Partial Oxidation of Propylene to Acrolein

Final Design Presentation April 23, 2008 Kerri M. May Megerle L. Scherholz Christopher M. Watts

Overview
Introduction Process Background Design Process
Determination of Volume Pressure Drop Multiple Reactions Heat Effects

Optimization Final Design Conclusion

Introduction
Design of fixed-bed reactor Production of acrolein by partial oxidation
CH2 = CH - CH3 + O2 CH2 = CH CHO + H2O

13,500 Mtons/year with a 2 week downtime

Corresponds to 0.007941 kmol/s

Original design: ideal/isobaric/isothermal Final design: pressure drop, multiple reactions and heat effects Optimized using selectivity and gain

Process Background
Literature Operating Conditions (1,2)
Temperature (C) Pressure (atm) Percent Conversion Inlet Percent of Propylene (mol %) 2 Inlet Percent of Air (mol %) 98

250-450

1-3.4

85

Process Background Continued

Assumptions
Parameter Particle Size Bulk Density Packed Bed Void Fraction Tube Diameter Viscosity of Air at 390C Value 5 mm (3) 1415 kg-cat/m3-rxtr (4) 0.38 (4) 1 in. (0.0254 m) 3.15 x 10-5 kg/m-s (5)

Coolant Temperature
Overall Heat Transfer Coefficient

673K (390C)
227 J/W-m2-K (3)

Given for final design Deviations for other models discussed

Process Background Continued

Stoichiometric Flow Rates
Inlet Compositions Outlet Compositions Mole (kmol/s) Propylene Oxygen Inert Nitrogen 0.0093420221 0.0888951791 0.0382188797 Mole (kmol/s) 0.0014013 0.0809545 0.3821888

Acrolein Water
Total

0 0
0.4804259982

0.0079407 0.0079407
0.480426

Process Background Continued

Catalyst chosen based on kinetics
Bismuth molybdate (6)

Co-current Heat Exchanger Fluid

Exothermic reaction Molten Salt used as coolant fluid Sodium tetrasulfide (7)
Melting temperature (294C)

Process Background Continued

Selectivity of Acrolein

Selectivity of Other Profitable Products

Gain

Process Background Continued

Reaction Kinetics of Byproducts (6,8)
Reaction Pathway

Assumptions:
Steady State Single-site oxygen adsorption Rate of oxidation of acrolein to carbon oxides is negligible compared to other rates

Process Background Continued

Reaction rates for the formation of acrolein and byproducts (6,8)
Where: r2 = rate of formation of acrolein, kmol/kgcat-s r3co2 = rate of formation of carbon dioxide, kmol/kgcat-s r3co = rate of formation of carbon monoxide, kmol/kgcat-s r4 = rate of formation of acetaldehyde, kmol/kgcat-s s ka = rate constant for oxygen adsorption, (kmol-m3)1/2/kgcat-s k12 = rate constant for propylene reaction to acrolein, m3/kgcat-s k13co2 = rate constant for propylene reaction to carbon dioxides, m3/kgcat-s k13co = rate constant for propylene reaction to carbon monoxide, m3/kgcat-s k14 = rate constant for propylene reaction acetaldehyde, m3/kgcat-s Co = concentration of oxygen, kmol/m3 Cp = concentration of propylene, kmol/m3 n12 = number of moles of oxygen which react with one mole of propylene to produce acrolein, kmol/kmol n13co2 = number of moles oxygen which react with one mole of propylene to product carbon dioxide, kmol/kmol n13co = number of moles of oxygen which react with one mole of propylene to produce carbon monoxide, kmol/kmol n14 = number of moles of oxygen which react with one mole of propylene to produce acetaldehyde, kmol/kmol

Process Background Continued

Rate Constants at 325, 350, and 390C
Units
ka, (kmol- m3)1/2/kgcat-s k12, m3/kgcat-s k13, m3/kgcat-s k14, m3/kgcat-s

350C
0.5281 0.41 2.190.14 2.70.18 0.2730.21

375C
0.999281.33 3.860.37 2.940.31 0.4520.55

390C
1.460970.15 5.380.35 2.700.27 0.6280.71

Pre-exponential Factors and Activation Energies

Rate Constants Pre-exponential Factor, A Activation Energy, E (kJ/mol)

ka

1073.975 (kmol-m3)1/2/kgcat-s

87.197232

k12
k13co2 k13co k14

631.754 (m3/kgcat-s)
0.00026 (m3/kgcat-s) 43401302 (m3/kgcat-s) 24.78652 (m3/kgcat-s)

