200824782 九、發明說明： 【發明所屬之技術領域】 本發明關於一種用於柴油引擎的廢氣淨化裝置，其可有 效地減少或去除一柴油引擎之廢氣中所含有的氮氧;匕物 (NOx)及微粒物質。 【先前技術】 ίο 15 20 因為燃油效率和優異可靠度，柴油引擎已被廣泛用在車 b船舶及-般工業用途，柴油引擎可被操作為具備一大 負載，使得對於柴油引擎的需求持續成長。又，在 高燃油效率車輛的3L汽車計晝或超 =專木（SuperCarPrGjeet) t中，幾已確定會採用柴油 引手，使付預料中對於裝有柴油引擎之車十 求。但由於從此等柴油車排放之 滷士二有更夕而 百分之40,已開發國家理解：:：大Μ染的大約 大部分責任。 ㈣木油引擎要對空氣污染負起 理規為章應付上述情況，每__化對於柴油車之廢氣的管 柴油車排放之空氣污染主〆 粒物質（m)造成。因此，疋由^氧化物⑽Ο及微 要對象是氮氧化物和微粒物質 ==廢氣管理規章的主 已開發出著重於柴油噴射之時間=付亡：管理規章，頃 得氮氧化物之濃度減低以及改二=廢氣再循環使 物質的相關技術。 手〗、、、&表現以減少微粒 關於用以減少氮氧化物的 ' 使用選擇性催化還原 ske96318.doc 7 200824782 f在忒方法中，氮氧化物在一觸媒上透過一還原 成氮氣和氧氣。 此％可利用氨、尿素或碳氫化合物當作選擇性催化還 2Γ之還原劑。但其—缺點是需要—單獨基礎設施以供 供應氰或尿素，且因此碳氫化物是較佳的還原劑。輕油、 2油、丙烯、丙烧、乙婦、及丁烯類均是碳氫化合物的 ίο 15 20 另方面，關於用以減少微粒物質的方法，頃已廣泛庫 Z油微㈣濾（卿）法，此方法依據回收-過遽器Γ 足到之微粒物質的方式可分類成一連續回收類型及一強 在連續回收法中，-氧化氮⑽)被-提供 卞，力粒過濾為之一前端的氧化觸媒轉化成二氧化氮 σ 2)以回收微粒物質。為主動回收微粒物質，在強制 :收法中利用辅助設備強制提高過濾器之溫度。在強制回 命去中存在著使電力透過形成於柴油微粒過濾器上之一 :極放電的方式、彻_電熱器、使過濾器之溫度提高的方 t藉由將—電漿反應器安裝在柴油微粒過濾器之-前端 Z而使微粒物質被回收的方式、或是使微粒被噴 麂掉的方式。 化二於柴油引擎之習知廢氣淨化裝置，頃已知-種廢氣淨 置2 ，中配備氧化觸媒的柴油微粒過濾器（DPF)設 k 一2氣通道之一上游侧，碳氫化合物選擇性還原型氮 原（DeNOx)觸媒設置在一下游側，且一柴油喷 1提供在該柴油微粒過濾器與該氮氧化物還原觸媒之 8 ske96318.doc 200824782 間。 但疋，習知廢氣淨化裝置不足以勝任在一中等溫度範圍 有效且同時地不僅去除氮氧化物、微粒物質更去除一氧化 碳（CO)及總碳氫化合物（THC)。 5 10 15 20 另一方面，頃已利用廢氣再循環（EGR)系統來減少氮 氧化物。整體而言，廢氣再循環系統已被以一種方法使用， 其中使廢氣從渦輪增壓器之一葉輪之一後端流到該渦輪增 壓器之-壓縮機之一前端以降低引擎之燃燒溫度並減少^ 氧化物。但上述方法的缺點在於由於大量微粒物質被包含 在從渦輪增壓器之葉輪排出的廢氣中，這些微粒物質對引 擎造成負擔且降低引擎之燃油效率。X，在上述方法中， 因廢氣再循環率之增加而減少且微粒物質因 之增加而增加，藉由廢氣再循環方式減少氮 ίΠίΓ限。此外’由於廢氣再循環（egr)系統 制的閥及一用以降低待循環之廢氣 η，她冷卻器’引擎之佈局因其複 n高，故在運用上述系統時會有缺點。 國專利公開案第3二=:糸統:問題的技術’在韓 綠。A_ Μ A ^ 刚端的廢氣再循環 ，泉在5亥專利中，廢氣再循環線 -廢氣再猶環冷卻器及類似物，且，，手控制益和 提升裝置之建構容易度。但該專财之—部^ 化物之減少仙僅由該廢氣再 、點》由於氮氧 孔冉線進行，廢氣所含氮氧 ske96318.doc 9 200824782 化物之減少效率實質為低。 又，以廢氣再循環系統搭配氮氧化物還原（DeN〇x)觸 媒使用的廢氣淨化裝置揭示在美國專利第號 中，該專利揭示用以使廢氣從說氧化物還原（DeNOx)觸 5 Ϊ之Γ上端再循環到—進氣歧管的廢氣再循環系統。但如 前所述i該專利之缺點在於因為含有大量微粒物質的廢氣 被再循Ί粒物f對引擎造成負擔且降低引擎之燃油效 ; Λ專利之廢氣再循環系統包括一廢氣再循環閥及 一用以控制該閥的控制器’使得裝置的構造複雜化。 10【發明内容】 —本發明之發明人已發明一種經申請為韓國專利申請案 ^ 10-2005-0102494號的廢氣淨化裝置’該裝置具備自廢 : 游依序女裝的氮氧化物還原觸媒和柴油微粒過 濾器及-安裝在該氮氧化物還原觸媒之一上 =器。相較於習知廢氣淨化系統，該申請案所揭示之裝置的 矚氮氧化物減少效率比較好。但為了符合近 氧1 匕物減t效率的需求’本發明人已研究該廢氣淨/匕裝ί 且取終開發出更進-步含有廢氣再循環線的廢氣淨化裝 20 …因此，本發明之一目標是提出一種用於柴油引擎的廢氣 大ί 一氮氧化物還原觸媒和—柴油微粒過濾 ™且〃、有大巾田增強的氮氧化物減少表現。 、事化又4發=一。目標是提出一種用於柴油引擎的廢氣 乎化衣置，，、在250 C-600t之一溫度（此為廢氣之實際 ske963l8.doc 10 200824782 溫度）具有優異的氮氧化物減少表現、高效微粒物質去除 效率且有能力去除一氧化碳（c〇)及總碳氣化合 (THC )。 為達成上述目標，本發明人已努力發明用於柴油引擎的 5廢氣二化衣置’其包括自廢氣流之一上游相繼提供的氮氧 化物=原觸媒單元和柴油微粒過濾單元；一提供在該 化物還原觸媒單元之一前端部分的柴油喷射器；及一二以 醍使廢氣之-部分從該柴油微粒過滤單元之一後端送到一引 擎之一進氣歧管的廢氣再循環線。 10 i本發明關於一種用於柴油引擎的廢氣淨化裝置，其可有 效地減少或去除一柴油引擎之廢氣中所含有的氮氧化物 (NOx)及微粒物質，更特定言之，本發明提出—種用於 柴油引擎的廢氣淨化裝置，其中自廢氣流之一上游相繼提 供一氮氧。化物還原（DeN0x)觸媒單元及一柴油微粒過濾 =jDPF)單疋，—柴油喷射n提供在該氮氧化物還原觸媒 釀單兀之一前端部分，且一廢氣再循環（EGR)線經提供用 以使廢氣之一部分從該柴油微粒過濾單元之一後端送到一 引手之一進氣歧管。其中，該廢氣再循環（EGR )線不包 含一單獨附加調整閥或一控制器。 20 又，依據本發明之廢氣淨化裝置可更進一步包括一柴油 氧化觸媒（DOC)，一柴油氧化觸媒可放在一柴油噴射#器 之一可端部分、介於該柴油噴射器與一氮氧化物還原觸媒 之間、介於該氮氧化物還原觸媒與一柴油微粒物質去除過 濾器之間、或是介於該柴油微粒物質去除過濾器與該廢氣 ske963l8.d〇c 11 200824782 一柴油氧化觸媒可被提 再循環線之一入口段之間，且至少 供在上述位置。 以下更詳細地說明本發明。 依據本發明用於柴油引擎之廢氣淨化裝置喷射柴油以 5在一氮氧化物還原觸媒單元（以下簡稱、、DeN〇x觸媒單元 減少氮氧化物（以下簡稱'N〇j，經由柴油之燃燒作用 減少累積到一柴油微粒過濾器（以下簡稱、、DPF〃）單元 的微粒物質（PM)並同時去除—氧化碳（c〇)和總碳氣 ίο 本發明揭示附有一廢氣再循環（以下簡稱 )線的廢氣淨化裝置，該EGR線用於將廢氣之一 部分從該DPF之-後端引導至一進氣歧管以減少Ν〇χ。 在依據本發明之廢氣淨化裝置中，Ν〇χ之一部分因提供 該EGR線而去除，且Ν〇χ在提供於一排氣通道中的 觸媒去除，故本發明之廢氣淨化裝置可比習知廢氣淨化裝 置更有效地去除氮氧化物。又，氮氧化物更進一步被施加 於位在DeN〇x觸媒單元-後端之DPF上的觸媒去除，故 有一2點為依據本發明之廢氣淨化裝置的氮氧化物減少效 率顯著優於習知廢氣淨化裝置，且Ν〇χ的減少效果在 °C -350°C之一中等溫度範圍内變得高效。 2〇 在本發明中，微粒物質絕大部分在該DPF單元上去 除。在柴油係在DeN〇x觸媒單元之一前端噴射的情況中， 柴油在通過該DeN〇x觸媒單元的同時均勻分布，因此該 DPF再生之一溫度可被降低。 人 又，本發明可更有效地去除在習知廢氣淨化裝置中去除 ske96318.doc 12 200824782 的一氧化碳（CO)及總碳氫化合物（thc)。 由於一氧化碳無法在媒單元中去除，若僅存 在者DeNOx觸媒早元’ 一氧化碳的量會增加。但在本發明 中，一氧化碳可因該DPF單元之鉑族組份而在2〇(rc或更 5 高之一溫度被有效地去除。 又，總碳氳化合物不會在DeNOx觸媒單元中去除。特 定言之’若用柴油當作還原劑噴射以去除氮氧化物，則廢 ®氣所含碳氫化合物的量會比不喷射柴油之情況多。為解決 上述問題，在本發明中，使廢氣通過DeNOx觸媒單元使得 未經反應增多的碳氳化合物可在該DPF單元上有效地去 除0 再者，若有至少一柴油氧化觸媒（D〇c)被提供在柴 油噴射器之一前端部分、該柴油喷射器與一氮氧化物還原 觸媒之間、該氮氧化物還原觸媒與一柴油微粒過濾器之 /5間、或是該柴油微粒過濾器與該廢氣再循環線之一入口段 _之間，该柴油氧化觸媒將廢氣内的一氧化氮（NO )轉化成 二氧化氮（N〇2)以促使該柴油微粒過濾器中之再循環作 用順暢進行，且如此有可能提高包含可溶性有機餾分在内 之總碳氫化合物（THC)的減少效率。 20 依據本發明用於柴油引擎的廢氣淨化裝置是在250°C -600°C之一溫度（此為廢氣之實際溫度）具有優異氮氧化 物減少表現及絕佳微粒物質去除效率的廢氣淨化裝置，本 發明之優點在於藉由喷射柴油來進行氮氧化物之選擇性還 原，且同時藉由廢氣再循環來進行氮氧化物之減少，使得 13 ske96318.doc 200824782 氮氧化物減少效率顯著提高，且微粒物質可由在氮氧化物 還原觸媒之一後端提供的微粒過濾器有效地去除。 再者，不管會造成與廢氣溫度相關之氮氧化物減少表現 差異的引擎操作狀態是如何，本發明之廢氣淨化裝置具有 5 —絕佳的氮氧化物減少表現及一去除微粒物質、一氧化碳 和碳氫化合物的優異效率。 【實施方式】 II 本發明之以上及其他目標、特徵和優點將在以下參照隨 附圖式進行說明之較佳實施例中顯露。 ίο 以下參照隨附圖式說明本發明之實施例。 一作為本發明之一實施例放在柴油引擎之排氣通道内 的廢氣淨化裝置示於圖1。依據圖1，一 DeNOx觸媒單元 1位於廢氣流之一上游側，且一 DPF單元2與該DeNOx 觸媒單元串聯，且一柴油喷射器3安裝在該DeNOx觸媒單 15 元之一前端部分。一連接該DPF單元之一後端與一進氣歧 • 管5的EGR線4放在一引擎之渦輪增壓器之一壓縮機之一 上端。依據本發明之EGR系統的優點在於該系統不具有附 加EGR冷卻器、EGR閥及EGR控制器，使得該裝置易於 建構。廢氣之一部分依據進氣歧管5内之空氣流自動地流 20 入EGR系統内，且此廢氣與進氣空氣混合然後通過渦輪增 壓器6之壓縮機6a進入引擎7。柴油引擎7之廢氣經由渦 輪增壓器之一葉輪6b排放。DeNOx觸媒單元1及柴油微 粒過濾器（DPF) 2相繼設置在排氣通道内，且柴油喷射 器3放在該DeNOx觸媒單元之一前端部分。較佳來說，依 14 ske96318.doc 200824782 據本發明之廢氣淨化裝置之廢氣 …w⑽，此EGR率依二(：)率在ο.1 ^ ^ ^ 卞依據廢乳再循環線之直徑 :二1 ίΓΓ率是0.1%或更小，則幾乎得不到吨 5 10 15 20 微粒物-Α果廢乳再循環率超過15%，則引擎排放的 =物貝胃大幅增加，對該DPF過遽器 咖地發揮功能。若廢氣再循環率被縣成在 ίί二且、除了藉由DeN0x觸媒單元1得到的nox減少 有微粒物幅提广的吨減少效率。又，廢氣所含所 P V —貝 PF單元2去除，而從位於DeNOx觸媒單 =一前端之柴油喷射器3射出的柴油通過該DeN〇x觸媒 油均勻分布使得該DpF回收之一溫度可被降低。 :二猎：-進油泵（圖中未示）使其從一油箱卩流入該柴 :嘴射器然後從該柴油噴射器射出，欲射出之柴油量及柴 油射出之時間係由一柴油噴射控制單元1〇控制。 依0據本發明之廢氣淨化裝置中的DeN〇x觸媒單元1、 PF單元2及柴油喷射器3例示於圖3和圖4。圖3示出 由一層氮氧化物還原觸媒層組成的DeN〇x觸媒單元，且圖 4不=由多層氮氧化物還原觸媒層組成的DeN〇x觸媒單 兀。參=圖4,在DeNOx觸媒單元中，乡層DeN〇x觸媒相 鄰地堆$且相繼設置。若由多層DeN〇x觸媒堆疊相繼設置 以形成该媒單元，則廢氣通過的表面積加大，且 因此可增強NOx減少效率。又，Ν〇χ減少效率可藉由以彼 此不同之觸媒製造DeN〇x觸媒層或是改變觸媒含量的方 15 ske96318.doc 200824782 式提南，使得DeNOx觸媒單元在多種溫度範圍中具有優異 γ〇χ減少效率且不管會造成與廢氣溫度相關之氮氧化物減 >表現差異的引擎操作狀態是如何均會有優異ΝΟχ減少表 現0 5 10 15 20 上面支承著銀組份、銅組份或類似物的觸媒被用來當作 依據本發明之DeN〇x觸媒單元’可用來支承銀組份的材料 係從處於分解狀態之銀（Ag)、氧化銀（Ag2〇)、氣化銀 ^AgCU、硝酸銀（AgN〇3)、硫酸銀（Ag2S〇4)或以上之 此口，g中選出，且可用來支承銅組份的材料係從處於還 原狀態之銅（Cu)、氧化銅、醋酸銅、氮化銅、硫酸銅或 以上之混合物當中選出。氧化叙（a12〇小二氧化矽 (Si〇2)、二氧化鈦（Ti〇2)、二氧化鈽（Ce〇2)、二氧化錯 (Zr〇2 )或沸石可被用來當作支承觸媒的薄塗層 (washcoat)’且可使用從上述材料選出之二或更多種材料 之混合物。