TW200936240A

TW200936240A - Ammonia-decomposing catalyst, and method for treatment of ammonia-containing exhaust gas with the catalyst

Info

Publication number: TW200936240A
Application number: TW097148573A
Authority: TW
Inventors: Tomoo Ikoma; Takanobu Sakurai
Original assignee: Nikki Universal Co Ltd
Priority date: 2007-12-12
Filing date: 2008-12-12
Publication date: 2009-09-01
Also published as: JPWO2009075311A1; TWI406708B; WO2009075311A1; JP5384368B2

Abstract

Disclosed are: a catalyst which can decompose ammonia into nitrogen that is non-toxic; and a method for treating an ammonia-containing exhaust gas. Specifically disclosed is an ammonia-decomposing catalyst, which is characterize by the following items (a) to (d): (a) the catalyst is one for treating an ammonia-containing exhaust gas; (b) the catalyst comprises copper oxide (component 1), zeolite (component 2), a noble metal (component 3), a phosphorus (component 4) and optionally an inorganic oxide (component 5); (c) the catalyst has a copper oxide content of 2 to 40 parts by weight relative to the total amount (100 parts by weight) of copper oxide and zeolite; and (d) the catalyst has a phosphorus content of 0.01 to 5 wt% relative to the total weight of copper oxide and zeolite in terms of P content.

Description

200936240 九、發明說明：【發明所屬之技術領域】本發明係關於-種將氨分解成無錢之觸媒及含氨排氣之處理方法。【先前技術】含氨排氣由於例如電子材料製造工業、肥料製造工業、使用脫硝設備之工廠等產生源較多，多數具有惡臭，多數㈣人體有害’故而業界正謀求對其之處理。來自該等排 ® 线之排氣通常為如下組成：除氨以外，主成分為空氣，此外亦含有1〜10容量。/。之水蒸汽。作為與此完全不同之排出源的排氣，可列舉以水蒸汽為主成分之含氨氣體。即，於污水處理等中開始採用氛氣提製程，該製程中會大量排出含氨水蒸汽。對於處理該排氣觸媒於水蒸汽濃度極高之氣體J裒境之基礎上，需要氨分解活性較高，抑制氮氧化物之生成而將4轉化為說與瘳水、即氮選擇性較高，進而亦需要耐受對硫化水素之觸媒毒的耐久性較高。先前以來介紹有多種氨分解觸媒，並闡述了以下效果： 4分解率較高，不易產生NOx等氮氧化物副產物，不易引八肢化〇物所致之觸媒劣化等。然而，若觀察該等觸媒 _解舌眭°平铷結果，則係使用水蒸汽濃度為2〜10容量0/0 -來》平價氨分解活性，而未觀察到對水蒸汽濃度更高王署4立1 τ. 見之氣進行處理的例子。具體有如下之報告。作為使伴隨排水處理而排出之氨以外的含有機氮化合物 136838.doc 200936240 之排氣進行接觸氧化而轉化成A、C〇2以及h2〇的觸媒，報告有在二氧化鈦及/或二氧化鈦•二氧化梦上承載V〇2、 WO3、及鈀之觸媒（參照專利文獻。作為含有如丙烯腈之有機氮化合物之排氣處理觸媒，介紹有：以沸石或Ah〇3、Si〇2、Ti〇2、Zr〇2等金屬氧化物為載體’而承載選自Fe、Cu、Ag、Co中之1種或2種以上而成的觸媒，以高選擇率將丙烯腈轉化成n2(參照專利文獻 2)。作為不使用貴金屬之觸媒，介紹有：在8丨〇2/八丨2〇3為1〇以上之沸石上承載或混合有Μη之觸媒，即使在過量氧之存在下，亦可一面抑制NO或Ν〇2之生成，一面將氨轉化成 Nd參照專利文獻3及4)。又’關於限定於分解氨之觸媒，報告有以下技術。作為氨分解觸媒’介紹有：在Ti〇2.Si〇2、或 Ti02_Si〇2，Zr02之複合氧化物上承載v、w、Mo中之任一種、與貴金屬而成的觸媒’其分解活性較高、且由硫化合物所致之活性降低較少（參照專利文獻5)。然而，使用水分 2%、NH3濃度50〜400 ppm、H2S濃度30 ppm之排氣時，該觸媒僅表示出較高之初始活性結果，並未揭示出證明其耐久性之資料。有文獻介紹有在Ti〇2上承載V、W中之任一種、與Pt或lr 而成的氨分解觸媒，並揭示其對水蒸汽濃度為10%、NH3 濃度為10 ppm、S〇2濃度為100 ppm之排氣進行3000小時處理後的氨分解率為88〜93%，且具有較高之耐久性（參照專 136838.doc 200936240 利文獻6)。有文獻介紹有在沸石、γ_氧化銘氧化鈦等上承載第 8族金/⑼等）而成之氨除去觸媒（參照專利文獻7)。該觸媒在氧與氫氣共存下在常溫〜·。c下將氨除去，但尚不明了其疋否為將NH3轉化成乂之觸媒。有文獻介紹有在氧化紹、二氧化鈦或二氧切載體上，200936240 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for treating ammonia into a solvent-free catalyst and an ammonia-containing exhaust gas. [Prior Art] Ammonia-containing exhaust gas is produced by many industries such as the electronic material manufacturing industry, the fertilizer manufacturing industry, and factories that use denitration equipment. Most of them have bad odors, and most (4) humans are harmful. Therefore, the industry is seeking to deal with them. The exhaust gas from the row of wires is usually composed of the following components: in addition to ammonia, the main component is air, and also contains 1 to 10 capacities. /. Water vapor. As the exhaust gas which is a completely different discharge source, an ammonia-containing gas containing water vapor as a main component can be cited. That is, in the sewage treatment and the like, an atmosphere extraction process is started, and a large amount of ammonia-containing water vapor is discharged in the process. In order to treat the exhaust gas catalyst in a gas environment with extremely high water vapor concentration, it is required to have a high ammonia decomposition activity, inhibit the formation of nitrogen oxides, and convert 4 into a ratio of hydrophobicity to nitrogen, that is, nitrogen selectivity. High, and thus also need to withstand the durability of the catalytic toxicity of sulphide hydrate. A variety of ammonia decomposition catalysts have been introduced in the past, and the following effects have been described: 4 The decomposition rate is high, and it is not easy to generate nitrogen oxide by-products such as NOx, and it is not easy to induce catalyst degradation caused by cockroaches. However, if the results of these catalysts are observed, the water vapor concentration is 2~10 capacity 0/0 - to "flat ammonia decomposition activity, and no higher concentration of water vapor is observed. The Department of Health has set an example of 1 τ. See the gas for processing. Specifically, there are the following reports. The catalyst containing the nitrogen-containing compound 136838.doc 200936240 other than ammonia discharged in association with the wastewater treatment is subjected to contact oxidation to be converted into A, C〇2, and h2〇, and is reported to be in titanium dioxide and/or titanium dioxide. Catalysts for carrying V〇2, WO3, and palladium on oxidative dreams (refer to the patent literature. As an exhaust gas treatment catalyst containing an organic nitrogen compound such as acrylonitrile, there are introduced: zeolite or Ah〇3, Si〇2 A metal oxide such as Ti 2 or Zr 〇 2 is a carrier and carries a catalyst selected from one or more of Fe, Cu, Ag, and Co, and converts acrylonitrile into n 2 at a high selectivity ( Refer to Patent Document 2). As a catalyst that does not use a noble metal, there is a catalyst that carries or mixes Μη on a zeolite of 8丨〇2/八丨2〇3 of 1〇 or more, even in the presence of excess oxygen. Further, it is also possible to convert ammonia into Nd while suppressing the formation of NO or Ν〇2, and refer to Patent Documents 3 and 4). Further, regarding the catalyst limited to decomposition of ammonia, the following techniques are reported. As an ammonia decomposition catalyst, an introduction is made to carry a catalyst of any one of v, w, and Mo, and a noble metal on a composite oxide of Ti〇2.Si〇2, or Ti02_Si〇2, and Zr02. The activity is high and the activity by the sulfur compound is less reduced (refer to Patent Document 5). However, when exhaust gas having a moisture content of 2%, an NH3 concentration of 50 to 400 ppm, and an H2S concentration of 30 ppm was used, the catalyst showed only a high initial activity result, and no evidence of durability was revealed. There are literatures on the introduction of any of V, W on Ti〇2, and ammonia decomposition catalysts with Pt or lr, and revealed that the concentration of water vapor is 10%, the concentration of NH3 is 10 ppm, S〇2 The ammonia decomposition rate after treatment for 3000 hours of exhaust gas having a concentration of 100 ppm is 88 to 93%, and has high durability (refer to 136838.doc 200936240, Document 6). There is a literature on ammonia-removing catalysts in which a Group 8 gold/(9) or the like is supported on zeolite, γ_ oxidized titanium oxide or the like (see Patent Document 7). The catalyst is kept at room temperature under the coexistence of oxygen and hydrogen. The ammonia is removed under c, but it is not known whether it is a catalyst for converting NH3 into hydrazine. There are literatures on the oxidation, titanium dioxide or dioxate carrier,

將銅、銘、鐵、鉻、鎳、猛金屬或其氧化物、進而始金屬類進行硫酸化之氨分解觸媒，並揭示藉由㈣化分解活性與N2選擇性。然而，該觸媒僅表現出水分濃度為 2%時之初始活性（參照專利文獻8)。本申請人發現，含有氧化鋼以及滞石、較好的是除該等以外還含雜氧化物、或貴金屬，來作為以前新穎时有機氮化合物或含氨排氣之處理觸媒組成的觸媒，其對氮化合物之分解率較高’且氮選擇性亦較高，從而提出專利申請（參照專利文獻9)。該觸媒係氨分解活性極高且乂產率亦較高的優異觸媒》然而’存在以下應解決之課題：與水蒸汽濃度為2〜1〇容量％之含氨排氣相比，例如將水蒸汽濃度為2〇容量％以上、進W0〜70容量％之排氣t的氨分解時，即便為相同觸媒’氨分解率亦會降低、且長時間使用時活性會降低等。 _ 另一方面，已知磷在接觸分解反應中會防止沸石之脫氧化鋁現象（參照非專利文獻丨）。 [專利文獻1]日本專利特開2〇〇ι_293480號公報 136838.doc 200936240An ammonia decomposition catalyst which sulphates copper, indium, iron, chromium, nickel, a sulphide metal or an oxide thereof, and further a metal, and reveals a decomposition activity and an N2 selectivity by (iv). However, this catalyst exhibits only the initial activity when the water concentration is 2% (refer to Patent Document 8). The Applicant has found that it contains a oxidized steel and a stagnation stone, and preferably contains a hetero-oxide or a noble metal in addition to the above, as a catalyst composed of a conventional novel organic nitrogen compound or a treatment catalyst containing ammonia exhaust gas. In addition, the decomposition rate of the nitrogen compound is high and the nitrogen selectivity is also high, so that a patent application is filed (refer to Patent Document 9). The catalyst is an excellent catalyst having an extremely high ammonia decomposition activity and a high yield of ruthenium. However, there is a problem to be solved as compared with an ammonia-containing exhaust gas having a water vapor concentration of 2 to 1 〇% by volume, for example. When ammonia having a water vapor concentration of 2% by volume or more and W0 to 70% by volume of ammonia is decomposed, the ammonia decomposition rate of the same catalyst is lowered, and the activity is lowered when used for a long period of time. On the other hand, it is known that phosphorus prevents the phenomenon of deoxidized aluminum in zeolite in the contact decomposition reaction (see Non-Patent Document 丨). [Patent Document 1] Japanese Patent Laid-Open No. 2〇〇ι_293480 No. 136838.doc 200936240

