Thermochemistry-Based Process Simulation with ChemApp...
Transcript of Thermochemistry-Based Process Simulation with ChemApp...
Thermochemistry-Based Process
Simulation with ChemApp,
SimuSage, and ChemSheet
Stephan Petersen, GTT-Technologies, Herzogenrath, Germany
Toronto, October 20, 2017
GTT-Technologies
Modelling and simulation tools• The Integrated Thermochemical Databank
System
... to perform interactive and phase diagram
calculations
• The Thermochemical Library
(Gibbs Energy Minimizer) for your Software
... to add thermochemical equilibrium
calculations to your or third-party software
• The Component Library for Rapid Process
Modelling
... to create ChemApp-based complex process
simulations with Delphi/Lazarus
• The Thermochemistry Add-In
for Microsoft Excel™
... to add thermochemical equilibrium
calculations to your Excel spreadsheets
The
Thermochemistry Library
for your Software
GTT-Technologies
What is ChemApp?
• Due to the complexity of the matter, in-house
programming of corresponding state-of-the-art code is
next to impossible
• A demand exists for specialized, reliable code in the form
of modules
• For these reasons, ChemApp was developed from
ChemSage within the framework of a European “Science”
project
• Since 1996 ChemApp has been available for a wide range
of platforms
A variety of programs from various areas would benefit from
the ability to perform complex, multicomponent, multiphase
chemical equilibrium calculations, or even depend on it.
GTT-Technologies
What is ChemApp?
SOLGASMIX
(Grandfather)
1971-1984
ChemSage
(Interactive program)
since 1988
ChemApp
(Programmer‘s library)
since 1996
ChemSheet
(ChemApp for Excel)
since 1999
SimuSage
(Process simulation
components for Delphi)
2002
FactSage
(ChemSage merged
with FACT-Win)
since 2001
GTT-Technologies
Keys benefits and characteristics
• Fast
• Multi-Compiler, Multi-Platform
• Clean, structured, and extensively documented set
of interface procedures
• Reliable convergence without ever needing to set
starting points
• Supports widest range of solution phase models
and thermochemical data
• Can process all thermochemical data extracted
from FactSage databases
• Under constant development and improvement
GTT-Technologies
ChemApp usage
... is a module of 3rd party programs
CFX, OpenFOAM,
Fluent
AspenPlus, PRO/II,
BALAS
Comsol (under development)
... is partially contained in other GTT products
(FactSage)
... is used in custom programs
Dedicated simulation
programs by GTT,
Customers‘ own
programs
... is wholly contained in other GTT products
ChemSheet SimuSage
KilnSimu (VTT)
GTT-Technologies
Sources of data-files (1)
• Extracted from databases using FactSage
(from FACT, SGTE, and various other
databases)
• Taken from GTT's library of application-
specific data-files
• Custom-made by GTT
• Created by the user (for instance with the
help of CSFAP)
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Sources of data-files (2)Standard databases available for FactSage
• CRCT
Pure substance database
Oxide database for slags,
glasses, ceramics,
refractories
Salt database
Hall aluminum database
Aqueous database (ideal
solution, Pitzer, Helgeson)
Miscellaneous databases
for sulfides, liquid alloys,
etc.
Pulp and paper database
• GTT
GTT oxide database
• Cooperative development
(CRCT – Spencer Group –
GTT)
Copper alloy database
Lead alloy database
Light metal database
Steel database
Ultrapure silicon database
• SGTE
Pure substance database
General alloy database
Noble metal database
Nuclear database
• Other
Thermodata nuclear database
GTT-Technologies
Cement Process
Rotary Kiln
Pre-
Calciner C1
C2C3
C4
SP Fan
Raw Meal
Max 1450 oC
Fuel(Coal)
Clinker
Cooler
• Counter-Current Process
• 12 (or more) System Components
Fe-Ca-K-Cl-S-Si-Al-Mg-Na-O-N-C
• Formation of Clinker Phases
Alite 3CaO*SiO2
Belit Ca2SiO4, Fe2SiO4,Mg2SiO4
Aluminat 3CaO*Al2O3
Ferrite Ca2Al2O5 Ca2Fe2O5
Solid Flow
Gas Flow
Copyright © Ube Research Laboratory, Corporate Research & Development, Ube Industries, Ltd., Japan
GTT-Technologies
Waste and Byproduct Utilization in
Cement Factories
Inorganic Waste(Raw)Sewage
Public refuse incineration ash
Water supply sludge
Coal ash
Gypsum
Slag
Controlled soil
Hydraulic cake
Organic Waste(Alternative Fuel)Waste plastics
Waste oil
Waste tire
Waste pachinko panels
Waste tatami mats
Bone meal
Copyright © Ube Research Laboratory, Corporate Research & Development, Ube Industries, Ltd., Japan
GTT-Technologies
Cyclone clogging caused by
Chloride and Sulfate accumulationRaw Meal
C4
C3
C2
C1
Coating
Build upAccumulation of Chloride and Sulfate
Formation of low melting point component
Cyclone clogging
Plant Operation Shutdown !