在上述材料當中，減少氮氧化物之最優異表現 係由使用氧化鋁當作薄塗層獲得。 冷薄塗層係以-塗覆在一支撐件上的狀態使用，較佳來說 溥塗層之使用量以全觸媒含量為基準是〇 5§/^3至4 g/m3。此時若薄塗層含量小於〇 5g/in3，則所支承觸媒之 絕對量不足，使得觸媒之表現明顯降低，且如果薄汾層 量超過4—，則觸媒之表現不會有任何增長 ： 製造此觸媒。 谷匆 氮氧化物還原觸媒之支撐件县— 制、-熱安定陶瓷或金屬 衣仏之肌通式㈣’更詳細地說可以堇青石蜂巢結構體為 ske963 1 8.doc 16 200824782 例0 又’若至少一柴油氧化觸媒（D0C)提供在柴油噴射 器之一前端部分、該柴油噴射器與氮氧化物還原觸媒之 間、該氮氧化物還原觸媒與一柴油微粒過濾器之間、或該 5柴油微粒過濾器與廢氣再循環線之一入口段之間，則該柴 油氧化觸媒將廢氣中之一氧化氮（NO)轉化成二氧化氮 (N〇2 )以促使該柴油微粒過濾器中之一回收作用順暢進 ⑩行，且有可能提高包含可溶性有機餾分在内之總碳氫化合 物（THC )的減少效率。 10 15200824782 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to an exhaust gas purifying apparatus for a diesel engine, which can effectively reduce or remove nitrogen and oxygen contained in exhaust gas of a diesel engine; And particulate matter. [Prior Art] ίο 15 20 Because of fuel efficiency and excellent reliability, diesel engines have been widely used in marine and general industrial applications. Diesel engines can be operated with a large load, so that the demand for diesel engines continues to grow. . In addition, in the 3L car meter or SuperCarPrGjeet t of high fuel efficiency vehicles, it has been determined that diesel engines will be used to make the demand for the diesel engine. However, since the emissions from these diesel vehicles are even higher than 40%, the developed countries understand that::: Most of the responsibility for large-scale dyeing. (4) The wood oil engine should be responsible for the air pollution. The regulation is to deal with the above situation. Each __ is caused by the air pollution of the diesel vehicle. Therefore, 疋 by oxide (10) Ο and the main object is nitrogen oxides and particulate matter == exhaust gas management regulations have developed a focus on diesel injection time = pay: management regulations, the concentration of nitrogen oxides is reduced And the second technology = related technology of exhaust gas recirculation. Hand, 、, & performance to reduce the use of particles to reduce nitrogen oxides. Selective catalytic reduction ske96318.doc 7 200824782 f In the hydrazine process, nitrogen oxides are reduced to nitrogen on a catalyst. oxygen. This % can be used as a reducing agent for the selective catalysis of ammonia, urea or hydrocarbons. However, it has the disadvantage of requiring a separate infrastructure for the supply of cyanide or urea, and thus hydrocarbons are preferred reducing agents. Light oil, 2 oil, propylene, acrylic, female, and butene are all hydrocarbons. ίο 15 20 In other respects, the methods used to reduce particulate matter have been extensively used in Z oil micro (four) filtration. ), this method can be classified into a continuous recovery type and a strong in the continuous recovery method based on the method of recovering - passing through the particulate matter, - nitrogen oxide (10)) is supplied - 卞, force particle filtration is one The oxidation catalyst at the front end is converted to nitrogen dioxide σ 2) to recover particulate matter. In order to actively recover particulate matter, the auxiliary equipment is used to force the temperature of the filter in the forced: receiving method. In the forced reincarnation, there is a method of passing electric power through one of the diesel particulate filters: a pole discharge method, a heat exchanger, and a temperature for increasing the temperature of the filter by mounting the plasma reactor The manner in which the front end Z of the diesel particulate filter is such that the particulate matter is recovered or the particulate is squirted. The conventional exhaust gas purification device of the diesel engine is known as a kind of exhaust gas net 2, and the diesel particulate filter (DPF) equipped with an oxidation catalyst is provided on the upstream side of one of the k-2 gas passages, and the hydrocarbon selection A reducing nitrogen source (DeNOx) catalyst is disposed on a downstream side, and a diesel fuel spray 1 is provided between the diesel particulate filter and the nitrogen oxide reduction catalyst between 8 ske96318.doc 200824782. However, conventional exhaust gas purification devices are not sufficient to be effective in a moderate temperature range and at the same time not only remove nitrogen oxides, particulate matter but also remove carbon monoxide (CO) and total hydrocarbons (THC). 5 10 15 20 On the other hand, exhaust gas recirculation (EGR) systems have been utilized to reduce nitrogen oxides. In general, the exhaust gas recirculation system has been used in a method in which the exhaust gas flows from the rear end of one of the impellers of the turbocharger to the front end of the compressor of the turbocharger to reduce the combustion temperature of the engine. And reduce ^ oxide. However, the above method has the disadvantage that since a large amount of particulate matter is contained in the exhaust gas discharged from the impeller of the turbocharger, the particulate matter imposes a load on the engine and lowers the fuel efficiency of the engine. X, in the above method, the decrease in the exhaust gas recirculation rate is increased and the particulate matter is increased due to the increase, and the nitrogen gas is reduced by the exhaust gas recirculation method. In addition, due to the valve of the exhaust gas recirculation (egr) system and the use of a gas η to reduce the amount of exhaust gas η to be circulated, the layout of her cooler's engine is high, so there are disadvantages in using the above system. National Patent Publication No. 3 = =: SiS: The Technology of the Problem 'in Han Green. A_ Μ A ^ The exhaust gas recirculation at the end, the spring in the 5 Hai patent, the exhaust gas recirculation line - the