Mississippi State University

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Honors Theses Undergraduate Research

5-1-2020

Process Simulation for Styrene Prodcution from Toluene and

Methanol
Deonante Frazier
Mississippi State University

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Frazier, Deonante, "Process Simulation for Styrene Prodcution from Toluene and Methanol" (2020).
Honors Theses. 78.
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 Process Simulation for Styrene Production from Toluene and Methanol

By

Deonante Frazier

A Thesis,

Approved By:

Dr. Bill B. Elmore:

Dr. Seth Oppenheimer

Dr. Larry Pearson

A Thesis,
Submitted to the Faculty of
Mississippi State University
in Partial Fulfillment of the Requirements
for the Provost Scholarship

Mississippi State, Mississippi

May 2020

[Author]
Name: Deonante Frazier

Date of Degree: May 1, 2020

Institution: Mississippi State University

Major Field: Chemical Engineering

Major Professor: Bill B. Elmore

Title of Study: Simulation

Pages in Study: 47

Requirement for Provost Scholarship

Process simulators have been integral in the design and optimization of various chemical

processes. These simulators feature drag and drop modular process equipment that allows users

to input conditions and specifications to model that equipment’s behavior within the simulation.

Streams of chemicals preloaded in the system interact with the process equipment in the program

in the attempt to model physical phenomena. Even though CHEMCAD offers an expansive suite

of process equipment, there are processes that includes equipment that may not be included. It

can be a challenge to determine a way to use CHEMCAD’s existing process equipment to match

the desired outcome. In this study, a chemical process that employs the reaction between toluene

and methanol to yield styrene is simulated using CHEMCAD. The simulation must be able to

produce 350,000 tons of styrene per year. In addition, there are other design specifications that

must be met within the process. These specifications help to define the way in which the

CHEMCAD simulation is built. Once the simulation is completed, sensitivity analysis and

controllers are added to the simulation to increase the accuracy of the simulation.

KEYWORDS: toluene, CHEMCAD, Simulation, Styrene, methanol, Process

2
Contents
CHAPTER 1 ................................................................................................................................... 6
I. INTRODUCTION ....................................................................................................................... 6

1.1 Introduction to Process Simulators .................................................................................... 6

1.2 Introduction into CHEMCAD and Styrene ........................................................................ 8
1.3 Inputting Process into CHEMCAD .................................................................................... 8
1.4 Design Basis: .................................................................................................................... 11

II. METHODS............................................................................................................................... 15

2.1 Selecting Chemical Components for Use in CHEMCAD ............................................... 15

2.2 Selecting Thermodynamic Models for CHEMCAD ........................................................ 16
2.3 Selecting Topology for Simulation .................................................................................. 19
2.4 Selecting the Properties of Feed Stream .......................................................................... 23
2.5 CHEMCAD Specifications .............................................................................................. 25
2.5.1 Heat Exchangers ........................................................................................................ 25
2.5.2 Controllers ................................................................................................................ 27
2.5.4 Decanter Conditions .................................................................................................. 31
2.5.5 Reactor ...................................................................................................................... 38
2.5.5 Mixers and Dividers: ................................................................................................ 39
2.5.6 Distillation Towers (Shortcut Tower): ..................................................................... 40

III. RESULTS ............................................................................................................................... 42

3.1 Meeting Specifications ..................................................................................................... 43

3.2. Stream Tables ..................................................................................................................... 45

References ..................................................................................................................................... 46

3
List of Figures:

Figure 1 Chemical Selection Dialog Box .................................................................................. 16

Figure 2 A screenshot of the Thermodynamic Settings from CHEMCAD ............................... 18
Figure 3 A screenshot of the Controller UnitOps in CHEMCAD ............................................. 19
Figure 4 PFD of Chemical Process ............................................................................................ 21
Figure 5 Screenshot of CHEMCAD simulation ....................................................................... 22
Figure 6 Edit Streams Dialog Box ............................................................................................. 23
Figure 7 Heat Exchanger parameter dialog box ........................................................................ 26
Figure 8 Controller Parameter CHEMCAD Dialog Box ........................................................... 28
Figure 9 Component Separator Dialog Box............................................................................... 35
Figure 10 Parameter Dialog Box for Flash Drums .................................................................... 36
Figure 11 Stochiometric Reactor Parameter Dialog Box .......................................................... 39
Figure 12 Shortcut Distillation Tower Dialog Box.................................................................... 40

List of Tables:

Table 1 CHEMCAD Thermodynamic Modelling Application Table ....................................... 17

Table 2 Heat Exchanger Specification ....................................................................................... 25
Table 3 Antoine Equation Constants ......................................................................................... 32
Table 4 Molar percent of the gaseous stream exiting the Decanter ........................................... 37
Table 5. Stream Tables generated by CHEMCAD ....................................................................... 45

