REACCIONES REACCIONES YY REACTORES REACTORES GAS-LÍQUIDO GAS-LÍQUIDO
Prof. Antonio Monzón ARQ. Curso 2008-2009
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Reacciones y Reactores Gas-Líquido 1. Reacciones Gas-Líquido Industriales 2. Tipos de Reactores Gas-Líquido 3. Transferencia de Materia con Reacción Química 3.1. Reacción de pseudo-primer orden 3.2. Regímenes de reacción 3.3. Reacción de segundo orden 3.4. Cálculo del factor de aceleración, E, y de j A
4. Elección del Tipo de Reactor 5. Diseño de Reactores Gas-Líquido
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Reacciones y Reactores Gas-Líquido En un gran número número de reacciones reacciones industrialmen industrialmente te importantes, importantes, se lleva a cabo una reacción entre un gas y un líquido . El objetivo habitual es la obtención de un determinado producto , como por
ejemplo un hidrocarburo clorado tal como el clorobenceno, obtenido por reacción entre el cloro gas y el benceno líquido.
En otras ocasiones, el
líquido es simplemente el medio de reacción , que
puede contener, o no, un catalizador, y los reactantes y productos son todos gaseosos.
En otros casos el objetivo es
separar un componente de una mezcla
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Reacciones y Reactores Gas-Líquido Sistemas de Absorción con Reacción Química
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Reacciones y Reactores Gas-Líquido Procesos Gas-Líquido Industriales Absorción de gases ácidos
Absorción de SO3 en ácido sulfúrico diluido Absorción de NO2 en ácido nítrico diluido Eliminación de CO2 y H 2S por absorción en disoluciones alcalinas
Oxidación de compuestos orgánicos con Oxígeno o aire
Oxidación de parafinas a ácidos Oxidación de p-xileno a ácido tereftálico Oxidación de ciclohexano a ciclohexanona Oxidación de ciclohexano a ácido adípico Oxidación de tolueno a ácido benzóico Oxidación de acetaldehido a ácido acético Oxidación de etileno a acetaldehido Oxidación de cumeno a hidroperóxido de cumeno
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Reacciones y Reactores Gas-Líquido Procesos Gas-Líquido Industriales Halogenaciones Halogenacione s
Halogenación (HBr, HCl) de alcoholes a halogenuros halogenur os de alquilo Halogenación Halogenación (HBr) de olefinas a bromuros de alquilo Halogenación (HCl) de vinilacetileno a cloropreno
Otras reacciones
Absorción de CS 2 en disoluciones acuosas de aminas para obtención de ditiocarbamatos Absorción isobutileno en ácido sulfúrico Absorción butenos en ácido sulfúrico para obtención de butanoles secundarios Absorción de butadieno con complejos cuprosos Absorción de acetileno en disoluciones de ClCu para
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Reacciones y Reactores Gas-Líquido Tipos de Reactores Gas-Líquido
En los reactores gas-líquido alguno de los componentes de la fase gaseosa se disuelve en la fase líquida reaccionando con
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Reacciones y Reactores Gas-Líquido Tipos de Reactores Gas-Líquido
La velocidad global del proceso esta determinada por las velocidades de transferencia de materia en el gas y en el líquido y por la velocidad de la reacción química.
