Chemical Reaction Engineering Dr. Robert P. Hesketh Dr.

Concetta LaMarca

Yousef Ghotok Joseph Havelin Wednesday, 23rd April 2008

Outline
      

Background, Process Reactions, and Rate Expressions Initial Calculations Case I  Reactor Volume Using Simple Reaction Rate Expression Case II  Pressure Drop and Reactor Configuration Case III  Multiple Reactions Case IV  Energy Balance for Multiple Reactions Case V  Optimization of Reactor Design

800 tons per year . By 1985.000 tons per year US Production: 273. and Rate Expressions  Maleic anhydride is a cyclic organic chemical with formula C4H2O3. Bergman and Frisch discovered synthesizing maleic anhydride from n-butane by catalyzing the oxidation reaction.Background.359. Process Reactions. all commercial producers of maleic anhydride in the US used n-butane as their feed.       Primary Use: Synthesis of Unsaturated Polyester Resins N-butane is the most common feedstock used in production of maleic anhydride. Worldwide Production: 1.

and side reactions produce carbon monoxide.Background.  Reactor Type  Fixed-Bed Reactor  Advantages: easy use and low maintenance demand  Disadvantages: hot spots and pockets of diluted butane  .  Catalyst used is vanadium-phosphorus oxide ((VO)2P2O7). and Rate Expressions The partial oxidation of n-butane at the surface of the catalyst produces maleic anhydride and water. carbon dioxide and water. Process Reactions.

Background. Process Reactions. and Rate Expressions  Balanced Stoichiometric Equation: Cases I and II  C4H10 + 3. and V     .1048 · 106 exp(-15649/T) [m3/kgcat-sec] Reactions From the Oxidation of N-Butane: Cases III. IV.5O2 → C4H2O3 + 4H2O Rate Equation: Cases I and II  rM = k 1 · CB Pseudo-First Order Rate Constant: Cases I and II  k1 = 8.

IV and V   Reaction Rate Expressions: Cases III. and Rate Expressions  Reaction Pathway Diagram: Cases III.Background. IV and V  Rate Constants and Parameters . Process Reactions.

Initial Calculations  Assumptions:  Open system at steady state  Negligible changes in kinetic and potential energy  Negligible work  14 days’ worth of downtime per year  Inlet gas 1.7 mol% n-butane  80% conversion rate. side reactions not considered in this preliminary stage  25.000 tons/year production rate  Reference temperature = 25 ºC = 298 K .

00210 .02942 0 .03362 -0.82417 18.09816 .48852 -0.47993 .60568 .00841 -0.61065 4.14099 13.82417 0 Final (kg/s) .Initial Calculations  Stoichiometric Tables:  Molar Stoichiometric Table Species H2O C4H10 O2 N2 C4H2O3 Total  Initial (kmol/s) 0 0.62222 Mass Stoichiometric Table Species H2O C4H10 O2 N2 C4H2O3 Total Initial (kg/s) 0 0.44455 0 18.44455 .12758 0.08231 13.60568 -0.12213 3.00042 Final (kmol/s) .13751 .03362 .01051 0.13751 Change (kg/s) 0.00841 .61802 Change (kmol/s) 0.00841 .94133 0 0.47993 0 0.

5 bar .44  Particle Diameter = 5 mm  Inlet Pressure = 1.Case I  Additional Assumptions: Isothermal Reactor Model to Estimate the Reactor Volume  Isothermal Temperature = 673 K  Bulk Density = 900 kgcat/m3  Void Fraction = 0.

0981338 MALEI-01 0 8.4799 0.0084 .08333 m3  Aspen Plus®: RPLUG Reactor  Stream Flows Substream: MIXED FEED PRODUCT Mole Flow (kmol/sec) VAPOR VAPOR BUTANE 0.0982 0.0021 0.1276 0.08E-03 OXYGEN 0.1276 0.4799 0.0105 2.0105 0.0336756 NITROGEN 0.42E-03 WATER 0 0.4799  Stream Flows Species H2O C4H10 O2 N2 C4H2O3 Initial (kmol/s) 0 0.4799 0 Final (kmol/s) 0.0336 0.Case I  Polymath: Isothermal Packed Bed Reactor Model  Results Variable Conversion Catalyst Wt. Bulk Density VRXTR Value 0.8000043 57675 kg 900 kgcat/m3 64.

