Material Balances

Design Project

Production of Phthalic Anhydride from o-Xylene

The most common method for production of phthalic anhydride is by oxidation of o-xylene.
Phthalic anhydride is used in the manufacture of plasticizers (additives to polymers to give them
more flexibility) and polyesters, among other applications. Additional information on phthalic
anhydride, it uses, and its manufacture are available.1 The purpose of this project is to determine
the “best” process configuration for a phthalic anhydride from o-xylene process subject to
constraints which will be defined later.

A suggested process flow diagram is in Figure 1. You should use this as a starting point.
However, any change that you can justify that does not violate the laws of nature is allowed.
Your assignment is to develop a “best” case, where “best” is dependent upon economic
considerations. The primary issue is how much recycle is necessary/desirable in order to satisfy
the flammability limit constraint described below. However, there may be other alternatives
which improve process economics which you are left on your own to consider.

Process Description

The raw materials are air and o-xylene. The o-xylene feed, which contains 5 wt% inert
impurities is vaporized in unit V-701. Air, which may be assumed to contain only O2 and N2, is
mixed with recycle, if there is any recycle, and heated. The hot air and vaporized o-xylene are
mixed and sent to a fluidized bed reactor. The contents of Stream 7 must be below the LFL of o-
xylene, which is 1 mole%. In this reactor, essentially 100% of the o-xylene is reacted. Most
goes to form phthalic anhydride, but some complete and incomplete combustion of o-xylene
occurs, some maleic anhydride is formed, and a heavy impurity is also formed. The selectivities
are given later. The reactor effluent enters a complex series of devices known as switch
condensers. The net result is that all light gases and water leave in Stream 9, with small amounts
of both anhydrides, and the phthalic anhydride, maleic anhydride, inerts, and heavy impurity
leave in Stream 10. The “dirty air” in Stream 9 must be treated before it can be vented, and this
is an additional expense. It is also possible to recycle some of the “dirty air.” Any “dirty air”
not recycled must be sent to a scrubber, in which the anhydrides are scrubbed into water. The
water is then sent to an on-site waste water treatment plant, and an operating charge is assessed.
The contents of Stream 10 are sent to a series of two distillation columns which produce liquid
waste (Streams 13 and 16) which is burned for fuel. No economic credit is allowed. The
product in Stream 15 must be 99.9 mass % phthalic anhydride. This process must produce
75,000 metric tons/year of phthalic anhydride.
2
 3

Process Details

Feed Streams

Stream 1: air, consisting of 79% N2 and 21% O2 - free

Stream 2: o-xylene with 5 wt % inert impurity

Equipment

Compressor (C-701): increases pressure of air feed from 1 atm to 3 atm

Vaporizer (E-701): vaporizes o-xylene feed which is already above 3 atm

Fired Heater (H-701): heats air to reaction temperature

Reactor (R-701): the following reactions occur:

C8 H10 + 3O2 → C8 H 4 O3 + 3H 2 O
o − xylene phthalic
anhydride

C8 H10 + 7.5O2 → C 4 H 2 O3 + 4H 2 O + 4CO2

maleic anhydride

The selectivity for the phthalic anhydride reaction is 70%, for the complete combustion
of o-xylene is 15%, for the incomplete combustion of o-xylene is 5%, for maleic
anhydride is 9%, and for the heavy impurity is 1%. The heavy impurity consumes a
negligible amount of oxygen and produces a negligible amount of light gases.

Switch Condensers (SC-701): These are a complex set of condensers. Phthalic

anhydride is first condensed as a solid (desublimated) and then melted. There are three
condensers, one in the desublimation mode, one in the melting mode, and one in stand-by
mode.
 4

The recovery of phthalic anhydride is done using a set of switch condensers that
desublimate the phthalic anhydride using cooled oil. This unit operation has been
modeled as a component separator with the following fractions leaving in the off gas.

o-Xylene 1.00
Oxygen 1.00
Nitrogen 1.00
Water 1.00
Carbon Dioxide 1.00
Carbon Monoxide 1.00
Phthalic Anhydride 0.010
Maleic Anhydride 0.89
Heavy Impurity 0.00

Distillation Column (T-701): Here, 99% of the phthalic anhydride and all of the heavy
impurity goes to Stream 14. All of the inert and enough of the maleic anhydride to allow
Stream 15 to satisfy its purity requirement go to Stream 13.

Distillation Column (T-702): Here, 99.9% of the phthalic anhydride, and any remaining
maleic anhydride go to Stream 15, and all of the heavy impurity goes to Stream 16.

Economic Analysis

When evaluating alternative cases, the following relationship should be used:

EAOC = -(product value - feed cost - other operating costs - capital cost annuity)

EAOC is an equivalent operating cost. A negative EAOC means there is a profit. It is

desirable to minimize the EAOC; i.e., a large negative EAOC is very desirable.

Phthalic anhydride is valued at $1.54/kg, and o-xylene costs $0.80/kg. The capital cost
annuity is an annual cost associated with plant construction (kind of like mortgage payments),
and may be assumed to be $2.4×106/yr. The other operating costs are for compression and for
waste treatment.

Compression costs are:

⎡⎛ P ⎞
0.3 ⎤
$ / h = 0.007 m& ⎢⎜⎜ out ⎟⎟ − 1⎥ m& in kg/h
⎢⎝ Pin ⎠ ⎥
⎣ ⎦

Air treatment is accomplished by absorption of the organic matter into water, with the light
gases vented to the atmosphere. The water is then sent to a waste water treatment plant. The
 5

cost is based upon the amount of organic matter (phthalic and maleic anhydrides) in Stream 11.
The cost is:

$500 / 1000 kg organic matter

Other Information

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

You should assume that two streams that mix must be at identical pressures.

Deliverables

Each group must deliver a word processed report. It should be clear and concise. The format
is explained 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 computational strategies. The report appendix should contain details of
calculations that are easy to follow. Calculations which can not be followed easily will lose
credit.