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Reacciones y Reactores Gas-Líquido Tipos de Reactores Gas-Líquido El diseño de un reactor gas-líquido sigue dos etapas: a) La elección del tipo de reactor adecuado
definición de las condiciones de operación
parámetros
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Reacciones y Reactores Gas-Líquido
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Reacciones y Reactores Gas-Líquido Tipos de Reactores Gas-Líquido Torre de relleno En
estas columnas el líquido y el gas pasan en corrientes paralelas, paralelas, o en
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Reacciones y Reactores Gas-Líquido Transferencia de Materia con Reacción Química Flujo molar de A por unidad de volumen, j A Flujo en la fase líquida: Coeficiente individual de transferencia en la fase líquida
' j A = a ⋅ [ N A ]0 = a ⋅ E ⋅ [ N A ]0 = a ⋅ E ⋅ k A L (C Ai − C A L ) Flujo en la fase fase gas: Coeficiente Coeficiente individual individual de transferencia transferencia en en la fase gas
j
k
(
)
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Reacciones y Reactores Gas-Líquido Transferencia de Materia con Reacción Química Coeficientes volumétricos volumétricos globales de transferencia de materia
1
=
K AG a 1 K a
=
1
+
H A
k AG a E ⋅ k A L a 1
E ⋅ k a
+
1 H ⋅ k a
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Reacciones y Reactores Gas-Líquido Transferencia de Materia con Reacción Química
Regímenes de Reacción El valor del módulo Ha determina el régimen de reacción, presentándose tres casos: a) Reacción lenta: Ha<0.3
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Reacciones y Reactores Gas-Líquido Reacción Reacción Reacc ión muy muy lenta: lenta: Ha<0.3 Ha<0.3 E=1
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Reacciones y Reactores Gas-Líquido Reacción Reacc ión muy lenta: Ha<0.3 E=1 p A C B
C A
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Reacciones y Reactores Gas-Líquido Reacción muy lenta: Ha<0.3 E=1
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Reacciones y Reactores Gas-Líquido
Reacción muy lenta: Ha<0.3 '
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Reacciones y Reactores Gas-Líquido Solución Soluciónejemplo ejemplo11(cont.) (cont.)
i 1
2 3 4 5 6 7 8
E 153,0931 92,3270 105,5006 102,0401 102,9087 102,6881 102,7439 102,7298
C Ai 0,31377 0,43123 0,39886 0,40688 0,40484 0,40536 0,40522 0,40526
N 2 239,03 173,92 188,04 184,33 185,26 185,02 185,08 185,07
E ( 23) 92,3270 105,5006 102,0401 102,9087 102,6881 102,7439 102,7298 102,7334
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Reacciones y Reactores Gas-Líquido Solución Soluciónejemplo ejemplo11(cont.) (cont.) i
E
E ( 25)
E ( 26)
E ( 27)
E ( 28)
E ( 29)
1 2
153,0931 92,3270
110,8688 99,3781
112,0298 100,2876
113,5230 102,3835
111,2916 98,0354
112,0329 112,0329 100,2906 100,2906
3
105,5006
102,3529
103,3470
105,2906
101,4393
103,3501 103,3501
4
102,0401
101,6027
102,5767
104,5590
100,5785
102,5797 102,5797
5
102,9087
101,7930
102,7721
104,7447
100,7967
102,7752 102,7752
6
102,6881
101,7448
102,7226
104,6977
100,7414
102,7256 102,7256
7
102,7439
101,7570
102,7352
104,7096
100,7554
102,7382 102,7382
8
102,7298
101,7539
102,7320
104,7066
100,7519
102,7350 102,7350
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Reacciones y Reactores Gas-Líquido Elección Elección del del Tipo Tipo de de Reactor Reactor En la elección elección del tipo de reactor reactor mas apropiad apropiado o para llevar llevar a cabo una reacción gas-líquido han de adecuarse las caracterís características ticas de la reacción, especialmente especialmente de su cinética, cinética, con las características características de los posibles reactores a considerar.