Chloride Conc. Sulfate Conc.
Raw Meal 60ppm 200ppm
C4 430ppm 2,000ppm
C3 840ppm 4,900ppm
C2 1,630ppm 11,100ppm
C1 11,880ppm 35,000ppm
Clinker 70ppm 4,400ppm
Chloride ;KCl, NaCl
Sulfate ;K2SO4,CaSO4 etc
Copyright © Ube Research Laboratory, Corporate Research & Development, Ube Industries, Ltd., Japan
GTT-Technologies
ChemApp Equilibrium Block in Aspen Plus
Copyright © Ube Research Laboratory, Corporate Research & Development, Ube Industries, Ltd., Japan
GTT-Technologies
Aspen Plus Flowsheet
Copyright © Ube Research Laboratory, Corporate Research & Development, Ube Industries, Ltd., Japan
ChemApp Equilibrium Block
Coal
ProductRaw
Off-Gas
Rotary Kiln and Cooler
Pre-heater +Pre-Calciner
Bypass Gas Recycle Line
Chloride Bypass
Burner
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Chloride and Sulfate at High Temperature
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
800 900 1000 1100 1200 1300 1400 1500
3×K2Ca2(SO4)3
CaSO4Slag-CaSO4
Slag-MgSO4
Slag-K2SO4Slag-Na2SO4
Liq. or Solid K2SO4
Temperature C
S c
om
pound
s in
Soli
d+
Sla
g m
ol
5.0vol% O2
Chloride
SulfateSulfate
Copyright © Ube Research Laboratory, Corporate Research & Development, Ube Industries, Ltd., Japan
GTT-Technologies
High-Chlorine Bypass System
Dust Collector
Pre-Heater
Clinker Cooler
Kiln
Chloride Circulation
Raw Meal
Bypass
Fuel
Design Point
of Bypass Ratio
Chloride containing Waste can be
used as an alternative raw materials
Allowable Limit of Cl is 1,600ppm
per Clinker production
GTT-Technologies
• Advanced fuel analysis, complex multiphase equilibrium
calculations, and CFD were used to create a novel way of
predicting the behavior of biomass ash in fluidized bed
boilers.
• The goal is to minimize downtime of biomass reactors, which
is mainly due to the behavior of ash in slag buildup and
corrosion.
• ChemApp and Fluent have been used successfully in
predicting the behavior of ash particles in the reactor.
• The main job of ChemApp is the calculation of the liquid
phase fraction, which, when determined to be between 0.15
and 0.7 for a given temperature and particle composition, will
cause the particles to stick to the walls.
ChemApp & Fluent
at Åbo Akademi University(with Christian Mueller, Process Chemistry Group)
GTT-Technologies
Novel Way of Predicting Biomass Ash Behavior
Deposition Prediction
Fuel Data - Chemical Fractionation
Operational Data
Thermodynamic Equilibrium
Code - ChemApp®
Advanced Fuel Analysis
CFD Code - Fluent®
Ash Particle Trajectories/
Near-Wall Investigation
Computational Fluid Dynamics
Exchange
of Boundary Conditions
Exchange
of Boundary Conditions
Copyright © Åbo Akademi University,
Process Chemistry Group
GTT-Technologies
Copyright © Åbo Akademi University,
Process Chemistry Group
Velocity Distribution [m/s]
in a BFBC Freeboard
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Particle Temperature [K]
GRID
AIRINLETS
1050-1150 (K)
1150-1250 (K)
1250-1350 (K)
GRID
AIR INLETS
1050-1150 (K)
1150-1250 (K)
1250-1350 (K)
Copyright © Åbo Akademi University,
Process Chemistry Group
Ash Particle Distribution
on the BFBC Backwall
GTT-Technologies
GRID
AIR INLETS
1050-1150 (K)
1150-1250 (K)
1250-1350 (K)
Boiler Wall, 02.06.2000
Copyright © Åbo Akademi University,
Process Chemistry Group
Ash Particle Distribution
on the BFBC Backwall
GTT-Technologies
Not only equilibrium calculations
are possible
• The properties of metastable phases are calculated as
well. Phases and phase constituents can be selectively
assigned a metastable status.