The project is due December 9, 2009, at the beginning of class.

Computational Methods

You may not use CAD software, but should use Excel spreadsheet calculations. Before
developing a spreadsheet, you must solve the material balance by hand for at least one case to
demonstrate that the spreadsheet is set-up correctly.

Groups

A student design group will consist of 4 group members. You are encouraged to choose a
partner for this project to form a pair. When you have formed a pair, please write your names on
the chart posted on Dr. Kugler’s door. Dr. Kugler will combine pairs to form groups of four.
Group assignments will be made on November 12.

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.
 6

References

1. “Phthalic Acids and other Benzenepolycarboxylic Acids,” Kirk-Othmer Encyclopedia of

Chemical Technology, on-line version, 10/18/2001. (This encyclopedia is accessible from
any University computer at http://www.libraries.wvu.edu/databases. An older print version
is available in the Evansdale Library reference section.)
 Design Project
Energy Balances and Numerical Methods

Production of Phthalic Anhydride from o-Xylene

The subject of this project is a process for manufacturing 75,000 metric tons/year of a liquid
containing 99.9% phthalic anhydride, subject to constraints which will be defined later in this
document. The project is a continuation (of sorts) of the project you completed last semester for
material balances. However, there are important differences in the two, including assumptions
and products.

A suggested process flow diagram (PFD) is attached (Figure 1). You should use this as a
starting point. However, any change that you can justify (and that does not violate the laws of
nature) is allowed. Your assignment is to develop an optimum case based upon an objective
function defined later. It is your job to define the decision variables, and to choose and
implement a method to arrive at an optimum design.

Process Description

See Figure 1. The raw materials are air and o-xylene. The o-xylene feed, which may be
considered pure and at 0.75 atm, is pumped to 3 atm and then vaporized in a fired heater, H-701.
Air, which may be assumed to contain only O2 and N2, is mixed with recycle, if any, compressed
to 3 atm, and heated in E-701. The hot air and vaporized o-xylene are mixed and sent to a
packed-bed reactor, R-701. The o-xylene content of Stream 8 must be either below the lower
flammability limit (LFL) of o-xylene (1 mole %) or above the upper flammability limit (UFL) of
o-xylene (6 mole %). For the purposes of the present preliminary design only, assume that the o-
xylene mole fraction into R-701 must be less than 5 mol %. (This avoids heat-transfer gradients
in the reactor design.) Under these conditions, assume that 100% of the o-xylene is reacted in R-
701. Most of the o-xylene reacts to form phthalic anhydride, some complete combustion of o-
xylene occurs, and some maleic anhydride is formed. The yields depend upon the reactor
temperature, as indicated later. The reactor temperature is controlled by a molten-salt loop,
Streams 21-23. Stream 9, the reactor effluent, which is at 2 atm, enters a complex series of
devices known as a switch condenser set (SC-701). The feed to the switch condensers may be
no higher than 180°C; hence, the reactor effluent must be cooled before entering SC-701. The
net result of the switch condensers is that all of the phthalic anhydride and maleic anhydride
leaves in Stream 12, while Stream 11 contains all light gases and water. The mixture of gases in
Stream 11 is termed “dirty air.” It may be recycled (Stream 16) but at least some of it must be
vented in a purge stream (Stream 15). The “dirty air” must be treated before it can be vented, and
this is an expense. Treatment (not shown in the PFD) consists of scrubbing the anhydrides into
water, which is then sent to a waste-water plant. The contents of Stream 12 are sent to a
distillation tower, T-701, which produces liquid waste (Stream 13) that is burned for fuel. The
product in Stream 14 must be 99.9 wt % phthalic anhydride. This process must produce 75,000
metric tons/year of phthalic anhydride.
2
 3

Process Details

Feed Streams

Stream 1: air, consisting of 79% N2 and 21% O2. No charge.

Stream 2: o-xylene at 0.75 atm and 100°C. Cost provided in Table 5.

Switch-Condenser Streams

Stream 10: Reactor outlet composition, vapor phase, pressure ≤ 2 atm, temperature ≤ 180°C.

Stream 11:“Dirty Gas,” vapor phase, 1 atm, 130°C.

Stream 12: Mixture of phthalic anhydride and maleic anhydride, liquid phase, 1 atm, 150°C.

Effluent Streams

Stream 13: Waste organic material, may be burned in fired heater H-701 for credit.
Assume that the energy content of this stream is its lower heating value.

Stream 14: Phthalic anhydride product, 75,000 metric tons/yr, 99.9 wt % pure.

Stream 15: Air to waste treatment (scrubber and waste-water plant).

The appropriate cost is charged, see below.

Equipment

Compressor C-701:
The compressor increases pressure of the air feed from 1 atm to 3 atm at the valve outlet.
The compressor may be assumed to be adiabatic. In that case, the compressor power
may be calculated as:

⎧⎪⎛ P ⎞
0.286 ⎫⎪
W& s [kW] = 20,000m& [kmol/s]⎨⎜⎜ out ⎟⎟ − 1⎬ (1)
⎪⎩⎝ Pin ⎠ ⎪⎭

where m& [kmol/s] is the total molar flow rate of the inlet stream. Equation 1 includes the
compressor efficiency.

In general, the ratio of outlet to inlet pressure (compression ratio) in a compressor is

between 3 and 5. If a compression ratio greater than 5 is needed, compressors are usually
staged, with cooling between the compressor stages (“intercooling”), but not after the last
stage. If you choose to do this, the compression ratio for each stage should be identical,
 4

and the intercooling should be to 50°C. The PFD that you draw should accurately
represent the chosen compressor configuration.

The compressor increases the temperature of the stream being compressed according to:

0.286
Tout ⎛ Pout ⎞
=⎜ ⎟⎟ (2)
Tin ⎜⎝ Pin ⎠

where T is absolute temperature.

The cost of electricity to run the compressor is a utility cost and is given below.

Pumps:
Pump P-701 increases pressure of the o-xylene feed from 0.75 atm to 3 atm at the valve
outlet.

