vicinity of the US Nitrogen facility, but according to SERCSP, there may be some potential storage capacity in the Mt. Simon basin of middle Tennessee, approximately 125 miles from the facility. technically feasible. Based on this analysis of geologic storage options, it is clear that the CO2 from the CO2 vents at the US Nitrogen facility would have to be transported by pressurized pipeline at least 100 miles. Based on Figure 4.3 of the IPPC Special Report on Carbon Dioxide Capture and Storage (page 191), the initial investment for just the pipeline, not including booster stations and not accounting for the hilly, mountainous terrain of northeast Tennessee and southwestern Virginia, ranges from $400,000 to $1,000,000 per kilometer. Based on a pipeline 160 kilometers long, the investment just for the US Nitrogen pipeline would be at least $64,000,000 which is equal to an annualized cost of approximately $10,225,000. At this annual cost, the cost per ton of CO2 transported would be about $115. For this reason, transport of the CO2 from the US Nitrogen CO2 vents to a geologic formation was determined to be economically infeasible and no further analysis of storage in geologic formations was conducted. Although no extensive investigation has been undertaken, these oil fields potentially provide a sequestration opportunity that can be considered potentially

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.2.2.1.3.1.4

Terrestrial Ecosystems

Terrestrial sequestration is the enhancement of CO2 uptake by plants that grow on land and in freshwater, as well as the enhancement of carbon storage in soils where it may remain more permanently stored. Terrestrial sequestration provides an opportunity for relatively low-cost CO2 emissions offsets. Examples include tree-plantings, no-till farming, and forest preservation. To date, there are no actual commercial applications of terrestrial sequestration of a CO2 stream of 90,000 tons per year, therefore, the terrestrial sequestration option was considered technically infeasible and was not further evaluated as BACT. 4.2.2.2 Proposed BACT

Based on this analysis of CCS, a CO2 emission limit of 45,394.3 TPY using process (i.e., combustion) efficiencies in the primary reformers (see Section 4.2.1.1) is proposed as BACT. This would apply to both Trains 1 and 2 of the Ammonia Plant. (See Appendix B for a detailed description of the basis for this limit.) 4.2.3 N2O Emissions from the Nitric Acid Plant N2O is an unwanted by-product of the manufacture of nitric acid. It is formed alongside the main, desired product during the catalytic oxidation of NH3 in air over noble metal gauzes. a potent greenhouse gas with a Global Warming Potential (GWP) of 310. The production of nitric acid takes place in three main process steps as indicated by the following reactions: 1. NH3 combustion to form NO: N2O is

NH3 is reacted with air on noble metal catalyst in the oxidation section of nitric acid plants. Nitric oxide and water are formed in this process according to the following equation: 4NH3 +5O2 4NO+6H2O Simultaneously, N2O, nitrogen and water are formed as well, in accordance with the following equations: 4NH3 +3O2 2N2 +6H2O 4NH3 +4O2 2N2O+6H2O
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

NO yield depends mainly on pressure and temperature in the NH3 oxidation process and usually is in a range of 95% to 97%. 2. NO is oxidized to nitrogen dioxide (NO2): 2NO+O2 2NO2 3. Absorption of NO2 in water to form nitric acid (HNO3): 3NO2 + H2O 2HNO3 + NO

Based on similar nitric acid plant designs where the N2O has been measured with no reduction systems installed, it is estimated that the N2O formation across the NH3 oxidation catalyst at the US Nitrogen plant will be on the order of 1,500-1,800 ppm. Therefore, this is the concentration used in this analysis as the uncontrolled concentration. 4.2.3.1 There N2O Reduction Methods are three categories of control technologies/methods available for reducing

the N2O concentration in this emission source. These three categories are, in descending order of removal efficiency: (1) tertiary, (2) secondary and (3) primary controls. Tertiary controls/methods reduce N2O by installing a catalytic reactor either upstream or downstream of the tail gas expansion unit following NH3 oxidation. Tertiary processes can be further broken down into two technologies/methods. Catalytic reduction uses a hydrocarbon over a noble metal catalyst to chemically reduce all the oxygen in the tail gas, including the chemical oxygen (i.e., NO, N2O and NO2), while catalytic decomposition uses a specially formulated catalyst to chemically decompose the N2O to nitrogen and oxygen. Secondary controls/methods reduce N2O immediately after it is formed in the NH3 oxidation step. This control/method employs a specially formulated catalyst to decompose the N2O to nitrogen and oxygen.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

Primary controls/methods reduce the amount of N2O formed in the NH3 oxidation step. This is accomplished by modifying the catalyst used in the oxidation process and/or modifying the operating conditions of the process.

4.2.3.1.1

Primary Controls/Methods Upon leaving the NH3 oxidation

Primary reduction is accomplished in the following manner.

reactor, some of the N2O is destroyed in the part of the plant upstream of the absorption tower by high temperature homogeneous gas phase decomposition and by catalytic decomposition on platinum deposits formed from metal lost from the NH3 oxidation catalyst. This takes place in all nitric acid plants and can be enhanced by providing residence time at elevated temperatures above 800oC. For the US Nitrogen nitric acid plant, this reduction method can reduce the N2O from 1,500-1,800 ppm to approximately 500 ppm. It has been assumed that once the reactant gas is lowered to less than 500oC, all N2O reduction ceases and the N2O acts as an inert gas through the rest of the process and is discharged in the exhaust stack with the rest of the tail gas, which is mainly nitrogen. Primary control is considered technically feasible for the US Nitrogen nitric acid plant. 4.2.3.1.2 Secondary Controls/Methods This secondary reduction takes place across a catalyst that is

Secondary N2O reduction is classified as a reducing step that takes place directly underneath the NH3 oxidation catalyst. the NH3 oxidation reactor. With this secondary reduction process, the reactor design must take into account design parameters that limit catalyst loss and hold NH3 bypassing to a minimum. Also, with secondary reduction, the NH3 oxidation reactor design must incorporate the needed volume for the placement of the reducing catalyst directly below the platinum gauze. This is very costly because the reactor design must be more robust to handle the higher pressure drop across the NH3 oxidation reactor. Higher pressure drop across the reactor lowers the usable life of the reactor and causes bypassing of NH3 around the platinum catalyst. NH3 bypassing occurs when the clearances in the reactor catalyst hold-down system become distorted beyond the ability of gasketing. NH3 will bypass the platinum catalyst and the secondary reaction of NH3 to nitrogen and water
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specially formulated to selectively reduce N2O and to not affect the NO that is produced in

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

will take precedence over formation of NO. This bypassing leads to adverse reactions that lower the NH3 conversion efficiency. As mentioned earlier, the US Nitrogen facility will make use of existing nitric acid plant equipment which is being re-located to the Greene County facility. It is not practical to incorporate the changes to the plant design that would be required for secondary control, therefore, secondary control is not considered technically feasible for the US Nitrogen nitric acid plant. 4.2.3.1.3 Tertiary Reduction

