Date: May 201 2

Subject: Statistical Evaluation of CEMS Data to Determine the NO

(Updated Memo for Final Standard) Nitric Acid NSPS Review EPA Contract No. EP RTI Project No. 02103199.000.001 From: Melissa Icenhour To: Natha n Topham

OAQPS/SPPD/M U. S. Environmental Protection Agency Research Triangle Park, NC 27711 As a result of the Section 114 I nformation Collection Request (ICR), EPA received continuous emission monitoring sy stem (CEMS) data from multiple nitric acid plants. The CEMS data represent NO X emissions from the nitric acid trains during summary o f the CEMS data received from the nitric acid trains and Table 3 . Only data from the most recent y ear was considered in the anal ys es. Some facilities only submitted one y ear of data so we onl y considered one year of data from to bias the anal ys is toward a plant with more data. As shown in Table 1 , Table 2 , and Table 3 with Selective Cataly

tic Reduction (SCR) Reduction (NSCR) , and one nitric acid train with Hydrogen Peroxide Injection (HPI ) (North Bend and Sacramento) supplied 2010 data, El Dorado Nitrogen supplied data from July 2010 through June 2011, Dy no Nobel Deer Island and PCS Geismar supplied 2009 data from Train 5, Train 4, and Train 3.

1 Statistical Evaluation of CEMS Data to Determine the NO X Emission Standard (Updated Memo for Final Standard) Nitric Acid NSPS Review EPA Contract No. EP - D - 11 - 084; Work Assignment No. 0 - 0 1

02103199.000.001 OAQPS/SPPD/M I C G (D243 - 02) U. S. Environmental Protection Agency Research Triangle Park, NC 27711

114 I nformation Collection Request (ICR), EPA received continuous emission monitoring sy stem (CEMS) data from multiple nitric acid plants. The CEMS data

emissions from the nitric acid trains during day - to - day operating conditions. f the CEMS data received from the nitric acid trains are shown in Table 1 Only data from the most recent y ear was considered in the anal ys es. Some facilities only submitted one y ear of data so we onl y considered one year of data from all submissions so as not to bias the anal ys is toward a plant with more data. , and Table 3 , we received CEMS data for three nitric acid trains with Selective Cataly

tic Reduction (SCR) , three nitric acid trains with Non - Selecti , and one nitric acid train with Hydrogen Peroxide Injection (HPI ) (North Bend and Sacramento) supplied 2010 data, El Dorado Nitrogen supplied data from July Dy no Nobel Deer Island and Agrium Ken newick supplied 2009 data, PCS Geismar supplied 2009 data from Train 5, Train 4, and Train 3. Emission Standard

114 I nformation Collection Request (ICR), EPA received continuous emission monitoring sy stem (CEMS) data from multiple nitric acid plants. The CEMS data day operating conditions. A are shown in Table 1 , Table 2 , Only data from the most recent y ear was considered in the anal ys es. Some facilities only all submissions so as not , we received CEMS data for three nitric acid trains Selecti ve Catal yt ic , and one nitric acid train with Hydrogen Peroxide Injection (HPI ) . Agrium (North Bend and Sacramento) supplied 2010 data, El Dorado Nitrogen supplied data from July supplied 2009 data,2

The CEMS data from JR Simplot were not in terms of the standard (lb NO X /ton acid) and were not supplied as hourly

averages. T he data were not directly comparable to the data from the other two nitric acid trains using NSCR so the nitric acid train at JR Simplot is not included in the anal ys es. Train 3 and Train 4 at PCS Geismar w ere not included in the anal ys e s because the train s only operat ed during 15 % of 2009. The train s did not operate at all during the months of February , March, April, May , June, July , August, and December. S ufficient data to evaluate the long term performance of controls for this analy sis were not available as there are only portio ns of 4 months of data , No CEMS data from other ye ars were supplied for Train 4. T he other ye ars of CEMS data were not used for Train 3 because th e nitric acid plant is not using a best performing SCR. According to a telephone conversation between EPA’s Bill Neuffer and Jeremy Richard of PCS Geismar, the SCR is located after the gas expander and is thus an atmospheric SCR. According to Mr. Richard, this prevents optimal mixing of gas and ammonia , leading to higher NO X emissions . He felt that the unit could be improved to meet a lower emissions limit on a consistent basis. The CEMS data include periods of startup and shutdown but exclude non - operating periods. Non - operatin g periods were indicated by the plants as “Down” or “Plant Down” for the lb/ton acid value (Agrium and El Dorado) or the flow rate of the ammonia feed was zero pounds per hour (PCS Geismar). Just before the NSPS was proposed, the EPA received CEMS data from Dy no Nobel Deer Island . T here was insufficient time to include th ese data in the analy ses prior to proposal . During the comment period, commenters noted a few mistakes in the anal ys es for the facilities that the EPA did evaluate prior to proposal . Als o, the EPA has slightly modified the NO X emissions calculation equation for the 30 - day rolling emission rate . The new equation assumes that each hour that the unit was operating during the 30 day period is weighted the same. The equation used at proposal equally

weighted eac h day

that the unit was operating regardless of how many hours during each day

the unit operated . On partial operating day s with startup or shutdown events, the methodology could have caused the emissions during those events to be weigh ted too heavily in the 30 day

rolling emission rate . As an update to the earlier memo (Docket ID EPA - HQ - OAR - 2010 - 0750 - 0082), this memo shows the 30 day

rolling emission rates used at proposal , shows how the 30 day rolling emission rates change after modifying the calculation and includes the updated calculation methodology . Also, the updated memo includes the anal ys es of data from Dy no Nobel Deer Island and Agrium Kennewick that were not included at proposal.3