1 0 0 10000 20000 30000 Catalyst Weight (kg) 40000 50000 60000 .5 375°C 400°C 425°C 0.7 Conversion of n-butane 0.4 0.8 0.3 450°C 0.6 350°C 0.Case I  Polymath: Isothermal Packed Bed Reactor Model  Effect of Catalyst Weight and Temperature on Conversion Effect of Catalyst Weight and Temperature on Conversion 1 0.9 0.2 0.

Case II  Additional Assumptions: Pressure Drop in the Fixed-Bed Reactor Must not Exceed 1/10 the Initial Pressure  Pressure drop along the length of the reactor .

8008841 60500 kg  Aspen Plus®: RPLUG Reactor  Stream Flows for Single Tube Reactor Substream: MIXED FEED PRODUCT Mole Flow (kmol/sec) VAPOR VAPOR BUTANE 0.0105 0.2222 m3  Stream Flows Species H2O C4H10 O2 N2 C4H2O3 Initial (kmol/s) 0 0.Case II  Polymath: Isothermal Packed Bed Reactor Model  Results Variable Conversion Catalyst Wt.0981009 8.4799 PRODUCT VAPOR 2.0105 0.097918 MALEI-01 0 8.1276 0 0 0.1276 0.4799 0.4799 0 Final (kmol/s) 0.07E-03 0.0105 2.48E-03 WATER 0 0.0336371 0.4799 0.43E-03 0.02E-03 OXYGEN 0.0337133 0.0981675 0.4799 Bulk Density 900 kgcat/m3 VRXTR 67.0020907 0. Value 0.4799 .1276 0.0339223 NITROGEN 0.0084093  Stream Flows for Multi-Tube Reactor Substream: MIXED Mole Flow (kmol/sec) BUTANE OXYGEN MALEI-01 WATER NITROGEN FEED VAPOR 0.

6 0.3 0.1 0 648K 673K 698K 723K 623K Old 648K Old 673K Old 698K Old 723K Old 0 10000 20000 30000 Catalyst Weight (kg) 40000 50000 60000 .8 0.2 0.7 623K Conversion of n-butane 0.9 0.5 0.Case II  Polymath: Isothermal Packed Bed Reactor Model  Effect of Catalyst Weight and Temperature on Conversion Effect of Catalyst Weight and Temperature on Conversion 1 0.4 0.

Case II  Polymath: Isothermal Packed Bed Reactor Model  Effect of Length on Pressure Drop Effect of Length on Pressure Drop 90 80 70 Pressure Drop % 60 50 40 30 20 Dp=7mm Dp=14mm 10 0 0 1 2 3 4 5 6 7 Length of Reactor (m) .

961 8.8 T (K) 673 673 673 Pressure Drop % 8.8 136546.97 .Case II  Comparison of Three Models # of Tubes Polymath Aspen Single Tube Aspen Multi-Tube 1 1 37220 Po (Pa) 150000 150000 150000 Pf (Pa) 135500 136543.97 8.

0187201 Species C4H10 O2 N2 C4H2O3 H2O CO CO2   Aspen Plus®: RPLUG Reactor  Stream Flows for Multi-Tube Reactor Species C4H10 O2 N2 C4H2O3 H2O CO CO2 Initial (kmol/s) 0.00841679 0.05065 0 0 0 0 Final (kmol/s) 0.0845672 0.05065 0.194784 1.0219936 0.0187316  Stream Flows Species C4H10 O2 N2 C4H2O3 H2O CO CO2  Stream Flows for Single Tube Reactor Initial (kmol/s) 0.023 0.80742 212000 kg 900 kgcat/m3 235.0084034 0.00841548 0.0219996 0.1946573 1.023 0.0219674 0.05065 0.00440171 0.0884504 0.0187264 .2793 1.00440319 0.2793 1.0044292 0.05065 0 0 0 0 Final (kmol/s) 0.Case III  Additional Assumptions:  Side reactions and byproducts are taken into consideration Polymath: Isothermal Packed Bed Reactor Model  Results Variable Conversion Catalyst Weight Bulk Density VRXTR Value 0.2793 1.023 0.5556 m3 Initial (kmol/s) 0.1946679 1.05065 0 0 0 0 Final (kmol/s) 0.0845759 0.05065 0.