For all pumps, the cost of energy may be neglected.

Fired Heater H-701:

The fired heater vaporizes the o-xylene feed and heats the vapor to any temperature. H-
701 is fueled with natural gas (ng) and/or Stream 13.

Heat Exchangers:
Heat exchanger E-701 heats the air feed, Stream 6. The air temperature of the exit
stream, Stream 7, may not exceed a value which is 5°C lower than the inlet temperature
of the appropriate type of steam used for heating.

Temperature constraints of heat exchangers associated with other pieces of equipment are
provided separately below.

Reactor (R-701):
The reactor feed may be no lower than 300°C. The catalyst is active to produce phthalic
anhydride only between 300°C and 420°C. The reactor temperature and the temperature
of the reactor outlet stream are to be controlled by the molten-salt loop, described below.

The following reactions occur:

C8 H10 + 3O2 → C8 H 4O3 + 3H 2O

(3)
o − xylene phthalic anhydride

C8 H10 + 7.5O2 → C4 H 2O3 + 4 H 2O + 4CO2

(4)
maleic anhydride

The complete combustion of o-xylene also occurs:

 5

C8 H 10 + 10.5O2 → 5 H 2 O + 8CO2 (5)

Yield data are in Table 1. These data are approximate and are to be used only for this
design project this semester, not for more complex versions to be completed in
subsequent semesters.

Table 1
Yields of Products from Oxidation of o-Xylene
T(°C) maleic anhydride CO2 phthalic anhydride
300 1.00 0.00 0.00
320 0.536 0.0339 0.425
340 0.215 0.102 0.683
360 0.100 0.200 0.700
380 0.0463 0.356 0.598
400 0.0215 0.602 0.377
420 0.00 1.00 0.00

Molten-Salt Loop:
Streams 21 - 23 contain the proprietary molten salt HiTec. Its properties may be found
in Reference [1]. The molten salt removes the heat generated by the exothermic heat of
reaction in Reactor R-701. The heat removed is then used to make high-pressure steam
(in E-702) from boiler feed water (bfw), with an appropriate credit being taken for the
steam made. The pressure of the bfw into E-702 may be assumed to be the pressure of
high-pressure steam. The temperature of Stream 21 may not exceed a value which is
10°C lower than Stream 9, and the temperature of Stream 23 must exceed a value which
is 10°C higher than that of the high-pressure steam formed in E-702.

Switch Condensers (SC-701):

These are a complex set of three condensers that operate in a semi-continuous mode. The
inlet stream is first cooled by cold oil so that the anhydrides are desublimated (condensed
as solids). Then hot oil is passed through the same condenser so that the solids are
melted. At any given time, one condenser operates to desublimate, one to melt, the third
as standby, and the feed is switched between the three. We will not consider the details of
this operation here.

The feed to SC-701 may not exceed 180°C, so E-703 removes the necessary heat. The
pressure must be less than or equal to 2 atm. For the purpose of this project,
specifications for Streams 11 and 12 are given above. The heat load for SC-701 must be
assumed to be the equivalent of three times the total amount needed to cool Stream 10 to
Stream 12 and Stream 11. This is the heat load necessary to heat and cool the oil heat-
transfer medium. The oil is in a closed loop, hence the cost of the oil may be neglected.
 6

Distillation Column (T-701):

Here 99% of the phthalic anhydride in Stream 12 goes to Stream 14. Of the maleic
anhydride in Stream 12, 99% goes to Stream 13. Stream 17, which goes to Condenser E-
704, must be a saturated vapor. The molar flow rate of Stream 17 must be 10 times that of
Stream 13. Stream 18 re-enters the distillation column as a saturated liquid. Stream 19
must be a saturated liquid and Stream 20 must be a saturated vapor. The molar flow rate
of Stream 20 must be one-third that of Stream 14. T-701 must operate at a pressure low
enough to make Stream 20 vaporize at a temperature that has a value no higher than 5°C
lower than the temperature of the high-pressure steam used as the heat source for E-705.

Recycle

It is possible to recycle some of the “dirty” air from Stream 11 to mix with Stream 2, as
long as there is sufficient purge (Stream 15). It is your job to determine the optimal
recycle-to-purge ratio. The purge stream must go to the waste treatment unit with the
appropriate charge taken.

Physical Property Data

Use data from Reference [2] or from any handbook. The following data are not readily
available in these references. You may use these for this project only.

Some vapor heat capacities are given in Table 2.

Table 2. Heat Capacities of Organics

C p [cal/mole/ K] = a + bT + cT 2 + dT 3 , T in [K], range 150°C - 450°C
a 10 × b 105 × c 107 × d
o-xylene
-3.786 1.424 -8.224 1.798
phthalic
-1.064 1.562 -1.023 2.411
anhydride
maleic
-3.123 0.8323 -5.217 1.156
anhydride

Liquid heat capacity for any organic compound is given by Equation (6).
C p [cal/mole/ °C] = 41.69 + 7.773 X 10 − 2 T , T in [°C], range 125°C - 200°C (6)

Some data on vapor pressures are given in Table 3.

 7

Table 3. Vapor Pressure Data

ln P*[ mmHg] = A −
B
, T in [K], range 100°C - 300°C
T −C
A B C
o-xylene
16.1156 3395.57 59.46
phthalic
15.9984 4467.01 83.15
anhydride
maleic
16.2747 3765.65 82.15
anhydride

Data on normal heats of vaporization and the corresponding normal boiling points are given
in Table 4.

Table 4. Heats of Vaporization at Normal Boiling Point

ΔĤ v [ cal/mole] Tb [°C]
o-xylene 8,800 144.4
phthalic anhydride 11,850 284.5
maleic anhydride 5,850 202.0

Economic Analysis

Objective Function

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

EAOC = -(product value - feed cost - capital cost annuity - other operating costs) (7)

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 value of phthalic anhydride (the product) and the cost of o-xylene (the feed) are
provided below in Table 5.