❹ [專利文獻2]日本專利特開2〇〇4_58〇19號公報 [專利文獻3]曰本專利特開2〇〇7_21482號公報 [專利文獻4]日本專利特開2007-216082號公報 [專利文獻5]日本專利特開平7_289897號公報 [專利文獻6]日本專利特開平8_131832號公報 [專利文獻7]曰本專利特開平1〇_249165號公報 [專利文獻8]曰本專利特開平8_173766號公報 [專利文獻9]國際公開第2006/006702號手冊 [非專利文獻 1] J. Catalysis, vol. 248, pp29〜37 (2007) 【發明内容】 [發明所欲解決之問題] 因此’本發明之目的在於提供： (!)將氨分解，抑制ΝΟχ等氮氧化物之生成，將氨轉化成Νζ，而使其無害化之觸媒； (2)以高效率將氣體中含有水蒸汽濃度為1〇容量％以上、進^為20〜70容量％之高濃度水蒸汽的排氣中之氨分解成氮之觸媒； (3)不僅具有初始活性’即使對含硫化合物之排氣進行處理亦具有耐久性的觸媒。若為將如上所述之水蒸汽濃度較高之排氣或含硫化合物之排氣中之氨分解的觸媒，則勿庸置疑其對該等成分之濃度更低的排氣，亦會發揮有效之作用。 [解決問題之技術手段] 而進行努力研究，從而本發明者等為了實現上述目的 136838.doc 200936240 完成本發明。本發明之氨分解觸媒及如下所述：氣之處理方法發明1 : 一種氨分解觸媒，其係 (a) 對含氨排氣進行處理之觸媒， (b) 含有氧化銅（成分丨） • 3)、及填(成分4)，成刀2)、責金屬(成分 ⑷氧化銅含量相對於氧化銅與上述罾量份而為2〜40重量份， 4 1〇〇重 ⑷=量（m目對於氧化銅與彿石之重量量％〜5重量％。置發明2 : 一種氨分解觸媒，其係 (a) 對含氨排氣進行處理之觸媒， (b) 含有氧化銅（成分丨） )那石（成分2)、貴金屬（成分 3)、磷（成分4)以及選自Ti〇2、ZrO、霤 2 Zr〇2、Si02、及 Ce〇2.Zr〇中之至少1種無機氧化物（成分5)， (c) 氧化鋼含量相對於氧化孔化銅與上述沸石之總計100重量份而為2〜40重量份，以及 ⑷填含量（p)相對於氧化鋼與彿石之重量和而為〇〇1重量％〜5重量％。發明3 : 種排氣處理方法’其包含使含氨排氣與上述觸媒接觸’而將氨分解成氮之步驟。 136838.doc -10- 200936240 其他發明在下文中進行明確說明。如以上所述，本發明之觸媒含有氧化鋼、沸石、貴金屬以及碌。再者，如上述「先前技術」之項目中所述，在非專利文獻1中已知攝在接觸分解反應中可防止沸石之脫氧 . 化鋁現象。 [發明之效果] 本發明之觸媒係如下之高活性且耐久性較高之氨分解觸 Φ 媒其在用於對尤其是如水蒸汽濃度為10〜70容量％之極向的含氨排氣進行處理時，可長期保持高Μ%轉化率，可極^產生ΝΟχ等氮氧化物副產物而轉化成n2。進而含有峨之本發明之觸媒，與不含磷之觸媒相比，亦可見等氮氧化物之生成降低之意料之外的效果。【實施方式】 (術語之定義等）本說明書所用術語之含義，只要無特別說明則如下所 ❿述：分解率：表示與觸媒接觸前與接觸後之排氣中之氨濃度的比率（％)。 Ν〇χ生成率及ΝζΟ生成率：表示與觸媒接觸後之排氣中所生成的N〇x濃度或乂0濃度相對於接觸前之排氣中之氨漢度的比率（°/〇)。氮氧化物.係指^^(^與Ν2〇兩者，有時表示為Ν〇χ等。[Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. 2007-216082 [Patent Document 4] Japanese Patent Laid-Open No. Hei. No. 2007-216082 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 9] International Publication No. 2006/006702 Handbook [Non-Patent Document 1] J. Catalysis, vol. 248, pp29 to 37 (2007) [Summary of the Invention] [Problems to be Solved by the Invention] Therefore, the present invention The purpose is to provide: (!) to decompose ammonia, inhibit the formation of nitrogen oxides such as helium, convert ammonia into helium, and make it harmless catalyst; (2) The concentration of water vapor contained in the gas is high efficiency 1〇% by volume or more, 20% to 70% by volume of high-concentration steam in the exhaust gas to decompose ammonia into a nitrogen catalyst; (3) not only has initial activity' even if the sulfur-containing compound is treated It also has a durable catalyst. In the case of a catalyst which decomposes ammonia in a exhaust gas having a high water vapor concentration or a sulfur-containing compound as described above, it is undoubted that the exhaust gas having a lower concentration of the components will also be exerted. Effective role. [Technical means for solving the problem] The present inventors have completed the present invention in order to achieve the above object 136838.doc 200936240. The ammonia decomposition catalyst of the present invention is as follows: Gas treatment method Invention 1: An ammonia decomposition catalyst which is (a) a catalyst for treating an ammonia-containing exhaust gas, (b) contains copper oxide (component 丨) 3), and fill (ingredient 4), forming a knife 2), responsible metal (component (4) copper oxide content relative to copper oxide and the above-mentioned amount of the amount of 2 to 40 parts by weight, 4 1 weight (4) = amount (m for the weight of copper oxide and budstone% to 5% by weight. According to the invention 2: an ammonia decomposition catalyst, which is (a) a catalyst for treating ammonia-containing exhaust gas, (b) containing copper oxide (Component 丨)) that stone (ingredient 2), precious metal (ingredient 3), phosphorus (ingredient 4), and at least selected from the group consisting of Ti〇2, ZrO, slip 2 Zr〇2, SiO 2 , and Ce〇2.Zr〇 1 inorganic oxide (component 5), (c) an oxidized steel content of 2 to 40 parts by weight relative to 100 parts by weight of the total of oxidized pores and the above zeolite, and (4) a content (p) relative to the oxidized steel and The weight of the Buddha stone is 〇〇1% by weight to 5% by weight. Invention 3: A method for treating exhaust gas 'which includes contacting an ammonia-containing exhaust gas with the above-mentioned catalyst' The step of decomposing ammonia into nitrogen. 136838.doc -10- 200936240 Other inventions are explicitly described below. As described above, the catalyst of the present invention contains oxidized steel, zeolite, precious metal, and the like. In the case of the non-patent document 1, it is known that the deoxidation and aluminumation of the zeolite can be prevented by the contact decomposition reaction. [Effects of the Invention] The catalyst of the present invention is highly active and durable as follows. High ammonia decomposition Φ medium can be used for the treatment of ammonia-containing exhaust gas, especially in the extreme direction of water vapor concentration of 10 to 70% by volume, and can maintain a high conversion rate of Μ% for a long period of time. The nitrogen oxide by-product is converted into n2. Further, the catalyst of the present invention containing ruthenium has an unexpected effect of lowering the formation of nitrogen oxides as compared with the catalyst containing no phosphorus. (Definition of terms, etc.) The meanings of the terms used in the present specification are as follows, unless otherwise specified: Decomposition rate: the ratio (%) of the ammonia concentration in the exhaust gas before and after contact with the catalyst. Twins Rate and enthalpy production rate: the ratio of the concentration of N〇x or 乂0 generated in the exhaust gas after contact with the catalyst to the ammonia in the exhaust gas before the contact (°/〇). Refers to ^^(^ and Ν2〇, sometimes expressed as Ν〇χ, etc.

Ns產率：表示自分解率減去與觸媒接觸後之排氣中Ν〇χ 等之生成率所得的數值。即為與觸媒接觸前之氨中轉化成 136838.doc 200936240 N22比例。新觸媒：表示剛製備後或立即用於排氣處理之階段的觸媒°將新觸媒之活性稱為初始活性。使用觸媒：表示長期對排氣進行處理後之觸媒。在評價 . 時，測定觸媒之耐久性、使用觸媒之活性等。以下詳細說明本發明之内容。本發明之氨分解觸媒包含氧化銅（成分丨）、沸石（成分參 )貝金屬（成分3)以及填（成分4)，較好的是進而含有Ns yield: a value obtained by subtracting the rate of generation of ruthenium or the like in the exhaust gas after contact with a catalyst. That is, the ammonia before the contact with the catalyst is converted into a ratio of 136838.doc 200936240 N22. New Catalyst: A catalyst that indicates the stage of the exhaust gas treatment immediately after preparation or immediately. The activity of the new catalyst is referred to as the initial activity. Use catalyst: Indicates the catalyst after long-term treatment of exhaust gas. At the time of evaluation, the durability of the catalyst, the activity of using the catalyst, and the like were measured. The contents of the present invention are described in detail below. The ammonia decomposition catalyst of the present invention contains copper oxide (component enthalpy), zeolite (component ginseng) bismuth metal (component 3), and filler (ingredient 4), and preferably further contains

Ti02、Zr02、Si〇2、Ce〇2及 Ce〇2.Zr〇2 中之】種或 2 種無機氧化物（成分5)而成之組合物，可成型為適合於排氣處理之各種形狀而進行使用，亦可承載於各種形狀之載體（支持體）上而進行使用。氧化銅本發明所使用之氧化銅(成分”係指含銅之氧化物包括含銅複合氧化物，可列舉以通SCu〇x(〇 45$χ$丨七之 Φ 組成式表示之氧化鋼，典型的是^〇及ChO，包括A composition of Ti02, Zr02, Si〇2, Ce〇2, and Ce〇2.Zr〇2 or a combination of two inorganic oxides (ingredient 5), which can be formed into various shapes suitable for exhaust treatment For use, it can also be carried on a carrier (support) of various shapes. Copper Oxide The copper oxide (component) used in the present invention means that the copper-containing oxide includes a copper-containing composite oxide, and examples thereof include an oxide steel represented by a Φ composition formula of SCu〇x (〇45$χ$丨7). Typical is ^〇 and ChO, including

