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WO2016177923A1 - Method for treating nitrogen oxides from thermal energy storage by means of molten salts - Google Patents

Method for treating nitrogen oxides from thermal energy storage by means of molten salts Download PDF

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Publication number
WO2016177923A1
WO2016177923A1 PCT/ES2016/070321 ES2016070321W WO2016177923A1 WO 2016177923 A1 WO2016177923 A1 WO 2016177923A1 ES 2016070321 W ES2016070321 W ES 2016070321W WO 2016177923 A1 WO2016177923 A1 WO 2016177923A1
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Prior art keywords
nitric acid
nitrogen oxides
molten salts
thermal energy
hno
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Spanish (es)
French (fr)
Inventor
Julien Stanislas Aimé Rzepkowski
Sergio TUSET MÉNDEZ
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INFUSER APS
Condorchem Envitech Sl
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INFUSER APS
Condorchem Envitech Sl
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases

Definitions

  • the object of the present invention is a process for the treatment of nitrogen oxides from storage of thermal energy by molten salts and more specifically of the emissions of nitrogen oxides (NOx). Field of application of the invention.
  • This invention is applicable in the treatment of gases (NOx) from thermal energy storage systems; for example, but not limited to solar thermal power plants.
  • molten salt technology is known to store a large amount of thermal energy and then use it for electricity generation.
  • Some of the salts used in this technology are sodium nitrate or potassium nitrate and although this technology of molten salts provides important advantages of use, it presents some drawbacks such as the release during heating and decomposition of nitrogen oxides (NOx) in form of discontinuous and variable concentration emissions.
  • NOx nitrogen oxides
  • SCR selective catalytic reduction
  • N02 nitrogen dioxide
  • NO nitrogen monoxide
  • the applicant of the present invention is unaware of the existence of a background that allows the recovery of residual products from thermal storage by salts with the characteristics of the present invention.
  • the process for the treatment of nitrogen oxides from storage of thermal energy by means of molten salts object of this invention, has characteristics oriented to allow a high yield in the elimination of NOx, up to 99.999% and its transformation into a valuable product that can be reused as salts in the tanks of the thermal energy storage.
  • This process comprises the following phases: a) the cooling of the gas stream from the thermal storage tanks by molten salts, from a temperature of 200-800 ° C. up to a temperature between 0 - 90 ° C. and b) the treatment of the gas stream, previously cooled, by a photo-oxidation process, obtaining extremely reactive OH and ozone radical molecules towards nitrogen monoxide (NO) and nitrogen dioxide (N0 2 ). c) the transformation of nitrogen oxides (NO and N0 2 ) into nitric acid (HN0 3 ) by the reaction of OH radicals with nitrogen dioxide N0 2 , N0 2 + OH
  • phase b) there is a great reactivity of ozone 0 3 towards nitrogen oxide NO: NO + 0 3 - N0 2 + 0 2 ; and the reaction is catalyzed between ozone 0 3 with water H 2 0 by UV lamps to create radicals OH: 0 3 + H 2 0 - 2 OH + 0 2 .
  • phase c the following side reactions that may occur must also be considered:
  • the neutralization of nitric acid is carried out with sodium hydroxide (NaOH), or with potassium hydroxide (KOH), respectively obtaining sodium nitrate (NaN03), or potassium nitrate (KN0 3 ), which are reusable salts in the thermal energy storage system itself using molten salt technology, or in other applications.
  • FIG. 1 shows a diagram with the different phases or stages of the process for the treatment of nitrogen oxides from the gaseous emissions of thermal energy storage tanks by molten salts.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to a method for treating nitrogen oxides from thermal energy storage by means of molten salts, said method comprising: a) cooling a gas flow emanating from thermal storage by means of molten salts, to a temperature of between 0 and 90 ºC; b) treating the previously cooled gas flow by means of a photo-oxidation process, NO + O3→ NO2 + O2; O3 + H2O→ 2 OH + O2, producing radical molecules OH and ozone; c) transforming the nitrogen oxides (NO and NO2) into nitric acid (HNO3) by means of the reaction NO2 + OH→ HNO3, d) absorption of the nitric acid (HNO3) into a scrubber and neutralisation of the nitric acid (HNO3) with a chemical product for the transformation thereof into a salt, and e) crystallisation of said salt for the reuse thereof.

