Table of Contents

ProMax Level IIAdvanced Simulation Methods Agenda ............................................... iv Customizing ProMax ............................................................................................................. 1 Modifying Options.xml File ............................................................................................ 1 Exercise 1: Add New Property to Process Streams ................................................... 2 Exercise 2: Add New Option in Drop Down Menu ................................................... 2 Exercise 3: New Tool Tip for Process Streams ......................................................... 2 Exercise 4: Create a Custom Unit Set ........................................................................ 2 Modifying Column Hardware.xml File ........................................................................... 3 Modifying Pipe Segment Data.xml File .......................................................................... 4 Creating Personalized Watermarks .................................................................................. 5 Exercise 5: Changing the ProMax Watermark .......................................................... 5 Property Stencils and Examples............................................................................................. 6 Recycles/Solvers and Prioritization ..................................................................................... 11 Exercise 6: Simple Example Demonstrating Prioritization Concept ....................... 12 Exercise 7: Prioritization of a Large Multi-Flowsheet Plant ................................... 13 User Value Sets .................................................................................................................... 14 Defining a User Value ................................................................................................... 14 Displaying a User Value in a Property Table ................................................................ 15 Modifying or Creating a Report for the User Value Set ................................................ 15 User Value Set Problems: .............................................................................................. 16 Exercise 8: Steam Rate Property User Value .......................................................... 16 Exercise 9: Tail Gas Ratio User Value .................................................................... 17 Exercise 10: Grains per 100 SCF User Value .......................................................... 17 Heat Exchanger Rating ........................................................................................................ 18 Exercise 11: Crude Oil Shell & Tube Exchanger .................................................... 18 Exercise 12: Rating a Multi-Sided Compact Heat Exchanger ................................. 20 ProMax Calculator Methods ................................................................................................ 22 Use of JScript in Simple Solvers ................................................................................... 22 Exercise 13: DEPG Acid Gas Removal with JScript Simple Solver ....................... 23 Exercise 14: MDEA Sweetening with JScript Simple Solver ................................. 24 Use of Advanced Calculators......................................................................................... 25 Creating an Advanced Calculator ............................................................................ 26 Accessing and Specifying the Advanced Calculator ............................................... 26 Advanced Specifiers ...................................................................................................... 27 Complex Mixed Refrigerant Plant Example ............................................................ 27 Exercise 15: XCHG-100 Hot End Approach Advanced Specifier .................... 28 Exercise 16: XCHG-101 Advanced Specifier ................................................... 29 Exercise 17: InterStage Pressure Advanced Specifier ....................................... 29 Advanced Solvers .......................................................................................................... 30 Exercise 18: Sulfur Hydrogenation Reactor Advanced Solver................................ 30

Exercise 19: Crude Oil Exchanger Advanced Solver .............................................. 32 Advanced Calculator Using Excel ................................................................................. 33 Exercise 20: Example Problem with Excel Calculator ............................................ 34 Advanced Column Configurations ...................................................................................... 35 Column Set-up ............................................................................................................... 35 Column Execution and Convergence............................................................................. 36 Column Fails to Execute .......................................................................................... 36 Column Fails to Converge ....................................................................................... 37 Exercise 21: Demonstration of Reboiler Options .......................................................... 39 Exercise 22: Sour Water Stripper with Pump-around and Thermosyphon Reboiler ..... 41 Exercise 23: Glycol Unit with Attached Stahl Column ................................................. 42 Exercise 24: Stabilizer with Heavy Liquid Draw .......................................................... 43 Reactors................................................................................................................................ 44 General Review of Chemical Reactions ........................................................................ 44 Reaction Sets .................................................................................................................. 46 General Reaction Information.................................................................................. 46 Equilibrium Reactions ............................................................................................. 46 Conversion Reactions .............................................................................................. 47 Kinetic Reactions ..................................................................................................... 47 Exercise 25: Defining a Simple Reaction Set .......................................................... 48 Reactor Blocks in ProMax ............................................................................................. 49 Gibbs Minimization Reactors .................................................................................. 50 Exercise 26: Incinerator/Fired-Boiler, Gibbs Minimization Reactor ................ 51 Equilibrium Reactor Blocks in ProMax ................................................................... 52 Exercise 27: Steam Methane Reforming (SMR), Equilibrium Reactor ............ 53 Exercise 28: COS Hydrolysis in an Equilibrium Reactor .................................. 54 Conversion Reactor Blocks in ProMax.................................................................... 55 Exercise 29: HF Alkylation using a Conversion Reactor .................................. 56 Exercise 30: Defining a Catalytic Reaction Set ................................................. 57 Plug Flow Reactor Blocks in ProMax ..................................................................... 58 Exercise 31: Water Shift Reactors, Plug Flow Reactor ..................................... 59 Stirred Tank Reactor Blocks in ProMax .................................................................. 60 Exercise 32: Allyl Chloride Production (CSTR and PFR) ................................ 61

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ProMax Level IIAdvanced Simulation Methods Agenda

Day 1 Customizing ProMax Modifying the Options.xml File Modifying Column Hardware.xml File Modifying Pipe Segment Data.xml File Creating additional personalized stencils Creating personalized watermarks Property Stencils and Examples Adding the Property Stencils to your ProMax project Recycles/Solvers and Prioritization Techniques for improved solve time Troubleshooting User Variable Sets Creation of user-defined variables Examples of using user value sets Exchanger Ratings HEX Rating Day 2 ProMax Calculator Methods Use of JScript language in simple solvers Advanced specifiers and examples Advanced solvers and examples Excel Calculator Advanced Column Specifications and Troubleshooting Tower Types Available Associated Equipment Draw Types Available Pump-around loops Tips to help converge columns Day 3 Review of Reactions Reaction Sets Defining reaction sets Using reaction sets in reactors Rating Double-sided Reactors Reactors Gibbs Minimization Conversion Equilibrium Plug Flow Stirred Tank iv

Customizing ProMax
ProMax offers many different methods to customize it to your particular needs and usages. Several XML files are available to modify many options of ProMax, personalized stencils may be created allowing for easy drag-and-drop placement of complex units, watermarks can be customized, and binary interaction parameters can be calculated and modified based on any additional information you may have available.

Modifying Options.xml File

Included in your installation of ProMax is an Options.xml file. This file stores many of the preferences and options which are default to ProMax for all users of a computer, or for individual users. Some of the options available are: Saving all files as either Visio v2002 or Visio v2003 Modifying color blindness options to suit individual needs Changing the Process Stream (PStream) properties and order shown in the Project Viewer Managing both the information shown and the unit set shown in PStream tooltips Customizing the report options o Page Sizes (e.g. the default can be A4 for European users) o PStream Properties shown. The report follows separate rules than the Project Viewer and can be different. Altering the default units for any stream property Including additional common units (those that appear in the drop-down boxes in the Project Viewer) Creating custom unit sets if no default unit sets match your needs Changing the heat exchanger tabular data order Modifying the column tray data internals Including different composition bases By default the file location is: %AllUsersProfile%\Application Data\Bryan Research & Engineering Inc\ProMax3\Data

Warning: Always back-up your original Options.xml file before modifying

Exercise 1: Add New Property to Process Streams

Modify your Options.xml file to include the Normal Volumetric Flow Rate as a default value shown in the Project Viewer for all PStreams. Hint: most properties are used at some point in the Options.xml file and can be found by searching the document. If a property is not available in the XML file, all properties and their respective enumeration strings are listed in the VBA Object Browser. You can access this from ProMax by going to the Tools menu, then selective Macros and Visual Basic Editor from the options listed. Once this opens, you can then find the object browser under the View menu. In the list of Classes, scroll to pmxPhasePropEnum to find the list of Phase Property enumeration strings (e.g., pmxPhaseMassCp for the Mass Cp value).

Exercise 2: Add New Option in Drop Down Menu

Add an option for tonb/yr in the drop-down menu for your mass flow rate in all PStreams. Hint: these are classified as common units in the Options.xml file.

Exercise 3: New Tool Tip for Process Streams

Allow the molecular weight of your process streams to be shown automatically as a tool-tip when your mouse cursor hovers over a stream. Hint: these are classified as tool tips in the Options.xml file.

Exercise 4: Create a Custom Unit Set

Make a new unit set available for use within ProMax. Start with the kJ - bar unit set, and make the following changes: Standard Vapor Volumetric Flow: m^3/d instead of m^3/h Normal Vapor Volumetric Flow: Nm^3/d instead of Nm^3/h Standard Liquid Volumetric Flow: bbl/d instead of lpm Pressure: barg instead of bar

Modifying Column Hardware.xml File

Similar to the Options.xml file, the Column Hardware.xml file allows further customization and additions to ProMax. Specifically, the options provided with this file include: Customizing structured and random packing materials Modifying many parameters, including those seen in the sample code below:
- <Hardware Name="User Defined Random Packing"> <Item Name="pmxRandomPackingTypesEnum">pmxRandomPackUserDefined</Item> <Item Name="pmxPackingMaterialTypesEnum">pmxPackingMaterialMetal</Item> <Item Name="pmxRandomPackingFactor">130.0</Item> <Item Name="pmxRandomPackingSurfaceArea">101.7060367</Item> <Item Name="pmxRandomPackingVoidFraction">0.965</Item> <Item Name="Nominal Diameter">0.0508</Item> <Item Name="Billet Cfl">1.61</Item> <Item Name="Billet Cp">0.75</Item> <Item Name="Billet Ch">0.784</Item> <Item Name="Billet CL">1.218</Item> <Item Name="Billet Cv">0.362</Item>

- <Hardware Name="User Defined Structured Packing"> <Item Name="pmxStructuredPackingTypesEnum">pmxStructPackUserDefined</Item> <Item Name="pmxPackingMaterialTypesEnum">pmxPackingMaterialMetal</Item> <Item Name="pmxStructuredPackingFloodModelEnum"> pmxStructuredPackFloodModelBilletSchultes</Item> <Item Name="pmxStructuredPackingSurfaceArea">250</Item> <Item Name="pmxStructuredPackingVoidFraction">0.988</Item> <Item Name="Billet Cfl">2.464</Item> <Item Name="Billet Cp">0.292</Item> <Item Name="Billet Ch">0.554</Item> <Item Name="Billet CL">1.068</Item> <Item Name="Billet Cv">0.406</Item>

By default the file location is: %AllUsersProfile%\Application Data\Bryan Research & Engineering Inc\ProMax3\Data