• ChemApp as a module can also be embedded in more
complex models, which take kinetic and time-
dependent effects into account (several interdependent
local equilibria instead of one global equilibrium).
• The Constrained Equilibrium concept (Koukkari et al.)
allows for the formulation of additional constraints,
which are specified in the ChemApp data-file.
ChemApp does not only allow for the calculations of
equilibrium calculations.
SimuSage - The Component Library for Rapid Process Modelling
GTT-Technologies
Why would SMS Siemag start
developing SimuSage?• Programs like FactSage are great tools for point
calculations, range calculations, phase diagrams, etc.
• What about processes, i.e. multiple reactors
interconnected via streams? Recycle/feedback
streams? Dynamic behavior? A library of other unit
operations like mixers, splitters, heat exchangers?
• Since ChemApp necessarily involves coding: What
about doing this quickly, with a minimum amount of
coding? Including a user interface that somebody other
than the developer can use?
• And what if you want to give your ready-made
simulation to somebody else?
GTT-Technologies
What is SimuSage?
• SimuSage is a ChemApp-based set of
Delphi/Lazarus components for process
simulation/flowsheeting tasks (sequential
modular approach)
ChemAppDelphi™
Lazarus+ =
Stream
Stream
Mixer Stream
Equil.
ReactorStream
StreamPhase
Splitter
Stream
Stream
GTT-Technologies
• ... is a set of visual and
non-visual components
– Visual programming
– RAD (Rapid Application
Development)
SimuSage ...
GTT-Technologies
A model for the prediction of precipitate
formation during steel making
Piotr R. Scheller1 , Stephan Petersen2, Qifeng Shu3, Klaus Hack2
1Prof. em. TU Bergakademie Freiberg2GTT Technologies GmbH, Herzogenrath, Germany
3University of Science and Technology Beijing, Beijing, China
GTT-Technologies
• Steel cleanliness is a major
issue
• Ever increasing requirement
for strict control of inclusion
composition and amount
during ladle treatment
• Tasks in ladle metallurgy:• Adjustment of chemical
composition
• Adjustment of temperature
• Separation of inclusions
• …
Intention:
to develop a robust model predicting the inclusion composition
and amount which can be used on-line in the industrial process
(using a standard PC)
GTT-Technologies
Zhang, Proc. VDEh-CSM Seminar,
Düsseldorf, 2014
After alloying
in LF
Ca-Si-(Al)-O Al-Mg-O
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Model DescriptionReaction sites and parameters implemented in the Model
- A multi component, multi phase high temperature
chemical reactor
1: Mixing in the ladle
2: Slag-Metal reaction
3: Inclusion separation
4: Lining interaction with steel
and slag
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Tank1 Tank2 Tank3 Plume
Slag2 Slag1Slag Phase
Steel Phase
(with NMI)
NMINMINMINMI
NMI
separation
Lining Lining Phase
Model DescriptionSchema of the model
Lining
separation
GTT-Technologies
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
5 100 195 290 385 480 575 670 765 860 955 1050 1145
Time/s
[Al]/w
t%Tank1
Tank2
Tank3
Plume
Analysed
Comparison between calculated [Al] and industrial analysed
[Al] during ladle treatment
Model Validation
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0
0.0002
0.0004
0.0006
0.0008
0.001
0.0012
0.0014
5 90 175 260 345 430 515 600 685 770 855 940 1025 1110 1195
Time/s
[O]/
wt%
[O]
[O]-analysed
Comparison between calculated oxygen activity a[o] and industrial a[o] measurement
during ladle treatment. The first drop is due to Al-deoxidation. The other drops could
be connected with the seperation and modification of inclusions.
