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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

AspenTech

AspenTechs Plantelligence Solution


TM

Design
Enable the
True Potential
to be attained

Determine the
True Potential
to be achieved

Model
Operate

Manage

Evaluate
performance against
True Potential

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

The Opportunity :
Enormous Economic Returns

The
Opportunity

Industry
Average
Plantelligence

Best
Practices

True
PotentialTM
1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

Core Competencies

ERP

Design
Operate

Models

Manage

Business Process Expertise


IT Integration
Manufacturing and
Integrated Supply Chain
Expertise
Deep Process
Knowledge
Intelligent Field

OCS
Plantelligence

Electronics , Computer Engineering,


Network Communication
1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

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.
Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

SEP

AspenTech

TARGETED INDUSTRIES

Inorganic chemicals
Specialty chemicals
Mining and metals

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

Solids and Electrolytes Plus (SEP)


Process Simulator
COMP1

Phase Equilibria
Vapor-liquid-solid
VaporVapor-liquidliquid-liquidliquid-solid

R1OUT

Reactor

Databanks
Ions
Dilute electrolytes
Solids

Physical Properties
Cp, H, G, S
U
K

Plantelligence

Stream Structure
PSD moments
PSD
Ions

VAP-A

SEP1

GAS1

POWDER1

SteadySteady-state simulation
AspenPlus
Dynamic Simulation
AspenDynamics

Unit Operations
crystallizer
ion exchange
dryers
electrolytic cells

Process Models
Fertilizers
Caustics
Metals
Amines
etc.
Thermodynamic
Models
Zemaitis
Chen
Pitzer
EOS
1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

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

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

S E P Models for the Fertilizer Industry

NH3

Nitric
Acid
Ammonium
Nitrate

CO2

Urea

Phosphate Rock
Sulfur

Potash Ore
Plantelligence

Sulfuric
Potash
Acid

Potash

Diammonium
Phosphate
Phosphoric
Acid

Box Code
Red - Available
Yellow - Under development
White - Planned
1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

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
Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

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.

Achieving True Potential

AspenTech

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
Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

NITRIC ACID - PROPERTIES


Pure water - cooling water and steam
Modified RKS for polar nonelectrolyte mixtures
Electrolyte NRTL

Fine-tuned parameters high, known accuracy


Plantelligence

1998 AspenTech All Rights Reserved.

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AspenTech

Electrolyte NRTL and Chemistry


High Accuracy for thermodynamic
properties:
Vapor-liquid equilibrium
Enthalpy
Density

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

Partial Pressures of HNO3 and H2O Over Aqueous Nitric Acid


1

Partial Pressure (bar)

100C
0.1
60C
0.01

0.001

0.0001
0
Plantelligence

0.2

0.4
0.6
x (HNO3)

0.8

1
1998 AspenTech All Rights Reserved.

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AspenTech

Txy
Diagram for Aqueous Nitric Acid at 1 Atmosphere
400

Temperature (K)

390
Dew Point

380
Bubble Point

370

360

350
0
Plantelligence

0.2

0.4

0.6

x, y (HNO3)

0.8

1
1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

NITRIC ACID PLANT SECTIONS


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

Plantelligence

1998 AspenTech All Rights Reserved.

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AspenTech

Nitric Acid Flowsheet Sections


Front Section
Air
Compressor
Liquid
Ammonia

Plantelligence

Oxidation of
NH3 to NO
Vaporizers

NO Gas

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Nitric Acid Flowsheet Sections


Middle Section
NOx Gas
NO Gas

Oxidation
of
NO to NO2

Dimerization
of
NO2 to N2O4

Condensation
to form
aqueous
HNO3
Nitric Acid
Condensate

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

Nitric Acid Flowsheet Sections


Towers Section

Water
NOx Gas
Nitric Acid
Condensate

Plantelligence

Absorption
of N2O4 into
water to
form HNO3

Turbine
Expansion
Degas Product
Stream

Exhaust

Nitric Acid
Product

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Achieving True Potential

AspenTech

Countercurrent NOx Gas Cooler


NOx Gas
Coolant Out

NOx Gas
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
Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

Absorption Tower

Several vapor and liquid


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

Plantelligence

1998 AspenTech All Rights Reserved.

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Rigorous Tower Model Reactions and MassTransfer Species


Vapor Phase

Interface

Liquid Phase

mo NO(L)
N O (G) mo N O (L)
HNO (G) mo HNO (L)
H O (G) mo H O (L)
NO(G)

o 2NO
mo N O

2NO + O2
2NO2

Plantelligence

N2O4 + H2O

mo HNO

+ HNO2

1998 AspenTech All Rights Reserved.

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AspenTech

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

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

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

AspenTech

Features of AspenTechs 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
Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

Features of AspenTechs 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

Plantelligence

1998 AspenTech All Rights Reserved.

Achieving True Potential

AspenTech

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.