exhaust gas re-cooling cooler and the like, and, the ease of construction of the hand control and lifting device. However, the reduction of the mono-chemicals of the special wealth is only caused by the exhaust gas and the point, due to the nitrogen-oxygen pore line, and the reduction efficiency of the nitrogen-oxygen ske96318.doc 9 200824782 is substantially low. Further, an exhaust gas purifying apparatus using an exhaust gas recirculation system in combination with a nitrogen oxide reduction (DeN〇x) catalyst is disclosed in U.S. Patent No. 1, which discloses that the exhaust gas is removed from the oxide (DeNOx). The upper end is then recirculated to the exhaust gas recirculation system of the intake manifold. However, as mentioned above, the patent has the disadvantage that the exhaust gas containing a large amount of particulate matter is burdened by the particulate matter f and reduces the fuel efficiency of the engine; the patented exhaust gas recirculation system includes an exhaust gas recirculation valve and A controller 'to control the valve' complicates the construction of the device. 10 [Summary of the Invention] - The inventors of the present invention have invented an exhaust gas purifying device which has been applied for Korean Patent Application No. 10-2005-0102494, which has a self-destruction: NOx reduction contact of the women's clothing The medium and the diesel particulate filter are mounted on one of the nitrogen oxide reduction catalysts. Compared to conventional exhaust gas purification systems, the apparatus disclosed in the application has a better reduction efficiency of niobium oxynitride. However, in order to meet the demand for the near-oxygen 1 减 减 reduction efficiency, the inventors have studied the exhaust gas net/armor ί and finally developed a more advanced exhaust gas purification device 20 containing the exhaust gas recirculation line. One of the goals is to propose a gas-reducing catalyst for diesel engines, a nitrogen oxide reduction catalyst, and a diesel particulate filter, and a nitrogen oxide-enhanced NOx reduction performance. And things are 4 and then = one. The goal is to propose an exhaust gas-discharging device for diesel engines that has excellent nitrogen oxide reduction performance and high-efficiency particulate matter at a temperature of 250 C-600 t (this is the actual ske963l8.doc 10 200824782 temperature of the exhaust gas). It removes efficiency and has the ability to remove carbon monoxide (c〇) and total carbon gas (THC). In order to achieve the above object, the inventors have endeavored to invent a five-gas exhaust gas disintegration device for a diesel engine, which includes nitrogen oxides provided from one of the exhaust gas streams successively = a primary catalyst unit and a diesel particulate filter unit; a diesel injector at a front end portion of the reduction catalyst unit; and an exhaust gas recirculation for exhaust gas to a portion of the exhaust gas from a rear end of the diesel particulate filter unit to an intake manifold of an engine line. 10 i The present invention relates to an exhaust gas purifying apparatus for a diesel engine, which can effectively reduce or remove nitrogen oxides (NOx) and particulate matter contained in exhaust gas of a diesel engine, and more specifically, the present invention proposes An exhaust gas purifying apparatus for a diesel engine in which a nitrogen gas is sequentially supplied from one of the exhaust gas streams. a reduction (DeN0x) catalyst unit and a diesel particulate filter = jDPF) single helium, - diesel injection n is provided at one of the front end portions of the nitrogen oxide reduction catalyst brewing unit, and an exhaust gas recirculation (EGR) line An intake manifold is provided for delivering a portion of the exhaust from one of the rear ends of the diesel particulate filter unit to a lead. Wherein the exhaust gas recirculation (EGR) line does not include a separate additional regulating valve or a controller. Further, the exhaust gas purifying apparatus according to the present invention may further comprise a diesel oxidation catalyst (DOC), and a diesel oxidation catalyst may be placed in one end portion of a diesel fuel injection device, between the diesel injector and the Between the nitrogen oxide reduction catalysts, between the nitrogen oxide reduction catalyst and a diesel particulate matter removal filter, or between the diesel particulate matter removal filter and the exhaust gas ske963l8.d〇c 11 200824782 A diesel oxidation catalyst can be provided between one of the inlet sections of the recycle line and at least in the above position. The invention is explained in more detail below. According to the present invention, an exhaust gas purifying device for a diesel engine injects diesel fuel with a nitrogen oxide reduction catalyst unit (hereinafter referred to as a DeN〇x catalyst unit to reduce nitrogen oxides (hereinafter referred to as 'N〇j, via diesel fuel) Combustion reduces the particulate matter (PM) accumulated in a diesel particulate filter (hereinafter abbreviated as DPF) and simultaneously removes carbon monoxide (c〇) and total carbon gas. The present invention discloses an exhaust gas recirculation (hereinafter) Referred to as the line of exhaust gas purification device for directing a portion of the exhaust gas from the rear end of the DPF to an intake manifold to reduce enthalpy. In the exhaust gas purification device according to the present invention, A part of the EGR line is removed by the provision of the EGR line, and the catalyst provided in an exhaust passage is removed, so that the exhaust gas purifying apparatus