JP2510913B2 - Method for removing nitrogen oxides in exhaust gas - Google Patents
Method for removing nitrogen oxides in exhaust gasInfo
- Publication number
- JP2510913B2 JP2510913B2 JP3293719A JP29371991A JP2510913B2 JP 2510913 B2 JP2510913 B2 JP 2510913B2 JP 3293719 A JP3293719 A JP 3293719A JP 29371991 A JP29371991 A JP 29371991A JP 2510913 B2 JP2510913 B2 JP 2510913B2
- Authority
- JP
- Japan
- Prior art keywords
- fuel
- exhaust gas
- denitration
- catalyst
- alumina
- 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.)
- Expired - Fee Related
Links
- 239000007789 gas Substances 0.000 title claims description 57
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 26
- 239000003054 catalyst Substances 0.000 claims description 54
- 239000000446 fuel Substances 0.000 claims description 48
- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002828 fuel tank Substances 0.000 claims description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- 239000003502 gasoline Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010763 heavy fuel oil Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Chemical class 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000003921 oil Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000001294 propane Substances 0.000 description 18
- 239000000295 fuel oil Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- -1 mordenite type Chemical compound 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
-
- 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
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はディーゼルエンジンもし
くはリーンバーンのガソリンエンジンに付設された排ガ
ス脱硝装置に還元剤として燃料を注入して排ガス中の窒
素酸化物を除去する方法、特に燃料の注入方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for injecting fuel as a reducing agent into an exhaust gas denitration device attached to a diesel engine or a lean burn gasoline engine to remove nitrogen oxides in the exhaust gas, and more particularly to a method for injecting fuel. Regarding
【０００２】[0002]
【従来の技術】各種化学工業や、燃焼ボイラーや、自動
車等から排出される窒素酸化物は大気汚染物質として問
題視されており、その効果的除去法の実現が期待されて
いる。2. Description of the Related Art Nitrogen oxides emitted from various chemical industries, combustion boilers, automobiles, etc. are regarded as problems as air pollutants, and it is expected that an effective removal method will be realized.
【０００３】従来、排ガス中の窒素酸化物を除去する方
法の一つとして、アンモニアガスを還元剤とする触媒還
元法が実用化されている。この方法では、排ガス中に多
量の酸素が共存していても利用できる利点があるが、還
元剤としてのアンモニアガスが必須であり、自動車等の
移動式の発生源や中小型の発生源の場合には使用しにく
い。Conventionally, a catalytic reduction method using ammonia gas as a reducing agent has been put into practical use as one of methods for removing nitrogen oxides in exhaust gas. This method has the advantage that it can be used even if a large amount of oxygen coexists in the exhaust gas, but ammonia gas as a reducing agent is essential, and in the case of mobile sources such as automobiles or small and medium-sized sources Difficult to use for.
【０００４】一方、ガソリンエンジンの排ガスでは、一
酸化炭素と炭化水素の二酸化炭素と水への酸化反応およ
び窒素酸化物の窒素ガスへの還元反応を同時に行なう三
元触媒が実用化されている。しかし、この触媒は理論空
燃比付近で使用されなければならず、過剰な酸素を含む
ディーゼルエンジン排ガスやガソリンエンジン排ガスに
は適用し得ないという大きな欠点がある。On the other hand, in the exhaust gas of a gasoline engine, a three-way catalyst has been put into practical use, which simultaneously carries out an oxidation reaction of carbon monoxide and hydrocarbons into carbon dioxide and water and a reduction reaction of nitrogen oxides into nitrogen gas. However, this catalyst has to be used in the vicinity of the stoichiometric air-fuel ratio, and has a major drawback that it cannot be applied to diesel engine exhaust gas or gasoline engine exhaust gas containing excess oxygen.
【０００５】このような事情から、この出願の出願人
は、過剰な酸素を含む排ガスを、金属を担持してもよい
水素化改質ゼオライト触媒と、有機化合物の共存下で接
触させる窒素酸化物の除去方法（特開平２−１４９３１
７号および特開平３−１８１３２１号）、および金属を
担特してもよいγ−アルミナまたはシリカ・アルミナ触
媒と、過剰な酸素を含む排ガスを、有機化合物の共存下
で接触させる窒素酸化物の除去方法（特願平２−２８１
５３０号）を提案している。Under these circumstances, the applicant of the present application has proposed that a nitrogen oxide in which an exhaust gas containing excess oxygen is brought into contact with a hydrogenation reforming zeolite catalyst which may carry a metal in the presence of an organic compound. Removal method (JP-A-2-14931)
No. 7 and JP-A-3-181321), and a γ-alumina or silica-alumina catalyst which may carry a metal, and an exhaust gas containing excess oxygen are contacted in the presence of an organic compound. Removal method (Japanese Patent Application No. 2-281)
No. 530) is proposed.
【０００６】この窒素酸化物の除去方法は、多量の酸素
が共存する排ガスにも適用可能であり、しかも還元剤と
しての有機化合物は、アルコール、ケトン、エーテルな
どのほか、天然ガス、プロパンガスおよび軽油、重油な
どの燃料を使用し得るという大きな特徴を有する。This method of removing nitrogen oxides can be applied to exhaust gas in which a large amount of oxygen coexists, and organic compounds as reducing agents include alcohols, ketones, ethers, etc., as well as natural gas, propane gas and It has a great feature that fuel such as light oil and heavy oil can be used.