Tertiary reduction of N2O occurs in the tail gas stream prior to the tail gas entering the hot gas expander. The tail gas, containing approximately 500 ppm of N2O, enters a reactor where the gas is contacted with a specially formulated catalyst. acid plants in the past to reduce NOX. With NSCR, a reagent fuel, such as natural gas, is used to reduce both NOX and N2O over a catalyst to produce N2 and water. Catalysts for NSCR are usually based on platinum, vanadium pentoxide, iron oxide or titanium. NSCR systems require a minimum inlet temperature of 900F to ignite natural gas. As its name implies, NSCR is non-selective catalytic reduction, meaning that it reduces all oxidized components in the tail gas. Consequently, to preferentially reduce NOX and N2O in the gas stream, all of the free oxygen must first be reduced. This oxygen reduction is an exothermic process which produces about 295F per 1% of oxygen destroyed. The US Nitrogen nitric acid plant will have an inlet tail gas free oxygen concentration of 2.9%, the reduction of which would add about 855F to the gas stream. Since this would result in a tail gas temperature well above any catalyst operating temperature, the tail gas would have to be cooled prior to entering the NSCR. NSCR has a N2O reduction efficiency of 80-95%. With NSCR systems, most of the hydrocarbons from the natural gas are converted to CO2 and CO, resulting in additional emissions of 6,000-7,000 ppm CO2 and 300-400 ppm of CO, as well as some 10-20 ppm of unburned hydrocarbons. With catalytic decomposition, no additional reducing agents or additives are required and no undesirable by-products, such as CO2, CO, or unburned hydrocarbons are emitted. The basis of decomposition technology is to decompose the N2O to form N2 and O2. A catalyst is used to drive the decomposition. This catalyst is stable in the presence of NOX and NH3, allowing placement either upstream or downstream of an SCR used to reduce NOX. Catalytic decomposition is also
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Tertiary reduction technologies fall into

two categories catalytic reduction and catalytic decomposition. NSCR has been used in nitric

PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

easier to operate than NSCR and begins reducing N2O during plant startup much earlier than does NSCR. Both of the tertiary processes described above are considered technically feasible for the US Nitrogen nitric acid plant. 4.2.3.2 Economic Analysis Detailed

Based on the foregoing description of the technically feasible options for control of N2O emissions from the US Nitrogen facility, a financial comparison of the options was conducted. the analysis.
Table 4-7 Financial Comparison of Nitric Acid Plant N2O Reduction Options1 Primary Tertiary Reduction Tertiary Reduction Reduction Using NSCR Using Catalytic Decomposition Inlet N2O (TPY) 2,047.0 581.4 581.4 Outlet N2O (TPY) 581.4 24.1 29.1 Reduction Efficiency (%) 72 96 95 N2O Removed (TPY) 1,465.6 557.3 552.3 N2O Removed (TPY CO2e) 454,336 165,9222 171,232 Total Capital Investment ($) $189,980 $379,960 $2,255,932 Capital Recovery Cost ($/yr) $30,351 $60,703 $360,411 O&M Annual Expense ($/yr) $76,584 $166,295 $270,572 Total Annual Cost ($/yr) $106,936 $226,998 $630,983 Cost of CO2e Removed ($/T) $0.24 $1.37 $3.69

financial analysis worksheets are included in Appendix G, while Table 4-7 summarizes the results of

Notes:
1. 2.

See Appendix G, Tables G-8 through G-10 for detailed financial worksheets. As a result of the combustion of the natural gas in the NSCR, an additional 6,841 TPY of CO2 is produced. Therefore, the net CO2e removed is 172,763 TPY N2O as CO2e minus 6,841 TPY CO2 produced.

As can be seen from Table 4-7, primary controls have the lowest cost per ton CO2e removed, while tertiary controls have the highest. 4.2.3.3 Energy Impacts

NSCRs consume electrical energy and natural gas. The additional electrical usage attributable to N2O reduction is estimated to be 7.5 MWh/yr, while the additional natural gas consumed that is attributable to N2O reduction is estimated to be 23 MMscf/yr (23,460 MMBtu/yr). Catalytic decomposition requires an additional 385 MWh/yr in electrical usage.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

4.2.3.4

Environmental Impacts

NSCRs consume natural gas. The additional electrical usage of both NSCR and catalytic decomposition will result in the indirect emission of NOX, SO2, and CO2 from the generation of electricity. As stated earlier, with the NSCR system, most of the hydrocarbons from the natural gas are converted to CO2 and CO, resulting in additional emissions of 6,000-7,000 ppm CO2 and 300-400 ppm of CO, as well as some unburned hydrocarbons. However, as noted earlier, NSCR reduces both N2O and NOX. 4.2.3.5 Proposed BACT

To determine the economic reasonableness of each of the control options evaluated in Table 4-7, a comparison was made of the cost per short ton of CO2e removed for each option to the price of Carbon Financial Instruments (CFIs) traded on the Chicago Climate Exchange (CCX) over the past year (mid-May 2010 through mid-May 2011). It should be noted that trades on the CCX are generally based on voluntary reductions. the CCX is $1.51/short ton CO2e. The average price traded over the past year on This average price was based primarily on trades of offsets

such as agricultural CH4 offsets, agricultural soil offsets, coal mine CH4 offsets, forestry offsets, fuel switching offsets, landfill CH4 offsets, organic waste disposal CH4 offsets, and renewable energy offsets. For comparative purposes, the current value of Certified Emission Reductions (CERs) in Europe (where GHG emission reductions are mandated) on the Intercontinental Exchange (ICE) is approximately $11.50/short ton CO2e. Based on this analysis, the per ton cost of primary control, as well as that of tertiary control using NSCR, are within the range of prices per ton of CO2e currently being traded in the voluntary US market. Although the cost per ton to reduce N2O using NSCR is lower than the cost of making an equal reduction using catalytic decomposition, US Nitrogen strongly prefers to use catalytic decomposition. Catalytic decomposition systems are much easier to operate, require no consumption of additional resources like natural gas, result in no additional direct emissions of pollutants (CO, CO2, and unburned hydrocarbons), and are much quicker and easier to operate during startup and shutdown. Consequently, a N2O emission limit of 29.1 TPY (9,021 TPY CO2e) using a combination of the primary controls described above and catalytic decomposition is proposed as BACT. the nitric acid plant. This approach will result in about a 98% reduction in N2O emissions from

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

5.0

AIR QUALITY ANALYSIS

An air quality modeling analysis was conducted to assess the ambient impacts from the proposed project. This analysis satisfies the regulatory requirements for: Source Impact Analysis of 40 CFR 52.21(k), and Air Quality Analysis of 40 CFR 52.21(m).

The source impacts analysis requires a demonstration that the project will not cause or contribute to a violation of a NAAQS or any applicable maximum allowable increase over the baseline concentration (increment). Air quality analysis requirements address the potential requirement for preconstruction ambient air quality monitoring. The air quality analysis quantifies only the impacts of the pollutants that are emitted in amounts in excess of PSD significant emission levels. For the proposed project, NOX emissions will be emitted in significant quantities and were therefore evaluated in the modeling analysis. Only the emissions from the proposed new facility were initially evaluated in the Source Impact Analysis of 40 CFR 52.21(k) and Air Quality Analysis of 40 CFR 52.21(m) for determining if the project significantly impacted local air quality. The resultant modeled concentrations were In addition, there are Class I areas are compared to the ambient significance levels for Class II areas.

six Class I areas that are located within 300 km of the US Nitrogen facility. and are afforded a greater degree of air quality protection. Class II areas.

pristine areas (e.g., National Parks and Wilderness Areas) that have been designated by Congress All other areas are designated as

The FLMs were contacted and, based upon project emissions and distance from the nearest Class I area, they determined that a more detailed evaluation was not required. However, there are several receptors at the Great Smoky Mountain National Park that are less than 50 km (but greater than 45 km) from the proposed site. As a result, these receptors were modeled to determine if there would be any NO2 or plume impacts at this park. The results of this significant impacts analysis demonstrate that the proposed project will result in ambient impacts of NOX in excess of Class II significance levels. Therefore, a refined air quality analysis to calculate concentrations for comparison to the NAAQS and increments was required for this pollutant. NAAQS and increment impacts were determined to be acceptable. NO2 Class I impacts were determined to be less than significant. In addition, the near-field visibility analysis
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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

results demonstrate that visibility is will not be affected. Furthermore, the preconstruction ambient monitoring exemption levels were determined not to be exceeded. A more detailed description of the modeling procedures and results is presented in Appendix C.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

