WO2022254735A1 - Appareil et procédé de traitement d'ammoniac en excès - Google Patents

Appareil et procédé de traitement d'ammoniac en excès Download PDF

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Publication number
WO2022254735A1
WO2022254735A1 PCT/JP2021/024702 JP2021024702W WO2022254735A1 WO 2022254735 A1 WO2022254735 A1 WO 2022254735A1 JP 2021024702 W JP2021024702 W JP 2021024702W WO 2022254735 A1 WO2022254735 A1 WO 2022254735A1
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WO
WIPO (PCT)
Prior art keywords
ammonia
unit
component
reduction catalyst
surplus
Prior art date
Application number
PCT/JP2021/024702
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English (en)
Japanese (ja)
Inventor
望 服部
聡一郎 櫻井
一孝 島田
Original Assignee
株式会社三井Ｅ＆Ｓマシナリー
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 株式会社三井Ｅ＆Ｓマシナリー filed Critical 株式会社三井Ｅ＆Ｓマシナリー
Priority to KR1020237035482A priority Critical patent/KR20230158084A/ko
Priority to JP2021538972A priority patent/JP6940727B1/ja
Priority to CN202180096900.9A priority patent/CN117425768A/zh
Publication of WO2022254735A1 publication Critical patent/WO2022254735A1/fr