Description

DESCRIPCIÓN  DESCRIPTION

Título. Procedimiento para el tratamiento de óxidos de nitrógeno procedentes de almacenamiento de energía térmica mediante sales fundidas. Title. Procedure for the treatment of nitrogen oxides from thermal energy storage by molten salts.

Objeto de la invención. El objeto de la presente invención es un procedimiento para el tratamiento de óxidos de nitrógeno procedentes de almacenamiento de energía térmica mediante sales fundidas y más concretamente de las emisiones de óxidos de nitrógeno (NOx). Campo de aplicación de la invención. Object of the invention. The object of the present invention is a process for the treatment of nitrogen oxides from storage of thermal energy by molten salts and more specifically of the emissions of nitrogen oxides (NOx). Field of application of the invention.

Esta invención es aplicable en el tratamiento de gases (NOx) procedentes de sistemas de almacenamiento de energía térmica; por ejemplo, aunque no de forma limitativa en centrales solares térmicas. This invention is applicable in the treatment of gases (NOx) from thermal energy storage systems; for example, but not limited to solar thermal power plants.

Estado de la técnica. State of the art

Actualmente es conocida la tecnología de sales fundidas para almacenar gran cantidad de energía térmica y aprovecharla posteriormente para la generación de electricidad. Currently, molten salt technology is known to store a large amount of thermal energy and then use it for electricity generation.

En las centrales térmicas solares se concentra la luz del sol en una torre que contiene las sales, pudiendo alcanzar hasta los 800°C, siendo conducidas estas sales fundidas por tuberías hasta un intercambiador donde se utiliza la energía térmica acumulada por las mismas para generar electricidad. In the solar thermal power plants, sunlight is concentrated in a tower that contains the salts, being able to reach up to 800 ° C, these molten salts being conducted by pipes to an exchanger where the thermal energy accumulated by them is used to generate electricity .

Algunas de las sales utilizadas en esta tecnología son el nitrato sódico o el nitrato de potasio y si bien esta tecnología de sales fundidas proporciona importantes ventajas de utilización, presenta algunos inconvenientes como la liberación durante el calentamiento y descomposición en de óxidos de nitrógeno (NOx) en forma de emisiones discontinuas y de concentración variable. Some of the salts used in this technology are sodium nitrate or potassium nitrate and although this technology of molten salts provides important advantages of use, it presents some drawbacks such as the release during heating and decomposition of nitrogen oxides (NOx) in form of discontinuous and variable concentration emissions.

Esto hace necesario la utilización de un sistema de tratamiento de dichos gases NOx. This necessitates the use of a NOx gas treatment system.

Una técnica conocida para el tratamiento de estos gases NOx es la tecnología de reducción catalítica selectiva (SCR) que reduce las emisiones de óxido de nitrógeno (NOx) mediante el uso de un catalizador. Esta tecnología (SCR) se aplica normalmente en procesos de combustión ofreciendo una reducción de hasta un 95% de NOx. A known technique for treating these NOx gases is selective catalytic reduction (SCR) technology that reduces nitrogen oxide (NOx) emissions by using a catalyst. This technology (SCR) is normally applied in combustion processes offering a reduction of up to 95% NOx.

Otra técnica conocida para el tratamiento de los óxidos de nitrógeno es el lavado de gases que resulta efectivo en el caso del dióxido de nitrógeno (N02) que es soluble en agua, pero no en el caso del monóxido de nitrógeno (NO) que no es soluble en agua y proporciona un bajo rendimiento. Another known technique for the treatment of nitrogen oxides is the washing of gases that is effective in the case of nitrogen dioxide (N02) that is soluble in water, but not in the case of nitrogen monoxide (NO) which is not Water soluble and provides low performance.

