JP2006029147A - Exhaust gas cleaning system and exhaust gas cleaning method - Google Patents

Exhaust gas cleaning system and exhaust gas cleaning method Download PDF

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JP2006029147A
JP2006029147A JP2004206425A JP2004206425A JP2006029147A JP 2006029147 A JP2006029147 A JP 2006029147A JP 2004206425 A JP2004206425 A JP 2004206425A JP 2004206425 A JP2004206425 A JP 2004206425A JP 2006029147 A JP2006029147 A JP 2006029147A
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exhaust gas
reducing agent
urea
cylinder
temperature
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Masashi Gabe
我部　　正志
Taiji Nagaoka
大治 長岡
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Isuzu Motors Ltd
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    • 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]
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
    • 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
    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
    • 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
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B2275/00—Other engines, components or details, not provided for in other groups of this subclass
    • F02B2275/14—Direct injection into combustion chamber
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Output Control And Ontrol Of Special Type Engine (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an exhaust gas cleaning system and an exhaust gas cleaning method capable of improving the low temperature activity of a selective contact reduction catalyst for removal of NOx using urea water solution without using ammonia which is a dangerous solution, and difficult to handle with. <P>SOLUTION: In the exhaust gas cleaning system 10, the selective contact reduction catalyst 16 to remove nitrogen oxygen is provided in an exhaust passage 4 of an internal combustion engine 1 so as to remove nitrogen oxide in the exhaust gas. A feeder 14 of a reducing agent into an exhaust pipe is provided in the exhaust passage on the upstream side of the selective contact reduction catalyst 16. An injector 15 of reducing agent into a cylinder to feed reducing agent into the cylinder 2 of the internal combustion engine 1 is installed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、内燃機関の排気ガス中のＮＯｘを選択接触還元触媒を用いて浄化する排気ガス浄化システム及び排気ガス浄化方法に関するものである。   The present invention relates to an exhaust gas purification system and an exhaust gas purification method for purifying NOx in exhaust gas of an internal combustion engine using a selective catalytic reduction catalyst.

ディーゼルエンジン等のエンジン（内燃機関）から排出される微粒子状物質（ＰＭ）、ＮＯｘ、ＣＯそしてＨＣ等は、年々規制が強化されてきている。この規制の強化に伴い、エンジンの改良のみでは規制値への対応ができなくなってきている。そこで、エンジンに触媒を用いた排気ガス後処理装置を着装して、エンジンから排出されるこれらの物質を低減する技術が採用されている。   Regulations for particulate matter (PM), NOx, CO, HC, and the like discharged from an engine (internal combustion engine) such as a diesel engine have been strengthened year by year. Along with this stricter regulation, it has become impossible to meet the regulation value only by improving the engine. Therefore, a technique is adopted in which an exhaust gas aftertreatment device using a catalyst is attached to the engine to reduce these substances discharged from the engine.

この従来技術の一つに、図４に示すような、選択接触還元触媒（ＳＣＲ触媒）に尿素を供給して、排気ガス中のＮＯｘを浄化する排気ガス浄化システム２０がある。このシステム２０は、３４％程度の尿素水溶液を貯蔵する尿素タンク２１と尿素水排気管内噴射弁２２を有する尿素噴射システムと、尿素加水分解機能及びアンモニア還元機能を有する選択接触還元触媒２３とを有して構成される。   As one of the prior arts, there is an exhaust gas purification system 20 for purifying NOx in exhaust gas by supplying urea to a selective catalytic reduction catalyst (SCR catalyst) as shown in FIG. This system 20 includes a urea injection system having a urea tank 21 for storing about 34% urea aqueous solution and a urea water exhaust pipe injection valve 22, and a selective catalytic reduction catalyst 23 having a urea hydrolysis function and an ammonia reduction function. Configured.

この排気ガス浄化システム２０では、尿素タンク２１から尿素水排気管内噴射弁２２により排気通路（排気管）４内に添加された尿素は、前段の加水分解機能によって、「（ＮＨ2 ）2 ＣＯ＋Ｈ2 Ｏ→２ＮＨ3 ＋ＣＯ2 」の反応により、排気ガス中の熱と燃焼によって生成された水蒸気からアンモニアを生成する。 In this exhaust gas purification system 20, urea added from the urea tank 21 into the exhaust passage (exhaust pipe) 4 by the urea water exhaust pipe injection valve 22 is converted into “(NH 2 ) 2 CO + H 2 by the hydrolysis function of the previous stage. By the reaction of “O → 2NH 3 + CO 2 ”, ammonia is generated from the heat in the exhaust gas and the water vapor generated by the combustion.

そして、後段のアンモニア還元機能により、この生成したアンモニアを還元剤として、「６ＮＯ＋４ＮＨ3 →５Ｎ2 ＋６Ｈ2 Ｏ」と「４ＮＯ＋４ＮＨ3 ＋Ｏ2 →４Ｎ2 ＋６Ｈ2 Ｏ」の反応により、選択接触ＮＯｘ還元を行いＮＯｘを浄化する。この反応は、酸素が共存する場合でも進み、一酸化窒素（ＮＯ）の１モルに対して、アンモニア（ＮＨ3 ）の１モルの反応となる。 Then, by the subsequent ammonia reduction function, selective catalytic NOx reduction is performed by the reaction of “6NO + 4NH 3 → 5N 2 + 6H 2 O” and “4NO + 4NH 3 + O 2 → 4N 2 + 6H 2 O” using the generated ammonia as a reducing agent. To purify NOx. This reaction proceeds even when oxygen coexists, and becomes 1 mol of ammonia (NH 3 ) per 1 mol of nitric oxide (NO).

