Material Balances

Design Problem -- Acrylic Acid Production

Acrylic acid is produced by the catalytic partial oxidation of propylene in the presence of steam
at elevated temperature and ambient pressure. We wish to begin the design of a process to produce
50,000 metric tons of acrylic acid per year. Your job for this semester is to analyze a simplified
acrylic acid production process and to suggest profitable operating conditions.

Figure 1 is a flow diagram of a simplified process for acrylic acid production. Figure 1 is also
simplified; in particular, pumps (to raise the pressure) and other equipment extraneous to the present
level of design are not included. In the simplified process, propylene, air (a source of oxygen), and
steam are mixed and fed to the reactor at 4.3 atm. The reactions occurring within the reactor are as
follows:

C3 H 6 + 1.5O2 → C3 H 4O2 + H 2O
(1)
propylene acrylic acid

C3 H 6 + 4.5O2 → 3CO2 + 3H 2O
(2)
propylene

Eq. (1) is the desired acrylic acid production reaction and Eq. (2) is the undesired propylene
combustion reaction. The outlet stream from the reactor is then flashed to a lower pressure and a
different temperature, such that some of the water and some of the acrylic acid form a liquid phase.
The vapor phase and the liquid phase leave the light-gas separator in separate streams. The vapor
phase is incinerated. The liquid phase is further separated into pure acrylic acid and pure (waste)
water.

Process Streams
Stream 1: This stream may be assumed to be pure propylene (polymer grade).

Stream 2: This stream is compressed air containing water vapor at an amount that would saturate
the air at 25°C and 1 atm. Air is assumed to consist of 21 mol% oxygen and 79 mol%
nitrogen on a water-vapor-free basis.

Stream 3: This stream is steam at 160°C and 6 atm.

Stream 4: This is a mixture of Streams 1-3. It should contain the following mole fractions:
propylene - 0.05, air (includes oxygen, nitrogen, and water vapor) - 0.55, steam added
in Stream 3 - 0.40

Stream 5: This vapor stream is the reactor effluent. The valve in this stream lowers the pressure and
changes the temperature for the separators.
 3

Stream 6: This vapor stream contains all components in Stream 5 other than water and acrylic acid.
The water and acrylic acid are partitioned between Streams 6 and 7 according to Raoult’s
law.

Stream 7: This liquid stream contains only water and acrylic acid.

Stream 8: This vapor stream contains pure acrylic acid.

Stream 9: This liquid stream contains pure water.

Process Units
Acrylic Acid Reactor (R-301)

In this reactor, the reactions in Eqs. (1) and (2) occur. The selectivity and conversion at various
temperatures are given in Table 1. These values are for the reactor operating pressure of 4.3 atm and
are independent of the amount of oxygen present, as long as propylene is the limiting reactant.

Table 1
Selectivity and Conversion at Different Temperatures

Temperature Selectivity Conversion of Propylene

(°C) (moles acrylic/ moles CO2)

200 10.0 0.04

250 10.0 0.05
300 9.77 0.11
350 8.91 0.22
400 7.24 0.36
450 4.90 0.50
500 2.45 0.63
550 0.891 0.76
600 0.655 0.83
650 0.610 0.85

Light-Gas Separator (S-301)

In this separator, all light components other than acrylic acid and water exit in Stream 6. The
acrylic acid and water are partitioned between Streams 6 and 7 according to Raoult’s law. For acrylic
acid, the vapor-pressure relationship is:
 4

5450.06
ln P* (mm Hg) = 19.776 − (3)
T (K)

For this semester, you may assume that both the temperature and the pressure of this unit can be
varied independently and at no cost.

Acrylic Acid Separator (S-302)

In this separator, assume that all acrylic acid exits in Stream 8, and all water exits in Stream 9.
This means that the separator is behaving “perfectly.” This is an approximation which we are using
this semester but which may not be used in future semesters.

Assignment
Your assignment is to perform material balances on this process to determine the gross profit at
different operating conditions. The gross profit is defined as:

gross profit = value of products - cost of reactants (4)

For this semester, the only product that has value is acrylic acid. The reactants are propylene and
steam. The market prices for acrylic acid and propylene may be found in the Chemical Marketing
Reporter, which may be found in the Evansdale library; for the former species, use the value for
99+% acrylic acid. The price for steam is $6.50/1000 kg. In your report, you should also discuss
other expenses associated with acrylic acid production which are not included in the gross profit (Eq.
4) and how these additional expenses would affect the (actual) profit.

You should calculate material balances for the following cases:

Groups designated A: reactor at 200°C, 300°C, 400°C, 500°C, 600°C

Groups designated B: reactor at 250°C, 350°C, 450°C, 550°C, 650°C

Both groups should analyze their reactor cases for the following conditions in S-301:

Constant pressure of 1 atm: T = 40°C, 50°C, 60°C

Constant temperature of 50°C: P = 1 atm, 2 atm, 3 atm

The goal is to determine the optimum operating conditions, i.e., those yielding the maximum gross
profit. The above cases must be done; however, you may run additional cases, at your discretion, by
interpolating reactor performance data, or by moving outside the temperature and pressure range in
S-301 to suggest more profitable operating conditions.