【０００７】しかしながら、これらの有機化合物の効果
は、種類によって大きな差があり、例えばゼオライト系
の触媒を用い、注入する有機化合物の量と排ガス中のＮ
Ｏｘ重量比を同一にして比較すると、プロパンを注入し
たときの脱硝率に比べて軽油もしくは重油などの燃料を
注入した時の脱硝率が低く、プロパンと同じ脱硝率を得
ようとするとより多くの軽油または重油を注入しなけれ
ばならないという問題があった。これは、軽油もしくは
重油の成分の平均分子量がプロパンの数倍あり、同じ重
量で比較するとモル数が数分の一となり、そのため脱硝
反応速度が低下したか、あるいは軽油や重油の成分の分
子が大きいために脱硝触媒の細孔内に拡散しにくく、脱
硝反応が起こりにくくなったものと思われる。However, the effects of these organic compounds differ greatly depending on the type. For example, the amount of the organic compound to be injected and the N in the exhaust gas are used by using a zeolite-based catalyst.
Comparing the same Ox weight ratio, the denitrification rate when injecting fuel such as light oil or heavy oil is lower than the denitrification rate when injecting propane. There was a problem that light oil or heavy oil had to be injected. This is because the average molecular weight of the gas oil or heavy oil component is several times that of propane, and the number of moles is a fraction of the same weight, and the denitration reaction rate has decreased, or the molecules of the gas oil and heavy oil components are Since it is large, it is difficult for the catalyst to diffuse into the pores of the denitration catalyst, and the denitration reaction is unlikely to occur.
【０００８】このような事情から、脱硝装置において、
脱硝率が高いプロパンを還元剤として用いることが考え
られるが、このものはディーゼルエンジンやガソリンエ
ンジンに用いられる燃料とは異なるものであるため、別
途プロパンを容易する必要がある。例えばトラックでこ
の方法を採用すると、トラックに燃料タンクの他にプロ
パンの補充を義務づけるとすると、操作が煩雑となる。
またガソリンスタンドでも設備が必要となり、安全上の
対策を講じなければならないなど、種々の問題が出てく
る。Under such circumstances, in the denitration device,
It is possible to use propane having a high denitration rate as a reducing agent, but since this is different from the fuel used in diesel engines and gasoline engines, it is necessary to use propane separately. For example, if this method is adopted in a truck, the operation becomes complicated if the truck is obliged to replenish propane in addition to the fuel tank.
In addition, various problems will arise, such as the need for facilities at gas stations and the need to take safety measures.
【０００９】一方、操作上の利点を考慮して、軽油やガ
ソリン等の燃料を還元剤として使用すると、脱硝率を高
めるために、吹き込み量を増加しなければならず、結果
的に燃費の低下につながってしまう。On the other hand, if a fuel such as light oil or gasoline is used as a reducing agent in consideration of operational advantages, the injection amount must be increased in order to increase the denitration rate, resulting in a reduction in fuel consumption. Will lead to.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、燃料
タンクの燃料を利用して、ディーゼルエンジンもしくは
リーンバーンのガソリンエンジンの排ガス脱硝装置の還
元剤として用いることができ、かつ脱硝率が高く、しか
も操作上あるいはコスト面でも有利な排ガス中の窒素酸
化物の除去方法を提供することにある。An object of the present invention is to use fuel in a fuel tank as a reducing agent for an exhaust gas denitration device for a diesel engine or a lean burn gasoline engine, and to provide a high denitration rate. Another object of the present invention is to provide a method for removing nitrogen oxides in exhaust gas which is advantageous in terms of operation and cost.
【００１１】[0011]
【課題を解決するための手段】このような目的は、下記
（１）〜（３）の構成によって達成される。Such an object is achieved by the following constitutions (1) to (3).
【００１２】（１）排ガス脱硝装置に還元剤として燃料
を注入し、ディーゼルエンジンもしくはリーンバーンの
ガソリンエンジンの排ガス中の窒素酸化物を除去する方
法において、前記脱硝装置の前方に前処理装置を設け、
前記エンジン用の燃料タンクから燃料の一部をこの前処
理装置に送り、この燃料を熱分解または接触分解して気
体状低分子量成分を得、気液分離により気体状低分子量
成分と残余の燃料とに分離し、気体状低分子量成分を前
記脱硝装置に注入し、残余の燃料を前記燃料タンクに戻
すことを特徴とする排ガス中の窒素酸化物の除去方法。(1) In a method of injecting fuel as a reducing agent into an exhaust gas denitration device to remove nitrogen oxides in exhaust gas of a diesel engine or a lean burn gasoline engine, a pretreatment device is provided in front of the denitration device. ,
A part of the fuel is sent from the fuel tank for the engine to the pretreatment device, the fuel is pyrolyzed or catalytically decomposed to obtain a gaseous low molecular weight component, and the gaseous low molecular weight component and the residual fuel are separated by gas-liquid separation. A method for removing nitrogen oxides in exhaust gas, characterized in that a gaseous low molecular weight component is injected into the denitration apparatus and the remaining fuel is returned to the fuel tank.
【００１３】（２）前記気体状低分子量成分は気体状オ
レフィンを含む上記（１）に記載の排ガス中の窒素酸化
物の除去方法。(2) The method for removing nitrogen oxides in exhaust gas according to the above (1), wherein the gaseous low molecular weight component contains a gaseous olefin.