Hopcahte(銅錳氧化物）等以含銅複合氧化物之形式存在氧化銅。 • 本發明之㈣巾的氧化鋼具有較高地維持分解活性以及 N2產率之作用’其含量相對於氧化銅與沸石之總計⑽重量份為2〜4G重量份，更好的是重量份，尤其好的是 10〜30重#份。若氧化銅之比例未滿2重量份，則有Ν〇χ等之生成增加，結果導致…產率降低之情形，另一方面，Χ若氧化銅之比例超過40重量份，則相對的彿石之比例變少右 136838.doc -12· 200936240 分解率降低。氧化銅係與以下所述之沸石及無機氧化物一起在觸媒中均勻混合，在與其他成分之粒子的共存下，發揮觸媒作用，因此，就與其他成分均句分散之方面而言，較好的是 ❹其平均粒徑為〇·1 μηι以上' 100 μηι以下之粒子。作為使氧化銅包含在觸媒中之方法，特別好的是使用上述氧化銅之固體粒子作為起始原料。作為另一方法，亦可將含有含銅化合物、例如硫酸銅或乙酸銅等銅鹽之水與其他觸媒成分混合，並含浸於觸媒中，在空氣環境下於 300〜繼。C下進行锻燒，藉此將銅鹽轉換成氧化銅，而使其含有氧化銅。沸石至於本發明之觸媒，係將沸石粒子（成分2)與其他成分混合而形成觸媒。本發明中可用之沸石可為天然品亦可為合成品，作為天然品之沸石，可列舉：絲光沸石 © (m〇rdenite)、毛沸石（⑷㈣e)、鎂鈉針彿石（ferrierite)、菱彿石（chabazite)。作為合成品，可列舉：乂型彿石、γ型彿石、刪型彿石、㈣沸石。本發明中可用之沸石除了質 •子型师）外，亦可為錄離子或Na、K等驗金屬，Mg、ca 等驗土金屬，Fe等第8族金屬，Co等第9族金屬’犯等第1〇族金屬中之任一金屬置換型’可使用該等之㈣多種以 ^之混合物。本發明中所使用之沸石為了在與其他成分丘存下發揮觸媒作用，就均勾分散方面而言，較好的是_ 均粒控為0.1 μηι以上、1〇〇μηι以下之粒子。 136838.doc •13- 200936240 貴金屬作為本發明中所使用之貴金屬（成分3),可列舉·· Pt、Hopcahte (copper manganese oxide) or the like exists in the form of a copper-containing composite oxide. • The oxidized steel of the (four) towel of the present invention has a high activity of maintaining decomposition activity and N2 yield, and its content is 2 to 4 parts by weight, more preferably parts by weight, based on the total (10) parts by weight of the copper oxide and the zeolite. Good is 10 to 30 weights #份. If the proportion of the copper oxide is less than 2 parts by weight, the formation of ruthenium or the like is increased, resulting in a decrease in the yield of the product. On the other hand, if the ratio of the copper oxide exceeds 40 parts by weight, the opposite buddha The proportion is reduced to the right 136838.doc -12· 200936240 The decomposition rate is reduced. The copper oxide is uniformly mixed with the zeolite and the inorganic oxide described below in a catalyst, and acts as a catalyst in coexistence with particles of other components. Therefore, in terms of dispersion of other components, It is preferred that the ruthenium has an average particle diameter of 〇·1 μηι or more and less than 100 μηι. As a method of including copper oxide in a catalyst, it is particularly preferable to use the solid particles of the above copper oxide as a starting material. Alternatively, water containing a copper compound such as copper sulfate or copper acetate may be mixed with other catalyst components and impregnated into the catalyst in an air atmosphere at 300 rpm. The calcination is carried out under C, whereby the copper salt is converted into copper oxide to contain copper oxide. Zeolite As for the catalyst of the present invention, zeolite particles (component 2) are mixed with other components to form a catalyst. The zeolite usable in the present invention may be either a natural product or a synthetic product. As a natural product zeolite, mordenite © (m〇rdenite), erionite ((4) (four) e), magnesium sodium ferrierite, rhodium Buddha stone (chabazite). Examples of the synthetic product include a ruthenium type buddha, a gamma type buddha stone, a ruin type buddha stone, and a (four) zeolite. In addition to the mass and sub-types of the zeolite used in the present invention, it is also possible to record ions or Na, K, etc., soils such as Mg, ca, etc., Group 8 metals such as Fe, and Group 9 metals of Co. Any of the metal-substituted types of the first-lane metal may be used as a mixture of the above-mentioned (four) kinds. The zeolite used in the present invention is preferably a particle having a uniform particle size of 0.1 μηι or more and 1 μηηι or less in order to exhibit a catalytic action with other components in the form of a catalyst. 136838.doc •13- 200936240 Precious metal As the precious metal (component 3) used in the present invention, Pt,

Rh、Ir、該等之合金的丨種或2種以上。該等貴金屬中’ Pt對分解活性及…產率之提昇的效果較大，故而尤佳。Rh, Ir, or an alloy of these or two or more. Among these precious metals, 'Pt has a greater effect on the decomposition activity and the increase in the yield, and is therefore particularly preferable.

至於觸媒中之貴金屬元素的含量，就發揮氨之分解反應方面而β ’相對於氧化銅與彿石之重量和較好的是⑺重量 ΡΡ二以上、5_重量Ppm以下。於氨含量為1〇容量卿^容量％、水蒸汽濃度為!容量％〜10容量％之排氣處理中就氨刀解率、N0jN20之生成率之抑制、觸媒成本之抑制方面而言，較好的是貴金屬含量為10重量ppm〜1000重量 p—pm之範圍。於氨含量為卜5容量％及水蒸汽濃度為1〇, 容量％、其中為20〜70容量％、尤其是為30〜70容量％之排軋處理中，就提昇氨分解率方面而言，貴金屬含量較好的是100重量ppm〜5000重量ppm，更好的是500重量ppm〜5〇〇〇重量ppm之範圍。其原因在於：若未滿上述貴金屬含量，則有分解率不充分，未分解之氨增加之情形；另一方面，若超過上述含量，則有亦無法期待與成本相稱之活性提昇之情形。因此，根據所處理之排氣的性狀、反應條件及所使用之時間（耐久性），來確定貴金屬含量即可。 (含有貴金屬之方法）作為使觸媒中含有貴金屬之方法，例示有： (i)使貴金屬鹽之水溶液含浸氧化銅及沸石之粒子混合物的方法。 136838.doc 14· 200936240 (ii)在含有兩成分之漿料中添加貴金屬鹽之方法。 (Hi)預先製作承載有貴金屬之氧化銅或沸石粒子，再將其與其他成分混合之方法。 (iv)預先製作承載有責金屬之無機氧化物粒子、例如承載有鉑之Ti〇2粒子（以下將其表示為pt/Ti〇2。），再將其與其他成分混合之方法^As for the content of the noble metal element in the catalyst, the decomposition reaction of ammonia is exerted, and the weight of β ′ relative to the weight of the copper oxide and the buddling stone is preferably (7) by weight or more and not more than 5 parts by weight of Ppm. In the exhaust gas treatment in which the ammonia content is 1 〇 capacity ^ % capacity and the water vapor concentration is 5% by volume to 10 vol%, the ammonia cleavage rate, the suppression of the generation rate of N0jN20, and the suppression of the catalyst cost are It is preferred that the precious metal content is in the range of 10 ppm by weight to 1000 ppm by weight. In the row rolling treatment in which the ammonia content is 5% by volume and the water vapor concentration is 1 Torr, the capacity % is 20 to 70% by volume, and particularly 30 to 70% by volume, in terms of increasing the ammonia decomposition rate, The noble metal content is preferably in the range of from 100 ppm by weight to 5,000 ppm by weight, more preferably from 500 ppm by weight to 5% by weight. The reason for this is that if the content of the noble metal is less than the above, the decomposition rate is insufficient and the undecomposed ammonia is increased. On the other hand, if the content exceeds the above content, the increase in activity commensurate with the cost cannot be expected. Therefore, the precious metal content can be determined depending on the properties of the exhaust gas to be treated, the reaction conditions, and the time (durability) used. (Method of Containing Precious Metal) As a method of containing a noble metal in a catalyst, (i) a method of impregnating an aqueous solution of a noble metal salt with a mixture of particles of copper oxide and zeolite is exemplified. 136838.doc 14· 200936240 (ii) A method of adding a precious metal salt to a slurry containing two components. (Hi) A method of preparing copper oxide or zeolite particles carrying a noble metal in advance and mixing it with other components. (iv) A method of preparing inorganic oxide particles carrying a responsible metal, for example, Ti〇2 particles carrying platinum (hereinafter referred to as pt/Ti〇2), and mixing them with other components in advance^

於本發明之氨分解觸媒中，與上述⑴〜㈣之方法相比，（iv)方法中所得之觸媒的活性及耐久性優異故而尤佳。因此，使用 Pt/Ti02、Pt/ZrC>2、pd/Tic>2、Pd/Z02、In the ammonia decomposition catalyst of the present invention, the catalyst obtained in the method (iv) is excellent in activity and durability as compared with the methods (1) to (iv) above. Therefore, Pt/Ti02, Pt/ZrC>2, pd/Tic>2, Pd/Z02,