なお、この選択接触還元触媒２３は、尿素加水分解機能を有する触媒を前段に配置し、アンモニア還元機能を有する触媒を後段に配置して形成する場合もあるが、アンモニア還元選択ＮＯｘ触媒中に加水分解機能を持たせて形成する場合もある。   The selective catalytic reduction catalyst 23 may be formed by arranging a catalyst having a urea hydrolysis function in the previous stage and a catalyst having an ammonia reduction function in the subsequent stage. It may be formed with a decomposition function.

しかしながら、この従来の尿素選択接触還元触媒２３を用いた排気ガス浄化システム２０では、ＮＯｘ浄化率が、図３の実線Ａで示すように、３００℃位から著しく低下してしまうという問題がある。つまり、添加した尿素から前段の加水分解反応によって還元剤のアンモニアを生成しているが、この尿素加水分解反応が吸熱反応であるため、低温における活性が低く、そのために、システム全体として、低温域におけるＮＯｘ浄化活性が低下してしまうのである。   However, in the exhaust gas purification system 20 using the conventional urea selective catalytic reduction catalyst 23, there is a problem that the NOx purification rate is remarkably reduced from about 300 ° C. as shown by the solid line A in FIG. In other words, ammonia as a reducing agent is generated from the added urea by the preceding hydrolysis reaction, but since this urea hydrolysis reaction is an endothermic reaction, the activity at low temperatures is low, and as a result, the entire system is in a low temperature range. The NOx purification activity in this will decrease.

一方、図３の破線Ｂで示すように、直接アンモニアを添加する場合には、選択接触還元触媒において、加水分解反応の必要が無くなるため、低温でもＮＯｘ浄化活性は高い。従って、選択接触還元触媒にアンモニアを供給すれば高い低温活性を得ることができる。しかしながら、アンモニアは、危険溶液であり、取り扱いが尿素水溶液ほど手軽にはできないという問題がある。   On the other hand, as shown by the broken line B in FIG. 3, in the case of directly adding ammonia, the selective catalytic reduction catalyst eliminates the need for a hydrolysis reaction, so that the NOx purification activity is high even at low temperatures. Therefore, high ammonia activity can be obtained by supplying ammonia to the selective catalytic reduction catalyst. However, ammonia is a dangerous solution and has a problem that it cannot be handled as easily as an aqueous urea solution.

このアンモニアを使用した排気ガス浄化装置としては、アンモニア化合物添加により選択還元が行われるアンモニア化合物選択還元触媒と、排気ガスの空燃比がリーンのときにＮＯｘを吸蔵し、排気ガス中の酸素濃度が低下すると吸蔵したＮＯｘを放出・還元するＮＯｘ吸蔵還元型触媒とを排気通路に備えて、高回転・高負荷運転のときにアンモニア化合物選択還元触媒を機能させ、その他のときにはＮＯｘ吸蔵還元型触媒を機能させる内燃機関の排気浄化装置が提案されている（例えば、特許文献１参照。）。   The exhaust gas purifying apparatus using ammonia includes an ammonia compound selective reduction catalyst that performs selective reduction by adding an ammonia compound, and stores NOx when the air-fuel ratio of the exhaust gas is lean, and the oxygen concentration in the exhaust gas is reduced. The exhaust passage is equipped with a NOx occlusion reduction type catalyst that releases and reduces the NOx occluded when it is lowered. The ammonia compound selective reduction catalyst functions during high-speed and high-load operation, and the NOx occlusion reduction type catalyst at other times. An exhaust gas purifying device for an internal combustion engine to function is proposed (for example, refer to Patent Document 1).

しかしながら、この内燃機関の排気浄化装置の場合には、ＮＯｘ吸蔵還元型触媒は高温の排気ガスに曝されると劣化が激しいので、劣化対策が必要になるという問題や、排気通路の切り替えを必要とする場合には、ＮＯｘを吸蔵したＮＯｘ吸蔵還元型触媒の再生時の制御が複雑となると共にＮＯｘが大気中へ放出されてしまうというスリップの問題も発生する。   However, in the case of this exhaust gas purification device for an internal combustion engine, the NOx occlusion reduction type catalyst is severely deteriorated when exposed to high-temperature exhaust gas. In this case, the control at the time of regeneration of the NOx occlusion reduction type catalyst that occludes NOx becomes complicated, and the problem of slip that NOx is released into the atmosphere also occurs.

また、触媒を使用することなく、酸化窒素を分解させる脱硝装置として、内燃機関におけるシリンダあるいは排気ポートの排気弁の近接部に、アンモニア、または、アンモニア前駆物質（尿素等）を燃焼排ガス中に添加する噴射弁を設けて、排ガスをキヤリアガスとして適用することにより、機構の小型化、コスト節減とともに脱硝性能、信頼性を向上した内燃機関の排気脱硝装置が提案されている（例えば、特許文献２参照。）。   In addition, as a denitration device that decomposes nitric oxide without using a catalyst, ammonia or an ammonia precursor (such as urea) is added to combustion exhaust gas in the vicinity of the exhaust valve of a cylinder or exhaust port in an internal combustion engine. There has been proposed an exhaust denitration device for an internal combustion engine that is provided with an injection valve that applies exhaust gas as a carrier gas and has improved denitration performance and reliability as well as miniaturization of the mechanism and cost reduction (see, for example, Patent Document 2) .)