Warning: Always back-up your original Column Hardware.xml file before modifying

Modifying Pipe Segment Data.xml File

Similar to the Options.xml and Column Hardware.xml files, the Pipe Segment Data.xml file allows further customization and additions to ProMax. Specifically, the options provided with this file include: New fittings and their resistance coefficients New ground type and their diffusivity New insulation types and their thermal conductivity Note: the ID number points ProMax to specific information in its database. When modifying any item, the ID must be deleted.
- <Type Name="pmxPSFittingType"> - <Entry Name="45 ell, standard" ID="{676A9D6D-2401-4962-824B4F9DD3574F49}"> <Item Name="pmxPSResistanceCoeff">0.35</Item> </Entry> - <Type Name="pmxPSGroundType"> - <Entry Name="Default" ID="{52E41E57-B399-4B99-9AE80EEDF42EDC2B}"> <Item Name="pmxPSGroundThermalConductivity">2.42303</Item> <Item Name="pmxPSGroundDiffusivity">1.032256E-06</Item> </Entry> - <Type Name="pmxPSInsulationType"> - <Entry Name="Linde evacuated superinsulation" ID="{38DE8277EA64-44D7-A339-937A9647FC97}"> <Item Name="pmxPSInsulationThermalConductivity">0.0004</Item> </Entry>

By default the file location is: %AllUsersProfile%\Application Data\Bryan Research & Engineering Inc\ProMax3\Data

Warning: Always back-up your original Pipe Segment Data.xml file before modifying

Creating Personalized Watermarks

ProMax allows for customization of the watermark. You can remove the Bryan Research & Engineering watermark and have no remaining background picture, or you may add your own picture instead. To remove or change the watermark, follow these steps: 1. Go to the Background page of the project, typically the last sheet tab at the bottom of the Visio page. 2. Right click anywhere on the Background page and choose View, then Layer Properties 3. De-selecting Visible and Print will disable the watermark, but allow it to later be re-enabled through the same process. 4. If you wish to permanently delete the Bryan Research & Engineering watermark from this project, select the Watermark layer, and click on the Remove button. 5. If you would like to add your own watermark to the page, any picture placed on the page will be shown on all other pages. To add a picture, click on the Insert menu item, then insert, picture, and from file, then browse to the picture you would like inserted. 6. To change the transparency of the newly added picture, right click on the object, select Format, then Picture. On the Image Control tab is an effect Transparency. 7. This must be done for each project you wish to change the watermark on. 8. To apply a change for all newly created ProMax projects, a template file must be changed in a similar manner. This template file is found by default in the folder C:\Program Files\Bryan Research & Engineering Inc\ProMax2\Templates o The template file is Project-A.vst for US customers. o The template file is Project-A4.vst for those customers using the A4 size paper. o Once you have created the file you would like to use, save it as a .vst file and replace the Project-A.vst or Project-A4.vst file in the Templates folder. o Note: new upgrades and releases of ProMax will override these changes. Please keep an additional copy of your modification for future use in a separate location.

Exercise 5: Changing the ProMax Watermark

Following the instructions above, change the watermark of a blank project to one of the images found in the Miscellaneous folder that was copied to your computer at the beginning of the training course.

Property Stencils and Examples

The following stencils are included with ProMax, however are not loaded by default. These provide some extended capabilities, and can be loaded by following these steps: 1. In ProMax, select File then Shapes 2. Locate the Stencil titled ProMax Property Stencil and select it 3. The ProMax Help file includes help topics on the Property Stencils There are several Property Calculator examples within the ProMax Property Stencil; most are made from the Property Calculator with VPScript added for functionality. In this collection, most of the objects function as is while the Solver/Specifier Example requires a small amount of VBScript code. These examples are as follows: Single Line Property Displays a single ProMax Property on PFD Property Input Allows input (when shape is selected) of editable ProMax properties directly from PFD Property Connector The Property Connector shape is a visual representation of data sharing between shapes. It displays no data itself, but transfers its moniker to another shape. It adds its property to a connected Property Calculator grid, or the one allowed property for the other basic shape types. The Connector contains a partial moniker (an offset) selectable via the Object Tree. The remainder of the moniker comes from the attached block or stream. A moved or copied connector retains its offset moniker if attached to a similar ProMax object, and will automatically retrieve the same property. Property Calculator This shape displays properties that are calculated from other ProMax Objects. Unlike the other basic shapes, the user may add multiple ProMax properties and local variables. Using VBScript, custom calculations are made, displayed, and even returned to ProMax during Solve. More information on this can be found in the Help. Streams Cn+ GPM This Property Calculator example displays a process streams Cn+ GPM. The carbon number cutoff (n) for this property is stored in the local constant called intMinCAtoms, and can be adjusted. Note: units are std gal / MSCF.

Sum I/O Property This Property Calculator example sums a given property for all inlet or outlet streams. Select the target stream property of a stream of the desired type (inlet or outlet) in the Edit Variable dialog. Combining a new Sum I/O Property with a Property Connector that the moniker offset selected and connects to the desired stream type (inlet or outlet) produces the same effect. API Vapor Relief Area This Property Calculator example calculates the API Relief Valve Area for a vapor stream. This should be used as an example only; please use our stream analysis for Relief Valve sizing. API Steam Relief Area The steam-only (vent to atmosphere) version of API relief valve sizing, utilizes the same inputs as above with the exception of maximum backpressure. This should be used as an example only; please use our stream analysis for Relief Valve sizing. Data Exchange This Property Calculator example exchanges a ProMax property between ProMax and an embedded Excel workbook in a bidirectional manner. Selecting cells with the mouse can update the input box. Solver/Specifier Example This Property Calculator example is a shell that with appropriate VBScript edits supplies a value to a script-based ProMax Calculator. 1. Create a new ProMax calculator for the input variable you want to control. You will enter the Measured Variables in the Stencil dialog rather than on the calculator dialog. 2. In the Property Calculator Edit dialog, modify the moniker of CalcSource to reference the target ProMax Calculator Source. 3. Add Measured Variables to the grid that reference the required properties; then press Edit Script Function. 4. Use the added measured variables to design the Specifier value function, or the Solver residual error function and place this formula in the VBScript in place of the number 1 next to the comment Assign value to calculator. Cn+GPM Solver Example This Property Calculator/Connector example calculates a stream Cn+GPM to drive a script based ProMax Solver. The Process stream for the Cn+GPM calculation is selected by connecting the unconnected end of the Property Connector to the target stream.

Cn+ Flow/Frac This Property Calculator example displays the flow or fraction sum of Cn+ compounds in a process stream. This has a similar behavior to the Cn+GPM calculation but has a user selectable composition basis accessible through the Edit dialog. Flow Duplicator Example This Property Calculator transfers a process stream composition and sets the flow from one connected stream to the other. The Property connector with the double arrow connects to the reference stream, while the other connector designates the target stream. Solver priority, flow basis and flow specification are set via the Edit dialog. Only when a valid destination stream is connected can the flow specification be set (via the Edit dialog or direct entry in the shape). UA Wizard This Property Calculator example offers the user the capability to control heat exchanger performance. UA, minimum approach, LMTD and %OD may be targeted by controlling outlet stream conditions or unit duty. The tool queries the user for key decisions and automatically sets up a Simple ProMax Calculator when connected to a heat-integrated exchanger or separator. Elemental Flow Example This Property Calculator example sums the flow of a given element in a process stream. The element is defined by symbol in variable "TargetElement". A Companion element, assigned to variable "CompanionElement", restricts the molecules included in the sum. For Example, the organic carbon flow is calculated by setting the target element to C and the companion element to H. Clearing the companion element (or setting it to ) removes this restriction. Copy Stream Conditions This example transfers a process streams conditions from one connected stream to the other. This differs from the Flow Duplicator Example in that the flow spec is set from the source stream. The destination stream must be completely empty before connecting to this Property Calculator. This shape transfers molar enthalpy, pressure and component mole fraction automatically while a simple ProMax solver is used to set the destinations molar flow. [Cn+] Solver This example sums the flow or fraction of compounds containing n or more carbon atoms in a process stream to drive a script based ProMax Solver. The predefined Simple solver is linked to the shape via the dialog that appears on drop or double clicks.

Pipeline Mach Example Connect this example to a pipeline to display the maximum fluid Mach number. If a user set flow exists on the inlet or outlet process streams, a script based ProMax Solver is automatically setup to drive the maximum fluid Mach number to the value defined in TargetMach. Flow Multiplier Example This example transfers a process streams composition, temperature, and pressure from one connected stream to the other. This stencil then allows for the connected stream to have a multiple of the flow rate set by the original stream. The default is 2, doubling the flow rate. Orifice Plate The Orifice Plate may be used to simulate either an orifice plate or a nozzle/venturi, and is capable of solving for outlet pressure, inlet pressure, or mass flow. Membrane The membrane block simulates an asynchronous vapor phase separation using permeability data. This depends on the type and thickness of polymer used; patent, literature and vendor references should be used for the most appropriate values. This model operates irrespective of equipment geometry, and can provide separation based on a fixed area, or find required area for a desired separation. Component GPM This example displays the GPM for a component in a process stream (where GPM is Gallons Per MSCF). Salt Example This shape calculates the amounts of the compounds whose ions comprise a salt and the amount of water required to obtain a specified weight percent salt. The required amounts of the compounds are automatically added to a selected stream. Chart The Chart tool allows the user to generate simple plots such as a column temperature profile, or temperature by increment across an exchanger. Date Example Dragging this shape to the flowsheet automatically displays the Project and flowsheet names, page number, and dates created, saved, modified and solved. Phase Envelope Example This example is a modification of the Chart tool, and displays the phase diagram for a specified stream, with an X marking stream conditions.

Heat Transfer Example This example is a modification of the Chart tool, and displays the heat transfer curve for a specified exchanger. Sum Component Flow/Frac. This sums the flow or fraction of compounds that are defined by an array of names. Predefined groups include amines, BETX, mercaptans and Sx. Oil/Water Emulsion Example This example modifies the viscosity and specific gravity or an existing Single Oil to mimic an oil/water emulsion. The oil to be modified should be defined before dragging the shape to the flowsheet. Depressurization Example This will estimate an orifice diameter required to depressurize a vessel to a given pressure in a given amount of time. You will specify the vessel volume, vent pipe diameter, initial pressure, downstream pressure, target pressure, time to reach pressure, heat input into the vessel, etc P/H Diagram This example is a modification of the Chart tool, and displays the pressure-enthalpy curve for a specified stream. Inline Flow Multiplier This transfers a process stream conditions and composition from one stream to another, with an option to multiply the flow rate by a userdefined multiple. The inlet stream should be connected to the small inlet arrow on the block. Not all conditions must be transferred. HTRI Data Transfer This shape is designed to transfer data directly from a ProMax heat transfer unit operation to an HTRI (Heat Transfer Research Inc._ input file. A licensed copy of the HTRI software must be installed on the computer to use this tool. Inlet and outlet conditions for heat transfer, as well as thermodynamic property data required by HTRI are exported. Block Calculator Designer This tool allows the user to create a ProMax shape with associated preset properties, User Values and/or Calculators from an existing ProMax shape. This shape can be saved in a new shape stencil for later use. Shape Converter This shape allows the user to convert an ordinary Visio shape into a ProMax block. The new block can be saved for future use.