Pt/Ce〇2.Zr〇2等承載有貴金屬之無機氧化物粒子，對觸媒之耐久性的提昇尤其有效。 ' 磷在本發明之氨分解觸媒中，含有氧化銅、彿石、貴金屬元素’並且含有麟(成分4)，鱗(成分4)之量係以氧化銅與沸石之重量和為基準，而選自元素狀磷(P)為0.01重量％以上、較好的是〇.〇5重量％以上、1〇重量％以下、較好的是5 ㈣以下之範圍。考慮排氣之組成即氨濃度、硫化合物之含量、水蒸汽濃度等’以及處理條件即所處理之溫觸媒之㈣時料而確定磷含量即可，若含量過低^有 :久昇之效果不充分之情形，另一方面，若磷含量過咼’則有初始活性降低之情形。含氨排氣根據排出源而有所不同，但大體上含有硫化合物，進而係大量地含有水蒸汽之排氣，^於= 環境氣體下於反應溫度下長期使用’則容易引起因劣化^ 136838.doc 200936240 致之活性降低，利用本發明之含磷觸媒會產生以下特別顯著之效果：不易引起活性降低，保持長期之分解活性性能，保持較高之N2產率。含有磷進而亦可有效地防止對含有硫化氫、噻吩、硫化物等硫化合物之氨排氣進行處理時的活性降低。進而含有磷之本發明之觸媒可見如下效果：新觸媒與使用觸媒之氨之分解率均較高，並且可使1^(^等副產物之產生減少。 (磷之含有方法） @ 為了使觸媒中含有磷，可採用下述任一方法： (i) 預先製備利用磷化合物預先對氧化銅、彿石或後述無機氧化物中任意1種或2種以上之成分進行處理而成的粒子’再將其進行混合，藉此製備觸媒組合物之方法； (ii) 在將各觸媒成分混合而成之漿料中添加磷化合物，再將該漿料塗佈於支持體上，然後進行加熱處理之方法； (iii) 將不含鱗之觸媒組合物塗佈於支持體等上，而製作 • 觸媒層，然後使含磷之水溶液含浸該觸媒層，繼而進行力〇熱處理之方法；該等之中特別是（iii)之方法對对久性的提昇較為有效。為了含有填而使用之含填化合物可例示：鱗酸 (H3P04)、偏磷酸、磷酸二氫銨（NH4H2P〇4)、磷酸氫二錢 ((NH4)2HP〇4)等水溶性磷酸，該等之Na、K或銨鹽之類的無機鹽，或有機酸酯。將該等磷化合物之水溶液含浸在沸石或無機氧化物等觸媒成分或觸媒中，在常溫〜i50°C下將其乾燥，繼而在 136838.doc • 16- 200936240 500〜600°C下進行煅燒’藉此可製成含磷之觸媒。無機氧化物Inorganic oxide particles carrying precious metals such as Pt/Ce〇2.Zr〇2 are particularly effective for improving the durability of the catalyst. 'Phosphorus contains the copper oxide, bergeon, precious metal element' in the ammonia decomposition catalyst of the present invention and contains lin (component 4), and the amount of the scale (component 4) is based on the weight of the copper oxide and the zeolite. The elemental phosphorus (P) is selected from the group consisting of 0.01% by weight or more, preferably 5% by weight or more, 1% by weight or less, and more preferably 5 (four) or less. Considering the composition of the exhaust gas, that is, the ammonia concentration, the sulfur compound content, the water vapor concentration, etc., and the treatment conditions, that is, the temperature of the treated catalyst (4), the phosphorus content may be determined, if the content is too low, there is: In the case where the effect is insufficient, on the other hand, if the phosphorus content is too high, the initial activity is lowered. The ammonia-containing exhaust gas differs depending on the discharge source, but generally contains a sulfur compound, and is a exhaust gas containing a large amount of water vapor, which is likely to cause deterioration due to long-term use under ambient gas at the reaction temperature. .doc 200936240 The resulting activity is reduced, and the use of the phosphorus-containing catalyst of the present invention produces the following particularly remarkable effects: it is less likely to cause a decrease in activity, maintains long-term decomposition activity, and maintains a high N2 yield. The phosphorus is contained and the activity of the ammonia exhaust gas containing sulfur compounds such as hydrogen sulfide, thiophene or sulfide is preferably prevented from being lowered. Further, the catalyst of the present invention containing phosphorus has the following effects: The decomposition rate of the new catalyst and the ammonia using the catalyst is high, and the generation of by-products such as 1^(^) can be reduced. (Phosphorus inclusion method) @ In order to contain phosphorus in the catalyst, any one of the following methods may be used: (i) pre-preparation of any one or two or more kinds of components of copper oxide, ceramsite or an inorganic oxide described later by a phosphorus compound. The particles are further mixed to prepare a catalyst composition; (ii) a phosphorus compound is added to the slurry obtained by mixing the respective catalyst components, and the slurry is coated on the support. And then performing a heat treatment; (iii) applying a scale-free catalyst composition to a support or the like to form a catalyst layer, and then impregnating the catalyst layer with a phosphorus-containing aqueous solution, and then performing a force 〇 Heat treatment method; among them, especially the method of (iii) is effective for improving the durability. For the filling compound used for filling, squaric acid (H3P04), metaphosphoric acid, ammonium dihydrogen phosphate can be exemplified. (NH4H2P〇4), hydrogen phosphate ((NH4)2 HP〇4), such as a water-soluble phosphoric acid, an inorganic salt such as Na, K or an ammonium salt, or an organic acid ester. The aqueous solution of the phosphorus compound is impregnated with a catalyst component or a catalyst such as a zeolite or an inorganic oxide. In the middle, it is dried at normal temperature ~ i50 ° C, and then calcined at 136,838.doc • 16-200936240 500 to 600 ° C, thereby making a phosphorus-containing catalyst.

在本發明之觸媒中，含有氧化銅（成分1)、沸石（成分 2)、貴金屬（成分3)、及磷（成分4)，並且含有選自二氧化鈦（Τι02)、氧化鍅（Zr〇2)、二氧化矽（si〇2)、及二氧化鈽氧化锆之複合氧化物或固溶體（以Ce〇2.Zr〇2表示、: Zr〇2莫耳比為n3〜3:1)中之至少1種無機氧化物（成分y，此情況對責金屬之作用即分解活性之提昇、特別是長期使用中的分解活性之持續性提昇特別有效。丨中特別是及Zr〇2會使長期使用中的分解活性之持續效果優異。至於 :無機氧化物在觸媒中之含4，相對於氧化銅與沸石之重里和100重量份而為丨〜％重量份，較好的是5〜4〇重量份， ^好的是1G〜4G重量份。若含量超過50重量份，則其他成分之含量之比例會相對降低’從而分解活性降低，又，若未滿1重量份，則無法發揮效果。特別有效的疋如上所述，在觸媒中以承載貴金屬之狀態含有該無機氧化物。例如預先準備預先在Ti〇2粒子上承載相對於Ti〇2而為i 00重量ppm〜5重量％ppm之pt而成的丁办 :子(將其表示為Pt/Ti〇2。），並將該粒子與其他成分混口，藉此可製備含有貴金屬以及無機氧化物之觸媒組合 >至於本發明中所使用之無機氧化物粒子之尺寸，為了有效發揮觸媒組合物中之貴金眉一、 T之貝金屬成分之功能，較好的是平均粒徑為0.1 μηι以上、100 μηι以下之粒子。 136838.doc 200936240 本發明中所用之Ti〇2可用於製備脫硝觸媒等排氣處理觸媒等。即，較好的是BET比表面積為5〜2〇〇 m2/g，更好的是 10〜150 m2/g。The catalyst of the present invention contains copper oxide (component 1), zeolite (component 2), noble metal (component 3), and phosphorus (component 4), and contains titanium oxide (Τι02) and cerium oxide (Zr〇2). ), a composite oxide or solid solution of cerium oxide (si〇2) and cerium oxide zirconia (expressed as Ce〇2.Zr〇2, Zr〇2 molar ratio is n3~3:1) At least one inorganic oxide (component y), which is particularly effective for the action of the responsible metal, that is, the improvement of the decomposition activity, especially the long-term use of the decomposition activity. In particular, Zr〇2 will The long-term use of the decomposition activity is excellent in the sustained effect. As for the inorganic oxide in the catalyst, the content of 4, relative to the weight of the copper oxide and the zeolite and 100 parts by weight, is 丨% by weight, preferably 5~ 4 parts by weight, ^good is 1G to 4G parts by weight. If the content exceeds 50 parts by weight, the ratio of the content of other components will be relatively lowered', so that the decomposition activity is lowered, and if it is less than 1 part by weight, it cannot be used. The effect is particularly effective as described above, in the catalyst to carry precious metals In this state, the inorganic oxide is contained. For example, it is prepared in advance to carry a pt of i 00 ppm by weight to 5% by weight ppm relative to Ti 〇 2 on Ti 2 particles, which is expressed as Pt/ Ti〇2)), and the particles are mixed with other components, whereby a catalyst combination containing a noble metal and an inorganic oxide can be prepared. As for the size of the inorganic oxide particles used in the present invention, in order to effectively touch The function of the metal components of the noble gold eyebrows and the T-shells in the medium composition is preferably particles having an average particle diameter of 0.1 μηι or more and 100 μηι or less. 136838.doc 200936240 Ti〇2 used in the present invention can be used for An exhaust treatment catalyst such as a denitration catalyst is prepared, that is, a BET specific surface area of 5 to 2 〇〇m 2 /g, more preferably 10 to 150 m 2 /g.

