Nonisothermal Plug-Flow Reactor

Introduction
This model considers the thermal cracking of acetone, which is a key step in the production of acetic anhydride. The gas phase reaction takes place under nonisothermal conditions in a plug-flow reactor. As the cracking chemistry is endothermic, control over the temperature in the reactor is essential in order to achieve reasonable conversion. When the reactor is run under adiabatic conditions, the model shows how the conversion of acetone can be affected by mixing the reactant with inert. Furthermore, it is illustrated how to affect the conversion of acetone by means of a heat exchanger supplying energy to the system. The example details the use of the predefined Plug-flow reactor type in the Reaction Engineering Lab and how to set up and solve models describing nonisothermal reactor conditions. You will learn how to model adiabatic reactor conditions as well as how to introduce heat exchange.

Model Definition
This model is related to an example found in Ref. 1. An essential step in the gas-phase production of acetic anhydride is the cracking of acetone (A) into ketene (K) and methane (M):

(10-60) The rate of reaction is

(10-61) where the rate constant is given by the Arrhenius expression

(10-62) For the decomposition of acetone described above, the frequency factor is activation energy is

A1 = 8.21014 (1/s), and the

E1 = 284.5 (kJ/mol).

Chemical reaction takes place under nonisothermal conditions in a plug-flow reactor, illustrated

schematically in Figure 10-29.

Figure 10-29: The Plug-flow reactor is a predefined reactor type in the Reaction Engineering Lab. Species mass balances are described by:

(10-63) where

Fi is the species molar flow rate (mol/s), V is the reactor volume (m3), and Ri is the species rate

expression (mol/(m3s)). Concentrations needed to evaluate rate expressions are found from:

(10-64) where

v is the volumetric flow rate (m3/s). By default, the Reaction Engineering Lab treats gas phase

reacting mixtures as being ideal. Under this assumption the volumetric flow rate is given by:

(10-65) where

p is the pressure (Pa), Rg denotes the ideal gas constant (8.314 J/(molK)), and T is the

temperature (K). The reactor energy balance is given by:

(10-66) In Equation 10-66,

unit volume (J/(m3s)), and

Cp,i represents the species molar heat capacity (J/(molK)), ws is the shaft work per Q denotes the heat due to chemical reaction (J/(m3s)):

(10-67) where

Hj is the heat produced by reaction j. The term Qext represents external heat added or removed

from the reactor. The present model treats both adiabatic reactor conditions:

and the situation where the reactor is equipped with a heat exchanger jacket. In the latter case given by: (10-68)

Qext is

where

U is the overall heat transfer coefficient (J/(m2sK)), a is the effective heat transfer area per unit of reactor volume (1/m), and Tamb is the temperature of the heat exchanger medium (K). The
Reaction Engineering Lab automatically sets up and solves Equation 10-63 and Equation 10-66 as the

predefined Plug-flow reactor type is selected. As input to the balance equations you need to supply the chemical reaction formula, the Arrhenius parameters, the species thermodynamic properties, as well as the inlet molar feed of reactants. Following the step-by-step instructions below, you will first model the cracking of acetone in an adiabatic plug-flow reactor. See how the acetone conversion varies with the ratio of reactant to inert in the inlet stream. In second model, add the effects of a heat exchanger jacket and observe how the added energy drives the reaction to completion.

Working with Thermodynamic Polynomials

Reaction Engineering Lab uses the following set of polynomials as default expressions describing species thermodynamic properties:

(10-69)

(10-70)

(10-71)

Cp,i denotes the species heat capacity (J/(molK)), T the temperature (K), and Rg the ideal gas constant, 8.314 (J/(molK)). Further, hi is the species molar enthalpy (J/mol), and si represents its
Here, molar entropy (J/(molK)). A set of seven coefficients per species are taken as input for the polynomials above. The coefficients is associated with the species enthalpy of formation (at 0 K), and the coefficient species entropy of formation (at 0 K). The format outlined by Equation 10-69 through Equation 10-71 is referred to as CHEMKIN or NASA format (Ref. 2). This is a well established format, and database resources list the needed coefficients for different temperature intervals. Many web based data resources exist for CHEMKIN thermodynamic data and otherwise (Ref. 3). It is therefore often a straight forward task to assemble the thermodynamic data required and then import it into your reaction model.

a1 through a5 relate to the species heat capacity, the coefficient a6 a7 comes from the

CREATING A THERMODYNAMIC DATA FILE

CHEMKIN thermodynamic files typically contain blocks of data, one block for each species. Such a data block is illustrated in Figure 10-30 for gas phase acetone.

Figure 10-30: Thermodynamic data block on the CHEMKIN format. The first line starts with the species label, given with a maximum of 18 characters, followed by a 6 character comment space. Then follows a listing of the type and number of atoms that constitute the species. The

G comments that this is gas phase data. The line ends with listing of three temperatures,

defining two temperature intervals. Lines 2 through 4 contain two sets of the polynomial coefficients,

a1 through a7. The first set of coefficients is valid for the upper temperature interval, and the second
for the lower interval. A complete CHEMKIN thermodynamics file has the structure illustrated in Figure 10-31.