しかしながら、この装置では、触媒作用を利用することなく、直接アンモニアで窒素酸化物を還元しているので、触媒利用よりも浄化率が低くなるという問題や、排気ガスが高温の時には、反応が進行してアンモニアが窒素酸化物になってしまうという問題がある。   However, in this device, nitrogen oxides are directly reduced with ammonia without using a catalytic action, so that the purification rate is lower than when using a catalyst, and the reaction proceeds when the exhaust gas is hot. Then, there is a problem that ammonia becomes nitrogen oxides.

また、吸気通路、燃焼室、及び排気通路の少なくとも一つにＨＣ等の還元剤を添加する添加装置を備えて、運転情報と添加量との関係を学習しながら、添加量を最適化しつつ、排気通路の選択還元触媒で浄化する排気浄化装置が提案されている（例えば、特許文献３参照。）。   In addition, an addition device that adds a reducing agent such as HC to at least one of the intake passage, the combustion chamber, and the exhaust passage, while learning the relationship between the operation information and the addition amount, while optimizing the addition amount, An exhaust gas purification device that purifies with a selective reduction catalyst in an exhaust passage has been proposed (see, for example, Patent Document 3).

しかしながら、この装置では、排気系に添加したＨＣがスモークを発生する場合が有り、ＨＣの燃焼により触媒が高温になるという問題がある。
特許第３５１８３９８公報 特許第２５９２１１９号公報 特開平１０−３１１２１２号公報 However, in this apparatus, HC added to the exhaust system may generate smoke, and there is a problem that the catalyst becomes high temperature due to combustion of HC.
Japanese Patent No. 3518398 Japanese Patent No. 2592119 JP-A-10-311212

本発明はこの問題を解決するためになされたものであり、本発明の目的は、危険溶液で取り扱いの難しいアンモニアを使用せずに、尿素水溶液を用いながら、ＮＯｘ浄化に対する選択接触還元触媒の低温活性を向上できる排気ガス浄化システム及び排気ガス浄化方法を提供することにある。   The present invention has been made to solve this problem, and an object of the present invention is to use a low temperature of a selective catalytic reduction catalyst for NOx purification while using an aqueous urea solution without using ammonia that is difficult to handle in a hazardous solution. An object of the present invention is to provide an exhaust gas purification system and an exhaust gas purification method capable of improving the activity.

上記の目的を達成するための本発明に係る排気ガス浄化システムは、内燃機関の排気通路に窒素酸化物を浄化する選択接触還元触媒を備えて、排気ガス中の窒素酸化物を浄化する排気ガス浄化システムにおいて、前記選択接触還元触媒の上流側に排気通路に還元剤を供給する還元剤排気管内供給装置を備えると共に、内燃機関の筒内に還元剤を供給する還元剤筒内噴射装置を設けて構成される。   In order to achieve the above object, an exhaust gas purification system according to the present invention includes a selective catalytic reduction catalyst that purifies nitrogen oxides in an exhaust passage of an internal combustion engine, and exhaust gas that purifies nitrogen oxides in the exhaust gas. In the purification system, a reducing agent exhaust pipe supply device for supplying the reducing agent to the exhaust passage is provided upstream of the selective catalytic reduction catalyst, and a reducing agent in-cylinder injection device for supplying the reducing agent into the cylinder of the internal combustion engine is provided. Configured.

この還元剤筒内噴射装置には、直接、内燃機関の筒内（シリンダ内）に還元剤を供給する装置のみならず、吸気通路に還元剤を噴射して筒内に還元剤を供給する装置も含む。   This reducing agent in-cylinder injection device not only directly supplies the reducing agent into the cylinder (inside the cylinder) of the internal combustion engine, but also supplies the reducing agent into the cylinder by injecting the reducing agent into the intake passage. Including.

この構成により、排気管尿素噴射に加えて、エンジンの筒内への筒内尿素噴射を併用することができるようになるので、筒内の燃焼熱を利用して尿素を加水分解して、アンモニアを生成することができる。従って、比較的取り扱いが容易な尿素を用いながら、アンモニア添加の場合の選択接触還元触媒効果も奏することができるようになる。従って、尿素添加の場合の選択接触還元触媒効果の低温における活性低下を補うことができ、選択接触還元触媒を使用した排気ガス浄化システムの低温活性を向上できる。   With this configuration, in addition to exhaust pipe urea injection, in-cylinder urea injection into the cylinder of the engine can be used in combination, so urea is hydrolyzed using the combustion heat in the cylinder, and ammonia Can be generated. Therefore, the selective catalytic reduction catalytic effect in the case of ammonia addition can be achieved while using urea that is relatively easy to handle. Therefore, it is possible to compensate for the decrease in activity at a low temperature of the selective catalytic reduction catalyst effect in the case of urea addition, and it is possible to improve the low temperature activity of the exhaust gas purification system using the selective catalytic reduction catalyst.