of the present invention can remove nitrogen oxides more efficiently than the conventional exhaust gas purifying apparatus. Nitrogen oxide is further applied to the catalyst removal on the DPF located at the rear end of the DeN〇x catalyst unit, so there is a point in which the nitrogen oxide reduction efficiency of the exhaust gas purifying device according to the present invention is significantly better than that of the Xi The exhaust gas purifying device is known, and the reducing effect of the crucible becomes efficient in a moderate temperature range of °C - 350 ° C. 2 In the present invention, most of the particulate matter is removed on the DPF unit. In the case of injection at the front end of one of the DeN〇x catalyst units, the diesel fuel is evenly distributed while passing through the DeN〇x catalyst unit, so that one of the temperatures of the DPF regeneration can be lowered. In addition, the present invention can be more effective. Removal of carbon monoxide (CO) and total hydrocarbons (thc) from ske96318.doc 12 200824782 in conventional exhaust gas purification devices. Since carbon monoxide cannot be removed in the medium, if only the DeNOx catalyst is present, 'carbon monoxide The amount may increase. However, in the present invention, carbon monoxide may be effectively removed at a temperature of 2 〇 (rc or 5 higher) due to the platinum group component of the DPF unit. Further, the total carbon ruthenium compound is not in the DeNOx contact. Removed from the media unit. Specifically, if diesel is used as a reducing agent to remove nitrogen oxides, the amount of hydrocarbons in the waste gas will be more than that in the case of not spraying diesel. To solve the above problems, hair The exhaust gas is passed through the DeNOx catalyst unit so that the carbon monoxide compound having no increase in reaction can be effectively removed on the DPF unit. Further, if at least one diesel oxidation catalyst (D〇c) is provided in the diesel injector a front end portion, between the diesel injector and a nitrogen oxide reduction catalyst, between the nitrogen oxide reduction catalyst and a diesel particulate filter, or the diesel particulate filter and the exhaust gas recirculation Between one of the inlet sections of the line, the diesel oxidation catalyst converts nitrogen monoxide (NO) in the exhaust gas into nitrogen dioxide (N〇2) to promote smooth recycling in the diesel particulate filter, and It is thus possible to increase the reduction efficiency of total hydrocarbons (THC) including soluble organic fractions. 20 The exhaust gas purifying device for a diesel engine according to the present invention is an exhaust gas purifying device having excellent nitrogen oxide reduction performance and excellent particulate matter removal efficiency at a temperature of 250 ° C to 600 ° C (this is the actual temperature of the exhaust gas). The invention has the advantages that the selective reduction of nitrogen oxides is carried out by injecting diesel oil, and at the same time, the reduction of nitrogen oxides by exhaust gas recirculation, so that the nitrogen oxide reduction efficiency of 13 ske96318.doc 200824782 is remarkably improved, and The particulate matter can be effectively removed by a particulate filter provided at the back end of one of the nitrogen oxide reduction catalysts. Furthermore, the exhaust gas purifying device of the present invention has 5 - excellent nitrogen oxide reduction performance and a removal of particulate matter, carbon monoxide and carbon, regardless of the engine operating state which causes a difference in the performance of nitrogen oxides associated with exhaust gas temperature. Excellent efficiency of hydrogen compounds. The above and other objects, features and advantages of the present invention will become apparent from The embodiments of the present invention are described below with reference to the accompanying drawings. An exhaust gas purifying device placed in an exhaust passage of a diesel engine as an embodiment of the present invention is shown in Fig. 1. According to Fig. 1, a DeNOx catalyst unit 1 is located on the upstream side of one of the exhaust gas streams, and a DPF unit 2 is connected in series with the DeNOx catalyst unit, and a diesel injector 3 is installed at a front end portion of the DeNOx catalyst unit 15 . An EGR line 4 connecting one of the rear ends of the DPF unit to an intake manifold 5 is placed at one of the compressors of one of the turbochargers of an engine. An advantage of the EGR system in accordance with the present invention is that the system does not have an additional EGR cooler, EGR valve, and EGR controller, making the device easy to construct. A portion of the exhaust gas is automatically flowed into the EGR system in accordance with the flow of air within the intake manifold 5, and this exhaust gas is mixed with the intake air and then enters the engine 7 through the compressor 6a of the turbocharger 6. The exhaust gas of the diesel engine 7 is discharged via an impeller 6b of one of the turbochargers. The DeNOx catalyst unit 1 and the diesel particulate filter (DPF) 2 are successively disposed in the exhaust passage, and the diesel injector 3 is placed at a front end portion of the DeNOx catalyst unit. Preferably, according to the exhaust gas ...w (10) of the exhaust gas purifying device of the present invention, the EGR rate is at ο.1 ^ ^ ^ 卞 according to the diameter of the waste milk recycling line: 1 ΓΓ 是 rate is 0.1% or less, then almost no ton 5 10 15 20 particulate matter - 废 fruit waste milk recycling rate of more than 15%, the engine emissions = material shell