The capital cost annuity is an annual cost associated with the one-time costs for plant
construction (like a car payment). A list of capital costs for each piece of equipment is provided
below in Table 6. These can be added to obtain the total installed cost (FCI). The capital cost
annuity is related to FCI as follows:

i(1 + i ) n
capital cost annuity = FCI (8)
(1 + i ) n − 1
 8

where i is the interest rate (as a fraction) and n is the plant life, in [y]. For the purposes of this
project, take i = 0.15 and n = 10.

The other operating costs are for compression and for waste treatment. The power needed for
compression is provided in Equation (1). The cost of electricity to furnish this power is provided
below.

Air treatment is accomplished by absorption of the organic matter into water, with the light
gases vented to the atmosphere. The water is then sent to a waste-water treatment plant. The
cost is based upon the volume of vapor sent to the treatment plant and the mole fraction of
organic matter (phthalic and maleic anhydrides) in Stream 11 or 15:

Cost [$ / y ] = 10 − 4V&tot (0.5 + 1000 xor ) (9)

where

V&tot = total volume of “dirty air” to be treated [m3 STP/y]

xor = mole fraction of organics in “dirty air” stream. Note that CO2 is not an organic!

Raw Material Costs/Product Value

These are provided in Table 5 below. When using these numbers, you should be aware that
they may be modified later, so write programs, spreadsheets, etc. with this in mind.

Table 5. Material Prices

Material Price [$/kg]
phthalic anhydride 1.25
o-xylene 0.80

Utility Costs/Credits

Low-Pressure Steam (618 kPa, saturated, cost or credit) $13.28/GJ

Medium-Pressure Steam (1135 kPa, saturated, cost or credit) $14.19/GJ

High-Pressure Steam (4237 kPa, saturated, cost or credit) $17.70/GJ

Natural Gas (446 kPa, 25°C, cost) $11.00/GJ

Waste Stream 13 used as a fuel source (credit) $9.00/GJ

Electricity $0.06/kW-h

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

 9

There is a cost for boiler feed water only if the steam produced enters process streams.
If, on the other hand, the steam produced does not enter a process stream and is
subsequently condensed, then 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

Equipment Costs

Preliminary equipment costs for the plant are given in Table 6. More up-to-date costs will be
provided by early March. Each cost is for an individual piece of equipment, including
installation.

Table 6. Equipment Costs

Equipment Installed Cost
[in thousands of dollars]
Isothermal packed-bed reactor 5,000
Adiabatic packed-bed reactor, per stage 100
Vessel 100
Distillation column 500
Heat exchanger 300
Pump 40
Compressor Larger of {4,000 and 0.0189 ( W& s [W])0.8}
Fired Heater 11 × 10A where
A = 0.8 log10[Q] – 0.5
and Q is the heat duty [kW]

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 as

location of process equipment, whether or not to add or remove equipment). 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. Determining the optimum number of staged compressors with
intercooling is an example of a topological optimization.
 10

Parametric optimization involves determining the best operating parameters for the chosen
process topology. It is your responsibility to define appropriate decision variables. It is
suggested that you look carefully at the efficient use of raw materials and the purge/recycle ratio
for Stream 11, and correlate the reactor temperature with separation costs. 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.

Other Information

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

You should assume that two streams that mix must be at identical pressures.

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.

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 may be forthcoming.

Deliverables

Written Report

Each group must deliver a word-processed report. It should be clear and concise and should
adhere to the prescribed format. The format is explained in the Written Report Guidelines,
provided as a separate document. Reports not adhering to the prescribed format will receive
significant deductions and will have to be rewritten. The body of the report should be short,
emphasizing only the results and explaining why the results presented are optimal. When
presenting results for different cases, graphs are often superior to tables (but see discussion in the
Guidelines). The report appendix should contain details of calculations. These calculations
should be annotated so that they are easy to follow; calculations that cannot be followed easily
will lose credit. Computer output without detailed explanations is not appropriate; neatly hand-
written calculations are best.

The written report is due on Friday, April 23, 2010 by 3:00 pm.
 11

Oral Report

There will be oral presentations of project results in the ChE 202 class on Tuesday, April 27,
2010. Oral presentations will continue on April 28, 2010, since we will probably be unable to
complete all presentations on April 27, 2010.

Oral Presentation Guidelines are also provided. These should be followed in your
presentations.

Project Review

There will be a project review in the ChE 230 class on Thursday, April 29, 2010.

Grading

Anyone not participating in this project will be subject to actions as noted in the syllabi for
ChE 202 and ChE 230.

The grades for the oral presentation and written report will be composite grades for the
entire team. Therefore, group preparation and feedback are recommended.

The report grade for each course will be based on the technical content pertinent to that
course (including the response to questions during the oral presentation), the overall technical
content (including that pertinent to the other class), the oral presentation, and the written report.
The grades for the oral presentation and written report will take into account the quality of the
writing or the oral presentation and the adherence to the prescribed format.

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

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

References

1. http://www.coastalchem.com/PDFs/HITECSALT/HITEC%20Heat%20Transfer%20Salt.pdf

2. Felder, R.M. and R.W. Rousseau, Elementary Principles of Chemical Processes (3rd ed. 9th
printing), Wiley, New York, 2005.
 Fluid Mechanics, Heat Transfer, Thermodynamics
Design Project

Production of Phthalic Anhydride

Your assignment is to continue evaluating the details of a process to produce 75,000 tonne/y
of phthalic anhydride from o-xylene. This is the amount of phthalic anhydride in the product
stream, not the total mass of the product stream.

A base-case process flow diagram (PFD) is shown in Figure 1. You should use this as a
starting point. Your assignment is to complete the mini-designs described later in this document.