4
 NOMENCLATURE

Q Amount of heat transferred in kJ

M Mass of heated substance in g

ΔT Change in temperature in °C

pi Partial pressure of a compound, i

yi Mole fraction of a compound, i, in a mixture

Antoine’s Equation physical constants to

A, B, C determine compound’s vapor pressure at a

given pressure and temperature

Mole fraction of methanol in the organic

X o, m
stream

Mole fraction of methanol in the aqueous

X a, m
stream

Xf, m Mole fraction of methanol in the feed stream

Mole fraction of methanol in the gaseous

X g, m
stream

P Pressure

Vapor pressure of methanol at a given

P m *(T)
temperature, T

5
 CHAPTER 1

I. INTRODUCTION

1.1 Introduction to Process Simulators

Process simulators, appearing near the late 1970’s, pioneered a novel way in which designing

chemical engineering processes can be completed. At first, many engineers completed most of

the plant’s specifications by hand, such as material and energy balances. Longer iterative

processes, such as calculating the enthalpy of streams containing a mixture of various chemicals

were tedious and arduous to complete. To ease in calculations heuristics were created. Heuristics,

otherwise known as “Experienced-Based Principles” are rule-of -thumb calculations that are

derived by analyzing the design of previous chemical plants. Through this analysis, “shortcuts”

can be determined. These shortcuts can give an engineer a range of where the calculation should

be numerically. These heuristics can give rough estimates; however, for overall design, these

calculations should not be used. (Turton, Bailie, Whiting, Shaeiwitz, & Bhattacharyya, 2012).

Once process simulators were created, process simulators can be created using more accurate

calculations in comparison to heuristics.

Most process simulators have a similar structure in which a user may begin to simulate the

process. Each part of process simulators intrinsically works together to provide the user with the

necessary tools to accurate depict a process. According to Analysis, Synthesis, and Design of

Chemical Processes, the following is a list of basic computational element involved in creating a

process simulator.

6
 1. Component Database

2. Thermodynamic Model Solver

3. Flowrate Sheet Builder

4. Unit Operation Block Solver

5. Data Output Generator

6. Flowsheet Generator

In a similar sense, Turton (2013) states that each Element of Process Simulators are interwoven

with steps that the user must take in order to complete the simulation successfully, outlined in the

list below.

1. Select all the chemical components that are required in the process form the component

database.

2. Select the thermodynamic models required for the simulation. These may be different

from different pieces of equipment.

3. Select the topology of the flow sheet to be simulated by specifying the input and output

streams for each stream for each piece of equipment.

4. Select the properties (temperature, pressure, flow rate, vapor fraction, and composition)

of the feed streams to the process.

5. Select the equipment specifications (parameters) for each piece of equipment in the

process.

6. Select the way in which the results are to be displayed.

7. Select the convergence method and run the simulation.

For this study, each of the steps outlined below will be used to simulate the process of styrene

production from toluene and methanol using the process simulator, CHEMCAD.

7
1.2 Introduction into CHEMCAD and Styrene

CHEMCAD was first introduced in 1983 as microCHESS. Over a timespan of two to three

years, CHEMCAD has evolved to help many chemical engineering simulate “ initial design of

new process, optimization or de-bottlenecking of existing process, heat exchanger sizing,

pressure and flow balancing of complex piping networks” and many other challenges that

chemical engineers may face (CHEMSTATIONS, 2016, p. 2). CHEMCAD features drag and

drop style equipment, named “UnitOps”, that can simulate real-life physical equipment. Each

type of UnitOps has its own set of parameters. These parameters give CHEMCAD specifications

on how these UnitOps systems should run in the program. After setting each parameter for the

UnitOps and selecting and defining other parts of the simulation, CHEMCAD is ready to tackle

any problem or challenge that may arise.

One current chemical engineering challenge is to optimize and diversify the ways in which

styrene is made. Styrene is widely used in a myriad of products. These products include

“refrigerator liners, medical devices, food containers, polystyrene foam, and composite products.

In 2013, the global demand for styrene is 27,180,000 metric tons, growing each year (The

Styrene You Know: Uses and Benefits, 2013). This study aims to simulate a process using

toluene and methanol to produce styrene.

1.3 Inputting Process into CHEMCAD

In order to input this process into CHEMCAD, a brief process description is needed. This

process description follows the PFD diagram shown on page 21.

Saturated liquid streams, streams 2 and 3, are carrying methanol and toluene, respectively. These

streams are directed to vaporizers to heat each stream so that the compounds are vaporized. The

hot reactor effluent is flowing counter-currently in the tube-side of the exchanger. From there,

8
the newly vaporized streams are mixed into one stream, Stream 5, and it passes through an

interchanger heat exchanger, with reactor effluent flowing cross-currently on the tube side. From

there, the mixed reactant stream goes into the fired heater raising the temperature of Stream 6

from 304.7 °F to 977 °F. The reactor is operating at 82% conversion of toluene. The toluene will

follow two reaction pathways, with one reaction creating Styrene, and the other reaction creating

ethylbenzene. The selectivity towards the Styrene reaction is 72%. The reactor pressure is set at

5.52 atm, and the operation is considered adiabatic. The reactor effluent, labeled as Stream 10,

leaves the reactor at 825.31 °F, containing ethylbenzene, water, styrene, hydrogen, toluene, and

methanol is pumped into the interchanger first, warming up the reactants in Stream 5. The

effluent leaves the interchanger at 772 °F and enters the toluene vaporizer as Stream 11. After

vaporizing the incoming toluene stream, the effluent travels to the methanol vaporizer to

vaporize the incoming methanol as well, labeled as Stream 12. Leaving the vaporizer, the

effluent is at 285 °F and is subsequently cooled to 100 °F by cooling water before entering the

decanter, labeled as Stream 14. The decanter has three outlet streams, streams 16, 17, and 18.

Stream 16 contains toluene, methanol, ethylbenzene and styrene, and this stream goes into T-

101. Stream 17 contains small amounts of volatized compounds of styrene, ethylbenzene, water,

toluene, methanol, and all the hydrogen produced. This stream goes as an off-gas product.