そして、上記の排気ガス浄化システムにおいて、排気ガス温度が、所定の判定温度を超える場合には、前記還元剤排気管内供給装置により還元剤を排気通路に供給し、排気ガス温度が、前記所定の判定温度以下である場合には、前記還元剤筒内噴射装置により還元剤を筒内に供給するように構成される。   In the exhaust gas purification system, when the exhaust gas temperature exceeds a predetermined determination temperature, the reducing agent exhaust pipe supply device supplies the reducing agent to the exhaust passage, and the exhaust gas temperature is When the temperature is equal to or lower than the determination temperature, the reducing agent is supplied into the cylinder by the reducing agent in-cylinder injection device.

この排気ガス温度に対する所定の判定温度には、排気ガス温度がこの所定の判定温度を超えている場合には、選択接触還元触媒が活性温度を超え、排気ガス温度がこの所定の判定温度以下の場合には、選択接触還元触媒が活性温度以下となる温度が選ばれる。   When the exhaust gas temperature exceeds the predetermined determination temperature, the selective catalytic reduction catalyst exceeds the activation temperature and the exhaust gas temperature is equal to or lower than the predetermined determination temperature for the exhaust gas temperature. In such a case, the temperature at which the selective catalytic reduction catalyst is below the activation temperature is selected.

また、上記の排気ガス浄化システムにおいては、還元剤としては、アンモニア前駆物質である尿素水溶液やカルバミン酸アンモニウム等を用いることもできるが、還元剤が尿素水溶液である場合には取り扱いが容易となるので、尿素水溶液を用いることが好ましい。   In the exhaust gas purification system described above, the reducing agent may be urea aqueous solution or ammonium carbamate that is an ammonia precursor. However, when the reducing agent is urea aqueous solution, the handling becomes easy. Therefore, it is preferable to use an aqueous urea solution.

また、上記の目的を達成するための本発明に係る排気ガス浄化方法は、内燃機関の排気通路に窒素酸化物を浄化する選択接触還元触媒を備えると共に、該選択接触還元触媒の上流側に配置され、排気通路に尿素水溶液を供給する還元剤排気管内供給装置と、内燃機関の筒内に尿素水溶液を供給する還元剤筒内噴射装置を備えて、排気ガス中の窒素酸化物を浄化する排気ガス浄化システムにおいて、前記選択接触還元触媒の温度が尿素の加水分解の活性温度を超える場合には、前記還元剤排気管内供給装置により尿素水溶液を排気通路に供給し、前記選択接触還元触媒の温度が尿素の加水分解の活性温度以下である場合には、前記還元剤筒内噴射装置により尿素水溶液を筒内に供給し、前記還元剤筒内噴射装置より供給された尿素水溶液を、内燃機関の筒内の燃焼熱により、アンモニアに加水分解し、該アンモニアにより、前記選択接触還元触媒で窒素酸化物を浄化する方法として構成される。   In addition, an exhaust gas purification method according to the present invention for achieving the above object includes a selective catalytic reduction catalyst that purifies nitrogen oxides in an exhaust passage of an internal combustion engine, and is disposed upstream of the selective catalytic reduction catalyst. An exhaust gas for purifying nitrogen oxides in exhaust gas, comprising a reducing agent exhaust pipe supply device for supplying urea aqueous solution to the exhaust passage and a reducing agent in-cylinder injection device for supplying urea aqueous solution into the cylinder of the internal combustion engine In the gas purification system, when the temperature of the selective catalytic reduction catalyst exceeds the activation temperature of urea hydrolysis, an aqueous urea solution is supplied to the exhaust passage by the supply device in the reducing agent exhaust pipe, and the temperature of the selective catalytic reduction catalyst Is below the activation temperature of urea hydrolysis, the urea aqueous solution is supplied into the cylinder by the reducing agent in-cylinder injection device, and the urea aqueous solution supplied from the reducing agent in-cylinder injection device is The heat of combustion of the cylinder of the engine, hydrolyzed into ammonia by the ammonia, and a method for purifying nitrogen oxides in the selective catalytic reduction catalyst.

この方法により、比較的取り扱いが容易な尿素を用いながら、選択接触還元触媒の温度によって、筒内尿素噴射と排気管尿素噴射を使い分けて、低温時には、筒内の燃焼熱を利用してアンモニアを選択接触還元触媒に供給することができるので、低温域におけるＮＯｘ浄化の活性低下を補うことができる。   With this method, while using urea, which is relatively easy to handle, the in-cylinder urea injection and the exhaust pipe urea injection are selectively used according to the temperature of the selective catalytic reduction catalyst. Since it can supply to a selective catalytic reduction catalyst, the activity fall of NOx purification | cleaning in a low temperature range can be supplemented.