En el documento EP 2307813, con prioridad del documento US 8318084 se describe un método y un dispositivo para la limpieza de la contaminación del aire basado en un proceso de foto-oxidación consistente en acelerar los mecanismos de auto limpieza de la atmósfera, es decir una combinación ajustada de gases atmosféricos, vapor de agua, ozono y luz ultravioleta. In EP 2307813, with priority of US 8318084, a method and a device for cleaning air pollution based on a photo-oxidation process consisting of accelerating the self-cleaning mechanisms of the atmosphere, ie a tight combination of atmospheric gases, water vapor, ozone and ultraviolet light.

El solicitante de la presente invención desconoce la existencia de antecedentes que permitan realizar una recuperación de productos residuales procedentes de almacenamiento térmico mediante sales con las características propias de la presente invención. The applicant of the present invention is unaware of the existence of a background that allows the recovery of residual products from thermal storage by salts with the characteristics of the present invention.

Descripción de la invención Description of the invention

El procedimiento para el tratamiento de óxidos de nitrógeno procedentes de almacenamiento de energía térmica mediante sales fundidas, objeto de esta invención, presenta unas características orientadas a permitir un elevado rendimiento en la eliminación de NOx, de hasta el 99, 999% y su transformación en un producto de valor que se puede reutilizar en forma de sales en los tanques del almacenamiento de energía térmica. The process for the treatment of nitrogen oxides from storage of thermal energy by means of molten salts, object of this invention, has characteristics oriented to allow a high yield in the elimination of NOx, up to 99.999% and its transformation into a valuable product that can be reused as salts in the tanks of the thermal energy storage.

Este procedimiento, comprende las fases siguientes: a) el enfriamiento de la corriente gaseosa procedente de los tanques del almacenamiento térmico mediante sales fundidas, desde una temperatura de 200 - 800°C. hasta una temperatura comprendida entre 0 - 90 °C. y b) el tratamiento de la corriente gaseosa, enfriada previamente, mediante un proceso de foto-oxidación, obteniendo moléculas radicales OH y ozono extremadamente reactivas hacia el monóxido de nitrógeno (NO) y el dióxido de nitrógeno (N02). c) la transformación de los óxidos de nitrógeno (NO y N02) en ácido nítrico (HN03) mediante la reacción de los radicales OH con dióxido de nitrógeno N02, N02 + OHThis process comprises the following phases: a) the cooling of the gas stream from the thermal storage tanks by molten salts, from a temperature of 200-800 ° C. up to a temperature between 0 - 90 ° C. and b) the treatment of the gas stream, previously cooled, by a photo-oxidation process, obtaining extremely reactive OH and ozone radical molecules towards nitrogen monoxide (NO) and nitrogen dioxide (N0 2 ). c) the transformation of nitrogen oxides (NO and N0 2 ) into nitric acid (HN0 3 ) by the reaction of OH radicals with nitrogen dioxide N0 2 , N0 2 + OH

-> HN03, d) la absorción del ácido nítrico mediante el lavado de los gases (scrubber) y la neutralización del ácido nítrico (HN03) en una solución de agua y un producto químico, transformándolo en una sal; y e) la cristalización y reutilización de dicha sal en el propio sistema de almacenamiento de energía térmica. En la fase b) hay una gran reactividad del ozono 03 hacia el óxido de nitrógeno NO: NO + 03 - N02 + 02; y se cataliza la reacción entre del ozono 03 con agua H20 mediante lámparas de UV para crear radicales OH : 03 + H20 - 2 OH + 02. -> HN0 3 , d) the absorption of nitric acid by scrubbing the gases (scrubber) and neutralization of nitric acid (HN03) in a solution of water and a chemical, transforming it into a salt; and e) crystallization and reuse of said salt in the thermal energy storage system itself. In phase b) there is a great reactivity of ozone 0 3 towards nitrogen oxide NO: NO + 0 3 - N0 2 + 0 2 ; and the reaction is catalyzed between ozone 0 3 with water H 2 0 by UV lamps to create radicals OH: 0 3 + H 2 0 - 2 OH + 0 2 .

En la fase c) hay que considerar también las siguientes reacciones secundarias que se puede producir: In phase c) the following side reactions that may occur must also be considered:

NO + OH -> HN02 NO + OH -> HN0 2

3N02 + H20 -> 2 HNO3 + NO 3N0 2 + H 2 0 -> 2 HNO 3 + NO

03 + N02 -> 02 + N03 Sin embargo, estas reacciones secundarais son mucho más lentas que las reacciones principales mencionadas y no son relevantes en el proceso final. 0 3 + N0 2 -> 0 2 + N0 3 However, these secondary reactions are much slower than the main reactions mentioned and are not relevant in the final process.