Figure 10-31: Thermodynamic data file on the CHEMKIN format. The keyword

thermo always starts the text file. The subsequent line lists three temperatures,

defining two temperature intervals. These intervals are used if no intervals are provided in the species specific data. Then follows the species data blocks, in any order. The keyword end is the last entry in the file. The data file reproduced in Figure 10-31 is used in the present model. It was constructed by creating a text-file with species data blocks from the Sandia National Labs Thermodynamics resource (Ref. 4).

USING SUBSETS OF THERMODYNAMIC COEFFICIENTS

In some instances, not all coefficients

a1 through a7 are available. Coefficients may also be on a format

differing from the NASA or CHEMKIN style. Input parameters can still be put on the form of Equation 10-69 to Equation 10-71, as illustrated below.

For species A, K, M, and N2, Ref. 1 lists polynomials for the heat capacity on the form:

(10-72) Furthermore, the species enthalpies of formation at

Tref = 298 K are provided:

h(298)

SPECIES

a1'

a2'

a3'

26.63

0.183

-45.86e-6

-216.67e3

20.04

0.0945

-30.95e-6

-61.09e3

13.39

0.077

-18.71e-6

-71.84e3

N2

6.25

8.78e-3

-2.1e-8

The data in the table above can be correlated with the polynomials given by Equation 10-69 and Equation 10-70 by noting the relations:

(10-73)

(10-74) Using Equation 10-73 and Equation 10-74, you find the coefficients to enter in the Reaction Engineering Lab GUI.

SPECIES

a1

a2

a3

a6

3.20

2.20e-2

-5.52e-6

-2.79e4

2.41

1.14e-2

-3.72e-6

-8.54e3

1.61

9.26e-3

-2.25e-6

-9.87e3

N2

0.752

1.06e-3

-2.53e-9

-2.71e2

Read more about how to work with thermodynamic data in the section Working with Predefined Expressions on page 90 of the Reaction Engineering Lab Users Guide.

Results
In a first model, the plug-flow reactor is run under adiabatic conditions. The reactor is fed with a total molar flow of 38.3 mol/s. The inlet stream consists of a mixture of reactant acetone and inert nitrogen, as specified by:

Figure 10-32 shows the reactor temperature as a function of the reactor volume for the mixing conditions,

Afrac = 1, 0.5, 0.1, and 0.01. As the cracking of acetone is endothermic, the reactor

temperature decreases along the reactor length; the effect being more pronounced as the fraction

acetone increases. Figure 10-32: The reactor temperature (K) as a function of reactor volume (m3), plotted for a number of feed conditions. Figure 10-33 shows the conversion of acetone for the different mixing conditions. Conversion increases although the concentration of acetone decreases, due to the temperature effects. When pure

acetone (Afrac = 1) enters the reactor conversion is no more than 24% at the reactor oulet.

Figure 10-33: The conversion of acetone (%) as a function of reactor volume (m3), plotted for a number of feed conditions. Figure 10-34 shows the reaction rates as a function of reactor volume. Note that under the simulated conditions reaction rates decrease as conversion increases, thereby affecting the net production rate

of ketene and methane. Figure 10-34: The rate of the acetone cracking reaction (mol/(m3s)) as a function of reactor volume (m3), plotted for a number of feed conditions. Figure 10-35 shows the temperature profile of the plug-flow reactor (Afrac = 1) as a heat exchanger supplies energy to the reacting system. Initially the energy consumption of the cracking reaction is dominant, and the temperature in the system drops. As the reaction rate drops off, the heat exchanger starts to heat up the system. The heating rate decreases with the temperature difference

between the heat exchanger medium and reacting fluid.

Figure 10-35: Temperature (K) as a function of volume (m3), for a reactor equipped with a heat exchanger jacket. Figure 10-36 shows the conversion of acetone along with the reaction rate (Afrac = 1). Comparing with Figure 10-33 and Figure 10-34, note how the heat exchanger allows for relatively high reaction rates

while maintaining high conversion. Figure 10-36: The conversion of acetone (%) and reaction rate (mol/(m3s)) as a function of reactor volume (m3).

References
1. H.S. Fogler, Elements of Chemical Reaction Engineering 3rd Ed., Prentice Hall PTR, 1999, example 8-7, pp. 462468. 2. S. Gordon and B.J. McBride, Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouquet Detonations, NASA-SP-273, 1971. 3. See, for example, http://www.comsol.com/reaction 4. http://www.ca.sandia.gov/HiTempThermo/index.html

Model Library path:

Process_Chemistry/nonisothermal_plugflow

Modeling Using COMSOL Reaction Engineering Lab

MODEL NAVIGATOR
1Start the Reaction Engineering Lab. 2In the Model Navigator, click the New button to launch the main user interface.

OPTIONS AND SETTINGS

1Click the Model Settings button on the Main toolbar. 2Select Plug-flow from the Reactor type list. 3Select the Calculate thermodynamic properties check box. 4Select the Include energy balance check box. 5On the General page, type 162e3 in the p edit field. 6Click the Init page, and type 1035 in the T(V0) edit field. 7Click Close.
Now, define a number of constants that will be used later.