本発明の排気ガス浄化システム及び排気ガス浄化方法によれば、排気管尿素噴射に加えて、エンジンの筒内への筒内尿素噴射を併用することにより、比較的取り扱いが容易な尿素を用いながら、アンモニア添加の場合の選択接触還元触媒効果も奏することができ、尿素添加の場合の選択接触還元触媒効果の低温における活性低下を補うことができ、選択接触還元触媒を使用した排気ガス浄化システムの低温活性を向上できる。   According to the exhaust gas purification system and the exhaust gas purification method of the present invention, in addition to exhaust pipe urea injection, in-cylinder urea injection into the cylinder of the engine is used in combination, while using urea that is relatively easy to handle. In addition, the selective catalytic reduction catalytic effect in the case of ammonia addition can also be exhibited, and the decrease in activity at a low temperature of the selective catalytic reduction catalytic effect in the case of urea addition can be compensated, and the exhaust gas purification system using the selective catalytic reduction catalyst Low temperature activity can be improved.

次に、図面を参照して本発明に係る排気ガス浄化システム及び排気ガス浄化方法の実施の形態について説明する。   Next, an embodiment of an exhaust gas purification system and an exhaust gas purification method according to the present invention will be described with reference to the drawings.

図１に、この排気ガス浄化システム１０の構成を示す。この排気ガス浄化システム１０では、エンジン（内燃機関）１の排気通路４に、窒素酸化物（ＮＯｘ）を浄化する選択接触還元触媒（ＳＣＲ触媒）１６を備える。この選択接触還元触媒１６は、貴金属（白金等）や遷移金属（銅、コバルト、バナジウム等）を、ゼオライト、シリカ／アルミナ、アルミナ、シリカ、チタニア等の担体に担持して形成される。   FIG. 1 shows the configuration of the exhaust gas purification system 10. In the exhaust gas purification system 10, a selective contact reduction catalyst (SCR catalyst) 16 that purifies nitrogen oxides (NOx) is provided in the exhaust passage 4 of the engine (internal combustion engine) 1. The selective catalytic reduction catalyst 16 is formed by supporting a noble metal (such as platinum) or a transition metal (such as copper, cobalt, or vanadium) on a support such as zeolite, silica / alumina, alumina, silica, or titania.

また、それと共に、この選択接触還元触媒１６の上流側に還元剤排気管内供給装置１４と、エンジン１の筒内（シリンダ内）２に還元剤を供給する還元剤筒内噴射装置１５を設けて構成される。   At the same time, a reducing agent exhaust pipe supply device 14 and a reducing agent in-cylinder injection device 15 for supplying the reducing agent to the cylinder (cylinder) 2 of the engine 1 are provided upstream of the selective catalytic reduction catalyst 16. Composed.

そして、還元剤としての尿素水溶液を、還元剤排気管内供給装置１４と還元剤筒内噴射装置１５に供給するために、尿素水タンク１１と尿素水ポンプ１２と尿素水コモンレール１３を設ける。また、排気通路４の選択接触還元触媒１６の上流側に排気ガス温度センサ１７を設ける。   In order to supply the urea aqueous solution as the reducing agent to the reducing agent exhaust pipe supply device 14 and the reducing agent in-cylinder injection device 15, the urea water tank 11, the urea water pump 12, and the urea water common rail 13 are provided. Further, an exhaust gas temperature sensor 17 is provided upstream of the selective catalytic reduction catalyst 16 in the exhaust passage 4.

更に、燃料噴射弁３の制御等を含むエンジン１の制御と共に、還元剤噴射制御を行う制御装置（エンジンコントロールユニット：ＥＣＵ）１８が設けられており、排気ガス温度センサ１７からの入力を基に、還元剤排気管内供給装置１４と還元剤筒内噴射装置１５を制御して、尿素水の供給を制御する。   Further, a control device (engine control unit: ECU) 18 that performs reductant injection control together with control of the engine 1 including control of the fuel injection valve 3 and the like is provided, based on an input from the exhaust gas temperature sensor 17. Then, the reducing agent exhaust pipe supply device 14 and the reducing agent in-cylinder injection device 15 are controlled to control the supply of urea water.

そして、この構成の排気ガス浄化システム１０において、排気ガス浄化方法は、図２に例示するような制御フローに従って行われる。   In the exhaust gas purification system 10 having this configuration, the exhaust gas purification method is performed according to the control flow illustrated in FIG.

エンジン１の運転が開始され、排気ガスの浄化が始まると、図２の制御フローも開始され、ステップＳ１１で排気ガス温度センサ１７により排気ガス温度Ｔｇの検出が行われる。そして、次のステップＳ１２で、排気ガス温度Ｔｇが所定の判定温度Ｔｇ０と比較される。   When the operation of the engine 1 is started and the purification of the exhaust gas is started, the control flow of FIG. 2 is also started, and the exhaust gas temperature sensor 17 detects the exhaust gas temperature Tg in step S11. Then, in the next step S12, the exhaust gas temperature Tg is compared with a predetermined determination temperature Tg0.

