Material Balances Project

Ethylbenzene

Ethyl benzene (EB) is used as a chemical intermediate in making styrene, the building block for
manufacturing polystyrene. It is a major commodity chemical that is produced throughout the
world. A byproduct of the process is diethyl benzene (DEB) that is an intermediate in divinyl
benzene manufacture. Since the demand for styrene is far greater than the demand for divinyl
benzene, the selectivity for our process should favor ethyl benzene production.

Ethyl benzene is produced by coupling ethylene and benzene with an acidic catalyst. Diethyl
benzene forms when ethylene reacts with ethyl benzene. The formation of multiply-substituted
benzenes is limited by running the reaction with a large excess of benzene. The reactions that
produce EB and DEB are

C6H6 + C2H4 → C6H5C2H5 ζ1

C6H6 + 2C2H4 → C6H4(C2H5)2 ζ2

where ζι is the extent of reaction. The selectivity of these reactions is determined by the feed
ratio and processing conditions. A simplified process flow diagram is shown in the appended
figure.

Process Description

Fresh benzene (Stream 1) and ethylene (Stream 2) are combined with a recycle stream containing
unreacted benzene and a small amount of ethyl benzene. The combined stream is fed to a reactor
where all of the ethylene in the feed reacts. The reactor effluent (Stream 4) is cooled so that
most of the benzene, ethyl benzene, and diethyl benzene condenses. An ethane impurity from the
ethylene feed as well as some benzene and ethyl benzene vapor are purged from the process and
used as fuel gas. The condensed liquid is fed to the first distillation column. A high purity
benzene stream is removed from the top of the column and recycled. The bottoms from the first
column are sent to a second distillation column. The second column produces high-purity ethyl
benzene in the top stream and diethyl benzene in the bottom. Data on the composition of these
streams are provided in a following section.

Additional Process Information

Stream 1 – Assume that benzene is pure.

Stream 2 – The ethylene feed contains 7.0 mol% ethane as an impurity. Ethane does not react
but moves through the process as an inert gas until it is purged in Stream 5.
Stream 3 – Benzene-to-ethylene molar ratio is adjusted to control reaction selectivity. Use a
10:1 ratio when making hand calculation.
R-301 – The limiting reactant achieves 100% conversion. Reaction selectivity is
determined by B3/E3 ratio. See relationship below.
Stream 5 – Fuel gas composition is 40 mol% ethane, 55 mol% benzene and 5 mol% ethyl
benzene.
Stream 7 – Recycle stream composition is 99.2 mol% benzene and 0.8 mol% ethyl benzene.
Stream 9 – Overhead stream composition is 99.6 mol% ethyl benzene, 0.4 mol% benzene.
Stream 10 – Bottoms stream composition is 90 mol% diethyl benzene, 10 mol% ethyl benzene.

Reaction Information

The selectivity for ethyl benzene production is a function of benzene-to-ethylene ratio. This
relationship is expressed as

1 .2
ζ 2 = ⎛ E3 ⎞
⎜ ⎟
ζ 1 ⎜⎝ B 3 ⎟⎠

However, the size of T-301 limits the B3/E3 ratio to a maximum value of 12.

Operating Costs

Much of the expense in manufacturing ethyl benzene is associated with utility costs like
compressing gases to reaction pressure and evaporating liquids for separation in distillation
towers. These costs cannot be estimated well in a first chemical engineering course. Therefore,
utility costs may be ignored this semester. The difference between product price and feedstock
cost should be called revenue. It should not be called profit, since operating and other expenses
have not been included.

ethylene cost = $ 0.77 /kg

benzene cost = $ 1.22 /kg
EB price = $ 1.54 /kg
DEB price = $ 0.76 /kg
Fuel gas value = $ 0.54 /kg

Problem

You, the engineering team, are to optimize the operation of the EB process in order to produce
100,000 metric-tons/yr (100,000,000 kg/yr). Your goal is to minimize operating costs and
maximize revenue. You are constrained by the selectivity of the reaction and by the size of T-
301 used for separating and recycling excess benzene.

Group Formation

A design group is to consist of two members. You are encouraged to make groups by
yourselves. When you have formed a group, please turn in the names of group members to Dr.
Kugler. He will combine groups to make 3- or 4-person design teams. A list of design teams
will be provided on November 12.

Computations

You are expected to use a spreadsheet for material balance and cost calculations. The first step
should be solving the material balance by hand calculations. Use a basis of n2 = 100 kmol/h and
the reactor-feed ratio of B3/E3 = 10. After completing the hand calculation, set up the
2
spreadsheet to do the material balance when you specify B3/E3 ratio. Copy results into a stream
B

table. These first steps, including pencil-written hand calculations, should be included as an
appendix to your report to demonstrate that calculations were done correctly.

After producing a stream table on your spreadsheet using kmol units, convert kmol units to mass
on a second stream table, then scale so that EB meets production goal. Profit or loss for selected
operating conditions can be calculated from scaled-stream-table data.

Reports

Each team will be expected to prepare a written report recommending the best operating
procedures for the EB process. This report is due at 3:00 PM, Wednesday, December 7. The
report should follow the Department’s design-report guidelines. Data should be in the form of
graphs and tables, since this serves both to condense results and make them easily
understandable. The appendix should include your spreadsheet and a hand calculation of the
10/1 case.

Report Authors

Although work on a group report can never be divided equally, only those members making
substantial contributions to the final report should be listed as authors.

3
 Energy Balances and Numerical Methods
Design Project

Production of Ethylbenzene
Ethylbenzene is the primary raw material used to make styrene. Styrene is polymerized into
polystyrene, one of the most important polymers in the chemical industry. The usual practice in
the chemical industry is to have ethylbenzene and styrene processes on the same site. Like most
ethylbenzene/styrene facilities, there is significant heat integration between the two plants. The
ethylbenzene reaction is exothermic, so steam is produced, and the styrene reaction is
endothermic, so energy is used in the form of steam.

The purpose of this project is to continue a preliminary analysis to determine the feasibility
of constructing a chemical plant to manufacture 80,000 tonne/y of ethylbenzene. The raw
materials are benzene and ethylene.

A suggested process flow diagram (PFD) is shown in Figure 1. You should use this as a
starting point. Your primary task is to recommend operating conditions for heat exchanger E-
301 and flash vessel V-301 that maximize the equivalent annual operating cost, or EAOC (This
term is defined later). Process improvements that increase the EAOC are also desired. Any
changes that you can justify, which not violate the laws of nature, are allowed. Your assignment
is to develop a “best” case, where “best” is dependent upon economic considerations, i.e.,
EAOC. In reporting your best case, clearly indicate the modified process and state the operating
conditions for the modified process and the corresponding EAOC. Also, state any
recommendations you have for additional process improvements that you were not able to
incorporate into the process calculations.