stomach increased significantly, the DPF over the DP The function of the coffee and the coffee. If the exhaust gas recirculation rate is reduced to ίί2, in addition to the nox obtained by the DeN0x catalyst unit 1, the ton reduction efficiency of the particulate matter is enhanced. Moreover, the PV-Bei PF unit 2 contained in the exhaust gas is removed, and the diesel fuel injected from the diesel injector 3 located at the front end of the DeNOx catalyst unit = a front end is evenly distributed through the DeN〇x catalyst oil so that the temperature of the DpF recovery can be Being lowered. : Two hunting: - an oil pump (not shown) causes it to flow from a tank into the diesel: the nozzle is then fired from the diesel injector, and the amount of diesel to be injected and the time of diesel injection are controlled by a diesel injection. Unit 1 is controlled. The DeN〇x catalyst unit 1, the PF unit 2, and the diesel injector 3 in the exhaust gas purifying apparatus according to the present invention are exemplified in Figs. 3 and 4. Fig. 3 shows a DeN〇x catalyst unit composed of a layer of a nitrogen oxide reduction catalyst layer, and Fig. 4 is not a DeN〇x catalyst unit composed of a multilayer nitrogen oxide reduction catalyst layer. Referring to Fig. 4, in the DeNOx catalyst unit, the rural layer DeN〇x catalysts are stacked adjacent to each other and are successively set. If a plurality of layers of DeN〇x catalyst stacks are successively disposed to form the medium unit, the surface area through which the exhaust gas passes is increased, and thus the NOx reduction efficiency can be enhanced. Moreover, the reduction efficiency can be achieved by making the DeN〇x catalyst layer or changing the catalyst content by using different catalysts from each other, so that the DeNOx catalyst unit can be used in various temperature ranges. The engine operating state with excellent γ〇χ reduction efficiency and regardless of the difference in performance of nitrogen oxides associated with exhaust gas temperature is excellent. ΝΟχ Reduced performance 0 5 10 15 20 Supported silver component, copper The catalyst of the component or the like is used as the DeN〇x catalyst unit according to the present invention. The material which can be used to support the silver component is from the silver (Ag), silver oxide (Ag2〇) in a decomposed state, Gasified silver ^AgCU, silver nitrate (AgN〇3), silver sulfate (Ag2S〇4) or above, selected from g, and the material that can be used to support the copper component is from copper (Cu) in a reduced state, Copper oxide, copper acetate, copper nitride, copper sulfate or a mixture of the above is selected. Oxidation (a12〇 small cerium oxide (Si〇2), titanium dioxide (Ti〇2), cerium oxide (Ce〇2), dioxins (Zr〇2) or zeolite can be used as a supporting catalyst A washcoat' and a mixture of two or more materials selected from the above materials may be used. Among the above materials, the most excellent performance of reducing nitrogen oxides is obtained by using alumina as a thin coating. The cold-thin coating is used in a state of being coated on a support member. Preferably, the amount of the ruthenium coating is 〇5§/^3 to 4 g/m3 based on the total catalyst content. If the content of the thin coating is less than 〇5g/in3, the absolute amount of the supported catalyst is insufficient, so that the performance of the catalyst is remarkably lowered, and if the amount of the thin layer exceeds 4, the performance of the catalyst does not increase any more: Manufacture of this catalyst. Guxi NOx reduction catalyst support county - system, - heat stability ceramic or metal 仏 仏 muscle formula (four) 'in more detail, the cordierite honeycomb structure is ske963 1 8.doc 16 200824782 Example 0 'If at least one diesel oxidation catalyst (D0C) is provided at the front end of one of the diesel injectors Between the diesel injector and the nitrogen oxide reduction catalyst, between the nitrogen oxide reduction catalyst and a diesel particulate filter, or between the 5 diesel particulate filter and an inlet section of the exhaust gas recirculation line, The diesel oxidation catalyst converts one of the nitrogen oxides (NO) in the exhaust gas into nitrogen dioxide (N〇2) to promote the recovery of one of the diesel particulate filters into 10 rows, and it is possible to improve the inclusion of soluble organic Reduction efficiency of total hydrocarbons (THC) within the fraction. 10 15
20 較佳使用内有銀組份、銅組份或以上之混合物的觸媒致 使上述組份含量以薄塗層之重量為基準是〇1 _%至 wt%。若上述組份含量小於〇] wt%，則發揮催化功能之 組份的絕對量不夠，故觸媒之表現明顯較差；且如果上述 組份含量超過l〇wt%，則組份以對於反應較不利之金屬 元素的狀態存在，故觸媒之表現明顯較差。 又，鉑族組份額外被支承在依據本發明之DeN〇x觸媒 =以在250_600r之一溫度範圍（此為廢氣之實際溫度） =到更優異的氮氧化物減少表現。依據本發明之氮氧化物 還原觸媒的氮氧化物減少表現在25〇_6〇〇〇C之一溫度範圍 (此為廢氣之實際溫度）為優異，且在鉑族組份額外被支 ，的案例巾’ DeNQx觸媒具有在35(M5Gt：之-溫度範圍 得到更優異之氮氧化物減少表現的特性。 可田作被支承在DeN〇x觸媒單元中之鉑族貴金屬的金 屬可由從m銀、錢選出之—種組份或是二或 17 ske963 1 8.doc 200824782 更多種組份之混合物構成。可彻概始、氯化把、 =胺纪、及類似物當作把之原料…可利用氯鈾； 又胺亞硝酸鉑、雙胺四氯化鉑、及類似物當作鉑之原料. i可利用氯⑽、硝酸姥、六氯化三魏、及類似物i作 鍺之原料。又’較佳來說翻族金屬含量在〇〇〇〇1 ίο 15 範圍内、更佳在0.0005 _至〇 2 _範圍内、 仏在0.001 Wt%i 0.1 wt%範圍内。若鈾族金屬含量 於〇侧1 wt% ’雜族金屬無法協助DeN〇x觸媒單 =現，且如果鈾族金屬含量超過〇 5wt%，則邮 媒早7C的表現會快速變差。 卿是—種内部支承有—㈣觸媒的㈣器，被支承 =始族觸媒的it素係從由H豸、及鍺組成之群中 =一=《多者。始或把是比較適合被支承當作鈾族觸媒 由兀,、DPF中支承之鉑族觸媒的含量是在薄塗層支撐件 之0.01 wt%至5 Wt%範圍内。若鉑族觸媒含量少於〇 〇1 7則不會產生微粒物質去除效果，絲仙族觸媒含量 =:，DPF之表現不會更進一步提升，使得此情況 就經潸方面來說不利。 20 《過濾^，氧化作用助催化組份可額外被支承在 。氧化作用助催化組份可扮演抑制二氧化硫之氧化 =用或是提高鉑族觸媒之表面活性的角色。整體而言，鉑 t觸媒在可溶性有機餾分之氧化反應中具有高活性。但 疋’輕油所含之硫之燃棟產物的二氧化硫（s〇2)被氧化 亚轉化成硫酸鹽。因此，會產生微粒物質反過來增多的不 ske963l8.d〇c 18 200824782 ίο 15 20 想要結果。為改善上述問題，可將從凱、鶴或翻當中選出 之一或多種觸媒組份額外用在鉑族觸媒中。較佳來說，從 釩:鶴或錮當中選出之一或多種觸媒組份的含量在薄塗層 支撐件中之0.01 wt%至2 Wt%範圍内。若上述觸媒組份含 量小於0.0lwt%’則不會產生抑制亞硫酸氣之氧化作用的 效果，且如果上述觸媒組份含量超過2wt%，則上述觸媒 組份之添加沒有意義’使得添加該觸媒組份不符經濟效 益。