この排気ガス温度Ｔｇに対する所定の判定温度Ｔｇ０には、排気ガス温度Ｔｇがこの所定の判定温度Ｔｇ０を超えている場合には、選択接触還元触媒１６の触媒温度Ｔｃが加水分解のための活性温度Ｔｃ０を超え、また、排気ガス温度Ｔｇがこの所定の判定温度Ｔｇ０以下の場合には、選択接触還元触媒１６の触媒温度Ｔｃが加水分解のための活性温度Ｔｃ０以下となる温度が選ばれる。この温度は、例えば、燃焼室出口の排気ガス温度で、３５０℃程度、選択接触還元触媒１６の入口の排気ガス温度Ｔｇや触媒温度Ｔｃで２５０℃〜３００℃である。   When the exhaust gas temperature Tg exceeds the predetermined determination temperature Tg0, the catalyst temperature Tc of the selective catalytic reduction catalyst 16 is the activation temperature for hydrolysis when the exhaust gas temperature Tg exceeds the predetermined determination temperature Tg0 with respect to the exhaust gas temperature Tg. When Tc0 is exceeded and the exhaust gas temperature Tg is equal to or lower than the predetermined determination temperature Tg0, a temperature at which the catalyst temperature Tc of the selective catalytic reduction catalyst 16 is equal to or lower than the activation temperature Tc0 for hydrolysis is selected. This temperature is, for example, about 350 ° C. at the exhaust gas temperature at the outlet of the combustion chamber, and 250 ° C. to 300 ° C. at the exhaust gas temperature Tg and the catalyst temperature Tc at the inlet of the selective catalytic reduction catalyst 16.

このステップＳ１２の比較で、排気ガス温度Ｔｇが所定の判定温度Ｔｇ０以下の場合には、ステップＳ１３で、筒内尿素噴射制御を行って、還元剤筒内噴射装置１５より筒内２に尿素水溶液を供給すると共に、排気管尿素噴射制御を中止して、還元剤排気管内供給装置１４からの排気通路４内への尿素水溶液の供給を停止する。これを所定の時間の間、即ち、排気ガス温度Ｔｇをチェックするインターバルの間行い、ステップＳ１１に戻る。   If the exhaust gas temperature Tg is equal to or lower than the predetermined determination temperature Tg0 in the comparison in step S12, in-cylinder urea injection control is performed in step S13, and the urea aqueous solution is introduced into the cylinder 2 from the reducing agent in-cylinder injection device 15. And the exhaust pipe urea injection control is stopped, and the supply of the aqueous urea solution from the reducing agent exhaust pipe supply device 14 into the exhaust passage 4 is stopped. This is performed for a predetermined time, that is, during an interval for checking the exhaust gas temperature Tg, and the process returns to step S11.

この排気ガス温度Ｔｇが低く、ＮＯｘ浄化活性が低くなるエンジン１の低負荷運転領域の極微小噴射量では、尿素を主燃焼前の圧縮始め行程でエンジン１の筒内２に噴射し、主燃焼の燃焼熱を利用して尿素加水分解反応を行わせてアンモニアを生成する。噴射量が多くなるに従い燃焼温度が高くなり、アンモニアが窒素酸化物になってしまうので、筒内２の温度が比較的低い温度のときに噴射する。   At a very small injection amount in the low load operation region of the engine 1 where the exhaust gas temperature Tg is low and the NOx purification activity is low, urea is injected into the cylinder 2 of the engine 1 in the compression start stroke before the main combustion, and the main combustion Ammonia is generated by performing a urea hydrolysis reaction using the heat of combustion of the. As the injection amount increases, the combustion temperature increases, and ammonia becomes nitrogen oxides. Therefore, injection is performed when the temperature in the cylinder 2 is relatively low.

より具体的には、低負荷運転領域でもある程度の噴射量がある場合には、メイン噴射終了後から、ＡＴＤＣ９０°位までの範囲で尿素噴射を行う。吸熱反応であるので、ある程度の温度が必要であり、また、ＡＤＴＣ９０°をすぎると、噴射した尿素水溶液がシリンダ内面に付着し、この尿素水溶液がエンジンオイルの希釈や錆の発生の原因となるためである。また、燃焼温度や排気ガスの温度により噴射時期を決定し、温度が高いとき程、遅い方にずらす。   More specifically, when there is a certain amount of injection even in the low load operation region, urea injection is performed in a range from the end of main injection to about ATDC 90 °. Since it is an endothermic reaction, a certain temperature is required, and if it exceeds ADTC 90 °, the injected urea aqueous solution adheres to the cylinder inner surface, and this urea aqueous solution causes dilution of engine oil and generation of rust. It is. Also, the injection timing is determined based on the combustion temperature and the exhaust gas temperature, and the higher the temperature, the slower it is shifted.

そして、この筒内２で発生したアンモニアが選択接触還元触媒１６に供給される。そのため、前段尿素加水分解反応が不要となり、低温でもＮＯｘを還元できるようになる。なお、直接、筒内２に尿素水溶液を噴射する代わりに、吸気行程中に、吸気通路（吸気管）５に尿素を噴射して筒内２に尿素を供給してもよい。   The ammonia generated in the cylinder 2 is supplied to the selective catalytic reduction catalyst 16. Therefore, the pre-stage urea hydrolysis reaction becomes unnecessary, and NOx can be reduced even at a low temperature. Instead of injecting the urea aqueous solution directly into the cylinder 2, urea may be injected into the intake passage (intake pipe) 5 and supplied to the cylinder 2 during the intake stroke.