Chemical Reaction

The production of EB takes place via the direct addition reaction between ethylene and
benzene:

C6 H 6 + C2 H 4 → C6 H 5C2 H 5
(1)
benzene ethylene ethyl benzene

The reaction between ethylbenzene and ethylene to produce di-ethylbenzene also takes place:

C6 H 5C2 H 5 + C2 H 4 → C6 H 4 (C2 H 5 )2
(2)
ethyl benzene ethylene diethyl benzene

Additional reactions between di-ethylbenzene and ethylene yielding tri- and higher ethyl benzene
are also possible. However, in order to minimize these additional reactions, the molar ratio of
benzene to ethylene is kept high, at approximately 8:1.
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Process Details

Streams and Equipment Details

Stream 1: Benzene – at 25°C and 2000 kPa, assumed pure

Stream 2: Ethylene – at 25°C and 2000 kPa, 93 mol % ethylene, 7 mol % ethane

Stream 3: feeds adjusted based on recycle composition to have 8:1 benzene/ethylene

ratio

Stream 4: mixed feed heated to 400°C

Stream 5: 100% conversion of limiting reactant in R-301, the selectivity for ethyl
benzene production is a function of benzene-to-ethylene ratio. This
relationship is expressed as
1 .2
ξ 2 = ⎛ E3 ⎞ (3)
⎜ ⎟
ξ 1 ⎜⎝ B 3 ⎟⎠

where ξi is the extent of reaction for the reactions in Equations 1 and 2, and
the subscript 3 refers to the molar content of ethylene (E) and benzene (B) of
Stream 3. The size of T-301 limits the B3/E3 ratio to a maximum value of 12.
B

Stream 6: vapor/liquid mixture, steam may be produced in E-301, cooling water may
also be used, the temperature and pressure of Stream 6 are decision variables

Stream 7: fuel gas purge, credit may be taken for fuel gas based on HHV

Stream 8: mostly benzene, ethylbenzene, and di-ethylbenzene, the sole purpose of V-301
is to allow the vapor and liquid mixture in Stream 6 to separate at the same
temperature and pressure as Stream 6

Stream 9: benzene recycle

Stream 10: ethylbenzene/di-ethylbenzene mixture

Stream 11: product ethylbenzene, 2 ppm di-ethylbenzene maximum

Stream 12: di-ethylbenzene to waste treatment

Distillation Column Information

Distillation Column (T-301)

This column runs at 150 kPa. Separation of benzene from ethylbenzene and di-
ethylbenzene occurs in this column. Of the benzene in Stream 8, 99% enters Stream 9.
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Similarly, 99% of the ethylbenzene and all of the di-ethylbenzene in Stream 8 enters
Stream 10.

Heat Exchanger (E-302)

In this heat exchanger, the some of the contents of the stream leaving the bottom of T-
301 entering to E-902 are vaporized and returned to the column. The amount returned to
the column is equal to the amount in Stream 10. The temperature of these streams is the
boiling point of ethylbenzene at the column pressure. The heat required may be
estimated by the heat of vaporization of each component at the boiling point of
ethylbenzene at column pressure. There is a cost for the amount of steam needed to
provide energy to vaporize the stream; this is a utility cost. The steam temperature must
always be higher than the temperature of the stream being vaporized.

Heat Exchanger (E-303)

In this heat exchanger, the contents of the top of T-301 are partially condensed from
saturated vapor to saturated liquid at the column pressure. You may assume that benzene
and all heavier components condense completely and that any ethylene and ethane
present do not condense and are vented from E-903 (not shown) and enter the fuel gas
stream. Condensation occurs at the boiling point of each condensing component at the
column pressure. There is a cost for the amount of cooling water needed; this is a utility
cost. The cooling water leaving E-303 must always be at a lower temperature than that of
the stream being condensed. The ratio of Stream 9 to the stream recycled back to T-301
is 1/3.

Distillation Column (T-302)

This column runs at the 150 kPa. Separation of ethylbenzene and di-ethylbenzene occurs
in this column. The maximum amount of di-ethylbenzene in Steram 11 is 2 ppm, and
99.9 % of the ethylbenzene in Stream 10 enters Stream 11.

Heat Exchanger (E-304)

In this heat exchanger, the some of the contents of the stream leaving the bottom of T-
302 are vaporized and returned to the column. The amount returned to the column is
equal to the amount in Stream 12. The temperature of these streams is the boiling point
of di-ethylbenzene at the column pressure. The heat required may be estimated by the
heat of vaporization of each component at the boiling point of di-ethylbenzene at column
pressure. There is a cost for the amount of steam needed to provide energy to vaporize
the stream; this is a utility cost. The steam temperature must always be higher than the
temperature of the stream being vaporized.
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Heat Exchanger (E-305)

In this heat exchanger, the contents of the top of T-302 are condensed from saturated
vapor to saturated liquid at the column pressure. Condensation occurs at the boiling point
of each condensing component at the column pressure. There is a cost for the amount of
cooling water needed; this is a utility cost. The cooling water leaving E-305 must always
be at a lower temperature than that of the stream being condensed. The ratio of Stream
11 to the stream recycled back to T-302 is 2/3.

Economic Analysis

When evaluating alternative cases, the objective function to be used is the Equivalent Annual
Operating Cost (EAOC), defined as

EAOC = -(product value - feed cost – utility costs – waste treatment cost - capital cost annuity)

A negative value of EAOC means there is a profit. It is desirable to minimize EAOC; i.e., a
large negative value of EAOC is very desirable.

Utility costs are those for steam, cooling water, boiler-feed water, natural gas, and electricity.

The capital cost annuity is an annual cost (like a car payment) associated with the one-time,
fixed capital cost of plant construction and installation. A list of fixed capital costs on an
installed basis (“installed cost”) for all pieces of equipment will be provided by mid-March.

The capital cost annuity is defined as follows:

i (1 + i ) n
capital cost annuity = FCI (2)
(1 + i ) n − 1

where FCI is the installed cost of all equipment; i is the interest rate; and n is the plant life, in
[y]. For accounting purposes, take i = 0.15 and n = 10.

Optimization

You will learn optimization methods in ChE 230. The objective function (EAOC) is defined
above. You should consider both topological and parametric optimization.

