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WO2025026572A1 - Procédé et système de combustion d'ammoniac - Google Patents

Procédé et système de combustion d'ammoniac Download PDF

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Publication number
WO2025026572A1
WO2025026572A1 PCT/EP2024/025219 EP2024025219W WO2025026572A1 WO 2025026572 A1 WO2025026572 A1 WO 2025026572A1 EP 2024025219 W EP2024025219 W EP 2024025219W WO 2025026572 A1 WO2025026572 A1 WO 2025026572A1
Authority
WO
WIPO (PCT)
Prior art keywords
burners
ammonia
combustion
flue gas
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/025219
Other languages
English (en)
Inventor
Martin Murer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Selas Linde GmbH
Original Assignee
Selas Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Selas Linde GmbH filed Critical Selas Linde GmbH
Publication of WO2025026572A1 publication Critical patent/WO2025026572A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23N—REGULATING OR CONTROLLING COMBUSTION
    • F23N1/00—Regulating fuel supply
    • F23N1/02—Regulating fuel supply conjointly with air supply
    • F23N1/022—Regulating fuel supply conjointly with air supply using electronic means
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/10—Nitrogen; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23N—REGULATING OR CONTROLLING COMBUSTION
    • F23N2237/00—Controlling
    • F23N2237/02—Controlling two or more burners
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23N—REGULATING OR CONTROLLING COMBUSTION
    • F23N2239/00—Fuels
    • F23N2239/04—Gaseous fuels