又’由於鹼金屬譬如鉀（κ)、鎂（Mg)及類似物在 低溫下具有流動能力，驗金屬提高翻族觸媒之表面活性促 進觸媒與微粒物質間之接觸，從而提高反應比。較佳來說， =屬含量在薄，撐件中之0 01 _至i爾圍 媒之含量小於0.01wt%，則不會產生提高始族觸 ^ =比的效果，且如果驗金屬含量超過lwt%，則上 祕立屬之添加沒有意義，使得添加驗金屬不符經濟效 二欽U Γ用處(Al2〇3)、二氧化石夕(Si〇2)、二氧 广二氧化錦（Ce〇2)、二氧化結（响或滞 述材賴之二或更多種二=問題可使用從上 、，依據本發明之DPF利用經過在氮氧化 丽端部分氧化噴射柴油之作用加熱的廢去’广并之- 粒物質。為了就算在DPF之 ^去除累知的微 運用哭, /现度過度升兩的情況仍安全地 運用過4為，此時最好支撐件 =王地 青石、含有碳切（Sic)的陶瓷或、，上異耐熱特質的堇 合金的合金材料製造。在支撐7^ ^合金或FeCr 干系田具有優異耐熱特質之 ske963l8.d〇 19 200824782 材料製造的案例中’優點在於儘管回收dpf時會產生高、θ 的熱，該裝置仍能安全地運作，且有可能藉由二用過 粒物質被氧化時產生之熱來節省被噴射的柴油。 以下就較佳實施例更詳細地說明本發明。但應理解到本 5發明之實施例可被修改成多種態樣且本發明之範圍並不侷 限於以下說明之特定實施例。 〔實驗實例1〕 _ 依下述方式製造氮氧化物還原（DeN0x)觸 化鋁粉末（表面積：210 rri/gr，孔隙容積：〇·5 'cc/gr，比 10重·仏8 g/cc )、醋酸及二次蒸餾水混合在一起，然後藉由 一濕式球磨機研磨該混合物24小時以製造均勻的氧化鋁 漿。上述混合物經濕式球磨機研磨致使氧化鋁之平均粒徑 為2微米至8微米。 工 將製得氧化鋁漿薄塗布於直徑為1125英对、長度為3 15英吋且蜂窩密度為4〇〇 cpsi (每平方英吋之蜂窩數）的堇 _青石蜂巢結構物致使氧化紹之支承量變《3 。使锻燒 爐内之溫度以3。〔〕/分鐘之速率從正常溫度升高到12〇 °c，然後使該氧化鋁漿在12(rc之溫度烘乾3小時。接下 來使舞X燒爐内之溫度以3 /分鐘之速率從12〇°C升高到 20 550°C，然後使氧化鋁漿在55(rc之溫度緞燒3小時。 接下來’使支承著氧化鋁的脫水堇青石浸潰於一藉由溶 解硝酸銀和鉑氯酸當作鉑前驅物製得的溶液，致使氧化鋁 中之銀含量為2.0 wt%且鉑觸媒組份含量為〇 〇〇1 wt%， 然後將脫水堇青石如同用於薄塗布氧化鋁之條件在l2(rc 20 ske96318.doc 200824782 之溫度锻燒3小時且在550°C之溫度锻燒3小時。 〔實驗實例2〕 依下述方式製造柴油微粒過濾器（DpF )。在一内容積 為2公升的燒瓶内’使252公克之聚乙烯吡嘻烧酮（從 5 Aldrich Chemical Corp·取得，平均分子量為1〇 〇〇〇)溶於 1公升之稀釋水中以造出均勻溶液。將3〇 4公克之鉑氯酸 及1公升之甲醇添加於該均勻溶液然後攪拌此溶液。使此 ⑩溶液在80 c之溫度回流6小時並過濾以獲得2,070公克之 暗褐色鉑膠體溶液，其中鉑含量為〇·62 wt%。將15 4公 10克之鉬酸銨及10公克之氫氧化鉀分別放到250毫升之稀釋 水中，然後攪拌稀釋水以造出鉬之水溶液及鉀之水溶液。 將上述製得鉑膠體溶液、鉬之水溶液及鉀之水溶液以相 同重量比混合在一起藉以獲得用於催化過濾器的金屬鹽膠 體〉谷液。使用直徑為11 ·25英忖、長度為〗4英叶且蜂窩密 15度為200 cpsi的壁流形狀陶瓷過濾器（從 _得）當作催化過濾為之支撐件。使藉由二氧化鈦及二氧化 矽混合製得之7 wt%薄塗層溶液沈積在蜂巢狀單塊物上然 後烘乾並煅燒該蜂巢狀單塊物。用於催化過濾器的混合膠 體溶液被支承在薄塗層支撐件上使得薄塗層支撐件中之鉑 20含量變成0·27 wt%、鉬含量變成〇 16 wt%且鉀含量變成 0.077 wt%。使膠體溶液在12(rc之溫度烘乾3小時且在 550 C之1度瓜燒4到6小時以產出該柴油微粒過濾器。 〔實例1〕廢氣淨化裝置之表現評估 將依據實驗實例1製成之氮氧化物還原觸媒及依據實 21 ske96318.doc 200824782 ::例2製成之柴油微粒過濾器彼此連 不錄鋼製的外殼。如圖！所例示，將一直徑 =製管件連接到位在卿後端之一排氣管之一側寸表之 面且連接到渴輪增壓哭 再循環(舰)率為二…-側。此時’所得廢氣 依用於大型柴油車之Japanl3Mode 及微粒物質減少的測試。使用韓 丁》平估u減少 、β认r a开的引手進仃上述評估測試。將一 ίο 15 :輪增壓器和一中間冷卻器施用於所用引擎。在引擎功率 计之測试楔式中規定的指定R P M和扭矩條件下進行測 :ί 1 :日！，用來進行測試的柴油是硫含量為5 〇 p p m的極 測試結果顯示一氧化碳減少⑽，碳氯化 :y m亂氧化物減少55%且微粒物質減少⑽ 或更多。 減表丄，Daew°°MGt⑽生產之引擎評估廢氣減少及微 粒物質減少的測試結果。 CO HC NO 基準值 g/Kwh - 0.880 0.262 8.137 裝置安裝後 (g/Kwh ) 0.062 卜 0.177 3.629 減少率（％ ) 92.9% 55.4% 93.1% 〔比較實例1〕廢氣淨化裝置之表現評估_2 將依據貝驗實例1製成之氮氧化物還原觸媒及依據實Preferably, the catalyst having a silver component, a copper component or a mixture thereof is used so that the component content is 〇1 _% to wt% based on the weight of the thin coating layer. If the content of the above component is less than 〇] wt%, the absolute amount of the component exhibiting the catalytic function is insufficient, so the performance of the catalyst is significantly poor; and if the content of the above component exceeds 10% by weight, the component is more The state of the unfavorable metal element exists, so the performance of the catalyst is significantly poor. Further, the platinum group component is additionally supported in the DeN〇x catalyst according to the present invention = in a temperature range of 250_600r (this is the actual temperature of the exhaust gas) = to a more excellent nitrogen oxide reduction performance. The reduction of nitrogen oxides of the nitrogen oxide reduction catalyst according to the present invention is excellent in a temperature range of 25 〇 6 〇〇〇 C (this is the actual temperature of the exhaust gas), and is additionally supported in the platinum group component. The case towel' DeNQx catalyst has a characteristic of reducing the performance of nitrogen oxides at 35 (M5Gt: - the temperature range is more excellent. The metal of the platinum group noble metal supported by the DeN〇x catalyst unit can be obtained from m silver, money selected as a component or two or 17 ske963 1 8.doc 200824782 a mixture of more components. Can be used to start, chlorination, = amine, and the like Raw materials... can use uranium uranium; amine platinum nitrite, bis-platinum tetrachloride, and the like as raw materials for platinum. i can use chlorine (10), cerium nitrate, triammonium hexachloride, and the like i as hydrazine The raw material. Also, it is preferable that the content of the metal is in the range of 〇〇〇〇1 ίο 15, more preferably in the range of 0.0005 _ to 〇2 _, and 仏 is in the range of 0.001 Wt%i 0.1 wt%. The metal content of the group is 1 wt% on the 〇 side. 'The heterogeneous metal cannot assist the DeN〇x catalyst single = now, and if the uranium metal contains If it exceeds 〇5wt%, the performance of the postal medium 7C will deteriorate rapidly. Qing is a type of internal support (4) catalyst (4), supported by the original family of the elemental system from H豸, and 锗Among the group of groups = one = "many. It is more suitable to be supported as a uranium catalyst. The content of the platinum group catalyst supported in the DPF is 0.01 wt% of the thin coating support. To the range of 5 Wt%. If the platinum group catalyst content is less than 〇〇1 7 , the particulate matter removal effect will not occur. The silky catalyst content =:, the performance of the DPF will not be further improved, making this situation It is unfavorable in terms of hydrazine. 