作為本發明中所使用之&〇2,單斜晶系、正方晶系、立方晶系均可，較好地可利用通常市售之Zr〇2粉末、特別是比表而積為10 m2/g以上之多孔粉末。又，亦可利用複合系之 ΖΓ〇2、例如 Zr〇2.nCe〇2、Zr〇2.nSi〇2、Zr〇2 π㈣此處’ η約為0.25〜0.75)等。本發明中所使用之_2包括具有沸石結構之高矽沸石、例如絲光沸石。 (觸媒之製備、成形）本發明之觸媒組合物可為粉體狀，亦可為聚料狀。又，在實用中通常製成粒狀等成形粒子而使用，或者以承載於蜂寓狀載體等支持體之公知的排氣處理觸媒形態而使用。以下，以蜂窩狀觸媒為例對製備方法進行說明。在水中添加氧化銅粒子、沸石粒子、貴金屬化合物及鱗化合物，並視需要添加黏合劑而製作漿料。作為另一態樣’如已述預先另外製備承載有貴金屬之無機氧化物: 子，可將該承載粒子添加至上述聚料中。χ，碟化合物如已述’可預先成蜂窩承載不含鱗化合物之觸媒層，然後含浸鱗化合物水溶液。具體而t ’係藉由包括薄塗或浸塗之公知方法將含有該觸媒組合物之漿料塗佈於例如蜂寫狀支持體上’繼而於1()〇〜15(rc下進行乾燥，進而於则〜鮮C 下進仃1〜10小時之煅燒處理。使含磷化合物之溶液含浸以上述方式而獲得之成形觸媒’並可在相同條件下再次進行 136838.doc -18· 200936240 乾燥以及锻燒。所使用之支持體之形狀並無特別限定，較好的是氣體流通時所產生之差壓較小、且與氣體之接觸面積較大的形狀。較好的形狀包括：蜂窩狀、片狀、網格狀、纖維狀、 • 管狀、滤紙狀。支持體之材質並無特別限定，可列舉：堇冑石、氧隸等公知之觸媒載體，碳纖維，金屬纖維，玻璃纖維’陶瓷纖維，鈦、鋁、不鏽鋼等金屬。為了將本發明之觸媒成形或承載於支持體上，可適當混合無機黏合劑或有機黏合劑而使用。作為無機黏合劑之具體例，可列舉：膠體二氧化石夕、二氧化石夕溶膝、氧化銘溶膠、矽酸溶膠、二氧化鈦溶膠、水鋁土、白土、高嶺土、海泡石（sepiolite)。含氨排氣之處理方法繼而，以下對排氣之處理方法進行說明。作為使用本發明之氨分解觸媒之含氨排氣，並無特別限 Φ 冑’例如可列舉··來自半導體工場等各工場之含氨排氣，焦炭爐排氣，來自排煙脫硝製程之茂漏含氨氣體，由對污水處理場、污泥處理設施等之含氨排水之汽提所產生排出之排氣。 . 可應用本發明之含氨氣體之氨濃度例如為10容量ppm〜5 合量％。使含氨氣體以及空氣與本發明之觸媒接觸，將氨轉化成無害之氮以及水，而進行氧化分解。該氧化分解溫度根據排氣中之性狀（水蒸汽濃度或氨漠度）、反應條件（溫度、空間速度）、觸媒劣化程度等而適當決定，較好的是 136838.doc -19- 200936240 選自通常為20G〜5啊、較好的是25G〜45Gt之溫度範圍。考慮到氣體之性質（氨濃度或水蒸汽漠度）或氨分解率之目標值等’處理對象排氣相對於觸媒之空間速度（sv)自 100〜100000 hr-1之範圍進行適當選擇即可。較好的是將供給至觸媒反應器之氣體中的氨濃度調整為 3容量％以下’較好的是2容量％以下。若氨濃度超過3容量 %，則因反應所致之發熱’觸媒層之溫度會過度上升而容易引起觸媒劣化。As the &2 used in the present invention, a monoclinic system, a tetragonal system, or a cubic system may be used, and a commercially available Zr〇2 powder, particularly a specific product, may be used, and the product is 10 m2. Porous powder of /g or more. Further, it is also possible to use 复合2 of the composite system, for example, Zr〇2.nCe〇2, Zr〇2.nSi〇2, Zr〇2 π(4) where η is about 0.25 to 0.75). The _2 used in the present invention includes a sorghum zeolite having a zeolite structure, such as mordenite. (Preparation and Forming of Catalyst) The catalyst composition of the present invention may be in the form of a powder or a polymer. Further, in practice, it is usually used as a shaped particle such as a granular material, or in the form of a known exhaust gas treating catalyst carried on a support such as a bee-shaped carrier. Hereinafter, a preparation method will be described by taking a honeycomb catalyst as an example. Copper oxide particles, zeolite particles, a noble metal compound, and a scale compound are added to water, and a binder is added as needed to prepare a slurry. As another aspect, the carrier particles may be added to the above-mentioned polymer as described above in which an inorganic oxide-bearing inorganic oxide is additionally prepared. Alternatively, the dish compound may be pre-formed into a honeycomb-bearing catalyst layer containing no scale compound and then impregnated with an aqueous solution of the scaly compound. Specifically, the slurry containing the catalyst composition is applied to, for example, a bee-like support by a known method including thin coating or dip coating, and then dried at 1 () 〇 15 (r) And then calcining the mixture with the fresh C for 1 to 10 hours. The solution of the phosphorus-containing compound is impregnated with the forming catalyst obtained in the above manner and can be performed again under the same conditions 136838.doc -18· 200936240 The shape of the support to be used is not particularly limited, and it is preferably a shape in which a differential pressure generated during gas flow is small and a contact area with a gas is large. Preferred shapes include: honeycomb The material of the support is not particularly limited, and examples thereof include known catalyst carriers such as vermiculite and oxygen, carbon fiber, metal fiber, and glass fiber. 'Ceramic fiber, metal such as titanium, aluminum, stainless steel, etc. In order to shape or load the catalyst of the present invention on the support, an inorganic binder or an organic binder may be appropriately mixed and used. As a specific example of the inorganic binder, it may be listed. : colloidal dioxide, sulphur dioxide, oxidized sol, ceric acid sol, titanium dioxide sol, bauxite, clay, kaolin, sepiolite. Treatment of ammonia-containing exhaust gas, The method of treating the exhaust gas is described. The ammonia-containing exhaust gas using the ammonia decomposition catalyst of the present invention is not particularly limited to Φ', for example, ammonia-containing exhaust gas from various workshops such as a semiconductor factory, and a coke oven Exhaust gas, which is a leaking ammonia-containing gas from a flue gas denitration process, and is exhausted by a stripping strip containing ammonia drainage of a sewage treatment plant, a sludge treatment facility, etc. The ammonia-containing gas to which the present invention can be applied The ammonia concentration is, for example, 10 to 5 ppm by volume. The ammonia-containing gas and air are brought into contact with the catalyst of the present invention, and ammonia is converted into harmless nitrogen and water to be oxidatively decomposed. The traits (water vapor concentration or ammonia desertity), reaction conditions (temperature, space velocity), degree of catalyst deterioration, etc. are appropriately determined, and it is preferably 136838.doc -19- 200936240 selected from usually 20G to 5 It is preferably a temperature range of 25 G to 45 Gt. Considering the nature of the gas (ammonia concentration or water vapor infiltration) or the target value of the ammonia decomposition rate, etc., the space velocity (sv) of the treated exhaust gas relative to the catalyst is The range of 100 to 100,000 hr-1 may be appropriately selected. It is preferred to adjust the ammonia concentration in the gas supplied to the catalytic reactor to 3 vol% or less, preferably 2 vol% or less. When the amount is more than 3% by volume, the temperature due to the reaction is excessively increased, and the temperature of the catalyst layer is excessively increased to cause deterioration of the catalyst.

又’在對不含充分的分解反應所必需之氧的排氣進行處理時’在觸媒反應器之入口，自外部混入空氣或含氧之氣體而使氧量/理論必需氧量比達到1G3〜⑽較好的是 P可此處，理淪必需氧量係根據式（丨）而得之化學計量氧量，反應器之入口氨濃度為10容量％時，氧濃度為〇·77〜7·5容量％ ’較好的是0.83〜3.8容量％。 4NH3+302 —6H2〇+2N2 · . ·⑴ 以下，介紹污水處理場排氣之例子。利用脫水機對污水處理場之污泥進行脫水，並藉由蒸館汉備對所產生之排水進行蒸餾。若需要則進而設置自外部人入蒸π或蒸汽與氮’以促進水分及氨蒸發的分離裝置。利用分離槽將含有藉由蒸館而分離之氨的水蒸汽分離為水與乱，在回收排熱後，將含有高濃度水分以及氨之蒸汽 (β含氨#^氣）導入至觸媒反應裝置中，$外自外部導入必需量之空氣，與觸媒接觸而將氨分解成氮與水蒸汽，而進行無害化處理°肖製程之概要例如在專利文獻日本特開 136838.doc 200936240 2〇〇2-28637號公報中作了介紹。 /Γ之觸媒可較好地用於處理來自活性污泥處理之排 =排氣係利用觸媒並具有過於苛刻之組成：水細 ::二0容量％、硫化合物之S成分為10〜重量ppm、氰為100谷量ppm〜3容量具餘0卩分為虱。即本發明之觸媒發揮特別有效之彳七Μ > 用的排氣，除了氨以外，實質上係以水泰以及說為主體名产“ 體之氧體。進而，對含有硫化合物之排In addition, when the exhaust gas containing oxygen necessary for the decomposition reaction is not treated, 'at the inlet of the catalyst reactor, air or oxygen-containing gas is mixed from the outside to make the oxygen/theoretical oxygen ratio reach 1G3. Preferably, P is here, and the oxygen content is a stoichiometric amount of oxygen according to the formula (丨). When the inlet ammonia concentration of the reactor is 10% by volume, the oxygen concentration is 〇·77~7. • 5 vol% is preferably 0.83 to 3.8 vol%. 4NH3+302 —6H2〇+2N2 · . (1) The following is an example of the exhaust of a sewage treatment plant. The dewatering machine is used to dewater the sludge in the sewage treatment plant, and the drainage produced by the steaming plant is distilled. If necessary, a separate device for steaming π or steam and nitrogen to promote evaporation of water and ammonia is provided. The water vapor containing the ammonia separated by the steaming hall is separated into water and chaos by using a separation tank, and after the heat is recovered, the steam containing high concentration of water and ammonia (β-containing ammonia gas) is introduced into the catalyst reaction. In the apparatus, the necessary amount of air is introduced from the outside, and the ammonia is decomposed into nitrogen and water vapor by contact with the catalyst to perform decontamination treatment. For example, the patent document is disclosed in Japanese Patent Laid-Open No. 136838.doc 200936240. It is introduced in the Gazette No. 2-28637. / Γ 触可可可可可可可触触触触触触触触触触触触排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气排气The weight is ppm, the cyanide is 100, the amount of ppm is ~3, and the capacity is 0. That is, the exhaust gas used in the catalyst of the present invention is particularly effective in the use of exhaust gas, in addition to ammonia, in essence, it is produced by the water and the main body of the body of the body. Further, the row containing the sulfur compound

⑨特別好的是使用本發明之觸媒。由上述活性污泥處理所排出之姑g 出之排虱為一例，但當然並不限定於此，該等以外，當然亦可用 * 、二氧為主成分之通常的含氨排氣處理。 [實施例] , 以下’基於實施例對本發明進行詳細說明。但本發明並不限定於該等實施例。觸媒之製備 <承载有貴金屬之無機氧化物粒子之製備> <Pt(0.7)/Ti〇2粒子及 Pt(2」）/Ti〇2fe 子 > 在蒸發皿中，向二硝基二胺鉑之水溶液(Pt濃度：4.5重量。/。)添加Ti〇2粉末(MiUennium公司製造、平均粒徑：i哗、表面積.60 m /g)，充分含浸後，在溫度80〜90°C下 -面授拌-面使水分蒸發，並進行乾燥，然後，進而在乾燥機中加熱至15(TC ’並將所得粉末在空氣中、戰之溫度下緞燒1小時’而獲得承載有〇·7重量％之以(金屬成分)的 Τι〇2粒子（將其表示為Pt(0.7)/Ti〇2。）。 136838.doc 21 200936240 藉由相同之方法獲得承載有2.1重詈。/ 里重/〇之鉑的Ti02粒子 (Pt(2.1)/Ti02)。 <Pt(0.7)/ZrO2> 使用Zr〇2粒子（Millennium公司製造、平均粒徑：i㈣、 BET比表面積：H)0 mVg)，藉由相同之操作而獲得承載有 0.7 重量。/〇之鉑的 Zr02粒子（pt(〇.7)/Zr〇2)。 <Pd(3.5)/Ti02> 於硝酸鈀之水溶液（Pd濃度：10重量％)中添加上述Ti〇2 θ 粉末，藉由相同之操作，而獲得承載有35重量。乂之以的It is particularly preferred to use the catalyst of the present invention. The excretion by the above-mentioned activated sludge treatment is an example, but it is of course not limited thereto, and it is of course possible to use a normal ammonia-containing exhaust gas treatment mainly composed of * and dioxane. [Examples] Hereinafter, the present invention will be described in detail based on examples. However, the invention is not limited to the embodiments. Preparation of Catalyst & <Preparation of Inorganic Oxide Particles Carrying Precious Metals> <Pt(0.7)/Ti〇2 Particles and Pt(2")/Ti〇2fe Sub> In Evaporation Dish, Dinitrate A solution of bisphosphonium platinum (Pt concentration: 4.5% by weight) was added with Ti 2 powder (manufactured by MiUennium Co., Ltd., average particle diameter: i 哗, surface area: 60 m / g), and fully impregnated at a temperature of 80 to 90. °C-surface-mixing-surface to evaporate water and dry it, then further heat it to 15 (TC ' in the dryer and saturate the obtained powder in air at a temperature of 1 hour) 7·7 wt% of (metal component) Τι〇2 particles (represented as Pt(0.7)/Ti〇2.) 136838.doc 21 200936240 Obtained by the same method with 2.1 heavy 詈. Ti02 particles of platinum/palladium (Pt(2.1)/Ti02). <Pt(0.7)/ZrO2> Zr〇2 particles (manufactured by Millennium, average particle diameter: i (four), BET specific surface area: H) 0 mVg), obtained by the same operation, has a weight of 0.7. / Zr02 particles of platinum (pt (〇.7) / Zr〇2). <Pd(3.5)/Ti02> The above Ti〇2 θ powder was added to an aqueous solution of palladium nitrate (Pd concentration: 10% by weight), and 35 parts by weight were obtained by the same operation. Awkward