Process Details

Unit 1700 produces phthalic anhydride (PA) via the partial oxidation of o-xylene using air.
The following reactions occur:

C 6 H 4 (CH 3 ) 2 + 3O2 → C 6 H 4 (CO ) 2 O + 3H 2 O

(1)
o - xylene phthalic anhydride

15
C 6 H 4 (CO ) 2 O + O2 → 8CO2 + 2 H 2 O
2 (2)
phthalic anhydride

21
C 6 H 4 (CH 3 ) 2 + O2 → 8CO2 + 5 H 2 O
2 (3)
o - xylene

15
C 6 H 4 (CH 3 ) 2 + O2 → C 2 H 2 (CO ) 2 O + 4CO2 + 4 H 2 O
2 (4)
o - xylene maleic anhydride

C 2 H 2 (CO ) 2 O + 3O2 → 4CO2 + H 2 O

(5)
maleic anhydride

In order to operate safely, the reaction mixture, Stream 7, must be kept below the lower
flammability limit of 1 mol% of o-xylene in air. The oxidation of o-xylene occurs in catalyst-
filled tubes to facilitate heat removal. The reactions that take place are highly exothermic, and
the temperature everywhere in the reactor must be very carefully controlled. The catalyst,
vanadium pentoxide (V2O5), sinters above a temperature of 400°C.
2
Feed Streams and Effluent Streams

Stream 1: air from the atmosphere that is dried first, so at 25°C and 80 kPa

Stream 2: o-xylene – at 25°C and 101.325 kPa – assumed pure

Stream 12: contains all light gases in Stream 11

Stream 14: maleic anhydride by-product – can be sold

Stream 15: phthalic anhydride product – must contain 75,000 tonne/y of PA

Base-Case Equipment Information

Compressor (C-1701)

This compressor increases the pressure of the air feed to a sufficient value so that the reactor
inlet is at 300 kPa. The compressor is adiabatic with a 60% efficiency. In the base case,
there is only one stage.

Pump (P-1701 A/B)

This pump increases the pressure of liquid o-xylene feed to a sufficient pressure so that
Streams 5 and 6 mix at the same pressure and so the reactor inlet, Stream 7, is at 300 kPa. It
is assumed that there is a 10 kPa pressure drop at the mixing point of Streams 5 and 6. The
pump is adiabatic with an 80% efficiency.

Heat Exchanger (E-1701)

This heat exchanger preheats the air or precools the air to 240°C, using high-pressure steam
or cooling water. The process-side pressure drop is 35 kPa for Chemcad simulations. For
the heat transfer design, the pressure drop on the shell side and the tube side should be
calculated based on the design details.

Heat Exchanger (E-1702)

This heat exchanger vaporizes the o-xylene to 240°C. The process-side pressure drop is 35
kPa.

Reactor (R-1701)

This is a shell-and-tube reactor, similar to a heat exchanger. The catalyst is in the tubes, and
a heat-removal fluid, molten salt, is in the shell. The heat load must be calculated. The
reactor exit temperature is to be 360°C, and the pressure drop is 80 kPa, packed bed reactor.
At this exit temperature, the selectivity for MA, PA, and CO2 are 0.1, 0.7, and 0.2,
respectively. Of the CO2 formed, 70% comes from combustion of PA, 20% from
combustion of MA, and 10% from combustion of o-xylene. The o-xylene conversion is
100%. The reactor can be simulated on Chemcad by using a “stoichiometric reactor.” A
single pseudo-reaction that accounts for both the stoichiometry and the selectivity must be
determined and used in the reactor simulation.

Heat Exchanger (E-1703)

This heat exchanger cools the reactor effluent, while recovering some heat by generating
high-pressure steam. The effluent temperature is 15°C above the temperature of high-
pressure steam. The pressure drop on the process side is 40 kPa.

Heat Exchanger (E-1704)

This heat exchanger further cools the reactor effluent, while recovering some heat by
generating low-pressure steam. The effluent temperature is 10°C above the temperature of
low-pressure steam. The pressure drop on the process side is 40 kPa.

Heat Exchanger (E-1705)

This heat exchanger cools the reactor effluent using cooling water. The effluent temperature
is 45°C. The pressure drop on the process side is 40 kPa.

Switch Condensers (SC-1701)

These are a complex set of three condensers that operate in a semi-continuous mode. The
inlet stream is first cooled by cold oil so that the anhydrides are desublimated (condensed as
solids). Then hot oil is passed through the same condenser so that the solids are melted. At
any given time, one condenser operates to desublimate, one to melt, the third on standby, and
the feed is switched between the three. The details of this operation will not be considered
here.

The feed to these condensers in Stream 11 must be at 45°C and 100 kPa. All of the light
gases and o-xylene go to Stream 12, and 1% of the PA and 2% of the MA go to Stream 12.
This unit should be modeled on Chemcad using a “component separator.”

Tower (T-1701)

This tower, which is actually a distillation column, separates the PA and MA. A “component
separator” should be used on Chemcad. Distillation columns are not perfect separators.
Therefore, 99.8% of the maleic anhydride in Stream 13 enters Stream 14, and 99.8% of the
phthalic anhydride in Stream 13 enters Stream 15.
Assignments
The assignment consists of the following “mini-designs.”

1. Fluid Mechanics – (ChE 310)

You are to optimize the design of the feed section of the process, which includes Streams 1-
7, P-1701 A/B, C-1701, E-1701, and E-1702. The stream conditions should be taken from the
base-case simulation performed in Mini Design #5.

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

⎛A ⎞
EAOC = CAP ⎜ , i, n ⎟ + AOC (6)
⎝P ⎠

where CAP ($) is the capital investment for the compressors, the heat exchangers, and the piping,
AOC ($/y) is the annual operating cost, which includes utility costs for the heat exchangers and
compressors, and

i(1 + i)
n
⎛A ⎞
⎜ , i, n⎟ =
[ ]
(7)
⎝P ⎠ (1 + i) n − 1

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

The costs for the piping components are given in the Appendix. The optimal pipe diameter
and schedule number of each stream, the pump duty, and the compressor duty that minimizes the
EAOC must be determined.

