Achieving True Potential ®

AspenTech®

Advanced Process Design of

Nitric Acid Plants

Ralph Grob and Paul Mathias

Aspen Technology, Inc.
4 December 1998

Presented at:
Nitric Acid Conference
Valley Lodge, Magaliesburg
3-4 December, 1998
© 1998 AspenTech All Rights Reserved.
 Achieving True Potential ®
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AspenTech’s Plantelligence Solution TM

Determine the
Design True Potential
to be achieved
Enable the
True Potential
to be attained
Model
Operate
Manage Evaluate
performance against
True Potential

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 Achieving True Potential ®
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The Opportunity :
Enormous Economic Returns

The
Opportunity

Industry Best True

Average Practices PotentialTM
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 Achieving True Potential ®
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Core Competencies

ERP Business Process Expertise

IT Integration

Design
Manufacturing and
Integrated Supply Chain
Operate Models Expertise
Deep Process
Manage Knowledge

Intelligent Field
OCS Electronics , Computer Engineering,
Network Communication
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Solids and Electrolytes Plus“

• Industry-specific layered product.
- Specialized property and equipment models
- Molecular and stream attributes (e.g., PSD)
- Standard, proven process simulations
• Expertise in targeted industries.
- We know, understand your technology
- Technology transfer, consulting and support
• Long-term commitment to customer
success.
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“ 
SEP TARGETED INDUSTRIES

• Inorganic chemicals
• Specialty chemicals
• Mining and metals

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Solids and Electrolytes Plus (SEP™)

Process Simulator
COMP1

Phase Equilibria
• Vapor-liquid-solid VAP-A Stream Structure
• Vapor-
Vapor-liquid-
liquid-liquid-
liquid-solid • PSD moments
R1OUT

• PSD
Reactor SEP1 • Ions

GAS1

Databanks Process Models

• Ions POWDER1

• Fertilizers
• Dilute electrolytes • Caustics
• Solids • Metals
• Steady-
Steady-state simulation
• AspenPlus“ • Amines
• Dynamic Simulation • etc.
• AspenDynamics“
Physical Properties
• Cp, H, G, S Thermodynamic
• U Unit Operations Models
• K • crystallizer • Zemaitis
• ion exchange • Chen
• dryers • Pitzer
• electrolytic cells • EOS
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Core Capabilities of SEP Technology

• Comprehensive strength of Aspen

Engineering suite
• Focus on engineering science of
systems containing solids and
electrolytes
• Expertise in process engineering of
target industries - inorganic
chemicals, metals and mining

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 Achieving True Potential ®
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S E P Models for the Fertilizer Industry

Nitric
NH3
Acid
Ammonium
Nitrate
CO2 Urea
Diammonium
Phosphate
Phosphate Rock
Phosphoric
Sulfuric Acid
Sulfur Potash
Acid
Box Code
Red - Available
Potash Ore Potash
Yellow - Under development
White - Planned
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Benefits of Process Modeling

• Gain a deeper understanding of the
process
• Investigate process enhancements,
safety
• Improve control
• Improve environmental compliance
• Reduce energy costs
• Utilize wide range of raw-material blends
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Benefits of Nitric Acid Modeling

• MARKET FORCES
• 80% into fertilizer industry - demand is cyclical
• OPERATIONAL CHALLENGES
• Emissions limitations are critical when demand is high
• Yield is critical when demand is low
• Ammonia oxidation is sensitive to temperature, pressure,
reactor space velocity - catalyst losses must be minimized
• Absorber must be optimized for off design and normal
conditions, and within NOx emissions limits
• CAPITAL PROJECTS
• Debottleneck absorber
• Add air compression, new columns
• Evaluate piping changes to reduce side reactions, improve
yields
Plantelligence• Add advanced or multi-variable control
™
© 1998 AspenTech All Rights Reserved.
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Challenges of Nitric Acid Modeling

• Multiple reactions occur in most equipment, including

pipes, gas coolers, heat exchangers and condensers
• Performance is flow rate and pressure sensitive
• Special physical properties are needed for nitric acid
VLE and heat of mixing calculations
• Many recycle streams for heat and power integration
• Absorption tower has rate-limited and equilibrium
vapor and liquid reactions, rate-limited mass transfer,
and cooling coils on most trays