Ti02粒子（Ρ(Κ3.5)/Ή02)。 <Pt(0.35)/SiO2> 於二硝基二胺鉑水溶液中添加二氧化矽粉末（日產化學公司製造、CARIACT 10、平均粒子徑：1〇 _)，藉由相同之操作’而獲得承載有0.35 wt%之Pt的二氧化矽粒子 (Pt(0.35)/SiO2)。 <Pd(5.0)/Al2O3>Ti02 particles (Ρ(Κ3.5)/Ή02). <Pt(0.35)/SiO2> The cerium oxide powder (manufactured by Nissan Chemical Co., Ltd., CARIACT 10, average particle diameter: 1 〇) was added to an aqueous solution of dinitrodiamine platinum, and the carrier was obtained by the same operation. There is 0.35 wt% of Pt cerium oxide particles (Pt(0.35)/SiO2). <Pd(5.0)/Al2O3>

P 於硝酸纪之水溶液（Pd濃度：10重量％)中添加八12〇3粉末’藉由與Pt(0.7)/Ti〇2粒子相同之操作，而獲得承載有 5.0重量％之 Pd的 Al2〇3粒子（Pd(5.0)/Al2O3；)。 <Pt(2.1)/Ce〇2-Zr02> 使用CeOyZrO2複合氧化物（第一希元素公司製造、Ce: Zr莫耳比4 : 6、平均粒徑：1 pm、BET比表面積：77 m2/g)以及二硝基二胺銘水溶液，藉由相同之操作，而獲得承載2.1 重量％2Pt的 Ce02.Zr02粒子(Pt(2.1 )/Ce02.Zr02)。 136838.doc -22· 200936240 <Pd(5)/Mor> 使用H型絲光沸石（東曹（Tosoh)製造：Si〇2/Al2〇3莫耳比 1 8)以及硝酸鈀之水溶液’藉由相同之操作，而獲得承栽有5重量％之Pd的絲光沸石粒子（Pd(5)/Mor)。 <觸媒之製備> 以下’對實施例及比較例之觸媒的製備方法進行說明。再者，將所得各觸媒之組成匯總示於表1。觸媒E-1及觸媒C-1之製備 <觸媒C-l> 於去離子水68 g中添加Η型絲光沸石（東曹製造： Si〇2/Al2〇3莫耳比為IS、下述表1中以「（M〇r.)表示」1 〇5 g、氧化銅粉末（Chemirite製造）18 g及上述Pt(0.7)/Ti〇j4 子1 8 g ’並添加作為黏合劑的二氧化矽溶膠（日產化學公司製造、含有20重量％之Si〇2)l 87 g’充分授拌而製作觸媒漿料。繼而’於菫青石製之蜂窩載體（微孔數：2〇〇微孔/平方英吋、長50 mmx寬50 mmX高50 mm、容積：0.125 L) 上，藉由薄塗法塗佈觸媒漿料，於15〇°C下乾燥2小時，於 500°C下煅燒1小時’而獲得每1 L蜂窩承載有120 g觸媒層之觸媒C-1。〈觸媒E-1 a> 將上述觸媒C-1浸潰於磷酸水溶液（p濃度為2.2重量％) 中’使麟酸水溶液滲入觸媒層中後再取出，吹空氣將附著於觸媒層之外部的溶液去除後，進行稱量，以觸媒層中之磷酸溶液的吸水量達到每丨L蜂窩為135 g的方式，視需要 136838.doc -23- 200936240 重複該操作，而使其含浸填酸°繼而於150°c下乾燥2小時，繼而利用馬弗爐在空氣環境下’於500°C下锻燒1小時，而獲得鱗含量之元素（P)為3.〇重量％的觸媒E-la(本發明之觸媒）。 <觸媒E-lb> 除了使用上述Pt(〇.〇7)/Ti〇2粒子代替Pt(〇.7)/Ti02粒子以外，以與觸媒C-1之製備條件相同之條件，製備蜂窩型觸媒，繼而將該觸媒浸潰於填酸水溶液（P濃度為〇.7重量％) 中’另外以與觸媒E-la相同之方法進行處理，而獲得填含量（P)為1.0重量％的觸媒E-lb(本發明之觸媒）。 <觸媒C-2> 除了使用ZSM-5沸石（SiOVAhO3莫耳比為38)代替H型絲光沸石以外，以與觸媒c-1相同之方法製備觸媒c_2。 <觸媒E-2>P is added to the aqueous solution of nitric acid (Pd concentration: 10% by weight) to add 8 12 〇 3 powder 'by the same operation as the Pt (0.7) / Ti 〇 2 particles, to obtain Al 2 承载 carrying 5.0% by weight of Pd 3 particles (Pd(5.0)/Al2O3;). <Pt(2.1)/Ce〇2-Zr02> Using CeOyZrO2 composite oxide (manufactured by Daisei Co., Ltd., Ce: Zr molar ratio 4: 6, average particle diameter: 1 pm, BET specific surface area: 77 m2/g) And a dinitrodiamine aqueous solution, by the same operation, obtained Ce02.Zr02 particles (Pt(2.1)/Ce02.Zr02) carrying 2.1% by weight of 2Pt. 136838.doc -22· 200936240 <Pd(5)/Mor> using H-type mordenite (manufactured by Tosoh: Si〇2/Al2〇3 molar ratio 18) and aqueous solution of palladium nitrate The same operation was carried out to obtain mordenite particles (Pd(5)/Mor) bearing 5% by weight of Pd. <Preparation of Catalyst> The following describes the preparation method of the catalyst of the examples and the comparative examples. Further, the composition of each of the obtained catalysts is shown in Table 1. Preparation of Catalyst E-1 and Catalyst C-1 <Catalyst C-l> Η-type mordenite was added to 68 g of deionized water (manufactured by Tosoh: Si〇2/Al2〇3 molar ratio is IS In Table 1 below, "(M〇r.)" 1 〇 5 g, copper oxide powder (manufactured by Chemirite) 18 g, and the above Pt (0.7) / Ti〇j4 sub 1 8 g ' are added as a binder. The cerium oxide sol (manufactured by Nissan Chemical Co., Ltd., containing 20% by weight of Si〇2) l 87 g' is sufficiently mixed to prepare a catalyst slurry. Then the honeycomb carrier made of cordierite (micropores: 2〇) 〇Micropores/square inch, length 50 mmx width 50 mmX height 50 mm, volume: 0.125 L), coated with catalyst slurry by thin coating, dried at 15 ° C for 2 hours at 500 ° The calcination was carried out for 1 hour at C to obtain a catalyst C-1 carrying 120 g of a catalyst layer per 1 L of the honeycomb. <Catalyst E-1 a> The above catalyst C-1 was immersed in an aqueous phosphoric acid solution (p concentration was 2.2% by weight) The aqueous solution of the linonic acid is infiltrated into the catalyst layer and then taken out, and the air is added to remove the solution adhering to the outside of the catalyst layer, and then weighed to obtain the water absorption amount of the phosphoric acid solution in the catalyst layer. Each 丨L cell is 13 5 g mode, if necessary, 136838.doc -23- 200936240 Repeat this operation, so that it is filled with acid ° and then dried at 150 ° C for 2 hours, and then use the muffle furnace in the air environment 'at 500 ° C After calcination for 1 hour, the element (P) having a scaly content of 3.% by weight of the catalyst E-la (the catalyst of the present invention) was obtained. <Catalyst E-lb> In addition to using the above Pt (〇.〇) 7) / Ti 〇 2 particles instead of Pt (〇. 7) / Ti02 particles, a honeycomb type catalyst was prepared under the same conditions as those for the preparation of the catalyst C-1, and then the catalyst was immersed in an aqueous acid solution. (P concentration: 7. 7 wt%) was treated in the same manner as in the catalyst E-la to obtain a catalyst E-lb (catalyst of the present invention) having a filling content (P) of 1.0% by weight. <Catalyst C-2> Catalyst c_2 was prepared in the same manner as catalyst c-1 except that ZSM-5 zeolite (SiOVAhO3 molar ratio of 38) was used instead of H-type mordenite. -2>

除了使用磷酸水溶液（P濃度為Q.7 wt%)以外，以與觸媒 E-lb相同之方法對觸媒c_2進行磷酸處理為1.0%的觸媒E_2(本發明之觸媒）。 <觸媒C-3> 而獲得含磷（P) 2粒子以除了使用上述_._〇2粒子代替pt(〇7)/Ti〇外’以與觸媒C·1相同之方法獲得觸媒C_3。 <觸媒E-3> M興觸媒E-lb相獲得含物為觸媒 <觸媒C-4> 觸媒）。 136838.doc •24- 200936240 除了使用上述Pt(〇.7)/Zr02粒子代替pt(〇 7)/TiQ2粒子以外，以與觸媒C-1相同之方法製備觸媒c_4。 <觸媒E-4> 以與觸媒E-1 b相同之方法對觸媒C-4進行構酸處理，而製備含填（P)為1.0%的觸媒E-4(本發明之觸媒）。 <觸媒C-5> 使用於去離子水68 g中混合上述η型絲光沸石117 g、氧化銅粉末6 g及上述Pt(0.7)/Ti〇2粒子18 g及上述二氧化碎溶 @ 膠187 g而製作的觸媒漿料，以與觸媒c—丨相同之方法獲得觸媒C-5。 <觸媒E-5> 使用觸媒C-5，以與觸媒E-lb相同之方法進行磷酸處理’而製備含磷（P)為1.0重量％的觸媒E-5(本發明之觸媒）。 <觸媒E-6> 除了使用上述Η型絲光沸石87 g、上述氧化銅粉末％ g 及上述Pt(0.7)/Ti〇2粒子36 g以外’以與觸媒C-1及觸媒e_ lb相同之方法獲得含磷（P)為1.0%的觸媒E_6(本發明之觸媒）。 <觸媒E-7> 於去離子水68.5 g中添加Η型絲光沸石87 g、氧化銅36 g、二硝基二胺鉑水溶液（Pt濃度2.0°/。)3 g及作為黏合劑的二氧化石夕溶膠（含有2 0 %之二氧化石夕），進行充分授拌而製作聚料。以與觸媒C-1相同之方法將該漿料承载為蜂寫狀。繼 136838.doc -25- 200936240 而以與觸媒E_lb相同之方法進行磷酸處理，為1.0 wt%的鱗媒E-7(本發明之觸媒）。如 ’備含磷（P) E-7係不含無機氧化物’且將p 所7^ ’該觸媒 <觸媒〇6> 傷者。於去離子水68.7 g令添加H型絲光沸石 .The catalyst c_2 was subjected to phosphoric acid treatment to 1.0% of the catalyst E_2 (the catalyst of the present invention) in the same manner as the catalyst E-lb except that an aqueous phosphoric acid solution (P concentration: Q.7 wt%) was used. <Catalyst C-3> and obtaining phosphorus-containing (P) 2 particles to obtain a touch in the same manner as the catalyst C·1 except that the above _._〇2 particles were used instead of pt(〇7)/Ti〇 Media C_3. <Catalyst E-3> M-catalyst E-lb phase The content of the catalyst was obtained as a catalyst <catalyst C-4> catalyst. 136838.doc •24- 200936240 Catalyst c_4 was prepared in the same manner as Catalyst C-1 except that the above Pt(〇.7)/Zr02 particles were used instead of pt(〇7)/TiQ2 particles. <Catalyst E-4> Catalyst C-4 was subjected to acid treatment in the same manner as the catalyst E-1 b to prepare a catalyst E-4 containing 1.0% of (P) (the present invention) catalyst). <Catalyst C-5> The above-mentioned n-type mordenite 117 g, 6 g of copper oxide powder, and 18 g of the above Pt(0.7)/Ti〇2 particles and the above-mentioned disolute-dissolving agent were mixed using 68 g of deionized water. Catalyst slurry prepared by molding 187 g of gum was obtained in the same manner as the catalyst c-oxime. <Catalyst E-5> Using a catalyst C-5, phosphoric acid treatment was carried out in the same manner as the catalyst E-lb' to prepare a catalyst E-5 containing phosphorus (P) of 1.0% by weight (the present invention catalyst). <Catalyst E-6> In addition to the above-mentioned fluorene type mordenite 87 g, the above copper oxide powder % g and the above Pt(0.7)/Ti〇2 particles 36 g, 'with the catalyst C-1 and the catalyst e_ The catalyst E_6 (catalyst of the present invention) containing 1.0% of phosphorus (P) was obtained by the same method of lb. <Catalyst E-7> 87 g of mordenite mordenite, 36 g of copper oxide, aqueous solution of dinitrodiamine platinum (Pt concentration: 2.0°/.) 3 g and binder as a binder were added to 68.5 g of deionized water. The cerium oxide sol (containing 20% of the dioxide dioxide) is fully mixed to prepare a polymer. The slurry was carried in a bee-like manner in the same manner as the catalyst C-1. Phosphoric acid treatment was carried out in the same manner as the catalyst E_lb, following 136838.doc -25-200936240, to be 1.0 wt% of the sizing agent E-7 (the catalyst of the present invention). For example, 'phosphorus (P) E-7 does not contain inorganic oxides' and p is 7^' the catalyst <catalyst 〇6> Adding H-type mordenite to 68.7 g of deionized water.