When doing a Chemcad simulation, pressure drops in pipes are often ignored (unless a pipe
is put in as a “unit’). In this optimization only, the pump and the compressor outlet pressures
must be sufficient to overcome the pressure drops in the equipment, at the mixing point, and in
the pipes. The base-case pressure drops for the heat exchangers should be used.

To evaluate the amount and cost of piping required for the mini-design, it may be assumed
that C-1701, P-1701, E-1701, and E-1702 are at grade (ground level). The suction line for the
compressor is 0.5 m above grade, and the discharge line for the compressor is 1.5 m above grade.
The suction line for the pump is 0.3 m above grade, and the discharge line from the pump is 1 m
above grade. The equivalent length of the pipe for Stream 3 is 3 m, the equivalent length of the
pipe for Stream 5 is 5 m, the equivalent length of the pipe for Stream 4 is 3 m, the equivalent
length of Stream 6 is 2 m, and the equivalent length of Stream 7 is 15 m, including 10 m as an
increase in elevation. For this mini-design only, both E-1701 and E-1702 may be assumed to be
horizontal, 1-2 exchangers, with the feed 1.5 m above grade and the discharge 0.5 m above
grade.
2. Heat Transfer – (ChE 311)

A detailed design of E-1701 is required for base-case conditions. It should be assumed that
utilities are available at the conditions specified in the Appendix of this problem statement. For
this heat exchanger design, the following information should be provided:
• Diameter of shell
• Thickness of shell wall
• Number of tube and shell passes
• Number of tubes per pass
• Tube pitch and arrangement (triangular/square/..)
• Number of shell-side baffles, if any, and their arrangement (spacing, pitch, type)
• Diameter, tube-wall thickness, shell-wall 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

The maximum heat exchanger length is 20 ft, and the shell diameter should be the minimum
required for the stated duty. A detailed sketch of the exchanger should be included along with a
set of comprehensive calculations in an appendix to the mini-design.

3. Thermodynamics – (ChE 320)

The equivalent annual operating cost, EAOC, for the compressor section of the process
should be minimized with the following in mind:

• The air feed should be taken from the inlet conditions (80 kPa and 25°C) and compressed
to the reactor feed conditions (300 kPa). According to the compressor manufacturer, the
maximum compressor operating temperature should be 200°C. Therefore, the compressor
section must be optimized within these constraints.

The optimization for this mini-project should include the cost of the compressor(s), 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 6) 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 feed section including the compressor. The EAOC was defined in Equations
6 and 7.

4. 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 as well as the impact of any extreme process
conditions. The purpose of the safety analysis report is to make management aware of risks to
personnel due to extreme operating conditions as well as 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
discussion 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, an aspect of your process design
that addresses one of these safety concerns should be explained.

5. Chemcad/Process Improvements

A Chemcad simulation of the base case of the process shown in Figure 1 should be provided.
Process improvements that do not violate the laws of physics may be suggested. An explanation
of the rationale for such process improvements should be provided, including an economic
analysis, if possible. Since there is no reactor cost available at this time, it may be omitted from
any economic analysis. Since the reactor is effectively a constant, the optimum is not affected,
but the EAOC is off by a constant value.

Other Information

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

Suggested Plan of Attack

The safety analysis can begin as soon as the project is distributed. A good place to find
MSDS sheets is http://siri.org. The Chemcad simulation can also be done immediately. Once
the Chemcad simulation is done, the fluid mechanics optimization, the heat exchanger design,
and the compressor optimization can be completed.

Deliverables

Written Reports

Each group must deliver a report written using a word processor. Three identical copies
should be submitted, one for each instructor, unless an electronic copy is requested by the
instructor after this document is distributed. The written project reports for all groups, regardless
of presentation date, are due by 11:00 a.m. Thursday, December 2, 2010. 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 preferred software for
preparing PFDs is Corel Draw. A PFD from Chemcad is unacceptable; however, it should be
included in the appendix along with a Consolidated Chemcad Report for the base case. The
Consolidated Chemcad Report should contain stream compositions, but not stream properties.
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-design.”
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. In either case,
your calculations should be clear and all assumptions made should be explained and justified.
Calculations that cannot be easily followed and that are not explained will lose credit.

Since this project involves “mini-designs,” it is suggested that the report be organized as
follows. There should be a general abstract, which summarizes the results of your work,
emphasizing what you found, not what you did. There should also be an introduction, which
orients the reader to the problem. 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” with
detailed calculations that are clearly written and easy to follow.

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%

For a more detailed set of evaluation criteria that we will use, see the following web site (design
project assessment, oral report assessment, written report assessment):
http://www.che.cemr.wvu.edu/ugrad/outcomes/rubrics/index.php

Each report will be assessed separately by each of the three instructors. A historical account
of what each group did is neither required nor wanted. Results and explanations should be those
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, December 2, 2010, from 11:00
a.m. to 2:00 p.m. and on Friday, December 3, 2010, from 11:00 a.m. to 1:00 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 310, ChE 311,
and ChE 320. Anyone failing to present with his or her group is subject to a minimum one-
letter-grade deduction from the project grade.

Project Review

There will be a project review at 11:00 a.m. on Friday, December 10, 2010. Attendance is
expected.

Teams

This project will be completed in teams of 3 or 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 the project proceeds,
questions from the class will require revisions and/or clarifications. It is important to be aware
that these revisions/clarifications may be forthcoming.
 Appendix
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 than the minimum, the minimum
attribute value should be used 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, the price
for multiple, identical, smaller pieces of equipment should be used.