6.0

ADDITIONAL IMPACT ANALYSIS The depth of the analysis

PSD regulations require an additional impacts analysis of each pollutant emitted by a source, including the analysis of the effects on local soils and vegetation. the sensitivity of local soils and vegetation. performed generally depends on existing air quality, the quantity of air emissions, and Greene County is currently as an attainment or unclassified area with respect to each criteria pollutant NAAQS. Based on the results of modeling discussed in Section 5.0 Air Quality Analysis and in Appendix C, this project will not result in ambient air quality impacts above any of the PSD significance levels and all pollutant concentrations beyond the facility boundary are below their applicable de minimis monitoring levels. 6.1 Growth Analysis

Air quality impacts projected for the area as a result of general commercial, residential, industrial, and other growth associated with this project are expected to be insignificant. Greene Country experienced a 9.4% growth in population during the past decade, bringing the total population to 68,831. The US Nitrogen facility, when fully operational, will employ approximately eighty employees; thus, a maximum of eighty new households could be added to the surrounding communities, including Greene County. Such a population increase would add <0.5% to Greene Countys total population. Due to the nature of the project and projected population increases, US Nitrogen anticipates negligible emissions from associated growth in the local area. 6.2 Soils Analysis

Because most air pollutants are ultimately deposited primarily upon soil, the potential impact of these pollutants on terrestrial ecosystems is important. Pollutant emissions can impact the soil, ground and surface waters, and plant growth. In some cases these pollutants can accumulate in the soil system or become concentrated in plants and animals. In other instances, these pollutants may cause leaching of soil nutrients (e.g., acid deposition) or contribute to nutritional imbalances in plant communities (e.g., excessive nitrogen deposition). The NOX emissions from the facility are not expected to have any significant impact on soils that would affect vegetative growth or chemical composition of the soil. The site is located in Greene County, Tennessee, near the Midway community, in

the Mosheim Geological Quadrangle. Land use in the immediate vicinity of the plant varies widely, being primarily industrial to the north of the site, residential to the south and east, and agricultural to the west.

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0

Soils in the immediate vicinity of the plant site are predominately well to intermediately drained Dunmore and Dandridge loams composed of silts and shaly and cherty clays. the Great Valley are predominately Statler shaly silt loams. are 12-30%. It is not anticipated that soils in the area would be adversely impacted by any of the additional emissions resulting from the project. 6.3 Vegetation Impacts Soils along There are some steep slopes to

the eastern site boundary along the ridgeline (up to 60%), but generally slopes in the area

Total pollutant impacts from this project are not expected to approach threshold levels for pollutant damage to vegetation in the area. The potential impacted vegetation is mostly residential and forest vegetation. The NOX maximum modeled 1-hr impact of 56.7 g/m3 is 6% of the maximum hourly screening concentration of 940 g/m3.
3

The screening concentration level for NOX is

3,760 g/m over a 4-hour period as listed in A Screening Procedure for the Impacts of Air Pollution

Sources on Plants, Soils, and Animals (US EPA, Dec 1980). All other criteria pollutants do not
require such assessment due to their insignificant emission rates. Most of the designated vegetation screening levels are equivalent to or less stringent than the NAAQS and/or PSD increments; therefore, satisfaction of NAAQS and PSD increment assures compliance with sensitive vegetation screening levels. Acute levels of pollutants demonstrated to cause plant growth effects are not anticipated to be approached as a result of facility emissions. Furthermore, chronic pollution effects, either direct effects or possible effects from secondary pollutants formed such as ozone, are not anticipated. This is due to the low increment in pollutant loading that is anticipated to result from the emissions. Specifically, the following table characterizes injury threshold concentrations for NOX for plants native to the Southeastern United States:

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PSD Permit Application US Nitrogen Midway, Tennessee August 2011, Revision 1.0
Table 6-1 Injury Threshold Concentrations for NOX Common Name Scientific Name NOX Bryophyte (moss) Various Bryophyte sp. 65 (24 hours) Birch Betula sp. 120 (chronic) Common Sunflower Helianthus annuals 375 (chronic) Alfalfa Medicago sativa 1,000 (5 hours) >5,240 (1 hour) Peach Prunus persica >2,100 (3 hours) Garden Pea Pisum sativum 850 (7 hours) Cultivated Tobacco Nicotiana tabacum 2,000 (3.5 hours) Perennial ryegrass Lolium perenne 125 (chronic)

Note:

Source: World Health Organization, 2000

With a modeled 1-hour maximum impact 56.7 g/m3, US Nitrogen will not surpass even the lowest threshold of impact 65 g/m3 for 24 hours for common moss. As such, US Nitrogen will not have a significant impact or cause injury to nearby vegetation.

6-3

Appendix A Application Forms

Appendix B Emission Calculations

Appendix C Air Dispersion Modeling and Class II Visibility Analysis

Appendix D Correspondence with Federal Land Managers

Appendix E RBLC Search Summary Tables

Appendix F Austin Powder Cost of Capital

Appendix G BACT Financial Analysis Worksheets

Office of Air and Radiation

October 2010

AVAILABLE AND EMERGING TECHNOLOGIES FOR REDUCING GREENHOUSE GAS EMISSIONS FROM THE NITRIC ACID PRODUCTION INDUSTRY

Available and Emerging Technologies for Reducing Greenhouse Gas Emissions from the Nitric Acid Production Industry

Prepared by the Sector Policies and Programs Division Office of Air Quality Planning and Standards U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711

October 2010

Table of Contents Abbreviations and Acronyms Introduction Description of the Nitric Acid Production Process N2O Emissions and Nitric Acid Production Process Summary of Control Measures Primary Controls Secondary Control Tertiary Controls Selective Catalytic Reduction Energy Efficiency Improvements EPA Contacts References Appendix A Southeast Idaho Energy Appendix B - US Nitric Acid Plants Appendix C CDM Monitoring Reports p.1 p.2 p.2 p.5 p.5 p.7 p.7 p.9 p.12 p.13 p.15 p.16 p.18 p.19 p.21

II.

III.

Abbreviations and Acronyms atm BACT Btu Btu/lb CAR CDM CHP CO2 CO2e EU GHG H2 IPCC IPPC JI kg N2O/tonne kg CO2e/tonne lb N2O/ton MTPD N2 NH3 NO NO2 NOx NSCR N2 O4 N2O O2 PSD SCR TPD Pressure in atmospheres Best Available Control Technologies British Thermal Unit Btu per lb of 100% nitric acid Climate Action Reserve Clean Development Mechanism Combined Heat and Power Carbon dioxide Carbon dioxide equivalent European Union Greenhouse Gases Hydrogen Intergovernmental Panel on Climate Change Industrial Pollution Prevention and Control Joint Implementation kilograms of N2O per tonne of 100% nitric acid kilograms of CO2e per tonne of 100% nitric acid pounds of N2O per ton of 100% nitric acid Million tons per day Nitrogen Ammonia Nitric oxide Nitrogen dioxide Nitrogen oxides Nonselective Catalytic Reduction Nitrogen tetraoxide Nitrous oxide Oxygen Prevention of Significant Deterioration Selective Catalytic Reduction Tons per day

