Appendix I Full process flow diagram - based on Luyben (2009)

Figure 7. Full process flow diagram (PFD) of cumene production

Appendix II Separation section Aspen Simulation

5-RECYCL

3-FUEL 7-PROD CONDENSE DISTL2 DISTL1 2-FFLASH FLASH 6-BOT TOM 8-BOT TOM 4-FDIST1

Figure 8. Aspen simulation model for separation section of cumene production. Table 7. Summary of overall result from Aspen Simulation. Stream No. From To Substream: MIXED Phase: Component Mole Flow BENZENE PROPYLEN PROPANE CUMENE P-DIPB Component Mole Fraction BENZENE PROPYLEN PROPANE CUMENE P-DIPB Component Mass Flow BENZENE PROPYLEN KG/HR KG/HR 8511.26 372.83 8511.26 372.83 664.8 286.29 7846.47 86.54 7843.71 86.54 2.75 0 2.75 0 0 0 KMOL/HR KMOL/HR KMOL/HR KMOL/HR KMOL/HR 108.96 8.86 8.06 94.39 2.79 108.96 8.86 8.06 94.39 2.79 8.51 6.8 5.62 0.83 0 100.45 2.06 2.44 93.56 2.79 100.41 2.06 2.44 0 0 0.04 0 0 93.56 2.79 0.04 0 0 93.43 0.03 0 0 0 0.13 2.75 Vapor Mixed Vapor Liquid Liquid Liquid Liquid Liquid CONDENSER Unit 1 2 CONDENSER FLASH 3 FLASH 4 FLASH DISTL1 5 DISTL1 6 DISTL1 DISTL2 7 DISTL2 8 DISTL2

0.488 0.04 0.036 0.423 0.013

0.488 0.04 0.036 0.423 0.013

0.391 0.313 0.258 0.038 0

0.499 0.01 0.012 0.465 0.014

0.957 0.02 0.023 0 0

0 0 0 0.971 0.029

0 0 0 0.999 0

0 0 0 0.045 0.955

PROPANE CUMENE P-DIPB Component Mass Fraction BENZENE PROPYLEN PROPANE CUMENE P-DIPB Mole Flow Mass Flow Volume Flow Temperature Pressure Vapor Fraction Liquid Fraction Solid Fraction Molar Enthalpy Mass Enthalpy Enthalpy Flow Molar Entropy Mass Entropy Molar Density Mass Density Average Molecular Weight

KG/HR KG/HR KG/HR

355.42 11345.14 452.75

355.42 11345.14 452.75

247.69 99.88 0.48

107.73 11245.26 452.27

107.73 0 0

0 11245.26 452.27

0 11229.75 5.64

0 15.5 446.63

0.405 0.018 0.017 0.539 0.022 KMOL/HR KG/HR L/MIN K BAR 223.06 21037.4 6367.44 623.15 30.25 1 0 0 GJ/KMOL CAL/GM GJ/HR CAL/MOL-K CAL/GM-K MOL/CC GM/CC 0.09 234.68 20.67 -45.96 -0.49 0 0.06 94.31

0.405 0.018 0.017 0.539 0.022 223.06 21037.4 6674.74 363.18 1.75 0.1 0.9 0 0.01 36.99 3.26 -81.64 -0.87 0 0.05 94.31

0.512 0.22 0.191 0.077 0 21.76 1299.14 6259.2 363.18 1.75 1 0 0 0.02 69.6 0.38 -40.67 -0.68 0 0 59.69

0.398 0.004 0.005 0.57 0.023 201.3 19738.26 415.54 363.18 1.75 0 1 0 0.01 34.84 2.88 -86.07 -0.88 0.01 0.79 98.06

0.976 0.011 0.013 0 0 104.91 8037.99 161.92 329.71 1.6 0 1 0 0.05 152.16 5.12 -56.88 -0.74 0.01 0.83 76.62

0 0 0 0.961 0.039 96.38 11700.28 271.16 448.95 1.75 0 1 0 -0.01 -11.44 -0.56 -111.06 -0.91 0.01 0.72 121.4

0 0 0 0.999 0.001 93.5 11238.14 259.74 446.72 1.7 0 1 0 0 -8.36 -0.39 -109.73 -0.91 0.01 0.72 120.19

0 0 0 0.034 0.966 2.88 462.13 11.32 505.51 1.85 0 1 0 -0.06 -82.77 -0.16 -162.1 -1.01 0 0.68 160.39

Appendix III Material and energy balance Condenser

m h P ! m c c pc (Tcb  Tca ) ! q

Where m h = rate of condensation of vapor and P = latent heat of vaporization of vapor. Flash Drum
V ! VoF * F L ! F V dV Sh ! F1  F2 dt M F ( xi C pi )  Q ! M D ( xi C pi )  M D P  M B ( xi C pi )

Distillation Column
F ! DB

F xF ! D x D  B x B
F H F  q r ! D H D  B H B  qc

Appendix IV - Optimization Procedure Tray Diameter and Tray Spacing

93.2117432 93.2117431 Cumene(kmol/hr) Cumene(kmol/hr) 93.2117430 93.2117429 93.2117428 93.2117427 93.2117426 93.2117425 0 1 2
Bubble cap Sieve Valve

93.2117430 93.2117429 93.2117429 93.2117428 93.2117428 93.2117427 93.2117427 93.2117426 93.2117426 3 4 0.4 0.5 0.6 0.7 Tray Spacing (m) Figure 10. Effect of tray spacing on the amount of cumene produced for different type of tray for Distillation 1. 0.3
bubble cap sieve Valve

Tray diameter (m) Figure 9. Effect of tray diameter on the amount of cumene produced for different type of tray for Distillation 1.