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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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to the treatment of surplus ammonia.
  • Liquefied ammonia (LNH3) is used in marine diesel engines that use ammonia as part of their fuel. For safety reasons, the liquefied ammonia must be depressurized and released into the atmosphere when the engine is stopped or in an emergency. Since ammonia affects the human body, it cannot be released into the atmosphere as it is. Therefore, it is necessary to remove the ammonia with an abatement device.
  • a selective reduction catalyst unit is used to remove nitrogen oxides generated by combustion of raw materials such as heavy oil. Large amounts of urea, ammonia, and ammonia compounds are required as reducing agent materials and stored in tanks.
  • Patent Document 1 discloses an emission control system and related method for treating an exhaust gas stream.
  • US Pat. No. 5,300,004 includes the use of an ammonia production system to provide ammonia for injection into the exhaust gas stream as a reductant for a selective reduction catalyst.
  • Patent Document 1 requires stockpiling of ammonium hydroxide, which is a raw material for generating ammonia as a reducing agent for the selective reduction catalyst.
  • the technology disclosed in Patent Literature 1 does not effectively utilize surplus ammonia generated from an engine or the like.
  • An object of the present invention is to provide a surplus ammonia processing apparatus and processing method that can effectively utilize surplus ammonia.
  • a first aspect of the present invention is A surplus ammonia treatment device in a marine diesel engine that uses ammonia as part of the fuel and is connected to a selective reduction catalyst unit, a separation vessel for containing the waste liquid from the marine diesel engine and separating the oil and ammonia components; a transport unit that supplies the ammonia component separated in the separation vessel to the selective reduction catalyst unit;
  • a surplus ammonia treatment device having
  • a second aspect of the present invention is A method for treating surplus ammonia in a marine diesel engine that uses ammonia as part of its fuel and is connected to a selective reduction catalyst unit, comprising: containing waste liquid from the marine diesel engine; separating the waste liquid into an oil component and an ammonia component; supplying the separated ammonia component to the selective reduction catalyst unit; This is a method for treating excess ammonia.
  • surplus ammonia treatment apparatus and treatment method of the present invention surplus ammonia can be effectively used.
  • FIG. 1 is a schematic diagram of the surplus ammonia processing unit 1 of this embodiment.
  • the surplus ammonia treatment unit 1 has a separation vessel 2 and a transport section 6 .
  • the separation container 2 may have a separation section 3 .
  • the extraction unit 4 may be attached to the separation container 2 .
  • the oil extracted in the separation container 2 is stored in the lower part of the separation container 2 and sent to the bilge tank 30, which will be described later. Therefore, it is desirable to install the extraction part 4 on the upper part of the separation container 2 .
  • Separation vessel 2 contains effluent from each unit of a marine diesel engine that uses ammonia as part of its fuel. Specifically, as shown in FIGS. 4 and 5 , waste liquid from the fuel supply unit 21 , the reducing agent supply unit 22 of the selective reduction catalyst, and the marine diesel engine unit 23 is stored in the separation container 2 . Ammonia is supplied to a fuel supply unit 21, a reducing agent supply unit 22, and a marine diesel engine unit 23 from an ammonia fuel tank 20 installed on board. Therefore, the effluent contains excess ammonia. In addition, when the separation container 2 uses the principle of specific gravity separation, it is desirable that the waste liquid flows in from the upper part of the separation container 2 . 4 and 5, solid line arrows indicate the flow of the ammonia component, and broken line arrows indicate the flow of the drain.
  • the separation container 2 separates the waste liquid into oil and ammonia components. For example, when using the principle of specific gravity separation, the waste liquid that has flowed into the separation container 2 is separated into an oil component and an ammonia component due to the difference in specific gravity.
  • the separation container 2 may have a separation section 3 .
  • the separation unit 3 separates the waste liquid that has flowed into the separation container 2 into oil and ammonia components using, for example, the principles of filter separation, cyclone separation, and centrifugal separation.
  • the separated oil is supplied to the bilge tank 30.
  • the separated ammonia component is supplied to the transportation section 6 via the extraction section 4 and the storage section 5, as shown in FIGS.
  • the extractor 4 removes impurities that may be contained in the liquefied ammonia separated by the separation vessel 2 . Therefore, when the separated ammonia component is ammonia gas, depending on the state of the waste liquid discharged from the marine diesel engine unit 23 or the like, the ammonia component may be transported to the transport section 6 without going through the extraction section 4 and the storage section 5 . may be supplied. Moreover, as shown in FIG. 3, when the separated ammonia component is ammonia water, the ammonia component may be supplied to the storage unit 5 without passing through the extraction unit 4 in the same manner.
  • the extraction unit 4 mainly removes inorganic substances such as calcium compounds and metal pieces with a filter, but the removal method is not limited to a filter or the like. Especially when using a filter, a filter with a pitch of about 10 micrometers is preferable from the viewpoint of removal rate.