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Recycles/Solvers and Prioritization

Both recycles and solvers used in ProMax have an associated priority value. This value determines the order in which ProMax attempts to solve any nested or dependent recycles and solvers. Recycles o Each ProMax recycle, whether material or energy, is defined as a solver based on its function. o By default, each recycle is assigned a priority of 1 when placed on the drawing page. o The user must then take control of the proper prioritization for each recycle to solve most efficiently. User-defined Solvers o Each solver defined by the user also has a priority. o By default each user defined solver is assigned a value of 0 upon creation. o The user also has the ability to define the priority of these solvers to help obtain the most efficient solution. Troubleshooting o The priority is determined by the highest value assigned; the higher the numerical value, the higher the priority. o ProMax looks only at relative values, therefore numbers can be skipped. For example, all priorities on the first flowsheet can be numbered in the 400s, the second flowsheet in the 300s, etc o It is usually best to solve the inner loop dependent solvers first and then work your way out. This may not always be the case. o A Grouping function is available to have a group of solvers evaluated simultaneously since several solvers may have shared dependencies. o If a solver appears to be stuck on iteration 1, and continues to repeat this there could be an issue with dependencies with your current set-up. Often selecting the box skip dependency check can assist with this issue, but it will place any solver with this selected as the lowest priority, which could increase the solve time.

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Exercise 6: Simple Example Demonstrating Prioritization Concept

Open the project named Recycle and Solver Priority Example from the solved folder to illustrate these principles. This example is an actual working facility owned by Crosstex Energy. It consists of two demethanizer plants, one common deethanizer with overhead treating, a depropanizer, debutanizer and associated utilities. The simulation contains a total of 15 recycles and user defined solvers. The priority of each is critical to obtaining a reasonable solution time.

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Exercise 7: Prioritization of a Large Multi-Flowsheet Plant

Open Exercise 7 Prioritization of a Large Multi-Flowsheet Plant from the training session files. Find a sensible order for the simulation to solve its calculators and recycles. This plant contains a DEA Amine Unit, two Claus Trains, an MDEA tail gas clean up unit and an incinerator. Depending on the priorities of the recycles and the calculators included in this simulation, the solve time can range from many hours to only a few minutes. Additional Process Information Flowsheet 1: DEA Flowsheet The DEA unit removes hydrogen sulfide (H2S) and carbon dioxide (CO2) from the Sour Gas inlet, creating a sweet gas. The stripper then will clean the DEA of the absorbed H2S and CO2. The overhead acid gas stream is then treated in the sulfur recover units. Flowsheet 2: SRU-A Flowsheet The sulfur recover units burn the acid gas with air, then pass the gas over specialized catalysts to change as much H2S into sulfur as possible. This sulfur is then removed from the process stream. A calculator is included to adjust the Dry Basis Air stream flow rate until the Tail Gas stream has a 2 mol H2S to 1 mol SO2 ratio; this provides the best conversion. Sulfur condensing on a catalyst bed leads to deactivation of the catalyst, thus an additional calculator is included on stream 25. This calculator adjusts the temperature so that the reactor outlet temperature stays 15C above the dew point of the outlet stream. Flowsheet 3: SRU-B Flowsheet Similar to Flowsheet 2, this flowsheet includes a 2:1 ratio Tail Gas solver on the Dry Basis Air stream, and a Dew Point solver on stream 13. This flowsheet also includes the hydrogenation reactor. This reactor converts any remaining sulfur back to hydrogen sulfide so the following MDEA unit can remove it from the stream. For this hydrogenation reactor to work correctly, the temperature and hydrogen levels must be maintained. A calculator has been included to adjust the fuel gas flow rate in stream 21 to solve for a 2 mol% H2 content in the reactor outlet Another calculator has been included to adjust the air flow rate in stream 25 to achieve an outlet temperature from the reactor of 315C. Flowsheet 4: MDEA Flowsheet The outlet from the hydrogenation reactor is then cooled in a Quench Tower, and fed to an amine absorber. This absorber then removes the hydrogen sulfide from the Tail Gas before it is sent to the incinerator. The amine is then stripped of the hydrogen sulfide in the MDEA stripper, and this off gas is then recycled back to the SRUs.

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User Value Sets

A user value is typically a property defined by the user which is not available in ProMax, but can also be a reference value, composition or property A user value set can contain a single user value or multiple user values. User values can be assigned a short moniker, and can be used in calculators or displayed in property tables, and can be included in a ProMax Report. The user value is defined using a simple specifier to relate properties or to set a reference value.

Defining a User Value

1. To define a user value set, open the Project Viewer by double-clicking on any stream or block from the flow sheet view, or through the ProMax drop down menu or toolbar. Then right click on the User Value Sets item in the navigation tree on the left side, and click "Add..." 2. In the User Value Set dialog, click the Add... button at the bottom to open the User Value Selection dialog. a. First specify the units. The units can be standard units already used by the program, unrecognized units, or user defined units. User defined units must be compatible with the program. Unrecognized units are for display only, and are treated as dimensionless by the program. b. Type in a descriptive name for the user value in the name field at the bottom. c. Be sure the "Associate with a New Specifier" checkbox is selected if you wish for this value to be related to or calculated from other values. d. Click the OK button to exit the dialog. 3. Bounds are optional. If an upper bound and/or lower bound are set and the enforce bounds check box is selected, a warning is issued any time the value of the parameter exceeds the specified bounds. a. Example: A reboiler steam rate is set as a user value (units of kg/l), and the parameter values are 0.08 (lower bound) and 0.2 (upper bound). If the value of the steam rate falls to 0.07, a warning is issued stating that the parameter is outside the specified bounds. 4. Right click on the blue Parameter field and select "Show Calculator" to open the Simple Specifier dialog associated with the user value. a. Add any independent variables to be used in defining the user value. b. In the specified variable field, type in an equation to define the user value, or a constant representing the user value. c. Close the simple specifier dialog.

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Displaying a User Value in a Property Table

User values can be displayed in a property table. Although it is not necessary to specify a short moniker for the user value, it is much more convenient to use a short descriptive name rather than the very long full moniker for the property. To generate a short moniker, open the user value set dialog in the Project Viewer and right-click the blue parameter field for the user value of interest. Select "Add to Short Moniker List" from the pop-up menu. In the short moniker dialog, type a short moniker in the field at the bottom and click the Add/Reset Short Moniker button. Drag a property table from the ProMax Streams stencils and place on the flow sheet. Double-click the property table to open the dialog, and in the lower left corner of the dialog, click the Moniker radio button and leave the short moniker check box selected. Available selections will include all short monikers for the project. Select the short moniker you want displayed in the property table by clicking on it and clicking the arrow button to transfer to the displayed selections. Click OK to exit the property table dialog.

Modifying or Creating a Report for the User Value Set

To access the defined user values, open the Project Viewer and find the user value set in the navigation tree. Right click on a user value set to display the options Show, Delete, Rename, and Report. Selecting Show is the same as double-clicking on the item to open it.

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User Value Set Problems:

The following three exercises all reference the previously solved Exercise 7: Prioritization of Large Multi-Flowsheet Plant

Exercise 8: Steam Rate Property User Value

A commonly used parameter in an amine unit is the steam rate, which might be referred to as the kg of steam supplied to the stripper reboiler per liter of amine solution circulated. Set up a User Value Set for the steam rate on the MDEA SCOT unit from Exercise 7: Prioritization of a Multi-Flowsheet Plant. 1. Select the Amine Unit simulation with the reboiler being heated by utility steam. 2. To create a user value set, open the Project Viewer and right click on the User Value Sets item in the navigation tree on the left side, and click "Add..." 3. In the User Value Set dialog, click the Add... button at the bottom to open the User Value Selection dialog. a. Click on User Defined Units and type "kg/l" in the units field. b. Type "Steam Rate" in the name field at the bottom. c. Be sure the "Associate with a New Specifier" checkbox is selected if desired. d. Click the OK button to exit the dialog. 4. Rename the user value set to Steam Rate be more descriptive 5. Right click on the blue parameter field and select "Show Calculator" to open the simple specifier dialog associated with the Steam Rate user value set. a. Add independent variables for the steam mass flow rate and the amine standard liquid volumetric flow rate. Double-check that the amine flow rate and the steam flow rate are on the same basis (i.e. both are a rate per minute), then click OK to exit the property moniker dialog. b. Type in the equation "SteamFlow/AmineFlow" for the specified value, assuming your variables are named SteamFlow and AmineFlow. c. Close the simple specifier dialog. 6. Open the Steam Rate user value set dialog again, right-click on the blue parameter field and select "Add to Short Moniker List" to open the moniker builder dialog. 7. Type "Steam_Rate" as the short moniker and click the Add/Reset Short Moniker button. 8. Drag a property table from the ProMax Streams stencil and place on the flow sheet. 9. Double-click the property table to open the dialog, and in the lower left corner of the dialog, click the Moniker radio button and leave the short moniker check box selected. Available selections will include all short monikers for the project. Select the Steam_Rate moniker by clicking on it, then click the arrow button to transfer to the Displayed Selections. Click OK to exit the property table dialog. 16

Exercise 9: Tail Gas Ratio User Value

A parameter often used in a Claus Sulfur Recovery unit is the Tail-gas H2S to SO2 molar ratio, which is typically controlled to be as close to 2 as possible. Create this Tail-gas H2S to SO2 Ratio User Value for both Claus trains and display the parameter in a Property Table for the flowsheet from Exercise 7: Prioritization of a Large Multi-Flowsheet Plant.

Exercise 10: Grains per 100 SCF User Value

A parameter sometimes used in an amine unit is the concentration of H2S in the treated gas in units of grains per 100 SCF. A typical specification is 1/4 grain, which is the equivalent of about 4 ppmv H2S. Create this H2S Concentration User Value on the DEA unit of Exercise 7: Prioritization of a Large Multi-Flowsheet Plant and display the value of the parameter in a Property Table.