When reporting the results of all cases, graphs are superior to tables. You should plot graphs of
gross profit vs. reactor temperature, with different curves on the same plot for different separator
temperatures and pressures.
 5

It is assumed that this problem will be solved either using a spreadsheet, a program like Mathcad,
or by writing a computer program in Fortran or C. Solving this problem with only hand calculations
is unacceptable.

Hint: Since it is easier to perform material balances from feed to product, choosing a feed basis
and then scaling up to the desired acrylic acid production rate is recommended.

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

The information in this document is considerably simplified, and consequently is valid for this
project only. Unless specifically stated in class, you may not use information in this document for
future projects. Additional information, e.g., physical properties, may be found in standard references
(Refs. 1, 2).

Groups

You should form your own groups immediately and inform Professor Dadyburjor of the
membership of the groups. Groups should contain either 3 or 4 members. Anyone not able to join
a group should contact Professor Dadyburjor immediately.

Deliverables
You must deliver a report prepared by a word processor and conforming to the document entitled
Written Design Reports which you will receive. All graphs and tables must be generated by
computer. It is your responsibility to keep sufficient back-up copies of your work. Computer failure,
hard-disk failure, a corrupted floppy disk, etc., are not necessarily excuses for a penalty-free
extension. The report is due on December 1, 1997 at 4:45 p.m. Late reports will be penalized one
grade per day.

The appendix to your report should contain sample spreadsheets or computer programs. The
appendix should also contain a set of detailed hand calculations for your optimum case, to prove the
validity of your computer calculations.

Revisions
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.
 6

References
1. Felder, R.M. and R.W. Rousseau, Elementary Principles of Chemical Processes, 2nd edition,
Wiley, New York (1986).

2. Perry, R.H. and D. Green, eds., Perry’s Chemical Engineering Handbook, 6th edition, McGraw-
Hill, New York (1984).
 Energy Balances and Numerical Methods
Design Project

Production of Acrylic Acid

Process Description
Figure 1 is a preliminary process flow diagram (PFD) for the acrylic acid production process.
The raw materials are propylene and oxygen. Steam in added to provide thermal ballast. The
propylene feed may be assumed pure vapor at 446 kPa. The air feed, which may be considered to
contain only oxygen, nitrogen, and water is also at 446 kPa. The steam is saturated at 446 kPa.
The feeds are mixed and sent to the reactor (R-301) in which acrylic acid is formed. There
reactions which occur are shown below. The reactor effluent is sent to a separation unit (S-301)
in which all light gases (oxygen, nitrogen, carbon dioxide, and propylene) are separated as vapor
in Stream 7. Stream 7 is split into Streams 8 and 9. Stream 8 is a recycle stream containing
propylene, oxygen, nitrogen, and carbon dioxide. A pump is required in this stream which is not
shown. Stream 9 is incinerated. Stream 10, containing water and acrylic acid is sent to a
distillation column (T-301) to produce purified acrylic acid. The desired acrylic acid production
rate is 50,000 metric tons/yr.

Process Details
Feed Streams

Stream 1: propylene, pure vapor, 25°C and 446 kPa

Stream 2: air at 218°C and 446 kPa

(it has been compressed from atmospheric pressure causing the temperature
increase - the annual cost for this compression is $1.22M per compressor)
water present in amount to saturate air at 25°C and 1 atm

Stream 3: low-pressure steam

Stream 4: feed mixture should have the following components:

air (containing oxygen, nitrogen, and water vapor) 55 mole %
steam (added as steam) 40 mole%
propylene 5 mole %
you must determine the stream temperature

Effluent Streams

Stream 9: waste gas stream to incinerator, credit may be taken for LHV of fuel
 3

Stream 11: waste water stream, treatment cost $50.00/106 kg

must contain less than 0.05 wt % acrylic acid

Stream 12: acrylic acid product, 99.9 wt% purity.

Equipment

Reactor (R-301):

The following reactions occur:

C3 H6 + 15. O2 → C3 H 4O2 + H 2O
propylene acrylic acid
C3 H6 + 4.5O2 → 3CO2 + 3H 2O

Selectivities and conversions at various temperatures are given in Table 1. These values
are for the reactor operating pressure of 446 kPa and are independent of the amount of
oxygen present, as long as propylene is the limiting reactant. Part of your assignment is to
determine the best exit reactor temperature.

