MXPA01000735A - Produccion de gas de sintesis mediante reformacion de vapor. - Google Patents
Produccion de gas de sintesis mediante reformacion de vapor.Info
- Publication number
- MXPA01000735A MXPA01000735A MXPA01000735A MXPA01000735A MXPA01000735A MX PA01000735 A MXPA01000735 A MX PA01000735A MX PA01000735 A MXPA01000735 A MX PA01000735A MX PA01000735 A MXPA01000735 A MX PA01000735A MX PA01000735 A MXPA01000735 A MX PA01000735A
- Authority
- MX
- Mexico
- Prior art keywords
- reactor
- gas
- steam reforming
- reforming catalyst
- effluent
- Prior art date
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
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Abstract
Un procedimiento para la preparacion de gas rico en hidrogeno y monoxido de carbono, mediante reformacion de vapor de un material de abastecimiento de hidrocarburo en presencia de un catalizador reformador de vapor, soportado como pelicula delgada sobre la pared de un reactor, que comprende los pasos de (a) hacer pasar de manera opcional un gas de proceso del material de abastecimiento de hidrocarburo a traves de un primer reactor, con una pelicula delgada de catalizador reformador de vapor soportada sobre paredes del reactor en relacion conductora de calor con una corriente de gas caliente; (b) hacer pasar efluente desde el primer reactor a un reactor tubular subsecuente provisto con una pelicula delgada de catalizador reformador de vapor y/o comprimidos de catalizador reformador de vapor, y calentado mediante quemado de combustible, obteniendo asi un efluente de gas de vapor parcialmente reformado y una corriente de gas caliente de gas de chimenea; (c) hacer pasar el efluente desde el segundo reactor a un reformador autotermico; y (d) extraer del reformador autotermico una corriente de gas caliente, de gas de producto rico en hidrogeno y monoxido de carbono.
Description
PRODUCCIÓN DE GAS DE SÍNTESIS MEDIANTE REFORMACIÓN DE VAPOR
MEMORIA DESCRIPTIVA
La presente invención está dirigida a la producción de gas de síntesis mediante reformación de vapor de un material de abastecimiento de hidrocarburo en contacto con material catalizado. El término material catalizado se usa para un sistema catalizador en donde una capa de catalizador se fija sobre una superficie de otro material, por ejemplo superficies metálicas. El otro material sirve como la estructura de soporte que da fuerza al sistema. Esto permite diseñar formas de catalizador las cuales no tendrían suficiente fuerza mecánica por sí mismas. El sistema de la presente consta de tubos en los cuales una capa delgada de catalizador reformador se coloca sobre la pared interior. Arreglos alternativos pueden comprender tubos con una capa de catalizador sobre el exterior, placas con recubrimiento de catalizador u otras formas adecuadas. El gas de síntesis se produce a partir de hidrocarburos mediante reformación de vapor por las reacciones (1 )-(3):
m C H n H O CO + — H - ?H (1) n m 2 298
CO + H 0 ^ CO H ?H 41 U/ ol (2) 2 298
CH + H 0 C0 + 3 H - ?H 206 kJImol (3)
4 2 2 298 J
Un segundo método para producción de gas de síntesis es reformación autotérmica (ATR, por sus siglas en inglés). En reformación autotérmica, la combustión de la alimentación de hidrocarburo se lleva a cabo con cantidades de oxígeno subestequiométricas, mediante reacciones de flama en una zona de combustión de quemador y, subsecuentemente, reformación de vapor del material de abastecimiento parcialmente quemado en un lecho fijo de catalizador reformador de vapor. El oxidante puede ser aire, aire enriquecido u oxígeno puro. Un tercer método para producción de gas de síntesis, es la combinación de hacer pasar primero la alimentación de hidrocarburo a través de un lecho fijo de catalizador reformador y subsecuentemente, hacer pasar la alimentación parcialmente reformada a través de un reformador autotérmico. El lecho fijo puede comprender un número de tubos colocados en un horno encendido. Esta combinación se denomina reformación en dos pasos o reformación primaria seguida por reformación secundaria, y es particularmente adecuada para producción de gas de síntesis para producción de metanol y amoniaco. Controlando la cantidad de reformación que ocurre en el reformador de vapor de lecho fijo antes de ATR, puede producirse gas de síntesis que tenga la estequiometría correcta para síntesis de metanol, o un gas de síntesis que tenga la relación correcta de hidrógeno a nitrógeno para síntesis de amoniaco. La tecnología de reformación de vapor de la técnica más avanzada hace uso de catalizador reformador en forma de comprimidos de varios tamaños y formas. Los comprimidos de catalizador se colocan en reactores de lecho fijo (tubos reformadores). La reacción reformadora es endotérmica. En reformadores convencionales, el calor necesario para la reacción se suministra desde el medio ambiente