  • the storage unit 5 stores liquefied ammonia supplied directly from the separation vessel 2 or via the extraction unit 4.
  • a vaporizer 8 is attached between the storage section 5 and the transport section 6 .
  • the ammonia gas when ammonia gas exists as a gas phase in the upper part of the storage unit 5 , the ammonia gas may be directly supplied to the selective reduction catalyst unit 61 by a blower without passing through the vaporizer 8 .
  • aqueous ammonia when aqueous ammonia is supplied to the selective reduction catalyst unit 61 and the like, water or a neutralizing agent is injected into the storage unit 5 from above as shown in FIG.
  • a concentration adjustment unit 9 may be installed near the outlet of the storage unit 5 and connected to the transport unit 6 so that ammonia water having a predetermined concentration can be supplied.
  • the transport section 6 when supplying ammonia gas as a reducing agent, the transport section 6 supplies the ammonia gas sent from the vaporizer 8 to the selective reduction catalyst unit 61 .
  • the transport section 6 when ammonia water is supplied as the reducing agent, the transport section 6 supplies the ammonia water to the selective reduction catalyst unit 61 .
  • the fuel may be supplied from the transport section 6 to a pump unit 62 provided in the fuel supply unit 21 instead of the selective reduction catalyst unit 61 .
  • the selective reduction catalyst unit 61 or the pump unit 62 can be selected as the supply destination from the transport section 6, or a combination thereof may be selected.
  • the selective reduction catalyst unit 61 is directly or indirectly connected to the marine diesel engine unit 23 .
  • the oil separated in the separation container 2 is supplied to the bilge tank 30. Since a small amount of liquefied ammonia is mixed and dissolved in the oil and impurities extracted in the extraction unit 4 , they are similarly supplied to the bilge tank 30 . Since the ammonia gas obtained from the bilge tank 30 cannot be released into the atmosphere as it is, the abatement device 7 is used. In order to release ammonia into the atmosphere, the abatement device 7 adjusts the ammonia gas to a concentration that does not affect the human body. For example, the abatement device 7 adjusts the ammonia concentration to about 25 PPM or less.
  • the storage unit 5 temporarily stores the scrubber water.
  • Ammonia is a highly toxic substance, but is highly soluble in water. Therefore, the ammonia water supplied to the transport unit 6 via the storage unit 5 is unlikely to be mixed with the ammonia gas volatilized from the liquefied ammonia.
  • a method of absorbing ammonia gas into water is called a scrubber. Scrubbers are low cost and easy to operate.
  • the vaporizer 8 is attached between the storage section 5 and the transport section 6. However, in order to prevent stress corrosion cracking, it is preferable to install a vaporizer 8 just before the transport section 6 .
  • heat source for the evaporator 8 heat from cooling water of the marine diesel engine unit 23 and exhaust gas can be used in addition to heat from electricity. As a result, together with the surplus ammonia processing unit 1, environmental friendliness is enhanced.
  • the concentration adjustment section 9 is attached to the storage section 5.
  • the concentration adjustment unit 9 supplies ammonia water at a predetermined concentration to the transportation unit 6 .
  • the density adjustment unit 9 is a density meter or a densitometer.
  • the density adjuster 9 is a density meter that can measure more easily than a densitometer. It is more preferable to acquire in advance the relationship between the measured value of the density meter and the concentration. For example, when the density meter in optical measurement shows a numerical value of 0.912, the ammonia water concentration is about 15%. The ammonia water concentration is about 40% at maximum in a saturated state.
  • the selective reduction catalyst unit 61 it is preferable that the aqueous ammonia concentration is high.
  • FIG. 2 is one aspect of the present embodiment, and is an overall view of a surplus ammonia processing unit when ammonia gas is supplied. Waste liquid discharged from a fuel supply unit 21, a selective reduction catalyst reducing agent supply unit 22, and a marine diesel engine unit 23 shown in FIGS.
  • the separation container 2 recovers liquefied ammonia, which is surplus ammonia contained in the waste liquid.
  • the separation container 2 uses the principle of gravity separation, the separated oil is stored in the lower part of the separation container 2.
  • liquefied ammonia is stored in the upper part of the separation vessel 2 .
  • Oil stored in the lower part is supplied to the bilge tank 30 .
  • liquefied ammonia mixed with oil and impurities extracted in the extraction unit 4 is also supplied to the bilge tank 30 .
  • Ammonia gas obtained from the bilge tank 30 is treated by the abatement device 7 and then released to the atmosphere.
  • the oil contained in the waste liquid is, for example, seal oil used for fuel injection valves of the fuel supply unit 21 and marine diesel engine unit 23 .
  • seal oil used for fuel injection valves of the fuel supply unit 21 and marine diesel engine unit 23 .
  • propane gas molecules themselves which are the main component, do not have polarity. Therefore, the propane gas molecules are mixed with the seal oil and can be treated as fuel.
  • ammonia molecules themselves have polarity. Therefore, the ammonia molecules do not mix with the seal oil, making it difficult to treat it as fuel. Therefore, in the separation vessel 2, the oil and liquefied ammonia are separated.
  • the liquefied ammonia separated in the separation container 2 is supplied to the storage section 5 via the extraction section 4 or directly.