Stream 18 contains all the water produced in the reaction including a set amount of methanol that

may have fractionated along with the water. This water is sent to a wastewater facility to be

cleaned and sent to the municipal wastewater system. Stream 16 enters T-101, which is a tray

column, with 24 theoretical stages and a R/R MIN of 1.6. The distillate stream of T-101, labeled as

stream 22, contains the unreacted toluene and methanol, and this stream is recycled back into the

reactant stream. This stream has less than five weight percent of ethylbenzene and Styrene. The

9
bottoms stream of T-101 contains the crude styrene and ethylbenzene. The bottoms stream,

labeled as Stream 22, enters tower T-102. T-102 is a tray column with 75 trays. This tower will

produce the ethylbenzene product stream in the distillate, and it will also produce the styrene

product in the bottom stream. The ethylbenzene product stream can have 0.8 weight percent at

most, of toluene, and three weight percent of styrene. The styrene product can only have up to

300 ppm of ethylbenzene in the stream.

10
1.4 Design Basis:

This process has various design specifications that exist to help define the process more

accurately. In addition, these specifications given allow for ease in calculation when designing

the process within CHEMCAD.

Overall Process Assumptions:

• The process is in steady state operation.

• The plant must have a capacity of 350,000 tons per year of crude styrene with less than

300 ppm of ethylbenzene present within the final product stream

• The working year equates to 8322 hours of operation.

• The pressure drop across pipes are negligible.

• Methanol and toluene streams are considered free of impurities.

Feed:

• Both feeds, toluene and methanol, are entering the process as a saturated liquid at 5.52

atm.

• The specific quantity of each feed stream is calculated so that the reactants enter the

reactor in stochiometric ratios.

• The feed streams are pulling the reactants from a tank that is that is not factored into the

CHEMCAD simulation.

Heat Exchangers:

• The toluene and methanol vaporizers, HX-101 and HX-102, are used to vaporize the

saturated liquid feeds of the respective feed streams. The feed streams (Streams 1 and 2)

11
 are fed via tube side, while the reactor effluent is used to heat the feed on the shell side

(Streams 3 and 8).

• The number of tubes is not calculated during this preliminary determination.

• There is a 0.13 atm pressure drop across the heat exchanger.

• It is assumed that Stream 4 and Stream 19 is fully vaporized before mixing to form

Stream 5.

• The Interchanger (HX-104) is used to condense the reactor effluent (stream 9) to a

saturated liquid using cooling water, entering HX-104 at 88 °F (Stream 12). The cooled

reactant fluid must be cooled to 100 °F. The cooling water must not be heated over

100 °F.

Fired Heater:

• This heater must heat the incoming reactants in Stream 9 to 977 °F before the reactants

enter the reactors.

• Any radiant heat loss from the fired heater is neglected.

• There is a 0.70 atm pressure drop.

Reactor:

• The reactor is modeled as a packed bed reactor with a bulk density of 1000 kg/m3 and a

void fraction of 0.4.

• The reactor is adiabatic.

• The reactor involves two chemical reactions, with one yielding styrene and one yielding

ethylbenzene. The reactor is split into two reactors for the two separate reactions in

CHEMCAD.

12
 • The feed of toluene and methanol entering the reactor must be equimolar.

• There is a pressure drop of 0.70 atm across the reactor.

• The two reactions occurring within the reactor are assumed to be irreversible.

• The overall conversion of toluene is 0.72.

• The selectivity regarding the styrene reaction is 0.68.

Decanter

• The decanter is a phase separator that takes the condensed reactor effluent and separates

the effluent into three streams: an aqueous stream, gaseous stream, and an organic stream.

• The gaseous stream will contain all hydrogen created from the reactor as well as amounts

of Styrene, toluene, methanol, and ethylbenzene.

• There is a negligible amount of water within the organic stream.

• These amounts will be calculated using Raoult’s Law to determine the partial pressure of

each substance in the gaseous phase.

• The aqueous stream contains all the water created in both reactions as well as a

significant amount of methanol. For ease in calculation, a partition coefficient, 1.32, is

used to determine the actual amount of methanol of that leaves via the aqueous stream.

• The organic stream contains all the rest of the feed that is not contained within the

aqueous and gaseous streams.

Vaporizers:

• The vaporizers are shell and tube heat exchangers.

• Reactor effluent is pumped to the shell-side of the exchanger, and the incoming feed is

pumped to the tube-side of the exchanger.

13
 • There is a pressure drop of 0.13 atm.

Tower:

• The distillate stream from T-101 recycles unused methanol and toluene and is routed

back to the beginning of the process.

• Column temperature must not exceed over 300 °F.

• Fractional Recovery of the light keys in both T-101 and T-102 is 0.999 and for the

bottoms is 0.001.

14
 CHAPTER II

II. METHODS

2.1 Selecting Chemical Components for Use in CHEMCAD

From chemical reactions being carried out in this simulation, the components listed below should

be selected in from CHEMCAD’s component database. CHEMCAD’s component database hosts

up to 2476 chemicals. Each of these chemicals holds physical property constant data for that

specific component. For instance, selecting methanol allows CHEMCAD to auto populate the

physical parameters for that compound, including Antoine’s Equation constants, densities at

various temperatures, heat capacity constants, and more. CHEMCAD also supports both

common names and IUPAC names, and CAS numbers, and chemical formulas to help users find

their desired compound quickly. For clarity, these are the equations that will be used in the

simulation.

