1. Improved Nitric Acid Production via Cobalt Oxide Catalysis for use in Ammonia-based Fertilizers
University of Illinois at Chicago
Department of Chemical Engineering
CHE 397 Senior Design II
April 24, 2012
Mentor: Bill Keesom
Thomas Calabrese (Team Leader)
Cory Listner
Hakan Somuncu
David Sonna
Kelly Zenger

2. Today’s Agenda Recap of Questions from the Previous Meeting
Project Overview
Design Basis
Block Flow Diagram
Process Flow Diagram
Catalyst Choice
Environmental Issues Review
Economics
Process Safety Review
Report

3. Project Overview
The nitric acid plant will be located in the Bakken Formation of the Williston Basin, located in Northwest North Dakota.
Over 1.85 trillion cubic feet natural gas 3 3

4. Project Overview
Wellhead gas will be purified by the Gas Purification Team and sent to the Ammonia Team.
Ammonia Team will produce ammonia and send it to the Nitric Acid Team.
Nitric Acid Team will convert ammonia to nitric acid.
Nitric acid will be sent to Ammonium Nitrate Team

5. 5 5

6. Design Basis Produce 3,289 TPD of 63% wt. nitric acid solution (~14M)
Starting Reagents
Ammonia (NH3) – TPD
Air – 10,332 TPD
Products
63% wt. Nitric Acid Solution (HNO3) - 3,289 TPD
Steam (1,250 psi, 970F) – 1,843 TPD
Environmental Concerns
Oxides of Nitrogen (NOx) (<200 ppm)
Nitrous Oxide (N2O) (<200 ppm)

7. Ostwald Process Industry Standard for Nitric Acid Production
Ammonia Oxidation
Nitrogen Monoxide Oxidation
Absorption of Nitrogen Dioxide with Water
Primary Chemical Reactions
Oxidation of Ammonia to Nitrogen Monoxide 4NH3 (g) + 5O2 (g)  4NO (g) + 6H2O (g)
Oxidation of Nitrogen Monoxide to Nitrogen Dioxide 2NO (g) + O2 (g)  2NO2 (g)
Reaction of Nitrogen Dioxide to Nitric Acid 2NO2 (g) + O2 (g) + 2H2O (l)  4HNO3 (aq)

8. Block Flow Diagram 8 8

9. Process Flow Diagram

10. Benefits of Cobalt Oxide
Platinum-Rhodium
Cobalt Oxide (Co3O4)
Cost ($/short ton of HNO3 produced)
$3 - $4
$ $0.75
Lifespan
3-4 months
12 months
Downtime
4 hours to replace gauze at end of lifespan
Remove Rhodium Oxide buildup (every 3-4 weeks)
None
Conversion Efficiency
93% - 96%
95% - 98%
Operating Parameters
24-95 psi, °F
0-95 psi, °F
Use
Very common, industry standard
New, commercial use
Drawbacks
Cost, lifespan, and greater N2O formation
New reactor design, deactivation to CoO

11. Controlling N2O Release
Primary Methods-reduce N2O formed during ammonia oxidation
70-85% efficiency
Add an “empty” reaction chamber between the catalyst bed and the first heat exchanger (increase residence time)
Modify the catalyst used during the ammonia oxidation
Secondary Methods-reduce N2O formed immediately after ammonia oxidation (Selective Catalytic Reduction)
Up to 90% efficiency
Secondary catalyst is used to promote N2O decomposition by increasing the residence time in the ammonia burner
2N2O (g)  2N2 (g) + O2 (g)

12. Controlling N2O Release
Tertiary Methods-reduce N2O from or to the tail gas (Non-Selective Catalytic Reduction)
80-98+% efficiency
A reagent fuel (e.g. H2 from an ammonia plant purge) is used over a catalyst to produce N2 and water
Alternatively, following SCR the tail gas is mixed with ammonia and reacts over a second catalyst bed to give N2 and water
Catalytic Reduction : burning
Molecular sieve: Selectively absorb NO2 and return to absorption tower
Wet Scrubber: React the NOx through an aqueous solution, turns NOx into solid nitrates or salts 12