17

Heat Exchanger Rating

Exercise 11: Crude Oil Shell & Tube Exchanger
The first objective is to define two hypothetical oil components and use the heat exchanger rating utility within ProMax. Use the following information to create the lube and crude oil components and define the feed streams. A drawn version of this may be found in the training session files saved as Exercise 11 Crude Oil Shell & Tube Exchanger. Lube Oil Properties: Volume Average Boiling Pt Temperature of Low T Viscosity Low Temperature Viscosity Temperature of High T Viscosity High Temperature Viscosity Crude Oil Properties: Volume Average Boiling Pt Inlet Conditions: Temperature 230C Pressure 2.75 bar Mass Flow 28,000 kg/hr

425C 150C 7.7cP 260C 1.4cP

310C

Inlet Conditions: Temperature 150C Pressure 2.75 bar Mass Flow 130,000 kg/hr

Additional Process Information: The composition of each feed will be pure Lube or Crude oil. Assume a 0.3 bar pressure drop on each side of each exchanger. The crude oil is split equally to E3 and E4. Use the following temperature conditions: L1 = 225C, L2 = 215C, L3 = 207C and Lube Oil Out = 200C Upon successful execution, define each exchanger based on the attached exchanger specification sheet. You may use the Export and Import functions of the rating utility to aid in this operation.
Crude Oil Out Crude Oil In

Mixer 3 6 7

Splitter

Lube Oil In E1

L1 E2

L2 E3

L3 E4

Lube Oil Out

5 4

18

19

Exercise 12: Rating a Multi-Sided Compact Heat Exchanger

A natural gas stream with the conditions and composition listed below is to be cooled to -75C before being throttled to a lower pressure. Set up a complex exchanger which uses the flashed vapor and liquid to cool the natural gas. Determine whether or not the exchanger will perform based on the following ALPEMA datasheet. You must draw this flowsheet. Inlet Gas Conditions: Temperature 25C Pressure 55 bar Flow Rate 35,000 Nm3/h Composition (mol %): Methane 85.0 Ethane 5.0 Propane 3.5 n-Butane 2.0 i-Pentane 1.0 n-Pentane 1.0 n-Hexane 0.5 Carbon Dioxide 2.0

Additional Process Information: Throttle the gas to 42 bar. The flash vapor side should reference the inlet gas stream and should exit 3C cooler than stream Inlet Gas. Determine the outlet temperature of the liquid required to balance the complex exchanger duty. Remember that your exchanger sides A, B and C may not match with the sides A, B and C of the specification sheet on the following page. Also note that the layers A, B and C do not necessarily correspond with the sides A, B and C of the exchanger.

Flash Vapor

Inlet Gas

2 VLVE-100

Flash

Flash Liquids

XCHG-100

20

21

ProMax Calculator Methods

ProMax offers many options to help you arrive at your desired solution. These solvers and specifiers range from very simple concepts to very complex and elaborate solution methods. The primary options available are: Simple solvers and specifiers Using JScript in simple solvers to arrive at slightly more difficult specifications Using JScript or VBScript in advanced solvers and advanced specifiers allowing for much more complex equations and methods to solutions Grouping simple solvers together. Using the Excel calculator in advanced calculators Using VBA, C#, C++, etc

Use of JScript in Simple Solvers

Simple Solvers created in ProMax utilize a simple JScript code. Typically these calculators are set up as a single function to solve for a single specification. However, there is additional functionality available in the simple solver than is typically used. The following examples take advantage of both the simplicity of the simple solver and the added functionality of this JScript coding. If-Then-Else statements can be used; however these occasionally will not work as expected due to the tolerances that ProMax allows in its solutions. A better approach is the Math.max function available if attempting to have a solution that meets two different specifications. Please refer to our Help menu regarding the full functionality of JScript.

22

Exercise 13: DEPG Acid Gas Removal with JScript Simple Solver
Simulate an AGR Contactor used to remove both CO2 and H2S from the feed stream. Create a single simple solver, using JScript functionality, to find the necessary DEPG flow rate to assure always meeting both 5 mol% CO2 and 35 ppm(mol) H2S in the sweet gas. Assume a saturated inlet gas with the following composition: Conditions: Temperature Pressure Flow Composition H2S CO2 C1 C2 Methyl Mercaptan Mole % 9 16 67.9 7 0.1

35 C 38 bar 11,500 Nm3/h

Additional Process Information Assume the Lean DEPG stream is 97.2 mass% DEPG, and contains residual H2S and CO2 each at 0.005 mass%; also assume the stream is 18 C Questions: Part 1 1. What is the necessary flow rate of the DEPG to meet the required specifications? 2. Which specification is determining this? Part 2 Now change the inlet composition to have 12 mol% H2S and 13 mol% CO2 1. What is the required flow rate of the DEPG to meet the required specifications? 2. Which specification is determining this?
Sweet Gas

Lean DEPG

AGR Tower

Dry Sour Gas Saturator

Wet Sour Gas

Water Saturant Rich DEPG

23

Exercise 14: MDEA Sweetening with JScript Simple Solver

Simulate an MDEA sweetening tower to sweeten the water-saturated sour gas to 12 ppmv H2S. However, also ensure that the rich loading does not exceed 0.45 mol total acid gas/mol amine. Create a simple solver, using JScript functionality, to ensure that both specifications are met, starting with the unsolved Exercise 14 Simple MDEA for Scripting Simple Solver file in the training session files. This file is executed, but not at the optimized conditions. Conditions: Temperature Pressure Flow 34 C 70 barg 11000 Nm3/h Composition H2S CO2 C1 C2 C3 C4 Mole % 0.5 3 90 5 1 0.5

Additional Process Information The regenerator has a condenser temperature of 48C, and a reboiler steam rate of 0.12 kg/l amine. The rich flash operates at 5 barg, and the lean/rich exchanger heats the rich amine entering the regenerator to 100C. The amine is a 40 wt% solution Questions What flow rate is required to meet the specifications above? What flow rate is required to meet these specifications if the MDEA mixture is diluted over time to 36 wt%? Which constraint is controlling this flow rate?
Sweet Gas Makeup Lean Amine Cooler Duty 1 14 Recycle Guess Lean Amine Cooler Lean Amine to Absorber Circulation Pump Duty Saturator Dry Basis Sour Gas Sour Feed 7 Rich Amine Absorber Saturant (Water) 5 19 Rich Flash Lean/Rich Exch 6 10 2 1 Amine Circulation Blowdown 3 Recycle VSSL-100 4 Condenser Duty Circulation Pump Makeup/Blowdown Acid Gas

10 Lean Amine DTWR-101 2

K-100 Reboiler Duty

Utility Steam vg

Utility Condensate

24

Use of Advanced Calculators

advanced calculators are specifiers or solvers with multiple calculated and measured variables They offer extreme flexibility but are more complicated to create Like their simple counterparts, calculations in advanced specifiers are specification calculations and calculations in advanced solvers are objective function calculations Mathematically discontinuous functions are prone to convergence failure in the solver Several types of advanced calculators are available: Script-, Event-, Excel-, VBA- and External-based Applications of advanced calculators o Grouping functionality of multiple simple calculators into a single calculators o Consolidation of calculator codecan view all code at a single time o More complicated mathematical expressionsnot limited to single line expressions o Can obtain additional ProMax data not available in simple calculators (e.g., pure component properties) o Used in solvers when there is a multivariable relationship rather than a single variable relationship Script type calculators allow both Jscript (used in simple calculators) and VBScript by user selection o Requires writing a subroutine in the selected language to specify parameters or to evaluate solver objective functions o Jscript is a case sensitive language while VBScript is case insensitive o VBScript has similar syntax to VBA (Visual Basic for Applications) used to write macros in Microsoft Office applications o Complete documentation for both languages is available in the Help>ProMax Help->Scripting Reference menu item Excel based advanced calculators o Used when calculations are more naturally available in Excel o Like exporting and importing, require an OLE embedded Excel Workbook in the ProMax project o Involves extra overhead relative to script calculators including OLE Workbook and data transfer between two processes o Should restrict use to cases where calculations need to be made in Excel

25

Creating an Advanced Calculator

1. Open the Project Viewer and right-click on calculator node in the navigation tree. 2. Click on "Add..." in the pop-up menu to open the Calculator Specification dialog. 3. Select Specifier or Solver from the Calculator Specification dialog. 4. Select Script or Excel from the Calculator Specification dialog. 5. Click OK to save your choices.

Accessing and Specifying the Advanced Calculator

To open the Advanced Specifier dialog or the Advanced Solver dialog, locate the Specifier or Solver in the Project Viewer navigation tree and double-click on the item, or right click on the item and select "Show" from the pop-up menu. After accessing the Advanced Calculator, select variables from the Advanced Solver or Advanced Specifier dialogs by clicking on the "Add..." buttons. Click on the "Setup..." button to open the Scripting Development Environment dialog. Select JScript or VBScript as the scripting language by clicking on your selection at the top of the dialog. Write the Advanced Solver or Specifier script: Function Calculator(m,r) is executed by ProMaxs solver every time a calculated variable (or residual error) associated with this calculator is required. Variable m contains the measured variables and is accessed by m(NAME) Where: NAME is a string containing the variable's Name. For example: m("MyMeasuredVariable") Variable "r" passes back the residuals or calculated variables and is set by r(NAME) = ... r.Ready(NAME) returns a Boolean that signifies which Calculated Variable needs to be calculated.

26

Advanced Specifiers
Complex Mixed Refrigerant Plant Example
The following three exercises will show how to use advanced specifiers to control various properties of a project. In this example, calculators are used to set the temperature out of selected sides of the complex exchangers and the pressure for the first two stages of compression in a 3 stage compressor. This file can be found in your training session files as Exercise 15, 16, 17 Complex Heat Exchangers with Mixed Refrigerant. The unsolved version is executed, however does not include any of the Advanced Specifiers covered in the next several pages.