93.2117430 93.2117430 Cumene(kmol/hr) 93.2117430 93.2117430 93.2117429 93.2117429 93.2117429 93.2117429 0 1

bubble cap sieve Valve

93.2117432 93.2117431 Cumene (kmol/hr) 93.2117431 93.2117430 93.2117430 93.2117429 93.2117429 4 0.2 0.3

bubble cap sieve valve

2 3 Tray diameter(m)

0.4 0.5 0.6 Tray Spacing (m)

0.7

Figure 11. Effect of tray diameter on the amount of cumene produced for different type of tray for Distillation 2.

Figure 12. Effect of tray spacing on the amount of cumene produced for different type of tray for Distillation 2.

24-inch spacing of sieve tray would contribute to a lower value of capital cost.

Preliminary Operating Condition - Sensitivity Analysis

1 0.9 Fraction (mol or weight) Fraction (mol or weight)
Benzene Recycle

1 0.9
Cumene Purity Benzene in Fuel Gas

0.8 0.7 0.6 0.5 0.4 0.3 345 350 355

0.8 0.7 0.6 0.5 0.4 0.3

Benzene Recycle Cumene Purity

360

365

370

98

100

102

104

106

108

110

Temperature (K) Figure 13. Sensitivity analysis of mol or weight fraction as a function of Temperature.

Distillate Rate Distillation 1 (kmol/hr) Figure 14. Sensitivity analysis of mol or weight fraction as a function of distillate rate of Distillation 1.

1 0.9 Fraction (mol or weight) Fraction (mol or weight) 0.8 0.7 0.6 0.5 0.4 0.3 0 10 20 30 40 Feed Stage Distillation 1 Figure 15. Sensitivity analysis of mol or weight fraction as a function of feed stage of Distillation 1.

1 0.9 0.8
Cumene Purity

Benzene Recycle Cumene Purity Benzene in Fuel Gas

0.7 0.6 0.5 0.4 0.3 0.2 0 10 20

Benzene Recycle Benzene in Fuel Gas

30

40

Feed stage Distillation 2 Figure 16. Sensitivity analysis of mol or weight fraction as a function of feed stage of Distillation 2.

1 0.9 Fraction (mol or weight)

Benzene Recycle

0.8 0.7 0.6 0.5 0.4 0.3 88 90 92

Cumene Purity Benzene in Fuel Gas

94

96

98

Distillate Rate Distillation 2 (kmol/hr) Figure 17. Sensitivity analysis of mol or weight fraction as function of distillate rate of Distillation 2.

Design Optimization - NPV (Net Present Value) Analysis Simplified Economic Analysis NPV ! C I  Where: CI = Initial capital investment N = Total project lifetime (assume 15 years) R = Receipts (product sales) X = Operating costs I = Bank interest rate (assume 10%) t = Tax Rate based on combined Federal and State rate (assume 40.1%)

R  X j 1  t 1  i j j !1
n

800000 700000 600000 500000 Cost ($/yr) 400000 300000 200000 100000 0 0.2 0.7 1.2 1.7 2.2 2.7 Reflux Ratio Figure 18. Fixed Cost, Labor Cost, and Utility Cost as a function of Reflux ratio related to number of stages (From Figure 2) for Distillation 1 3.2 3.7 4.2 4.7 5.2
Fixed Cost Utility Cost

Labor Cost

250000

200000
Fixed Cost Utility Cost

Cost ($/yr)

150000

Labor Cost

100000

50000

0 0.12 0.14 0.16 0.18 0.2 0.22 0.24 0.26 0.28 0.3 Reflux Ratio Figure 19. Fixed Cost, Labor Cost, and Utility Cost as a function of Reflux ratio related to number of stages (From Figure 2) for Distillation 2

Appendix V
Detailed calculation 1. Flash drum area calculation
Table 8. Parameter values for flash drum.

