Problems

Managing Heat effects

Optimization
Make the most product from the least reactant
Optimization of Desired Product
Reaction Networks
Maximize yield,
moles of product formed per mole of reactant consumed
Maximize Selectivity
Number of moles of desired product formed per mole of
undesirable product formed
Maximum Attainable Region see discussion in Chapt. 7.
Reactors (pfrs &cstrs in series) and bypass
Reactor sequences
Which come first
 Managing Heat Effects
Reaction Run Away
Exothermic
Reaction Dies
Endothermic

Preventing Explosions
Preventing Stalling
 Temperature Effects
On Equilibrium
On Kinetics
 Equilibrium Reactor-
Temperature Effects
Single Equilibrium
aA +bB rR + sS Vant Hoff eq.

aRr aSs Grxn

o
d ln K eq H rxno
K eq a a exp , 2
a A aB RT dT RT
ai activity of component I
Gas Phase, ai = iyiP,
i== fugacity coefficient of i
Liquid Phase, ai= i xi exp[Vi (P-Pis) /RT]
i = activity coefficient of i
Vi =Partial Molar Volume of i
Overview of CRE Aspects related to Process Design

Le Chateliers Principle
1. Levenspiel , O. (1999), Chemical Reaction Engineering, John Wiley and Sons , 3rd ed.
 Unfavorable Equilibrium

Increasing Temperature Increases the

Rate
Equilibrium Limits Conversion
Overview of CRE Aspects related to Process Design

1. Levenspiel , O. (1999), Chemical Reaction Engineering, John Wiley and Sons , 3rd ed.
 Feed Temperature, Hrxn

Adiabatic
Adiabatic
Cooling

Heat Balance over Reactor

Q = UA Tlm
Reactor with Heating or Cooling

Q = UA T
 Kinetic Reactors - CSTR & PFR
Temperature Effects
Used to Size the Reactor
Used to determine the reactor dynamics
Reaction Kinetics

C
dC j
rj k (T ) Cii
dt i 1

EA
k (T ) ko exp
RT
 PFR no backmixing
Used to Size the Reactor
Xk
dX
V Fko
0
rk

Space Time = Vol./Q

Outlet Conversion is used for flow sheet
mass and heat balances
 CSTR complete backmixing
Used to Size the Reactor

Fko X k
V
rk
Outlet Conversion is used for flow sheet
mass and heat balances
 Unfavorable Equilibrium

Increasing Temperature Increases the

Rate
Equilibrium Limits Conversion
Various Reactors, Various
Reactions X k
dX
V Fko
0
rk

Fko X k
V
rk
Reactor with Heating or Cooling

Q = UA T
Temperature Profiles in a
Reactor
Exothermic Reaction

Recycle
Best Temperature Path
Optimum Inlet Temperature
Exothermic Rxn
 Managing Heat Effects
Reaction Run Away
Exothermic
Reaction Dies
Endothermic

Preventing Explosions
Preventing Stalling
 Inter-stage Cooler

Lowers Temp.

Exothermic Equilibria
 Inter-stage Cold Feed

Lowers Temp
Lowers Conversion

Exothermic Equilibria
Optimization of Desired Product
Reaction Networks
Maximize yield,
moles of product formed per mole of reactant consumed
Maximize Selectivity
Number of moles of desired product formed per mole of
undesirable product formed
Maximum Attainable Region see discussion in Chapt. 6.
Reactors and bypass
Reactor sequences
Reactor Design for Selective
Product Distribution
S,S&L Chapt. 7
 Overview
Parallel Reactions
A+BR (desired)
AS
Series Reactions
ABC(desired)D
Independent Reactions
AB (desired)
CD+E
Series Parallel Reactions
A+BC+D
A+CE(desired)
Mixing, Temperature and Pressure Effects
 Examples
Ethylene Oxide Synthesis
CH2=CH2 + 3O22CO2 + 2H2O

CH2=CH2 + O2CH2-CH2(desired)
 Examples
Diethanolamine Synthesis

/ O\
CH 2 CH 2 NH 3 HOCH 2CH 2 NH 2
/ O\
CH 2 CH 2 HOCH 2CH 2 NH 2 ( HOCH 2CH 2 ) 2 NH (desired )
/ O\
CH 2 CH 2 ( HOCH 2CH 2 ) 2 NH ( HOCH 2CH 2 ) 3 N
 Examples
Butadiene Synthesis, C4H6, from Ethanol

