dchema thermophysical properties
TRANSCRIPT
Dr. Richard SASS
Reliable Process Modelling with AccurateThermophysical Property Data and Modelsusing DETHERM
Workshop SFGP – 18 June 2010
Presentation Roadmap
• Importance of having accurateThermophysical Property Data andModels for the product design
• Workflow of an optimization withDETHERM
2 Workshop SFGP – 18 June 2010
Motivation
• Example: Modeling of a separation of anAcetone-Water mixture using a well-known simulator– Binary parameter are very good for
modeling the VLE
3 Workshop SFGP - 18 June 2010
Acetone/Water: VLE
4 Workshop SFGP - 18 June 2010
Motivation
• Example: Modelling of a separationof an Acetone-Water mixture usinga well-known simulator- Binary parameter are very good for
modeling the VLE- HE modeling with these parameters
can be improved
5 Workshop SFGP - 18 June 2010
Aceton/Wasser: HE
6 Workshop SFGP - 18 June 2010
Higher precision of models for physical properties
• Use of specifically adapted thermodynamic models,especially in the region of high or low temperature /pressure
• Modeling with reliable sets of parameters optimizedwith raw experimental data
7 Workshop SFGP - 18 June 2010
Important properties (1)
• Phase Equilibria– Boiling and melting points– vapor pressure– fugacity and activity coefficients– solubility (Henry's constants, Ostwald or Bunsen coefficients)
• P-V-T behavior– Density, volume, compressibility, critical constants
8 Workshop SFGP - 18 June 2010
What is DETHERM?
• One of the world’s largest factual databases for rawthermophysical property data
• 6.92 million data sets for 146,800 systems (31,600pure substances and 115,200 mixtures)
• updated yearly– Average growth last 10 years: 8 % p.a.
• parts are published in printed form as “DECHEMAChemistry Data Series”
9 Workshop SFGP - 18 June 2010
Content of database
• Phase Equilibria(VLE, LLE, SLE)
• PVT-Data• Thermodynamic Properties• Transport Properties• Interfacial Properties• Electrolyte data• Total: 211 Properties
Data for design and operationof chemical plants
10 Workshop SFGP - 18 June 2010
11 Workshop SFGP - 18 June 2010
inventor question
12 Workshop SFGP - 18 June 2010
? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?? ?
Motivation: Connecting two worlds
Measured data(discrete values)
Simulator(equation orientated,
model based)
Never forget : The reliability of a (process) simulation issubstantially based on the precision of the thermodynamic
models used ...
Regression andOptimizer
13 Workshop SFGP - 18 June 2010
DPP – Main objectives
• close the gap betweenraw thermophysical dataand process simulation
• optimized workflow
• pluggablethermodynamics
• compare models– with data– among each other
Workshop SFGP - 18 June 2010
Data Preparation Package
Objectives:• Selection
• Comparison• Analysis• Management
•• RegressionRegression
of thermophysical data and models
15 Workshop SFGP - 18 June 2010
The Architecture
Databases•DETHERM•DIPPR•NIST•TRC•...
Simulators•Aspen•ProSim •PRO II•...
Thermodynamic Modules•IK-CAPE•Aspen Properties•Simulis•Custom DPP GUI & COREDPP GUI & CORE
RawData
ModelParameters
End UserThermoInterface
ThermoInterface
OptimizerOptimizer
Graphicssubsystem
Graphicssubsystem
Neutral FileInterface
Neutral FileInterface
16 Workshop SFGP - 18 June 2010
The Optimizer
• Simultaneous correlation– of different data types / systems– with different error functions– e.g. VLE + LLE + HE + γ∞ + Azeotrops
• Model parameter transformation– 1:1– Different ranges -> equal ranges– Bounded -> Unbounded
• Equality constraints on parameters possible• Combination with Maximum Likelihood Algorithm (ML) possible
... is the ... is the ... is the ... is the corecorecorecore element of DPP element of DPP element of DPP element of DPP
Workshop SFGP - 18 June 2010
Workshop SFGP - 18 June 2010
DETHERM Software SuiteDETHERM Software Suite
Process SimulatorProcess Simulator
DPP and DETHERM
• DPP regression tool couplesdatabase with simulator.