Table 1
Selectivity and Conversion at Different Temperatures

Temperature Selectivity Conversion of Propylene

(°C) (moles acrylic/ moles CO2)

200 10.0 0.04

250 10.0 0.05
300 9.77 0.11
350 8.91 0.22
400 7.24 0.36
450 4.90 0.50
500 2.45 0.63
550 0.891 0.76
600 0.655 0.83
650 0.610 0.86

Separator (S-301):

In this separator, all components other than acrylic acid and water exit in Stream 7. The
acrylic acid and water vapor are partitioned between Streams 7 and 10 according to
Raoult’s law. Part of your task is to determine the optimum temperature and pressure for
this separator. The separator pressure must be below 446 kPa. Note: The vapor pressure
expression given in last semester’s design project is not applicable here. You must
determine such an expression on your own.
 4

Distillation Column (T-301):

In this distillation column, the water and acrylic acid in Stream 10 are separated. The
column operates at vacuum conditions. Specifications are as follows. The column
pressure is determined by the boiling point of acrylic acid at its maximum allowable
temperature, 90°C. This is also the temperature of Stream 12. The temperature of
Stream 11 is the boiling point of water at the pressure of the column. Energy
requirements are described with the heat exchange equipment, below.

Heat Exchanger (E-301):

In this heat exchanger, you may assume that one-half of the flow of Stream 12, containing
pure acrylic acid, is vaporized from saturated liquid to saturated vapor at 90°C. The cost
is for the amount of low-pressure steam needed to supply the necessary heat.

Heat Exchanger (E-302):

In this heat exchanger, water is condensed from saturated vapor to saturated liquid at a
rate three times the flow of Stream 11. The cost is for the amount of refrigerated water
needed to remove the necessary energy.

Equipment Costs

The equipment costs for the acrylic acid plant are given below. Each cost is for an individual
piece of equipment, including installation.

Equipment Installed Cost

in millions of $

reactor 7.4
compressor 7.8
distillation column 0.4
(not including reboiler and
condenser)
vessel 0.2
any heat exchanger 0.1
miscellaneous equipment not 0.1
shown on the process flow
diagram

If you cool Stream 6 as part of the flash, you will need to add the cost of a heat exchanger to
the cost of a vessel to calculate the installed cost of S-301.
 5

Utility Costs
Low-Pressure Steam (446 kPa, saturated) $5.00/1000 kg

Medium-Pressure Steam (1135 kPa, saturated) $7.31/1000 kg

High-Pressure Steam (4237 kPa, saturated) $8.65/1000 kg

Natural Gas or Fuel Gas (446 kPa, 25°C) $3.00/GJ

Electricity $0.05/kW h

Boiler Feed Water (at 549 kPa, 90°C) $2.54/1000 kg

Cooling Water $0.16/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 $1.60/GJ

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

Data
Use data from Reference [1] or from any handbook (such as Reference [2]). The following
data are not readily available in these references.

Liquid Heat Capacity

Assume that the liquid heat capacity for benzene given in Reference [1] is valid for all
other organic liquids.

Vapor Heat Capacity

for acrylic acid: 1.742 + 0.3191T - 2.352´10-4T 2 + 6.975´10-8T 3 J/mole K T (K)

Vapor Pressures
Vapor pressures may be interpolated or extrapolated from the following data:
 6

normal boiling point additional vapor pressure point

T (K) T (K) P (MPa)
propylene 225 365 4.620
acrylic acid 391 615 5.674

Normal heat of vaporization

for acrylic acid: 32.94 kJ/mole

Heat of formation
for acrylic acid: -336,500 kJ/kmole

Economic Analysis
When evaluating alternative cases, the following objective function should be used. It is the
equivalent annual operating cost (EAOC), and is defined as

EAOC = -(product value - feed cost - other operating costs - 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 costs for acrylic acid (the product) and propylene (the feed) should be obtained from the
Chemical Marketing Reporter, which is in the Evansdale Library.

Other operating costs are utilities, such as steam, cooling water, natural gas, and electricity.

The capital cost annuity is an annual cost (like a car payment) associated with the one-time,
fixed cost of plant construction. A list of capital costs for all pieces of equipment will be provided
by Spring Break. You will learn to calculate the annuity value in ChE 38.

Optimization
We will learn optimization methods in ChE 38. The objective function (EAOC) is defined
above. It is your responsibility to define appropriate decision variables. If there are too many
decision variables to do a reasonable optimization, it is your responsibility to determine, with
appropriate justification, which ones most significantly affect the objective function and focus on
only those decision variables.

Other Information
You should assume that a year equals 8000 hours. This is about 330 days, which allows for
periodic shut-down and maintenance.
 7

You should assume that two streams that mix must be at identical pressures. Pressure
reduction may be accomplished by adding a valve. These valves are not shown on the attached
flowsheet, and it may be assumed that additional valves can be added as needed. In general, flow
occurs from higher pressure to lower pressure. Pumps increase the pressure of liquid streams,
and compressors increase the pressure of gas streams. The two locations where pumps are
needed are Streams 11 and 12, to remove material from the tower operating at vacuum
conditions. A small compressor or blower is also needed in Stream 8. For purposes of this design
only, you may assume that Stream 8 is at whatever pressure is needed to allow it to mix with
Stream 4, and that there is no cost associated with this pressure increase.

