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Modeling Of Reactive Distillation

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Modeling of Reactive Distillation

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  1. Modeling of Reactive Distillation
  2. Outline ' Overview of Reactive Distillation Project Overview Tower Design Steady-State Models Dynamic Models and Control Individual Work Column Design and Operation Validation of Models Preliminary Dynamics and Control Studies Future Work
  3. Reactive Distillation Homogeneous or Heterogeneous/ Catalytic Distillation First Patents in 1920s Applied in 1980s to Methyl Acetate ' Common applications: Ethylene Glycol MTBE, TAME, TAA
  4. Favorable Applications Match between reaction and distillation temperatures Difference in relative volatility between product and one reactant Fast reaction not requiring a large amount of catalyst Others: liquid phase reaction, azeotrope considerations,exothermic reactions
  5. Subawalla Approach 1. Decide on a Pre-reactor - Rate of reaction - > 1/2 of initial reaction rate at 80% of equilibrium conversion 2. Pressure 3. Location of Zone 4. Estimate Catalyst - Isothermal Plug-flow reactor with ideal separators 5. Design Tower - Size reaction zone ' Catalyst requirements ' Column diameter - Determine reactant feed ratio - Feed location - Reflux ratio ' High reflux rate - 2-3 times non-rxtive column - Diameter ' Through-put ' Catalyst density
  6. Project Overview Design and Construct TAME Column Validate Steady State Models Develop Dynamic Models Test Control Algorithms
  7. TAME Chemistry Exothermic Equilibrium Limited 45-62% at 50-80 C Azeotropes ' Catalyst: Amberlyst-15 Methanol can inhibit rates. Rihko and Krause (1995) MeOHSa KB 2 TAMESa MeOHSa + 2MIB TAMESa MeOHSa + 2M2B ICB3 TAMESa TAME + sa ICB6 2M2Be2MIB ICB5 Sa is a vacant adsorption site.
  8. Pilot Plant (SRP) 0.152-meter diameter column Finite reflux 7 meters of packing in 3 sections Fisher Deltav Control Koch' s Katamax packing C5 from Cat Cracker Pre-Reactor Makeup MeOH Unreacted C5, MeOH Reactive Distillation Column Recycle 3.7 atm TAME Back - Cracking Reactor Mixing Tank
  9. SRP Pilot Plant 'Koch — Spool section, Katamax, Catalyst ,SRP - $145k 11
  10. Steady-State Multiplicity Bravo et al. (1993) Observed multiple steady-states in TAME CD Hauan et al. (1997) dynamic simulation provided evidence in MT BE system Nijuis et al. (1993) found multiplicity in MTBE system ' Jacobs and Krishna (1993) found multiplicity in MTBE system
  11. Steady-State Distillation Models Trayed Tower: Equilibrium Model L. X. • 1 + V J IYi,j+1 Rate Model NY = NIL Packed Tower: Continuous Model
  12. 0.05 0.04 0.03 0.02 0.01 0 -0.01 2 -0.02 -0.03 -0.04 -0.05 -0.06 TAME Reaction Rates Comparison of Reaction Rates — RADFRAC — RateFRAC Stage (Condenser-I)
  13. TAME Concentration Profile 0.90 0.80 0.70 0.60 0 0.50 0.40 0.30 0.20 0.10 0.00 Comparison of TAME Profiles — RADFRAC — RateFRAC Stage (Condenser-I )
  14. Effective Reaction Rate Traditionally simulations use intrinsic reaction rate. Effective rate is a function of intrinsic rate and diffusion limitations. Molefraction
  15. Fisher Deltav Visual Basic Matlab, Visual Studio State Estimation Temperature Profiles Online Analyzers ' Control Algorithms PID Linear MPC Non-Linear MPC
  16. Individual Work ' Design and Construct RD Column for Novel System Steady State Model Validation Dynamic Models and Control Study
  17. Novel System Kinetic Reaction Not Equilibrium limited Equilibrium Isomers Exothermic Kinetics from CSTR Experiments Feed is dominated by inerts Replace hazardous heterogeneous catalyst 3 Isomer Distribution for Reactive Systems O 50 45 40 35 30 25 20 15 10 5 1 — Plug-flow Reactor — CD Column 2 3 Isomer 4 5