Complex Heat Exchangers with Mixed Refrigerant

13 - Residual

Q-7 43 42 Q-3 CMPR-101 41 FAXR-100 Q-4 CMPR-102 44

Q-8 45 FAXR-101 Q-5 CMPR-103 46

Q-9 47 XCHG-102 TRM-1 49

Refrig Drum 50 VLVE-103 XCHG-101 55 51

56

58 MIX-101

57 VLVE-102

54

53 VLVE-101

52

12 MIX-100 Q-6 CMPR-100 4

11

10

DeC2 Condenser 3 8 9 1

1 - Feed Gas

2 Cold Separator 5 6 VLVE-100

Q-1 7 Deethanizer

15

15 DeC2 Reboiler Q-2

XCHG-100 7 14 16 - LPG

27

Exercise 15: XCHG-100 Hot End Approach Advanced Specifier

Create an Advanced Specifier to set the temperature of Stream 54 to 4C below the feed stream 1-Feed Gas, and Stream 11 and Stream 4 both 2C below the feed stream, which has a known temperature. The use of an Advanced Specifier allows for a single calculator instead of 3 different Simple Specifiers. Please refer to page 28 for the flowsheet diagram. To view the Advanced Specifier dialog, open the Project Viewer and click on the Calculators node in the Navigation Tree to the left. Then double-click on "XCHG-100 Hot End Approach Advanced Specifier". This Specifier uses the following Variables:
Calculated Variable THRef (Stream 54 Temperature) THColumn (Stream 11 Temperature) THFlash (Stream 4 Temperature) Measured Variable TIn (1-Feed Gas Temperature) TIn (1-Feed Gas Temperature) TIn (1-Feed Gas Temperature) Function* Stream 54 is 4C Below the Feed Gas Temperature Stream 11 is 2C Below the Feed Gas Temperature Stream 4 is 2C Below the Feed Gas Temperature

Variables can be added using the Moniker Tree or from pre-defined Short Moniker variables. For this example, the temperatures of streams 54, 11 and 4 should all be added as Calculated Variables. Each of these Calculated Variables should then have an Associated Measured Variable assigned as the temperature of the inlet stream (1-Feed Gas). In the Advanced Specifier dialog, click the "Code Source..." button to view the Scripting Development Environment dialog. This code sets the temperatures of the three streams relative to the 1-Feed Gas temperature.

28

Exercise 16: XCHG-101 Advanced Specifier

Referring to the Complex Mixed Refrigerant Plant Example on page 28, create an Advanced Specifier to Set the temperature in Stream 56 exiting the complex exchanger XCHG101 (Side A outlet) equal to the known temperature of Stream 52 (Side C outlet). Set the pressure of Stream 58 out of the exchanger (Side B outlet) equal to the known pressure of Stream 54 (compressor CMPR-101 suction). Setting this pressure will determine the temperature of Stream 58 (Side B outlet)

Exercise 17: InterStage Pressure Advanced Specifier

Referring to the Complex Mixed Refrigerant Plant Example on page 28, create an Advanced Specifier to Set the outlet pressures for the 1st and 2nd stages of compression such that the compression ratios for each stage are approximately equal. Use the equations o 1st Stage Outlet Pressure = Inlet Pressure * (Discharge Pressure / Inlet Pressure) ^ (1/3) o 2nd Stage Outlet Pressure = Inlet Pressure * (Discharge Pressure / Inlet Pressure) ^ (2/3) Inlet Pressure = Stream 54 Discharge Pressure = Stream 46 1st Stage Outlet = Stream 42 2nd Stage Outlet = Stream 44

29

Advanced Solvers
Exercise 18: Sulfur Hydrogenation Reactor Advanced Solver
The Simple Sulfur Hydrogenation Reactor example illustrates how to model a Hydrogenation or "TGCU" Reactor and the associated Reducing Gas Generator or "RGG" Reactor. An unsolved version can be found in the training session files as Exercise 18 Sulfur Hydrogenation Reactor.

From Claus Beds Stream: Inlet Conditions: Temperature 140C Pressure 0.6 barg Flowrate: 100 kmol/h

Composition H2 N2 CO CO2 H2S SO2 H2O

Mol % 0.575 39.2 0.005 35.5 0.48 0.24 24.0

Simulation Discussion The Bone Dry Air stream is saturated to 70% in block Saturator then mixed with the Fuel gas before being fed to the Reducing Gas Burner. Use 100% Methane as the Fuel gas in this example. The Reducing Gas Burner effluent is mixed with the tail gas "From Claus Beds" before being fed to the Hydrogenation Reactor. The Hydrogenation Reactor converts all sulfur species to H2S before being fed to the Tail Gas Cleanup Unit (TGCU). This is an adiabatic reactor Type "Gibbs Minimization" with Gibbs Set Sulfur Hydrogenation. Reducing gas is required to convert all sulfur species to H2S. This reducing gas can be "pure" hydrogen or can be provided by a Reducing Gas Generator (RGG). The RGG provides H2 and CO by burning fuel gas, and is modeled as an adiabatic reactor Type "Gibbs Minimization" with Gibbs Set "Burner. Excess H2 should be present in the Hydrogenation Reactor effluent (about 1%) to assure that all sulfur species have been converted to H2S. The Hydrogenation Reactor outlet temperature should be maintained at 260C 370C by adjusting the amount of Fuel gas fed to the RGG. The Advanced Solver "Hydrolyzing Bed Solver" simultaneously feeds enough air to the RGG to achieve 1% H in the Hydrogenation Reactor effluent and enough Fuel gas to the RGG to achieve a Hydrogenation Reactor outlet temperature of 370C.
2

30

Following is the Advanced Solver dialog:

Click the "Code Source..." button to view the VBscript for the Solver.

31

Exercise 19: Crude Oil Exchanger Advanced Solver

Using the previously solved Exercise 11, define an advanced calculator that will automatically determine the exchanger performance such that you have an excess of 5% surface area at the converged conditions. The exchanger percent over design will be your measured variable within the solver. You will have four calculated variables that represent the four lube oil outlet temperatures from each exchanger. The code source should be written to calculate the lube oil outlet temperature from each exchanger that results in an exchanger with 5% over design.

Crude Oil Out

Crude Oil In

Mixer 3 6 7

Splitter

Lube Oil In E1

L1 E2

L2 E3

L3 E4

Lube Oil Out

5 4

32

Advanced Calculator Using Excel

Requires OLE embedding an Excel workbook in the ProMax project. If you already have a worksheet, copy it to a ProMax OLE-embedded workbook. Variables are selected in ProMax just like with script based calculators Must map all variables to ranges in Excel for exporting and importing Calculations are performed by the Excel engine All data must be transferred across process boundary which can be relatively slow The first screen looks identical to the previous examples. 1. Select your variable you want ProMax to vary. 2. Select the variables you want ProMax to look at for information. 3. Set any Solver priorities and bounds. 4. Select Setup under Excel type

The next screen allows you to link ProMax with Excel. Each variable should be linked to a specific cell or range in Excel. Variables on the left are the measured variables; the information that will be put into Excel. The variable on the right is the residual function, which will be solved to zero by ProMax.

In the Excel sheet, variables linked to ProMax will have a small red triangle in the upper corner of their cell. The worksheet should be set up to have a residual function that will equal zero when the correct answer has been reached. This is titled Objective Function returned to ProMax in the example to the left.

33

Exercise 20: Example Problem with Excel Calculator

Use an advanced calculator to adjust either the duty or temperature change across the exchanger so that the UA ProMax calculates matches the UA calculations from an existing Excel worksheet. An unsolved version of both the ProMax and Excel files are available as Exercise 20 Double Pipe Exchanger using Advanced Solver in Excel. The Excel sheet performs heat transfer calculations based on the Sieder-Tate equation. This equation estimates the Nusselt number as:
0.14 0.8 Re 3 Pr 1 b w

N Nu
NPr Cp k

0.023 N N
; N Re

Dv

; N Nu

hD k

The Excel workbook will calculate the clean and service overall heat transfer coefficients based on tube outside area and also calculate the UA product. The purpose of the advanced solver in ProMax is to drive the UA product calculated by ProMax equal to that calculated in the Excel workbook from the heat transfer coefficient calculation. All properties of the inlet and outlets that are required to evaluate the heat transfer coefficients must be made measured variables and exported to Excel. These include the temperatures, mass heat capacities, mass densities, viscosities, and thermal conductivities. Additionally the mass flow rates of each fluid must also be selected as measured variables for export to Excel. The calculations in the Excel workbook require the viscosities in kg/(ms).

A double pipe heat exchanger is available to heat 4455 kg/hr of cold benzene at 27C. A stream of 2870 kg/hr of toluene at 70C is available for this purpose. The heat exchanger has the following characteristics: Property Inside pipe ID Inside pipe OD Outside pipe ID Tube length Tube thermal conductivity Value 3.5 cm 4.25 cm 5.25 cm 33.5 m 59 W/(mC)

Benzene will be placed in the tube and toluene in the annulus. Use a fouling resistance of 0.00018 Cm2/W on both sides. If the above heat exchanger is selected for this service, what will be the discharge temperatures for both the benzene and the toluene?

34

Advanced Column Configurations

Column Set-up
ProMax allows almost any column configuration to be created. Some of the primary options available are: Multiple Tower Types o Columns can be configured as liquid-liquid, vapor-liquid or vapor-light liquid-heavy liquid o Equilibrium, TSweet Kinetics, TSweet Alternate Stripper, Polar Liquid and Non-Polar Liquid tower types are available to accurately solve the column Connected Condensers and Reboilers o For ProMax to recognize a condenser or reboiler as part of the column, these must be associated in the Project Viewer, Process Data tab at the bottom o Associated condensers and reboilers do not require a recycle block for the returning streams. These blocks, once associated, are actually considered an additional stage to the tower. Thus any stream exiting the tower and entering either the condenser or reboiler is treated as a pumparound stream. o These associated blocks will solve simultaneously with the column, and any specifications for the additions can be made inside the main column. Reboiler Options o There are many variations of reboilers that can be simulated in ProMax. These include both bottoms reboilers and side reboilers o Thermosyphons, forced flow and kettle reboilers are available o Side reboilers can include same stage returns, thermosyphon types, forced flow types and even direct energy injection to the stage Connected Side Strippers o The specifications for these side columns can be made in the main column o All connected columns are executed simultaneously, and no recycles are necessary for streams returning to the main column from an attachment. Vapor and Liquid Draws o By default, the draw off the tray is a light liquid o Right-click on the tray in the Project Viewer, Connections tab to change this default to either vapor, or heavy liquid (available only in a VLLE tower). Pump-around Loops o Can include pumps and heat exchangers. Splitters can also be used, but will require an additional pump-around estimate as a specification in the tower. o Specification can be made in the main tower, or in the heat exchangers 35

Column Execution and Convergence

While ProMax will allow almost any column configuration, occasionally these configurations or the specifications set can be difficult to converge. Below are some hints and steps to take to help these towers converge.

Column Fails to Execute

These are some steps to take if the column does not attempt to solve when the execute button is pressed. Specify Column Pressure Check the stage data, summary grouping to make certain that the top and bottom stage pressures are set, or that the "Pressure Change" parameter is specified. Check Degrees of Freedom Check the specifications tab to make certain there are 0 degrees of freedom. Add specifications if necessary. Confirm No Conflicting Specifications This condition should be noted in the message log as an over-specification. An example of conflicting specifications would be setting both boil-up ratio and reboiler heat duty. Check Condenser and Reboiler A pressure drop should be specified in the reboiler and in the condenser, if present. Also verify that energy streams are attached to the condenser and/or reboiler. Fully Specify all Pump-around Blocks If the distillation column has a pump-around with a heat exchanger, pump or other block, check that the pressure drop and any required specifications have been made. Also check that an energy stream is attached to the heat exchanger if it is single sided and to any pumps or compressors. Add Required Pump-around Estimates Be sure required estimates have been made, especially if the column has a pump-around or side column. Duty or flow ratio estimates might be required. Designate Condensers and Reboilers If a condenser or reboiler is added to a column, it must be specified in the column process data tab.