Topological optimization involves considering different process configurations (such

location of process equipment, whether or not to add or remove equipment). Recall that you may
alter the process configuration in any way that improves the economic performance, as long as it
does not violate the laws of nature. It is suggested that you look carefully at the efficient use of
raw materials and the production of steam for use in the styrene process. It is possible to add
additional heat exchangers and separation vessels to Stream 7 to improve the separation of raw
materials.
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Parametric optimization involves determining the best operating parameters for the chosen
process topology. It is your responsibility to define appropriate decision variables. If there are
too many decision variables to do a reasonable parametric optimization, it is your responsibility
to determine, with appropriate justification, which ones most significantly affect the objective
function. Then you should focus on only those decision variables. This is called a Pareto
analysis.

Utility Costs

Low-Pressure Steam (618 kPa, saturated, cost or credit) $7.78/1000 kg

Medium-Pressure Steam (1135 kPa, saturated, cost or credit) $8.22/1000 kg

High-Pressure Steam (4237 kPa, saturated, cost or credit) $9.83/1000 kg

Natural Gas or Fuel Gas (446 kPa, 25°C)

cost $6.00/GJ
credit $5.00/GJ

Electricity $0.06/kWh

Boiler Feed Water (at 549 kPa, 90°C) $2.45/1000 kg

(There is a cost for boiler feed water only if the steam produced enters process streams.
If, on the other hand, the steam produced is subsequently condensed, it can be made into
steam again. In that case, there is no net cost for boiler feed water.)

Cooling Water $0.354/GJ

available at 516 kPa and 30°C, return pressure ≥ 308 kPa
return temperature should be no more than 15°C above the inlet temperature

Refrigerated Water $4.43/GJ

available at 516 kPa and 5°C, return pressure ≥ 308 kPa
return temperature should be no higher than 15°C

Low-temperature Refrigerant $7.89/GJ

available at -20°C

Very low-temperature Refrigerant $13.11/GJ

available at -50°C

Process Water $0.067/1000 kg

available at desired pressure and 30°C

Waste Water Treatment $56/1000 m3

based on total volume treated
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Data

All required data may be found on the CD that came with your textbook [1]. For this project,
and for this project only, you may use data on that CD outside the range of applicability shown
in the data base. It is suggested that you clearly state this assumption in your written report.

Additionally, the following raw material and product costs should be used:

Raw Material or Product price

benzene 2.00/gal
ethylene 0.88/kg
ethylbenzene 1.10/kg

Equipment Costs

The equipment costs for the ethylbenzene plant are given below. Each cost is for an
individual piece of equipment, including installation. Any pieces of equipment not listed may be
considered inexpensive enough to be omitted.

Equipment Installed Cost

in millions of $

Reactor, R-301 0.5

Tower, T-301 1.0
Tower, T-302 0.65
Vessel, V-301 0.1
Any heat exchanger 0.25

Fired heater (H-301) installed cost in dollars:

11× 10 x
where
x = 2.5 + 0.8 log10 Q
where Q is the heat duty in kW

Other Information

You should assume that a year equals 8000 hours. This is about 330 days, which allows for
periodic shutdown and maintenance.

Deliverables

Each group must deliver a word-processed report. It should be clear, concise and adhere to
the prescribed format. The format is explained in the written report guidelines, provided in a
separate document. When presenting results for different cases, graphs are superior to tables.
The body of the report should be short, emphasizing only the results and briefly summarizing
 8

computational strategies. The report appendix should contain details of calculations that are easy
to follow. Calculations that cannot be followed easily will lose credit.

The project is due April 24, 2006, at the beginning of class. There will be oral presentations
of project results on that day. Oral presentations will continue on April 25, 2006, if we are
unable to complete all presentations on April 24, 2006. Oral presentation guidelines will be
provided in a separate document.

Anyone not participating in this project will automatically receive an F for ChE 202 and ChE
230, regardless of other grades earned in this class.

Grading

The report grade for each class will be based on the technical content pertinent to that class,
which includes the response to questions during the oral presentation (60%), the oral presentation
(20%), and the written report (20%). The grade for the written report portion will include the
quality of the writing, the quality of the presentation, and the adherence to the prescribed format.
The grade for the oral presentation will be a composite grade for the entire team. Therefore,
group preparation and feedback are recommended. The grade for the technical content is self
explanatory.

The documents on the following web site provide an indication of the expected attributes of a
design report.

http://www.che.cemr.wvu.edu/ugrad/outcomes/rubrics/index.php

Groups

You will work on this project in groups of 4. More details of group formation and peer
evaluation will be discussed in class.

Revisions

As with any open-ended problem, i.e., a problem with no single correct answer, the problem
statement above is deliberately vague. The possibility exists that, as you work on this problem,
your questions will require revisions and/or clarifications. You should be aware that these
revisions/clarifications may be forthcoming.

References

1. Himmelblau, D. M. and J. B. Riggs, Basic Principles and Calculations in Chemical

Engineering (7th ed.), Prentice Hall, Englewood Cliffs, NJ, 2004.
 Fluid Mechanics, Heat Transfer, Thermodynamics
Design Project

Production of Ethylbenzene
We continue to investigate the feasibility of constructing a new, grass-roots, 80,000 tonne/y,
ethylbenzene facility. As part of the feasibility study, we would like you to investigate some of
the details of the proposed plant and of the thermodynamics of the components involved in the
process.

Chemical Reaction

The production of EB takes place via the direct addition reaction between ethylene and
benzene:

C6 H 6 + C2 H 4 → C6 H 5C2 H 5
(1)
benzene ethylene ethyl benzene

The reaction between ethylbenzene and ethylene to produce di-ethylbenzene may also take place:

C6 H 5C2 H 5 + C2 H 4 → C6 H 4 (C2 H 5 ) 2
(2)
ethyl benzene ethylene diethyl benzene

and additional reactions between di-ethylbenzene and ethylene yielding tri- and higher ethyl
benzene are also possible. However, for this project, you may assume that the reaction in
Equation (1) is the only reaction that occurs as long as the molar ratio of benzene to ethylene is
kept high, at approximately 8:1.

Process Description

The PFD for the process is given in Figure 1. It should be used as a starting point for this
assignment.
2
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Process Details

Feed Stream and Effluent Streams

Stream 1: benzene feed at 25°C and 110 kPa

Stream 2: ethylene feed at 25°C and 200 kPa, is split so that the benzene to ethylene
ratio entering both reactors is fixed at 8/1. The feed contains 5 mol% ethane
impurity.

Stream 5: fired heater feed at 2000 kPa

Stream 7: R-301 feed at 380°C, same temperature for R-302 feed, benzene/ethylene ratio
at 8/1 for both reactors

Stream 13: fuel gas effluent stream

Stream 16: ethylbenzene product

Equipment

Ethylene Compressor (C-301)

The compressor increases the pressure of the feed ethylene from 200 kPa to 2000
kPa. The compressor may be assumed to be adiabatic with an efficiency of 75%. It
may be necessary to use staged compressors with intercooling.