Toluene (C 7 H 8 ) + Methanol (CH 3 OH) ⇌ Styrene (C 8 H 8 ) + Water (H 2 O) + Hydrogen (H 2 ) (1)

Toluene (C 7 H 8 ) + Methanol (CH 3 OH) ⇌ Ethylbenzene (C 8 H 10 ) + Water (H 2 O)

(2)

15
Upon selecting the K-value, CHEMCAD will choose a method to calculate the enthalpy of each

stream. For this process, since NRTL was chosen for the K-Value, CHEMCAD chose the LATE

method to calculate enthalpy. “Enthalpy is calculated using Latent Heat (LATE) in the liquid

and VLE [Vapor-Liquid Equilibrium] phases and E-o-S [Equation-of-State] (SRK) in the

superheated or gas phase.” (Edwards, 2008, p. 8). Figure 2 shows the “Thermodynamic Settings”

dialog box in CHEMCAD. Here, users can select the K-Value and H method to for CHEMCAD

to use. It is important to note that the CHEMCAD’s Thermodynamics Wizard built into

CHEMCAD may choose the wrong thermodynamic model. To help ensure that the user knows

which thermodynamic model is apt for each situation, Table 1 shows a table crafted by

CHEMCAD that outline specific applications in which each method should be chosen.

Table 1 CHEMCAD Thermodynamic Modelling Application Table

Note: Edwards, J. E. (2008, November). Process Modelling. Corporation web site:

https://www.chemstations.com/content/documents/Technical Articles/thermo.pdf,

17
Figure 2 A screenshot of the Thermodynamic Settings from CHEMCAD

18
2.3 Selecting Topology for Simulation

Figure 3 A screenshot of the Controller UnitOps in CHEMCAD

In order to simulate this process correctly, a PFD must be drawn of the process. Having a PFD of

the process allows users to accurately see the way in which streams are heading. The direction of

the streams is most definitely important to CHEMCAD simulations. The figure below shows a

depiction of one of the UnitOps in CHEMCAD. The left side has a dark blue dot, while the right

side has a dark pink dot. The incoming feeds are always tethered to a dark blue dot and the

outgoing feeds are always tethered to a dark pink dot. A pink dot from one UnitOps can connect

to the dark blue dot from another UnitOps as well. Once the PFD is finalized, different UnitOps

are dragged into the simulation in their respective locations.

The simulation will differ from the PFD in a few aspects that is beyond the user’s control. In a

normal PFD, a stream that is mixing with another stream is easy to show, such as Stream 7 on

the PFD (Recycle stream going into the incoming feed stream). Both streams will have to be

mixed using the UnitOps called Mixers. In addition, there are various controllers placed

throughout the simulation. These controllers are not included in the PFD since these controllers

are meant for solving purposes only. They do not have a physical equivalent. These type of

UnitOps are sometimes referred to as Phantom UnitOps.

Adding mixers and controllers also add extra streamlines to the simulation. For instance, from

the PFD, there is a controller placed in the middle of stream 15. The controller has no physical

19
representation, so it is left out of the PFD. However, in the simulation, when stream 15 enters the

controller, the outlet stream coming from the controller is listed as a new stream, rather than still

being stream 15. These streams are not there physically, so the numbering of streams between

the simulation and the PFD will be different.

Lastly, the two reactors and the two decanter tanks shown on both the PFD and CHEMCAD may

only be one unit for each. However, for clarity since the reactor and decanter are integrally

important to the process, the reactor and decanter were shown as two vessels rather than one.

The next two figures will show a full PFD and the simulation modeled after the PFD.

20
Figure 4 PFD of Chemical Process

21
Figure 5 Screenshot of CHEMCAD simulation

22
2.4 Selecting the Properties of Feed Stream

This process has two feed streams entering the simulation. A feed stream is depicted as an arrow

with a small pink dot at the top of the arrow. An example of these arrows is shown on the prior

Figure with toluene and methanol streams. When feed streams are created, the streams must be

specified. The figure below is an example of the “Edit Streams” dialog box in CHEMCAD.

Figure 6 Edit Streams Dialog Box

Figure 7 shows the Edit Stream dialog box for the incoming methanol stream. From the design

basis, the stream enters at 72 °F, and the pressure of the stream is at 5.52 atm. CHEMCAD must

23
only have two specifications of temperature, pressure, or vapor fraction. If there is only one

specification, CHEMCAD will show the error: “Feed Streams are not well defined. Calculation

bypassed.” CHEMCAD will not allow a third specification. Once each feed stream has two

specifications, depending on the temperature and pressure, CHEMCAD can determine if the

substance will be in the vapor phase or liquid phase. The button located on the upper left-hand

corner labeled as “Flash”, tells CHEMCAD to determine the current enthalpy for the stream. The

“Comp Unit” can allow users to freely change between units, such as lb/h or lbmol/h. The user

will input the numeric value of the quantity of the respective substances. This will determine the

ultimate amount of raw materials will be entering the process.

Using the stochiometric ratios given in the chemical equations, percent conversion and percent

selectivity, it was determined that there needs to be a flow of 1200 lbmol per hour of toluene

entering the process so that 350,000 tons of styrene is produced per year. Note: The working year

is equivalent to 8322 hours.

24
2.5 CHEMCAD Specifications

2.5.1 Heat Exchangers

There are eight heat exchangers in this process, with four of those exchangers being attached to

the distillation column UnitOps. The other four shell and tube heat exchangers must be specified

using the dialog box depicted in the figure below. CHEMCAD only allows one specification per

heat exchanger. CHEMCAD can also determine the changes in temperature of both outlet

streams without a specification. These specifications are designed around the outlet streams of

the exchanger. For instance, for HX-101, the outlet methanol Stream must be saturated vapor. In

the specification dialog box, the vapor fraction of the methanol outlet stream should be set to

“1”. In addition, each heat exchanger resulted in a pressure drop of 0.13 atm, which was

outlined in the design basis.