36

Column Fails to Converge

Check all Inlet Streams First and foremost check each of your column feed streams. If these are not at the expected conditions, then the column is more likely to fail. Check Specifications Confirm that the specifications do not imply an impossible separation. Delete Specification Tolerances If a tolerance is set, delete the value. In general, setting the specification tolerance is discouraged, as the program will automatically choose an optimal tolerance. Try Easier Specifications The ratio specifications automatically created by ProMax are natural variables for the solver. These specifications will be easiest for ProMax to solve, and may help obtain an initial column profile, allowing you to then enable a more difficult specification (such as component compositions, TVP, or temperatures). Confirm Vapor and Liquid on All Stages Vapor and liquid must be present on each stage of the distillation column. If the column does not have a condenser or reboiler, confirm that a feed containing some liquid or vapor, respectively, exists on the top or bottom stage. Change Enthalpy Model This option is found in the column Convergence tab; choices are Boston-Britt or Composition-Dependent. The default Boston-Britt should be used when there are no convergence problems. o Composition-Dependent is a unique enthalpy model and is useful for unstable or difficult-to-converge columns (e.g. ionic columns, especially amine strippers, or columns with extremely wide or narrow boiling point differences between the components). o The Composition-Dependent enthalpy model can be prohibitively slow for a large number of components in a non-electrolytic environment. If the column does not converge and oscillates within the first 50 iterations, stop execution and check the validity of input data, especially specifications. Change Inner Loop Model This option is also found in the column convergence tab; choices are BostonSullivan or Boston-Sullivan Non-ideal. Boston-Sullivan is the default and should be used when there are no convergence problems. o Boston-Sullivan Non-ideal is useful for unstable or difficult-to-converge columns (e.g. highly-loaded amine absorbers, absorbers where the amine becomes the limiting reagent and strippers operating near minimum reflux). o The Non-ideal model should be used in combination with the Composition-Dependent enthalpy model. This model can be prohibitively slow for a large number of components in a nonelectrolytic environment. 37

Add Initial Estimates Add initial estimates, especially for more "difficult" specifications such as component flows or draw temperatures. Reflux ratio and boil-up ratio estimates are often helpful, as are flow rate estimates for side draws. Change Column Type The polar liquid column type can aid convergence in columns which have a nonpolar vapor phase in contact with a polar liquid phase (e.g. methanol-protected cold process). Use K Damping Try changing the K damping parameter in the column convergence tab. o Although some damping is performed internally in the column calculations, specifying a K damping parameter can be beneficial. The value for the K damping should be non-negative integers up to about 10 (using too high of a value can lead to erroneous convergence). o Increasing the K damping can be useful if the outer loop error oscillates or when the error For staged column X the inner loop calculation failed due to an invalid stage temperature calculation. Enable/Disable Boston-Sullivan Kb Try using Boston-Sullivan Kb found in the convergence tab; or, if BostonSullivan Kb is enabled, clear the checkbox to disable. This parameter can aid convergence for very wide or very narrow boiling mixtures. Increase Maximum Iterations If the column appears to be converging, but exceeds the maximum iterations, this value can be increased in the solver grouping of the convergence tab. Monitor Specifications and Variables Monitor the specifications and variables in the tables on the specifications tab, and compare the calculated value to the specified target value. For example, if the reflux ratio is set to 1, the column fails, and the calculated value is 0.1, there is likely not enough liquid flow at the top of the column. Modify Variable Estimates and Bounds The column provides an estimate for variables if an estimate is not provided by the user. The Target values for these variables can be changed on either the specifications tab or convergence tab, variables grouping. Lower and upper bounds can also be specified. Add a Recycle to the Pump-around Loop If the column has a pump-around loop and fails to converge due to errors in the pump-around blocks or the loop itself, or if the column calculations are exceedingly slow, consider adding a recycle block to the pump-around loop. When the recycle is added to the loop, the pump-around effectively becomes a "draw". The draw rate is still specified in the column Specifications tab, but no pump-around estimates are required for exchangers or pumps in the loop.

38

Exercise 21: Demonstration of Reboiler Options

ProMax offers many options to model various reboiler types. The flexibility of ProMax allows for many different choices of both bottom reboilers, including Kettle and Thermosyphon types, and side reboilers. These options will allow your simulation to best match your operating conditions. Some of the possible configurations are demonstrated below.

Bottom Reboiler Options: Plug Flow Kettle: This is the default in ProMax; it looks identical to the Boiling Shell Kettle, but the heat transfer details are based on plug flow. In this case, a selection has been made to calculate the heat transfer details based on pool boiling for the shell side of the default kettle reboiler options. A thermosyphon reboiler can be modeled with a specified flow rate through the exchanger if a recycle is included.

Boiling Shell Kettle:

Thermosyphon with Recycle:

Thermosyphon without Recycle: No recycle is needed if the split to the reboiler is done through a fractional basis. Induced Flow: This models a full flow reboiler with partial liquid return to the column.

Boiling Shell Kettle

Thermosyphon with Recycle 23

Thermosyphon without Recycle

Induced Flow 43

13 6 1 2 1 4

33 1 8 1

Q-3

7 53 12 XCHG-103 Q-4 14 54

Q-5

Q-6

Q-7

12 24 55

28 56

12

38 57

12

18 Fixed Flowrate TS

34

58 Fixed Fraction TS 36

44

46 VSSL-100

26 19True Kettle Splitter 2 25 29 Recycle Splitter 3 39

45 Induced Flow Exch 60 Splitter 4 59 47 48

49

39

Side Reboiler Options: All Liquid to Exchanger: Duty may be directly to a stage of a distillation columns by simply attaching an energy stream. Same Stage Return: The same effect is obtained by drawing a liquid stream from the column and returning to the same stage after having passed through a separate heat exchanger. When removing material from one stage and returning to another stage you only need to specify the amount of the draw. No recycle is required. Additional equipment may also be modeled in the side reboiler pump-around loop. The type of equipment and how it is specified will determine if the column needs more information to solve.

Thermosyphon:

Forced Flow:

13 3 6 1 1 1 2 23 1 7 1

33

11 5 51 4 53 16 26 55 Vert Thermosyphon 56 25 10 4

12

58 7 36

PUMP-100 35 7

Q-1

7 54 Same Stage

15

Q-6 8 57 Forced Flow 37 8

52 Simple

12 4

12 14 Q-2 K-100

18

12 24 Q-3 K-101

28

12 34 Q-4 K-102

38

Q-5 K-103

19

29

39 Plug Flow 50 % Draw

QStream (=All Liq to Exch)

Return to same stage 50% Draw

Thermosyphon

40

Exercise 22: Sour Water Stripper with Pump-around and Thermosyphon Reboiler
Simulate a sour water stripper used to clean the ammonia and hydrogen sulfide from the feed stream. An unsolved version may be found in the training session files as Exercise 22 Advanced Column Example - Sour Water Stripper. Assume the following feed composition: Conditions: Temperature Pressure Flow Composition NH3 H2S Water Mole % 0.5 0.5 99

40 C 5 bar 45 m3/hr

Additional Process Information The cross exchanger heats the feed entering the tower to 80 C The Pump-around cooler can cool the pump-around to 60 C 60% of the bottoms is returned to the column through the reboiler The reboiler is used to vaporize 15% of the return stream The overhead should be at 2 bar, and the temperature should not get below 82 C to minimize ammonium salt formation; the temperature should otherwise be minimized to reduce water loss In most cases a reasonable pumparound duty estimate is required. Good estimates for this case are approximately -3 MW for the cooler and 6 MW for the reboiler.

41

Exercise 23: Glycol Unit with Attached Stahl Column

Add an attached column to the regenerator of the following glycol unit to enhance the stripping of water from the glycol. This file is saved in the training session files as Exercise 23 Advanced Column Example Stahl Column; the exercise file is a solved, working glycol unit, but with a less effective regenerator design than the following. Additional Process Information: Use 4 Nm3/h of dry gas as the stripping gas added to the Stahl Column. Assume 2 ideal stages for the Stahl Column

14 Dry Gas SPLT-100 7

Gas/Glycol HEX Glycol Pump 18 20 19 RCYL-1 Pump Hp 1 Glycol Contactor 17 16

TEG TEG Makeup

Blowdown Water Gas Condenser

Q
QRCYL-1 Q-100

1 Q-101 15 1 2

13 8 Saturator 9 Inlet Gas Reflux Coil Water (Saturant) Rich Flash 21 24 12 10 VLVE-100 11 Flash Gas 2 XCHG-100

6 VLVE-101

Glycol Regenerator

Reboiler

5 1

3 Lean TEG Reboiler Q

2 DTWR-100

Questions: 1. How does the new dry gas water content compare with the original case? 2. How does the lean glycol composition compare with the original case? 3. How do your BTEX emissions in the water gas compare with the original case?

42

Exercise 24: Stabilizer with Heavy Liquid Draw

Simulate the following stabilizer column based on the information provided. The simulation can be found in the training session files saved as Exercise 24 Advanced Column Example Stabilizer with Heavy Liquid Draw. Feed Conditions: Temperature: 50C Pressure: 15 bar Flow rate: 750 m3/hr Composition (mol%): Methane 3 Ethane 7 Propane 20 i-Butane 6 n-Butane 7 i-Pentane 4 n-Pentane 3 Cyclohexane 5 H2O 6 Hexane 4 Heptane Octane Nonane Decane C11 C12 C13 C14 C15 4 4 4 3 3 3 2 2 10

Additional Process Information The column has 10 ideal stages The feed is a three phase stream. Please configure the column to accommodate three phases and include a process draw from stage 2 to remove the water phase. Add a side reboiler that supplies 4.2x107 kJ/hr of energy to heat the light liquid drawn from stage 7 and returned to stage 8. The draw rate approaches a total draw from the stage. The reboiler should provide enough heat to obtain a temperature of 120C.