Component Benzene Propylene Propane Cumene p-DIPB

Mole Vapor Fraction y 0.39 0.31 0.26 0.04 0

Mole Liquid Fraction x 0.5 0.01 0.01 0.46 0.01

Liquid Density (kg/m3) 876.5 613.9 507.7 862 854.9

Vapor Density (kg/m3) 876.5 1.81 1.83 862 854.9

Molecular Weight (kg/kgmol) 78.11 42.08 44.1 120.19 162.27

Average Density MWl ! xi * MWi MWv ! yi * MWi Specific Volume Vl ! Density MWl Vl P * MWv Vv ! R * Tdrum Vl ! Permissible vapour velocity (Based on Blackwell Equation) Wv ! V * MWv Wl ! L * MWl Flv ! Vv Wl * Vl Wv
2

xi * MWi Vi

where R ! 8.3143 J/molK

Kdrum ! exp A  B * lnFlv  C * lnFlv  D * (ln( Flv )) 3  E * (ln( Flv )) 4

A ! 1.877478097; B ! 0.814580459; C ! 0.1870744085; D ! 0.0145228667; E ! 0.0010148518

Uperm ! Kdrum * Cross Sectional Area A! Diameter D!

Vl  Vv Vv

V * MWv Uperm * Vv

4* A 4

Height of Drum (Optimum Height of Flash Drum was 3 times Diameter)

H ! 3* D

2. Condenser area calculation (From Perry, 7th Edition) Assuming shell and tube heat exchanger q Uo(TLM (T 1  (T 2 (Th 2  Tc1)  (Th1  Tc 2) ! (TLM ! (Th 2  Tc1) (T 1 ln ln (Th1  Tc 2) (T 2 A! Uo ! 709.78291764 3. Reboiler area calculation (MSH, 7th Edition) Assuming Kettle reboiler A! q W 0.15 * P * VV * ? * g * ( VL  VV )A4 Parameter values (From Perry, 7th Edition):
1 2 1

W m 2 0C

N m N W (at 254 C) ! 0.02762 m W (at 184 C) ! 0.04136

! Heat of Vaporization KJ Kg KJ P (at 254 C) ! 1694.41 Kg P (at 184 C) ! 2000.23

Kg m3 Kg VV ! 5.62267 3 m m g ! 9.81 2 s VL ! 882.68736

4. Murphree Tray Efficiency calculation Calculating Gas diffusivity A0=10-8cm

a= b=

6.286 A0 5.349 A0

K K

cumene benzene

ab=

( a+

b)

Chapman-Enskog equation (BSL 2nd Edition) The feed to the first distillation column contains five components- benzene, propylene, propane, cumene and p-DIPB. The distillate contains mostly benzene while the bottom is dominated with cumene. In calculating for the gas diffusivity, we can simplify the interaction of the particles to simply between the cumene and benzene.

Calculating Liquid Diffusivity

Wilke-Chang equation (BSL 2nd Edition)

 Other Calculations

Calculating the efficiency

mi: slope of the equilibrium curve Equilibrium and operating line are of similar slope. Assume =1

Correcting for entrainment

Correct resulting tray efficiency for the effect of entrainment by Colburns equation

For the calculation of the efficiency of the second distillation column, the same equations are utilized; however several parameters have different values now:
a= b=

8.75 A0 6.286 A0

K K

p-DIPB cumene

Table 9. Summary of tray efficiency calculation.

Variable NTUG NTUL NTUOG EOG DE (ft2/s) EMV Ea Lists of symbols

Tray diameter Column diameter Area of column Active area Weir height Weir length Tray spacing Distance between weir Vapor volumetric flow rate Liquid volumetric flow rate Operating velocity Reflux Ratio Distillate Liquid rate Gas-phase transfer units Liquid-phase transfer units Gas-phase overall transfer units Clear liquid height in plate Schmidt number Pclet number Slope of the equilibrium curve Liquid residence time Average liquid path Local efficiency Eddy effective diffusivity

Distillation 1 1.5704 3.4616 1.0803 0.6605 0.0053 0.91 0.78

Distillation 2 1.1433 7.2662 0.9879 0.6276 0.0139 0.860 0.746

Tt Dt At Aa hw Lw Ts Zt qV qL Uop RR D L NTUG NTUL NTUOG Zc Sc Pe tL Lt EOG DE

Murphree efficiency without entrainment Efficiency with entrainment

EMV Ea

REFERENCES Bird, R. B., Stewart, W. E., & Lightfoot, E. N. (2007). Transport phenomena. New York, N.Y.: J. Wiley. Chemical engineering. (n.d.). Retrieved from http://www.che-digital.com/che/201004#pg1 Hodge, S. A. (2008). U.s. states lead the world in high corporate taxes. Retrieved from http://www.taxfoundation.org/publications/show/22917.html ICIS Chemical Business, http://www.icis.com/Home Luyben, W.L (2010). Design and Control of the Cumene Process, Industrial & Engineering Chemistry Research, 49(2), pp 719734. Retrieved March 13, 2010, from Applied Science Full Text database. McCabe, W. L., Smith, J. C., & Harriott, P. (2005). Unit operations of chemical engineering. New York, N.Y.: McGraw Hill. Perry, R. H. (1997). Perrys chemical engineers handbook. New York, N.Y.: McGraw-Hill. Turton, R., Bailie, R.C., Whiting, W.B., and Shaeiwitz, J.A. (1998). Analysis, synthesis, and design of chemical processes. Upper Saddle River, N.J.: Prentice Hall.