1

Improved Nitric Acid Production via Cobalt Oxide Catalysis for use in Ammonia-based Fertilizers

University of Illinois at ChicagoDepartment of Chemical Engineering

CHE 397 Senior Design IIApril 24, 2012

Mentor: Bill Keesom

Thomas Calabrese (Team Leader)Cory Listner

Hakan SomuncuDavid SonnaKelly 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

4

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

Project Overview

5

6

Design Basis Produce 3,289 TPD of 63% wt. nitric acid solution (~14M)

Starting Reagents Ammonia (NH3) – 571.5 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

9

Process Flow Diagram

10

Platinum-Rhodium Cobalt Oxide (Co3O4)

Cost ($/short ton of HNO3 produced)

$3 - $4 $0.50 - $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, 1490-1724 °F 0-95 psi, 1549 °F

Use Very common, industry standard

New, commercial use

Drawbacks Cost, lifespan, and greater N2O formation

New reactor design, deactivation to CoO

Benefits of Cobalt Oxide

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)

11

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

13

Economics: Materials

MaterialsMaterial 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

14

ICARUS Yearly Operating CostsItem Cost

Operating Labor $640,000Maintenance $905,000Supervision $200,000Operating Charges $230,000Plant Overhead $912,000Utilities $9,500,000TOTAL -$13,000,000/year

ICARUS Installed CostsItem Cost

Equipment (Installed Cost) $329,370,000Piping $1,900,000Civil $530,000Steel $100,000Instrumentation $1,000,000Electrical $2,500,000Paint $100,000Other $4,500,000G&A Overheads $1,000,000Contingencies $7,000,000TOTAL CAPITAL COST $348,000,000

Economics: ICARUS

15

Economics: NPV

• 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%

Yearly Profit

Item Cost

Materials +$225,032,372

Operation & Maintenance -$2,900,000

Utilities -$9,535,283

TOTAL Est. Profit: $213,000,000/year

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

17

Process Safety IIOther Safety Precautions Long-term exposure

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

18

Completed Report Open Report www.che397-nitric-acid.wikispaces.com

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. 2009. Available and Emerging Technologies for Reducing Greenhouse Gas Emissions from the Nitric Acid

Production Industry. U.S. Environmental Protection Agency. 2010. <http://www.epa.gov/nsr/ghgdocs/nitricacid.pdf>.

Best Available Techniques for Pollution Prevention and Control in the European Fertilizer Industry, Production of Nitric Acid. EFMA. 2000. <http://www.efma.org/PRODUCT-STEWARDSHIP-PROGRAM-10/images/EFMABATNIT.pdf>.

21

Questions?