20 "Filtering ^, the catalytic component of oxidation can be additionally supported. The oxidation promoting component can act to inhibit the oxidation of sulfur dioxide = use or enhance the surface activity of platinum-based catalysts. In general, the platinum t catalyst has high activity in the oxidation reaction of the soluble organic fraction, but the sulfur dioxide (s〇2) of the sulfur product of the sulfur contained in the light oil is sub-converted into sulfate by oxidation. , will produce particulate matter in turn increase not ske963l8.d〇c 18 200824782 ί ο 15 20 Want the result. To improve the above problem, one or more catalyst components selected from Kay, Crane or Float can be additionally used in the platinum group catalyst. Preferably, from vanadium: crane or sorghum The content of one or more catalyst components is selected in the range of 0.01 wt% to 2 Wt% in the thin coating support. If the content of the above catalyst component is less than 0.01 wt%, no inhibition of sulfurous acid gas is produced. The effect of oxidation, and if the above-mentioned catalyst component content exceeds 2% by weight, the addition of the above-mentioned catalyst component has no meaning - making the addition of the catalyst component uneconomical. Further, since alkali metals such as potassium (κ), magnesium (Mg) and the like have a flow ability at a low temperature, the metallization enhances the surface activity of the catalyzed catalyst to promote contact between the catalyst and the particulate matter, thereby increasing the reaction ratio. Preferably, if the content of the genus is thin, and the content of the 0 01 _ to i er of the struts is less than 0.01 wt%, the effect of increasing the ratio of the initial group is not generated, and if the metal content exceeds Lwt%, the addition of the genus of the genus is meaningless, so that the addition of metal inspection does not match the economic efficiency of the second U U Γ use (Al2 〇 3), dioxide dioxide (Si 〇 2), dioxane bismuth dioxide (Ce 〇 2), the second oxidation or the stagnation of the second or more two problems can be used from above, the DPF according to the present invention utilizes the waste heated by the action of oxidizing the diesel fuel at the oxidized end of the nitrogen oxide 'Guanghezhi- granules. In order to remove the tedious micro-use crying even in the DPF's ^, the situation of over-increasing two is still safely used 4, at this time the best support = Wang Diqingshi, contains Carbon-cut (Sic) ceramic or alloyed material of yttrium alloy with different heat-resistant characteristics. In the case of ske963l8.d〇19 200824782 material manufacturing with excellent heat resistance characteristics in supporting 7^^ alloy or FeCr dry field In the case that high, θ heat is generated when dpf is recovered, the device can operate safely. And it is possible to save the injected diesel by the heat generated when the granules are oxidized. The invention will be described in more detail below with respect to preferred embodiments, but it should be understood that the embodiment of the invention can be modified The invention is not limited to the specific examples described below. [Experimental Example 1] _ Nitroxide-reduced (DeN0x) touched aluminum powder was prepared in the following manner (surface area: 210 rri/gr, Pore volume: 〇·5 'cc/gr, more than 10 仏 8 g/cc), acetic acid and double distilled water were mixed together, and then the mixture was ground by a wet ball mill for 24 hours to produce a uniform alumina slurry. The above mixture was ground by a wet ball mill to have an average particle diameter of alumina of 2 μm to 8 μm. The alumina slurry was thinly coated to a diameter of 1125 inches, a length of 3 15 inches, and a honeycomb density of 4 inches. 〇cpsi (cell number per square inch of honeycomb) 青 青石 honeycomb structure causes the support amount of oxidation to change. 3. The temperature in the calciner is increased from normal temperature to 12 at a rate of 3. [...] 〇°c, then make the alumina The slurry was dried at 12 (rc temperature for 3 hours. Next, the temperature in the dance X furnace was increased from 12 ° C to 20 550 ° C at a rate of 3 / min, and then the alumina slurry was at 55 (rc The temperature is satin for 3 hours. Next, the dehydrated cordierite supporting alumina is immersed in a solution prepared by dissolving silver nitrate and platinum chlorate as a platinum precursor, resulting in a silver content of 2.0 in the alumina. The wt% and platinum catalyst component content is 〇〇〇1 wt%, and then the dehydrated cordierite is calcined at a temperature of 12 (r 20 ske96318.doc 200824782 for 3 hours and at 550° as conditions for thin coating of alumina). The temperature of C was calcined for 3 hours. [Experimental Example 2] A diesel particulate filter (DpF) was produced in the following manner. In a 2 liter inner flask, '252 grams of polyvinylpyrrolidone (obtained from 5 Aldrich Chemical Corp., average molecular weight of 1 〇〇〇〇) was dissolved in 1 liter of dilution water to create uniformity. Solution. 3 〇 4 g of platinum chloric acid and 1 liter of methanol were added to the homogeneous solution and the solution was stirred. The 10 solution was refluxed at 80 c for 6 hours and filtered to obtain 2,070 g of a dark brown platinum colloid solution having a platinum content of 〇·62 wt%. 15 4 g of ammonium molybdate and 10 g of potassium hydroxide were placed in 250 ml of diluted water, respectively, and then the diluted water was stirred to prepare an aqueous solution of molybdenum and an aqueous solution of potassium. The above-prepared platinum colloidal solution, an aqueous solution of molybdenum and an aqueous solution of potassium were mixed together in the same weight ratio to obtain a metal salt colloid>column solution for a catalytic filter. A wall-flow ceramic filter (from _) having a diameter of 11 · 25 inches, a length of 4 inches and a honeycomb density of 200 cpsi was used as a support for catalytic filtration. A 7 wt% thin coating solution prepared by mixing titanium dioxide and cerium oxide was deposited on a honeycomb monolith and then dried and calcined. The mixed colloidal solution for the catalytic filter is supported on the thin coating support such that the platinum 20 content in the thin coating support becomes 0. 