C2 H 5OH C2 H 4 H 2O
C2 H 5OH CH 3CHO H 2
C2 H 4 CH 3CHO C4 H 6 H 2O
 Rate Selectivity
Parallel Reactions
A+BR (desired)
A+BS k D ( D U ) ( D U )
Rate Selectivity SD/U rD
rU CA CB
kU
(D- U) >1 make CA as large as possible
(D U)>1 make CB as large as possible

(kD/kU)= (koD/koU)exp[-(EA-D-EA-U)/(RT)]
EA-D > EA-U T
EA-D < EA-U T
 Reactor Design to Maximize
Desired Product for Parallel Rxns.
 Maximize Desired Product

Series Reactions
AB(desired)CD
Plug Flow Reactor
Optimum Time in Reactor
Fractional Yield
1
CH 3CH 2OH ( g ) O2 CH 3CHO H 2O
2
5
CH 3CHO O2 2CO2 2 H 2O
2

(k2/k1)=f(T)
 Real Reaction Systems
More complicated than either
Series Reactions
Parallel Reactions
Effects of equilibrium must be considered
Confounding heat effects
All have Reactor Design Implications
 Engineering Tricks
Reactor types
Multiple Reactors
Mixtures of Reactors
Bypass
Recycle after Separation
Split Feed Points/ Multiple Feed Points
Diluents
Temperature Management with interstage
Cooling/Heating
PROB.- La reaccin reversible: A R es elemental y tiene los siguientes parmetros
cinticos: k1=7 seg-1 k2=5000 seg-1 E1=10000 cal/mol E2=20000 cal/mol.
Si la conversin es de 0.8:
a) Indique, utilizando un grfico de x vs T con r como parmetro, el rango en que
debera hallarse la temperatura ptima de operacin isotrmica, a fin de alcanzar la
conversin pedida.
b) Determine dicha temperatura ptima.
c) Determine el flujo de calor intercambiado por unidad de tiempo y volumen, sabiendo
que en la alimentacin no ingresa producto.
d) Indique cual debera ser la evolucin ptima, xA vs T, sabiendo que, por cuestiones
constructivas, el reactor no soporta ms de 800 K. Explique cmo calculara el tiempo
de operacin en este caso.
Datos adicionales:
L: 1000 Kg/m3 Cp = 1 kcal/(kg.C) Fraccin molar inicial de A: 0.5
PM: A=100 Solvente = 20
Una reaccin exotrmica A B se lleva a cabo en un reactor tubular no adiabtico en
estado estacionario, donde el calor de reaccin es removido por un refrigerante a la
temperatura Tr (constante a lo largo de la posicin axial). La mezcla reactiva ingresa al
reactor a una temperatura T0= 340 K y su densidad puede asumirse constante. El reactor
opera en condiciones de alta sensibilidad con respecto a Tr, por lo que se desea evaluar
la influencia de esta variable operativa sobre la conversin del reactivo A y sobre la
temperatura del reactor.
a. Grafique conversin vs. y temperatura vs. , para distintas temperaturas del
refrigerante: Tr = 335, 337 y 339 K. Analice el comportamiento observado en las
curvas anteriores.
b. Para cada valor de Tr: Cul es el tiempo espacial () necesario para alcanzar una
conversin del 65 %?
c. Grafique y analice los resultados anteriores en un plano temperatura vs conversin.
Incluir el caso de operacin adiabtica del reactor y comparar con los tres casos no
adiabticos.
Datos: Incremento de temperatura adiabtico: Tad = 146 K
4U / (dt CP) = 0,20 s-1 (constante a lo largo del reactor)
k = k0 exp(- E/RT) s-1 donde, k0 = 3,94 x 10 12. E/R = 11400 K
La siguiente reaccin en fase lquida, reversible, elemental se lleva a cabo en un CSTR: A B
La corriente de entrada tiene un caudal de 10 dm3/s, una concentracin de 2 M de A y una
temperatura de 310 K.
a. Calcule el volumen necesario para alcanzar el 90% de la conversin de equilibrio en un
CSTR operado en forma adiabtica.
b. Ahora considere una serie de reactores con enfriamiento entre etapas de manera que
la corriente es enfriada a 300 K en cada etapa. Cuntos reactores son necesarios para
alcanzar una conversin del 95% asumiendo que se alcanza el 99.9% de la conversin
de equilibrio
Datos: CpA = CpB = 50 cal/mol K Hr = -10000 cal/mol A
k = 5595,892 exp (3093,6/T) Kc = 4,775 x 106 exp (5011.5/T)