C3M User's Manual

Contents Installation .................................................................................................................................................... 3

Overview ....................................................................................................................................................... 4

Paths ............................................................................................................................................................. 5

Third Party Software ................................................................................................................................. 5

Species Cross Reference ............................................................................................................................... 7

Fuels .............................................................................................................................................................. 9

Kinetics Setup .............................................................................................................................................. 11

Context Menus ........................................................................................................................................ 12

Kinetic Package Settings (KPS) .................................................................................................................... 14

Pyrolysis .................................................................................................................................................. 14

MGAS .................................................................................................................................................. 14

CPD ...................................................................................................................................................... 15

FG-DVC ................................................................................................................................................ 16

PC Coal Lab .......................................................................................................................................... 17

Uncertainty Quantification ................................................................................................................. 18

See Uncertainty Quantification................................................................................................................... 18

Char Oxidation ........................................................................................................................................ 18

MGAS .................................................................................................................................................. 18

PC Coal Lab .......................................................................................................................................... 18

Moisture Release .................................................................................................................................... 19

MGAS .................................................................................................................................................. 19

PC Coal Lab .......................................................................................................................................... 19

Gasification ............................................................................................................................................. 20

MGAS .................................................................................................................................................. 20

PC Coal Lab .......................................................................................................................................... 20

Water Gas Shift ....................................................................................................................................... 21

MGAS .................................................................................................................................................. 21

Gas Phase Combustion ........................................................................................................................... 22

MGAS .................................................................................................................................................. 22

Calculating Kinetics ..................................................................................................................................... 23

Export Kinetics ............................................................................................................................................ 24

MFiX Validation ........................................................................................................................................... 26

Uncertainty Quantification ......................................................................................................................... 29

Help Menu .................................................................................................................................................. 37

Installation Notes:

• Start the C3M installation using "Run as Administrator". • Depending on the system configuration, the installation may require administrative

privileges. • Delete or move any pre-existing working and export directories.

Visual Studio 2010 redistributable is a required dependency of C3M. If it is already installed on the workstation, the following error dialog may be encountered, disregard and close the dialog.

Overview

1. Contains all list of all fuels including default and user defined. 2. Use to add and remove fuels. 3. The proximate and ultimate analysis for the selected fuel. 4. Kinetics to be calculated. 5. Starts the calculation of the kinetics for the selected fuel. 6. The stoichiometry and rates for the selected kinetic package and condition 7. The process which is currently limited to Gasification.

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Paths When launching C3M for the first time, it is important to set the paths to the necessary directories and to any third party executables Select "Set Paths" from the Tools->Options menu

The working and export directories can be left alone if desired because C3M will create them if they don’t already exist. If you have PC Coal Lab, FG-DVC and/or Alamo set the path to the executables.

After setting paths, close and re-launch C3M.

Third Party Software C3M interacts with several 3rd party software programs such as PCCL, FGDVC, ALAMO, R, PSUADE, minGW, MFIX, and Python. Software that is covered under a GPL (or similar license) is distributed within the C3M installer. Some software which C3M can interact with is not GPL and requires users to obtain a license and may involve monetary fees to do so. When this occurs, that software is not bundled with C3M, but a path variable can be set to the executable (see Paths) after the end user obtains and fully installs the software.

NOTE: PC Coal Lab (PCCL), FG-DVC, and ALAMO are third party software programs which are not packaged with C3M. NETL does not provide licenses to run this software. It is up to the user to obtain this software and/or pay any fees to obtain the licenses needed. Once rights have been obtained to run this software, C3M can interact with it after the paths to the fully functional executables are provided. NETL DOES NOT PROVIDE ANY WARRANTY, GAURONTEE,