【００１４】（３）前記脱硝装置の脱硝触媒層に用いる
触媒は、γ−アルミナ、シリカ・アルミナもしくは水素
化したゼオライト触媒、またはこのγ−アルミナ、シリ
カ・アルミナもしくは水素化したゼオライト触媒に銅、
亜鉛、バナジウム、クロム、マンガン、鉄、コバルトお
よびニッケルのうちの少なくとも１種を担持した触媒で
ある上記（１）または（２）に記載の排ガス中の窒素酸
化物の除去方法。(3) The catalyst used in the denitration catalyst layer of the denitration apparatus is γ-alumina, silica-alumina or a hydrogenated zeolite catalyst, or this γ-alumina, silica-alumina or a hydrogenated zeolite catalyst is copper,
The method for removing nitrogen oxides from exhaust gas according to (1) or (2) above, which is a catalyst supporting at least one of zinc, vanadium, chromium, manganese, iron, cobalt, and nickel.
【００１５】[0015]
【具体的構成】以下、本発明の具体的構成について詳細
に説明する。本発明では、ディーゼルエンジンもしくは
リーンバーンのガソリンエンジンの排ガス中の窒素酸化
物を除去する排ガス脱硝装置に、還元剤として、上記エ
ンジン用の燃料タンクの燃料、例えば軽油、重油（特に
Ａ重油）、ガソリンを利用するものである。Specific Structure The specific structure of the present invention will be described in detail below. In the present invention, in an exhaust gas denitration device for removing nitrogen oxides in exhaust gas of a diesel engine or a lean burn gasoline engine, as a reducing agent, a fuel in a fuel tank for the engine, such as light oil, heavy oil (particularly A heavy oil), It uses gasoline.
【００１６】この場合、還元剤として、軽油、重油など
の燃料を直接脱硝装置の脱硝触媒層に吹き込むのではな
く、脱硝装置の前方に前処理装置を設け、燃料タンクか
ら流れてくる燃料を前処理装置に通し、そこで熱分解ま
たは接触分解によって低分子量もしくは低沸点成分を富
化し、次いで、冷却器、気液分離器を通してガス成分を
分離し、これを脱硝触媒層に注入するものである。In this case, as a reducing agent, a fuel such as light oil or heavy oil is not directly blown into the denitration catalyst layer of the denitration device, but a pretreatment device is provided in front of the denitration device to remove the fuel flowing from the fuel tank. A low molecular weight or low boiling point component is enriched by thermal decomposition or catalytic cracking through a treatment device, and then a gas component is separated through a cooler and a gas-liquid separator, and this is injected into the denitration catalyst layer.
【００１７】このように、燃料を前処理することによっ
て脱硝反応の還元剤として有効な成分を富化分離し、こ
れを脱硝触媒層に注入することができ、燃料の還元剤と
しての効果を高めることができる。As described above, by pretreating the fuel, the component effective as a reducing agent for the denitration reaction can be enriched and separated, and this can be injected into the denitration catalyst layer to enhance the effect of the fuel as the reducing agent. be able to.
【００１８】また、本発明では、脱硝触媒層への還元剤
の注入と同時に、脱硝触媒層に注入されなかった残余の
燃料を燃料タンクに戻している。これにより燃料を無駄
にすることなく有効に還元剤として使用することができ
る。Further, in the present invention, at the same time when the reducing agent is injected into the denitration catalyst layer, the residual fuel not injected into the denitration catalyst layer is returned to the fuel tank. As a result, the fuel can be effectively used as a reducing agent without wasting it.
【００１９】また、残余燃料を燃料タンクに戻し、エン
ジンの燃料としても、エンジンの運転には何ら支障は生
じることはない。Further, even if the residual fuel is returned to the fuel tank and used as the fuel for the engine, there is no problem in the operation of the engine.
【００２０】さらに、このようにすれば、還元剤として
正味消費される燃料は脱硝触媒層に注入された燃料量に
等しく、量的な無駄は生じない。Further, in this way, the fuel that is net consumed as the reducing agent is equal to the fuel amount injected into the denitration catalyst layer, and no quantitative waste occurs.
【００２１】本発明では、前処理装置において、燃料を
熱分解もしくは接触分解する前処理を行なう。In the present invention, in the pretreatment device, the pretreatment of thermally decomposing or catalytically decomposing the fuel is performed.
【００２２】触媒を用いない熱分解の場合は燃料を高温
に加熱することが必要であり、５００℃以上、好ましく
は６００℃以上とすることが好ましい。また温度の上限
には特に制限はないが、高温にするには加熱に要するエ
ネルギーが多くなるので１０００℃以下とすることが好
ましい。In the case of thermal decomposition without using a catalyst, it is necessary to heat the fuel to a high temperature, preferably 500 ° C. or higher, and more preferably 600 ° C. or higher. The upper limit of the temperature is not particularly limited, but it is preferable to set the temperature to 1000 ° C. or lower because the energy required for heating to increase the temperature is high.