Benzene Feed Mixing Vessel (V-301)

provides reservoir of liquid for feed pump

Pump (P-301 A/B, includes spare pump)

pumps feed benzene to 2025 kPa

Feed Heater – a fired heater (H-301)

effluent at 2000 kPa

Reactors (R-301 and R-302)

adiabatic reactors, conversion in each reactor is 98%, pressure drop of 15 kPa

Heat Exchangers (E301 and E-302)

pressure drop of 25 kPa on the process side

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Flash Vessel (V-302)

This flash vessel provides for a one-stage flash separation of the light components
from the heavy components. It has a maximum operating pressure of 250 kPa. The
base-case conditions are 80°C and 110 kPa.

Distillation Column (T-301)

99.9 % of the benzene enters Stream 15. 99 % of ethylbenzene enters Stream 16,
operates at 110 kPa with Stream 15 at the saturation temperature of benzene at 110
kPa and with Stream 16 at the saturation temperature of ethylbenzene at 110 kPa.

Assignment
The assignment consists of the following “mini-designs.”

1. Fluid Mechanics and Heat Transfer

The purpose of this design project is to design and evaluate the performance of the cooling
loop consisting of E-301, E-302, E-303 and pump, P-302. The purpose of this loop is to
circulate a stream of coolant (Dowtherm™ A) through the reactor intercooler and reactor effluent
cooler and to use the energy to make steam in the Dowtherm™ cooler. The stream leaving the
pump is fed into the Dowtherm™ cooler and then may be fed either through the three exchangers
in series, as shown in Figure 1, or split between the two coolers, E-301 and E-302 and then
recombined prior to entering the pump. The properties of Dowtherm™ A are available from
ChemCAD. In order, to avoid degrading the Dowtherm™ A, its maximum temperature should
never exceed 400°C anywhere in the loop. Any steam produced in E-303 may be sold for profit,
the values for the different pressure levels of steam are given in Appendix 1.

Process Fluid Mechanics, ChE 310 Assignment

Design Problem

You are to optimize the design of the heating loop in conjunction with the heat transfer
assignment. The amount of heat to be removed from the process streams in E-301 and E-302
must be determined from a ChemCAD simulation using the base-case conditions given in this
assignment. For exchanger E-301, a detailed design is required and the required details are given
in the heat transfer assignment. For the two other exchangers, you may estimate their heat
transfer areas (and subsequently their costs) using the following overall heat transfer coefficients:

Liquid-liquid = 300 W/m2°C

Boiling liquid-liquid = 500 W/m2°C
Gas-liquid = 80 W/m2°C
Condensing gas-liquid = 400 W/m2°C
 5

You should remember that these exchangers may have several zones and that multiple
overall coefficients may have to be applied for a given exchanger.

The objective function for the optimization should be the Equivalent Annual Operating Cost
(EAOC, $/y) for the loop, that is defined as:

⎛A ⎞
EAOC = CAP ⎜ , i, n ⎟ + AOC − R (3)
⎝P ⎠

where CAP is the capital investment for all the equipment ($), AOC ($/y) is the annual operating
cost, R ($/y) is any revenue produced from the selling of steam, and

i(1 + i)
n
⎛A ⎞
⎜ , i, n⎟ =
[ ]
(4)
⎝P ⎠ (1 + i) n − 1

where i = 0.15 (15% rate of return) and n = 10 (ten-year plant life).

The cost for the pump, piping components, controls, and exchangers are given in Appendix
1. You are to determine the optimal pipe diameter (and pipe schedule) that minimizes the
EAOC. The pressure drops for each exchanger may be estimated as:

2 psi for the shell-side fluid

5 psi for the tube-side fluid

For E-301, which you will design in detail, you may use the above approximate pressure
drops in the calculations to determine optimal pipe diameter. However, in the heat exchanger
design, you should evaluate the pressure drops in E-301 using the appropriate relationships.

In order to evaluate the amount of piping required for the loop, you should sketch a piping
isometric showing the location of all equipment and all the appropriate pipe fittings. You may
assume that all the exchangers are located 10 ft above grade (ground level), and that the pump is
located at grade with the inlet 1 ft above grade and the outlet 2 ft above grade. The pump will be
installed in parallel with a spare and the piping arrangement should be similar to the one shown
in the piping isometric given in ChE 310. Assume that the three exchangers are arranged in a
horizontal row with approximately 12 ft between each exchanger and that the pump(s) are
located within 15 ft of the row of exchangers. A plot plan (looking vertically down on the loop)
and an elevation diagram (looking at a side view) are given in Figure 2.

The location and sizes of the equipment in Figure 2 are approximate since the design of the
equipment has not yet been performed. However, you may use these diagrams to estimate the
length of pipe and the number and types of pipe fittings required for the Dowtherm™ loop. You
should assume that for good control, the pressure drop across the control valve should equal 1/3
of the total frictional losses through the loop or 5 psi, whichever is the larger value.
 6

Plot Plan Elevation Diagram

Shell-side inlet Tube-side inlet

Shell-side inlet Tube-side inlet

E-301 12 ft
2 ft
2 ft

P-302A
E-302 Pump outlet
12 ft 10 ft
P-302B 4 ft
1 ft 2 ft

E-303 15 ft Pump inlet

Figure 2: Preliminary plot and elevation diagrams for the equipment in the Dowtherm™ loop.

Performance Problem

Once you have designed and optimized the Dowtherm™ loop, you should determine the
maximum heat transfer removal (from E-301 and E-302) possible for the system that you have
designed. This will correspond to having the control valve wide open and the pumps running
either in parallel or series (the better configuration will depend on your design). The pump
characteristics for a typical centrifugal pump are given in Equations (5) and (6)

7.1265
P ⎡ Q ⎤
= 1.1 − 0.1 ⎢ ⎥ (5)
Pdesign ⎣⎢ Qdesign ⎦⎥

2
⎛ Q ⎞
NPSH R (m of liquid at pump inlet conditions) = 5 + 2 ⎜
⎜ Qdesign ⎟⎟
(6)
⎝ ⎠

where Pdesign is the pressure increase developed across the pump at the design flowrate, Qdesign.
For this problem, you should calculate the new exit temperatures of the Dowtherm™ as it passes
through each heat exchanger and determine the additional heat transfer that occurs in each heat
exchanger.
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Process Heat Transfer, ChE 311 Assignment

Design of Heat Exchanger, E-301

You should perform a detailed design of E-301. You should assume that utilities are
available at the conditions specified in Appendix 1 of this problem statement. For this heat-
exchanger design, you should report the following information, as needed for the design:
• Diameter of shell
• Number of tube and shell passes
• Number of tubes per pass
• Tube pitch and arrangement (triangular/square/..)
• Number of shell-side baffles and their arrangement (spacing, pitch, type)
• Diameter, thickness, and length of tubes
• Calculation of both shell- and tube-side film heat transfer coefficients
• Calculation of overall heat transfer coefficient (you may assume that there is no
fouling on either side of the exchanger)
• Heat transfer area of the exchanger
• Shell-side and tube-side pressure drops (calculated, not estimated)
• Materials of construction
• Approximate cost of the exchanger

A detailed sketch of the exchanger should be included along with a set of comprehensive
calculations in an appendix to the mini-project.