For this semester only, assume the following relationship for a compression or expansion
operation:

0.286
 Tout   Pout 
  =  
 Tin   Pin 

Deliverables
Each group must deliver a report written using a word processor. The report should be clear
and concise. The format is explained in a separate document. Any report not containing a labeled
PFD and a stream table will be considered unacceptable. The stream table must include
temperature, pressure, phase, total mass flowrate, total molar flowrate, and component molar
flowrates. When presenting results for different cases, graphs are generally superior to tables.
The report appendix should contain details of calculations for the optimal case. These
calculations may be (neatly) hand-written. Calculations which can not be followed easily will lose
credit. Refer to the document entitled Written Design Reports for more information.

Each group will give an oral report in which the results of this project are presented in a
concise manner. The oral report should be no more than 15 minutes, and each group member
must speak. A 5-10 minute question-and-answer session will follow. Instructions for
presentation of oral reports will be provided in a separate document entitled Oral Reports.
However, the best way to learn how to present an oral report, other than actually presenting one,
is to make time to see some of the oral reports presented by the juniors the week before you are
to present your report. The presentations will most likely be on Wednesday, April 22, 1998,
between 11:00 am and 3:00 pm.

As mentioned in the cover memo, the written project report is due upon presentation of the
oral report. The oral reports will be Monday, April 27, 1998 (ChE 38 class) and Wednesday,
April 29, 1998 (ChE 41 class). There will be a project review on Friday, May 1, 1998 (ChE 41
class). In addition, everyone must attend at least one (and preferably both) of the senior design
presentations, either on Tuesday, April 28, 1998, or on Thursday, April 30, 1998 (substitutes for
Thursday ChE 38 class). Furthermore, attendance is required of all students during their
classmates’ presentations (this means in the room, not in the hall or the lounge). Failure to attend
any of the above required sessions will result in a decrease in one letter grade (per occurrence)
from your project grade in both ChE 38 and ChE 41.
 8

Anyone not participating in this project will automatically receive an F for ChE 38, regardless
of other grades earned in this classes.

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.

References
1. Felder, R. M. and R. W. Rousseau, Elementary Principles of Chemical Processes (2nd ed.),
Wiley, New York, 1986.

2. Perry, R. H. and D. Green, eds., Perry’s Chemical Engineering Handbook (6th ed.),
McGraw-Hill, New York, 1984.
 Fluid Mechanics, Heat Transfer, and Thermodynamics
Design Project

Production of Acrylic Acid

We are investigating the feasibility of constructing a new, grass-roots, 50,000 metric
tons/year, acrylic acid production facility. As part of the feasibility study, we would like you to
investigate some of the details of the feed and reaction sections of the proposed plant.

Acrylic Acid Production Reactions

The reactions are given below. The primary reaction is:

C3 H 6 + . O2 → C3 H 4O2 +
15 H2O
(1)
acrylic acid

The secondary reactions are:

C3 H 6 + 2.5O2 → C2 H4O2 + CO2 + H 2O

(2)
acetic acid

C3 H 6 + 4.5O2 → 3CO2 + 3H 2O
(3)

For the purposes of this preliminary evaluation, it is assumed that the reactions occur in a
fluidized bed of catalyst particles. Due to the characteristics of fluidized bed reactors, a maximum
propylene conversion of 90% is possible in the reactor. The selectivity for acrylic acid/acetic acid
is 13.5. The selectivity for acrylic acid/carbon dioxide formed in the combustion reaction
(Reaction (3)) is 1.6.

Reaction Section
The PFD for the reaction section is given in Figure 1. The propylene is stored in tanks which
are not shown. There are two tanks, each holding a one-day supply, one in a filling mode and the
other in a feeding mode. The propylene is stored at ambient temperature (which may be assumed
to be 25°C) as a vapor/liquid equilibrium mixture, and the feed to the process may either be vapor
(drawn from the top of the tank) or liquid (drawn from the bottom of the tank). The feed to the
reactor must be at 4.3 bar and the crude acrylic acid product (in the liquid phase) may not exceed
90°C. The pressure drops across process units at base case
 3

conditions are given in Table 1.

Table 1: Pressure Drops across Process Units in Feed Section

Unit ∆ P (bar)

mixing points 0.05

Reactor 0.80
any heat exchanger 0.35

The reactor feed must be at 4.3 bar and 190°C. Heat generated in the reactor is removed by
Dowtherm A , which is thermally regenerated in E-301. If the Dowtherm pressure is maintained
above 10 bar, it is not volatile up to 400°C. The reactor exit temperature is 290°C. Following
the reactor, the reaction products are quenched with sufficient deionized water to bring the
temperature of the stream to 200°C. The crude acrylic acid product is obtained by flashing the
quenched reactor effluent. It may be assumed that all light gases (N2, O2, CO2) leave in the vapor
phase. All other components distribute between the vapor and liquid phases. The temperature of
any liquid stream containing acrylic acid may never exceed 90°C to avoid spontaneous
polymerization.

Assignment
Your assignment consists of three “mini-designs.”