En un ejemplo de realización concreto la neutralización del ácido nítrico (HN03) se realiza con hidróxido de sodio (NaOH), o con hidróxido de potasio (KOH), obteniendo respectivamente nitrato de sodio (NaN03), o nitrato de potasio (KN03), que son sales reutilizables en el propio sistema de almacenaje de energía térmica mediante la tecnología de sales fundidas, o en otras aplicaciones. Descripción de las figuras. In a specific embodiment, the neutralization of nitric acid (HN0 3 ) is carried out with sodium hydroxide (NaOH), or with potassium hydroxide (KOH), respectively obtaining sodium nitrate (NaN03), or potassium nitrate (KN0 3 ), which are reusable salts in the thermal energy storage system itself using molten salt technology, or in other applications. Description of the figures.

Para complementar la descripción que se está realizando y con objeto de facilitar la comprensión de las características de la invención, se acompaña a la presente memoria descriptiva un juego de figuras en el que, con carácter ilustrativo y no limitativo, se ha representado lo siguiente: To complement the description that is being made and in order to facilitate the understanding of the characteristics of the invention, a set of figures is attached to the present specification in which, for illustrative and non-limiting purposes, the following has been represented:

- La figura 1 muestra un diagrama con las diferentes fases o etapas del procedimiento para el tratamiento de óxidos de nitrógeno procedentes de las emisiones gaseosas de los tanques de almacenamiento de energía térmica mediante sales fundidas. - Figure 1 shows a diagram with the different phases or stages of the process for the treatment of nitrogen oxides from the gaseous emissions of thermal energy storage tanks by molten salts.

Realización preferida de la invención. Preferred embodiment of the invention.

En la figura 1 se han representado esquemáticamente las fases del procedimiento descrito anteriormente, incluyendo: a) el enfriamiento de la corriente gaseosa de los tanques del almacenamiento térmico mediante sales fundidas b) el tratamiento de la corriente gaseosa mediante un proceso de foto- oxidación en el que se obtienen la moléculas radicales OH y ozono; c) la transformación de los óxidos de nitrógeno (NO y N02) en ácido nítrico (HN03) mediante la reacción N02 + OH -> HNO3, d) la absorción del ácido nítrico (HN03) en un scrubber y la neutralización del ácido nítrico (HN03) con un producto químico para su transformación en una sal y, e) la cristalización de dicha sal para su reutilización. The steps of the process described above have been schematically depicted in Figure 1, including: a) the cooling of the gas stream of the thermal storage tanks by molten salts b) the treatment of the gas stream by a photo-oxidation process in which are obtained the radical molecules OH and ozone; c) the transformation of nitrogen oxides (NO and N0 2 ) into nitric acid (HN0 3 ) by reaction N0 2 + OH -> HNO 3, d) the absorption of nitric acid (HN03) in a scrubber and the neutralization of nitric acid (HN03) with a chemical for its transformation into a salt and, e) the crystallization of said salt for reuse.

Una vez descrita suficientemente la naturaleza de la invención, se hace constar a los efectos oportunos que en la misma se pueden introducir los cambios que se consideren oportunos, siempre y cuando ello no suponga una alteración de las características esenciales de la invención que se reivindican a continuación. Once the nature of the invention has been sufficiently described, it is stated for the appropriate purposes that changes may be introduced therein, provided that this does not imply an alteration of the essential features of the invention claimed in continuation.