2. Thermodynamics – Optimization of the Ethylene Feed Compressor (ChE 320)

You should minimize the equivalent annual operating cost, EAOC, for the compressor
section of the process with the following in mind:

• The ethylene feed should be taken from the inlet conditions (200 kPa and 25°C) and
compressed.

The optimization for this mini-project should include the cost of the compressors, the cost of
heat exchangers, the cost of cooling water, and the cost of electricity. Raw material costs should
not be included, so CAP (the capital investment for equipment used in the equation for EAOC
given in Equation 3) includes only the installed cost of compressor stages and heat exchangers,
and annual operating costs include the electricity to run the compressor stages and the cost of
cooling water in the intercoolers, if used. Note that there is no revenue term for this mini-design.

The objective function for the optimization is the Equivalent Annual Operating Cost
(EAOC $/y) of the piping system including the compressor. The EAOC was defined in
Equations 3 and 4.
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3. Safety Analysis Report

When designing a chemical process, it is important to know the properties of the chemicals
being consumed and produced in the process. The reactivity and toxicity of the reactants and
products will not only affect the design but will also affect the procedures that might be
implemented during an unscheduled event such as an emergency shutdown. The purpose of the
safety analysis report is to make management aware of risks to personnel due to the flammability
and toxicity of all chemicals consumed or produced in the process. As a minimum, the MSDS
(material and safety data sheets) for all these chemicals should be provided in an appendix, and a
brief discussion of the major concerns for each chemical should be given as a separate section of
the report. This should include general concerns and concerns that are specific to the operating
conditions in this process. In addition, a brief discussion of possible safety hazards for each
piece of equipment in your process should be provided. Finally, a feature of your process design
that addresses one of these concerns should be explained.

4. Chemcad/Process Improvements

A Chemcad simulation of one case of the process shown in Figure 1 should be provided. It is
your choice whether this is a base case or a final case. You may suggest any process
improvements that do not violate the laws of physics. An explanation of the rationale for such
process improvements should be provided, including an economic analysis, if possible.

Other Information

You should assume that a year equals 8000 hours. This is about 330 days, which allows for
periodic shutdown and maintenance.

Deliverables

Written Reports

Each group must deliver a report written using a word processor. Three identical copies
should be submitted, one for each instructor. The written project reports are due by 11:00 a.m.
Thursday, November 30, 2006. Late projects will receive a minimum of a one letter grade
deduction.

The report should be clear and concise. For the correct formatting information, refer to the
document entitled Written Design Reports. The report must contain a labeled process flow
diagram (PFD) and a stream table, each in the appropriate format. The PFDs from Chemcad are
generally unsuitable unless you modify them significantly. Figure 1 should be used as a template
for your PFD. When presenting results for different cases, graphs are superior to tables. For the
optimal case, the report appendix should contain details of calculations that are easy to follow.
There should be separate appendices for each “mini-project.” These may be hand written if done
neatly. Alternatively, Excel spreadsheets may be included, but these must be well documented
so that the reader can interpret the results. Calculations that cannot be easily followed and that
are not explained will lose credit.
 9

Since this project involves “mini-designs,” it is suggested that the report be organized as
follows. There should be a general abstract and introduction. Then, there should be a results
section followed by a discussion section for each “mini-design.” General conclusion and
recommendation sections should follow. At a minimum, there should be one appendix for each
of the “mini-designs.”

In order to evaluate each group member’s writing skills, the results and discussion sections
for each mini-design should be written by a different group member. The authorship of each of
these mini-reports should be clearly specified in the report. Although the individual written
portions of the reports must be authored by a single group member, it is the intent of the
instructors that group members should help each other in writing different sections. To this end,
we recommend that you seek input, such as proofreading and critiques, from other members of
your group.

The reports will be evaluated as follows:

• course-specific technical content – 50%

• oral presentation – 20%
• written report – 20%
• technical quality of general sections (safety, simulation, etc.) – 10%

A historical account of what each group did is neither required nor wanted. Results and
explanations should be what are needed to justify your choices, not a litany of everything that
was tried. Each mini-report should be limited to 4-5 double space pages plus figures and tables.

Oral Reports

Each group will give an oral report in which the results of this project will be presented in a
concise manner. The oral report should be between 15-20 minutes, and each group member
must speak. Each group member should speak only once. A 5-10 minute question-and-answer
session will follow, and all members must participate. Refer to the document entitled Oral
Reports for instructions. The oral presentations will be Thursday November 30, 2006, from
11:00 a.m. to 2:00 pm. Attendance is required of all students during their classmates’
presentations (this means in the room, not in the hall or the computer room). Failure to attend
any of the above-required sessions will result in a decrease of one-letter grade (per
occurrence) from your project grade in ChE 310, ChE 311, and ChE 320.

Groups

You will work on this project in groups of 3 or 4. More details of group formation and peer
evaluation will be discussed in class.
 10

Revisions

As with any open-ended problem; i.e., a problem with no single correct answer, the problem
statement above is deliberately vague. The possibility exists that, as you work on this problem,
your questions will require revisions and/or clarifications. You should be aware that these
revisions/clarifications may be forthcoming.
 11

Appendix 1
Economic Data

Equipment Costs (Purchased)

Note: The numbers following the attribute are the minimum and maximum values for that
attribute. For a piece of equipment with a lower attribute value, use the minimum attribute value
to compute the cost. For a piece of equipment with a larger attribute value, extrapolation is
possible, but inaccurate. To err on the side of caution, you should use the price for multiple,
identical smaller pieces of equipment.