【００２３】具体的には、前処理装置を排ガス流路内に
設置し、排ガスの熱で加熱するだけでも、燃料の一部を
低分子量化することができ、したがって本発明の目的に
効果的に適用することができる。しかしさらには好まし
くは、ヒーターなどにより６００℃以上に加熱すればよ
く低分子化される燃料の割合が多くなり、エネルギー的
にも装置的にも有利となる。Specifically, even if the pretreatment device is installed in the exhaust gas passage and heated by the heat of the exhaust gas, a part of the fuel can be made to have a low molecular weight, which is effective for the purpose of the present invention. Can be applied to. However, more preferably, heating to 600 ° C. or higher with a heater or the like will increase the proportion of the fuel whose molecular weight is reduced, which is advantageous in terms of energy and apparatus.
【００２４】また、燃料の供給速度は、空間時間にして
０．０５〜５０秒とするのがよい。ここに、空間時間
は、熱分解部容積を毎秒の燃料ガス供給量（標準状態）
で除した値である。The fuel supply rate is preferably 0.05 to 50 seconds in space time. Here, the space time is the volume of the thermal decomposition unit and the fuel gas supply rate per second (standard state)
It is the value divided by.
【００２５】このような方法により、ガス化率が１０〜
８０％となる。By such a method, the gasification rate is 10 to 10.
It will be 80%.
【００２６】一方、触媒を用いた接触分解では、前処理
装置内で接触分解触媒に燃料を接触させればよく、燃料
の低分子化を低温でより効果的に行なうことができる。
このときの温度は３００〜８００℃とすればよく、熱分
解に比べ、１００〜２００℃程度低温とすることが可能
となり、排ガス熱による予熱で十分となることもある。On the other hand, in catalytic cracking using a catalyst, it suffices to bring the fuel into contact with the catalytic cracking catalyst in the pretreatment apparatus, and the lowering of the molecular weight of the fuel can be carried out more effectively at low temperatures.
The temperature at this time may be 300 to 800 ° C., and it is possible to lower the temperature by about 100 to 200 ° C. as compared with thermal decomposition, and preheating by exhaust gas heat may be sufficient.
【００２７】また、燃料の供給速度は、熱分解による場
合と同様とすればよく、触媒量との関係では、ＷＨＳＶ
（重量空間速度）が１〜１００hr-1、好ましくは５〜５
０hr-1とするのがよい。なお、ＷＨＳＶは、［１時間当
たりの処理量（g ）］／［触媒量（g ）］で定義される
ものである。The fuel supply rate may be the same as in the case of thermal decomposition, and in terms of the amount of catalyst, WHSV
(Weight space velocity) is 1 to 100 hr -1 , preferably 5 to 5
It is good to set it to 0 hr -1 . The WHSV is defined as [amount of treatment per hour (g)] / [amount of catalyst (g)].
【００２８】前処理用の触媒としては石油留分分解用と
して知られている種々の触媒を用いることができる。ま
た、このとき、コーキングによる接触分解触媒層の閉そ
くが起こらないこと等に注意して選定する必要がある。As the catalyst for pretreatment, various catalysts known for decomposing petroleum fractions can be used. Further, at this time, it is necessary to make a selection in consideration that clogging of the catalytic cracking catalyst layer does not occur due to coking.
【００２９】具体的にな接触分解触媒としては、活性白
土、シリカ・アルミナ、プロトンあるいは希土類イオン
交換超安定Ｙ型ゼオライトなどを挙げることができる。Specific examples of the catalytic cracking catalyst include activated clay, silica-alumina, proton or rare earth ion exchange ultrastable Y-type zeolite.
【００３０】このような触媒の詳細については、「触媒
学会編、“触媒講座第７巻”、講談社サイエンティフィ
ク（１９８５）、ｐ１０７〜ｐ１３０」に記載されてい
る。Details of such a catalyst are described in "Catalyst Society, edited," Catalyst Lecture, Vol. 7, "Kodansha Scientific (1985), p107 to p130.
【００３１】図１には、本発明に用いる前処理装置を説
明するための概略構成図が示されている。図１に示すよ
うに、前処理装置１は、熱分解用のものであり、ポンプ
１０を介して、燃料タンク２から送られてきた燃料２０
を熱分解する反応管１１を有する。そして、反応管１１
を加熱する加熱炉１２が反応管１１の周囲に設置されて
いる。加熱法としては、排ガスの熱によるもの、電気ヒ
ーターによるもの、あるいは両者を併用したものでもよ
い。また、加熱炉１２内であって反応管１１のまわりに
は熱電対１３が配置されており、反応管１１内の温度を
管理している。反応管１１の材質は、例えばステンレス
鋼等の燃料２０や燃料の反応成分に悪影響を与えず、か
つ熱伝導性の材質であれば、特に制限はない。また、そ
の形状にも特に制限はなく、通常、円柱状などとすれば
よく、大きさは、ガスの空間時間が０．０５〜５０秒と
なる程度とする。FIG. 1 is a schematic block diagram for explaining the pretreatment apparatus used in the present invention. As shown in FIG. 1, the pretreatment apparatus 1 is for thermal decomposition, and the fuel 20 sent from the fuel tank 2 via the pump 10 is used.
It has a reaction tube 11 for thermally decomposing. And the reaction tube 11
A heating furnace 12 for heating the reactor is installed around the reaction tube 11. As a heating method, a method using heat of exhaust gas, a method using an electric heater, or a combination of both may be used. Further, a thermocouple 13 is arranged around the reaction tube 11 in the heating furnace 12 to control the temperature in the reaction tube 11. The material of the reaction tube 11 is not particularly limited as long as it does not adversely affect the fuel 20 such as stainless steel or the reaction components of the fuel and is a material having thermal conductivity. Further, the shape thereof is not particularly limited, and may be a columnar shape or the like, and the size thereof is such that the space time of the gas is 0.05 to 50 seconds.