1. Optimization of the Feed Section. (ChE 110(fluids) and 142(thermo)) Refer to Figure
1. You are to determine the optimum pipe sizes for Streams 1-4. Equivalent pipe lengths
can be determined from the attached plot plan (Figure 2). Pipe runs are at 4 m elevation
off the ground, and you should add 90° elbows as necessary. The objective function is the
Equivalent Annual Operating Cost (EAOC) of the feed section ($/y). The EAOC is
defined as:

A 
EAOC = CAP , i, n + operating costs for feed section loop (4)
P 

where CAP = the installed cost of equipment in the feed section and

i(1 + i)
n
A 
 , i, n =
[ ]
(5)
P  (1 + i)n − 1

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

For the feed section, do not include tank costs, so CAP includes the cost of pipes, pumps
(if needed), and compressors and operating costs include the electricity to run the pumps
and/or compressors. You are also to size and cost the feed tanks (1 day of
 5

liquid storage needed – 2 tanks required, one for filling and one for feeding – assume 70%
full with liquid) and determine the conditions for propylene storage. Propylene is to be
stored as vapor/liquid mixture. Specify the elevation of the tank. We have a supply of
centrifugal compressors used in other plants. The compressor curves are also attached
(Figure 3). We would like the flexibility for 35% scale-up in the future.

2. Optimization of the Dowtherm AÔ Loop. (ChE 110 (fluids) and 111(heat)) The heat
exchanger, E-301, must be designed in detail. The heat exchanger, pipes, and pump
should be optimized together. CAP should include the costs of the pump, of the pipes,
and of the heat exchanger. Operating costs should include the cost of pumping and the
cost or credit for the heat removal medium in the heat exchanger. We also have a supply
pumps used in our other plants which we would like to use in this plant. The pump curve
is attached (Figure 4). This curve is for the pump having a 4 in impeller diameter. A 4.75
in impeller diameter can also be used. The pump efficiency is 80%, and is assumed
constant. The pump and pipes should be sized to allow for 35% scale-up in the future.
Equivalent pipe lengths should be determined from the attached plot plan (Figure 5). Pipe
runs are at 4 m elevation off the ground, and you should add 90° elbows as necessary.

3. Determination of Break-even Price for Crude Acrylic Acid. (all classes) A Chemcad
simulation for your best case should be presented. You may make any process
modifications that improve the BEP, but a full optimization is not required. The break-
even price (BEP) for crude acrylic acid product should be calculated. The best case is
defined as the optimum case for “mini-designs” 1 and 2, above, plus any other changes to
the process that you recommend. The break-even price for crude acrylic acid product is
calculated as follows:

A 
CAP , i, n + cost of reactants + operating costs - byproduct revenue
P 
BEP = (6)
kg acrylic acid in crude product

where CAP is the installed capital cost for the entire feed and reaction sections, including
the feed tanks.
 6

4
3500 rpm
Pout/Pin

2
2200 rpm

0
0 10 20 30 40 50 60 70

10-3 volumetric flowrate (m3/h)

Figure 3: Compressor Curves for C-301

 7

30

25
Total Dynamic Head (m)

20

15

10

0
0 200 400 600 800 1000 1200

Flow of Dowtherm A (m3/h)

Figure 4: Pump Curve for the Dowtherm A Pump

8
 9

Cost Data

Raw Materials
Propylene (polymer grade) see Chemical Marketing Reporter

Utility Costs

Low Pressure Steam (618 kPa saturated) $6.62/1000 kg

Medium Pressure Steam (1135 kPa saturated) $7.31/1000 kg

High Pressure Steam (4237 kPa saturated) $8.65/1000 kg

Natural Gas (446 kPa, 25°C) $3.00/GJ

Fuel Gas $2.75/GJ

use this price for fuel gas credit

Electricity $0.06/kW h

Boiler Feed Water (at 549 kPa, 90°C) $2.54/1000 kg

Cooling Water $0.16/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 $1.60/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

 10

Equipment Costs (Purchased)

Piping $/m = 5.0 (diameter, in)

0.8
Valves $100 (flow diameter, in)
for control valve with orifice plate, double the price

0.4
Pumps $630 (power, kW)

Heat Exchangers $1030 (area, m2)0.6

add 25% additional for boilers or evaporators

Compressors $770 (power, kW)0.96 + 400 (power, kW)0.6

Turbine $2.18´105 (power output, MW)0.6

assume 65% efficiency

Fired Heater $635 (duty, kW)0.8

assume 80% thermal efficiency
assume can be designed to use any organic compound as a fuel

Vessels $[1.67(0.959 + 0.041P - 8.3´10-6P2)]´10z

z = (3.17 + 0.2D + 0.5 log10L + 0.21 log10L2)
D = diameter, m 0.3 m < D < 4.0 m
L = height, m 3 < L/D < 20
P = absolute pressure, bar

Reactor assume to be $5 million

Storage Tank $1000V0.6

V = volume, m3
 11

Equipment Cost Factors

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

Material Factors
Carbon Steel 0.0
Stainless Steel 4.0

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

Heat Exchangers
For heat exchangers that do not have to be designed in detail, use the following
approximations for heat transfer coefficients to allow you to determine the heat transfer area and
heat exchanger cost:

situation h (W/m2° C)

condensing steam 6000

condensing organic 1000

boiling water 7500

boiling organic 1000

flowing liquid 600

flowing gas 60
 12

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

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 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, December 4, 1998. 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. 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 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 so neatly. Calculations that cannot be
easily followed will lose credit.

