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)

GTT-Technologies

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


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


GTT-Technologies

ChemApp Equilibrium Block in Aspen Plus


GTT-Technologies

Aspen Plus Flowsheet


ChemApp Equilibrium Block

Coal

ProductRaw

Off-Gas

Rotary Kiln and Cooler

Pre-heater +Pre-Calciner

Bypass Gas Recycle Line

Chloride Bypass

Burner

GTT-Technologies

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


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



Velocity Distribution [m/s]

in a BFBC Freeboard

GTT-Technologies

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)



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



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

GTT-Technologies

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

GTT-Technologies

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

GTT-Technologies

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


Full load Part load

Privileged Infeed of Renewable Energies in


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

GTT-Technologies

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


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


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!

thermochemistry-based process simulation with chemapp...

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