【００３２】また、反応管１１内には、蒸発を促進する
不活性な充填材１４を配設している。Further, in the reaction tube 11, an inert filling material 14 for promoting evaporation is arranged.
【００３３】このような前処理装置１によって熱分解さ
れた燃料は、冷却器６を経て冷却された後、気液セパレ
ータ３に導入され、気体成分である熱分解ガス３０と液
体成分である残余燃料２５に分離される。そして、熱分
解ガス３０は排ガス脱硝装置４に還元剤として注入され
る。一方、気液セパレータ３の下部に貯留した残余燃料
２５は、ポンプ４０を介して再び燃料タンク２内に戻さ
れる。The fuel pyrolyzed by the pretreatment apparatus 1 is cooled by the cooler 6 and then introduced into the gas-liquid separator 3, and the pyrolysis gas 30 which is a gas component and the residual gas which is a liquid component. It is separated into fuel 25. Then, the pyrolysis gas 30 is injected into the exhaust gas denitration device 4 as a reducing agent. On the other hand, the residual fuel 25 stored in the lower portion of the gas-liquid separator 3 is returned to the fuel tank 2 again via the pump 40.
【００３４】なお、図示例は、熱分解用の前処理装置を
示しているが、触媒による接触分解用とするときは、図
１の反応管１１の中に接触分解触媒を充填するものとす
ればよい。Although the illustrated example shows a pretreatment device for thermal cracking, when catalytic cracking with a catalyst is used, the reaction tube 11 in FIG. 1 may be filled with a catalytic cracking catalyst. Good.
【００３５】本発明における前処理装置は、図示例に限
らず、目的・用途に応じて種々の構成とすることができ
る。The pretreatment device in the present invention is not limited to the illustrated example, but may have various configurations according to the purpose and use.
【００３６】本発明において前処理装置によるガス分解
によって得られる低分子量のガス成分は、例えば軽油を
燃料とし、温度７００〜７５０℃、空間時間１０〜５０
秒の熱分解条件であるとき、ガス化率５４wt% 程度、水
素（９vol%程度）、メタン（２６vol%程度）、エタン、
エチレン（合計で３９vol%程度）、プロパン（１vol%程
度）、プロピレン（１６vol%程度）、ブテン（５vol%程
度）、ブタジエン（３vol%程度）、その他（１vol%程
度）であった。In the present invention, the low molecular weight gas component obtained by the gas decomposition by the pretreatment device uses, for example, light oil as a fuel, and the temperature is 700 to 750 ° C. and the space time is 10 to 50.
When the pyrolysis condition is second, the gasification rate is about 54 wt%, hydrogen (about 9 vol%), methane (about 26 vol%), ethane,
These were ethylene (about 39 vol% in total), propane (about 1 vol%), propylene (about 16 vol%), butene (about 5 vol%), butadiene (about 3 vol%), and others (about 1 vol%).
【００３７】これらのガス成分のなかでも、脱硝効果に
寄与するのは、水素およびメタンを除く成分と考えら
れ、特に、プロピレン、ブテン等のオレフィンの寄与が
大きいと考えられ、脱硝率が高いとされるプロパン以上
の効果があると考えられる。Among these gas components, it is considered that the components excluding hydrogen and methane contribute to the denitration effect, and in particular, the contribution of olefins such as propylene and butene is considered to be large, and the denitration ratio is high. It is thought to be more effective than propane.
【００３８】本発明の脱硝装置の脱硝触媒層に用いる脱
硝触媒は、γ−アルミナ、シリカ・アルミナあるいは水
素化したゼオライト触媒、またはこのγ−アルミナ、シ
リカ・アルミナあるいは水素化したゼオライト触媒に
銅、亜鉛、バナジウム、クロム、マンガン、鉄、コバル
トおよびニッケルのうちの少なくとも１種を担持した触
媒を用いることが好ましい。The denitration catalyst used in the denitration catalyst layer of the denitration apparatus of the present invention is γ-alumina, silica-alumina or a hydrogenated zeolite catalyst, or this γ-alumina, silica-alumina or a hydrogenated zeolite catalyst is copper, It is preferable to use a catalyst supporting at least one of zinc, vanadium, chromium, manganese, iron, cobalt and nickel.
【００３９】なかでも、金属を担持した触媒、特に水素
化したゼオライト触媒に金属を担持した触媒を用いるこ
とが好ましい。Among them, it is preferable to use a metal-supported catalyst, particularly a hydrogenated zeolite catalyst in which a metal is supported.
【００４０】ゼオライト触媒は、シリカ／アルミナ比を
５以上とするのがよい。The silica catalyst preferably has a silica / alumina ratio of 5 or more.
【００４１】ゼオライト触媒としては、例えばＹ型、Ｌ
型、オフレタイト・エリオナイト混晶型、モルデナイト
型、フェリエライト型、ＺＳＭ−５型などの合成ゼオラ
イト、あるいはモルデナイト型、クリノプチロライト型
などの天然ゼオライトであってもよく、いずれを用いて
もよい。As the zeolite catalyst, for example, Y type, L type
Type, offretite / erionite mixed crystal type, mordenite type, ferrierite type, ZSM-5 type, etc., or natural zeolite such as mordenite type, clinoptilolite type, etc. may be used. Good.
