ES2674558T3 - Método de tratamiento de gases de escape y aparato de desnitrificación/reducción de SO3 - Google Patents

Método de tratamiento de gases de escape y aparato de desnitrificación/reducción de SO3 Download PDF

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Publication number
ES2674558T3
ES2674558T3 ES15783949.9T ES15783949T ES2674558T3 ES 2674558 T3 ES2674558 T3 ES 2674558T3 ES 15783949 T ES15783949 T ES 15783949T ES 2674558 T3 ES2674558 T3 ES 2674558T3
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Prior art keywords
catalyst
exhaust gas
treatment method
denitrification
gas treatment
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Koji Higashino
Akihiro Sawata
Keiji Fujikawa
Masanao Yonemura
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)

Abstract

Un metodo de tratamiento de gases de escape que comprende las etapas de: anadir un hidrocarburo olefinico 3C-5C (hidrocarburo insaturado) a un gas de escape de combustion que incluye SO3 asi como NOx como un primer aditivo; y, a continuacion, poner en contacto el gas de escape de combustion con un catalizador que incluye un oxido constituido por uno o mas elementos seleccionados de entre el grupo que consiste en Ti, Si, Zr y Ce y/o un oxido mixto y/o un oxido complejo constituido por dos o mas de los elementos seleccionados de entre el grupo como portadores y que no incluye un metal noble, y de ese modo SO3 es tratado por reduccion a SO2.

Description

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(Preparación del catalizador B)
Se preparó un catalizador B como un catalizador típico que tiene una función de desnitrificación por amoniaco. Se mezclaron Ti(O-iC3H7)4, un alcóxido de Ti, y Si(OCH3)3, un alcóxido de Si, en una relación de 95:5 (% en peso) 5 (como TiO2, SiO2, respectivamente), la mezcla se añadió en agua a 80 °C para la hidrólisis, luego, la mezcla de reacción se agitó y se maduró, el sol producido se filtró, y el producto gelificado obtenido se lavó, se secó, y se calentó y se coció a 500 °C durante 5 horas para obtener un polvo de óxido complejo de TiO2-SiO2 (polvo de TiO2-SiO2). Se impregnaron metavanadato de amonio (NH3VO3) y paratungstato de amonio ((NH4)10H10W12O46·6H2O) en el óxido complejo usando una solución acuosa al 10 % en peso de metilamina, se introdujeron 0,6 % en peso de
10 V2O5 y 8 % en peso de WO3 por 100 % en peso de óxido complejo, el resultante se evaporó y se secó, y luego se calentó y se coció a 500 °C durante 5 horas. El polvo obtenido se usó como el catalizador B.
(Preparación del catalizador C)
15 Se preparó un catalizador C, un catalizador típico que tiene una función de desnitrificación por amoniaco. Se mezclaron Ti(O-iC3H7)4, un alcóxido de Ti, y Zr(Oi-C4h9)4, un alcóxido de Zr, en una relación de 95:5 (% en peso) (como TiO2, ZrO2, respectivamente), la mezcla se añadió en agua a 80 °C para la hidrólisis, luego, la mezcla de reacción se agitó y se maduró, el sol producido se filtró, y el producto gelificado obtenido se lavó, se secó, y se calentó y se coció a 500 °C durante 5 horas para obtener un polvo de óxido complejo de TiO2-ZrO2 (polvo de TiO2
20 ZrO2). Se impregnó paratungstato de amonio ((NH4)10H10W12O46·6H2O) en el óxido complejo usando una solución acuosa al 10 % en peso de metilamina, se introdujo 8 % en peso de WO3 por 100% en peso de óxido de complejo, el resultante se evaporó y se secó, y luego se calentó y se coció a 500 °C durante 5 horas. El polvo obtenido se usó como el catalizador C.
25 (Preparación del catalizador D)
Se preparó un catalizador que contenía titania (TiO2) solamente. Se coció un polvo de titania de tipo anatasa de la misma cantidad que el catalizador A a 500 °C durante 5 horas para preparar un polvo de catalizador D.
30 (Preparación de los Ejemplos de prueba 1 a 5)
Se añadió 80 % en peso de agua, respectivamente, a 20 % en peso de los catalizadores A a D, y la mezcla se pulverizó mediante un molino de bolas húmedo para obtener una suspensión de recubrimiento de lavado. A continuación se recubrió un material de base monolítica (cabeceo: 7,4 mm, espesor de pared: 0,6 mm) producido por 35 Cordierite con la suspensión mediante inmersión, y el producto obtenido se secó a 120 °C y luego se coció a 500 °C. La cantidad del recubrimiento fue de 100 g por área superficial de 1 m2 del material de base. Se usó como Ejemplo de prueba 1 un caso de usar el catalizador A y amoniaco (NH3) como el reductor de SO3. Por otro lado, se usó como Ejemplo de prueba 2 un caso de usar el catalizador A y propileno (C3H6) como el reductor de SO3. Se usó como Ejemplo de prueba 3 un caso de usar el catalizador B y C3H6 como el reductor de SO3. Se usó como Ejemplo de
40 prueba 4 un caso de usar el catalizador C y C3H6 como el reductor de SO3. Además, se usó como Ejemplo de prueba 5 un caso de usar el catalizador D y C3H6 como el reductor de SO3.
(Prueba I de eliminación de SO3)
45 Para las pruebas a escala experimental en las que se supone una máquina real, se añadió el reductor de SO3 al gas de escape de combustión, y se dejó que el gas de escape de combustión que contenía el reductor de SO3 fluyera a través del catalizador de los respectivos ejemplos de prueba instalado en el aparato de desnitrificación y reducción de SO3, y de ese modo, se examinó la variación de la concentración de SO3 (ppm) en el gas de escape de combustión en términos de 0,03 a 0,8 (1/VA (m2·h/Nm3) después de que el gas de escape de combustión fluyera a
50 través de la capa de catalizador. Los resultados de la prueba y las condiciones de la prueba se muestran en la Fig.
4. La concentración de SO3 se analizó mediante un método de titulación de deposición después de realizar el muestreo. En los dibujos, "VA" indica la velocidad de área (área total de contacto por cantidad de gas/catalizador), y "1/VA" significa el área total de contacto del catalizador con relación a la cantidad de gas. La unidad de 1/VA se indica como m2·h/Nm3.
55 La Fig. 4 muestra la variación de la concentración de SO3 (ppm) en términos de 0,03 a 0,08 m2·h/Nm3 en los Ejemplos de prueba 1 a 5. Con referencia a la Figura 4, en el Ejemplo de prueba 1, la concentración de SO3 a la entrada de la capa de catalizador no varió sustancialmente. En el Ejemplo de prueba 2, la concentración de SO3 a la entrada de la capa de catalizador disminuyó de aproximadamente 100 ppm a aproximadamente 40 ppm a 0,06
60 m2·h/Nm3. Por otro lado, en el Ejemplo de prueba 3, la concentración de SO3 a la entrada de la capa de catalizador disminuyó de aproximadamente 100 ppm a aproximadamente 20 ppm a 0,08 m2·h/Nm3. En el Ejemplo de prueba 4, la concentración de SO3 a la entrada de la capa de catalizador disminuyó de aproximadamente 100 ppm a aproximadamente 20 ppm a 0,08 m2·h/Nm3. Además, también en el Ejemplo de prueba 5, la concentración de SO3 a la entrada de la capa de catalizador disminuyó de aproximadamente 100 ppm a aproximadamente 25 ppm a 0,08
65 m2·h/Nm3.
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