I. Introduction This document is one of several white papers that summarize readily available information on control techniques and measures to mitigate greenhouse gas (GHG) emissions from specific industrial sectors. These white papers are solely intended to provide basic information on GHG control technologies and reduction measures in order to assist States and local air pollution control agencies, tribal authorities, and regulated entities in implementing technologies or measures to reduce GHGs under the Clean Air Act, particularly in permitting under the prevention of significant deterioration (PSD) program and the assessment of best available control technology (BACT). These white papers do not set policy, standards or otherwise establish any binding requirements; such requirements are contained in the applicable EPA regulations and approved state implementation plans. II. Purpose of this Document

This document provides information on control techniques and measures that are available to mitigate greenhouse gas (GHG) emissions from the nitric acid production industry at this time. Because the primary GHG emitted by the nitric acid production industry is nitrous oxide (N2O), the control technologies and measures presented in this document focus on this pollutant. While a large number of available technologies are discussed here, this paper does not necessarily represent all potentially available technologies or measures that that may be considered for any given source for the purposes of reducing its GHG emissions. N2O has a global warming potential that is 310 times that of CO2 due to its long atmospheric lifetime relative to carbon dioxide. The information presented in this document does not represent U.S. EPA endorsement of any particular control strategy. As such, it should not be construed as EPA approval of a particular control technology or measure, or of the emissions reductions that could be achieved by a particular unit or source under review. As of the date of this document, the only known BACT determination for GHG emissions in the nitric acid industry was made by the State of Idaho on November 30, 2009. The agency issued a Permit To Construct for the Southeast Idaho Energy, LLC plant Advanced Energy Center in American Falls, Idaho. More details on this determination are contained in Appendix A.

Description of the Nitric Acid Production Process (U.S. EPA, AP-42 Background Report) There are two different nitric acid production methods: weak nitric acid and high-strength nitric acid. The first method utilizes oxidation, condensation, and absorption to produce nitric acid at concentrations between 30 and 70 percent nitric acid. High-strength acid (90 percent or greater nitric acid) can be produced from dehydrating, bleaching, condensing, and absorption of the weak nitric acid. The basic process technology has not changed over time. Most US plants were built between 1960 and 2000. There are presently 39 active weak nitric acid production plants and one high-strength nitric acid production plant. These plants are listed in Appendix B.
2

Also, additional information is contained in, "Technical Support Document for the Nitric Acid Production Sector: Proposed Rule for Mandatory Reporting of Greenhouse Gases, January 22, 2009.

Weak Nitric Acid Production Weak nitric acid is produced by a three-step high-temperature catalytic ammonia oxidation process. An overall process flow diagram is shown in Figure 1. Each step of the process relates to a specific chemical reaction. A mixture of ammonia and water is reacted in a catalytic converter to produce nitric oxide (NO) and water. This exothermic reaction results in a 93 to 98 percent yield of NO. Higher temperatures and lower pressures result in a higher yield of NO while lower temperatures and higher pressures result in the production of more nitrogen (N2) and N2O. Oxidation temperatures typically range from 750 900 C (1,380 1,650 F). Conversion efficiency of ammonia to NO is 96 98%. (ACT p. 3-4) The heat byproduct is usually recovered and utilized for steam generation in a waste heat boiler. This steam is then used for liquid ammonia evaporation in addition to non-process plant requirements. The NO produced from ammonia oxidation is then oxidized. Residual oxygen and the NO process stream react in a cooler/condenser to form nitrogen dioxide (NO2) and nitrogen tetroxide (N2O4), a liquid dimer. This process step is temperature and pressure dependant. Low temperatures and high pressures result in better oxidation. The final step for the production of weak nitric acid is absorption. The NO2 and liquid dimer mixture are pumped into the bottom of an absorption tower, with additional liquid dimer introduced at a higher point in the tower. Deionized process water is added at the top of the absorption tower. The water flows countercurrently through the NO2/dimer mixture and absorption occurs on bubble cap or sieve trays. Any residual NO2 is removed by a secondary air stream. Weak nitric acid production utilizes either a single- or dual-stage pressure system. The most common employed method is single pressure. In a single pressure plant, air fed into the plant is compressed to the process pressure, and this single pressure is used in both the ammonia oxidation and nitrogen oxides absorption phases. Medium pressure plants operate at (4 -8 atm). High pressure plants operate at (8 14 atm). In 1991, the majority of new smaller capacity plants (< 300 TPD) used high pressure (US EPA, Dec. 1991). The dual pressure system is used because NO conversion is favored under lower pressures while NO2 and nitric acid formation are favored at higher pressures during the final reaction by combining low pressure ammonia oxidation with high pressure absorption. Ammonia oxidation is usually carried out at slightly negative pressure to about 4 atm. The reaction heat is recovered by a waste heat boiler, which supplies steam for the turbine driven compressor. After passing thru the cooler/condenser, the gases are compressed to the absorber pressure between 8 and 14 atm. In this system, the nitric acid produced during absorption is sent to an external bleacher where dissolved NO is removed. These gases are compressed and passed through the absorber. The resulting tail gas is sent back to the ammonia oxidizer, where it is heated and sent to an energy-recovery turbine. The resulting energy that is recovered is used to drive the compressor. Dual pressure plants have the advantage of superior ammonia conversion
3

efficiency i.e. less ammonia raw material is necessary to produce nitric acid. Further, dual pressure plants have a longer catalyst life, and require less frequent catalyst replacement. The disadvantage of dual pressure plants is their substantially higher capital cost for construction and installation versus single pressure plants.

Figure 1 - Process Flow Diagram for Weak Nitric Acid Production Single Pressure Source: U.S.EPA, January 1996.

High-Strength Nitric Acid Production Process High-strength nitric acid can be produced from the weak nitric acid. Figure 2 presents a process flow diagram of the high-strength nitric acid production process. The secondary production of high strength acid from weak acid is not known to result in additional N2O emissions. Sulfuric acid is fed with weak nitric acid into a packed dehydrating column. The resulting acid vapor is condensed to form 98 to 99 percent nitric acid.

Figure2ProcessFlowDiagramforHighStrengthNitricAcidProductionfromWeakNitricAcid

Source: U.S.EPA, January 1996.

N2O emissions and Nitric Acid Production Process N2O emissions from nitric acid are a byproduct of the process stream and therefore characterized as industrial process emissions. Ammonia oxidation is the main source of N2O emissions from nitric acid production. The amount of N2O formed depends on combustion conditions in the oxidizing unit, catalyst compositions, catalyst age, and burner design. The IPCC Guidelines for National Greenhouse Gas Inventories (2006) estimates that uncontrolled emissions are approximately 12 lb N2O/ton for low pressure processes, 17 lb N2O/ton for medium pressure processes, and 21.9 lb N2O/ton for high pressure processes. More details on N2O formation are contained in Perez-Ramirez, J. et al, 2003. In the US, N2O emissions contributed approximately 4.6% of total GHG emissions in 2008 in terms of CO2 equivalents. The nitric acid production process is the third largest source of N2O emissions in the US, comprising 6% of total N2O emissions or 19 million metric tons (tonnes) of CO2 equivalents (EPA 2010 Inventory).

II.

Summary of Control Measures

Table 1 summarizes the GHG control measures presented in this document. Where available, the table includes the emission reduction potential, energy savings, costs, and feasibility of each measure.

Table 1. Summary of GHG Control Measures in the Nitric Acid Production Industry
Pollutant Control Technology Emission Reduction (%) 30 - 85 70 -90 > 80 >80 Energy Savings Capital Costs ($/ton CO2e) Unknown Unknown 6.27 2.18 3.55 Operating Costs ($/ton CO2e) Unknown 0.12 0.97 0.14 0.22 0.14 1.91 Demonstrated in Practice?