Claims

REIVINDICACIONES 1. Procedimiento para el tratamiento de óxidos de nitrógeno procedentes de almacenamiento de energía térmica mediante sales fundidas; caracterizado porque comprende: a) el enfriamiento de una corriente gaseosa que contiene óxidos de nitrógeno, procedente de tanques de almacenamiento térmico mediante sales fundidas, desde una temperatura de 200 - 800°C. hasta una temperatura comprendida entre 0 - 90 °C. y b) el tratamiento de la corriente gaseosa, enfriada previamente, mediante un proceso de foto-oxidación, NO + 03 -> N02 + 02; 03 + H20 -> 2 OH + 02 obteniendo moléculas radicales OH y ozono extremadamente reactivas hacía el monóxido de nitrógeno (NO) y el dióxido de nitrógeno (N02). c) la transformación de los óxidos de nitrógeno (NO y N02) en ácido nítrico (HN03) mediante la reacción N02 + OH -> HNO3, d) la absorción del ácido nítrico (HN03) en un scrubber y la neutralización del ácido nítrico (HNO3) con un producto químico para su transformación en una sal 1. Procedure for the treatment of nitrogen oxides from thermal energy storage by molten salts; characterized in that it comprises: a) the cooling of a gas stream containing nitrogen oxides, from thermal storage tanks by molten salts, from a temperature of 200-800 ° C. up to a temperature between 0 - 90 ° C. and b) the treatment of the gas stream, previously cooled, by a photo-oxidation process, NO + 0 3 -> N0 2 + 0 2 ; 0 3 + H 2 0 -> 2 OH + 0 2 obtaining extremely reactive OH and ozone radical molecules to nitrogen monoxide (NO) and nitrogen dioxide (N0 2 ). c) the transformation of nitrogen oxides (NO and N0 2 ) into nitric acid (HN0 3 ) by reaction N0 2 + OH -> HNO 3, d) the absorption of nitric acid (HN03) in a scrubber and neutralization of nitric acid (HNO 3 ) with a chemical for its transformation into a salt e) la cristalización de dicha sal para su reutilización. e) crystallization of said salt for reuse. 2.- Procedimiento, según la reivindicación 1 , caracterizado porque comprende la neutralización del ácido nítrico (HN03) con hidróxido de sodio (NaOH) y la obtención de nitrato de sodio (NaN03). 2. Method according to claim 1, characterized in that it comprises neutralizing nitric acid (HN03) with sodium hydroxide (NaOH) and obtaining sodium nitrate (NaN03). 3.- Procedimiento, según la reivindicación 1 , caracterizado porque comprende la neutralización del ácido nítrico (HN03) con hidróxido de potasio (KOH) y la obtención de nitrato de potasio (KNO3). 3. Method according to claim 1, characterized in that it comprises neutralizing nitric acid (HN03) with potassium hydroxide (KOH) and obtaining potassium nitrate (KNO 3 ).
PCT/ES2016/070321 2015-05-04 2016-04-28 Method for treating nitrogen oxides from thermal energy storage by means of molten salts Ceased WO2016177923A1 (en)

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ES201530597A ES2540170B1 (en) 2015-05-04 2015-05-04 Procedure for the treatment of nitrogen oxides from thermal energy storage by molten salts
ESP201530597 2015-05-04

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1349887A (en) * 1970-02-20 1974-04-10 North American Rockwell Removal of nitrogen oxides and other impurities from gaseous mixtures
US4009244A (en) * 1974-04-19 1977-02-22 Mitsubishi Jukogyo Kabushiki Kaisha Process for removing oxides of nitrogen and sulfur from exhaust gases
US6649132B1 (en) * 2002-07-23 2003-11-18 The Boc Group, Inc. Process for the removal of impurities from gas streams
US20150107246A1 (en) * 2013-10-18 2015-04-23 Krishna Kumar Bindingnavale Ranga System and method for heat storage in solar thermal power plants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1349887A (en) * 1970-02-20 1974-04-10 North American Rockwell Removal of nitrogen oxides and other impurities from gaseous mixtures
US4009244A (en) * 1974-04-19 1977-02-22 Mitsubishi Jukogyo Kabushiki Kaisha Process for removing oxides of nitrogen and sulfur from exhaust gases
US6649132B1 (en) * 2002-07-23 2003-11-18 The Boc Group, Inc. Process for the removal of impurities from gas streams
US20150107246A1 (en) * 2013-10-18 2015-04-23 Krishna Kumar Bindingnavale Ranga System and method for heat storage in solar thermal power plants

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ES2540170B1 (en) 2016-01-18

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