WO2013088850A1 - Structure de pulvérisation d'urée aqueuse - Google Patents

Structure de pulvérisation d'urée aqueuse Download PDF

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Publication number
WO2013088850A1
WO2013088850A1 PCT/JP2012/078166 JP2012078166W WO2013088850A1 WO 2013088850 A1 WO2013088850 A1 WO 2013088850A1 JP 2012078166 W JP2012078166 W JP 2012078166W WO 2013088850 A1 WO2013088850 A1 WO 2013088850A1
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WO
WIPO (PCT)
Prior art keywords
exhaust
urea water
exhaust gas
evaporation pipe
pipe
Prior art date
Application number
PCT/JP2012/078166
Other languages
English (en)
Japanese (ja)
Inventor
重樹 岡崎
Original Assignee
日立造船株式会社
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 日立造船株式会社 filed Critical 日立造船株式会社
Priority to CN201280050990.9A priority Critical patent/CN103890335B/zh
Priority to KR1020147010650A priority patent/KR102001477B1/ko
Priority to CH00885/14A priority patent/CH707487B1/de
Publication of WO2013088850A1 publication Critical patent/WO2013088850A1/fr
Priority to DKPA201470377A priority patent/DK178838B1/en

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Classifications

    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting 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
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/08—Adding substances to exhaust gases with prior mixing of the substances with a gas, e.g. air
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/08—Adding substances to exhaust gases with prior mixing of the substances with a gas, e.g. air
    • F01N2610/085—Controlling the air supply
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/10—Adding substances to exhaust gases the substance being heated, e.g. by heating tank or supply line of the added substance
    • F01N2610/102—Adding substances to exhaust gases the substance being heated, e.g. by heating tank or supply line of the added substance after addition to exhaust gases, e.g. by a passively or actively heated surface in the exhaust conduit
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1453—Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
    • 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 is an exhaust gas that purifies by reacting nitrogen oxide (hereinafter referred to as “NOx”) in exhaust gas discharged from an internal combustion engine with a reducing agent under a selective reduction catalyst (hereinafter referred to as “SCR catalyst”).
  • NOx nitrogen oxide
  • SCR catalyst selective reduction catalyst
  • a denitration reactor equipped with an SCR catalyst is installed downstream of the exhaust pipe of the engine, and ammonia gas is added as a reducing agent to the exhaust passage upstream of the denitration reactor, so that NOx in the exhaust gas is removed in the denitration reactor.
  • a technique for purification is disclosed (Patent Document 1).
  • the ammonia gas generated by the hydrolysis is supplied to the SCR catalyst, whereby a denitration reaction such as the following formulas (2) and (3) is performed between ammonia and NOx in the exhaust gas on the SCR catalyst, NOx is decomposed into nitrogen and water and detoxified.
  • a denitration reaction such as the following formulas (2) and (3) is performed between ammonia and NOx in the exhaust gas on the SCR catalyst, NOx is decomposed into nitrogen and water and detoxified.
  • a muffler is provided as a means for promoting the generation of ammonia between the urea water addition nozzle and the NOx soot catalytic converter.
  • a nozzle for spraying urea water provided in the exhaust passage 104 upstream of the turbine 103 a of the turbocharger 103.
  • An evaporation pipe 107 for promoting hydrolysis of urea water sprayed from the nozzle 105 may be provided between the 105 and the SCR catalyst 106.
  • ammonia generated by hydrolysis of urea water is not uniformly diffused in the exhaust gas, and is supplied to the SCR catalyst 106 in a nonuniform state.
  • the progress of the denitration reaction of the above formulas (2) and (3) may be insufficient.
  • the conventional exhaust gas purifying apparatus uses a fuel containing a large amount of sulfur, the temperature of the exhaust gas is lowered by spraying urea water in an atmosphere where the ratio of SO 3 contained in the exhaust gas is high, ammonium sulfate, Byproducts such as acidic ammonium sulfate are likely to be produced. Further, in the conventional exhaust gas purifying apparatus, the sprayed urea water adheres to the wall surface, so that by-products such as cyanuric acid are easily generated.
  • the problem to be solved by the present invention is that the above-mentioned by-products have caused problems such as corrosion and blockage of the exhaust passage and degradation of the performance of the SCR catalyst.
