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Energy Balances, Numerical Methods
                                 Design Project

                                  Production of Acetone

Process Description
     Figure 1 is a preliminary process flow diagram (PFD) for the acetone production process.
The raw material is isopropanol. The isopropanol (IPA) feed is a near azeotropic mixture with
water at 88 wt % IPA at 25°C and 1 atm. The feed is heated, vaporized, and superheated in a
heat exchanger (E-401), and it is then sent to the reactor (R-401) in which acetone is formed.
The reaction that occurs is shown below. The reactor effluent is cooled and partially condensed
in a heat exchanger (E-402), and it is then sent to a separation unit (V-401) in which all of the
light gas (hydrogen) enters Stream 7 while the remaining components (acetone, IPA, and water)
distribute according to Raoult’s Law. Some of the acetone in Stream 7 is recovered by absorbing
it into pure water in T-401. The liquid in Stream 12 is distilled to produce “pure” acetone in
Stream 13 and waste water (containing IPA) in Stream 14. The desired acetone production rate
is 15,000 metric tons/yr.

Process Details
Feed Streams

   Stream 1:       isopropyl alcohol, liquid, 88 wt % IPA, 12 wt % water, 1 atm, 25°C

   Stream 9:       distilled process water, 3 bar, 25°C

Effluent Streams

   Stream 11:      off-gas stream to incinerator, credit may be taken for LHV of fuel

   Stream 13:      acetone product, liquid, 99.9 mol% purity, must contain 99.5 mol% of acetone
                   in Stream 12

   Stream 14:      waste water stream, treatment cost $50.00/106 kg
                   must contain less than 0.04 mole fraction IPA and acetone
3

Equipment

Heat Exchanger (E-401):

   This unit heats, vaporizes, and superheats the feed to 235°C at 2.2 bar. A pump, which is
   not shown and which you do not have to be concerned with this semester, increases the
   pressure of the feed to the indicated pressure.

Reactor (R-401):

   Following development of a new catalyst, only the following reaction occurs:

                        CH 3CHOHCH 3 → CH 3COCH 3 + H 2
                                                                                         (1)
                             IPA              acetone

   The reaction occurs at 350°C, and the conversion at this temperature is 90%. The reactor
   exit pressure is 1.9 bar. The reaction is endothermic with heat being supplied by hot
   molten salt.

Fired Heater (H-401):

   This unit heats the molten salt that provides heat to the reactor. Energy is supplied by
   combustion of natural gas, which may be assumed to be pure methane. The molten salt
   enters the fired heater at 360°C (Stream 3) and leaves the fired heater at 410°C (Stream
   4). The heat capacity of molten salt is 1.56 J/g K.

Heat Exchanger (E-402):

   This unit cools and partially condenses the reactor effluent. None of the hydrogen
   condenses. The exit pressure may be at any pressure below 1.6 bar and any temperature
   below 50°C that can be achieved by using cooling water (cw) or refrigerated water (rw) is
   possible.

Separation Vessel (V-401):

   This unit disengages the vapor and liquid effluent from E-402. In this separator, all
   hydrogen in the feed enters the vapor phase, Stream 7. All other components distribute
   according to Raoult’s Law at the temperature and pressure of E-402. The combination of
   E-402 and V-401 is often called a flash operation.

Absorber (T-401):

   Here, additional acetone is recovered by absorption into pure process water. The
   absorber operates at the same temperature and pressure as V-401 Stream 11 contains all
   of the hydrogen and the acetone and water which are not in Stream 10. Stream 10
4

   contains all of the IPA in Stream 7, 95% of the water in Streams 7 and 9. The amount of
   acetone in Stream 10 can be calculated from:

                                    y stream 11       1− A
                                                  =                                        (2)
                                     ystream 7        1 − A6

   where y is the mole fraction of acetone,

                                                   L
                                           A=                                              (3)
                                                  mV

   L is the total molar flowrate of liquid in Stream 9, and V is the total molar flowrate of
   liquid in Stream 7. The parameter m is an equilibrium constant that is a function of
   temperature and pressure

                                               3598 
                                    exp10.92 −      
                                 m=             T 
                                                                                           (4)
                                            P

   where T is in Kelvin and P is in atm.