1
NAME

Select the menu item Model>Constants, then enter the following data:
EXPRESSION

Ua

16500

T_amb

1150

A_frac 1 2Click OK. 3Select the menu item Model>Expressions, then enter the following data:
NAME EXPRESSION

X_A

(F0_A-F_A)/F0_A*100

4Click OK.

REACTIONS INTERFACE
1From the Model menu, select Reaction Settings. 2Create a new entry in the Reaction selection list by clicking the New button. 3Type A=>K+M in the Formula edit field. 4Select the Use Arrhenius expressions check box. 5Type 8.2e14 in the A edit field. 6Type 284.5e3 in the E edit field.

SPECIES INTERFACE
1While still in the Reaction Settings dialog box, click the Species tab. 2Verify that the Species selection list has the three species (A, K, and M).
Click the New button and type

N2 in the Formula edit field. This adds the inert species N2 to the

3reacting flow. 4Click the Feed Stream page.

Note that for a plug-flow reactor you need to specify the inlet molar flows (F0), in contrast to the batch reactor types, where you need to provide the initial species concentrations (c0).

5Select species A from the Species selection list and enter 38.3*A_frac in the F0 edit field.
Select species N2 from the Species selection list and enter

38.3*(1-A_frac) in the F0 edit

field. You will use the parameter Afrac to vary the mix of reactant and inert, for a constant molar flow

6at the inlet 7Click Close.

IMPORT THERMODYNAMIC DATA

Proceed to import the thermodynamics data file.

1Select File>Import>CHEMKIN Thermo Input File. 2Browse to the file nonisothermal_plugflow_thermo.txt and click the Import button.
You can inspect the loaded data in the Reaction Settings dialog box. Go to the Species>Thermo page and click the Polynomial coefficients edit field. Here you will find the thermodynamic coefficients

a1 through a7 for each species.

COMPUTING THE SOLUTION

1Open the Simulation>Solver Parameters dialog box. 2Type 3 in the Reactor volumes edit field. 3Clear the Stop If Steady State is reached first check box. 4Click OK. 5Click the Solve Problem button (=) on the Main toolbar.

POSTPROCESSING AND VISUALIZATION

The default plot shows the molar flows of the participating species as a function of the reactor volume. To create Figure 10-32, follow these steps:

1Choose Postprocessing>Plot Parameters (or click the corresponding button on the Main toolbar). 2Click the << button to remove all entries from the Quantities to plot list.
Select Temperature from the Predefined quantities list and click the Add Selected Predefined

3Quantities button, >. 4Select New Figure in the Plot in list. 5Select the Keep current plot check box. 6Click Apply. 7Select Model>Constants. 8Change the A_frac entry to 0.5, then click Apply. 9 Click the = button on the Main toolbar.

10Repeat Steps 8 and 9 for the A_frac values 0.1 and 0.01. 11Click the Figure 1 window. 12Click the Edit Plot button. 13Select the first Line entry, type A_frac = 1 in the Legends edit field.
Select the second Line entry, type Select the third Line entry, type

A_frac = 0.5 in the Legends edit field, and choose

14Triangle from the Line marker list.

A_frac = 0.1 in the Legends edit field, and choose Square A_frac = 0.01 in the Legends edit field, and choose Plus

15from the Line marker list.

Select the fourth Line entry, type

16sign from the Line marker list. 17Click OK to close the Edit Plot dialog. 18Click OK to close the Constants dialog.
Create Figure 10-33 and Figure 10-34 in the same fashion as just described, adding X_A and then Reaction rate 1 to the Quantities to plot list, found in the Plot Parameters dialog.

1In the Plot Parameters dialog box, clear the Keep current plot check box. 2Select Main axes from the Plot in list. 3Click OK.
Move on to see how conversion is affected as a heat exchanger jacket supplies heat to the reacting mixture.

OPTIONS AND SETTINGS

1Select the menu item Model>Model Settings. 2Click the Energy Balance tab. 3Type Ua*(T_amb-T) in the Qext edit field. 4Click Close. 5Select the menu item Model>Constants. 6Change the value A_frac entry to 1, then click OK.

COMPUTING THE SOLUTION

Click the Solve Problem button (=) on the Main toolbar.

POSTPROCESSING AND VISUALIZATION

To create Figure 10-35, follow these steps:

1Choose Postprocessing>Plot Parameters (or click the corresponding button on the Main toolbar). 2Click the << button to remove all entries from the Quantities to plot list.
Select Temperature from the Predefined quantities list and click the Add Selected Predefined

3Quantities button, >. 4Click Apply.

To create Figure 10-36, follow steps below:

1Click the << button to remove all entries from the Quantities to plot list. 2Select X_A from the Predefined quantities list and click the Add Selected Predefined

Quantities button, >. Select Reaction rate 1 from the Predefined quantities list and click the Add Selected

3Predefined Quantities button, >. 4Click OK. Related Topics

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