Since this project involves three “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 an appendix for each of
the three “mini-designs.” With this organization, there is no need for a separate section of the
report for each class, as suggested in the document entitled Written Design 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. A 5-10 minute question-and-answer session will follow. Refer to the document entitled
Oral Reports for instructions. The oral presentations will be December 4, 1998, from 11:00 a.m.
to 3:00 p.m., and possibly December 5, 1998, from 11:00 and to 1:00 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 110, ChE 111, and ChE
142.
 13

Groups
You may do this projects in a group of three or four. You should select your own groups.
Since there are 31 students doing the project, there will be eight groups. Seven groups will have
four members and one group will have three members.

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.
 Separations and Reactors

Acrylic Acid Production via the Catalytic Partial Oxidation of Propylene

Process Information

Background

Acrylic acid (AA) is used as a precursor for a wide variety of chemicals in the polymers and textile
industries. There are several chemical pathways to produce AA, but the most common one is via the
partial oxidation of propylene. The usual mechanism for producing AA utilizes a two step process in
which propylene is first oxidized to acrolein and then further oxidized to AA. Each reaction step
usually takes place over a separate catalyst and at different operating conditions. The reaction
stoichiometry is given below:

C3 H 6 + O2 → C3 H 4O + H 2O
Acrolein
1
C3 H 4O + O2 → C3 H 4O2
2
Acrylic Acid

Several side reactions may occur, most resulting in the oxidation of reactants and products. Some
typical side reactions are given below:

7
C3 H 4O + O2 → 3CO2 + 2 H 2O
2

3
C3 H 4O + O2 → C2 H 4O2 + CO2
2
Acetic Acid
9
C3 H 6 + O2 → 3CO2 + 3H 2O
2

Therefore, the typical process set-up consists of a two-reactor system with each reactor containing
a separate catalyst and operating at conditions so as to maximize the production of AA. The first
reactor typically operates at a higher temperature than the second unit.

Process Description

A base case process is shown in Figure 1. This process produces 50,000 metric tons per year of
99.9 mole % of acrylic acid (AA) product. The number of operating hours should be taken as 8000/yr.
The reactor in the process shown in Figure 1 uses a proprietary catalyst that eliminates the

1
2
production of the intermediate, acrolein. Therefore, this process requires only a single reactor. After
reaction, it is essential to cool the products (reactor effluent) quickly to avoid further homogeneous
oxidation reactions. This is achieved by rapidly quenching the reactor effluent, Stream 6, by injecting
deionized water into it. The homogeneous combustion reactions will not take place so long as the
reactor effluent is cooled to below 100ºC immediately after the reactor. Additional recovery of AA and
acetic acid (a by-product) from the gas, Stream 7, leaving the phase separator (V-301) is achieved in
the absorber, T-301.

The liquid stream, Stream 9, leaving the absorption section is a dilute aqueous acid. It is combined
with the liquid from the phase separator, V-301, to form the feed to the extractor section, Stream 13.
This stream is sent to the liquid-liquid extraction section, X-301, to remove preferentially the acid
fraction from the water prior to purification. There are several columns, exchangers, pumps, vessels,
and other miscellaneous equipment in X-301. Do not to attempt to design this section of the plant.
This part of the design will be contracted out to another company. The organic phase leaving X-301,
Stream 15, contains 99.5 % of the AA and acetic acid in Stream 13 and essentially no water or other
components. This is sent to the acid purification column, T-302, where 95% by mole acetic acid by-
product is produced overhead and 99.9 % by mole AA is produced as a bottom product and cooled
prior to being sent to storage.

The aqueous phase from the extractor, Stream 14, is sent to a wastewater treatment plant, where it
is decontaminated prior to being returned to the environment.

Reaction Kinetics and Reactor Configuration

The reactions taking place are all irreversible. The reaction kinetics for the catalyst used in this
process are given below:
3
C 3 H 6 + O2 → C 3 H 4 O2 + H 2 O Reaction 1
2
Acrylic Acid

5
C3 H 6 + O 2 → C 2 H 4 O 2 + CO 2 + H 2 O Reaction 2
2
Acetic Acid

9
C3 H 6 + O 2 → 3CO 2 + 3H 2 O Reaction 3
2

−E 
where − ri = ko ,i exp  i  p propylene poxygen
 RT 

Partial pressures are in kPa and the activation energies and pre-exponential terms for reactions 1-3 are
given below:

3
 i Ei ko,i
kcal/kmol kmol/m3reactor/h/(kPa)2

1 15,000 1.59×105

2 20,000 8.83×105

3 25,000 1.81×108

The kinetics presented above are valid in the temperature range, 250 – 330ºC. Above 330ºC the
catalyst starts to coke-up (carbon deposits on the surface of the catalysts causing it to deactivate), and
below 250ºC the rate of reaction drops off rapidly. Due to these effects, the catalysts should never be
operated outside of these temperature limits.