  • the urea water spray structure of the present invention is An exhaust gas purification apparatus having a denitration reactor provided between an exhaust manifold that collects exhaust gas discharged from an exhaust communication pipe connected to an exhaust port of an engine and an exhaust passage upstream of a turbine of a turbocharger
  • a urea spray structure capable of supplying ammonia to the SCR catalyst of the denitration reactor,
  • an evaporation pipe connected to the branch pipe branched from the air supply passage on the downstream side of the turbocharger compressor is disposed, and The most important feature point is that the evaporation pipe is provided with a nozzle for spraying urea water to the air introduced into the evaporation pipe through the branch pipe.
  • an evaporation pipe connected to a branch pipe branched from an air supply passage on the downstream side of a turbocharger compressor is arranged in an exhaust manifold, and urea water spray and ammonia are arranged in the evaporation pipe.
  • urea water spray and ammonia are arranged in the evaporation pipe.
  • the wall surface of the evaporation pipe provided in the exhaust manifold is sufficiently heated by the high-temperature exhaust gas immediately after being discharged from the exhaust communication pipe, and the temperature is also increased in the region where the urea water is sprayed. Therefore, it is possible to prevent the formation of by-products such as cyanuric acid. Also, even if a by-product is generated and adheres to the wall surface of the evaporation tube when the engine is in a low load state, the wall surface of the evaporation tube becomes hot again if the engine is in a high load state. Temporarily adhered by-products can be decomposed.
  • the present invention provides an exhaust gas purifying apparatus in which, when the proportion of SO 3 contained in the exhaust gas is high, or even when urea water is sprayed in a region where the temperature of the exhaust gas is lowered, secondary substances such as ammonium sulfate, acidic ammonium sulfate, and cyanuric acid are used.
  • An exhaust gas purification apparatus having a denitration reactor provided between an exhaust manifold that collects exhaust gas discharged from an exhaust communication pipe connected to an exhaust port of an engine and an exhaust passage upstream of a turbine of a turbocharger
  • a urea spray structure capable of supplying ammonia to the SCR catalyst of the denitration reactor
  • an evaporation pipe connected to the branch pipe branched from the air supply passage on the downstream side of the turbocharger compressor is disposed, and This is realized by adopting a urea water spraying structure in which a nozzle for spraying urea water to the air introduced into the evaporation pipe through the branch pipe is provided in the evaporation pipe.
  • reference numeral 1 denotes a 4-cylinder marine diesel engine to which the urea water spray structure of the present invention is applied, which is discharged from an exhaust communication pipe 2 connected to an exhaust port 1a provided in each cylinder head.
  • An exhaust manifold 3 that collects high-temperature exhaust gas and guides it to an exhaust passage 5 upstream of the turbine 4 a of the turbocharger 4 is provided.
  • the main part of the urea water spray structure of the present invention is mounted inside the exhaust manifold 3, is continuously disposed in the exhaust manifold 3, and is a denitration reactor provided between the exhaust passage 5 on the upstream side of the turbine 4 a.
  • 6 constitutes an exhaust gas purification device 7.
  • Reference numeral 4b denotes a compressor of the turbocharger 4
  • 8 denotes an air supply passage through which air compressed by the compressor 4b is sent.
  • an evaporation pipe 10 connected to a branch pipe 9 branched from a branch portion 8a of an air supply passage 8 on the downstream side of the compressor 4b is disposed.
  • the evaporation pipe 10 has one end connected to the branch pipe 9 and the other end opened to the exhaust manifold 3 through the ejection hole 10a.
  • Reference numeral 11 denotes a nozzle for spraying urea water to the air introduced into the evaporation pipe 10 through the branch pipe 9.
  • the air passing through the evaporation pipe 10 is compressed by the compressor 4b and is in a high temperature state, but this air is not introduced into the intake port of the engine 1 and does not contain SO 3 .
  • the urea water spray structure of the present embodiment introduces high-temperature air that does not contain SO 3 into the evaporation pipe 10 and promotes hydrolysis of urea water by spraying urea water on the air in the evaporation pipe 10. Even when a fuel containing a large amount of sulfur is used, it is possible to suppress the generation of by-products resulting from the reaction between ammonia and SO 3 .