Distillation Column (T-402):

   In this distillation column, the acetone, IPA, and water in Stream 12 are separated. The
   column operates at 1.4 bar. Specifications are as follows. The acetone must be 99.9
   mol% pure and 99.5 mol% of the acetone in the feed must be recovered in Stream 13.
   Stream 14 contains most of the water and IPA from Stream 12.

Heat Exchanger (E-403):

   In this heat exchanger, the contents of Stream 13 are condensed from saturated vapor to
   saturated liquid at a rate three times the flow of Stream 13. The cost is for the amount of
   cooling water needed to remove the necessary energy.

Heat Exchanger (E-404):

   In this heat exchanger, you may assume that one-half of the flow of Stream 14 is
   vaporized from saturated liquid to saturated vapor at 1.4 bar and is returned to the
   column. The cost is for the amount of low-pressure steam needed to supply the necessary
   heat.

An additional distillation column (T-403):

   You may choose to add an additional distillation column to process Stream 14 further.
   This column can recover a near azeotropic mixture of water and IPA (88 wt% IPA – with
5

       all of the acetone remaining in Stream 14) out of the top, with residual water and IPA out
       the bottom. If you choose to do this, you must recycle the IPA/water top product to the
       beginning of the process. The bottom product goes to waste water treatment. This
       distillation column needs two heat exchangers with similar energy specifications to E-403
       and E-404. This distillation column operates at 1.2 bar. You should only include this
       column if you decide it to be economically attractive

   Other Equipment

       It is required for two streams that mix to 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 at no cost.
       Flow occurs from higher pressure to lower pressure. Pumps increase the pressure of
       liquid streams, and compressors increase the pressure of gas streams. You may assume
       that a pump exists where ever you need one. For this semester only, there is no cost for
       pumps.


Equipment Costs

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


                           Equipment                     Installed Cost
                                                        in millions of $

                         Reactor, R-401                       1.5
                        Absorber, T-401                       0.03
                  Acetone distillation column T-              2.8
                                 402
                      including reboiler and
                            condenser
                  IPA distillation column T-403               0.1
                             (if added)
                      including reboiler and
                            condenser
                          Vessel, V-401                       0.07
                       Any heat exchanger                     0.05

                              Fired heater installed cost in dollars:
                                             11× 10 x
                                              where
                                      x = 2.5 + 0.8 log10 Q
                                 where Q is the heat duty in kW
6



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

   Process Water                                           $0.04/1000 kg
      available at 300 kPa and 25°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
          For IPA: 145 J/mole K

       Vapor Heat Capacity
          for IPA: 27.87 + 0.176 + 2.12´10-4T 2 - 4.09´10-7T 3 J/mole K    T (K)

       Vapor Pressures – Antoine’s Equation constants

                                                      B
                                      ln p* = A −                                       (5)
                                                    T +C

       (p* in mm Hg, T in K)
7


                                     A                 B             C
                     IPA           17.664            3109.3       -73.546
                   acetone         16.732            2975.9       -34.523


       Normal heat of vaporization
          for IPA: 56,900 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 cost for acetone is $0.88/kg. The cost for IPA is $0.72/kg IPA in the feed solution. The
value for hydrogen is $35/1000 std m3.

   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 early March.

   The capital cost annuity is defined as follows:

                              capital cost annuity = 0.2(capital cost)

Optimization
    We will learn optimization methods in numerical methods class. 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.
8

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 that 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 21, 1999,
between 11:00 a.m. and 3:00 p.m.