Pumps log10 (purchased cost ) = 3.4 + 0.05 log10 W + 0.15[log10 W ]2

W = power (kW, 1, 300)
assume 80% efficiency

Heat Exchangers log10 (purchased cost ) = 4.6 − 0.8 log10 A + 0.3[log10 A]2
A = heat exchange area (m2, 20, 1000)

Compressors log10 (purchased cost ) = 2.3 + 1.4 log10 W − 0.1[log10 W ]2

W = power (kW, 450, no limit)
assume 70% efficiency

Compressor Drive log10 (purchased cost ) = 2.5 + 1.4 log10 W − 0.18[log10 W ]2

W = power (kW, 75, 2600)

Turbine log10 (purchased cost ) = 2.5 + 1.45 log10 W − 0.17[log10 W ]2

W = power (kW, 100, 4000)
assume 65% efficiency

Fired Heater log10 (purchased cost ) = 3.0 + 0.66 log10 Q + 0.02[log10 Q ]2

Q = duty (kW, 3000, 100,000)
assume 80% thermal efficiency
assume can be designed to use any organic compound as a fuel

Vertical Vessel log10 (purchased cost ) = 3.5 + 0.45 log10 V + 0.11[log10 V ]2

V = volume of vessel (m3, 0.3, 520)

Horizontal Vessel log10 (purchased cost ) = 3.5 + 0.38 log10 V + 0.09[log10 V ]2

V = volume of vessel (m3, 0.1, 628)
 12

Additional Cost Information

Piping straight pipe $/m = 5.0 (nominal pipe diameter, in)(1+(sch #)/20)0.25
sch = schedule number for pipe
use the same sch number for fittings and valves

fittings (except valves) $/fitting = 50.0 (nominal pipe diameter, in)(1+(sch #)/20)0.25

Valves for gate (isolation) valves $100 (nominal pipe diameter, in)0.8 (1+(sch #)/20)0.25
for control valve use $1000 (nominal pipe diameter, in)0.8(1+(sch #)/20)0.25

Utility Costs

Low-Pressure Steam (618 kPa saturated) $7.78/GJ

Medium-Pressure Steam (1135 kPa saturated) $8.22/GJ

High-Pressure Steam (4237 kPa saturated) $9.83/GJ

Natural Gas (446 kPa, 25°C) $6.00/GJ

Fuel Gas Credit $5.00/GJ

Electricity $0.06/kWh

Boiler Feed Water (at 549 kPa, 90°C) $2.45/1000 kg

Cooling Water $0.354/GJ

available at 516 kPa and 30°C
return pressure ≥ 308 kPa
return temperature is no more than 15°C above the inlet temperature

Refrigerated Water $4.43/GJ

available at 516 kPa and 10°C
return pressure ≥ 308 kPa
return temperature is no higher than 20°C

Deionized Water $1.00/1000 kg

available at 5 bar and 30°C

Waste Treatment of Off-Gas incinerated - take fuel credit

Refrigeration $7.89/GJ

Wastewater Treatment $56/1000 m3

 13

Equipment Cost Factors

Total Installed Cost = Purchased Cost (4 + material factor (MF) + pressure factor (PF))

Pressure < 10 atm, PF = 0.0
(absolute) 10 - 20 atm, PF = 0.6
20 - 40 atm, PF = 3.0
40 - 50 atm, PR = 5.0
50 - 100 atm, PF = 10
does not apply to turbines, compressors, vessels,
packing, trays, or catalyst, since their cost
equations include pressure effects

Carbon Steel MF = 0.0

Stainless Steel MF = 4.0
 Separation Processes and Reaction Engineering
Design Project

Production of Ethylbenzene
We continue to investigate the feasibility of constructing a new, grass-roots, 80,000 tonne/y,
ethylbenzene (EB) facility (99.8 mol%), using benzene and ethylene as raw materials. As the
final part of the feasibility study, we would like you to study the details of the reactor and
separation section of proposed plant and then optimize the complete process. Your final design
should be an optimized process and should include all unit operations necessary to produce the
desired amount and purity of ethyl benzene.

Ethyl Benzene Production Reactions

The production of EB takes place via the direct alkylation reaction between ethylene and
benzene by acid catalysis:

C6 H 6 + C2 H 4 → C6 H 5C2 H 5
(1)
benzene ethylene ethyl benzene

The reaction between EB and ethylene to produce diethyl benzene (DEB) also takes place:

C6 H 5C2 H 5 + C2 H 4 → C6 H 4 (C2 H 5 )2
(2)
ethyl benzene ethylene diethyl benzene

The incoming benzene contains a small amount of toluene impurity (2 mole %). The toluene
reacts with ethylene to form ethyl benzene and propylene:

C6 H 5CH 3 + 2C2 H 4 → C6 H 5C2 H 5 + C3H 6

(3)
toluene ethyl benzene propylene

The rate laws for the reaction kinetics are discussed in Appendix 3. A new β-zeolite catalyst is
available as a cylindrical extruded pellet with diameter 2 mm and length 6 mm. For the sake of
calculations, you may assume that the catalyst behaves like a spherical particle with packed bed
voidage of 0.60. Effective diffusivity of catalyst (from catalyst manufacturer) is equal to 8×10-8
m3-gas/m-catalyst/s. You should assume that the maximum allowable catalyst temperature =
450°C.
 2

Specific Assignments

ChE 312

You are to determine the number of distillation columns required, their locations, their
sequence, and enough information for each column to determine their costs. The distillation
column that purifies the ethylbenzene should be designed in detail. A detailed design of a tray
tower includes number of trays, tray spacing, diameter, reflux ratio, active area, weir height, top
and bottom pressure specifications, and design of auxiliary equipment (heat exchangers, pump,
reflux drum, if present). A detailed design of a packed tower includes height, packing size and
type, and the same other specifications as in a tray tower. For all columns in this project, you
may assume that HETP = 0.6 m. For the distillation column, the better economical choice
between a packed and tray tower should be determined. For either a packed or a tray distillation
column, the optimum reflux ratio should be determined.

Note that a tower consists of a vessel with internals (trays or packing). The constraints on a
vessel are typically a height-to-diameter ratio less than 20. However, it is possible to extend this
ratio to 30 as long as the tower is less than about 3 ft (1 m) in diameter. For larger-diameter
towers, stresses caused by wind limit the actual height. Extra supports are needed for a height-
to-diameter ratio above 20, even for smaller diameter columns. Therefore, there is a capital cost
“penalty” of an additional 25% (only on the vessel) up to a ratio of 25, and a “penalty” of an
additional 100% up to a ratio of 30.

You must choose the operating pressures for each column subject to constraints of operating
temperature and available utilities. If vacuum columns are needed, pressure drop becomes a
significant concern. As an alternative to tray towers, packed towers with a low-pressure-drop
structured packing may be used. The packing factor as defined in Wankat1, p. 336, is that for
Raschig rings (ceramic). Assume the HETP for the structured packing to be 0.6 m (see the
definition of HETP in Wankat1, p. 332, and the relationship between HETP and HOG in Equation
15.36 in Wankat1.), and that the pressure drop is 0.2 kPa/m (0.245 inch water/ft).