Table 2 Heat Exchanger Specification

Name Type of Fluid in the Fluid in the Exchanger

Exchanger Shell Side Tube Side Specification
HX-101 Shell and Tube Heated Reactor Incoming The methanol
(methanol Exchanger Effluent methanol Feed outlet must be
Vaporizer) saturated vapor.
HX-102 (toluene Shell and Tube Heated Reactor Incoming The toluene
Vaporizer) Exchanger Effluent toluene Feed outlet must be
saturated vapor.
HX-103 Shell and Tube Heated Reactor Incoming No specification
(Interchanger) Exchanger Effluent methanol and added
toluene Feed
HX-104 Shell and Tube Heated Reactor Cooling Water -Reactor
(Product Exchanger Effluent Effluent must be
Condenser) at 100 °F.
-Cooling water
must also be at
100 °F.

25
HX-104 poses a problem. Here, there is a need for two specifications. However, CHEMCAD can

only support two specifications. CHEMCAD controllers can help solve this need.

Figure 7 Heat Exchanger parameter dialog box

26
2.5.2 Controllers

Controllers are a type of process equipment located within CHEMCAD. It has one inlet stream

and one outlet stream. These are used as the “Excel Solver” of CHEMCAD.

There are three controllers located within the simulation. These controllers ensure that all the

design specifications are met accurately. These specifications could be met without the use of a

controller, but it would take some time to accurately find the correct settings needed.

The first controller in the simulation ensures that the interchanger HX-104 has enough water

flow so that the reactor effluent reaches 100 °F and that the water being used to cool the

interchanger is set to 100 °F. In the specification window of each heat exchanger, CHEMCAD

offers various ways in which users can determine how the exchanger works. Users can set the

outlet temperature of the outlet tube side or outlet shell side streams, or users can set the vapor

fractions of the outlet streams of the tube and shell sides. However, it is important to note that

CHEMCAD can only handle one specification per heat exchanger. Natively, it is impossible for

CHEMCAD to control both temperatures of both tube-side and shell-side streams. In order to

control both stream temperatures, a controller is needed. The inlet of the cooling water on the

shell side is set as 88 °F, so the only variable pertaining to the cooling water that can be

modulated is the mass flow rate. Changing the mass flow of the water can allow for a change in

the heat transferred. Using the heat capacity equation,

Q = mcΔT

CHEMCAD will modulate the mass of water needed to reach the desired cooling water outlet

temperature.

27
Figure 8 Controller Parameter CHEMCAD Dialog Box

Figure 8 is the specification sheet for the controller. The mode of the controller can be set as

“Feed-Backward” or “Feed-Forward”. This refers to the position of the controller in relation to

the variable that it is controlling. For this simulation, the controller is placed downstream after

the variable that is being modulated, so the “Feed-Backward” option is chosen.

Right below “Adjust this variable”, users can determine the location in which the variable is

located within the simulation. Here, stream 22 is selected, which is stream number of the inlet

cooling water in the simulation (This stream is labeled as stream 12 on the PFD). Once the

stream is selected, the “Variable” section will feature a drop-down menu. This drop-menu

includes all the physical properties that can be changed of that chosen stream, including Total

Mass Rate, Component Mass Rate, and Temperature. In this case, the mass flow rate of the water

is selected to be adjusted. Next, under the “Until This” section, there is a similar setup as the

28
previous section. This is the section in which the user inputs dependent variable that will change

in response to the independent variable. Since the native heat exchanger specification is already

setting the temperature of the outlet tube side (reactor effluent) to 100 °F, the temperature of the

outlet cooling water is chosen to be the dependent variable.

In the last section, under the “Is equal to this target”, this is the target goal at which the

dependent variable will reach. Since the desired goal is for the outlet water stream temperature to

only reach 100 °F, the constant “100” is inputted in the box. After the controller specification is

finished, the simulation will determine the exact mass flow rate of the cooling water needed to

reach the desired goal.

The second controller in the simulation ensures that the feed going into the reactor is equimolar

in respect to toluene and methanol. The controller is placed on stream 10 when using the PFD. In

the process, not all the toluene and methanol are used in the reaction, so there is a recycle stream.

The methanol in the recycle stream is always less abundant than the toluene in the recycle stream

because some of the methanol exits the reactor effluent along with the water in the aqueous

stream produced by the decanter. In addition, the way in which the distillation towers are

configured will also play in a role in the amount of methanol that is present within the recycle

stream. This reaction must be equimolar amounts of both toluene and methanol. The amount

extra methanol needed to make the reactor feed stream equimolar could be done by hand, but if a

change is made in the simulation, the amount may change, and the process would to be done

again, slowing down productivity. This controller is set to adjust the total molar flow rate of the

methanol feed stream (Stream 1 in the PFD) until the component molar flow rate of methanol is

equal to the component molar flow rate of toluene in stream 10. In Figure 8, under the “is equal

to this target” instead of typing the current molar flow rate of toluene in stream 10, the stream

29
number is selected instead. Once the stream number is inputted, the variable is changed to the

Total Component Rate” of the toluene. If done in this manner, if the molar flow rate of the

toluene changes, the flow of the methanol will change in response. The controller’s tolerance can

be set by the user; for this application, the tolerance was set at ±0.001.