N2O N2O N2O N2O

Primary Secondary NSCR Other Tertiary Controls

None None None None

Yes Yes Yes Yes

Source: EPA 2006; European Commission August 2007 Three types of controls exist for N2O at nitric acid plants based on the location of the control within the nitric acid production process: (Durilla, 2009) Primary reduces the amount of N2O formed in the ammonia oxidation step. This can be done by modifying the catalyst used in the oxidation process and/or modifying the operating conditions of this process Secondary reduces N2O immediately after it is formed in the ammonia oxidation step. Tertiary reduces N2O by installing a catalytic reactor either upstream or downstream of the tailgas expansion unit following ammonia oxidation.

The most common applied controls are secondary and tertiary controls. These control technologies employ abatement or decomposition control techniques. These technologies are capable of and typically achieve greater than 80 percent reduction of N2O emissions. A 2006 EPA economic report constructed marginal abatement curves to be used for modeling the cost of emissions reductions of non-CO2 greenhouse gases globally in the 2010 to 2020 timeframe (EPA, June 2006). In the nitric acid sector, the report utilized engineering reports to characterize catalytic reduction methods developed by several companies. The capital costs for control technology ranged from $2 to $6 per ton of carbon equivalent removed. Operating costs ranged from $0.14 to $1.91 per ton carbon equivalent removed (US EPA; June 2006). Most of the technologies discussed here were first developed in Europe to support national commitments or emissions targets established under the Kyoto Protocol. Under the recently updated European Union Industrial Pollution Prevention and Control (IPPC) Directive, member countries are required to set permit limits for N2O emissions based on the best available technologies. Controls have also been evaluated in the context of offsets programs such as
6

Climate Action Reserve (CAR), Clean Development Mechanism (CDM), and Joint Implementation (JI) under the Kyoto Protocol. Detailed descriptions on the monitoring of emissions with application of these controls at plants located world-wide are found at the United Nations Framework Convention on Climate Change website: http://unfccc.int. Information on N2O controls and related projects is available on CARs website at http://www.climateactionreserve.org/how/protocols/adopted/nap/current-nitric-acid-productionproject-protocol/. Detailed descriptions on monitoring of emissions with the application of these controls at plants located world-wide are found at the United Nations Framework Convention on Climate Change web site: http://unfccc.int. (8/13/09 email Carolyn Slaughter to Bill Neuffer). A count of the projects listed in the CDM shows 66 nitric acid lines using N2O controls at nitric acid plants outside the US. Fifty three lines use secondary controls and 13 use tertiary controls (http://cdm.unfccc.int/Projects/projsearch.html). These numbers do not include the use of nonselective catalytic reduction (NSCR) which is used in 14 process trains in the US. Also, there are at least another 10 European lines using secondary controls and 4 additional European lines using tertiary controls. (European Commission, August 2007). At an adhoc European Climate Change Programme (ECCP) stakeholders meeting, benchmark values of GHG emissions from various industries were discussed. These values represent the average performance (arithmetic mean) of the 10% most efficient installations. The value for nitric acid was 342 kg CO2e/tonne or 1.1 kg N2O/tonne or 2.2 lb N2O/ton. Units using NSCR were excluded in this calculation as units are not required to monitor other GHG (methane, CO2) that are emitted from NSCR units. (Product Benchmark, 2010). Primary Control Suppression of N2O formation One primary control is the extension of the NH3 oxidation reactor. Yara has developed and patented a technology that consists of an empty reaction chamber of approximately 10 ft in length between the platinum catalyst and the first heat exchanger. This allows an additional residence time of 1 to 3 seconds. Reductions are estimated to be 70% to 85% (4 to 6 lb N2O/ton 100% acid or about 400 ppm). This technique is applicable to new plants with low additional investments. For existing plants, costs are much higher as a new reactor may be required along with other plant modifications. (European Commission, August 2007). Another primary control is modifying the ammonia oxidation gauzes. These catalysts can be improved platinum catalysts. A few plants have shown a 30 -40 % N2O reduction. Alternative oxidation catalysts (not platinum based) can achieve 80 90% reduction but lower NO is produced. (European Commission, August 2007). Data from 14 European units with improved oxidation catalyst showed a range of 3.6 9.7 kg N2O/tonne (7.2 19.4 lb N2O/ton). The average was 6.2 kg N2O/tonne (12.4 lb N2O/ton). (European Commission, February 2008).

Secondary Control - Catalytic N2O decomposition in the Oxidation Reactor For this control, a catalyst is located immediately downstream of the NH3 oxidation step. Using this catalyst, N2O is decomposed to N2 and O2 almost instantly as shown in Equation 1. Four companies (Yara, BASF, Johnson Matthey, and Hereaus) have developed selective catalysts for the removal of N2O. The catalyst is contained in the ammonia burner and is termed selective as it promotes the reaction (1) below the decomposition of N2O to N2 and O2. No major modification of the ammonia oxidation reactor is typically required and the installation of this catalyst has shown no effect on ammonia conversion. The placement of the catalyst in the ammonia burner allows for reduction of N2O emissions by increasing the residence time of the gas in the burner. The average lifetime for the pellet catalyst is 4 years (ICAC, 2009). Up to 90% reduction is possible (ICAC, 2009) and rates of 130 to 400 ppm of N2O are achievable. Yaras system (Figure 3) was first installed in 2002 and is presently operating in 17 plants. The plants applying the secondary controls range in size from 200 to 2,650 million tons per day (MTPD). 2 N2O - 2N2 + O2 (1) One reference states this control has the lowest capital cost as minimal modifications are required to the reactor for the ammonia oxidation catalyst. There are no additional operating costs. A total of 63 process lines at nitric acid plants worldwide have implemented this technology. As drafts of this report were being prepared, no US nitric acid facility was known to have installed or applied secondary controls in the U.S. (Durilla, 2009). However, a recent article discusses a secondary catalyst being installed at El Dorados Nitrogen LPs Baytown, Texas plant (Industrial GHG, 6/17/10). The project is expected to begin operating before July 1, 2010. The facility has applied to obtain GHG emission credits under the Climate Action Reserve program. Also, Terra Industries has installed secondary catalysts in Yazoo City, Mississippi and Claremore, Oklahoma. Emission test results for secondary control were obtained from 2 sources European Commission (February 2008) and monitoring reports from CDM projects (Appendix C). These results are summarized in Table 2. The CDM includes 2 units with percent reductions (9, 39%) much lower than the other 34 units tested. Thirty of the 36 units tested had efficiencies greater than 70%. Twenty four of 36 units had efficiencies greater than 80%. Table 2. N2O Emission Test Results- Secondary Controls (lb N2O/ton)
Source Units tested Range 1.8 5.0 3.0 3.8* 0.15 11.6 Average 3.2 3.4* 4.1 EC 8 EC 4* CDM Projects 36 * With Improved oxidation catalyst % Reduction Range Unknown Unknown 9 98 % Reduction Average Unknown Unknown 76

Figure 3 Yara Secondary N2O Control from Nitric Acid Production


Source: ICAC, 2009.