  18. Novel System Data Standard Conditions at 50 psig Over 26 Experiments --—-- Low Average standard Deviation o E Overhead Vapor Temp DA-220-1 DA-220-2 DA-220-3 Reactive Zone DA-220-4 Tl-21 5 DA-210-1 DA-210-2 DA-210-3 DA-210-4 25 20 15 10 5 0 Reboiler Temp
  19. Novel System Data Profiles for 35 psig at Standard Conditions Hi --—-- Lo Average Stnd Dev o Overhead DA-220-1 Vapor Temp DA-220-2 DA-220-3 Reactive Zone DA-220-4 Tl-215 DA-210-1 DA-210-2 DA-210-3 DA-210-4 25 20 15 10 5 0 Reboiler Temp
  20. Simulation Validation - 50 psig Column Data and Simulation for Standard Flows at 50 psig 10 15 20 25
  21. Simulation Validation Simulation and Data for Standard Flows at 35 psig 10 15 20 35 psi 25
  22. Effect of Pressure Effect of Varying Pressure — 25 psig 35 psig — 50 psig — 75 psig 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
  23. Effect of Varying Feed Rate Effect of Varying Reactant Feed Rates — 25 g/min A and 10 g/min B — 75 g/min A and 10 g/min B 1 00 g/min A and 10 g/min B — 150 g/min A and 20 g/min B 10 11 12 13 14 15 16 17 18 19 20 21 22 23
  24. Dynamic Modeling and Control Study Aspen Custom Modeler/ Aspen Dynamics Validate Steady State Solution Validate Dynamic Studies Develop Control Algorithms PID Linear MPC NLMPC
  25. Aspen Custom Modeler ' Formerly Speed-Up and DynaPlus Equation Solver Aspen Properties Plus Tear Variables automatically selected ' Solves Steady-State and Dynamic 1 2 Equations vs. Variables 10 x x Dynamic Events and 10 Task Automation
  26. Validation of Dynamic Simulator Comparison of ACM and Aspen Plus Radfrac Results ACM w/Tear Aspen Plus 1 2 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
  27. Feed Disturbance With Manual o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.75 1.1 C - Production 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Time Hours Stream Results 1.25 1.5 1.75 Time Hours 2 2.1 2.2 2.3 Control 2.4 2.5 2.6 2.7 2.8 2.9 2.75 3 0.25 0.5 2.25 2.5
  28. Control of Reactive Distillation ' Configurations DB LV BV, LB... , Goals Conversion Product Purity LIT v Duty
  29. Control of Reactive Distillation Bartlett and Wahnschafft (1997) Simple Feed-Forward/ Feed-Back PI Scheme Sneesby et al. (1999) Two point control with linear conversion estimator Kumar and Daoutidis (1999) Showed linear controllers unstable for ethylene glycol systems Demonstrated possible Nonlinear MPC scheme
  30. Dependency of Conversion on Reboiler Duty and Reflux Ratio Variability of Conversion with Manipulated Variables 0.8 c 0.6 0 0.4 0.2 1.5 0.5 2.5 x 10 1.5 Molar Reflux Ratio Reboiler Duty (MMkcalhr)
  31. Conversion vs Reboiler Duty Conversion 1 07 04 r Molar Renux Rato of 1.9 Rebo•er (M*cür)
  32. Single Tray Conversion Estimation Dependency of Conversion on Temperature Conversion
  33. Temperature (C) ? O.OOOOOE+OO 5.??????-?8 ? .??????-?7 ? .5?????-?7 2.??????-?7 • 2.5?????-?7 3.5?????-?7 4.??????-?7 4.5?????-?7 5.??????-?7
  34. Feed Disturbance With Manual Control o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.75 1.1 C - Production 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Time Hours Stream Results 1.25 1.5 1.75 Time Hours 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.75 3 0.25 0.5 2.25 2.5
  35. Feed Disturbance with Simple PID 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Control C-Production 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 0.25 0.5 0.75 Time Hours Stream Results 1.25 1.5 1.75 Time Hours 2.25 2.5 2.75
  36. Conclusion and Future Comparison of Reaction Rates TAME Tower Collect Data Validate Models Developing Advanced Models Improvements Work 0.05 0.04 0.03 0.02 0.01 -0.01 2 -0.02 8-0.03 -0.04 -0.05 -0.06 — RADFRAC - - - RateFRAC Stage (Condenser-I) New chemical system Adjust for better dynamic studies Novel System Validate Dynamic Models Develop Control Algorithms o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.1 C-Production 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3 Time Hours

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