Definitions

  • the present invention relates to a method and a combustion arrangement for combusting ammonia.
  • Ammonia may be an attractive fuel and a “storage form” for hydrogen less difficult to handle than compressed or liquefied hydrogen gas.
  • ammonia has a higher energy density, at 12.7 MJ/L, than even liquid hydrogen, at 8.5 MJ/L.
  • Liquid hydrogen has to be stored at cryogenic conditions of -253 °C, whereas ammonia can be stored at a much less energy- intensive -33 °C.
  • ammonia though hazardous to handle, is much less flammable than hydrogen. Due to the wide use of ammonia in agriculture, an ammonia infrastructure already exists. Worldwide, about 180 Mt of ammonia are produced annually, and 120 ports worldwide are already equipped with ammonia terminals.
  • Ammonia may be used for co-firing in thermal power plants, for example, in order to provide additional energy, but also to provide better control of nitrous oxides formation.
  • JP 2020-112280 A discloses a furnace comprising a plurality of burners which are adapted to use pulverized coal as a fuel, the coal being introduced into the burners by being entrained by combustion air in a combustion air tube.
  • an inner tube in the combustion air tube is provided.
  • JP 2018-096680 A A similar arrangement is disclosed in JP 2018-096680 A.
  • a method for combusting ammonia provided in a combustion feed using a combustion arrangement comprising a combustion section, a flue gas section, and a plurality of burners is proposed, wherein the plurality of burners are operated using the combustion feed, and wherein a flue gas formed in the combustion section is passed through the flue gas section.
  • a first group of the plurality of burners are operated using first ratio of oxygen to ammonia and a second group of the plurality of burners are operated with a second ratio of oxygen to ammonia, wherein the second ratio of oxygen to ammonia is lower than the first ratio of oxygen to ammonia.
  • the first ratio of oxygen to ammonia is a super-stoichiometric ratio
  • the second ratio of oxygen to ammonia is a stoichiometric or slightly sub-stoichiomatric ratio.
  • the proposed method solves a main challenge for selective catalytic and non-catalytic nitrous oxide reduction steps, which is a good distribution of ammonia in the flue gas and the added capital and operating cost of the injection system, as also discussed further below in connection with certain embodiments.
  • a selective catalytic and/or non-catalytic nitrous oxide reduction may be performed in the flue gas section. That is, one or more zones configured for selective catalytic and/or non-catalytic nitrous oxide reduction may be provided in the flue gas section.
  • a “zone” for non-catalytic nitrous oxide reduction as referred to herein may be a sub-section of the flue gas section corresponding to an appropriate temperature window with optionally no specific apparatus features.
  • aspects as proposed herein include tweaking some of the burners to produce an ammonia slippage (i.e., leave an amount of ammonia in uncombusted state) which can react in the temperature window for a selective non-catalytic nitrous oxide reduction zone and/or further downstream also in a selective catalytic nitrous oxide reduction zone or system.
  • This can be achieved by adjusting the supply of air or another oxygencontaining gas mixture, or even pure oxygen, to the burners which can be provided as state-of-the-art burners.
  • Some burners will, as proposed herein, run on higher excess air so that the overall complete combustion in the furnace is achieved. These are the burners of the first group of burners as mentioned before. Other burners will run close to stoichiometry or slightly sub-stoichiometric to leave over some unreacted ammonia. These are the burners of the second group of burners as mentioned before.
  • the first ratio of oxygen to ammonia and the second ratio of oxygen to ammonia may be expressed as lambda or air-fuel equivalence values, as generally known to the skilled person.
  • the first ratio of oxygen to ammonia may correspond to a lambda value in a range from 1.1 to 2, particularly from 1.1 to 1.5
  • the second ratio of oxygen to ammonia may correspond to a lambda value in a range from 0.5 to 1.1 , particularly 0.9 to 1.1.
  • the values may also be expressed in fuel-air equivalence ratios or phi values, as also known to the skilled person.
  • literature e.g. Elbaz et al., “Review on the recent advances on ammonia combustion from the fundamentals to the applications”, Fuel Communications 2022, Volume 10, Page 100053, e.g., Figure 31.
  • the combustion feed comprises ammonia in a content of 1% to 100% on a molar, mass or volume basis.
  • the present invention may therefore be used in connection with a large type of different feeds.
  • the burners of the second group (operated at lower ratios of oxygen to ammonia) may, in embodiments as proposed herein, be distributed among the burners of the first group in the combustion section according to a predefined distribution pattern, particularly at a roof of the combustion section.
  • the burners of the second group may, in certain embodiments, be distributed among the burners of the first group in the combustion section according to a predefined distribution pattern to reach such a good and even distribution.
  • This may be a regular or irregular distribution pattern which may be selected by the skilled person accordingly and depending on local concentrations observed, for example.
  • the first group of burners may comprise a first number of burners, particularly a first total number of burners
  • the second group of burners may comprise a second number of burners, particularly a second total number of burners, wherein the first (total) number of burners may be equal to or larger than the second (total) number of burners.
  • the first (total) number of burners may particularly be an integer multiple of the second (total) number of burners, wherein an integer may particularly be 1 , 2, 3, 4, 5, 6 or an integer larger than 6.
  • the plurality of burners may be assigned to the first group of burners and to the second group of burners depending on the combustion feed, i.e., they may be operated flexibly with higher or lower stoichiometric ratios, particularly depending on an ammonia content of the combustion feed or any other parameter.
  • At least some of the plurality of burners may be arranged in the combustion section and/or at least some of the burners may be arranged in the flue gas section. While the subsequent explanations mainly relate to roof burners in the combustion section, embodiments of the invention may also be applied to ammonia reheat burners for a tail end selective catalytic reduction system which are arranged not in the combustion section but in the flue gas section.
  • At least some of the plurality of burners may, in embodiments of the present invention, comprise dedicated ports for the combustion feed and/or for an oxidator gas to adapt the first ratio of oxygen to ammonia and/or the second ratio of oxygen to ammonia. These may also be additional ports such that the main combustion of a burner is not disturbed.
  • the burners can be modified with some having extra air nozzles while others have extra fuel nozzles or even dedicated ammonia nozzles for furnaces running on dual fuel systems.
  • an ammonia slip reduction unit may be arranged, particularly downstream of the selective catalytic and/or non-catalytic nitrous oxide reduction zone(s), in the flue gas section, in order to reduce ammonia emissions.