また、ステップＳ１２の比較で、排気ガス温度Ｔｇが所定の判定温度Ｔｇ０を超えている場合には、ステップＳ１４で、排気管尿素噴射制御を行って、還元剤排気管内供給装置１４より排気通路４内に尿素水溶液を供給すると共に、筒内尿素噴射制御を中止して、還元剤筒内噴射装置１５からの筒内２への尿素水溶液の供給を停止する。これを所定の時間の間、即ち、排気ガス温度Ｔｇをチェックするインターバルの間行い、ステップＳ１１に戻る。   If the exhaust gas temperature Tg exceeds the predetermined judgment temperature Tg0 in the comparison in step S12, exhaust pipe urea injection control is performed in step S14, and the exhaust passage 4 is supplied from the reducing agent exhaust pipe supply device 14. The urea aqueous solution is supplied to the inside, and the in-cylinder urea injection control is stopped, and the supply of the urea aqueous solution from the reducing agent in-cylinder injection device 15 to the in-cylinder 2 is stopped. This is performed for a predetermined time, that is, during an interval for checking the exhaust gas temperature Tg, and the process returns to step S11.

この排気ガス温度Ｔｇが高く、ＮＯｘ浄化活性が高くなるエンジン１の中・高負荷運転領域では、選択接触還元触媒１６で尿素を加水分解できるので、排気通路４に供給された尿素を前段尿素加水分解反応によりアンモニアに変えて、ＮＯｘを浄化することができる。また、高温度域において筒内尿素水噴射を中止することにより、筒内において、尿素が高温のために反応が進行してＮＯｘになってしまうのを防止することができる。   In the middle / high load operation region of the engine 1 where the exhaust gas temperature Tg is high and the NOx purification activity is high, urea can be hydrolyzed by the selective catalytic reduction catalyst 16, so that the urea supplied to the exhaust passage 4 can be hydrolyzed in the preceding stage. NOx can be purified by changing to ammonia by a decomposition reaction. In addition, by stopping the in-cylinder urea water injection in the high temperature range, it is possible to prevent the reaction from proceeding to NOx due to the high temperature of urea in the cylinder.

そして、これらの各ステップの繰り返しが、エンジン１の運転が停止されるまで行われる。エンジンキーがオフされると、ステップＳ２０の割り込みが生じ、ステップＳ２１で筒内尿素噴射制御の停止と排気管尿素噴射制御の停止等の終了作業を行ってから、この制御フローをストップする。   These steps are repeated until the operation of the engine 1 is stopped. When the engine key is turned off, an interruption in step S20 occurs, and in step S21, after completion work such as stopping in-cylinder urea injection control and stopping exhaust pipe urea injection control, the control flow is stopped.

この制御により、排気ガス温度Ｔｇが、所定の判定温度Ｔｃを超える場合には、還元剤排気管内供給装置１４により還元剤である尿素水溶液を排気通路４に供給し、排気ガス温度Ｔｇが、所定の判定温度Ｔｃ以下である場合には、還元剤筒内噴射装置１５により尿素水溶液を筒内２に供給することができる。   By this control, when the exhaust gas temperature Tg exceeds a predetermined determination temperature Tc, the reducing agent exhaust pipe supply device 14 supplies the urea aqueous solution, which is a reducing agent, to the exhaust passage 4, and the exhaust gas temperature Tg is predetermined. When the temperature is equal to or lower than the determination temperature Tc, the reducing agent in-cylinder injection device 15 can supply the urea aqueous solution to the cylinder 2.

上記の構成の排気ガス浄化システム及び排気ガス浄化方法によれば、排気通路４内への尿素水噴射に加えて、エンジン１の筒内２への尿素水噴射を併用することができるようになるので、筒内２の燃焼熱を利用して尿素を加水分解して、アンモニアを生成することができる。そのため、比較的取り扱いが容易な尿素を用いながら、アンモニア添加の場合の選択接触還元触媒効果も奏することができるようになる。   According to the exhaust gas purification system and the exhaust gas purification method configured as described above, urea water injection into the cylinder 2 of the engine 1 can be used in addition to urea water injection into the exhaust passage 4. Therefore, urea can be hydrolyzed using the combustion heat in the cylinder 2 to generate ammonia. Therefore, the selective catalytic reduction catalytic effect in the case of ammonia addition can be exhibited while using urea that is relatively easy to handle.

従って、尿素添加の場合の選択接触還元触媒効果の低温における活性低下を補うことができ、選択接触還元触媒１６を使用した排気ガス浄化システム１０のＮＯｘの浄化に対する低温活性を向上できる。   Therefore, it is possible to compensate for the decrease in activity at a low temperature of the selective catalytic reduction catalyst effect in the case of urea addition, and it is possible to improve the low temperature activity for NOx purification of the exhaust gas purification system 10 using the selective catalytic reduction catalyst 16.

本発明に係る実施の形態の排気ガス浄化システムの構成を示す図である。It is a figure which shows the structure of the exhaust gas purification system of embodiment which concerns on this invention. 本発明に係る実施の形態の排気ガス浄化方法の制御の例を示す図である。It is a figure which shows the example of control of the exhaust gas purification method of embodiment which concerns on this invention. 尿素添加とアンモニア添加の場合の選択接触還元触媒のＮＯｘ浄化率と触媒温度との関係を示す図である。It is a figure which shows the relationship between the NOx purification rate of a selective catalytic reduction catalyst in the case of urea addition and ammonia addition, and catalyst temperature. 従来技術の排気ガス浄化システムの構成を示す図である。It is a figure which shows the structure of the exhaust-gas purification system of a prior art.