Time, s
a[o
],
%
Mitg
lied
de
r H
elm
ho
ltz-G
em
ein
sch
aft
Modelling of coal combustion with SimuSage
within the VerSi project
Matthias Dohrn, Michael Müller
Masood Azizi, Klaus Hack, Moritz to Baben
Forschungszentrum Jülich, Institute for Energy and Climate Research,
IEK-2, Thermochemistry
GTT-Technologies
GTT Usermeeting 2017, Herzogenrath, 29th June 2017
SlaggingFouling
42
1400°C
1100°C
950°C
600°C
Weber et al. (2013)
Zbogar et al. (2005)
Weber et al. (2013)
Weber et al. (2013)
Deposit build-up
Full load Part load
Privleiged Infeed of Renewable Energies in
the Power Supply System
Full load Part load
Privleiged Infeed of Renewable Energies in
the Power Supply System
Full load Part load
Privileged Infeed of Renewable Energies in
the Power Supply System
43
Situation in Germany
44
Cycling Induces Temperature Shift
High load Low load
Full Model
45
Short Model
46
Example calculation
47
South African (Kleinkopje) hard coal
calculation without quartz bypass
Example calculation
48
South African (Kleinkopje) hard coal
Comparison (0% vs 20 % bypass)
Phases are higher in 0% calculationPhases are higher in 20% calculation
GTT-Technologies
TPbOptimizer
GTT-Technologies
TPbOptimizer
Objective
GTT-Technologies
SimuSage model
GTT-Technologies
Example optimization 1
Variable
Objective:
60 t/h
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Example optimization 2
Constraint
TBath <= 1200 C
Variable
Objective:
maximize
The Thermochemistry Add-Infor Microsoft Excel™
VTT Chemical TechnologyGTT-Technologies
ChemSheet Data Flow Diagram
Use of ChemSheet for Thermochemical Calculations
Thermodynamic Data
ChemApp
Excel Worksheet
ChemSheet
ChemSheet Code Flow Diagram
Use of ChemSheet for Thermochemical Calculations
StepIndex=StepIndex+1
StepIndex<StepCount
Update Excel worksheet
(formulas, tables, charts, ...)
StepIndex=0
Calculate Equilibrium
ReadData-file
Read Inputs
Write Outputs
Excel Define Name-dialog shows
the names that are automatically
defined by ChemSheet.
Tip If you don’t like name StepIndex you can
add a new name that refers to StepIndex
(=StepIndex) and use it.
Stack pipe -example
Use of ChemSheet for Thermochemical Calculations
This example uses tempe-rature as a target variable.Enthalpy change for eachstep is calculated using heattransfer from gas to ambientair through pipe wall. Gascools down as it exchangesheat with the surroundings.At the middle of the pipe anadditional air feed isintroduced.
Slag Window Applications in Steel-Making
Steels contain additions of aluminium (grainrefining) and sulphur (machinability). With these(or other) additives nozzle clogging can occurduring continous casting. Depending upon the O-and Ca-content of the steel, one can find at agiven temperature either, solid aluminates,aluminate + liquid oxide, liquid oxide only, orliquid oxide + CaS-precipitate in equilibrium withthe liquid steel. ChemSheet is used to calculateinjection doses for different grades of steel toensure plant operation within the liquid slagwindow.
Slag Window for C09 Steel
1550 C, O 75 ppm
0
10
20
30
40
50
60
70
80
0 200 400 600 800
Al [ppm]
Ca
[p
pm
]
CaS sat.
Ca_Al sat.
Sample Composition
C09
T [0C] 1550-1450
p [atm] 1
C [%] 0.01
S [%] 0.025
O [%] 0.0025-0.0075
Si [%] 0.04
Mn [%] 0.3
Ti [%] 0.02
Al [%] 0.03
Ca [%] 0.004
Slag Window for C09 Steel
1550 C, O 75 ppm
0
10
20
30
40
50
60
70
80
0 200 400 600 800
Al [ppm]
Ca
[p
pm
]
CaS sat.
Ca_Al sat.
Sample Composition
C09
T [0C] 1550-1450
p [atm] 1
C [%] 0.01
S [%] 0.025
O [%] 0.0025-0.0075
Si [%] 0.04
Mn [%] 0.3
Ti [%] 0.02
Al [%] 0.03
Ca [%] 0.004
C09
T [0C] 1550-1450
p [atm] 1
C [%] 0.01
S [%] 0.025
O [%] 0.0025-0.0075
Si [%] 0.04
Mn [%] 0.3
Ti [%] 0.02
Al [%] 0.03
Ca [%] 0.004
GTT-Technologies
Thank you for your attention!