Questions: 1. How many liters per minute of water are removed from stage 2? 2. How many liters per minute of condensate are produced? 3. What percent water recovery is achieved with the draw?
4

Three Phase Feed 8

1 2 3 4 5 6 6 3 7 8 9 10 1 K-100 Q-1 2 5 Stabilizer 9

XCHG-100

43

Reactors
General Review of Chemical Reactions
For reaction of form:

aA bB
b rA , rC a

cC dD
c rA , rD a d rA a

the rates of reaction of each species are related by:

rB

Rates are usually expressed in terms of moles per time per volume Heterogeneous catalytic reaction rates are frequently expressed in mole per time per mass of catalyst If above reaction is experimentally found to have the following rate expression:
rA kcCA1 CB2 CC3
2

the reaction is said to be of order 1 with respect to component A, order respect to B, and order 3 with respect to C Overall order of the reaction is
1 2 3

with

Order of a reaction must be determined experimentally, not from stoichiometry For liquid phase reactions, the bases for rate expressions are usually concentration (molarity or molality), mole or mass fractions, or activities. For gas phase reactions, the rate expression bases are usually partial pressure, fugacity or activity. Reactions are usually algebraically stated as
v A A vB B vC C v D D v N N 0

In the above convention, the stoichiometric numbers v i are negative for reactants and positive for products For reversible reaction in the liquid phase
2A R S

with a net rate for component A based on concentration given by:

rA
2 k cf C A

k cr C R CS

at thermodynamic equilibrium, rA

0, so the equilibrium constant is given by

Kc

k cf k cr

CR CS 2 CA

44

For gas phase reactions with a rate expression in terms of partial pressures:
rA
2 k cf p A

k cr p R pS

the equilibrium constant based on pressure would be

Kp k pf k pr pR pS 2 pA

Combined order of forward and reverse directions must be consistent with orders of the thermodynamic equilibrium constant of reaction Equilibrium constant can be calculated from thermodynamics using Gibbs free energies of formation if not specified Criterion for thermodynamic equilibrium of a reacting system based on rate of change for Gibbs free energy being zero:
vi
i

with chemical potentials defined as:

i

Gi

Gi

i RT ln a

i and the activity defined as a requirement,

/ f . When substituted into the equilibrium f i i

vi Gi

RT

ivi ln a

or

vi i

exp

vi Gi RT

exp

G RT

The above equation relates the equilibrium constant K and activities of components in the reacting mixture to the Gi for each pure component and defines the term G known as the standard Gibbs free energy change of the reaction. For a given standard state (which can be different for each component in the system), the Gibbs free energy change and consequently the equilibrium constant K are solely a function of temperature. For gas phase reactions, the standard state is usually the ideal gas state at unit pressure (1 atm, 1 bar, 1 psia, 1 Pa, etc.) so f i 1 (atm, bar, psia, Pa, etc.) and the equilibrium constant is expressed:
K vi f i

This requires the fugacities fi to be in the same pressure units as the unit pressure basis. Further, the Gi used to calculate the equilibrium constant must also be at the same unit pressure. If the reacting system is assumed to be an ideal gas,
K pivi

Liquid phase reactions usually use a different reference state so the general relationship using activities must generally be employed 45

Reaction Sets
Provides a grouping of reactions that will be used in a non-Gibbs free energy minimization reactor Contains one or more consistent reactions Reactors with simultaneous or consecutive reactions will use reaction sets with more than one reaction Reactions in a reaction set must be consistent with respect to type of reaction and thermodynamics Sets are created at the project level and are available for use in any environment Reaction sets must be added to an environment An individual reaction may be shared among multiple reaction sets Reactions within a set may be made active or inactive A reaction set is selected at the reactor level and may be customized in each reactor Reaction sets are created by right clicking the Reaction Sets node in the ProMax Project Viewer and selecting the Add menu item

General Reaction Information

Must provide all reactants and products in an individual reaction Stoichiometry of a balanced reaction must be provided using negative coefficients for reactants and positive coefficients for products A stoichiometric coefficient of zero can be used for inerts that may be needed in kinetic rate expressions Orders for kinetic and equilibrium reactions are required and ProMax requires thermodynamic consistency

Equilibrium Reactions
Used with reactions that occur quickly or attain thermodynamic equilibrium Unlike Gibbs Minimization reactions, equilibrium reactions are restricted to stoichiometry defined by the reaction set User supplied thermodynamic equilibrium expression of the form:
ln K A B T C ln T DT ET 2

46

Alternatively, equilibrium constant can be calculated internally from reaction standard Gibbs free energy change:

ivi a

exp

G RT

where vi are the stoichiometric numbers of each respective species. The standard Gibbs free energy change for a reaction is calculated by:
G vi Gi

Will provide same results as Gibbs minimization reactors if same components are considered and the equilibrium constant is obtained from Gibbs free energies

Conversion Reactions
Allows modeling where the conversion of a base component is stated as a user supplied quadratic function of temperature Base component must be selected The Priority is used with multiple conversion reactions in a setestablishes rank of reaction calculation

Kinetic Reactions
Require user specification of reaction rate constant equations through Arrhenius type expressions: Ea k kT n exp RT For bidirectional reactions, rates in both forward and reverse directions can be specified or only a single direction can be specified with the other direction calculated from equilibrium requirement:

kf kr

Overall reaction rate is determined from the reaction orders of the individual components, the forward and reverse reaction rates, and the adsorption term using one of the following equations:
N N

kf r kf
j 1

Cj f ,j AR
N

kr
j 1

C j r, j

Cj f ,j
j 1

1 K AR

C j r, j
j 1

kr K
j 1

Cj f ,j
j 1

C j r, j

AR

47

where C j is the concentration of the jth component in the user selected basis, and r , j are the order for the jth component in the forward and reverse f,j directions, respectively, and AR is the adsorption resistance which models the diffusion in and out of the pores of the catalyst. The k f and k r are calculated from the Arrhenius expression provided by the user. The adsorption resistance given by the general expression:
N n

AR

1
m

Km
j 1

C j m, j

where m, j is the order for the jth component in the mth adsorption term, and K m is the adsorption constant given also by an Arrhenius expression:

Km

k exp

Ea RT

The adsorption resistance is normally unity for non-heterogeneous catalysis reactions. Flexibility in concentration units for rate expressions and reaction orders Reactions occurring on a heterogeneous catalytic surface are usually based on mass of catalyst and require specification of catalyst particle density. Particle density and bulk density of the catalyst are related by:
b p

with

representing the void fraction of the catalyst bed

As with equilibrium reactions, the equilibrium constant expression can be obtained from user specification as a function of temperature or from its thermodynamic definition using the standard Gibbs free energy change of the reaction

Exercise 25: Defining a Simple Reaction Set

Create a reaction set in ProMax that can be used to model the first part of a steammethane reforming reaction. The reaction will be considered equilibrium, and has the form: Reaction: CH4 + H2O 3H2 + CO

Additional Information: Use methane as the conversion base Use Keq from Gibbs. Use negative coefficients for the reactants and positive coefficients for the products to balance the reaction Use an approach temperature of 0C

48

Reactor Blocks in ProMax

Types of reactors available in ProMax o Gibbs minimization o Equilibrium o Conversion o Stirred Tank o Plug flow All allow adiabatic and non-adiabatic calculation Tight integration into heat exchanger rating package Reaction usually occurs in a single phase but multi-phase reactions can be modeled All except Gibbs minimization require a single, user-defined, reaction set to be selected Reaction sets must be placed in environment before available in reactor Use single-sided reactor for adiabatic or duty specified units Use cross reactor when both a reactor and heat exchanger calculation is required to model coolant or heating mediumperformance of coolant or heating medium in exchanger can be modeled by specification of overall heat transfer coefficient Use program help to obtain more information and see examples distributed with program

49

Gibbs Minimization Reactors

Solves for thermodynamic equilibrium by minimizing the Gibbs free energy of the system Adiabatic, duty specified, or temperature specified calculation Usually does not utilize reaction setssimply place a reactor on the PFD and select the type to be Gibbs Minimization Only considers consumption and production of components selected by the user Environment must contain all desired reactants and productsthose missing will not be considered Several Gibbs sets are available in ProMax which preselect the reactants and products as well as constraints The General Gibbs set allows all components in the environment to reactlist usually must be limited to desired reactants and products Allows for constraints to be applied to the minimization calculation Number of constrains is limited by the number of reactants and products Several predefined constraints are available in ProMax which are used in burner and sulfur plant modeling Linear constraints are most general and allow the amount of a specified component in the effluent to be a linear function of the inlet

50

Exercise 26: Incinerator/Fired-Boiler, Gibbs Minimization Reactor

In this example, fuel gas and air are mixed, preheated, and fed to a burner to generate 9,000 kg/hr of 4.4 bar saturated steam. This file can be found in the training session files as Exercise 26 Combustor in Gibbs Minimization Reactor. Fuel Gas Conditions: Temperature: 21C Pressure: 3 bar Flow rate: 600 Nm3/h Composition: 100% Methane Additional Process Information: Add a specifier on the molar flow of the air feed to assure that 4% stoichiometric excess oxygen is available for combustion. Boiler feed water is 100 % Water and is supplied at 26 C and 4.4 bar, at 9,000 kg/hr. The fuel mixture leaves the preheater at 205 C. The burner is a Gibbs Minimization Reactor and all components participate in the combustion. Additional combustion products are CO2, CO, NO, and NO2. Add a solver which adjusts Fuel Gas rate to maintain a stack outlet temperature of 600 C. Air Feed Conditions: Temperature: 21 C Pressure: 1 barg Composition: 77.5 mol% 21 mol% 1.5 mol%

Nitrogen Oxygen Water

1 Air REAC-100 2 MIX-101 XCHG-101 5 4 Q-1 BFW 50 # Steam XCHG-100

Fuel

Questions: 1. What is the Fuel Gas rate in Nm3/h required to generate the required amount of steam? 2. How many moles/hr of oxygen are required to combust the fuel gas? 3. What is the temperature of exhaust gas leaving the preheater? 4. Basing off of the Gross Ideal Gas Heating Value, what is the steam cost per day to generate this steam? Assume energy costs are 3 pence/kWh or 5 Euro cents / kWh.

51

Equilibrium Reactor Blocks in ProMax

Uses reaction sets with equilibrium reactions enabled and optionally specified temperature dependent equilibrium constants Equilibrium constants calculated from Gibbs free energy change if not specified Adiabatic, duty specified, or temperature specified modeling Use single sided type reactor for adiabatic or duty specified units Use cross reactor when both a reactor and heat exchanger calculation is required to model coolant or heating medium Can provide same results as Gibbs minimization reactor depending on how reaction set is specified

52

Exercise 27: Steam Methane Reforming (SMR), Equilibrium Reactor

SMR is the predominant procedure for producing hydrogen. In this exercise we will finish defining the reaction set for this important reaction, and then model a pair of equilibrium reactors based on this reaction set. Part I: Defining the Reaction Set Expanding on Exercise 25 from page 48, create a reaction set in ProMax that can be used to model the following steam-methane reforming reactions. Reactions: 1. CH4 + H2O 3H2 + CO 2. CO + H2O CO2 + H2

For Reaction 1: Use methane as the conversion base, and use Keq from Gibbs. For Reaction 2: Use carbon monoxide as the conversion base, and use Keq from Gibbs Assume a 0C approach for both reactors.