ChE 325

Several reactor types may be considered for use in this design. They are an adiabatic, packed
bed reactor (a series of these with interstage cooling, if needed), an “isothermal,” packed bed
reactor, and a packed bed reactor with heat exchange. An “isothermal” reactor is defined here as
one with a specified outlet temperature, not necessarily the inlet temperature, and some form of
heat exchange is needed to add or remove the heat of reaction to maintain constant temperature.
Chemcad will model the entire reactor as “isothermal” at that temperature. It must be understood
that this situation is not physically realistic. In a reactor with heat exchange, the temperature
along the length of the packed-bed reactor is not constant. The temperature can be controlled by
varying the temperature and flowrate of the heat-transfer fluid, heat-transfer area, and the
catalyst/inert ratio. The suggested heat-transfer fluid is Dowtherm A™. If a heat-transfer fluid
is used, it is circulated in a closed loop through the reactor where its temperature is increased (if
the reaction is endothermic) or decreased (if the reaction is exothermic). Then, heat is added
(removed) from the fluid in a heat exchanger (or fired heater, if needed). The heat-transfer fluid
 3

is then pumped back to the reactor. Properties of the Dowtherm A™ can be obtained from
Chemcad.

For your best case, you should include a discussion of the temperature, pressure, and
concentration profiles obtained from Chemcad.

General

The entire ethylbenzene process should be optimized using decision variables of your
choosing. Decision variables should be chosen as those most strongly affecting the objective
function. There are topological optimization and parametric optimization. In topological
optimization, which is usually done first, the best process configuration is chosen. Parametric
optimization involves varying operating variables and should be done after topological
optimization is complete. Some examples of parameters that can be used as decision variables
are reactor temperature, pressure, and conversion and distillation column reflux ratio.

Economic Analysis

When evaluating alternative cases, the equivalent annual operating cost (EAOC) objective
function should be used. The EAOC is defined as

EAOC = -(product value - feed cost – utility costs – waste treatment cost - capital cost annuity)

A negative EAOC means there is a profit. It is desirable to minimize the EAOC; i.e., a large
negative EAOC is very desirable.

The capital cost annuity is an annual cost (like a car payment) associated with the one-time,
fixed cost of plant construction.

The capital cost annuity is defined as follows:

i (1 + i ) n
capital cost annuity = FCI (5)
(1 + i ) n − 1

where FCI is the installed cost of all equipment; i is the interest rate (take i = 0.15) and n is the
plant life for accounting purposes (take n = 10).

Report Format

This report should conform to the Department guidelines. It should be bound in a folder that
is not oversized relative to the number of pages in the report. Figures and tables should be
included as appropriate. An appendix should be attached that includes sample calculations.
These calculations should be easy to follow.

The written report is a very important part of the assignment. Poorly written and/or
organized written reports may require re-writing. Be sure to follow the format outlined in the
 4

guidelines for written reports. Failure to follow the prescribed format may be grounds for a re-
write.

The following information, at a minimum, must appear in the main body of the final report:

1. a computer-generated PFD (not a Chemcad PFD) for the recommended optimum case,

2. a stream table containing the usual items,

3. a list of new equipment for the process, costs, plus equipment specifications (presented
with a reasonable number of significant figures),

4. a summary table of all utilities used,

5. a clear summary of alternatives considered and a discussion, supported with figures, of

why the chosen alternative is superior,

6. a clear economic analysis which justifies the recommended case

7. a discussion section pertinent to each class plus a general discussion section for
optimization of the entire process

8. a Chemcad report only for your optimized case (in the Appendix). This must contain the
equipment connectivity, thermodynamics, and overall material balance cover pages;
stream flows; equipment summaries; tower profiles; and tray (packing) design
specifications (if you use Chemcad to design the trays (packing)). It should not contain
stream properties. Missing Chemcad output will not be requested; credit will be deducted
as if the information is missing.

Other Information

Unless specifically stated in class, the information in this document is valid for this project
only. Any information in the sophomore projects not specifically stated in this document is not
valid for this project.

Deliverables

Each group must deliver a report (two identical copies, one for each professor) written using
a word processor. The report should be clear and concise. The format is explained in the
document Written Design Reports. Any report not containing a labeled PFD and a stream table,
each in the appropriate format, will be considered unacceptable. PFDs from Chemcad are
generally unsuitable unless you modify them significantly. When presenting results for different
cases, graphs are superior to tables. For the optimum case, the report appendix should contain
details of calculations that are easy to follow. There should be separate appendices for each
class, ChE 312 and ChE 325, each containing calculations appropriate for the respective class.
 5

These may be handwritten if done so neatly. Calculations that cannot be easily followed will
lose credit.

Each group will give an oral report in which the results of this project will be presented in a
concise manner. The oral report should be between 15-20 minutes, and each group member
must speak once. Reports exceeding this time limit will be stopped. A 5-10 minute question-
and-answer session will follow. Instructions for presentation of oral reports are provided in a
separate document entitled Oral Reports. The oral presentations will be Wednesday, April 18,
2007, starting at 11:00 a.m. and running until approximately 3:00 p.m. Attendance is required of
all students during their classmates’ presentations (this means in the room, not in the hall or the
computer room). Failure to attend any of the above-required sessions will result in a decrease of
one letter grade (per occurrence) from your project grade in ChE 312 and ChE 325.

The written project report is due by 11:00 a.m. Wednesday, April 18, 2007. Late projects
will receive a minimum deduction of one letter grade.

In order to evaluate each team members writing skills, the results and discussion sections for
each specific assignment should be written by a different team member. The authorship of each
of these specific assignments should be clearly specified in the report. If a team has four
members, the member not authoring a specific assignment should author the cover
memorandum, abstract, introduction, and conclusion.

Revisions

As with any open-ended problem (i.e., a problem with no single correct answer), the problem
statement above is deliberately vague. The possibility exists that, as you work on this problem,
your questions will require revisions and/or clarifications of the problem statement. You should
be aware that these revisions/clarifications might be forthcoming.

References

1. Wankat, P., Equilibrium Staged Separation Processes, Prentice Hall, Upper Saddle River,
NJ, 1988.
 6

Appendix 1
Economic Data

Equipment Costs (Purchased)

Note: The numbers following the attribute are the minimum and maximum values for that
attribute. For a piece of equipment with a lower attribute value, use the minimum attribute value
to compute the cost. For a piece of equipment with a larger attribute value, extrapolation is
possible, but inaccurate.