Tertiary Controls Catalytic Reduction Nonselective Catalytic Reduction (NSCR) is a common control technology utilized at nitric acid production facilities to reduce NOx emissions where a reagent fuel, such as natural gas, propane, butane, or ammonia plant purge gas (mainly H2) is used as a reagent to reduce NOx, and N2O over a catalyst to produce N2 and water. Similar to a three-way catalytic converter, reductions of NOx and N2O occur while other emissions are oxidized. Catalysts for NSCR are usually based on platinum, vanadium pentoxide, iron oxide or titanium. Catalyst supports are typically made of alumina pellets or a ceramic honeycomb substrate. NSCR has a N2O reduction efficiency of 80-95 percent (European Commission, August 2007). As far as selection of a NOx control, NSCR is typically used at plants that have the capability to preheat tailgas to 200 - 450 C and requires a greater reagent input than SCR (RTI, 2009). As stated earlier, 14 process trains in the US use NSCR. These facilities have installed NSCR to control NOx emissions and as an additional benefit NSCR reduces N2O emissions. The emissions from one US plant with NSCR were 0.43 lb N2O/ton. In numerous nitric acid plants outside of the US, NSCR/catalytic reduction is used in conjunction with SCR. A European report (Fraunhofer, 2009) estimates that the average emissions from NSCR are 2.0 lb N2O/ton when the additional CO2 and methane emitted from operation of the NSCR are included. Average emissions from NSCR, according to this report, are shown in Table 3.

Table 3. Emissions from NSCR


Pollutant N2O Methane CO2 NOx NH3 50 4,500 1,000 150 100 Concentration (ppm) 0.66 1.5 0.04 Emissions (lb N2O/ton)

Uhde has developed a process referred to as EnviNOx. More details are shown in Figures 4 and 5. There are two variants of the EnviNOx process depending on the tail gas temperature. Variant 1 is discussed under the next section catalytic decomposition. Variant 2 is suitable for lower tail gas temperatures ranging from 300 to 520 C. The low temperature variant utilizes hydrocarbons, such as natural gas, to drive catalytic reduction. The reaction vessel is positioned upstream of the tailgas expander (turbine). Ammonia is mixed with the tailgas that contains both N2O and NOx. The mixture passes through a single catalyst bed where parallel reduction of the pollutants takes place. The addition of hydrocarbons to drive this reaction is not thought to produce significant CO2 emissions when compared to the reduction of N2O in the unit (Uhde, 2005). This process utilizes a tailgas reactor positioned directly upstream of the tailgas expander (turbine).

Figure 4 Uhde Combination N2O and NOX Control for Nitric Acid Production Plants Source: ICAC, 2009.

10

Figure 5 Uhde EnviNOx Reactor in Linz, Austria


Source: ICAC, 2009.

Sd-Chemie has developed an NSCR process for removal of N2O from tailgas streams. The EnviCat N2O is designed for tailgas temperatures less than 400C. This system was developed in cooperation with Uhde. A vanadium-free catalyst is used to convert N2O and NOx to nitrogen, oxygen, and water. This particular catalyst also removes the ammonia that was added to drive the reaction between the catalyst and N2O, thus preventing ammonia leakage. Conversion rates greater than 98 percent have been achieved with the EnviCat N2O system right below the platinum gauze (Sd-Chemie, n.d.). Sd-Chemie has another NSCR unit designed to reduce N2O and NOx emissions. The EnviCat unit works best for tailgas temperatures greater than 400C. This unit is a direct disintegration process with the catalyst positioned close to the reactor. Residual hydrocarbons are required in the tailgas stream to provide efficient control. Both N2O and NOx react with the hydrocarbons to break down the compounds to nitrogen and oxygen. In some cases, additional methane or hydrogen is necessary if the residual amount of hydrocarbons is too low for effective control (Sd-Chemie, n.d.).

11

Tertiary Controls Catalytic Decomposition Decomposition technology, which can be high temperature or low temperature, does not require any additional reducing agents or additives, and no undesirable byproducts are formed from the reaction. The basis of decomposition technology is to simply decompose N2O to form nitrogen and oxygen (ICAC, 2009). A catalyst is used to drive the decomposition. This catalyst is stable in the presence of NOx and ammonia, allowing placement either upstream or downstream of the SCR used to reduce NOx (ICAC, 2009). Decomposition can remove up to 99 percent of the N2O in the process stream. Uhde has developed a process referred to as EnviNOx. More details are shown in Figures 4 and 5. There are two variants of the EnviNOx process depending on the tail gas temperature. Variant 1 is discussed under this section catalytic decomposition. Variant 1 is good for higher tail gas temperatures ranging from 425 to 520 C. For these temperatures, EnviNOx is a two stage process. In the first stage, N2O is decomposed to oxygen and nitrogen in a catalyst bed. The resulting tailgas is then mixed with ammonia and enters a second catalyst bed where NOx is reduced to water vapor and nitrogen. The N2O is further removed in this catalyst bed. (Uhde, 2005 and ThyssenKrupp, 2005). Another decomposition technology is the CRI N2O Abatement Technology (C-NAT). A pellet catalyst is contained within a lateral flow reactor. The tailgas is forced laterally through the packed-bed design to achieve more efficient utilization of the catalyst surface area than traditional catalyst design. This technology works best at temperatures between 450C and 650C. Removal of N2O is typically within the range of 70-95 percent (CRI, 2009). Shell has a similar C-NAT system that operates at temperatures as low as 300C. Like the other direct decomposition systems, no additional reducing agents are required. The Shell CNAT system achieves greater than 98 percent reduction of N2O (ICAC, 2009). Emission test results for tertiary controls were obtained from 2 sources European Commission (February 2008) and monitoring reports from CDM projects (Appendix B). These results are summarized in Table 4. Table 4. N2O Emission Test Results- Tertiary Controls (lb N2O/ton)
Source EC CDM Projects Units tested 7 11 Range 0.02 0.48 0.41 2.2 Average 0.18 1.2 % Reduction Range Unknown 88 - 98 % Reduction Average Unknown 94

Selective Catalytic Reduction SCR is not an effective control technology for N2O emissions (Perez-Ramirez et al 2003). The CARs Nitric Acid Production Project Protocol elaborates that SCRs can have at least a slight unintentional impact on N2O emissions (+/- <5%) of total emissions (Climate Action Reserve, 2009).

12

Other Greenhouse Gas Emissions Nitric acid plants may also indirectly have emissions of carbon dioxide (CO2)and CH4 by consuming steam or electricity produced through the combustion of fossil fuels during startup. This is common for plants with steam powered compressors that require the use of natural gas at startup. Once the plant begins operating normally, the plant will generate enough steam to power the compressor. Also, the plant will also be able to export additional steam to the rest of the facility which offsets steam production that could be produced by burning fossil fuels. During this limited time period, carbon dioxide is produced. Also, CO2 and methane (in small amounts) can be emitted by nitric acid plants controlled by nonselective catalytic reduction (NSCR) and other catalytic reduction technologies. Estimates of these emissions were shown in Table 2. Methane is often the fuel. Combustion of methane or other organic fuels produces carbon dioxide. As far as CO2 (equivalent) is concerned, the CO2 emissions result in a less than a 2% increase in GHG compared to the 80% reduction in GHG obtained from controlling N2O emissions using NSCR. This less than 2% increase is also lowered when considering that much of the heat produced in NSCR is recovered in the expander which is then used to power the compressor which in turn powers the nitric acid plant. This reduces the amount of power needed from either a steam turbine or electric motor.