Si02/Al203 = 18)123 g、上述Pi(〇.7)/Ti〇2粒子 u ,造. 氧切溶膠187 g，進行充分授掉而製作聚料二= C-1相同之方法利用該漿料獲得觸媒c_6 ,、觸媒叫目同之方法而獲得含磷（1>)為1%的觸媒c心觸媒C6 _ 不含氧化銅之觸媒。、係 <觸媒E-8> 除了使用_.35卿2粒子18g代替Pt(〇7)/Ti〇2粒子Μ ^外’將以與觸媒CM相同之條件而製作的漿料承載為蜂寓狀。繼而以與觸媒E-lb相同之方法製備觸媒e_8(本發明之觸媒）。 ❿ <觸媒X> 於去離子水233 g中添加市售之脫硝觸媒(觸媒化成公司製造、刪-5)(藉由研缽將其製成粉末、採集6〇網篩下者。）131 g，添加上述以（〇 7)/Ti〇2粒子i8 5 g，並添加二氧化石夕溶膠黏合劑117 g，進行充分_而製作漿料，Z 與觸媒C-1相同之方法利用該漿料製備觸媒χ。 <觸媒Υ> 於γ-氧化鋁粉（Nikki_Universai(股）製造、粒徑：5〇〜1〇〇 μηι、比表面積150 m2/g)中添加二硝基二胺鉑硝酸水溶液 136838.doc -26- 200936240 (田中貴金屬製造）使Pd以重量比例計達到5.0%，並蒸發乾固後，於500°C下煅燒2小時而獲得Pt(5.0)/Al2O3粒子。將該200 g之Pt(5.0)/Al2O3粒子及50 g水鋁土進行混合，於其中添加60°/。硝酸25 g、離子交換水725 g而製成漿料。將其薄塗於成形支持體上，用壓縮空氣吹散其餘漿料，藉由乾燥器於150°C下將其乾燥3小時，再於500°C下煅燒2小時，而獲得含Pd為2.0%的觸媒Y。 [表1] ® 表1 觸媒名觸媒組成氧化銅〉弗石貴金J 1 無機氧化i 勿磷觸媒E-la 15 Mor” 85 Pt 0.1 Ti〇2 15 3 觸媒E-lb 15 Mor,， 85 Pt 0.01 Ti02 15 1 觸媒E-2 15 MFI. 85 Pt 0.1 Ti02 15 1 觸媒E-3 15 Mor” 85 Pd 0.5 Ti〇2 15 1 觸媒E-4 15 Mor·， 85 Pt 0.1 Zr02 15 1 觸媒E-5 5 Mor.， 95 Pt 0.1 Ti02 15 1 觸媒E-6 30 Mor·， 70 Pt 0.2 Ti02 30 1 觸媒E-7 15 Mor” 85 Pt 註1 0.05 木氺氺 0 1 觸媒E-8 15 Mor·, 85 Pt 0.05 Si02 0 1 觸媒C-1 15 Mor·， 85 Pt 0.1 Ti02 15 0 觸媒C-2 15 MFI. 85 Pt 0.1 Ti02 15 0 觸媒C-3 15 Mor., 85 Pd 0.5 Ti02 15 0 觸媒C-4 15 Mor·， 85 Pt 0.1 Zr02 15 0 觸媒C-5 5 Mor., 95 Pt 0.1 Ti02 15 0 觸媒C-6 0 Mor., 100 Pt 0.1 Ti02 15 1 觸媒X V-W Pt 0.1 Ti02 100 0 觸媒Y Pd 2.0 Al2〇3 100 0 註1 :於漿料中添加Pt化合物而進行承載 <活性評價試驗> 自上述各蜂窩型觸媒採集圓柱狀（直徑21 mm、長度50 mm) 之蜂窩型觸媒，將其填充至流通式反應裝置中，藉由表2 136838.doc -27- 200936240 所示之評價條件1或評價條件2對氨分解活性進行評價。 [表2] 表2活性評價條件評價條件1 評價條件2 試驗裝置流通式反應裝置供試氣體之組成供試氣體1 供試氣體2 νη3 5000 ppm 10,000 ppm 水蒸汽 2容量％ 50容量％氧 10容量％ 2容量％氮剩餘部分剩餘部分反應條件觸媒蜂窩之尺寸：直徑21 mmx長度50 mm 反應溫度 300°C ' 350〇C ' 400°C 空間速度、SV 10,000 hr-1Si02/Al203 = 18) 123 g, the above Pi (〇.7)/Ti〇2 particle u, 187 g of oxygen-cut sol, and fully obtained by the same method of making the aggregate 2 = C-1 The catalyst c_6 is obtained, and the catalyst is obtained by the same method to obtain a catalyst containing a phosphorus (1>) of 1% c-catalyst C6 _ a catalyst containing no copper oxide. , <catalyst E-8> In addition to using _.35 qing 2 particles 18g instead of Pt(〇7)/Ti〇2 particles 外 ^ outside', the slurry prepared under the same conditions as the catalyst CM is carried as The bee has a shape. Catalyst e_8 (the catalyst of the present invention) was then prepared in the same manner as the catalyst E-lb. ❿ <catalyst X> A commercially available denitration catalyst (manufactured by Catalyst Chemical Co., Ltd., 5-1) was added to 233 g of deionized water (pulverized by a mortar, and collected under a 6-inch mesh) .) 131 g, add the above (〇7)/Ti〇2 particles i8 5 g, and add 117 g of the SiO2 sol-gel binder, and make a sufficient slurry to make the Z the same as the catalyst C-1. The method utilizes the slurry to prepare a catalyst. <catalyst Υ> An aqueous solution of dinitrodiamine platinum nitric acid was added to γ-alumina powder (manufactured by Nikki_Universai Co., Ltd., particle size: 5〇~1〇〇μηι, specific surface area 150 m2/g) 136838.doc -26- 200936240 (manufactured by Tanaka Precious Metals) Pd was made up to 5.0% by weight, and after evaporation to dryness, it was calcined at 500 ° C for 2 hours to obtain Pt (5.0) / Al 2 O 3 particles. 200 g of Pt(5.0)/Al2O3 particles and 50 g of bauxite were mixed, and 60 ° / was added thereto. 25 g of nitric acid and 725 g of ion-exchanged water were used to prepare a slurry. It was thinly coated on a forming support, and the remaining slurry was blown off with compressed air, dried by a drier at 150 ° C for 3 hours, and then calcined at 500 ° C for 2 hours to obtain a Pd of 2.0. % Catalyst Y. [Table 1] ® Table 1 Catalyst name catalyst composition Copper oxide > Fushi gold gold J 1 Inorganic oxidation i Do not phosphorus catalyst E-la 15 Mor" 85 Pt 0.1 Ti〇2 15 3 Catalyst E-lb 15 Mor,, 85 Pt 0.01 Ti02 15 1 Catalyst E-2 15 MFI. 85 Pt 0.1 Ti02 15 1 Catalyst E-3 15 Mor” 85 Pd 0.5 Ti〇2 15 1 Catalyst E-4 15 Mor·, 85 Pt 0.1 Zr02 15 1 Catalyst E-5 5 Mor., 95 Pt 0.1 Ti02 15 1 Catalyst E-6 30 Mor·, 70 Pt 0.2 Ti02 30 1 Catalyst E-7 15 Mor” 85 Pt Note 1 0.05 Hibiscus 0 1 Touch Medium E-8 15 Mor·, 85 Pt 0.05 Si02 0 1 Catalyst C-1 15 Mor·, 85 Pt 0.1 Ti02 15 0 Catalyst C-2 15 MFI. 85 Pt 0.1 Ti02 15 0 Catalyst C-3 15 Mor . 85 Pd 0.5 Ti02 15 0 Catalyst C-4 15 Mor·, 85 Pt 0.1 Zr02 15 0 Catalyst C-5 5 Mor., 95 Pt 0.1 Ti02 15 0 Catalyst C-6 0 Mor., 100 Pt 0.1 Ti02 15 1 Catalyst X VW Pt 0.1 Ti02 100 0 Catalyst Y Pd 2.0 Al2〇3 100 0 Note 1: Pt compound is added to the slurry for carrying <activity evaluation test> From each of the above honeycomb type catalysts Cylindrical (21 mm diameter, 50 mm length) honeycomb catalyst filled into a flow-through reactor The ammonia decomposition activity was evaluated by the evaluation condition 1 or the evaluation condition 2 shown in Table 2 136838.doc -27- 200936240. [Table 2] Table 2 Activity evaluation condition Evaluation condition 1 Evaluation condition 2 Test device Flow-through reaction device Composition of test gas Test gas 1 Test gas 2 νη3 5000 ppm 10,000 ppm Water vapor 2% by volume 50% by volume Oxygen 10% by volume 2% by volume Residual part of nitrogen remaining Reaction condition Catalyst honeycomb size: diameter 21 mmx length 50 mm Reaction temperature 300 °C '350〇C ' 400°C Space velocity, SV 10,000 hr-1