The reactor configuration used for this process should be a packed bed reactor. Details about the
design of the reactor are given in the Appendix of this problem statement.

Safety Considerations

It is recommended that the steam-to-propylene ratio at the reactor inlet never be set less than 4:1
on a mole basis. This steam is used to inhibit the formation of coke on the catalyst below temperatures
of 330ºC.

As with any reaction involving the partial oxidation of a fuel-like feed material (propylene)
considerable attention must be paid to the composition of hydrocarbons and oxygen in the feed stream.
This stream is a potential explosion hazard. Operation outside of the explosion limits (LEL and UEL)
is strongly recommended for a packed bed reactor. The explosion limits for propylene in air at 25ºC
are LEL = 2.0 mol% propylene and UEL = 11.1 mol% propylene. At elevated temperatures and using
a 4:1 steam-to-propylene ratio (see above) in the feed, the lower explosion limit (LEL) is changed
significantly. In this case it is easier to define a minimum oxygen concentration (MOC) for the stream.
Below the MOC, flame propagation and hence explosions are not possible. For the packed bed reactor
you can assume an average value of MOC = 5.6 mol % oxygen. The UEL at typical temperatures
used for this reaction is 15.3 mol % propylene.

The second safety concern is that associated with the highly exothermic polymerization of AA
which occurs in two ways. First, if this material is stored without appropriate additives, then free
radical initiation of the polymerization can occur. This potentially disastrous situation is discussed by
Kurland and Bryant [1]. Secondly, AA dimerizes when in high concentrations at temperatures greater
than 90°C. Therefore, process conditions in the separation section (X-301 and T-302) should never
exceed this temperature.

4
CHEMCAD Hints
It is recommended that any simulation for this process be performed using the UNIQUAC K-value
and the SRK enthalpy options on CHEMCAD. These should give reasonable results for preliminary
process design.

For heat exchangers with multiple zones, it is recommended that you simulate each zone with
a separate heat exchanger. Actual equipment may include several zones, so costing should be
based on the actual equipment specifications.

For the distillation column and absorber, you should use the shortcut method (SHOR) to get
estimates for the rigorous distillation simulation (TOWR or SCDS). The shortcut method may be
used for T-302 until an optimum case is near. It is then expected that everyone will obtain a final
design using rigorous simulation of this column.

The fixed bed reactor should be modeled in detail, integrating the differential forms of the
material balance, mechanical energy balance, and heat transfer equations using POLYMATH. Dr.
Miller will give further information on this during ChE 172. The results from CHEMCAD for
this reactor should be compared to the solutions obtained using POLYMATH.

When simulating a process using “fake” streams and equipment, it is absolutely necessary that
the process flow sheet that you present not included any “fake” streams and equipment. It must
represent the actual process.

Project Objective

The objective of this project is to maximize the before-tax profit (BTF) defined below:

BTP = ∑ revenue from products and byproducts − ∑ cost of utilities - ∑ cost of raw materials

− ( 0.3)∑ Installed cost of equipment

All chemical prices can be obtained from the Chemical Marketing Reporter in the Evansdale Library.
Use the prices from the last issue for January 1999. A list of available utilities is attached in the
Appendix.

5
Specific Assignments
General

Optimize the process using decision variables of your choosing. You should choose as
decision variables the design variables most strongly affecting the objective function.

ChE 112 - Separations

Detailed designs of the absorber, T-301, and the acid purification tower, T-302, are required.
For both towers, you should specify the important design parameters, e.g., diameter, height,
number of trays/height of packing, % flooding, operating pressures and pressure drop across the
packing/trays, % open area on trays, etc. Supporting calculations and CHEMCAD outputs
should be provided in the appendix.

ChE 172 - Reactors

A detailed design of a packed bed reactor with countercurrent cooling should be provided in
your final report. Therefore, optimize the process for this reactor. You must choose and discuss
your choice of decision variables. At no place along the length of the process side of the reactor
should the temperature exceed 350°C. Also, the reactor process-side inlet temperature must be at
least 250°C so the reaction can commence. A filler material is available which has the same
density, diameter, void fraction, heat capacity, price, etc., of the catalyst. It is inert and may be
installed within the reactor without catalyzing the reaction. Since CHEMCAD has no allowance
for the Ergun equation, hand estimate the pressure drop on the process side of the reactor and
plug it into CHEMCAD for each simulation. Your design team must provide a copy of the design
equations that include the Ergun equation, and plots of coolant and reactor temperature, pressure,
and concentrations of the chemical species versus reactor length for the optimal reactor design.
Solve these equations using Polymath or another ordinary differential equation solver. Discuss
and compare both the analytical and CHEMCAD design at your optimum operating conditions.
Include a disc copy of your Polymath and CHEMCAD programs with your final report.

References

1. Kurland, J.J. and D.B. Bryant, “Shipboard Polymerization of Acrylic Acid,” Plant Operations
Progress, 6, 4, 203-207 (1987).