Los aspectos más importantes a considerar de un reactor son:
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Reacciones y Reactores Gas-Líquido Elección Elección del del Tipo Tipo de de Reactor Reactor Características Característicasde delos losreactores reactoresgas-líquido gas-líquido Tipo de Contactor
Area interfacial a 2 3 Volumen de película líquido (m /m ) Torre de Lluvia 1200 10-100, 60 Torre de Relleno 1200 10-350, 100 Torre de Platos 1000 100-200, 150 Torre de Pared Mojada 1000 10-100, 50 Torre de Burbujeo 200 50-600, 200 Tanque Agitado 20 100-2000, 200
ε ε L 3 3
(m /m ) 0.05 0.08 0.15 0.05 0.90 0.98
Volumen de líquido Volumen de película 2-10 10-100 40-100 10-50 150-800 4000-10000
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Reacciones y Reactores Gas-Líquido Elección Elección del del Tipo Tipo de de Reactor Reactor Coeficientes Coeficientesde detransferencia transferenciade demateria materiaen enreactores reactoresgas-líquido gas-líquido Tipo de Contactor
-4
kG .10 3 (mol/m .s.bar) Torre de Lluvia 0,5-2 Torre de Relleno 0,03-2 Torre de Platos 0,5-6 Torre de Pared Mojada 0,5-2 Torre de Burbujeo 0,5-2
(kG .a)10 -1 (s ) 0,05-2 0,003-51 0,5-12 0,5-160 0.25-12
4
k L .10 (m/s) 0,7-1,5 0,4-2 1-20 2-5 1-4
(k L .a)10 -1 (s ) 0,07-1,5 0,04-102 1-40 2-100 0,5-24
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Reacciones y Reactores Gas-Líquido Características Características de de las las Reacciones Reacciones Gas-Líquido Gas-Líquido Caso
Tipo de Reacción
a 2
ε ε L 3
(m /m )
Tipo de reactor
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Reacciones y Reactores Gas-Líquido Ejemplo Ejemplo22
Elegir el reactor mas adecuado para llevar a cabo una reacción gas-líquido de segundo orden global, entre un
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Reacciones y Reactores Gas-Líquido Solución Soluciónejemplo ejemplo22 * Según los datos de la tabla anterior, los valores de k AL son: - para torr torres es de burbu burbujeo: jeo: k AL = 1,0 10-4 - 4.10-4 m/s para pa ra tanque tanquess agitado agitados: s:
k = 0,3.10-4 4 10-4 m/s
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Reacciones y Reactores Gas-Líquido Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Una vez que se ha elegido el tipo de reactor, el diseño del reactor
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Reacciones y Reactores Gas-Líquido Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido (a) Parámetros cinéticos de la reacción. Es necesario conocer los
parámetros cinéticos:
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Correlaciones para el Diseño de Tanques Agitados Ecua Ec uaci ción ón de Ha Hass ssan an an and d Ro Robi bins nson on (1 (197 977) 7) Líquido no-electrolític no-electrolítico o ⋅ 2 QG nimp ε G = 0,11 ⋅ σ
Líquido electrolític electrolítico o
0 , 57
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Reactores tipo Tanque Agitado
Para el diseño de un tanque agitado agitado,, han de utilizarse las
ecuaciones del modelo de mezcla perfecta, perfecta , dado que se ha supuesto que tanto la fase gas como la fase líquida están continua agitación y mezcla.
La suposición de que el gas circula en mezcla perfecta implica que
la corriente del gas de salida del tanque tiene la misma composición que el gas retenido en el interior del mismo
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Reactores tipo Tanque Agitado Balance de materia ' j A = a ⋅ [ N A ]0 = ε L ⋅ (− r A ) = a ⋅ E ⋅ k A L ⋅ (C Ai − C A L ) = ε L ⋅ k 2 ⋅ C A L ⋅ C B L
C A L =
Ley de Henry:
C Ai
k 2 ⋅ C B ⋅ ε L 1 + k A ⋅ a ⋅ E L
L
C Ai =
p Ai H A
Dado que en estos reactores la resistencia de la fase gaseosa es despreciabl despreciablee frente a la de la fase líquida: p A ≅ p A
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Reactores tipo Tanque Agitado a,, se calcula a partir del El valor del área interfacial interfacial por unidad de volumen, volumen, a valor de ε burbujas, d d b. Dado que: ε L y del valor diámetro medio de las burbujas,
ε L = 1 − ε G Asumiendo que hay n hay n b burbujas por unidad de volumen de fase líquida, el volumen de la fracción de fase gas es: 3
ε G = nb ⋅ π ⋅ d b
El área interfacial por unidad de volumen es:
2
a = nb ⋅ π ⋅ d b
Combinando ambas expresiones se obtiene que: a =
6 ⋅ ε G d
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Reactores tipo Tanque Agitado
Este tipo de reactores se utilizan u tilizan en procesos como la oxidación de
hidrocarburos con aire u oxígeno, oxígeno, la oxidación de ciclohexano a ácido adípico, que es un intermed intermediario iario en la fabricación de poliésteres.