SERVICE, OR SUPPORT FOR PCCL, FG-DVC, CPD, ALAMO, R, PSUADE, MINGW, PYTHON OR ANY OTHER 3RD PARTY SOFTWARE THAT INTERACTS WITH C3M. These 3rd party software programs can change or be withdrawin from public availability without notice and these changes may break functionality when interacting with C3M. We make reasonable efforts to ensure proper function, but cannot make any gaurontees because these software programs are not in the development control of C3M developers. Please stick to the versions of the software specified below. Other version may work, but are not tested or validated in any way, use at your own risk. C3M works with PCCL version 4.1 and 4.3. To obtain PCCL 4.1 or 4.3, contact Stephen Niksa at Niksa Energy Associates LLC: neasteve@gmail.com C3M works with version 8.2.2 of FG-DVC. To obtain FG-DVC, contact Advanced Fuel Research, Inc: http://www.afrinc.com/products/fgdvc/fgdvc-description.htm C3M works with the 2014 preview version of ALAMO in 32 bit for windows. To obtain ALAMO, register for access on the CCSI website (www.acceleratecarboncapture.org) and obtain the 2014 preview version currently at https://www.acceleratecarboncapture.org/drupal/product/alamo-fortran?bt=2014.06.0 NOTE: ALAMO is currently a development program under the CCSI program. However, it will soon be transitioning to a private startup company. When this transition happens, the development versions may not be publicly available. If this happens before the next C3M release, please contact Nick Sahinidis at niksah@gmail.com

Species Cross Reference NOTE: In typical operation, no modifications to the cross reference are needed. If changes to the species are needed, select the desired species and click "Edit"

The species selection dialog displays a complete list of the species in the C3M species database. Search for the species by name, phase, cas, etc.

Fuels Existing fuels can be used or new fuels can be added. To add a new fuel, first click "Add/Remove" and select "Add".

Give the new fuel a name. Fill in the values for the proximate and ultimate analysis. The status boxes will verify that the PA and UA are valid. The PA and UA are valid if the conditions in the Summation box are met (displays Consistent PA and Consistent UA in a green box). If they are not met, one or both of the green boxes will be red. If they are red, double check the numbers you are putting in. If you are sure they are right, it may be that there is a small discrepancy in the values. You can click on "Normalize PA = 100" and "Normalize UA = 100" to force your values to comply with the conditions in the summation box. After clicking add, the new fuel will appear in the fuel panel of the main gui.

Kinetics Setup First Select the Chemistry Sub-model, which will populate the kinetic packages available.

Clicking a Kinetic Package will populate existing conditions. The Dynamic Report will show a description of the kinetics to be calculated.

To create a new condition, double click the desired Kinetic Package. Refrain from using paranthesis and special characters in the condition name. A settings package specific settings dialog will appear (See Kinetic Package Settings section). Adjust the settings as desired, click add, and the condition will appear in the condition list.

Clicking an existing condition will update the Dynamic Report with the calculated values.

To modify an existing condition double click a condition in the condition list.

Context Menus When a kinetic package is highlighted, right clicking will bring up a context menu

Clicking on "Help" will bring you to the section in the theory document for that chemistry sub-model

When a condition is highlighted, right clicking will bring up a context menu

Selection "Run Condition" will calculate a single condition.

Selecting "Open Folder" will open the file browser to the condition folder. This is a handy feature to use when validating calculations or to diagnose a problem.

Selecting "Copy Condition" provides the options to copy the condition to the current fuel or another fuel. When "Ok" is selected and a unique name is given, a folder will be created and all of the files and settings will be copied over to the new folder. This is a handy feature to use when running multiple very similar conditions. Simply create a copy of the condition and then edit the desired variable by double clicking the copied condition and making your change in the Kinetic Package Settings dialog that will open up.

Selecting "Plot Thermo Data" will provide options for plotting the thermodynamic properties for the given condition.

Selecting "Delete Condition" will delete the condition from the GUI and will remove the files and folder associated with that condition within the C3M Working directory which was specified in Paths.