The third controller used in this simulation is inputted so that the partition coefficient of the

methanol is satisfied. The partition coefficient states that the mole fraction of the methanol in the

organic phase divided by the mole fraction of the methanol in the aqueous stream. Since the

Decanter is being simulated via two Component Separators, the controller will be placed

downstream of the Component Separator that separates the aqueous stream from the organic

stream. Since each Component Separator works by the user inputting mole fractions for either

the top or bottom streams, these mole fractions are variables that can be manipulated by a

controller. From Figure 8, under the “Until This”, there is an option for “Arithmetic Operator”,

once this is selected, the controller can adjust the molar fraction of either the aqueous stream or

the organic stream so that when divided, the constant can equal 1.32.

30
2.5.4 Decanter Conditions

In the process, there is a three-phase separator, or decanter. This separator takes the reactor

effluent, and fractionates the product based on their state of matter. The decanter has four

streams. For simplicity, these streams have been named: the organic stream, aqueous stream,

gaseous stream, and feed stream. The gaseous stream exiting via the top of the decanter, carries

all the hydrogen and various amount of volatized styrene, toluene, methanol, and water.

There is no UnitOps available in CHEMCAD that can accurately model the decanter’s behavior.

The decanter must be modeled using a combination of UnitOps equipment. The first option is to

model the Decanter using two component separators, a type of UnitOps in CHEMCAD.

Component separators separates compounds in a stream based on user input with no other

calculation. One compound separator will separate the gaseous stream, and the other separator

will separate the aqueous stream. The second option is to model the decanter using a flash drum

(another type of UnitOps in CHEMCAD) and a component separator. A flash drum can

determine how much of the stream is volatized at a given V/F or temperature and pressure. Both

options are explored to see the differences in calculations.

2.5.4.1 First Decanter Model Operation:

In order to use two component separators, the amount of each substance that is volatized must be

determined. These varying amounts are calculated following Raoult’s Law. This law describes

this relationship between the molar fraction of volatized compounds and the vapor pressure of

each respective species :“If a gas at temperature T and pressure P contains a saturated vapor

whose mole fraction is y 1 (mol vapor/mol total gas), and if this vapor is the only species that

would condenses if the temperature were slightly lowered, then the partial pressure of the vapor

31
in the gas equals the pure-component vapor pressure p* i (T) at the system temperature” (Felder &

Rousseau, 2005, p. 249).

Raoult’s Law: p i = y i P = p i *(T)

Raoult’s Law will determine the partial pressure of the gaseous stream. In return, since the

overall pressure is known, the corresponding molar fractions can be calculated. However, in

order to apply Raoult’s Law, the pure-component vapor pressure must be calculated. Using the

constants in Table 3, Antoine’s Equation is applied to each chemical at 100 °F, or 38 °C. This

equation is given below.

Antoine’s Equation: p* = exp (A – B * (T + C)-1)

Table 3 Antoine Equation Constants *source

Chemical Name A B C
Methanol 7.88 1473.11 230.0
Water 7.97 1668.21 228.00
Toluene 6.96 1346.77 219.69
Styrene 7.07 1507.43 214.99
Ethylbenzene 6.96 1423.54 213.09

There is also an aqueous phase leaving the decanter. Due to the uncharged nature of the organic

compounds (ethylbenzene, toluene, styrene), these compounds easily separate from water;

however, methanol is partially attracted to water due to hydrogen bonding between the oxygen

attached to methanol’s alcohol functional group, and the hydrogens within the water molecules.

A partition coefficient was assumed; stating that the molar fraction of methanol in the Organic

Stream must be 1.32 bigger in magnitude when compared to the mol fraction of methanol present

within the aqueous stream.

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To ease in the calculations of modeling the decanter’s behavior, Excel Solver was used to

accurately determined the total amount of volatized amounts of the compounds leaving in the

Gaseous Stream.

To calculate the balance correctly, constraints must be aligned first. For all the compounds

entering the decanter from the feed stream, the mol fraction determined from the organic stream

for each respective compound was multiplied by the vapor pressure calculated by the Antoine’s

Equation, resulting in a product. This product is then divided by the total system pressure. Due

to Raoult’s Law, the product determined should equal the mol fraction of that respective

compound within the Gaseous Stream when multiplied by total pressure. If these products were

subtracted, the difference should be zero. This constraint is demonstrated by the following

equation for methanol.

P m *(T) * P = X o,m * P m

This difference was the first constraint inputted into Solver. At this point in the calculation, the

mol fractions of both the organic and gaseous streams are unknown, so estimates are inputted.

The molar fractions in both streams should equal one, which was listed as a constraint within

Excel Solver.

In addition, a separate balance was done on each respective compound. To ease in calculation,

accumulation within the decanter was neglected. Due to no accumulation and no reactions

occurring within the decanter, the amount entering the decanter should leave the decanter. The

respective amounts of each compound leaving via the gaseous, aqueous, and organic streams

were subtracted from the feed stream. The resulting difference should equal zero, and this

calculation was used as a constraint for Excel Solver. The equation below provides a

demonstration of this constraint using methanol.

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 X f,m – X o,m – X a,m – X g,m = 0

The partition coefficient is also inputted, whereas the mol fraction of methanol in the gaseous

stream should be 1.32 times bigger than the mol fraction of methanol in the aqueous stream. The

methanol molar fraction in the organic stream was divided by the molar fraction of methanol in

the aqueous stream, and the quotient was subtracted from 1.32. This calculation should equal

zero and was set as the last Excel solver constraint. After running Excel Solver, the following

stream compositions were generated. This partition coefficient equation is shown below.