  • the extractor 4 removes impurities that may be contained in the liquefied ammonia. Impurities are mainly volatile oils. When impurities are supplied to the selective reduction catalyst unit 61, oil adheres to the catalyst, degrading its performance. Therefore, it is desirable to install the extractor 4 in front of the reservoir 5 so as to remove the oil that could not be separated by gravity separation or the like in the separation vessel 2 . By removing impurities such as unnecessary oil, the efficiency of the selective reduction catalyst unit 61 is increased.
  • liquefied ammonia may be supplied directly from the separation container 2 to the storage unit 5 without passing through the extraction unit 4 .
  • the liquefied ammonia supplied to the storage unit 5 is supplied to the transportation unit 6 as ammonia gas by the vaporizer 8 . Further, ammonia gas is supplied to the selective reduction catalyst unit 61 and used as a reducing agent.
  • the reason why ammonia gas is supplied to the selective reduction catalyst unit 61 instead of liquefied ammonia is that the temperature of liquefied ammonia is considerably lower than the temperature at which the selective reduction catalyst unit 61 acts. It is efficient to gasify ammonia so that the catalytic action of the selective reduction catalyst unit 61 is enhanced.
  • the supply of steam pressure eliminates the need for pumps and cooling, increasing the energy efficiency of the entire system.
  • the carburetor 8 is preferably installed immediately before the transport section 6 in order to prevent stress corrosion cracking of each engine, pipes, and the like. Furthermore, as the heat source of the evaporator 8, cooling water of the marine diesel engine unit 23 and heat of the exhaust gas of the marine diesel engine unit 23 can be used in addition to heat from electricity. This improves environmental friendliness.
  • the ammonia gas obtained from the vaporizer 8 is preferably pressurized to, for example, about 6 bar, more preferably about 7 bar, and even more preferably about 8 bar. Specifically, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 bar, even within the range between any two of the numerical values exemplified here good. As a result, there is no need to install a booster in the transportation section 6, and the configuration of the surplus ammonia processing unit 1 can be simplified.
  • FIG. 3 is one aspect of the present embodiment, and is an overall view of a surplus ammonia processing unit when ammonia water is supplied.
  • the functions and configurations of the separation container 2, the separation section 3, and the extraction section 4 are the same as those of the first embodiment.
  • the storage unit 5 stocks the separated ammonia component directly from the separation container 2 or via the extraction unit 4 .
  • the ammonia component is changed to ammonia water.
  • aqueous ammonia is supplied to the selective reduction catalyst unit 61 through the transport section 6 .
  • Liquefied ammonia can also cause stress corrosion cracking.
  • a neutralizing agent such as dilute sulfuric acid
  • it must be passed through the abatement device 7 in order to discharge excess ammonia to the atmosphere.
  • the neutralizing agent in advance, the load on the abatement device 7 becomes lighter than when water is used.
  • the concentration adjustment unit 9 is installed in the storage unit 5.
  • the ammonia supplied from the transport section 6 is a very small part of the ammonia used in the selective reduction catalyst unit 61, and is used in a supplementary manner. Therefore, if the concentration of aqueous ammonia is constant, nitrogen oxides can be efficiently removed regardless of whether the engine is in steady or unsteady operation. It should be noted that although the concentration of ammonia in the concentration adjustment unit 9 is preferably as high as possible, there is no lower limit to the concentration.
  • Table 1 shows the results of a simulated reactor test conducted to investigate the relationship between the ammonia concentration in the concentration adjustment unit 9, the denitrification rate in the selective reduction catalyst unit 61, and the concentration of leaked ammonia before being released to the atmosphere.
  • the ammonia water flow rate ratio shown in Table 1 is a value when the flow rate at an ammonia water concentration of 14 w% is set to 1, and is a value adjusted so that the ammonia concentration with respect to the entire exhaust gas is about 500 PPM at the time of vaporization. be. This numerical value is the flow rate adjusted so that the concentration of nitrogen oxides is approximately 1:1, or the amount of ammonia is slightly reduced.
  • the reservoir 5 is part of the abatement device 7 .
  • ammonia cannot be released into the atmosphere as it is because it affects the human body. Ammonia must be removed by the abatement device 7 .
  • Methods for removing the harm include a method of diluting ammonia with gas such as nitrogen, and a method of absorbing ammonia in water such as a scrubber as described above.
  • the surplus ammonia obtained in the surplus ammonia processing unit 1 of the first embodiment and the second embodiment is supplied to the selective reduction catalyst unit 61, via the pump unit 62 as shown in FIG. It may be supplied to the fuel supply unit 21 . Alternatively, surplus ammonia may be supplied directly to the marine diesel engine unit 23 via the pump unit 62 . By sending ammonia water to the fuel supply unit, fuel efficiency is improved and the concentration of nitrogen oxides in the exhaust gas is reduced.
  • either the selective reduction catalyst unit 61 or the pump unit 62 may be selected, or both may be used together.
  • the volume ratio of surplus ammonia when used together may be determined by the user as appropriate. Depending on the operating conditions of the engine, supplying either one will improve the fuel efficiency of the ammonia as a whole. Further, by using both together, the efficiency is further improved.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth 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)
  • Exhaust Gas After Treatment (AREA)