Kinetic Package Settings (KPS)

Pyrolysis

MGAS

The Pyrolysis MGAS KPS allows the user to select one of 5 coal types. The coal type selects which kinetic parameters are used in the pyrolysis rate. MGAS parameters are only available for these specific 5 coal types. If the coal defined by the user is significantly different than one of these types, the kinetic expression will probably not be representative. The stoicheometry is based on a series of rules which follow from the proximate and ultimate analysis of the coal. For complete details the user should examine the MGAS Theory manual in which is available in the help menu. The specific gravity is that of the tar produced. This value is used to estimate the specific heat of the tar. For complete details see Estimation of Specific Heat of CHONS compounds in the Complete Theory document in the help menu

CPD

The Pyrolysis CPD KPS allows a user to run CPD like a standard TGA or Wire Grid experiment. Here T Initial is the initial temperature of the coal, T Final is the ultimate temperature of the coal, Heating Rate is the rate that the coal is heated from the initial temperature to the final temperature, Pressure is the reactor pressure, Total Time is the end time, and Tolerance is used to specify a different convergence criteria based on the slope of the mass loss rather than the end time. It is highly recommended that tolerance be checked and used because the python fitting algorithm needs a significant segment of time where there is no reaction to appropriately determine the final yield. The specific gravity is that of the tar produced. This value is used to estimate the specific heat of the tar. For complete details see Estimation of Specific Heat of CHONS compounds in the Complete Theory document in the help menu.

FG-DVC

The Pyrolysis FG-DVC KPS allows a user to run FG-DVC like a standard TGA or Wire Grid experiment. Here Pressure is the reactor pressure, Heating Rate is the rate that the coal is heated from the initial temperature to the final temperature, Initial Temperature is the initial temperature of the coal, Wall Temperature is the ultimate temperature of the coal (reactor set temperature), Time Step is the integration time step, and the specific gravity is that of the tar produced. This value is used to estimate the specific heat of the tar. For complete details see Estimation of Specific Heat of CHONS compounds in the Complete Theory document in the help menu. Users can specify a custom coalsd file by checking the "use existing coalsd output" check box and supplying the name

PC Coal Lab

The Pyrolysis PCCL KPS allows a user to run PCCL like a standard TGA or Wire Grid experiment. Here T initial is the initial temperature of the coal, T ultimate is the ultimate temperature of the coal, Heating Rate is the rate that the coal is heated from the initial temperature to the final temperature, Vol %O2 is the volume fraction of oxygen present, P is the reactor pressure, Time is the end time of the simulation, dp is the particle diameter, and the specific gravity is that of the tar produced. This value is used to estimate the specific heat of the tar. For complete details see Estimation of Specific Heat of CHONS compounds in the Complete Theory document in the help menu. The user can also choose which of the three pyrolysis models to use in PCCL on the top group box.

Uncertainty Quantification

See Uncertainty Quantification

Char Oxidation

MGAS

This menu is brought up because it is the default menu for MGAS. In the case of char oxidation, it only serves as an add or cancel function. Future versions of C3M will probably grey out the options or remove them.

PC Coal Lab

The options in this dialog are the same as those in PC Coal Lab pyrolysis. They are set this way because PCCL needs to know the extent of char conversion during pyrolysis to make inferences about the char oxidation kinetics.

Moisture Release

MGAS

The options are the same as those in MGAS pyrolysis. The specific gravity does not do anything is grayed out.

PC Coal Lab

The options in this dialog are the same as those in PC Coal Lab pyrolysis. They are set this way because PCCL uses the heating rate and fuel properties to make inferences about the heat transfer rate during moisture release.

Gasification

MGAS

The options are the same as those in MGAS pyrolsysis. The specific gravity does not do anything and will be greyed out in future versions of C3M.