27 wt%, the molybdenum content becomes 〇 16 wt%, and the potassium content becomes 0.077 wt%. . The colloidal solution was allowed to dry at a temperature of 12 (rc for 3 hours and melon at 550 C for 4 to 6 hours to produce the diesel particulate filter. [Example 1] Performance evaluation of the exhaust gas purification device will be based on Experimental Example 1 The prepared nitrogen oxide reduction catalyst and the diesel particulate filter made according to the actual 21 ske96318.doc 200824782:example 2 are not connected to the outer casing of the steel. As illustrated in the figure, a diameter = pipe joint is connected In the side of one of the exhaust pipes of the back end of the Qing Dynasty, and connected to the thirsty wheel, the supercharged crying recirculation (ship) rate is two...-side. At this time, the resulting exhaust gas is used in Japanl3Mode of large diesel vehicles. And the test for the reduction of particulate matter. Use the Korean Ding to estimate the u reduction, the β-recognition, and the above evaluation test. Apply a ίο 15: wheel supercharger and an intercooler to the engine used. Tested under the specified RPM and torque conditions specified in the test wedge: ί 1 : Day!, the diesel used for the test is a pole with a sulfur content of 5 〇ppm. The test results show a decrease in carbon monoxide (10), carbon chlorination: Ym chaotic oxide reduced by 55% and particulate matter reduction (10) or more. Subtraction, Daew°°MGt(10) engine for evaluating exhaust gas reduction and particulate matter reduction test results CO HC NO Reference value g/Kwh - 0.880 0.262 8.137 After installation (g/Kwh) 0.062 Bu 0.177 3.629 Reduction rate (%) 92.9% 55.4% 93.1% [Comparative Example 1] Performance evaluation of exhaust gas purification device_2 Nitrogen oxide reduction catalyst prepared according to the sample 1 of the test and the basis
PM 0.214 0.015 ske96318.doc 22 200824782 柴油微粒過遽器彼此連續地連接然後安置 於大型:“设’但僅排除實例1所用廢氣循環管。依用 物質anl3M°de進行評估廢氣減少及微粒 RPM^ 4。在引擎功率計之_模式中規定的指定 件下進行職。此時，絲進行測試的柴油 =爪a 1為50 Ppm的極低硫含量柴油。測試結 3乳二ST 92% :碳氫化合物減少34%，氮氧化物減少 8/且微粒物質減少93%或更多。 10 表2以Daewoo Motors生產之引簦嘴/士齒严i， 叙物m…一 一 之引手㈣廢氣減少及微 --"—---- 基準值 g/Kwh CO 0.880~ HC — 8.137 PM ~~0.214~~ 衣置女裝後 (g/Kwh ) '0.060 0.172 5.036 Γ 0.014 Urn > ψ (%J_ 34.3% 38.1% 93.4% 〔產業應用性〕 15 依據本發明用於柴油引擎之廢氣淨 2/^啊之—溫度（此為廢氣之實際溫度）m m二表現且具有高效微粒物質去除效率的廢氣淨 =士發明之優點在於藉由噴射柴油來進行氮氧化物 =擇：且同時藉由廢氣再循環來進行氮氧化物之 化物減少效率顯著提高，且微粒物質可由 “ m原觸女某之一後端提供的微粒過濾器有效地去 ske96318.doc 23 200824782 除。 、，再者’不管會造成與廢氣溫度相關之氮氧化物減少表現 ^異的^丨擎操作狀態是如何，本發明之廢氣淨化裝置具有 絶佳的氮氧化物減少表現及去除微粒物質、一氧化碳和碳 5 氫化合物的優異效率。 【圖式簡單說明】 圖1是一依據本發明之廢氣淨化裝置； _ 圖2是一示出氮氧化物及微粒物質依據廢氣再循環 (EGR)率之變化的曲線圖； 圖3疋一由一層氮乳化物還原觸媒層組成的氮氧化物 還原觸媒單元；且 圖4是一由三層氮氧化物還原觸媒層組成的氮氧化物 還原觸媒單元。 【主要元件符號說明】 5 1氮氧化物還原（DeN0x)觸媒單元 > 2柴油微粒過濾器（DPF)單元 3柴油喷射器 4廢氣再循環（EGR)線 5進氣歧管 6渦輪增壓器 6a壓縮機 6b葉輪 7柴油引擎 8空氣過濾器 ske96318.doc 24 200824782PM 0.214 0.015 ske96318.doc 22 200824782 The diesel particulate filter is continuously connected to each other and then placed in a large size: “Settings' only excludes the exhaust gas circulation pipe used in Example 1. The exhaust gas reduction and particulate RPM^ are evaluated according to the substance anl3M°de. Worked under the specified parts specified in the engine power meter mode. At this time, the diesel tested for the wire = claw a 1 is a very low sulfur content diesel of 50 Ppm. Test knot 3 milk two ST 92%: hydrocarbon The compound is reduced by 34%, the nitrogen oxides are reduced by 8/ and the particulate matter is reduced by 93% or more. 10 Table 2 is the lead-in mouth/stooth of the Daewoo Motors, the narrative m...the one (1) the exhaust gas reduction and Micro--"----- Reference value g/Kwh CO 0.880~ HC — 8.137 PM ~~0.214~~ After wearing women's clothing (g/Kwh) '0.060 0.172 5.036 Γ 0.014 Urn > ψ (%J_ 34.3% 38.1% 93.4% [Industrial Applicability] 15 According to the present invention, the exhaust gas net for the diesel engine is 2/^, the temperature (this is the actual temperature of the exhaust gas), and the exhaust gas with high efficiency of particulate matter removal is net. The advantage of the invention is that nitrogen oxides are produced by spraying diesel oil. At the same time, the NOx reduction efficiency is significantly improved by the exhaust gas recirculation, and the particulate matter can be effectively removed by the particulate filter provided by the rear end of the m-touch female, ske96318.doc 23 200824782. The exhaust gas purifying device of the present invention has excellent nitrogen oxide reduction performance and removal of particulate matter, carbon monoxide and carbon 5 hydrogen, regardless of the fact that the nitrogen oxides associated with the exhaust gas temperature are reduced in performance. 1 is a schematic diagram of an exhaust gas purifying apparatus according to the present invention; FIG. 2 is a graph showing changes in nitrogen oxides and particulate matter according to exhaust gas recirculation (EGR) rate; Fig. 3 is a nitrogen oxide reduction catalyst unit composed of a layer of nitrogen emulsion reduction catalyst layer; and Fig. 4 is a nitrogen oxide reduction catalyst unit composed of a three-layer nitrogen oxide reduction catalyst layer. Element Symbol Description] 5 1 Nitrogen Oxide Reduction (DeN0x) Catalyst Unit > 2 Diesel Particulate Filter (DPF) Unit 3 Diesel Injector 4 Exhaust Gas Recirculation (EGR) Line 5 Intake Manifold 6 turbocharger 6a compressor 6b impeller 7 diesel engine 8 air filter ske96318.doc 24 200824782
9中間冷卻器 10柴油喷射控制單元 11油箱 25 ske963189 intercooler 10 diesel injection control unit 11 fuel tank 25 ske96318