【００４２】上記ゼオライト触媒の詳細については、特
開平２−１４９３１７号、特開平３−１８１３２１号に
記載されており、ゼオライトを水素化する方法、あるい
は上記の金属元素を担持させる方法についても、特開平
２−１４９３１７号、特開平３−１８１３２１号に記載
されている。Details of the above-mentioned zeolite catalyst are described in JP-A-2-149317 and JP-A-3-181321, and a method for hydrogenating zeolite or a method for supporting the above-mentioned metal element is also specified. It is described in JP-A-2-149317 and JP-A-3-181321.
【００４３】また、γ−アルミナもしくはシリカ・アル
ミナに上記の金属元素を担持した触媒の詳細について
は、本出願人による特願平２−２８１５３０号に記載さ
れている。本発明においては、このような脱硝触媒との
組み合わせにおいて、脱硝率向上の効果が得られる。Details of the catalyst in which the above metal element is supported on γ-alumina or silica-alumina are described in Japanese Patent Application No. 2-281530 filed by the present applicant. In the present invention, in combination with such a denitration catalyst, the effect of improving the denitration rate can be obtained.
【００４４】なお、本発明においては、操作上、コスト
上の利点を有しつつ、プロパンなみの高い脱硝率を得る
ことができる。In the present invention, it is possible to obtain a denitrification rate as high as that of propane while having the advantages of operation and cost.
【００４５】また、本発明における排ガス中の窒素酸化
物（ＮＯX ）の含有量は１００〜３０００ppm 程度であ
る。Further, the content of nitrogen oxides (NO x ) in the exhaust gas in the present invention is about 100 to 3000 ppm.
【００４６】[0046]
【実施例】以下、本発明を実施例によって、具体的に説
明する。 実施例１ 直噴式ディーゼルエンジンを組み込んだデンヨー製エン
ジン発電機ＤＣＡ−６０ＳＰＨの排ガスについて脱硝試
験を行なった。このエンジンは軽油を燃料とするもので
ある。また、排ガスはＮＯX を約１３００ppm 含んでい
た。ただし、ＮＯX はほとんどＮＯのみであると考えら
れることから、以下の計算はＮＯのみと仮定して行なっ
た。EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 A denitration test was conducted on exhaust gas from a Denyo engine generator DCA-60SPH incorporating a direct injection diesel engine. This engine uses light oil as fuel. Further, the exhaust gas contained about 1300 ppm of NO X. However, since it is considered that NO x is almost only NO, the following calculation was performed assuming that only NO was used.
【００４７】このエンジンの排ガス脱硝装置の脱硝触媒
層に用いた触媒は、水素化した板戸産天然ゼオライトに
コバルトを担持した触媒（約８mm）であり、これを２リ
ットル充填して用いた。The catalyst used in the denitration catalyst layer of the exhaust gas denitration equipment of this engine was a catalyst (about 8 mm) in which hydrogenated natural zeolite from Itado was loaded with cobalt, and 2 liters of this was used.
【００４８】また、脱硝装置の前方に前処理装置を設け
て前処理を行なうときには、図１に示すような構成とし
た。このときの反応管は、ステンレス鋼（ＳＵＳ３０
４）製の内径２０mm、長さ５００mmのものとし、反応管
入口の軽油の注入部には、軽油の蒸発を促進するために
約２０cmのキャピラリーの予熱部を付けた。そして、熱
分解を行なうときは石英ウールを、接触分解を行なうと
きは触媒を反応管に充填した。なお、前処理によるガス
生成量は、軽油の供給量から気液分離器（気液セパレー
タ）中に溜まった液の量を差し引いて求めた。When a pretreatment device is provided in front of the denitration device to perform the pretreatment, the structure shown in FIG. 1 is used. At this time, the reaction tube is made of stainless steel (SUS30
4) The inner diameter was 20 mm and the length was 500 mm, and the gas oil injection part at the inlet of the reaction tube was provided with a preheating part of a capillary of about 20 cm in order to promote evaporation of the gas oil. Quartz wool was charged into the reaction tube for the thermal decomposition, and the catalyst was charged for the catalytic decomposition. The amount of gas produced by the pretreatment was determined by subtracting the amount of liquid accumulated in the gas-liquid separator (gas-liquid separator) from the amount of light oil supplied.
【００４９】まず、前処理装置を設けず、上記の脱硝装
置により、表１に示すように、還元剤としてプロパンあ
るいは軽油を用い、脱硝装置直前の配管部に還元剤を直
接注入して脱硝試験を行なった。このときの還元剤の注
入量は、還元剤／ＮＯX が重量比で２．０〜２．２とな
るようにした。First, as shown in Table 1, propane or light oil was used as a reducing agent by the above-mentioned denitration apparatus without providing a pretreatment apparatus, and the reducing agent was directly injected into a pipe section immediately before the denitration apparatus to perform a denitration test. Was done. The injection amount of the reducing agent at this time was such that the weight ratio of the reducing agent / NO x was 2.0 to 2.2.
【００５０】なお、軽油、プロパンは、いずれも市販の
燃料用のものである。The light oil and propane are both for commercial fuels.