PC Coal Lab

Most of the options in this dialog are the same as those in PC Coal Lab pyrolysis with the exception of the Calibration Factor and the gas composition. The Calibration Factor is very important to the accuracy of the gasification kinetics coming from the PCCL model. There is not enough experimental data available to derive an accurate empirical model for determining this parameter. At the moment, the best method is to compare the output of the model in the MFiX Validation tool within C3M to at least one experiment to set this factor correctly. Without

setting this parameter, the kinetics can be off by about +/- 2 orders of magnitude. However, case studies have shown that once this parameter is set to at least one experiment, PCCL does a reasonable job at predicting the kinetics of the same coal under varying temperature and gas environments. The gas environment within the test can be set in the Gas Composition boxes on the right side.

Water Gas Shift

MGAS

The options are the same as those in MGAS pyrolsysis. The specific gravity does not do anything and will be greyed out in future versions of C3M.

Gas Phase Combustion

MGAS

This menu is brought up because it is the default menu for MGAS. In the case of Gas Phase Combustion, it only serves as an add or cancel message box. Future versions of C3M will grey out the options.

Calculating Kinetics Clicking "Run" will calculate all the uncalculated conditions for the selected fuel.

A progress dialog will provide status updates.

Export Kinetics The calculate kinetics can be exported to MFiX, Fluent, Barracuda, and into a general report. Select Export from the File menu

First choose the fuel to export

The export process mirrors the setup process. Choose the sub-model to export, choose the package to export, and the check the condition to export. Repeat the process for any other sub-models to include. The Dynamic Report will reflect the selections made. Choose what format to export. Click Export. As of release 2015-3, Pyrolysis UQ with power, Alamo, and neural net fits cannot be exported to FLUENT.

MFiX Validation Kinetics calculated and exported from C3M can easily be validated against reference data or experiments using the MFIX Validation Tool in C3M. This tool uses a version of MFIX run in the background to run one of a small number of virtual experiments which mimic common experiments done with coals and other fuels. Currently, the stable version of C3M includes the TGA/Wire Grid simulator (TGA for short). The development version of C3M also includes a Drop-Tube simulator which will be coming available in upcoming stable releases. The virtual TGA allows users to take a solid (coal) and expose it to a temperature controllable environment and expose it to a variety of gas environments and monitor the results of the exposure. The TGA consists of two stacked cells. The bottom cells contain solid while the top are defined as gas only. By default, MFIX is run as a pseudo 1D reactor in the background with coupled mass, momentum, and energy being solved. In essence it is being treated as a fixed bed where the inlet temperature and gas composition can be defined (See Help Menu->MFiX TGA). This allows users to see the response of the solid mass and gases as they react. Users can plot average solid temperature, average gas temperature, inlet gas temperature, solid mass, cumulative exit gas composition, reaction rates, and reaction energy. All of these are key values which can be used to compare to experimental data in just a few minutes to validate that the kinetics are implemented properly before taking them to a large scale simulation. Since the MFIX Validation Tool runs MFIX in the background, an export in MFIX 2015 should be done first and put in a folder with a unique name. Once the kinetics are exported, select MFiX Validation from the Tools menu.

Once open, the C3M should display the MFIX Validation window (see below)

First select the run type. Currently the stable version of C3M only has the TGA enabled. Next, select the "Select Folder" button. This will bring up a folder selection dialog. Navigate to the exported MFIX 2015 folder created before opening the MFIX Validation window. Once the folder is selected or opened, click OK. If successful, the path to the folder should appear in the orange text box and the name of the export should be in the "Run Name" text box. From here, selecting the "Compile/Run" button will compile MFIX in the background and run it. It is important to note that the first time MFIX is compiled, it may take some time (5 to 10 minutes) because it is creating all of the object files needed to generate the executable. This should not be the case running further cases. Only the necessary object files are created that were different than before. Typically, it takes 10 to 15 seconds to compile before starting to run.

During the run the plot will be updated and both axes can variables can be controlled.

The y axis is controlled through the "Plot Variable" drop down box. Certain variables tracked in the simulation are available in this drop down box.

The x axis is controlled through the "X axis variable" drop down box. Options include time and a variety of temperature measures.