fuera de los tubos, usualmente mediante una combinación de radiación y convección hacia el lado exterior del tubo reformador. El calor se transfiere al lado interior del tubo mediante conducción de calor a través de la pared del tubo, y se transfiere a la fase de gas por convección. Finalmente, el calor se transfiere desde la fase de gas al comprimido de catalizador por convección. La temperatura del catalizador puede ser más de 100°C inferior a la temperatura de la pared interior del tubo en la misma posición axial del tubo reformador. Se ha encontrado que el transporte de calor es más eficiente cuando se usa material catalizado en el procedimiento de reformación de vapor. El transporte de calor hacia el catalizador ocurre por conducción desde la pared interior del tubo. Este es un mecanismo de transporte mucho más eficiente que el transporte por convección mediante la fase de gas. El resultado es que las temperaturas de la pared interior del tubo y el catalizador son casi idénticas (la diferencia por debajo de 5°C). Además, el grosor del tubo puede reducirse, véase más adelante, lo cual hace más pequeña la diferencia de temperatura entre el lado interior y el lado exterior del tubo reformador. Por lo tanto, es posible tener tanto una temperatura de catalizador más alta como una temperatura de tubo más baja, siendo las demás condiciones las mismas cuando se cambian los tubos reformadores convencionales por tubos de material catalizado. Es deseable una temperatura de pared exterior de tubo baja, debido a que esto prolonga la vida del tubo. Una temperatura de catalizador alta es ventajosa debido a que la velocidad de reacción aumenta con la temperatura, y debido a que el equilibrio de reacción (3) se desplaza a la derecha dando como resultado un mejor uso de la alimentación. La caída de presión en el tubo reformador catalizado es mucho menor que en el caso convencional para el mismo diámetro de tubo. Esto permite el uso de reactores de formas no tradicionales, por ejemplo tubos con diámetro pequeño, y seguir manteniendo una caída de presión aceptable. Un diámetro de tubo menor da como resultado una vida más larga para el tubo, tolera temperaturas más altas y reduce el consumo de material del tubo. Finalmente la cantidad de catalizador se reduce cuando se usan tubos reformadores de material catalizado, en comparación con el reformador convencional con una lecho fijo de catalizador reformador.
La cantidad pequeña de catalizador dicta el uso de un material de abastecimiento libre de venenos catalizadores. Esto puede obtenerse por ejemplo enviando el material de abastecimiento a través de un prereformador. La figura 1 muestra un ejemplo de una planta que produce gas de síntesis. La alimentación 2 se precalienta, se desulfura en la unidad 4, se mezcla con vapor de proceso 6, y luego se calienta antes de entrar en un prereformador adiabático 8. La corriente efluente del prereformador 8 se calienta en un serpentín intercambiador arreglado en el canal de gas de chimenea 12, y se envía al reformador tubular 14, en donde ocurre la conversión de metano a hidrógeno, monóxido de carbono y dióxido de carbono. El gas efluente se hace pasar al reformador autotérmico 16, en donde se lleva a cabo combustión con vapor oxidante 18. El procesamiento del gas efluente 20 corriente abajo del reformador autotérmico, depende del uso que se vaya a dar al producto. Material catalizado puede usarse en dos de las unidades mostradas en la figura 1 : 1. En el serpentín recalentador 10 para calentamiento del gas efluente del prereformador antes de entrar al reformador tubular 14. 2. En el reformador tubular 14. Esta invención provee un procedimiento para la preparación de gas rico en hidrógeno y monóxido de carbono, mediante reformación de vapor de un material de abastecimiento de hidrocarburo en presencia de un catalizador reformador de vapor, soportado como una película delgada sobre la pared de un reactor, que comprende los pasos de: (a) hacer pasar de manera opcional un gas de proceso de un material de abastecimiento de hidrocarburo a través de un primer reactor con una película delgada de catalizador reformador de vapor, soportada sobre paredes del reactor, en relación conductora de calor con una corriente de gas caliente; (b) hacer pasar efluente del primer reactor a un reactor tubular subsecuente provisto con una película delgada de catalizador reformador de vapor y/o comprimidos de catalizador reformador de vapor, y calentado mediante quemado de combustible, obteniendo así un efluente de gas de vapor parcialmente reformado y una corriente de gas caliente de gas de chimenea; (c) hacer pasar el efluente desde el segundo reactor a un reformador autotérmico; y (d) extraer del reformador autotérmico una corriente de gas caliente de gas de producto rico en hidrógeno y monóxido de carbono.