【００５１】これらを試験No. １〜３とする。These are designated as Test Nos. 1 to 3.
【００５２】また、上記において、還元剤／ＮＯX 比を
３．７とするほかは同様にして試験を行なった。これを
試験No. ４、５とする。Further, in the above, the same test was conducted except that the reducing agent / NO x ratio was 3.7. These are designated as Test Nos. 4 and 5.
【００５３】次に、前処理装置を設けた脱硝装置によ
り、前処理反応器中に石英ウールを詰め、軽油の熱分解
ガスによる脱硝試験を行なった。分解温度６００℃、軽
油供給速度２．９g/min のときのガス化率は２２wt% 、
分解温度７００℃、軽油供給速度１．２g/min のときの
ガス化率は５０wt% であった。Next, by using a denitration device provided with a pretreatment device, quartz wool was packed in the pretreatment reactor, and a denitration test was carried out by pyrolysis gas of light oil. At a decomposition temperature of 600 ° C and a gas oil supply rate of 2.9 g / min, the gasification rate is 22 wt%,
The gasification rate was 50 wt% at a decomposition temperature of 700 ° C and a light oil supply rate of 1.2 g / min.
【００５４】これらを軽油の熱分解条件に応じて、試験
No. ６、７とする。These were tested according to the pyrolysis conditions of light oil.
No. 6 and 7.
【００５５】さらに、前処理装置を設けた脱硝装置によ
り、前処理装置の反応管に、Ｌａを担持したＹ型ゼオラ
イトを充填し、反応温度６００℃、軽油のＷＨＳＶ＝１
３hr -1の条件で接触分解を行なった。このときのガス化
率は４０wt% であった。これを試験No. ８とする。Furthermore, the denitration device provided with the pretreatment device
In the reaction tube of the pretreatment device, La-loaded Y-type Zeora
Filled with water, reaction temperature 600 ° C, gas oil WHSV = 1
3 hr -1Catalytic decomposition was carried out under the conditions. Gasification at this time
The rate was 40 wt%. This is designated as Test No. 8.
【００５６】これらの試験No. １〜No. ８の脱硝率の結
果を表１に示す。表１には、排ガス温度、脱硝触媒のＳ
Ｖを併記している。Table 1 shows the results of the denitration rates of these tests No. 1 to No. 8. Table 1 shows the exhaust gas temperature and S of the denitration catalyst.
V is also shown.
【００５７】[0057]
【表１】 [Table 1]
【００５８】表１の結果から以下のことがわかる。The following can be seen from the results in Table 1.
【００５９】試験No. １〜No. ３の結果から明らかなよ
うに、軽油の脱硝効果はプロパンに比べて６割弱であ
り、還元剤の注入量を多くしても、軽油による脱硝率は
プロパンのそれの８割弱であった（試験No. ４、５）。As is clear from the results of tests No. 1 to No. 3, the denitrification effect of light oil is slightly less than 60% as compared with propane, and the denitrification rate of light oil does not increase even if the injection amount of the reducing agent is increased. It was a little less than 80% of that of propane (Test No. 4, 5).
【００６０】これに対し、前処理装置により軽油を前処
理してガス化したものを還元剤として用いた場合は、試
験No. ６、７と試験No. １との比較、あるいは試験No.
８と試験No. ４との比較から明らかなように、プロパン
と同等の脱硝効果が得られた。On the other hand, when gas oil obtained by pre-treating light oil by the pre-treatment device is used as the reducing agent, comparison between test Nos. 6 and 7 and test No. 1 or test No. 1 is carried out.
As is clear from the comparison between Test No. 8 and Test No. 4, a denitration effect equivalent to that of propane was obtained.
【００６１】そして、本発明では、プロパンを用いる場
合と異なり、燃料タンクの燃料を利用して還元剤とする
ものであるため、プロパン用の設備を新たに付設する必
要がなく、操作上あるいはコスト面でも有利である。ま
た、ガス化されない燃料を燃料タンクに戻して使用して
もエンジンの運転には、何ら支障がなかった。In the present invention, unlike the case where propane is used, the fuel in the fuel tank is used as the reducing agent, so that it is not necessary to additionally install a facility for propane, and the operation or cost is reduced. It is also advantageous in terms of aspects. Further, even if the ungasified fuel was returned to the fuel tank and used, the operation of the engine was not hindered.
【００６２】なお、上記の試験No. ６〜No. ８におい
て、軽油のかわりに、Ａ重油、ガソリンを用いて、これ
らを燃料とするエンジンで、それぞれ、上記と同様の脱
硝試験を行なったところ、プロパンなみの脱硝効果を示
した。In the above tests No. 6 to No. 8, a denitration test similar to that described above was carried out on an engine using A heavy oil and gasoline instead of light oil and using these as fuels. , Showed a denitration effect similar to that of propane.
【００６３】[0063]
【発明の効果】本発明によれば、エンジン用の燃料タン
ク内の軽油、重油、ガソリン等の燃料の一部を利用して
ガス化し、これを脱硝装置の還元剤として用いることが
できる。しかも、脱硝効率も良好である。また、燃料と
は異なるプロパンを用いる場合に比べ、操作上やコスト
面で格段と有利となる。According to the present invention, a part of fuel such as light oil, heavy oil and gasoline in a fuel tank for an engine can be gasified and used as a reducing agent for a denitration device. Moreover, the denitration efficiency is also good. In addition, compared to the case of using propane different from the fuel, it is significantly advantageous in terms of operation and cost.