1.32 = X o,m / X a,m

Setting all these constraints into Excel Solver, the respective molar fractions of each

compound within the gaseous stream was determined. In the simulation, the two component

separators will fractionate the incoming feed stream according to the mole fractions determined

via Excel Solver. Figure 9 shows the dialog box for setting the component separator’s

parameters. It is important to note that the user must calculate what percentage of each respective

compound is leaving via the gaseous stream or aqueous stream. For instance, the molar fraction

of the methanol leaving via the gaseous stream is 0.03, which equates to 26 lbmol per hour. 26

lbmol per hour is 12.9% of the methanol entering into the decanter, so for the component

separator parameter, the split fraction of the methanol leaving from the feed stream would be

0.129 instead of 0.03. If all a compound is going out in a stream, a “1” can be used.

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Figure 9 Component Separator Dialog Box

2.5.4.2 Second Decanter Operation

The second decanter modeling choice is using a combination of the flash drum UnitOps

and the component separator. The flash drum will calculate the volatized substances by using the

physical properties preloaded in CHEMCAD for each substance. Figure 10 shows the dialog box

to enter the flash drum’s parameters. Then, in the same fashion as the first decanter model, the

35
Then, in the same fashion as the first decanter model, the component separator is set to

fractionate the aqueous stream from the incoming feed stream.

Figure 10 Parameter Dialog Box for Flash Drums

2.5.4.3 Main Differences Between the Models

As outlined by Design Basis, all the hydrogen is assumed to exit via the gaseous stream. With a

component separator, all the hydrogen exited via the gaseous stream with no trace amount

exiting the decanter via the organic stream. However, if the flash drum is used, CHEMCAD uses

physical data to determine the volatility of the compounds. CHEMCAD had mostly all the

hydrogen leaving the decanter via the gaseous stream, with less than 1 lbmol of hydrogen exiting

via the organic stream.

In addition, there were differences in the exact amount of the volatized chemicals in the gaseous

stream. Table 4 shows the differences below.

36
Table 4 Molar percent of the gaseous stream exiting the Decanter

Chemical Name Using Excel Solver Using Flash Drum UnitOps

Styrene 0.43% 0.38%
Toluene 0.52% 0.52%
Methanol 3.02% 0.35%
Water 2.37% 3.75%
Hydrogen 93.44% 94.67%
Ethylbenzene 0.22% 0.33%

The main difference lies within the methanol mole fraction percentage. The Antoine’s Equation

constants for methanol that CHEMCAD used were different than the constants used in the Excel

Solver spreadsheet, resulting in a 26 lbmol per hour difference. Both models can be used;

however, the main difference would be in the amount of incoming methanol feed regulated by

controller #2. The first decanter model was ultimately chosen to model the decanter in the

simulation.

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2.5.5 Reactor

Before inputting the reactor within CHEMCAD, various reactor conditions were given as part of

the design basis. The reactor is to operate adiabatically at 977 °F and 4 atm. The conversion of

toluene is 82% percent. The selectivity of the toluene being converted to styrene is 72%. Even

though both reactions are reversible, in this study, the backwards reaction is negated, and the

reactions are irreversible moving in the forward direction only.

CHEMCAD offers a great deal of various reactors. These reactors are all designed to handle

specific types of chemical reactions. In this study, there are two reactors that can be used. The

first reactor type, the Stochiometric Reactor, is “the simplest reactor type that can be simulated”

(Turton, Bailie, Whiting, Shaeiwitz, & Bhattacharyya, 2012, p. 430). This reactor uses the

stochiometric ratios, conversion rates, temperature, and pressure to determine the amount of

product created. This reactor can only handle one reaction at a time. The second reactor type is

the Gibbs Reactor. This reactor calculates the reactor effluent composition using a “free energy

minimization technique” (Turton, Bailie, Whiting, Shaeiwitz, & Bhattacharyya, 2012, p. 431). In

this case, the reaction conversion, reaction selectivity, and reaction products are all determined

via CHEMCAD.

In this study, since there are specific conversion and selectivity rates, the Stochiometric Reactor

was chosen. Figure 11 shows the parameter dialog box. Here, the user determines the thermal

mode of the reactor, and the key component. CHEMCAD uses this component as the basis for

conversion. Since the reactor can only handle one reaction at a time, two Stochiometric Reactors

are used in the simulation.

38
Figure 11 Stochiometric Reactor Parameter Dialog Box

2.5.5 Mixers and Dividers:

In the same sense as the controllers, these UnitOps are used to join or separate chemical streams.

The only parameter that can be set is the outlet pressure of the mixer. There is one mixer in the

process that mixes the recycle stream with the incoming feed stream. This UnitOps is not shown

on the PFD.

39
2.5.6 Distillation Towers (Shortcut Tower):

Figure 12 Shortcut Distillation Tower Dialog Box

The figure above is a screenshot of the shortcut distillation tower parameter dialog box. In the

process, there is two different distillation towers. T-101 takes the organic stream from the

decanter and splits the toluene and methanol from the two products, styrene and ethylbenzene. T-

102 splits the toluene and ethylbenzene into separate product streams. CHEMCAD offers a

“Shortcut Column”, that allows for quick distillation without many specifications. Once the

Shortcut Column is completed, a rigorous model can be created, which requires more

specifications, such as the condenser duty, and reboiler duty.