Part II: Applying the Reaction Set Model an equilibrium reactor in which the reactions occurs as the reaction set was defined above, and an identical unit in which the approach for the steam-methane reaction has a 25 C approach temperature. Inlet stream conditions are: Conditions: Temperature Pressure Flow Composition H2O CH4 Mole % 85.0746 14.9254

365 C 15 bar 5,000 kmol/h

Additional Process Information The outlet of the reactor has a temperature of 800 C and pressure of 12.3 bar.

Q-1

Approach Inlet 1 SPLT-100 Q-2 Approach to Equilibrium Reactor

No Approach Equilibrium Reactor w/out Approach

53

Exercise 28: COS Hydrolysis in an Equilibrium Reactor

Carbonyl sulfide (COS) is a naturally occurring component of natural gas and liquefied petroleum gas (LPG). COS will hydrolyze (react with water) to form carbon dioxide and hydrogen sulfide according to the reaction (1) COS + H2O = H2S + CO2 COS may also produce carbon disulfide by the reaction: (2) CS2 + H2O = COS + H2S Calculate the equilibrium composition of the following feed at 20 C using an equilibrium reactor operating isothermally with the equilibrium constant Keq calculated from Gibbs. Inlet Feed Conditions: Conditions: Temperature Pressure Flow Composition CH4 COS H2S CO2 Water saturated Mole % 93.9 0.1 1.0 5.0

20 C 21 bar 50 kmol/h

Will much CS2 be present? Kohl and Riesenseld in their book Gas Purification report Terres and Wesemann have measured the following equilibrium constants at 20 C: ln K1 = 13.49 ln K2 = 22.69 Use these equilibrium constants to recalculate the equilibrium using the equilibrium reactor. The COS hydrolysis reaction is kinetically limited and does not go to complete equilibrium. A mole fraction of 0.01% COS is measured in the product. Use the bypass option in the equilibrium reactor to match the measured composition.

54

Conversion Reactor Blocks in ProMax

Conversion of base component specified by user as a quadratic function of temperature Requires a reaction set with conversion reactions specified and enabled All reactions must be conversion reactions May require ranking or prioritizing reactions when multiple reactions are present Adiabatic, duty specified, or temperature specified modeling Use single sided reactor for adiabatic or duty specified units Use cross reactor when both a reactor and heat exchanger calculation is required to model coolant or heating medium

55

Exercise 29: HF Alkylation using a Conversion Reactor

In HF alkylation C3, C4 and C5 olefins are combined in the presence of the acid catalyst to produce alkylate gasoline. Gerald Kaes in his book Refinery Process Modeling lists the following alkylate composition produced by reacting one mole of butene-1 with one mole of isobutane: Component: 2,2,4-Trimethylpentane 2,2,3-Trimethylpentane 2,3,3-Trimethylpentane 2,3-Dimethylhexane 2,5-Dimethylhexane 2,4-Dimethylhexane Part I Assuming a 6:1 isobutane to olefin ratio calculate the product composition using a conversion reactor. The feed conditions are 38C, 12 bar and a rate of 1000 lpm. The reactor is operated isothermally using 450,000 kg/hr of cooling water at 21C. What is the cooling water duty? Part II If this is a cross exchanger/reactor that is running isothermally, what is its UA? Sue the following parameters: Shell inside diameter Tube OD Tube pitch Tube length Tube thickness Inside corrosion allowance Tube layout Tube material of construction Number of tube passes Shell type Number of cross passes 900 mm 20 mm 30 mm 9150 mm 12 BWG 2 mm 30 triangular Monel ASTM B163 Ni 400 (UNS N04400) Annealed Seamless Tubes 3 CEN 18 (CAS #) (540-84-1) (564-02-3) (560-21-4) (584-94-1) (592-13-2) (589-43-5) Mole Fraction: 0.626 0.134 0.120 0.030 0.040 0.050

Assume the water conditions are unchanged from Part I. Does enough heat transfer area exist in this unit assuming a 1.7x10-4 Cm2/W fouling resistance on both sides?

56

Exercise 30: Defining a Catalytic Reaction Set

The heterogeneous catalytic synthesis of methanol was studied by Cappelli et al. (Ind. Eng. Chem. Process Des. Develop., Vol. 11, No. 2, 1972) in a FauserMontecatini reactor over ZnO and Cr2O3 based catalysts. The synthesis reaction is: CO + 2H2 <==> CH3OH In addition to the methanol synthesis reaction, an additional reaction occurs that cannot be neglected due to the fact that significant CO2 levels may be present in the feed: CO2 + H2 <==> CO + H2O At the temperatures of the reactor, the second reaction can be assumed to reach equilibrium and its equilibrium constant can be assumed to be of the form:
K f f CO H 2 O f f
CO 2 H2

where the f i are the fugacities of the indicated species in atm. The rate of methanol synthesis in kmol/hr-kg catalyst for the first reaction is given by:
rCH3OH f 2 f f CO H 2 CH3OH / K eq )3 A3 (1 Bf Cf Df Ef CO H2 CH3OH CO 2

The values of the constants are:

2.78 10 5 exp 1/ 3 AS
10

8280 RT
23850 RT 30500 RT 31250 RT 23850 RT

B 1.33 10 C D E 4.72 10 5.05 10 3.33 10

exp exp exp exp

14

12

10

with R = 1.9872 kcal/(kmol K). The value As is the specific surface area of the catalyst and is 70 m2/g. The bulk density of the catalyst bed is 1.5 g/cm3 with a porosity of 0.366. Create a reaction set in ProMax that can be used to model methanol synthesis described by this mechanism. Change the unit set for the project to kcal-bar to better handle the units.

57

Plug Flow Reactor Blocks in ProMax

Models reactor with a plug flow profile Requires a reaction set containing at least one kinetic reaction Additional equilibrium reactions possible in reaction set Calculations require integrating differential equations that describe the material and energy balances with the reaction equations in the reaction set Can calculate pressure drop in reactor through catalyst bed using one of several popular correlations Adiabatic or duty specifiedoutlet temperature specifications can only be achieved with a solver Duty specification is evenly distributed along length of reactor Use single sided reactor for adiabatic or duty specified units Use cross reactor when both a reactor and heat exchanger calculation is required to model coolant or heating medium

58

Exercise 31: Water Shift Reactors, Plug Flow Reactor

This system is used to convert carbon monoxide from the gas of an ammonia plant and water to hydrogen and carbon dioxide. Inlet stream conditions are: Conditions: Temperature Pressure Flow Composition CO H2O CO2 H2 N2 CH4 Mole % 7.879 39.394 4.788 34.424 13.212 0.303

354 C 26.53 atm 9280 kmol/h

Reaction:

CO + H2O CO2 + H2 -rCO = k (yCO yH2O yCO2yH2/K) / (379b)

Rate Expression in kmol/(hkg):

where: K=exp(-4.72 + 4800 / T) 422 T 589 K=exp(-4.33 + 4578 / T) 589 T 756 b = catalyst bulk density, kg/m3 T = temperature, K Iron Oxide Catalyst Reactor: k = exp(18.72 4900/T) =4 b = 1121 kg/m3 Particle density = 2018 kg/m3 Copper Zinc Oxide Catalyst Reactor: k = exp(15.73 1856/T) = 4.33 b = 1442 kg/m3 particle density = 2483 kg/m3

Additional Process Information The process stream is cooled to 213C before entering the Copper-Zinc Oxide Catalyst Reactor The iron oxide reactor is a 36 BWG single tube 5.9 m long with a 3.8 m outer diameter. Calculate the void fraction. The Copper-Zinc Oxide reactor is a 12 BWG single tube 4.27 m long with a 3.8 m outer diameter. Calculate the void fraction.

Inlet 1st Reactor

Outlet 1st Reactor Iron Oxide Catalyst Reactor XCHG-100

Q-1 Inlet 2nd Reactor

Outlet 2nd Reactor Copper-Zinc Oxide Catalyst Reactor

Adapted from Case Study 105 Chemical Reactor Design for Process Plants Vol. 2 Case Studies and Design Data by Howard F. Rase

59

Stirred Tank Reactor Blocks in ProMax

Outlet is the same as all points internal to reactorreacting system is perfectly mixed Requires a reaction set containing at least one kinetic reaction Additional equilibrium reactions possible in reaction set Calculations require solving material and energy balances simultaneously with reaction rates and equilibrium relationships defined in the reaction set Adiabatic, duty specified, or temperature specified modeling Use single sided reactor for adiabatic or duty specified units Use cross reactor when both a reactor and heat exchanger calculation is required to model coolant or heating medium Key variable is usually reactor volume which is established through the reactor length and diameternon-cylindrical forms must be specified as if cylindrical

60

Exercise 32: Allyl Chloride Production (CSTR and PFR)

A pilot plant reactor is planned to study the production of allyl chloride (CASN 107-05-1) from propylene and chlorine according to the reaction Cl2 + C3H6 CH2=CHCH2Cl + HCl (1)

A parallel addition reaction produces 1,2 dichloropropane (CASN 78-87-5): Cl2 + C3H6 The rate equations in mol/(cm3s) are: CH2ClCHClCH3 (2)

r1

0.9166 exp

63,267 RT

pC3 H 6 pCl2 , with T in K

r2

5.21x10 5 exp

15,956 RT

pC3 H 6 pCl 2 , with T in K

with R=8.31434 J/(molK) and the partial pressures in atm.

The feed consists of 4 moles propylene/mole chlorine at a combined rate of 0.4 kmol/h at 200C. Assume the pressure is constant at 2 bar. The reactor will be a 6100 mm long vertical tube of 55.54 mm OD. Calculate the composition and exit temperature from the adiabatic PFR reactor. Compare the results to those for a CSTR reactor of equal volume (11979 cm3). Instead of adiabatic, both the PFR and CSTR will be jacketed with boiling ethylene glycol which will hold the wall temperature constant at 200C. The inside heat-transfer coefficient may be taken as 28.4 W/(m2C). Compare the results to an adiabatic PFR and CSTR of the same dimension.

61

62

Notes

63

64

Notes

65