6
 Appendix

Cost Data

Equipment Costs (Purchased)

Pumps $630 (power, kW)0.4

Heat Exchangers $1030 (area, m2)0.6

Compressors $770 (power, kW)0.96 + 400 (power, kW)0.6

Turbine $2.18´105 (power output, MW)0.6

assume 65% efficiency

Fired Heater $635 (duty, kW)0.8

assume 80% thermal efficiency
assume can be designed to use any organic compound as a fuel

Vessels $[1.67(0.959 + 0.041P - 8.3´10-6P2)]´10z

z = (3.17 + 0.2D + 0.5 log10L + 0.21 log10L2)
D = diameter, m 0.3 m < D < 4.0 m
L = height, m L/D < 20
P = absolute pressure, bar

Catalyst $2.25/kg

Packed Tower Cost as vessel plus cost of packing

Packing $(-110 + 675D + 338D2)H0.97

D = vessel diameter, m; H = vessel height, m

Tray Tower Cost as vessel plus cost of trays

Trays $(187 + 20D + 61.5D2)

D = vessel diameter, m

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.

7
Equipment Cost Factors

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

Carbon Steel 0.0

Stainless Steel 4.0

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

Raw Materials Costs

Propylene (polymer grade) see Chemical Marketing Reporter

(available as a sat’d vapor at 25ºC)

Product Prices

Acrylic Acid (99.9 mol%) see Chemical Marketing Reporter

(1.0 bar, 40ºC)

Acetic Acid (95 mole% required) see Chemical Marketing Reporter

(1.0 bar, 40ºC)

Utility Costs

Low Pressure Steam (600 kPa saturated) $6.62/1000 kg

Medium Pressure Steam (1135 kPa saturated) $7.31/1000 kg

High Pressure Steam (4237 kPa saturated) $8.65/1000 kg

Natural Gas (446 kPa, 25°C) $3.00/GJ

Fuel Gas (446 kPa, 25°C) $2.75/GJ

Electricity $0.06/kW h

Boiler Feed Water (at 549 kPa, 90°C) $2.54/1000 kg

Distilled Deionized Water $1.00/1000 kg

8
Cooling Water $0.16/GJ
available at 516 kPa and 30°C
return pressure ≥ 308 kPa
return temperature is no higher than 45°C

Refrigerated Water $1.60/GJ

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

Refrigeration $60/GJ

9
 Design Information

Reactor Information

Packed Bed Reactor

Assume the catalyst for the packed bed reactor to have the following physical properties
Catalyst particle diameter, dp = 5 mm
Catalyst particle density, ρcat = 2100 kg/m3
Packing void fraction, ε = 0.45
Heat transfer coefficient from packed bed to tube wall, h = 50 W/m2ºC

Use standard tube sheet layouts as for heat exchangers.

It is suggested that either a molten salt or Dowtherm A heat transfer fluid is used in the reactor shell
to cool the catalyst filled tubes (just like a 1-shell – 1-tube pass heat exchanger with the catalyst filling
the tubes)
Properties of Dowtherm A and molten salt are given in Perry’s Handbook.
Due to the highly exothermic nature of the reaction the maximum tube diameter should be set at 1 inch.
You may wish to dilute the catalyst with inert packing – just assume that this packing has the same
physical properties as the catalyst but does not promote any reactions.

Purchased cost of packed bed reactor = $ 10,000/m2 of heat transfer surface

Solvent Extraction Unit, X-301

The design of the solvent extraction unit is very complicated and beyond the scope of the present
project. However, the following economic information is available for estimating the profitability of
the process:

Installed Cost of X-301 = 1.0×106[flowrate of water in Stream 13 (kmol/h)]0.3

Operating cost of X-301 = 0.7×106[flowrate of water in Stream 13 (kmol/h)]0.7

The above operating cost includes the cost of all utilities used by the unit, plus the cost of treating
the wastewater, Stream 14, and the cost of make-up solvent, Stream 12.

Heat Exchangers

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

10
 situation h (W/m2ºC)

Condensing steam 6000

Condensing organic 1000

boiling water 7500

boiling organic 1000

flowing liquid 600

flowing gas 60

11
 Other Information

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

Unless specifically stated in class, the information in this document is that which is valid for
this project only. Any information in the sophomore projects not specifically stated in this
document is invalid 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 optimal case, the report appendix should contain
details of calculations that are easy to follow. There should be separate appendices for each class,
ChE 112 and ChE 172, each containing calculations appropriate for the respective class. These
may be handwritten if done so neatly. Calculations that cannot be easily followed will lose credit.
A copy of the CHEMCAD output for the final optimized case should also be included in the
Appendix.

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. 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 21, 1999 starting at 11:00 a.m. and running until approximately 3:00
p.m. It is possible that some presentations will be on Thursday, April 22, 1999, beginning at
11:00 am. 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 112 and ChE 172.

The written project report is due by 11:00 a.m. Wednesday, April 21, 1999. Late projects will
receive a minimum of a one letter grade deduction.

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.

12