    As mentioned in the cover memo, the written project report is due on Monday, April 26,
1999, at 1:00 p.m. The oral reports will be Monday, April 26, 1999 (ChE 38 class) and
Wednesday, April 28, 1999 (ChE 41 class). There will be a project review on Thursday, April 30,
1999 (ChE 38 class). In addition, everyone must attend the senior design presentation on
Tuesday, April 27, 1999, unless you have organic chemistry or physics lab at that time.
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.

    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.
9

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 (7th ed.),
   McGraw-Hill, New York, 1997.

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Full design for acetone production

  • 1. Energy Balances, Numerical Methods Design Project Production of Acetone Process Description Figure 1 is a preliminary process flow diagram (PFD) for the acetone production process. The raw material is isopropanol. The isopropanol (IPA) feed is a near azeotropic mixture with water at 88 wt % IPA at 25°C and 1 atm. The feed is heated, vaporized, and superheated in a heat exchanger (E-401), and it is then sent to the reactor (R-401) in which acetone is formed. The reaction that occurs is shown below. The reactor effluent is cooled and partially condensed in a heat exchanger (E-402), and it is then sent to a separation unit (V-401) in which all of the light gas (hydrogen) enters Stream 7 while the remaining components (acetone, IPA, and water) distribute according to Raoult’s Law. Some of the acetone in Stream 7 is recovered by absorbing it into pure water in T-401. The liquid in Stream 12 is distilled to produce “pure” acetone in Stream 13 and waste water (containing IPA) in Stream 14. The desired acetone production rate is 15,000 metric tons/yr. Process Details Feed Streams Stream 1: isopropyl alcohol, liquid, 88 wt % IPA, 12 wt % water, 1 atm, 25°C Stream 9: distilled process water, 3 bar, 25°C Effluent Streams Stream 11: off-gas stream to incinerator, credit may be taken for LHV of fuel Stream 13: acetone product, liquid, 99.9 mol% purity, must contain 99.5 mol% of acetone in Stream 12 Stream 14: waste water stream, treatment cost $50.00/106 kg must contain less than 0.04 mole fraction IPA and acetone
  • 2.
  • 3. 3 Equipment Heat Exchanger (E-401): This unit heats, vaporizes, and superheats the feed to 235°C at 2.2 bar. A pump, which is not shown and which you do not have to be concerned with this semester, increases the pressure of the feed to the indicated pressure. Reactor (R-401): Following development of a new catalyst, only the following reaction occurs: CH 3CHOHCH 3 → CH 3COCH 3 + H 2 (1) IPA acetone The reaction occurs at 350°C, and the conversion at this temperature is 90%. The reactor exit pressure is 1.9 bar. The reaction is endothermic with heat being supplied by hot molten salt. Fired Heater (H-401): This unit heats the molten salt that provides heat to the reactor. Energy is supplied by combustion of natural gas, which may be assumed to be pure methane. The molten salt enters the fired heater at 360°C (Stream 3) and leaves the fired heater at 410°C (Stream 4). The heat capacity of molten salt is 1.56 J/g K. Heat Exchanger (E-402): This unit cools and partially condenses the reactor effluent. None of the hydrogen condenses. The exit pressure may be at any pressure below 1.6 bar and any temperature below 50°C that can be achieved by using cooling water (cw) or refrigerated water (rw) is possible. Separation Vessel (V-401): This unit disengages the vapor and liquid effluent from E-402. In this separator, all hydrogen in the feed enters the vapor phase, Stream 7. All other components distribute according to Raoult’s Law at the temperature and pressure of E-402. The combination of E-402 and V-401 is often called a flash operation. Absorber (T-401): Here, additional acetone is recovered by absorption into pure process water. The absorber operates at the same temperature and pressure as V-401 Stream 11 contains all of the hydrogen and the acetone and water which are not in Stream 10. Stream 10