EJEMPLO 1
Se probó un reactor reformador de material catalizado. La unidad de prueba consta de un sistema para proveer las alimentaciones al reactor, el reactor en sí, y equipo para tratamiento posterior y análisis del gas efluente del reactor. El reactor consta de un tubo de 6.35 mm que tiene 1050 mm de longitud, el cual está en los 500 mm de en medio, recubierto sobre la pared interior con catalizador reformador de vapor de níquel RKNR. El catalizador tiene la misma composición que el catalizador reformador de vapor en forma de comprimidos RKNR disponible de Haldor Topsoe A/S. El grosor de la capa de catalizador es 0.31 mm. El tubo del reactor catalizado se coloca en una caja hecha de metal sólido, la cual tiene un orificio que se cierra en forma hermética alrededor del tubo catalizador. Un número de ranuras fresadas, en las cuales se colocan termopares, se hace a lo largo del orificio. Uno de los termopares es móvil de modo que pueda obtenerse un perfil de temperatura de la pared del tubo catalizado. De manera adicional, se colocan termopares en el canal de gas en el tubo catalizado, que miden la temperatura del gas en la entrada y salida de la zona catalizada. El reactor con cubierta se coloca en un horno calentado eléctricamente, en el cual la temperatura puede controlarse por separado en 6 zonas diferentes. Los vapores de alimentación constan de hidrógeno, metano, dióxido de carbono y vapor. Los vapores de alimentación se mezclan y precalientan antes de entrar al reactor. Después del reactor, la corriente de gas efluente se enfría, el agua condensada se separa del gas, y la composición de gas se mide mediante un cromatógrafo de gases.
Se probaron dos grupos de condiciones. Un grupo a temperatura más baja para simular el uso de material catalizado en un serpentín precalentador (prueba No 1 ), y un grupo a temperatura más alta para simular un reformador tubular (prueba No 2). Las condiciones se muestran en el cuadro 1. La presión fue en ambos casos 28 bars manométricos. El perfil de temperatura impuesto a la pared del reactor, medido mediante el termopar móvil se muestra en la figura 2.
CUADRO 1
La composición de gas efluente medida se muestra en el cuadro 2. La composición de gas es sobre base seca.
CUADRO 2
El gas efluente en ambos casos, está en equilibrio con respecto a la reacción reformadora a la temperatura del gas de salida dentro de incertidumbre experimental. Esto demuestra que puede obtenerse en un reactor de material una conversión similar a un reactor de lecho fijo.
Claims (2)
1.- Un procedimiento para la preparación de gas rico en hidrógeno y monóxido de carbono, mediante reformación de vapor de un material de abastecimiento de hidrocarburo en presencia de un catalizador reformador de carbono soportado como película delgada sobre la pared de un reactor, que comprende ios pasos de (a) hacer pasar un gas de proceso del material de abastecimiento de hidrocarbono a través de un primer reactor (10), con una película delgada de catalizador reformador de vapor soportada sobre las paredes del reactor (10) en una relación conductora de calor con una corriente de gas caliente de gas de chimenea; (b) hacer pasar el efluente desde el primer reactor (10) a un reactor tubular subsecuente (14) provisto con una película delgada de catalizador reformador de vapor y/o comprimidos de catalizador reformador de vapor, y calentado mediante quemado de combustible, obteniendo así un efluente de gas de vapor parcialmente reformado y la corriente de gas caliente de gas de chimenea; (c) hacer pasar el efluente desde el segundo reactor (14) a un reformador autotérmico (16); y (d) extraer del reformador autotérmico (16) una corriente de gas caliente de gas de producto (20) rico en hidrógeno y monóxido de carbono.
2.- El procedimiento de conformidad con la reivindicación 1 , caracterizado además porque el catalizador reformador de vapor comprende metales nobles y/o níquel.
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BR112016021426B1 (pt) * | 2014-04-08 | 2022-01-04 | Haldor Topsøe A/S | Processo para o aquecimento e ignição de um atr ou pox e instalação para realizar o processo |
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AU752109B2 (en) | 2002-09-05 |
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CZ20004929A3 (en) | 2001-05-16 |
CZ294907B6 (cs) | 2005-04-13 |
PL192266B1 (pl) | 2006-09-29 |
ATE225314T1 (de) | 2002-10-15 |
CN1304380A (zh) | 2001-07-18 |
DE69808521T2 (de) | 2003-01-30 |
CA2337937C (en) | 2004-10-26 |
KR100401369B1 (ko) | 2003-10-17 |
US7060118B1 (en) | 2006-06-13 |
ES2185209T3 (es) | 2003-04-16 |
CN1117693C (zh) | 2003-08-13 |
NZ509100A (en) | 2002-09-27 |
EP1097105B1 (en) | 2002-10-02 |
NO328552B1 (no) | 2010-03-15 |
EA002517B1 (ru) | 2002-06-27 |
DE69808521D1 (de) | 2002-11-07 |
WO2000005168A1 (en) | 2000-02-03 |
EA200100134A1 (ru) | 2001-08-27 |
CA2337937A1 (en) | 2000-02-03 |
PL345848A1 (en) | 2002-01-14 |
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JP2002521295A (ja) | 2002-07-16 |
AU9067298A (en) | 2000-02-14 |
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