Data Preparation Package (DPP)
DETHERM InhouseDatabase
Thermo-dynamics module
18 Workshop SFGP - 18 June 2010
Regression: Result plot
19 Workshop SFGP - 18 June 2010
Simultaneaus VLE regression
γ∞
Isobaricvalues
Isothermalvalues Excess
Enthalpydata
Azeotropformation
T,X,Y
P,X,Y
20 Workshop SFGP - 18 June 2010
Binary LLE: Water/1-Butanol
Testing differentsetups/flavors of
NRTL over the fulltemperature range:
-30 – 130 °C
Testing differentsetups/flavors of
NRTL over the fulltemperature range:
-30 – 130 °C
21 Workshop SFGP - 18 June 2010
Binary LLE: THF/Water
System with twocritical points
System with twocritical points
22 Workshop SFGP - 18 June 2010
Ternary LLE
23 Workshop SFGP - 18 June 2010
Ternary LLE – Solutropic System
24 Workshop SFGP - 18 June 2010
GLE of CO 2 – Water up to 1600 bar
Simple Henry
Henry + NRTL
25 Workshop SFGP - 18 June 2010
GLE of CO 2 – Water, ambient pressure
Henry coefficient asfunction of temperature
Isopartial datawith p(CO 2) = 1 atm
26 Workshop SFGP - 18 June 2010
DETHERM
Example:Separation of the mixture:n-pentane/methanol
Workshop SFGP - 18 June 2010
Workflow (1)
• Example: Modelling of a separation of amixture n-pentane/Methanol
• Target temperature above 400 K• Maximum pressure approximately 25 bar
28 Workshop SFGP - 18 June 2010
Workflow (2) – n-pentane/methanol
• Approach:– NRTL activity coefficient model
together with• Peng-Robinson equation of state for
fugacity coefficients
• Data from DETHERM:• R.A. Wilsak et al. for VLE
29 Workshop SFGP - 18 June 2010
Workflow (3) – Data import from DETHERM
30 Workshop SFGP - 18 June 2010
Workflow (4) – Data import from DETHERM
31 Workshop SFGP - 18 June 2010
Workflow (5) – First regression
32 Workshop SFGP - 18 June 2010
Workflow (6) – First Thermodynamic consistency test – Improvement is necessary
33 Workshop SFGP - 18 June 2010
Workflow (6a) – First Thermodynamic consistency tes t – further improvement is necessary
Workflow (7) – Optimization Results
35 Workshop SFGP - 18 June 2010
Workflow (8) – Optimization Results
36 Workshop SFGP - 18 June 2010
Workflow (9) – Deviation plot
37 Workshop SFGP - 18 June 2010
Workflow (10) – Optimization Results
38 Workshop SFGP - 18 June 2010
DETHERM
Merci de votre attention
39 Workshop SFGP - 18 June 2010
DETHERM – The history
1976BMFT-Study „Demand for PhysicalProperty Data and Calculation methodswithin the Chemical Industry“
1979-1985Two projects (BMFT/AiF) for collection ofdata & methods
� 25 partners (Universities & Industry)
� Extension of the UHDE thermo compiler
Since 1986single BMFT / AIF-Projects
� e.g. PURE
40 Workshop SFGP - 18 June 2010
DETHERM: Data Packages (2) – Status 2010
Content of a dataset
• identification of substance(s)• systematical name,
synonyms
• sum formula, CAS-No.
• descriptors
• numerical data• description of data
• data, errors, remarks
• literature sources• bibliographic information,
abstract
42 Workshop SFGP - 18 June 2010
Producers of DETHERM
• DECHEMA
• DDBST
• FIZ CHEMIE
• Regensburg University
● property orientated packages
� maintained by independentexperts
� e.g. DDB, ELDAR, INFOTHERM
43 Workshop SFGP - 18 June 2010
What is the value of DETHERM?
• Extend the accuracy of yourprocess models
• Model components notavailable in your parameterdatabases
44 Workshop SFGP - 18 June 2010
Benefits using DETHERM
• Dependable and evaluated data
... independent and well known experts are collectingand evaluating the data packages.
... evaluated and checked data are guaranteed this way.
45 Workshop SFGP - 18 June 2010
Benefits using DETHERM
• Dependable and evaluated data• Completeness of data
... in the field of vapor-liquid-equilibrium data more than95 % of all data published worldwide are contained. IfDETHERM contains no data, it is not worth to check anyother source.
... yearly updates (in average 8 % per year)
46 Workshop SFGP - 18 June 2010
Benefits using DETHERM
47 Workshop SFGP - 18 June 2010
Benefits using DETHERM
• Dependable and evaluated data• Completeness of data• Inventor questions possible
... you need a component X with some specialproperties, for example a solvent with
- a boiling point bigger than 150 °C and- forming an azeotrope with component Y?- Searching a component having a given solubility in water
... just define the properties you need and search thedatabase, saving days of manual work.
48 Workshop SFGP - 18 June 2010
Benefits using DETHERM
• Dependable and evaluated data• Completeness of data• Inventor questions possible• Merging of data pools
... the inhouse systems allows to store own data sets.Customers can merge their own data pool with thedelivered one this way. All data can accessed andretrieved consistently the same way.
49 Workshop SFGP - 18 June 2010