Pumps log10 (purchased cost ) = 3.4 + 0.05 log10 W + 0.15[log10 W ]2

W = power (kW, 1, 300)
assume 80% efficiency

Heat Exchangers log10 (purchased cost ) = 4.6 − 0.8 log10 A + 0.3[log10 A]2
A = heat exchange area (m2, 20, 1000)

Compressors log10 (purchased cost ) = 2.3 + 1.4 log10 W − 0.1[log10 W ]2

W = power (kW, 450, 3000)
assume 70% efficiency

Compressor Drive log10 (purchased cost ) = 2.5 + 1.4 log10 W − 0.18[log10 W ]2

W = power (kW, 75, 2600)

Turbine log10 (purchased cost ) = 2.5 + 1.45 log10 W − 0.17[log10 W ]2

W = power (kW, 100, 4000)
assume 65% efficiency

Fired Heater log10 (purchased cost ) = 3.0 + 0.66 log10 Q + 0.02[log10 Q ]2

Q = duty (kW, 3000, 100,000)
assume 80% thermal efficiency
assume can be designed to use any organic compound as a fuel

Vertical Vessel log10 (purchased cost ) = 3.5 + 0.45 log10 V + 0.11[log10 V ]2

V = volume of vessel (m3, 0.3, 520)

Horizontal Vessel log10 (purchased cost ) = 3.5 + 0.38 log10 V + 0.09[log10 V ]2

V = volume of vessel (m3, 0.1, 628)

Catalyst $2.25/kg

Packed Tower Cost as vessel plus cost of packing

 7

Packing log10 (purchased cost ) = 3 + 0.97 log10 V + 0.0055[log10 V ]2

V = packing volume (m3, 0.03, 628)

Tray Tower Cost as vessel plus cost of trays

Trays log10 (purchased cost ) = 3.3 + 0.46 log10 A + 0.37[log10 A]2

A = tray area (m2, 0.07, 12.3)

Storage Tank log10 (purchased cost ) = 5.0 − 0.5 log10 V + 0.16[log10 V ]2

V = volume (m3, 90, 30,000)

Reactors For this project, the reactor is considered to be a vessel.

It may be assumed that pipes and valves are included in the equipment cost factors. Location
of key valves should be specified on the PFD.

Equipment Cost Factors

Total Installed Cost = Purchased Cost (4 + material factor (MF) + pressure factor (PF))

Pressure < 10 atm, PF = 0.0
(absolute) 10 - 20 atm, PF = 0.6
20 - 40 atm, PF = 3.0
40 - 50 atm, PR = 5.0
50 - 100 atm, PF = 10
does not apply to turbines, compressors, vessels,
packing, trays, or catalyst, since their cost
equations include pressure effects

Carbon Steel MF = 0.0

Stainless Steel MF = 4.0
 8

Utility Costs

Low Pressure Steam (618 kPa saturated) $7.78/GJ

Medium Pressure Steam (1135 kPa saturated) $8.22/GJ

High Pressure Steam (4237 kPa saturated) $9.83/GJ

Natural Gas (446 kPa, 25°C) $6.00/GJ

Fuel Gas Credit $5.00/GJ

Electricity $0.06/kWh

Boiler Feed Water (at 549 kPa, 90°C) $2.45/1000 kg

Cooling Water $0.354/GJ

available at 516 kPa and 30°C
return pressure ≥ 308 kPa
return temperature is no more than 15°C above the inlet temperature

Refrigerated Water $4.43/GJ

available at 516 kPa and 10°C
return pressure ≥ 308 kPa
return temperature is no higher than 20°C

Deionized Water $1.00/1000 kg

available at 5 bar and 30°C

Waste Treatment of Off-Gas incinerated - take fuel credit

Refrigeration $7.89/GJ

Wastewater Treatment $56/1000 m3

Any fuel gas purge may be assumed to be burned elsewhere in the plant at a credit of
$2.50/GJ. Steam produced cannot be returned to the steam supply system for the appropriate
credit. Steam produced in excess of that required in this process is purged with no credit.

Feed and Product Prices

Benzene feed $ 1.038 per kg

Ethylene feed $ 0.737 per kg
Ethyl benzene $ 1.38 per kg
 9

Appendix 2
Other Design Data

Heat Exchangers

For heat exchangers, use the following approximations for heat-transfer coefficients to
allow you to determine the heat transfer area:

situation h (W/m2°C)

condensing steam 6000

condensing organic 1000

boiling water 7500

boiling organic 1000

flowing liquid 600

flowing gas 60
 10

Appendix 3
Reaction Kinetics
The production of ethyl benzene (EB) takes place via the direct alkylation reaction between
ethylene (E) and benzene (B) by acid catalysis:

(1)

The reaction between EB and ethylene to produce diethyl benzene (DEB) also takes place:

(2)

Additional reactions between DEB and ethylene yielding tri- and higher ethyl benzene are also
possible. However, in order to minimize these additional reactions, the molar ratio of benzene to
ethylene is kept high, at approximately 8:1. The production of diethyl benzene is undesirable,
and its value as a side product is low. In addition, even small amounts of DEB in EB cause
significant processing problems in the downstream styrene process. Therefore, the maximum
amount of DEB in EB is specified as 2 ppm. Excess poly-substituted benzene may be directed
towards a waste stream or combusted to reclaim the energy value. In other EB facilities, the early
generations of solid acid catalysts were highly corrosive and had a relatively short life, e.g.
AlCl3, H3PO4 on clay, BF3 on alumina, and others require periodic regeneration. More recently,
solid acid catalysts based on zeolites have been demonstrated to have superior properties. Studies
in our research division have shown that a β-zeolite catalyst (FX-02) is an active and selective
catalyst for the alkylation of benzene with ethylene. FX-02 can be used with polymer-grade
ethylene as well as ethylene from fluid catalytic-cracking unit off-gas with concentrations as low
as 10-20%. FX-02 also operates at lower temperature and lower pressure than existing catalysts.
The incoming benzene contains a small amount of toluene impurity. The toluene (T)
reacts with ethylene to form ethyl benzene and propylene (P):

(3)

The rate law is based on a Langmuir-Hinshelwood absorption-reaction model, whereby absorbed

ethylene reacts with absorbed benzene and ethylbenzene. In addition, absorbed ethylene also
reacts with absorbed toluene and ethylbenzene. Reactions described by Equations 1-3 are
reversible reactions, where the rate laws correspond to Equations 4-6, respectively.
 11

The reaction rate constants and the equilibrium constants are shown in Tables 1, where r is the
rate law in mol/(g min), k is intrinsic rate constant, p is pressure in MPa, K is reaction
equilibrium constant, Ea is reaction activation energy in J/mol, R is the gas constant, and T is
temperature in Kelvin. The units of k vary depending on the form of the rate law.