Abstract

La présente invention concerne un appareil et un procédé de traitement d'ammoniac en excès, l'appareil et le procédé pouvant utiliser l'excès d'ammoniac de manière efficace. Un appareil de traitement d'ammoniac en excès selon la présente invention est destiné à être utilisé pour un moteur diesel marin 23, qui utilise de l'ammoniac comme partie du carburant et est relié à une unité de catalyseur de réduction sélective 61, est pourvu : d'un récipient de séparation 2 qui contient un liquide résiduaire provenant du moteur diesel marin et sépare un composant huileux et un composant ammoniac l'un de l'autre ; et une unité de transport 6 qui fournit le composant d'ammoniac séparé par le récipient de séparation 2 à l'unité de catalyseur de réduction sélective 61.
PCT/JP2021/024702 2021-06-03 2021-06-30 Appareil et procédé de traitement d'ammoniac en excès WO2022254735A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020237035482A KR20230158084A (ko) 2021-06-03 2021-06-30 잉여 암모니아 처리 장치 및 처리 방법
JP2021538972A JP6940727B1 (ja) 2021-06-03 2021-06-30 余剰アンモニアの処理装置および処理方法
CN202180096900.9A CN117425768A (zh) 2021-06-03 2021-06-30 剩余氨的处理装置以及处理方法

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JP2021-093873 2021-06-03
JP2021093873 2021-06-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7553730B1 (ja) 2024-01-30 2024-09-18 三菱化工機株式会社 潤滑油清浄システム及び潤滑油清浄方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01318716A (ja) * 1988-06-17 1989-12-25 Mitsubishi Heavy Ind Ltd 内燃機関の排気脱硝方法
US20050126513A1 (en) * 2002-01-29 2005-06-16 Fredrick Hendren On-board diesel oil and water emulsification system
WO2020183522A1 (fr) * 2019-03-08 2020-09-17 Ｊｆｅエンジニアリング株式会社 Moteur diesel
JP2020180567A (ja) * 2019-04-24 2020-11-05 株式会社ジャパンエンジンコーポレーション 舶用ディーゼルエンジン
CN112128034A (zh) * 2019-06-24 2020-12-25 日本发动机股份有限公司 船用内燃机

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01318716A (ja) * 1988-06-17 1989-12-25 Mitsubishi Heavy Ind Ltd 内燃機関の排気脱硝方法
US20050126513A1 (en) * 2002-01-29 2005-06-16 Fredrick Hendren On-board diesel oil and water emulsification system
WO2020183522A1 (fr) * 2019-03-08 2020-09-17 Ｊｆｅエンジニアリング株式会社 Moteur diesel
JP2020180567A (ja) * 2019-04-24 2020-11-05 株式会社ジャパンエンジンコーポレーション 舶用ディーゼルエンジン
CN112128034A (zh) * 2019-06-24 2020-12-25 日本发动机股份有限公司 船用内燃机

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7553730B1 (ja) 2024-01-30 2024-09-18 三菱化工機株式会社 潤滑油清浄システム及び潤滑油清浄方法

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