13. Economics: Materials Materials Material Requirement Base Cost
Total Cost [per year]
Air
10,344 TPD
$0.00/ton
$0.00
Ammonia Vapor
571.5 TPD
$350/ton
$73,009,125
Nitric Acid* (SOLD)
2,571.2 TPD
$220/ton
$206,467,360
Nitric Acid** (SOLD)
717.8 TPD
$300/ton
$78,599,100
Steam (SOLD)
1,843 TPD
$20/ton
$13,451,491
Cobalt Oxide Catalyst -
$0.50/ton acid
$476,454
TOTAL
+ $225,000,000/year
*Sold to Ammonium Nitrate, **Sold to Open Market 13 13

14. ICARUS Installed Costs ICARUS Yearly Operating Costs
Economics: ICARUS
ICARUS Installed Costs
Item
Cost
Equipment (Installed Cost)
$329,370,000
Piping
$1,900,000
Civil
$530,000
Steel
$100,000
Instrumentation
$1,000,000
Electrical
$2,500,000
Paint
Other
$4,500,000
G&A Overheads
Contingencies
$7,000,000
TOTAL CAPITAL COST
$348,000,000
ICARUS Yearly Operating Costs
Item
Cost
Operating Labor
$640,000
Maintenance
$905,000
Supervision
$200,000
Operating Charges
$230,000
Plant Overhead
$912,000
Utilities
$9,500,000
TOTAL
-$13,000,000/year 14 14

15. Economics: NPV Payback Period: 7 years Expected Plant Life: 20 years
Yearly Profit
Item
Cost
Materials
+$225,032,372
Operation & Maintenance
-$2,900,000
Utilities
-$9,535,283
TOTAL
Est. Profit: $213,000,000/year
Payback Period: 7 years
Expected Plant Life: 20 years
Interest Rate: 8%
Inflation Rate: 3%
Installation Time: 3 years
Installation Cost: $348 million
Net Present Value after 20 years: $984 million
Internal Rate of Return: 23.98% 15 15

16. Process Safety I
Large release of process chemicals due to catastrophic failure
Be prepared, emergency procedure with LECP
Prevention of release & associated problems :
Neutralizing materials
Initial construction of components
Release valves
Bunding, dikes
Ventilation
Fireproofing
Low release of process chemicals
Caused by operator error, poor maintenance
Large release: be prepared beforehand with in-depth study of potential hazards, evacuation plans
LEPC: Local Emergency Planning Committee:
-Write emergency plans to protect the public from chemical accidents;
-Establish procedures to warn and, if necessary, evacuate the public in case of an emergency;
-Provide citizens and local governments with information about hazardous chemicals and accidental releases of chemicals in their communities
Initial Construction: Ensure that proper materials and design specification are chosen, quality construction, equipment can handle conditions outside of the normal range of operation,
Relief valves to prevent a situation of overpressurization in the first place.
Neutralization: for nitric acid, we can either stock a weak base or use third-party materials
Operator error can include leaving a sample point open or a spill during loading and unloading 16 16

17. Process Safety II Other Safety Precautions Long-term exposure Noise
Maintain PEL and STEL as dictated by OSHA
Noise
Governed by OSHA, PEL of 90 dB
Maintain & lubricate equipment, sound barriers, limiting exposure
General protection
Insulate or guard heated surfaces on working floor
Good lighting
Railings & non-slip surfaces
Training, safety checklists
Chemical ex
Noise: 90 dB Time-Weighted Average, and above a certain threshold, we must implement Hearing Conservation Program for employees
Heated surfaces must be 7 feet from ground in areas if not guarded 17 17

18. Completed Report
Open Report

19. Summary Recap of Questions from the Previous Meeting Project Overview
Design Basis
Block Flow Diagram
Process Flow Diagram
Catalyst Choice
Environmental Issues Review
Economics
Process Safety Review
Report

20. References
Parkinson, Richard. UOP. Where Does It Go? An Introduction to the Placement of Process Equipment
Available and Emerging Technologies for Reducing Greenhouse Gas Emissions from the Nitric Acid Production Industry. U.S. Environmental Protection Agency <
Best Available Techniques for Pollution Prevention and Control in the European Fertilizer Industry, Production of Nitric Acid. EFMA < PROGRAM-10/images/EFMABATNIT.pdf>.

21. Questions?