77.074937
0 154.2247 71.1104734

Design Process
Reactor 1 Volume Volume (m3) Num. Tubes (1 Dia.) Reactor Dia. (m) Reactor Len. (m) Cat. Weight (kg-cat) 21696.1 N/A 13.6946 147.298 3.07 x 107 Reactor 2 Pressure Drop 4174.6 683600 21 12.05 5.91 x 106 Reactor 3 Mult. Reactions 22.51 17920 3.4 2.4792 31850 Reactor 4 Heat Effects 19.19 16880 3.3 2.24 27150

Particle Size (mm)

Nitrogen Feed (kmol/s) Oxygen Feed (kmol/s) Propylene Feed (kmol/s) Inlet Temp. (C) Inlet Pressure (atm) Pressure Drop (%) Acrolein Prod. (kmol/s) Propylene Conversion (%)

N/A
0.382188797 0.088895179 0.009342022 350 1 N/A 0.007953 85.13

3
0.3821888 0.08889518 0.000934202 350 3 0.37 0.0079428 85.02

5
0.4491963 0.0979275 0.0117625 390 3 7.97 0.0079426 84.99

5
0.439638 0.095847 0.011512 390 3 7.82 0.0079369 85.01

Optimization
Acrolein Selectivity
Greater at increased temperatures Improved when coolant and inlet temperatures are equal Higher pressure, higher selectivity

Other Usable Product Selectivity

Decreased at increased temperatures Favored at lower pressures Greater when coolant temperature less than the inlet temperature

Optimization Continued
Gain
Greater at increased inlet temperature Independent of coolant and inlet temperature relationship

Optimization Conclusion:
Focus on selectivity opposed to gain

Final Design
Operating Conditions
Temperature- 390C Pressure- 3 atm

Reactor Configurations
Volume- 19.08 m3 Diameter- 3.4 m Length- 2.01 m Number of Tubes- 17920 (1 Dia.)

Final Design Continued

Inlet Flows Polymath Aspen Plus (kmol/s) Outlet (kmol/s) Outlet (kmol/s) Nitrogen Oxygen Propylene Acrolein Acetyldehyde Carbon Monoxide Carbon Dioxide Water Total Pressure (Pa) Temperature (K) 0.439638 0.095847 0.011512 0 0 0 0 0 0.546997 303975 663 0.439638 0.0832387 0.0017208 0.0079412 0.0009053 0.0005578 0.0031814 0.0116804 0.5488637 284200 665.5059 0.439638 0.0821155 0.00170713 0.00795529 0.000906563 0.000561055 0.00317457 0.0116909 0.547749008 284080 665.644

Final Design Continued

Polymath Pressure Drop Conversion Selectivity of Acrolein Selectivity of Others Hot Spot Temperature Hot Spot. Location Gain 6.59 % 85.05 % 1.71 0.48 405.257 C 0.18 m 1.16 Aspen Plus 6.54 % 85.17 % 1.71 0.48 405.393 C 0.21 m 1.17

Final Design Continued

Temperature Profile

Conclusions
Reactor volume decreased with complexity increase Selectivity crucial to optimization Final model discussed would operate viably Changed reactor dimensions to optimize final design

Questions?

Works Cited
1. 2. 3. 4. 5. 6. 7. Maganlal, Rashmikant, et al. Vapor phase oxidation of propylene to acrolein. 6437193 United States, August 20, 2002. Chemical Database Property Constants. DIPPR Database [Online]. Available from Rowan Hall 3rd Floor Computer Lab. (Accessed on 1/24/2008). LaMarca, Concetta, PhD. Chemical Reaction Engineering Design Project. February 2008. Chemical Engineering Department, Rowan University, Glassboro. Transient Kinetics from the TAP Reactor System: Application to the Oxidation of Propylene to Acrolein. Creten, Glenn, Lafyatis, David S., and Froment, Gilbert F. Belgium: Journal of Catalysis, 1994, Vol. 154. Chemical Database Property Constants. DIPPR Database [Online]. Available from Rowan Hall 3rd Floor Computer Lab. (Accessed on 1/24/2008). The reaction network for the oxidation of propylene over a bismuth molybdate catalyst. Tan, H. S., Downie, J. and Bacon, D. W. Kingston : The Canadian Journal of Chemical Engineering, 1989, Vol. 67 Physical Properties Data Compilations Relevant to Energy Storage. II. Molten Salts: Data on Single and Multi-Component Salt Systems. G.J. Janz, C.B. Allen, N.P. Bansal, R.M. Murphy, and R.P.T. Tomkins Molten Salts Data Center, Rensselaer Polytechnic Institute, NSRDS-NBS61-II, April 1979 The kinetics of the oxidation of propylene over a bismuth molybdate catalyst. Tan, H. S., Downie, J. and Bacon, D. W. Kingston : The Canadian Journal of Chemical Engineering, 1988, Vol. 66

8.