Uncertainty Quantification The basic steps for using the UQ option in C3M are:

• Determine the type of UQ run that you want to do • Generate a sample space of the input variables • Run the kinetic package on the input sample space • Fit response surfaces to the output variables of the kinetic runs • Export the reaction rate data in a form compatible with MFIX

Determine the type of UQ run that you want to do There are four types of runs that can be done:

• CHONS / PCCL pyrolysis, devolatilization only • CHONS / CPD pyrolysis • CHONS / FG-DVC pyrolysis • CHONS / PCCL pyrolysis, devolatilization only, biomass option

Generate the sample space of the input variables

C3M uses PSUADE to generate the sample space. • Determine the input variables. Below are listed the possible input variables for each

type of run o CHONS / PCCL pyrolysis, devolatilization only (biomass and non-biomass)

Heating rate Temperature Pressure Initial residence time Particle diameter O2 percentage

o CHONS / CPD pyrolysis Heating rate Temperature Pressure Initial residence time

o CHONS / FG-DVC pyrolysis Heating rate Temperature Pressure Initial residence time Time step

• Set the type of sampling to be done. Supported sampling methods are: o Monte Carlo o LPTAU o Latin Hypercube

• For each input variable, set the following: o The type of distribution to be used (uniform or normal) o Minimum and maximum values o If a normal distribution is chosen, the mean and standard deviation

• Set the number of sample points to generate • Click on the “generate” button • You should verify that the sample points were correctly generated by using the “show

plot” option to visualize the results. If a problem occurred, trying clicking on “generate” again.

Run the kinetic package on the input sample space

• Set to constants any non-UQ input values needed by the kinetic package. For example, if temperature and heating rate were selected as UQ input variables, CPD requires values for initial temperature (usually 298.15 K), Pressure in Pascals, residence time, and a convergence tolerance.

• Set the number of threads to run. It is recommended to be less than or equal to the number of processors available.

Fit response surface to the output variables of the kinetic runs

• Choose the type of fit (linear, quadratic, cubic, etc.) • Click on the “submit all” button • Verify that the fitting finished correctly by visualizing the response surfaces for each

output variable • You can modify the type of fit for a specific output variable by selecting the variable,

setting the fit type, and clicking on the “submit” button underneath the fit type Export the reaction rate data in a form compatible with MFIX

• This is done as usual thru the export dialog.

Enter a condition name or select existing run

Select the Run Type

Input Conditions

Select the sampling method

Click "Set Input Variables" button

Choose an input variable

Select a distribution

Set the minimum and maximum values for the input variable

Select the number of data points to generate

Verify the results using the available plots

UQ Run

Available options vary by run type

PCCL

• T inital - Initial temperature in Kelvin • %O2 - percentage of oxygen • Starting Tirp - Starting total time

estimate • DP - particle diameter in microns • Heating Rate in Kelvin/second • Temperature in K • Pressure in Pascals • Kinetics Package - set by run type • # of threads - number of concurrent

instances • Status Bars

CPD

• T inital - Initial temperature in Kelvin • Max Tirp - Max total time • Heating Rate in Kelvin/second • Temperature in K • Pressure in Pascals • Tolerance • Kinetics Package - set by run type • # of threads - number of concurrent

instances • Status Bars

FG-DVC

• T inital - Initial temperature in Kelvin • Tirp - Starting total time estimate • Heating Rate in Kelvin/second • Temperature in K • Pressure in Pascals • Time Step in seconds • Number of time points to use for

slope calculation • Slope Tolerance • Kinetics Package - set by run type • # of threads - number of concurrent

instances • Status Bars

UQ Analysis

Variable - choose the variable to fit

Fit Type - select the type of fit

Submit All - fits all variables with selected fit type

Submit - fits selected variable with selected fit type

Log Fit - fitting using a logarithmic scale

Visualization and scatter plots

Sample plot

Help Menu The theory behind C3M is included in the Help Menu.