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 60% 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)

Storage Tanks log10 (purchased cost ) = 4.85 − 0.397 log10 V + 0.145[log10 V ]2

V = volume of tank (m3, 90, 30000)
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 schedule 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) $13.28/GJ

Medium-Pressure Steam (1135 kPa saturated) $14.19/GJ

High-Pressure Steam (4237 kPa saturated) $17.70/GJ

Natural Gas (446 kPa, 25°C) $11.00/GJ

Fuel Gas Credit none, but there is no treatment cost

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 – zero cost

Low-temperature Refrigerant $7.89/GJ

available at -20°C
 Very low-temperature Refrigerant $13.11/GJ
available at -50°C

Wastewater Treatment $56/1000 m3

Raw Material Costs/Product Value

Raw Material or Product price

o-xylene $0.80/kg
maleic anhydride $1.10/kg
phthalic anhydride $1.25/kg

Equipment Cost Factors

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

Pressure < 10 atm, PF = 0.0 does not apply to turbines, compressors, vessels,
(absolute) 10 - 20 atm, PF = 0.6 packing, trays, or catalyst, since their cost
20 - 40 atm, PF = 3.0 equations include pressure effects
40 - 50 atm, PR = 5.0
50 - 100 atm, PF = 10
100 - 200 atm, PF = 25

Carbon Steel MF = 0.0

Stainless Steel MF = 4.0
 Separations and Reaction Engineering
Design Project

Phthalic Anhydride Production

Your assignment is to continue evaluating the details of a process to produce 75,000 tonne/y
of phthalic anhydride from o-xylene. This is the amount of phthalic anhydride in the product
stream, not the total mass of the product stream. The purity is to be 99.9 mol% phthalic
anhydride.

Chemical Reactions

Based on your previous recommendations, this design is to operate above the UFL of o-
xylene at the reactor feed. However, since the UFL of phthalic anhydride is higher than that of
o-xylene, the UFL of the mixture will have to be calculated1, and the reactor exit must be above
the mixture UFL.

The oxidation reactions that take place are highly exothermic, and the temperature
everywhere in the reactor must be very carefully controlled. The catalyst, vanadium pentoxide
(V2O5), sinters above a temperature of 400°C. The reactions taking place are:

C6 H 4 (CH 3 ) 2 + 3O2 → C6 H 4 (CO) 2 O + 3H 2O

(1)
o-xylene phthalic anhydride

15
C6 H 4 (CO) 2 O + O2 → 8CO2 + 2 H 2O
2 (2)
phthalic anhydride

21
C6 H 4 (CH 3 ) 2 + O2 → 8CO2 + 5H 2O
2 (3)
o-xylene

15
C6 H 4 (CH 3 ) 2 + O2 → C2 H 2 (CO) 2 O + 4CO2 + 4 H 2O
2 (4)
o-xylene maleic anhydride

C2 H 2 (CO) 2 O + 3O2 → 4CO2 + H 2O

(5)
maleic anhydride

C6 H 4 (CH 3 ) 2 + 3O2 → C6 H 5 (COOH ) + CO2 + 2 H 2O

(6)
o-xylene benzoic acid
 2

15
C6 H 5 (COOH ) + O2 → 7CO2 + 3H 2O
2 (7)
benzoic acid

The kinetic expressions for these reactions all have the form:
Ea
−
− rA = ko e RT
p1 p2 (8)

where ko has units of kmol/m3-reactor/h/atm2, Ea has units of kcal/kmol, and pi are partial
pressures in atm. The constants for these reactions are given in Table 1.

Table 1: Kinetic Constants used for Reactions (Equations 1-7)

Reaction ko Ea 1 2
Number
1 4.12×1011 27,000 o-xylene oxygen
phthalic
2 1.15×1012 31,000 oxygen
anhydride
3 1.73×1011 28,600 o-xylene oxygen
4 2.25×1011 27,900 o-xylene oxygen
maleic
5 7.76×1011 30,400 oxygen
anhydride
6 5.00×1009 27,000 o-xylene oxygen
benzoic
7 5.00×1011 29,500 oxygen
acid

Specific Assignments

1. Separations Design

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 phthalic anhydride should be designed in detail. A detailed design of a
tray tower includes number of trays, tray spacing, diameter, reflux ratio, 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. Since the separation section of this process is
likely to operate at a vacuum, issues associated with vacuum columns might impact the choice
between a tray tower and a packed tower.

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
 3

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 for some packings is provided in Wankat2 p.
338. Assume the HETP for the structured packing to be 0.6 m (see the definition of HETP in
Wankat2, p. 332, and the relationship between HETP and HOG in Equation (15.36) in Wankat2.),
and that the pressure drop is 0.2 kPa/m (0.245 inch water/ft).

Note that any benzoic acid formed desublimates in the switch condensers with the
anhydrides. The o-xylene and the light gases are in the same stream, just like in the previous
project.

2. Reactor Design

Two reactor designs should be optimized separately and the one resulting in the lowest
EAOC should be identified. The reactor inlet pressure should be set to 300 kPa, but the choice of
reactor and the reactor inlet temperature are to be optimized.

The oxidation of o-xylene can take place in a packed-bed reactor with catalyst-filled tubes
that are cooled using a circulating stream of Dowtherm A.

An alternative reactor design for these highly exothermic reactions is a fluidized bed with
heat transfer tubes located in the reactor. A review of some pertinent design criteria for a
fluidized bed reactor is provided.

Operating flow should range from 20-30 times the minimum fluidization velocity, umf.

Catalyst particle size (dp) = 400 μm (400×10-6 m)

Catalyst particle density, ρp = 2,400 kg/m3
Catalyst bulk density, ρbulk = 1,350 kg/m3
Catalyst sinters above a temperature of 400°C

The minimum fluidizing velocity can be calculated from the correlation of Wen and Yu3

d p u mf ρ f
μ
[
= Re p,mf = (28.7) 2 + 0.0494Ar ]
0.5
− 28.7 (9)

where Ar is the Archimedes number and is given by

 4

( ρ p − ρ f ) ρ f d 3p g
Ar = (10)
μ2

and ρ, μ, and g have their normal meaning. Subscripts mf, p and f refer to minimum fluidizing,
particle, and fluid, respectively.

The pressure drop through the fluidized bed is given by:

ΔPbed = L (1 − ε )( ρ p − ρ f ) g (11)

where L is the height of the bed and ε is the bed void fraction. For a turbulent fluidized bed
operating at 20-30 times umf, you should assume that ε = 0.55. The pressure drop through
distributor plate and exit cyclones = 25% of bed pressure drop. The heat transfer coefficient
between tube wall and turbulent fluid bed = 300 W/m2K.