  • 4. 4 contains all of the IPA in Stream 7, 95% of the water in Streams 7 and 9. The amount of acetone in Stream 10 can be calculated from: y stream 11 1− A = (2) ystream 7 1 − A6 where y is the mole fraction of acetone, L A= (3) mV L is the total molar flowrate of liquid in Stream 9, and V is the total molar flowrate of liquid in Stream 7. The parameter m is an equilibrium constant that is a function of temperature and pressure  3598  exp10.92 −  m=  T  (4) P where T is in Kelvin and P is in atm. Distillation Column (T-402): In this distillation column, the acetone, IPA, and water in Stream 12 are separated. The column operates at 1.4 bar. Specifications are as follows. The acetone must be 99.9 mol% pure and 99.5 mol% of the acetone in the feed must be recovered in Stream 13. Stream 14 contains most of the water and IPA from Stream 12. Heat Exchanger (E-403): In this heat exchanger, the contents of Stream 13 are condensed from saturated vapor to saturated liquid at a rate three times the flow of Stream 13. The cost is for the amount of cooling water needed to remove the necessary energy. Heat Exchanger (E-404): In this heat exchanger, you may assume that one-half of the flow of Stream 14 is vaporized from saturated liquid to saturated vapor at 1.4 bar and is returned to the column. The cost is for the amount of low-pressure steam needed to supply the necessary heat. An additional distillation column (T-403): You may choose to add an additional distillation column to process Stream 14 further. This column can recover a near azeotropic mixture of water and IPA (88 wt% IPA – with
  • 5. 5 all of the acetone remaining in Stream 14) out of the top, with residual water and IPA out the bottom. If you choose to do this, you must recycle the IPA/water top product to the beginning of the process. The bottom product goes to waste water treatment. This distillation column needs two heat exchangers with similar energy specifications to E-403 and E-404. This distillation column operates at 1.2 bar. You should only include this column if you decide it to be economically attractive Other Equipment It is required for two streams that mix to 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 at no cost. Flow occurs from higher pressure to lower pressure. Pumps increase the pressure of liquid streams, and compressors increase the pressure of gas streams. You may assume that a pump exists where ever you need one. For this semester only, there is no cost for pumps. Equipment Costs The equipment costs for the acetone plant are given below. Each cost is for an individual piece of equipment, including installation. Equipment Installed Cost in millions of $ Reactor, R-401 1.5 Absorber, T-401 0.03 Acetone distillation column T- 2.8 402 including reboiler and condenser IPA distillation column T-403 0.1 (if added) including reboiler and condenser Vessel, V-401 0.07 Any heat exchanger 0.05 Fired heater installed cost in dollars: 11× 10 x where x = 2.5 + 0.8 log10 Q where Q is the heat duty in kW
  • 6. 6 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 Process Water $0.04/1000 kg available at 300 kPa and 25°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 For IPA: 145 J/mole K Vapor Heat Capacity for IPA: 27.87 + 0.176 + 2.12´10-4T 2 - 4.09´10-7T 3 J/mole K T (K) Vapor Pressures – Antoine’s Equation constants B ln p* = A − (5) T +C (p* in mm Hg, T in K)
  • 7. 7 A B C IPA 17.664 3109.3 -73.546 acetone 16.732 2975.9 -34.523 Normal heat of vaporization for IPA: 56,900 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 cost for acetone is $0.88/kg. The cost for IPA is $0.72/kg IPA in the feed solution. The value for hydrogen is $35/1000 std m3. 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 early March. The capital cost annuity is defined as follows: capital cost annuity = 0.2(capital cost) Optimization We will learn optimization methods in numerical methods class. 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.
  • 8. 8 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 that 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 21, 1999, between 11:00 a.m. and 3:00 p.m. As mentioned in the cover memo, the written project report is due on Monday, April 26, 1999, at 1:00 p.m. The oral reports will be Monday, April 26, 1999 (ChE 38 class) and Wednesday, April 28, 1999 (ChE 41 class). There will be a project review on Thursday, April 30, 1999 (ChE 38 class). In addition, everyone must attend the senior design presentation on Tuesday, April 27, 1999, unless you have organic chemistry or physics lab at that time. 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. 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.
  • 9. 9 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 (7th ed.), McGraw-Hill, New York, 1997.