  • the position where the nozzle 11 is provided is a region where the evaporation pipe 10 exists in the exhaust manifold 3 (an area other than A) rather than the area where the evaporation pipe 10 protrudes outside the exhaust manifold 3 (area A). ) Is preferable. This is because the wall surface of the evaporation pipe 10 can always be kept at a high temperature by direct contact with the high-temperature exhaust gas immediately after being discharged from the exhaust port of the exhaust communication pipe 2, so that the production of by-products due to the low temperature can be suppressed.
  • the evaporation pipe 10 is arranged so that the longitudinal direction of the evaporation pipe 10 is parallel to the direction in which the exhaust ports of the exhaust communication pipe 2 connected to the exhaust port 1a of each cylinder of the engine 1 are arranged.
  • the position of the nozzle 11 may be determined so that the region B where the urea water sprayed from the nozzle 11 flows faces the exhaust port of the exhaust communication pipe 2.
  • the SCR catalyst 6a that selectively reduces and removes NOx soot that is contained in the exhaust gas discharged from the engine 1 and causes environmental pollution such as acid rain and photochemical smog is interposed in the denitration reactor 6.
  • a desired catalyst such as a metal oxide catalyst such as alumina, zirconia, vanadia / titania or a zeolite catalyst may be used, and these catalysts may be combined.
  • the SCR catalyst 6a may be carried on a catalyst carrier having a honeycomb structure, for example, or may be charged in a cylinder and caged.
  • the urea water spray structure of the present invention supplies ammonia in a completely hydrolyzed state to the SCR catalyst 6a.
  • a hydrolysis catalyst 12 for promoting the hydrolysis of urea water is provided inside the evaporation pipe 10 and downstream of the nozzle 11 so as to further increase the efficiency of hydrolysis.
  • the hydrolysis catalyst 12 may be any catalyst that has an action of promoting ammonia generation.
  • a desired catalyst such as a titanium oxide catalyst or an alkali metal catalyst can be used.
  • an ejection hole 10a for ejecting ammonia generated by hydrolysis of urea water toward the SCR catalyst 6a is provided on the downstream side of the hydrolysis catalyst 12 of the evaporation pipe 10. Therefore, the ammonia gas generated by hydrolysis in the evaporation pipe 10 is ejected at a high pressure into the exhaust gas in the exhaust manifold 3 through the small-diameter ejection hole 10a, and is sufficiently diffused in the exhaust gas. Therefore, the progress of the denitration reaction does not become insufficient.
  • the evaporation pipe 10 including the nozzle 11 and the hydrolysis catalyst 12 is incorporated in the exhaust manifold 3, the evaporation pipe is provided in the exhaust passage 5 on the upstream side of the turbine 4a.
  • Space saving can be achieved compared with the conventional apparatus.
  • the exhaust passage leading to the turbocharger 4 can be shortened as compared with the conventional device in which the exhaust manifold and the exhaust pipe are arranged side by side, thereby reducing the loss of air pressure in the exhaust passage. This is also advantageous.
  • FIG. 13 indicates an air cooler provided in the air supply passage 8.
  • the air compressed by the compressor 4b rises in temperature and tends to expand. However, if expanded, the density of the air decreases and the amount of air decreases. 1 is supplied with air.
  • the position where the branch pipe 9 is branched from the air supply passage 8 (the position of the branch portion 8 a) is upstream of the air cooler 13. Is preferred. This is because, in the present invention, feeding hot air to the evaporation pipe 10 is advantageous in promoting hydrolysis of urea water.
  • the air supply 14 denotes a receiver tank provided on the downstream side of the air cooler 13.
  • the air is quickly supplied from the receiver tank 14, and when the pressure in the receiver tank decreases thereafter, the decrease is replenished by supply from the compressor 4b. Even when a large amount of air exceeding the capacity is needed instantaneously, the air supply is kept short.
  • the evaporation pipe connected to the branch pipe branched from the air supply passage on the downstream side of the compressor of the turbocharger is arranged in the exhaust manifold, Since the hydrolysis to ammonia is completed by spraying urea water, it is possible to suppress the formation of by-products such as ammonium sulfate and acidic ammonium sulfate even when using a fuel containing a large amount of sulfur.
  • the wall surface of the evaporation pipe provided in the exhaust manifold is sufficiently heated by the high-temperature exhaust gas immediately after being discharged from the exhaust communication pipe, the temperature does not become insufficient even in the area where the urea water is sprayed, such as cyanuric acid. It is possible to prevent the formation of by-products.
  • the urea water spray structure of the present invention can be applied not only to marine diesel engines but also to automobile diesel engines.