205 0.211 0.206 0.212 0.Case III  Polymath: Isothermal Packed Bed Reactor Model  Effect of Reaction Temperature on Selectivity of Maleic Anhydride Effect of Reaction Temperature on Selectivity of Maleic Anhydride 0.203 623 633 643 653 663 673 Temperature (K) 683 693 703 713 723 .209 Selectivity 0.208 0.207 0.21 0.204 0.

25 Molar Flows (kmol/s) 0.5 1 1.3 0.2 n-butane 0.1 Carbon Dioxide Oxygen 0.15 Maleic Anhydride Water Carbon Monoxide 0.5 2 2.5 4 4.5 5 .05 0 0 0.5 Reactor Length (m) 3 3.Case III  Aspen Plus®: RPLUG Reactor  Effect of Reactor Length on Molar Flows Effect of Reactor Length on Molar Flows 0.

442666667 .442666667 8.Case III  Comparison of Three Models # of Tubes Polymath Aspen Single Tube Aspen Multi-Tube 1 1 99200 Po (Pa) 150000 150000 150000 Pf (Pa) 137400 137336 137336 T (K) 673 673 673 Pressure Drop % 8.4 8.

Case IV  Additional Assumptions:  Non-isothermal  Energy Balance taken into consideration  Heat exchanger with constant coolant temperature. Ta = 673 K  Overall Heat Transfer Coefficient = 105 J/(m2*K*s) .

05065 0.8091979 173500 kg 900 kgcat/m3 192.023 0.0846545 0.05065 0 0 0 0 Final (kmol/s) 0.0188649 CO2 .0219706 0.023 0.2793 1.0219682 0.2793 1.0188673  Stream Flows Species C4H10 O2 N2 C4H2O3 H2O CO CO2 Initial (kmol/s) 0.00840391 0.05065 0 0 0 0 Final (kmol/s) 0.0846631 0.7778 m3  Aspen Plus®: RPLUG Reactor  Stream Flows for Multi-Tube Reactor Species C4H10 O2 N2 C4H2O3 H2O CO Initial (kmol/s) 0.0043884 0.00438659 0.0084033 0.05065 0.Case IV  Polymath: Non-Isothermal Packed Bed Reactor Model  Results Variable Conversion Catalyst Weight Bulk Density VRXTR Value 0.1945099 1.1945189 1.

5 1 1.5 2 2.5 4 Ta=683 K Ta=653 K Reactor Length (m) .5 3 3.Case IV  Aspen Plus®: RPLUG Reactor  Effect of Varying Ta On Hot Spot Effect of Varying Ta on Hot Spot 730 720 710 700 690 Temperature (K) Ta=673 K Ta=663 K 680 670 660 650 0 0.

00840391 0.7492456  Aspen To (K) 673 673 Ta (K) 673 NA FMAN (kmol/s) 0.2057866 0.00780377 FCO (kmol/s) 0.2063239 Real Isothermal .0077919 Selectivity 0.206338 Conversion 0.01739411 Selectivity 0.0084033 0.8091979 0.02042879 FCO2 (kmol/s) 0.02197067 0.01886732 0.2057963 0.Case IV  Comparison of Isothermal and Real Reactor Models:  Polymath Real Isothermal To (K) 673 673 Ta (K) 673 NA FMAN (kmol/s) 0.

70E+05 6.0254 4.95 0.778 142000 0.Case V  Optimal Reactor Conditions: To (K) Ta (K) Po (Pa) DOverall (m) dIndividual Tube (m) Length (m) Number of Tubes VRXTR (m3) Catalyst Wt (kg) Selectivity 673 673 1.204517  Criteria Met:  Minimal reactor size  Minimized cost  Constant selectivity throughout runs  Gain < 2  Pressure Drop < 10% .158975 74870 157.

Sign up to vote on this title
UsefulNot useful

Master Your Semester with Scribd & The New York Times

Special offer for students: Only $4.99/month.

Master Your Semester with a Special Offer from Scribd & The New York Times

Cancel anytime.