For modeling a fluidized bed, you should assume that the bed operates isothermally, i.e., the
bed of solids is well mixed. However, the gas flow through the solids bed is a mixture of plug
flow and by-passing. For this design, you should assume that 90% of the gas entering the bed
passes through in plug flow while the other 10% bypasses the catalyst, i.e., does not react. The
flow model for the reactor is shown in Figure 1.

90% of feed passes through bed in

10% of feed bypasses bed plug flow

Figure 1: Flow Model of Turbulent Fluidized Bed (Bed Temperature = Constant), Heat
Transfer Tubes not Shown but Should be Included in Design

For all surfaces in contact with phthalic anhydride, the recommended material of
construction is 304 stainless steel.

The cost of the packed bed reactor can be estimated by adding the cost of a shell-and-tube
heat exchanger to the cost of the process vessel required to house the catalyst tubes. The cost of
the fluidized bed reactor should be taken to be twice the cost of the sum of a shell-and-tube heat
exchanger and the process vessel required to house the heat transfer tubes.
 5

Remember that the required units in Chemcad for the reaction rate are kmol/m3reactor hr.
The reactor EAOC should include anything that will vary depending on your decision variables,
i.e., the cost to heat the feed and cool the reactor and product streams. For your best case, you
should include a discussion of the temperature, pressure, and concentration profiles obtained
from Chemcad.

3. Overall Design

The entire process should be optimized based on your choice of process topology and
parametric optimization of decision variables appropriately chosen based on their importance to
the decision variable.

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

⎛A ⎞
EAOC = CAP ⎜ , i, n ⎟ + AOC (12)
⎝P ⎠

where CAP ($) is the capital investment for the compressors, the heat exchangers, the reactor,
and the distillation columns, AOC ($/y) is the annual operating cost, which includes utility costs
for the heat exchangers (including those associated with the distillation columns and
compressors, and

⎛A ⎞ i(1 + i ) n
⎜ , i, n ⎟ =
⎝P [ ]
⎠ (1 + i ) n − 1
(13)

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

Other Information

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

Deliverables

Written Reports

Each team must deliver a report written using a word processor. Two identical copies should
be submitted, one for each instructor. The written project reports are due by 11:00 a.m.
Wednesday, April 20, 2011. 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 preferred software for
 6

preparing PFDs is Corel Draw. A PFD from Chemcad is unacceptable; however, it should be
included in the appendix along with a Chemcad report for the optimized case. 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. 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.

Since this project involves three “mini-designs,” it is suggested that the report be organized
with the following sections. There should be a general abstract and introduction. Then, there
should be a results section for the entire process, including the reactor and separators. The
discussion section should have a sub-section dedicated to the overall optimization, a sub-section
dedicated to the reactor design, and a sub-section dedicated to the separation design. A general
conclusion and recommendation section should follow. At a minimum, there should be separate
appendices for each mini-design containing detailed calculations that are clearly written, easy to
follow, and appropriate for the respective class.

In order to evaluate each team member’s writing skills, the results and discussion sections for
each mini-design should be written by a different team member. The authorship of each of these
mini-reports should be clearly specified in the report. If there is a fourth team member, this
person should author the introduction, conclusions, and recommendations. Although the
individual written portions of the reports must be authored by a single team member, it is the
intent of the instructors that team 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 team.

The reports will be evaluated as follows:

• course-specific technical content – 40%

• oral presentation – 20%
• written report – 20%
• overall optimization – 20%

For a more detailed set of evaluation criteria that we will use, see the following web site (design
project assessment, oral report assessment, written report assessment):
http://www.che.cemr.wvu.edu/ugrad/outcomes/rubrics/index.php

Each report will be assessed separately by both instructors. A historical account of what each
team did is neither required nor wanted. Results and explanations should be those 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.

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.
 7

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
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.

Oral Reports

Each team 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 team member must
speak. Each team 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 Wednesday April 20, 2011, from 12:00 noon to 3:00
pm and Thursday, April 21, 2011, from 11:00 am 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 312 and ChE 325.
 8

Teams

This project will be completed in teams of 3 or 4. More details of team formation and peer
evaluation will be discussed in class.

References

1. Crowl, D. A. and J. F. Louvar, Chemical Process Safety (2nd ed.), Prentice Hall PTR, Upper
Saddle River, NJ, 2002, pp. 233-234.

2. Wankat, P., Separation Process Engineering, (2nd ed.), Prentice Hall PTR, Upper Saddle
River, NJ, 2007.

3. Wen, C. Y. and Y. H. Yu, “A Generalized Method For Predicting The Minimum Fluidization
Velocity,” AIChE-J, 12, 610-612 (1966).
 9

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 than the minimum, the minimum
attribute value should be used 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, the price
for multiple, identical, smaller pieces of equipment should be used.

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 it 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
 10

Packed Tower Cost as vessel plus cost of packing

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)

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

Storage Tanks log10 (purchased cost ) = 4.85 − 0.397 log10 V + 0.145[log10 V ]2
V = volume of tank (m3, 90, 30000)

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.

Chemical Prices

See http://www.icis.com/StaticPages/a-e.htm.

Utility Costs

Low-Pressure Steam (618 kPa saturated) $13.28/GJ

Medium-Pressure Steam (1135 kPa saturated) $14.19/GJ

High-Pressure Steam (4237 kPa saturated) $17.70/GJ

Natural Gas (446 kPa, 25°C) $11.00/GJ

Fuel Gas Credit $9.00/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
 11

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

Low Temperature Refrigeration $7.89/GJ

Coolant stream at -20°C

Very Low Temperature Refrigeration $13.11/GJ

Coolant stream at -50°C

Wastewater Treatment $56/1000 m3

Equipment Cost Factors

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

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

Carbon Steel MF = 0.0

Stainless Steel MF = 4.0