Identifying and Working with

Thermodynamic Complexities with

Two Phase Mixtures
Julie D. Kister, PE
Air Products
Process Safety
Phast and Safeti User Conference
Hershey, PA
August 23, 2016
 Agenda
•Thermodynamic issue with a model of a two Phase Mixture
• Solutions to Dealing with the Issue
•Challenges
• Path Forward for future models

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Process Model in Phast

• Phast 6.7
• Vessel/Pipe Source Model
• Two component mixture
- Two hydrocarbons
- 5% Component A
- 95% Component B
• Phast :Pressurized gas
• Process: Two Phase mixture

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Mixture Thermodynamics

• Process Runs at equilibrium

Phase Envelope
• Data for H&MB calculated using
internal AP thermodynamic model

Temperature
- Mixture is within phase envelope
Dew Line
Bubble Line
Mixture
• Problem?
- How to work with the two % Component 1

models (Phast and AP thermos)

to best represent the process?

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Two Different Thermodynamic
Models
• Mixture created in Phast for two hydrocarbons
- DIPPR Database
- Equation of State = Soave Redlich Kwong
- Pseudo-component approach to modeling a mixture
• Mixture assumed not to change during different stages of
the modeling
- Properties Calculated using simple averaging equations.
- Used in model same way as properties for a pure
component.
- Equilibrium is one temperature/pressure point
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Two Different Thermodynamic
Models
• Internal AP Thermodynamic model
- Proprietary thermodynamic model based on data and
experience working with specific materials.
- Equilibrium is a phase envelope
• Models a two-phase region
- H&MB based on AP Thermo

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First Option:
Run Phast at Equilibrium
• Changed Process Conditions so that they no longer reflected the
actual process and are not in sync with AP Thermo models.

Phase Envelope

Temperature
Dew Line

Bubble Line

PHAST
Equilibrium

% Component 1

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First Option:
Run Phast at Equilibrium
• Phast Thermo different from AP Thermo data for both setting
pressure and setting temperature.
Phase Envelope

Temperature
Dew Line

Bubble Line

PHAST
Equilibrium

% Component 1

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Second Option:
Use Pure Component in Phast
• Run Vessel Pipe Source Model using a Pure Component B
- Predominant Component in Mixture (~95%)
- Heavier hydrocarbon. Results Conservative.
• Advantage: High Level of Confidence in Pure Component
Thermodynamics.
• Disadvantage: Resulted in unrealistic increase in project
risk.
• Equilibrium different for mixture versus pure component.

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Comparison of Mixture vs Pure
Component
• Flash Fire Envelope for Mixture compared to Pure Component.

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Third Option:
Use both Phast and AP Thermo
• Flash that occurs with initial release modeled using internal
spreadsheet
- AP Thermo used for thermodynamics
- Actual mixture of hydrocarbons used for flash
• Modeled in Phast using User Defined Source Model
- Input to the model comes from the internal spreadsheet
- Phast is used to model dispersion, pool formation, rainout,
etc.
- Modeled as 100% Component B
• Only use pure component in Phast
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User Defined Source Model Input

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Third Option:
Use both Phast and AP Thermo
Identify
Thermodynamic
Complexity in PHAST

Preform Flash outside

PHAST using priority
thermodynamic data

Add data to PHAST by

inputting into a User
Defined Source Model

PHAST Models:
dispersion, pool
formation, rainout, etc.

View Results in PHAST.

Complete Analysis

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Verifying Option to use both Phast
and AP Thermo
• Method verified by ‘Case 0’
- Pure Component B case modeled using both methods
• Vessel Pipe Source model with Pure Component B
• Internal spreadsheet and User Defined Source Model in
Phast with Pure Component B
- Similar results Case 0 VPS Case 0 UDS Case 0
Phast Model Vessel/Pipe User Defined
Source Model Source Model
Material Pure Comp B Pure Comp B
Thermo DIPPR AP Thermo
Flash Part of Phast AP
Model Spreadsheet
14 Air Products Internal Use Only Calculation
 Case 0 Verification

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Fourth Option:
Phast Multi-Component Add In
• Multi-Component Modeling
- Multi-Component Add In
- Multi-Component Vessel Mode
• Multi-Component approach to modeling
- Modeling of the two-phase region
- Changes in composition over the course of the release
• Limitations
- Cannot model liquid rainout, pool formation and
evaporation
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- Time-varying discharge calculations are not available
Challenges
• Identifying Problem
- Following work instruction would have resulted in using
Vessel Pipe Source Model with mixture modeled as a
Pressurized Gas
• Using and Comparing Multiple Models
- Phast versus AP Thermodynamic Models
- Real process data will not be available until project is
completed.
• Time Consuming Work around
- Method to use both Phast and AP Thermo models was
time consuming and required managing several
17 documents.
Path Forward for Future Models with
Two Phase Mixtures
• Pick option that best fits the situation
- Run Phast at Equilibrium
- Use Pure Component in Phast
- Use both Phast and Specific
Thermodynamic Model
- Phast Multi-Component Add In
• Other options
- Adjust Phast mixture properties
• Try a different equations of state
• Suggestions?
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Questions?
• Contact information
- Julie D. Kister, PE
- kisterjd@airproducts.com
- 610-481-2022

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Thank you
tell me more

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Additional Slides

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 Flash Fire Radius for Option
3 – UDS and AP Thermo

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