5.0

Energy Efficiency Improvements to Reduce other GHG Emissions (RTI, 2009) Energy Recovery

Nitric acid production is a net exporter of energy. Therefore, energy recovery is a valuable resource for these facilities. External sources of fuel can be minimized through recovery of energy from the production process. There are two exothermic reactions, oxidation and absorption, that produce more energy than the total production process consumes. Single and dual-pressure plants are used within the US. For new plants, dual-pressure is the most predominant design. However, there is not a substantial difference in the total energy required or recovered from the two designs. The energy requirements of controls should also be considered. As far as NOx controls, SCR units require less energy than NSCR units because they operate at lower temperatures. As shown earlier NSCR has the additional benefit of controlling N2O. The overall energy recovery is dependent on the design of the facility. Approximately 1,660 Btu/lb of 100% nitric acid (Btu/lb) is produced from the catalytic reactor. The absorption tower produces approximately 370 Btu/lb. All of this energy is potentially available for recovery. Additionally, the expansion unit has the potential to recover 80 percent of the mechanical energy used, or approximately 325 Btu/lb. This provides for an overall amount of energy available for recovery of approximately 1,955 Btu/lb. The potential CO2 equivalent emissions that are avoided by this level of steam energy recovery are 0.26 tonnes CO2e per ton of 100% nitric acid. An additional 0.77 tonnes CO2e per ton 100% nitric acid is avoided through electric energy production. However, the actual levels of energy recovery, due to economic and practical considerations, are around 50-65 percent of the theoretical values. Therefore, between 969 and 1,217 Btu/lb is available for recovery. This equates to an offset of 0.12 to 0.5 tonnes CO2e/ton HNO3.
13

Steam production is the most common form of energy recovery for process lines in nitric acid production. Heat from the process is typically recovered and used to generate a large portion of the steam needed elsewhere in the plant. During startup, natural gas is used to augment this steam when nitric acid production is at levels below those needed to recover enough steam for the rest of the facility. Although not widely practiced currently at nitric acid production facilities, bottoming cycle combined heat and power (CHP) could also be used for energy recovery at nitric acid plants. With this type of CHP system, steam would be generated from heat recovery at a higher pressure than is needed in the other processes and run through a steam turbine generator before being sent to the processes at the required pressure. The power generated could be used within the plant, offsetting power purchases from the grid. This would not result in direct CO2 reductions at the facility from the power produced, but indirect reductions from displacing grid power. The level of reduction is a function of the CO2 intensity of the displaced external power production. Energy Efficiency There are energy efficiency measures that can be implemented at nitric acid plants. These areas include building lighting and HVAC, motors, compressed air and pumps. Energy Star has not prepared an Energy Guide specific to nitric acid plants. A general guide Managing Your Energy, EPA Document #LBNL-3714E is available.

14

EPA Contacts

Bill Neuffer U.S. EPA OAQPS/SPPD/MMG Mail Code D243-02 Research Triangle Park, NC 27711 Phone: 919-541-5435 neuffer.bill@epa.gov

Nathan Frank U.S. EPA Region 5 77 W. Jackson Blvd Chicago, IL 60604 Phone: 312-886-3850 frank.nathan@epa.gov

Mausami Desai U.S. EPA OAR/OAP/CCD Washington, DC 20460 Phone: 202-343-9381 desai.mausami@epa.gov

15

References
Climate Action Reserve, October 1, 2010. List of GHG Projects . https://thereserve1.apx.com/myModule/rpt/myrpt.asp?r=111 Climate Action Reserve, December 2, 2009. Nitric Acid Production Project Protocol Reducing Nitrous Oxide from Process Gas Emissions. http://www.climateactionreserve.org/wpcontent/uploads/2009/12/Nitric_Acid_Production_Project_Protocol_Version_1.0.pdf CRI Catalysts Company (CRI), 2009. N2O Decomposition, October 2009. http://www.cricatalyst.com/products/environmental/n2o_Decomposition.aspx Durilla, Mike, 2009. NOx and N2O Control in Nitric Acid Plants, Environment Management. Air and Waste Management Association. November 2009 European Commission. August 2007. Integrated Pollution Prevention and Control. Reference Document on Best Available Techniques for the Manufacture of Large volume Inorganic Chemicals Ammonia, Acids and Fertilisers. fttp://ftp.jrc.es/pub/eippcb/doc/lvic_bref_0907.pdf European Commission. February 2008. Support for the Development and Adoption of Monitoring and Reporting Guidelines and Harmonised Benchmarks for N2O Activities for Unilateral Inclusion for the EU ETS for 2008-12. http://ec.europa.eu/environment/climat/emission/pdf/benchmarking/entec_study_2008 .pdf Fraunhofer Institute. Methodology for the free allocation of emission allowances in the EU ETS post 2012. Sector Report for the Chemical Industry. November 2009. http://ec.europa.eu/environment/climat/emission/pdf/bm/BM%20study%20%20Chemicals.pdf Institute of Clean Air Companies (ICAC), 2009. NOx and N2O Reductions in Nitric Acid Plants, PowerPoint Presentation, August 12, 2009. Industrial GHG, 6/17/2010. http://www.industrialghg.com/articleprint.jsp?article_id=6323 Perez-Ramirez, J., F Kapteijn, K. Schoffel, and J. A. Moulijn. Formation and Control of N2O in nitric acid production: Where do we stand today?. Applied Catalysis B: Environmental 44 (2003) pp 117-151. Product Benchmark State of Play. Presented at Ad-hoc ECCP Stakeholder meeting on benchmarking. Brussels. July 1, 2010.

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RTI International (RTI), 2009. Greenhouse Gas Industry Profile for the Nitric Acid Production Industry Draft Final Report, January 15, 2009, Research Triangle Park, NC. Slaughter, Carolyn. (cslaughter@icac.com), 13 August 2009. ICAC Nitric Acid Plant Presentation- Follow-up. E-mail to Bill Neuffer, (Neuffer.Bill@epa.gov). Sd-Chemie, n.d. Catalytic Emission Control for Nitric Acid Plants, Bruckmhl, Germany. http://www.sudchemie.com/scmcms/web/binary.jsp?nodeId=7106&binaryId=8671&preview=&dispo sition=inline&lang=en The Fertilizer Institute. List of Active Nitric Acid Facilities. September 9, 2009. Thyssen Krupp, 2005. Uhde EnviNOx Process for the Combined Reduction of N2O and NOx emissions from Nitric Acid Plants, Techforum, pp. 66-71, July 2005, Dsseldorf, Germany. http://www.thyssenkrupp.com/documents/Publikationen/Techforum/forum_07_05_en. pdf Uhde, 2005. Nitric Acid, Uhde and ThyssenKrupp, June 2005, Dortmund, Germany. http://www.uhde.eu/cgibin/byteserver.pl/pdf/broschueren/Duengemittel/Nitric_acid.pdf U.S.EPA. AP-42, Background Report. Nitric Acid, Fifth Edition, Section 8.8. Research Triangle Park, NC. January 1996. U. S. EPA. Alternative Control Techniques Document Nitric and Adipic Acid Manufacturing Plants. EPA-450/3-91-026. Research Triangle Park, NC. December 1991. U.S. EPA. Compilation of Air Pollutant Emission Factors, Volume 1: Stationary Point and Area Sources, AP-42, Fifth Edition, Chapter 8.8. Research Triangle Park, NC. January 1996. U.S. EPA. Global Mitigation of Non-CO2 Greenhouse Gases. EPA 430-R-06-005. Washington, DC. June 2006. U.S. EPA. Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990 2008. EPA 430-R-10-006. Washington, DC. April 15, 2010. U. S. EPA. Technical Support Document for the Nitric Acid Production Sector: Proposed Rule for Mandatory Reporting of Greenhouse Gases, January 22, 2009.