  • One or more heat recovery bundles may, in embodiments of the present invention, be arranged, particularly upstream and/or downstream of the selective catalytic and/or non-catalytic nitrous oxide reduction zone(s), in the flue gas section. This enables for an effective heat recovery but also has the effect of a further mixing of the ammonia in the flue gas.
  • the combustion arrangement is operated at a maximum temperature of less than 1.100 °C, particularly from 900 to 1.100 °C, in embodiments proposed herein. Since ammonia has relatively low flame temperature, operating close to stoichiometry does not result in excessive temperatures in the furnace.
  • the combustion arrangement for combusting ammonia provided in a combustion feed comprises a combustion section, a flue gas section, and a plurality of burners.
  • a selective catalytic and/or non-catalytic nitrous oxide reduction unit is arranged in the flue gas section.
  • the combustion arrangement is configured to operate the plurality of burners using the combustion feed, and to pass a flue gas formed in the combustion section through the flue gas section.
  • the combustion arrangement is configured to operate a first group of the plurality of burners using first ratio of oxygen to ammonia and a second group of the plurality of burners with a second ratio of oxygen to ammonia lower than the first ratio of oxygen to ammonia.
  • Figure 1 illustrates an arrangement according to an embodiment.
  • Figure 2 illustrates aspects of an arrangement according to an embodiment.
  • Combustion engineering measures for the reduction of nitrous oxides formation like air and fuel staging make use of reaction paths toward nitrogen gas, consuming some of the formed nitrogen monoxide on the way.
  • Post combustion nitrous oxides reduction measures like selective non-catalytic reduction (SNCR) and selective catalytic reduction (SCR) apply ammonia or urea injection to reduce the emissions from a combustion process to the required limits.
  • an ammonia slip catalyst ASC can be installed to decompose unreacted ammonia to nitrogen gas and water.
  • Combined systems use ammonia injection at the lower end of the selective non- catalytic nitrous oxides reduction temperature window so that some ammonia remains as slippage, which can than react in a downstream selective catalytic or non-catalytic nitrous oxides reduction zone at lower temperatures.
  • the reduction rate of both technologies may be advantageously combined.
  • an injection equipment of ammonia is conventionally necessary.
  • these are typically provided as lances for an injection of an ammonia solution surrounding the fire box, sometimes using steam or plant air for better distribution and mixing. Sometimes additional water is added to form bigger droplets for further penetration depth.
  • the temperature profile can change and a second or even third level of lances could be necessary since the selective non- catalytic nitrous oxides reactions work in the narrow temperature window of 850 to 1.050 °C. Above this temperature window, ammonia reacts to nitrogen monoxide in oxygen-containing flue gas. Below this window, ammonia will not react and become an emission or can unwantedly react in a downstream selective catalytic nitrous oxides reduction catalyst.
  • the ammonia is injected at lower temperature, so that the injection nozzles can be also located inside the flue gas duct.
  • An additional static mixer can help evenly distribute the ammonia in the flue gas before or upstream of the catalyst.
  • the ammonia may be injected in a recirculated flue gas stream, which is extracted from the heat recovery system at high enough temperatures to evaporate the injected ammonia.
  • the mixture of flue gas with high concentration of ammonia may afterwards injected in the main flue gas duct for good distribution of the ammonia.
  • FIG. 1 illustrates an arrangement 100 according to an embodiment.
  • Arrangement 100 comprises a combustion section 110 and a flue gas section 120.
  • the combustion section may also be referred to as a “furnace”, a “firebox”, etc.
  • the flue gas section is sometimes also referred to as a “convection section”.
  • a combustion feed 1 such as an ammonia- containing gas mixture of pure ammonia, may be supplied to arrangement 100, i.e., to a plurality of burners 111 , 112 which are, in the example illustrated, but not limiting the scope of the invention, arranged at a roof of combustion section 110.
  • a selective catalytic or non-catalytic nitrous oxide reduction unit 121 is arranged in the flue gas section 120 in a manner generally also known to the skilled person.
  • the plurality of burners 111 , 112 are operated using the combustion feed 1 , and a flue gas 2 formed in the combustion section 110 is passed through the flue gas section 120.
  • a first group of the plurality of burners which are referred to with reference numeral 111
  • a second group of the plurality of burners which are referred to with reference numeral 112
  • a second ratio of oxygen to ammonia lower than the first ratio of oxygen to ammonia.
  • the burners 111 , 112 can be modified with some having extra air nozzles while others have extra fuel nozzles or even dedicated ammonia nozzles for furnaces running on dual fuel systems. This is not shown for reasons of generality.
  • a plurality of heat recovery bundles 122 may be provided upstream and downstream of the catalytic or non-catalytic nitrous oxide reduction unit 121 .
  • Any type of heat recovery bundles can be used, and these may particularly be adapted for reaction feed heating, boiler feed heating, steam heating or superheating, and and heating of media used in processing of certain materials, such as typically the case in a convection zone of a steam cracking furnace.
  • steam tubes 113 or any other type of units for heating certain media are arranged between the burners 111 , 112, or some of them.
  • these may be coils for heating or reacting process gas like in steam cracker furnaces or direct reduction iron heaters or reaction coils filled with catalyst like in steam methane reformers or ammonia crackers.
  • Figure 2 illustrates different options for burner distributions according to certain embodiments in a schematic top (or bottom) view of a combustion section, such as the combustion section 110 shown in Figure 1.
  • a combustion section such as the combustion section 110 shown in Figure 1.
  • Three different options are illustrated as vertical rows A to C and a vertical double row D which are each enclosed by dashed lines. All options shown may be provided in a combustion section 10, either alone or in any combination advantageous.
  • Figure 2 illustrates how the burners 112 of the second group (which are illustrated as large black or filled circles and only partly indicated by reference numerals) may be distributed among the burners 111 of the first group (which are illustrated as large white or unfilled circles and are and only partly indicated by reference numerals) in the combustion section 110 according to a predefined distribution pattern.
  • the first group of burners 111 comprises a first number of burners 111 and the second group of burners 112 comprises a second number of burners 112 wherein, the first number of burners is, in row A, equal to the second number of burners 112 and larger in rows B and C as well as in double row D.
  • the first number of burners 111 is, in rows B and C as well as in double row D, an integer multiple of the second number of burners 112, wherein the integer is 3 in row B, 6 in row C, and 4 in double row D.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)