For the shortcut model, if user select the mode, “Design FUG wit hFenske feed tray location”,

the user will only have to input the Column pressure, pressure drop, R/Rmin, and the light key

component, and the heavy key component. It is important to note that when determining the light

40
key and heavy key split, this split is only applicable to the distillate stream. These “splits” are

referring to amount of each key component that will go into the distaillate stream.

In addition, selecting the condenser type changed the temperature of the distillate stream for T-

101. Having the condenser set at “Total”, the temperature of the distillate stream for T-101 is

147 °F; however, if the condenser is set at “Partial”, the temperature increased to 277 °F. This

increase in temperature caused a pinch zone error to occur within one of the Heat Exchangers.

Pinch zones occur when the LMTD or the “Log Mean Temperature Difference” of the heat

exchanger is negative or approaching zero. When this occurs, the two fluids flowing thorugh the

exchangers are already close in temperature. If the two streams are close to the same

temperature, there is very little heat transfer occuring. Without any heat transfer, CHEMCAD

cannot reach the specification of the heat exhcanger set by the user, and an error occurs.

41
 CHAPTER III

III. RESULTS

The data collected by CHEMCAD can be exported in multiple ways. Primarily, CHEMCAD

creates a stream report. A stream report essentially characterizes each stream based on the stream

numbers on the simulation. This report can be amended within the settings of CHEMCAD. The

data that the stream report gives includes the individual mass quantities and mass fractions of

each respective compound in the process. The report can also give more specialized information

about the streams, such as the stream’s enthalpy, specific gravity, and the specific heat

coefficient. The next table shows the stream report of the simulation. The stream table has been

modified to match the streams on the PFD.

42
3.1 Meeting Specifications

There are several specifications that were required to be met during this process. After creating

the simulation successfully, an overall stream report was generated, and several streams were

selected to show verification that these specifications were met.

1. The recycle stream (stream 7) must have a 4 weight % maximum of ethylbenzene

present, and the weight % sum of ethylbenzene and Styrene must not exceed 5%

a. From the stream report, (stream 7), ethylbenzene makes up 0.175 of the weight %

of the recycle stream. This is in part due to the specifications of the distillation

tower T-101.

2. Reactor influent must be equimolar going into reactor.

a. Stream 10 shows that the toluene and methanol have the same number of moles.

Controller 2 ensures that the incoming methanol feed rate is adjusted so that the

when the recycled methanol stream is added to the incoming feed stream, the raw

materials can be equimolar.

3. The reactor effluent must be condensed to a saturated liquid at 100 °F using HX-104, and

the cooling water outlet must leave HX-104 at 100 °F.

a. Controller 1 modulates the mass flow rate of the cooling water stream so that the

final temperature equilibrium between the reactor effluent and the cooling water

is 100 °F.

4. The amount of water and hydrogen in the organic phase are negligible.

a. Using a component separator as the decanter allows users to push all the water

into the aqueous phase, and all the hydrogen into the gaseous phase without any

trace of those two chemicals in the organic phase.

43
 b. If a flash drum and a component separator is used for the decanter instead of two

component separators, the amount of Hydrogen present within the organic phase

is only 0.654 lbmol/hr, which is a very small amount.

5. The molar fraction of methanol in the organic stream (stream 21) divided by the molar

fraction of the methanol in the aqueous stream (stream 16) must equal 1.32.

a. Controller 3 changes the component separator split fraction parameters so that this

specification must be met. The molar fraction of methanol in the organic phase is

0.0736 and the molar fraction of methanol in the aqueous phase is 0.0557, when

divided equals 1.32

6. The ethylbenzene product stream (stream 17) must have 0.8 weight % maximum of

toluene and 3 weight % of styrene

a. The ethylbenzene product stream has trace amounts of toluene and styrene

present within the system.

7. The styrene product stream can have at most 300 ppm of ethylbenzene present.

a. 12 pounds in a 38,396 lb per hour stream is 133 ppm, which is below the

specification.

8. There must be 350,000 tons of styrene produced yearly.

a. The simulation created yields 823 lbmol of styrene every hour. With the working

year equaling 8322 hours, this is equivalent to 356,148 tons of styrene produced

per year, which is slightly over the intended goal.

44
Table 5. Stream Tables generated by CHEMCAD

45
 References

CHEMSTATIONS. (2016). Microsoft Word - Chapter 1 - Introduction. Retrieved from

CHEMSTATIONS:
https://www.chemstations.com/content/documents/CHEMCAD_7_User_Guide.
pdf

Edwards, J. E. (2008, November). Process Modelling. Retrieved from Chemstations

Corporation web site:
https://www.chemstations.com/content/documents/Technical_Articles/thermo.p
df

Felder, R. M., & Rousseau, R. W. (2005). Elementary Principles of Chemical Processes.

Danvers, MA: John Wiley & Sons, Inc.

Smith, J., Van Ness, H., Abbott, M., & Swihart, M. (2018). Introduction to Chemical
Enginering Thermodynamics, 8th Edition. New York, NY: McGraw-Hill Education.

Styrene Information & Research Center. (2014). What is Styrene? Retrieved from
https://styrene.org/about-styrene/qa/

The Styrene You Know: Uses and Benefits. (2013). Retrieved from youknowstyrene.org:
https://youknowstyrene.org/the-styrene-you-know/uses-and-benefits/

Turton, R., Bailie, R. C., Whiting, W. B., Shaeiwitz, J. A., & Bhattacharyya, D. (2012).
Analysis, Synthesis, and Design of Chemical Processes, 4th Edition. Upper Saddle
River, NJ: Pearson Education, Inc.

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