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APPENDIX A SOUTHEAST IDAHO ENERGY, LLC POWER COUNTY ADVANCED ENERGY CENTER MERICAN FALLS, IDAHO
http://www.deq.idaho.gov/Applications/NewsApp/showNews.cfm?news_id=2848&CFID=217875&CFTOK EN=16675422

The following is a summary from the press release (link) provided above, the Statement of Basis and the Permit to Construct (PTC). The facility will produce fertilizer products through the gasification of coal and petcoke. A pure H2 stream is used to manufacture ammonia which is used to produce nitrogen-based fertilizers. The nitric acid produced will be approximately 57% concentration at a rate of 575 TPD of 100% acid. A final PTC was issued on 11/30/09 for this plant. As far as the nitric acid facility at this plant is concerned, the installation of an extended absorption tower and SCR is required for NOx control. Catalytic decomposition is required for N2O control. There are NOx, NH3 and N2O and emission limits for the plant. These limits are: For NOx, reduce NOx emissions by 4.2 tpy from the Nitric Acid Plant. The NOx emission limits are 50 ppmv, 0.60 lb/T, 14.4 lb/hr, and 63.0 TPY. There is an ammonia slip limit of 10 ppmv (dry) converted to 15 % oxygen. For N2O, reduce the N2O emissions by 90% by volume from 3000 ppmv to 300 ppmv. The N2O emission limit was based on a performance guarantee by the technology provider.

18

APPENDIX B US Nitric Acid Plants


Company Apache Nitrogen El Dorado Nitrogen Cherokee Nitrogen Agrium J R Simplot PCS Nitrogen Fertlizer Rentech Koch Nitrogen Coffeyville Resource Koch Nitrogen Angus Chemical Lyondell Chemical PCS Nitrogen Fertilizer Rubicon First Chemical Dyno Nobel Agrium Koch Chemical Dyno Nobel N-Ren Corp Agrium PCS Nitrogen Fertilizer Koch Nitrogen Dyno Nobel Dyno Nobel Air Products Dupont El Dorado Nitrogen Goodpasture Invista Invista Geneva Nitrogen Agrium Dyno Nobel Parent Co City Benson El Dorado Cherokee West Sacramento Helm Augusta East Dubuque Fort dodge Coffeyville Dodge Sterlington Lake Charles Geismar Geismar Pascagoula Louisiana Beatrice Beatrice Battle Mountain Carlsbad Cincinnati Lima Enid St Helens Donora Pasadena Beaumont Baytown Dimmitt Victoria Orange Geneva Kennewick Cheyenne State AZ AR AL CA CA GA IL IA KS KS LA LA LA LA MS MO NE NE NV NM OH OH OK OR PA TX TX TX TX TX TX UT WA WY

El Dorado

Potash Corp

Potash Corp

Potash Corp

LSB Industries

Orica USA

19

APPENDIX C - Summary of CDM Monitoring Reports from


http://cdm.unfccc.int/Issuance/index.html Plant Rhodia Haifa Chemicals N2 African Explosives ONPI Fosfertil Piacaguera NAP2 Fertilizers & Chemicals Deepak Fertilisers WNA III Shijazhuang Jinshi Sasoi -Sasolburg Jinxiang Line 1 Rhodia Haifa Chemicals N2 Abonos ColombianosNAN1 Yunnan Jiehua Shijazhuang Jinshi Rashtriya Chemical Abonos ColombianosNAN2 Deepak Fertilisers WNA I Location Brazil Israel South Africa Philippines Brazil Israel India China South Africa China Brazil Israel Colombia Control 2 2 2 2 2 2 2 2 2 2 2 2 2 Test Dates 9/15/08 5/11/09 5/20/09 3/24/09 ended 9/25/2007 ended 2/22/2010 3/21/09 7/28/09 06/07 -02/08 -03/16/10 6/27/083/13/09 12/11/088/3/09 3/2/08 5/15/08 ended 1/23/2007 1/08 -10/07 -Uncontrolled (lb/ton) 9.90 23.30 8.10 8.90 9.60 13.46 10.22 12.20 19.30 14.60 11.80 13.34 13.74 Controlled (lb/ton) 0.15 0.52 0.81 0.89 1.30 1.35 1.53 1.54 1.60 1.70 1.98 2.00 2.06 Efficiency 98% 98% 90% 90% 86% 90% 85% 87% 92% 88% 83% 85% 85%

China China India Colombia

2 2 2 2

ended 11/1/2007 3/14/09 9/8/09 ended 7/21/2009 10/07 --

10.80 13.10 23.80 16.12

2.20 2.30 2.40 2.42

80% 82% 90% 85%

India

11/09 -- 3/10

17.20

2.60

85%

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Plant Rashtriya Chemical Haifa Chemicals N4 Anhui HuainanLine4 Haifa Chemicals N1 Haifa Chemicals N1 Gujarat Narmada Valley Dongbu Hannong Chemicals Sasoi - Sasolburg Donghu Hannong Chemicals Haifa - N3 Haifa Chemicals N3 plant Sasoi-Secunda Wuiashan Line 2 Chuanhua Sasoi -Secunda Chongqing Fuyan Donghu Hannong Chemicals Tianji Line 1 Tianji Line 2

Location India Israel China Israel Israel India Korea South Africa Korea Israel Israel South Africa China China South Africa China Korea China China

Control 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

Test Dates 3/14/087/21/09

Uncontrolled (lb/ton) 25.00 18.20

Controlled (lb/ton) 2.60 2.73 3.16 3.40 3.56 3.60 4.31 4.90 5.90 6.00 6.00 6.40 6.70 7.90 8.20 8.50 8.60 10.90 11.30

Efficiency 90% 85% 79% 85% 85% 71% 80% 75% 72% 62% 62% 30% 50% 79% 9% 70% 60% 51% 61%

April 2009 -5/20/09 3/24/09 1/08 -10/29/09 1/15/10 01/27/07 -03/30/10 8/10/08 12/7/08 1/8/09 10/15/09 5/25/08 2/4/09 5/25/08 2/4/09 5/2/091/31/10 6/27/08 12/29/09 06/25/07 -8/31/084/26/09 10/20/084/1810 1/4/08 5/15/08 12/18/08 7/27/08 9/21/08 5/3/09

15.04 23.30 23.72 12.50 21.56 19.30 21.40 15.70 15.70 9.10 13.40 38.00 9.00 28.20 21.40 22.20 29.00

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Plant Tianji Line 3

Location China

Control 2

Test Dates 12/31/08 8/17/09 AVERAGE

Uncontrolled (lb/ton) 20.30 17.14 13.70 24.60 12.40 16.60 26.00 18.40 14.10 18.57 22.80 21.17 31.43 19.98

Controlled (lb/ton) 11.60 4.10 0.41 0.42 0.48 0.65 0.68 0.79 0.97 1.17 2.20 2.46 3.22 1.22

Efficiency 43% 76% 97% 98% 96% 96% 97% 96% 93% 94% 90% 88% 90% 94%

Hu-Chems - 4 Hu-Chems - 3 Omnia Fertilizer PANNA 3 Enaex Hu-Chems - 2 PANNA 3 Enaex Abu Qir Fertilizer PANNA 3 Enaex Pakarab Fertilizer Hanwha Corp Kaifeng Jinkai

Korea Korea South Africa Chile Korea Chile Egypt Chile Pakistan Korea China

3 3 3 3 3 3 3 3 3 3 3

3/1/09 6/30/09 3/1/09 6/30/09 2/1/09 5/31/09 7/1/09 9/30/09 3/1/09 6/30/09 4/1/09 6/30/09 3/10/09 6/30/09 9/1/07 -6/1/09 8/31/09 1/7/07 1/7/2007 AVERAGE

22