Abstract

L'invention concerne un procédé de combustion d'ammoniac disposé dans une charge de combustion (1) faisant appel à un système de combustion (100) comprenant une section de combustion (110), une section de gaz de combustion (120), et une pluralité de brûleurs (111, 112), la pluralité de brûleurs (111, 112) étant actionnés à l'aide de la charge de combustion, et un gaz de combustion (2) formé dans la section de combustion (110) passant à travers la section de gaz de combustion (120). Un premier groupe de la pluralité de brûleurs (111) est actionné à l'aide d'un premier rapport entre l'oxygène et l'ammoniac et un second groupe de la pluralité de brûleurs (112) est actionné avec un second rapport entre l'oxygène et l'ammoniac inférieur au premier rapport entre l'oxygène et l'ammoniac. L'invention concerne en outre un système de combustion correspondant (100).
PCT/EP2024/025219 2023-08-03 2024-07-23 Procédé et système de combustion d'ammoniac Pending WO2025026572A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23020367.1 2023-08-03
EP23020367.1A EP4502468A1 (fr) 2023-08-03 2023-08-03 Procédé et agencement pour la combustion d'ammoniac

Publications (1)

Publication Number Publication Date
WO2025026572A1 true WO2025026572A1 (fr) 2025-02-06

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PCT/EP2024/025219 Pending WO2025026572A1 (fr) 2023-08-03 2024-07-23 Procédé et système de combustion d'ammoniac

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EP (1) EP4502468A1 (fr)
WO (1) WO2025026572A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040060301A1 (en) * 2002-09-27 2004-04-01 Chen Alexander G. Multi-point staging strategy for low emission and stable combustion
EP2317098A1 (fr) * 2008-07-11 2011-05-04 Toyota Jidosha Kabushiki Kaisha Dispositif de commande de fonctionnement de turbine à gaz
JP2018096680A (ja) 2016-12-15 2018-06-21 一般財団法人電力中央研究所 アンモニアを混焼できる石炭燃焼装置
JP2020112280A (ja) 2019-01-08 2020-07-27 一般財団法人電力中央研究所 アンモニアを混焼できるボイラ装置及び火力発電設備
WO2022210710A1 (fr) * 2021-03-31 2022-10-06 三菱重工業株式会社 Procédé de fonctionnement de chaudière et dispositif de commande pour une chaudière
WO2023037867A1 (fr) * 2021-09-09 2023-03-16 三菱重工業株式会社 Chaudière, procédé de commande de chaudière et procédé de modification de chaudière

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040060301A1 (en) * 2002-09-27 2004-04-01 Chen Alexander G. Multi-point staging strategy for low emission and stable combustion
EP2317098A1 (fr) * 2008-07-11 2011-05-04 Toyota Jidosha Kabushiki Kaisha Dispositif de commande de fonctionnement de turbine à gaz
JP2018096680A (ja) 2016-12-15 2018-06-21 一般財団法人電力中央研究所 アンモニアを混焼できる石炭燃焼装置
JP2020112280A (ja) 2019-01-08 2020-07-27 一般財団法人電力中央研究所 アンモニアを混焼できるボイラ装置及び火力発電設備
WO2022210710A1 (fr) * 2021-03-31 2022-10-06 三菱重工業株式会社 Procédé de fonctionnement de chaudière et dispositif de commande pour une chaudière
WO2023037867A1 (fr) * 2021-09-09 2023-03-16 三菱重工業株式会社 Chaudière, procédé de commande de chaudière et procédé de modification de chaudière

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ALEXANDER H. TULLO: "Is ammonia the fuel of the future?", CHEMICAL AND ENGINEERING NEWS, vol. 99, no. 8, 2021
ELBAZ ET AL.: "Review on the recent advances on ammonia combustion from the fundamentals to the applications", FUEL COMMUNICATIONS, vol. 10, 2022, pages 100053
M.J. MURER: "Dissertation", 2014, TECHNISCHE UNIVERSITÄT, article "Numerical methods for efficient power generation from municipal solid waste"
T. KOLB: "Experimentelle und theoretische Untersuchungen zur Minderung der NO -Emission technischer Feuerungen durch gestufte Verbrennungsführung", VGB-KRAFTWERKSTECHNIK, vol. 70, no. 8, 1990

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