By selecting an emission limit based on t he highest average of emissions data from unit with BSER (which is SCR), we ensure that this limit reflects BSER but is also achievable during all periods by

facilities that have BSER equivalent controls. As shown by Table 4 , all six units are meeting the current Subpart G NO X emission standard of 3.0 lb NO X /ton acid . A ll SCR units are meeting the proposed Subpart Ga NO X emission standard of 0.50 lb NO X /ton acid, and one NSCR unit is meeting the proposed Subpart Ga NO X emission standard of 0.50 lb NO X /ton acid . T he HPI unit is not meeting the proposed Subpart Ga NO X emission standard of 0.50 lb NO X /ton acid . In conjunction with the memo entitled Agrium North Bend Analyses , finalizing a NO X emission standard of 0.50 lb/ton NO X /ton acid is recommended .4



### Table 1. NO **X** 

### CEMS Data **from SCR -**  **controlled Nitric Acid Units Company**  **Agrium —** 

**North Bend**  **Coffeyville Resources**

**Nitrogen Fertilizers, LLC**  **El Dorado**

**Nitrogen PCS Nitrogen**  ****

**Geismar Train 3**  **PCS Nitrogen**  

** Geismar** **Train 5** Basis Hourly

averages Requested from plant but

have not received Hourly averages 15 - minute

readings 15 - minute

readings Volume of data 1 year Requested from plant but have not received 1 year 3 years (was only operational 15% of 2009) 3 years 

### Table 2. **NO X**  

### CEMS Data **from NSCR -**  **controlled Nitric Acid Units Company**  **Agrium**  

** Sacramento** **Dyno Nobel**  

** Cheyenne** **(Acid Plant 1) Dyno Nobel**  ****

**Cheyenne (Acid Plant 2)**  **Dyno**

**Nobel -**  **Deer Island**  **JR**

**Simplot PCS** 

**Nitrogen**   ** Geismar** **( Train 4**  **)**

Basis Hourly ppm NA NA 1 minute readings (lb NO X /ton acid ) Monthly

avg ppm 15 - minute

readings (lb NO X /ton acid ) Volume of data 1 year (only

operating about 50% of the year) None None 1 year 3 years 1 year (only operating 15% of the year) 

### Table 3. NO **X** 

### CEMS Data from HPI **- controlled Nitric Acid Units**  **Company Agrium**  **— Kennewick**  Basis 2 minute readings (lb NO X /ton acid) Volume of data 3 year s5



### Table **4 . CEMS Data**  **— Highest**  **Average**

**Train 30 day rolling**  **emission rate**  **-- proposal**  **(lb NO X**  **/ton acid) 30 operating day rolling**  **emission rate (lb NO**  **X /ton acid)**  PCS Geismar - Train 5 (SCR) 0.39 0.35 Agrium North Bend (SCR) 0.50 0.41 El Dorado Nitrogen (SCR) 0.37 0.37 Dyno Nobel Deer Island (NSCR) ------ 0.21 Agrium Sacramento (NSCR) 1.81 0.96 Agrium Kennewick (HPI) ------ 0.72

### Figure **1 .**  **PCS Geismar Train 5 NO X**  

### Em **ission Data**

67



### Figure **2 .**  **Agrium North Bend NO X**  

### Em **ission Data**

0 0.1 0.2 0.3 0.4 0.5 0.6**l b** **N O** **X /** **t o** **n a** **c i** **d** 

## Agrium North Bend NO **X** 

## CEMS Data

proposal - 30 day rolling emission rate final - 30 operating day rolling emission rate8



### Figure **3 .**  **El Dorado Nitrogen NO X**  

### Emission Data

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5

6/21/2010 8/10/2010 9/29/2010 11/18/2010 1/7/2011 2/26/2011 4/17/2011 6/6/2011 7/26/2011**l b** **N O** **X /** **t o** **n a** **c i** **d** 

## El Dor **ado Nitr**  **og en NO**  **X** 

## CEMS Data

proposal - 30 day rolling emission rate final - 30 operating day rolling emission rate9



### Figure 4. Dyno Nobel Deer Island NO **X** 

### CEMS Data

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5

Dec - 18 - 2008 Feb - 06 - 2009 Mar - 28 - 2009 May - 17 - 2009 Jul - 06 - 2009 Aug - 25 - 2009 Oct - 14 - 2009 Dec - 03 - 2009 Jan - 22 - 2010**l b** **N O** **X /** **t o** **n a** **c i** **d** 

## Dyno **Nobel Deer Island**  **NO X**  

## CEMS Data

final - 30 operating day rolling emission rate10



### Figure **5 .**  **Agrium Sacramento NO X**  

### CEMS Data

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

12/18/2008 2/6/2009 3/28/2009 5/17/2009 7/6/2009 8/25/2009 10/14/2009 12/3/2009 1/22/2010**l b** **N O** **X /** **t o** **n a** **c i** **d** 

## Agrium Sacr **amento NO**  **X** 

## CEMS Data

proposal - 30 day rolling emission rate final - 30 operating day rolling emission rate11



### Figure 6 **. Agrium Kennewick**  **NO X**  

### CEMS Data

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

1/7/2009 2/26/2009 4/17/2009 6/6/2009 7/26/2009 9/14/2009 11/3/2009 12/23/2009**l b** **N O** **X /** **t o** **n a** **c i** **d** 

## Agrium K **ennewick NO**  **X** 

## CEMS Data

final - 30 operating day rolling emission rate