符号の説明Explanation of symbols

１ エンジン（内燃機関）
２ 筒内（シリンダ内）
３ 燃焼噴射弁
４ 排気通路（排気管）
１０ 排気ガス浄化システム
１１ 尿素水タンク
１２ 尿素水ポンプ
１３ 尿素水コモンレール
１４ 還元剤排気管内供給装置
１５ 還元剤筒内噴射装置
１６ 選択接触還元触媒（ＳＣＲ触媒）
１７ 排気ガス温度センサ
１８ 制御装置（ＥＣＵ）
Ｔｇ 排気ガス温度
Ｔｇ０ 所定の判定温度
Ｔｃ 触媒温度
Ｔｃ０ 加水分解のための活性温度
1 engine (internal combustion engine)
2 In-cylinder (inside cylinder)
3 Combustion injection valve 4 Exhaust passage (exhaust pipe)
DESCRIPTION OF SYMBOLS 10 Exhaust gas purification system 11 Urea water tank 12 Urea water pump 13 Urea water common rail 14 Reducing agent exhaust pipe supply device 15 Reducing agent cylinder injection device 16 Selective contact reduction catalyst (SCR catalyst)
17 Exhaust gas temperature sensor 18 Control unit (ECU)
Tg Exhaust gas temperature Tg0 Predetermined judgment temperature Tc Catalyst temperature Tc0 Activation temperature for hydrolysis

Claims (4)

内燃機関の排気通路に窒素酸化物を浄化する選択接触還元触媒を備えて、排気ガス中の窒素酸化物を浄化する排気ガス浄化システムにおいて、前記選択接触還元触媒の上流側に排気通路に還元剤を供給する還元剤排気管内供給装置を備えると共に、内燃機関の筒内に還元剤を供給する還元剤筒内噴射装置を設けたことを特徴とする排気ガス浄化システム。   An exhaust gas purification system that includes a selective catalytic reduction catalyst that purifies nitrogen oxides in an exhaust passage of an internal combustion engine, and purifies nitrogen oxides in exhaust gas. An exhaust gas purification system comprising: a reducing agent exhaust pipe supply device that supplies a reducing agent, and a reducing agent in-cylinder injection device that supplies the reducing agent into a cylinder of the internal combustion engine. 排気ガス温度が、所定の判定温度を超える場合には、前記還元剤排気管内供給装置により還元剤を排気通路に供給し、排気ガス温度が、前記所定の判定温度以下である場合には、前記還元剤筒内噴射装置により還元剤を筒内に供給することを特徴とする請求項１記載の排気ガス浄化システム。   When the exhaust gas temperature exceeds a predetermined determination temperature, the reducing agent exhaust pipe supply device supplies the reducing agent to the exhaust passage, and when the exhaust gas temperature is equal to or lower than the predetermined determination temperature, The exhaust gas purification system according to claim 1, wherein the reducing agent is supplied into the cylinder by the reducing agent in-cylinder injection device. 前記還元剤が、尿素水溶液であることを特徴とする請求項１又は２に記載の排気ガス浄化システム。   The exhaust gas purification system according to claim 1 or 2, wherein the reducing agent is an aqueous urea solution. 内燃機関の排気通路に窒素酸化物を浄化する選択接触還元触媒を備えると共に、該選択接触還元触媒の上流側に配置され、排気通路に尿素水溶液を供給する還元剤排気管内供給装置と、内燃機関の筒内に尿素水溶液を供給する還元剤筒内噴射装置を備えて、排気ガス中の窒素酸化物を浄化する排気ガス浄化システムにおいて、前記選択接触還元触媒の温度が尿素の加水分解の活性温度を超える場合には、前記還元剤排気管内供給装置により尿素水溶液を排気通路に供給し、前記選択接触還元触媒の温度が尿素の加水分解の活性温度以下である場合には、前記還元剤筒内噴射装置により尿素水溶液を筒内に供給し、前記還元剤筒内噴射装置より供給された尿素水溶液を、内燃機関の筒内の燃焼熱により、アンモニアに加水分解し、該アンモニアにより、前記選択接触還元触媒で窒素酸化物を浄化することを特徴とする排気ガス浄化方法。
A reducing agent exhaust pipe supply device that includes a selective catalytic reduction catalyst that purifies nitrogen oxides in an exhaust passage of an internal combustion engine, is disposed upstream of the selective catalytic reduction catalyst, and supplies an aqueous urea solution to the exhaust passage, and an internal combustion engine The exhaust gas purification system for purifying nitrogen oxides in the exhaust gas, comprising a reducing agent in-cylinder injection device for supplying urea aqueous solution into the cylinder of the exhaust gas, wherein the temperature of the selective catalytic reduction catalyst is the activation temperature of urea hydrolysis If the temperature of the selective catalytic reduction catalyst is equal to or lower than the activation temperature of urea hydrolysis, the reducing agent exhaust pipe supply device supplies urea aqueous solution to the exhaust passage. A urea aqueous solution is supplied into the cylinder by the injection device, and the urea aqueous solution supplied from the reducing agent in-cylinder injection device is hydrolyzed into ammonia by the combustion heat in the cylinder of the internal combustion engine, and the ammonia More, the exhaust gas purification method, characterized in that purifies nitrogen oxides in the selective catalytic reduction catalyst.
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