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NITRIC ACID - PROPERTIES

• Pure water - cooling water and steam

• Modified RKS for polar nonelectrolyte mixtures
• Electrolyte NRTL

Fine-tuned parameters -
high, known accuracy
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Electrolyte NRTL and Chemistry

High Accuracy for thermodynamic

properties:
• Vapor-liquid equilibrium
• Enthalpy
• Density

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Partial Pressures of HNO3 and H2O Over Aqueous Nitric Acid

1
100°C
Partial Pressure (bar)

0.1

60°C
0.01

0.001

0.0001
0 0.2 0.4 0.6 0.8 1
Plantelligence™
x (HNO3)
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Txy Diagram for Aqueous Nitric Acid at 1 Atmosphere

400

390
Dew Point
Temperature (K)

380

Bubble Point
370

360

350
0 0.2 0.4 0.6 0.8 1
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NITRIC ACID PLANT SECTIONS

• Gas-mixing
• Ammonia oxidation
• Nitric oxide oxidation
• Absorption
• Tail-gas treatment

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Nitric Acid Flowsheet Sections

• Front Section

Air
Compressor
Oxidation of
Liquid NH3 to NO
Ammonia NO Gas
Vaporizers

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Nitric Acid Flowsheet Sections

• Middle Section

NOx Gas
NO Gas Oxidation Dimerization Condensation
of of to form
NO to NO2 NO2 to N2O4 aqueous
HNO3
Nitric Acid
Condensate

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Nitric Acid Flowsheet Sections

• Towers Section

Water
Absorption Turbine
Expansion Exhaust
NOx Gas of N2O4 into
water to
Nitric Acid
form HNO3 Degas Product
Condensate Nitric Acid
Stream Product

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Countercurrent NOx Gas Cooler

NOx Gas NOx Gas
Coolant Out Coolant In

• Problem
• Two streams exchange heat with countercurrent
flow
• One stream has two reactions
• Solution
• Model with RPLUG and specify a countercurrent
coolant
• Use a design-spec to determine the exit
temperature of the coolant

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Absorption Tower

• Several vapor and liquid

phase reactions
• Rate-limited liquid-vapor
mass transfer
• UA-limited heat transfer

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Rigorous Tower Model Reactions and Mass-

Transfer Species

Vapor Phase Interface Liquid Phase

NO(G)mo NO(L)
2NO + O2 o 2NO 2 N O (G) mo N O (L)
2 4 2 4 N2O4 + H2O mo HNO 3 + HNO2

2NO2 mo N O 2 4 HNO (G) mo HNO (L)

3 3

H O (G) mo H O (L)
2 2

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NITRIC ACID ABSORBER

• Rate-based mass transfer, chemical reaction

• Bulk vapor and liquid on each tray perfectly mixed
• Optimum set of 4 gas-phase reaction
• Mass-transfer through gas and liquid films
• Estimated heat transfer to cooling coils
• Negligible heat loss to surroundings

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NITRIC ACID ABSORBER

Four gas-phase reactions:

2NO + O2 o 2NO2
2NO2 mo N2O4
N2O4 + H2O o HNO3 + HNO2
3HNO2 o H2O + HNO3 + 2NO

Plantelligence™ © 1998 AspenTech All Rights Reserved.

 Achieving True Potential ®
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Features of AspenTech’s Nitric Acid Plant

Model
• Simultaneous rate-limited and equilibrium
reactions are modeled in pipes, heat
exchangers, and condensers
• Property models were developed using
Aspen Plus electrolyte capability
• Compressors modeled using performance
curves
• Pressure drop calculated for each piece of
equipment based on volumetric flowrate

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 Achieving True Potential ®
AspenTech®

Features of AspenTech’s Nitric Acid Plant

Model

• Model is segmented for simulation of part

of plant or entire plant
• Rigorous and efficient absorber model for
accurate absorber and plant simulations
• Special summary report of nitric acid
concentration and production rates,
cooling water usage, power requirements,
and flue gas composition

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USES OF NITRIC ACID PLANT MODEL

• Verification of plant design

• Day-to-day analysis of equipment performance
• Plant optimization - Optimize cost function subject
to equipment performance and operating
constraints
• Debottlenecking studies - is tower or compressor
limiting?

Plantelligence™ © 1998 AspenTech All Rights Reserved.