【図１】本発明に用いる前処理装置を説明するための概
略構成図である。FIG. 1 is a schematic configuration diagram for explaining a pretreatment device used in the present invention.
１ 前処理装置 １１ 反応管 １２ 加熱炉 ２ 燃料タンク ３ 気液セパレータ ４ 脱硝装置 ２０ 燃料 ３０ 熱分解ガス 1 Pretreatment Device 11 Reaction Tube 12 Heating Furnace 2 Fuel Tank 3 Gas-Liquid Separator 4 Denitration Device 20 Fuel 30 Pyrolysis Gas
───────────────────────────────────────────────────── フロントページの続き (72)発明者 菊地 孝浩 千葉県柏市高田1201 財団法人 産業創 造研究所 柏研究所内 (72)発明者 田村 孝章 千葉県柏市高田1201 財団法人 産業創 造研究所 柏研究所内 (72)発明者 山本 弘孝 埼玉県川越市芳野台２−８−65 デンヨ ー株式会社技術研究所内 (56)参考文献 特開 平５−59933（ＪＰ，Ａ) 特開 平４−83516（ＪＰ，Ａ) ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Takahiro Kikuchi 1201 Takada, Kashiwa City, Chiba Prefecture Industrial Creation Laboratory, Kashiwa Research Center (72) Inventor Takaaki Tamura 1201, Takada, Kashiwa City, Chiba Institute of Industrial Creation Kashiwa Laboratory (72) Inventor Hirotaka Yamamoto 2-8-65 Yoshinodai, Kawagoe City, Saitama Denyo Co., Ltd. Technical Laboratory (56) Reference JP-A-5-59933 (JP, A) JP-A-4-83516 (JP, A)
Claims (3)
入し、ディーゼルエンジンもしくはリーンバーンのガソ
リンエンジンの排ガス中の窒素酸化物を除去する方法に
おいて、 前記脱硝装置の前方に前処理装置を設け、前記エンジン
用の燃料タンクから燃料の一部をこの前処理装置に送
り、この燃料を熱分解または接触分解して気体状低分子
量成分を得、気液分離により気体状低分子量成分と残余
の燃料とに分離し、気体状低分子量成分を前記脱硝装置
に注入し、残余の燃料を前記燃料タンクに戻すことを特
徴とする排ガス中の窒素酸化物の除去方法。1. A method of injecting a fuel as a reducing agent into an exhaust gas denitration device to remove nitrogen oxides in exhaust gas of a diesel engine or a lean burn gasoline engine, wherein a pretreatment device is provided in front of the denitration device. A part of the fuel is sent from the fuel tank for the engine to the pretreatment device, the fuel is pyrolyzed or catalytically decomposed to obtain a gaseous low molecular weight component, and the gaseous low molecular weight component and the residual fuel are separated by gas-liquid separation. A method for removing nitrogen oxides in exhaust gas, characterized in that a gaseous low molecular weight component is injected into the denitration apparatus and the remaining fuel is returned to the fuel tank.
ィンを含む請求項１に記載の排ガス中の窒素酸化物の除
去方法。2. The method for removing nitrogen oxides from exhaust gas according to claim 1, wherein the gaseous low molecular weight component contains a gaseous olefin.
は、γ−アルミナ、シリカ・アルミナもしくは水素化し
たゼオライト触媒、またはこのγ−アルミナ、シリカ・
アルミナもしくは水素化したゼオライト触媒に銅、亜
鉛、バナジウム、クロム、マンガン、鉄、コバルトおよ
びニッケルのうちの少なくとも１種を担持した触媒であ
る請求項１または２に記載の排ガス中の窒素酸化物の除
去方法。3. The catalyst used in the denitration catalyst layer of the denitration device is γ-alumina, silica-alumina or a hydrogenated zeolite catalyst, or this γ-alumina, silica.
The nitrogen oxide in the exhaust gas according to claim 1 or 2, which is a catalyst in which at least one of copper, zinc, vanadium, chromium, manganese, iron, cobalt and nickel is supported on an alumina or hydrogenated zeolite catalyst. Removal method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3293719A JP2510913B2 (en) | 1991-10-14 | 1991-10-14 | Method for removing nitrogen oxides in exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3293719A JP2510913B2 (en) | 1991-10-14 | 1991-10-14 | Method for removing nitrogen oxides in exhaust gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05103952A JPH05103952A (en) | 1993-04-27 |
| JP2510913B2 true JP2510913B2 (en) | 1996-06-26 |
Family
ID=17798360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3293719A Expired - Fee Related JP2510913B2 (en) | 1991-10-14 | 1991-10-14 | Method for removing nitrogen oxides in exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2510913B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4711425B2 (en) * | 2005-08-17 | 2011-06-29 | 株式会社デンソー | Exhaust gas purification device and exhaust gas purification method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0661427B2 (en) * | 1990-07-19 | 1994-08-17 | 株式会社日本触媒 | Nitrogen oxide removal method |
| JP2923382B2 (en) * | 1991-08-30 | 1999-07-26 | 日野自動車工業株式会社 | Exhaust gas purification equipment for diesel engines |
-
1991
- 1991-10-14 JP JP3293719A patent/JP2510913B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05103952A (en) | 1993-04-27 |
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