Estos procesos son extremadamente peligrosos ya que intervienen hidrocarburos hidrocarburos
volátiles que se mantienen a altas temperaturas en la fase líquida, trabajando a gran presión. Un fallo mecánico del reactor podría dar lugar a un escape de una nube de vapor altamente explosiva, con consecuenci consecuencias as desastrosas.
La determina determinación ción en las condiciones reales de reacción, reacción , de las caracte características rísticas del
equipo de agitación, agitación, del tipo de flujo flujo para el gas y el el líquido, del diámetro diámetro medio de
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Reactores tipo Tanque Agitado. Ejemplo 4
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Solución ejemplo 4
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Solución ejemplo 4 (cont.)
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Solución ejemplo 4 (cont.)
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Solución ejemplo 4 (cont.)
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Reactores tipo Torre de Burbujeo. Distintas relaciones H/D C
Alta H/DC Altos valores de: ε G , uG , a, j A
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Reactores tipo Torre de Burbujeo
Estas torres contienen en mismo volumen de líquido, líquido, el cual ocupa mucha más altura en la torre de menor sección (mayor valor de H/DC ).
Esto tiene dos ventajas: ventajas: a) Es má máss pr proba obabl blee que que el gas, gas, y posiblemente el líquido, líquido, circulen en un flujo próximo al flujo pistón y, b) Asum Asumiendo iendo que el el caudal caudal de entrada entrada de gas gas es el mismo mismo para para ambos tipos de torres, la velocidad superficial del gas a través
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Reactores tipo Torre de Burbujeo
Las torres de burbujeo operan a menor velocidad superficial que
las torres de relleno.
Por otra parte, las torres han de tener un DC >0,15 m. para evitar el
efecto pared y poder aplicar las correlaciones para el cálculo de los parámetros del reactor: k AL, k AG , a y ε G.
En las torres de baja relación H/Dc, la velocidad superficial toma
ya valores próximos al límite de la velocidad de arrastre del líquido, líquido , por tanto en las torres de alta relación H/D no puede aumentarse
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Dispersión Axial en Torres de Burbujeo
Aunque en las torres de burbujeo el modelo de flujo no es el de
flujo pistón con dispersión, se encuentra que este modelo predice bien los resultados experimental experimentales es obtenidos en este tipo de reactores.
Para un sistema bifásico gas-líquido, como el correspondiente a una
torre de burbujeo, el balance de materia en estado no-estacionario para un componente A de la fase gaseosa, teniendo en cuenta los términos
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Dispersión Axial en Torres de Burbujeo D AG
es el coeficiente de dispersión axial de A en la fase gas.
C A es la concentración de A en la fase gas.
El valor de ε εG tiene en cuenta la fracción de área transversal
ocupada por el gas, es decir la región en la que ocurre la dispersión del gas. D AL
se define para la fase líquida de forma similar a D AG.
A velocidades moderadas de la fase líquida, los coeficientes de
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Dispersión Axial en Torres de Burbujeo Para la fase gas, el
coeficiente de dispersión puede estimarse como: 3
uG ⋅ D1,5 D = 50 ⋅
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido
Dispersión Axial en Torres de Burbujeo El
modelo más realista para una torre de burbujeo considera flujo pistón
con dispersión para ambas fases, fases,
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Dispersión Axial en Torres de Burbujeo: Reacciones muy rápidas
Estas reacciones transcurren en su totalidad en la película que
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Dispersión Axial en Torres de Burbujeo: Reacciones muy rápidas
En una reacción muy rápida el reactante A es transferido a la fase
líquida, donde desaparece instantáneamente, a una velocidad que es
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Diseño Diseño de de Reactores Reactores Gas-Líquido Gas-Líquido Dispersión Axial en Torres de Burbujeo: Reacciones muy rápidas Solución analítica del balance de materia: 4 b
1 uG L
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Try Scribd FREE for 30 days to access over 125 million titles without ads or interruptions! Start Free Trial Cancel Anytime.
Trusted by over 1 million members
Try Scribd FREE for 30 days to access over 125 million titles without ads or interruptions! Start Free Trial Cancel Anytime.
Trusted by over 1 million members
Try Scribd FREE for 30 days to access over 125 million titles without ads or interruptions! Start Free Trial Cancel Anytime.