Abstract

Le problème décrit par la présente invention est de limiter la production de sous-produits même lorsque la proportion de SO3 contenue dans les gaz d'échappement est élevée ou lorsque l'urée aqueuse est pulvérisée dans une région à température de gaz d'échappement réduite. La solution de l'invention porte sur une structure de pulvérisation d'urée aqueuse pouvant apporter de l'ammoniac à un catalyseur SCR (6a) d'un réacteur à dénitrogénation (6) d'un dispositif de nettoyage (7) de gaz d'échappement équipé d'un réacteur à dénitrogénation (6) situé entre un collecteur d'échappement (3) qui collecte les gaz d'échappement rejetés depuis des tubes de raccordement d'échappement (2) qui sont raccordés aux orifices d'échappement (1a) d'un moteur (1), et d'un passage d'échappement (5) en amont d'une turbine (4a) d'un turbocompresseur (4). Un tube d'évaporation (10) raccordé à un tuyau de bifurcation (9) bifurquant d'un passage d'alimentation en gaz (8) en aval du compresseur (4b) du turbocompresseur (4) est disposé à l'intérieur du collecteur d'échappement (3) et une buse (11) qui pulvérise l'urée aqueuse dans l'air traversant le tube d'évaporation (10) est prévue. La présente invention a pour effet d'empêcher la corrosion et l'occlusion du passage d'échappement et peut également conserver des performances de catalyseur SCR favorables.
PCT/JP2012/078166 2011-12-13 2012-10-31 Structure de pulvérisation d'urée aqueuse WO2013088850A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201280050990.9A CN103890335B (zh) 2011-12-13 2012-10-31 尿素水喷雾结构
KR1020147010650A KR102001477B1 (ko) 2011-12-13 2012-10-31 요소수 분무구조
CH00885/14A CH707487B1 (de) 2011-12-13 2012-10-31 Harnstofflösung-Sprühanordnung.
DKPA201470377A DK178838B1 (en) 2011-12-13 2014-06-23 Urea solution spraying structure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-272391 2011-12-13
JP2011272391A JP5753485B2 (ja) 2011-12-13 2011-12-13 尿素水噴霧構造

Publications (1)

Publication Number Publication Date
WO2013088850A1 true WO2013088850A1 (fr) 2013-06-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/078166 WO2013088850A1 (fr) 2011-12-13 2012-10-31 Structure de pulvérisation d'urée aqueuse

Country Status (6)

Country Link
JP (1) JP5753485B2 (fr)
KR (1) KR102001477B1 (fr)
CN (1) CN103890335B (fr)
CH (1) CH707487B1 (fr)
DK (1) DK178838B1 (fr)
WO (1) WO2013088850A1 (fr)

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CN109395581A (zh) * 2018-12-17 2019-03-01 青岛双瑞海洋环境工程股份有限公司 船舶废气脱硝系统

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US9850794B2 (en) 2015-06-29 2017-12-26 General Electric Company Power generation system exhaust cooling
US10030558B2 (en) 2015-06-29 2018-07-24 General Electric Company Power generation system exhaust cooling
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KR20170135093A (ko) * 2016-05-30 2017-12-08 두산엔진주식회사 환원제 분해 시스템
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KR102137323B1 (ko) * 2018-11-20 2020-07-23 에이치에스디엔진 주식회사 선택적 촉매 환원 시스템
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CN113184879A (zh) * 2021-05-20 2021-07-30 山东省中医药研究院 一种利用纳米氧化铝催化尿素水解的方法

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JP2013124555A (ja) 2013-06-24
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CH707487B1 (de) 2017-05-15
JP5753485B2 (ja) 2015-07-22
DK201470377A (en) 2014-06-23
KR20140105435A (ko) 2014-09-01
DK178838B1 (en) 2017-03-13
CN103890335B (zh) 2017-06-09

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