<氣體分析方法> 氨：氣相層析法（TCD檢測器） NOx : Chemiluminescence(化學發光式）分析裝置 N20 :氣相層析法（TCD檢測器） <計算> NH3分解率（％) : 100-{(出口 NH3濃度）/(入口 NH3濃 Q 度)xl〇〇} NOx生成率（％):(出口 NOx濃度）/(入口 NOx濃度）xl00 Ν20生成率（％) : {(出口 Ν20濃度）χ2/(入口 ΝΗ3濃度）}Μ00 • Ν2產率: 100-{(100-ΝΗ3分解率）+ΝΟχ生成率+Ν20生成率} <耐久試驗〉在污水處理場之活性污泥排水之處理設備（含氨之水的汽提設備）的觸媒反應器中填充本發明之觸媒，如以下所述，進行約1年時間的實際排氣處理，藉此實施耐久試 136838.doc -28- 200936240 驗。在上述觸媒反應器中裝填總計1648個市售之氨分解觸媒 (1個蜂窩之尺寸：長150 mm、寬150 mm、高50 mm，容積：1·1 L)，而形成總容積為190 L之觸媒層。於本實施例之耐久性試驗中，將觸媒之一部分置換成本發明之觸媒及比較例之觸媒（上述尺寸的蜂窩狀觸媒），並裝填至觸媒反應器中，藉由表3所示之污水處理場排氣之組成及設備運轉條件，進行5000小時之耐久試驗。再者， ® 在本耐久試驗中，使用1.1 L之蓳青石製蜂窩狀載體代替上述0.1 25 L之莖青石製蜂窩狀載體，各觸媒之原料成分係利用使用與蜂窩之容積成比例之量，並根據上述各觸媒之製備條件而製作的1 · 1 L之蜂窩狀觸媒。 [表3] 表3污水處理場排氣處理條件處理氣體之組成水蒸汽平均、50容量％氨平均、1容量％氧(自外部供給）平均、2容量％硫化氫平均、100 ppm 氮剩餘部分運轉條件排氣之處理量每小時270000 L 反應溫度 350〇C 空間速度、SV 10000 hr·1 處理時間 1800小時、5000小時於耐久性評價中，將所填充之2個觸媒塊在處理1 800小時及5000小時之時刻各抽出1個，藉由表2所示之評價條件進行活性評價，並調查耐久性。測定結果 136838.doc -29- 200936240 <參考例1>排氣中之水蒸汽而對分解活性所造成的影響使·用觸媒E-lb，藉由表2所示之評價條件1及評價條件 2 ’進行氨分解試驗。結果示於表4。 [表4] 表4 觸媒E-lb *干價條件溫度、。c NH3分解率、 % ^^^生成率、 % N2〇生成率、 % N2產率、 % 條件1 300 "45 0.2 1.3 43.5 350 1〇〇 0 1.6 98.4 400 "Too 〇 3 2 〇6 4 ~~ 條件2 300 0 0 4.5 350 400 ~63~~~- 0 0 63 98.5 0.2 0.4 97.9<Gas Analysis Method> Ammonia: Gas Chromatography (TCD Detector) NOx: Chemiluminescence Analyzer N20: Gas Chromatography (TCD Detector) <Calculation> NH3 Decomposition Rate ( %) : 100-{(outlet NH3 concentration) / (inlet NH3 rich Q degree) xl〇〇} NOx formation rate (%): (outlet NOx concentration) / (inlet NOx concentration) xl00 Ν20 generation rate (%): { (Export Ν20 concentration) χ2/(inlet ΝΗ3 concentration)}Μ00 • Ν2 yield: 100-{(100-ΝΗ3 decomposition rate) + ΝΟχ formation rate + Ν20 generation rate} <endurance test> Active sewage in sewage treatment plant The catalyst reactor of the mud drainage treatment equipment (the stripping equipment containing ammonia water) is filled with the catalyst of the present invention, and the actual exhaust treatment is performed for about one year as described below, thereby implementing the endurance test 136838 .doc -28- 200936240 test. A total of 1648 commercially available ammonia decomposition catalysts (1 honeycomb size: 150 mm long, 150 mm wide, 50 mm high, volume: 1·1 L) were charged in the above-mentioned catalyst reactor, and the total volume was formed. 190 L of the catalyst layer. In the durability test of the present embodiment, one part of the catalyst was replaced by the catalyst of the invention and the catalyst of the comparative example (the honeycomb catalyst of the above size), and loaded into the catalyst reactor, by Table 3 The 5,000-hour endurance test was carried out for the composition of the sewage treatment plant and the operating conditions of the equipment. Furthermore, in this endurance test, 1.1 L of a cordierite honeycomb carrier was used instead of the above 0.1 25 L of a vanilla-green honeycomb carrier, and the raw material components of each catalyst were used in proportion to the volume of the honeycomb. And 1, 1 L of a honeycomb catalyst prepared according to the preparation conditions of the above respective catalysts. [Table 3] Table 3 Sewage treatment site Exhaust treatment conditions Composition of treated gas Average water vapour, 50% by volume Ammonia average, 1% by volume Oxygen (from external supply) Average, 2% by volume Hydrogen sulfide average, 100 ppm Nitrogen remaining Operating conditions Exhaust treatment capacity 270,000 L per hour Reaction temperature 350 〇C Space velocity, SV 10000 hr·1 Treatment time 1800 hours, 5000 hours In durability evaluation, the two catalyst blocks filled are processed at 1 800 At the time of hour and 5000 hours, one was taken out, and the activity evaluation was performed by the evaluation conditions shown in Table 2, and the durability was investigated. Measurement result 136838.doc -29- 200936240 <Reference example 1> Effect of water vapor in the exhaust gas on the decomposition activity The catalyst E-lb was used, and the evaluation condition 1 and evaluation shown in Table 2 were used. Condition 2 'Ammonia decomposition test. The results are shown in Table 4. [Table 4] Table 4 Catalyst E-lb * Dry price conditions Temperature, . c NH3 decomposition rate, % ^^^ generation rate, % N2〇 generation rate, % N2 yield, % condition 1 300 "45 0.2 1.3 43.5 350 1〇〇0 1.6 98.4 400 "Too 〇3 2 〇6 4 ~~ Condition 2 300 0 0 4.5 350 400 ~63~~~- 0 0 63 98.5 0.2 0.4 97.9

說明觸媒E-lb在評價條件1、於350〇C下之NH3分解率為在條件2下表現出63%之活性。即，可認為水蒸汽漢度較高之排氣處理與水蒸汽濃度較低之排氣處理相:匕，需要高活性之觸媒。 <參考例2> 觸媒X及觸媒Y與先前作為氨分解觸媒而介紹之觸媒類 7將觸媒x及觸媒γ裝填至污水處理場排氣處理設備 _藉二表2所不之條件2測定處理1800小時後之觸媒的活性（耐久性），結果示於表5A及表5B。 136838.doc 200936240 [表 5A] 表5A 觸媒X之活性觸媒X 溫度、°C nh3分解率、 NOx生成率、 N2〇生成率、 N2產率、 % % % % 新觸媒 300 7 0 0.5 6.5 350 93.4 1.7 16.6 75.1 400 100 2.5 15.4 82.1 處理1800 300 4.4 0 0 4.4 小時後 350 23.1 0 0.3 22.8 400 40.8 0.1 0.7 40 [表 5B] ❹ 表5B 觸媒Y之活性觸媒Y 溫度、°c nh3分解率、成率、 ν2ο生成率、 Ν2產率、 % % % % 新觸媒 300 100 6 27.3 66.7 350 100 21.3 40.3 38.4 400 100 40.4 39 20.6 處理1800 300 95.5 0.4 7.6 87.4 小時後 350 99.9 4.4 16.7 78.8 400 100 18.4 14.3 67.3 說明〇使用觸媒X之結果表示如下：NH3分解率較高為 93.40/〇(@ 350°C )，但N20之生成率較高為16.6%，因此N2產率較低為75.1%。又，在處理1800小時後，分解率大幅度 • 降低至23.1%(@ 350°C)。（參照表5A、圖3及圖4) 觸媒Y係氨分解率為1 〇〇%，就分解活性方面而言，具有優異之耐久性，但NOx等之生成率較高，結果乂產率較低之觸媒，而不適於本發明之目的。（參照表5B、圖3及圖4) 〈實施例1> 136838.doc -31 - 200936240 將觸媒C-1(比較例）及觸媒E-l(本發明之觸媒）的初始活性及财久性評價結果、以及藉由表2所示之評價條件2所測定的結果示於表6A(比較例之觸媒C-1)及表6B(實施例之觸媒 E-la)。 [表 6A] 表6A 觸媒C-1之活性比較例：觸媒< ------- 溫度、°c NH3分解率、 % NOx生成率、 % N2〇生成率、 % n2產率、 % 新觸媒 300 100.0 T4 一―~~ ------— 3.3 ος ^ 350 100.0 2.3 To Q4 7 400 100.0 4.1 ΤΊ ~ 91.8 處理1800 小時後 300 4.0 Α Λ ~~~ V/^Lf 0.0 4 350 4.1 0.0 " - 0.0 A 1 400 14.2 0.1 0.0 ΛΛ 1 處理5000 小時後 300 10.1 0.0 ~αο ————~~ ln.1 10.1 350 10.2 u.u 0.0 in 9 400 21.1 0.0 ' "αδ ~~~~ 21.1 •丨一- [表 6B] 表6B 觸媒E-la之活性實施例：觸媒E-fi ' 溫度、°C NH3分解率 % N〇x生成率、 % N2〇生成率、 % 新觸媒表理1800 小時後處理500石小時後Description Catalyst E-lb showed an NH3 decomposition rate at 350 °C under evaluation condition 1, and showed 63% activity under Condition 2. That is, it is considered that the exhaust gas treatment with a higher water vapor degree and the exhaust gas treatment phase having a lower water vapor concentration: 匕, a catalyst having high activity is required. <Reference Example 2> Catalyst X and Catalyst Y and the catalyst 7 previously introduced as an ammonia decomposing catalyst are loaded with the catalyst x and the catalyst γ to the sewage treatment plant exhaust gas treatment equipment. In the case of the condition 2, the activity (durability) of the catalyst after 1800 hours of the measurement was measured, and the results are shown in Table 5A and Table 5B. 136838.doc 200936240 [Table 5A] Table 5A Catalyst X Activity Catalyst X Temperature, °C nh3 Decomposition Rate, NOx Formation Rate, N2〇 Formation Rate, N2 Yield, % % % % New Catalyst 300 7 0 0.5 6.5 350 93.4 1.7 16.6 75.1 400 100 2.5 15.4 82.1 Treatment 1800 300 4.4 0 0 After 4.4 hours 350 23.1 0 0.3 22.8 400 40.8 0.1 0.7 40 [Table 5B] ❹ Table 5B Active Y of Catalyst Y Temperature, °c nh3 Decomposition rate, yield, ν2ο generation rate, Ν2 yield, % % % % New catalyst 300 100 6 27.3 66.7 350 100 21.3 40.3 38.4 400 100 40.4 39 20.6 Treatment 1800 300 95.5 0.4 7.6 87.4 hours after 350 99.9 4.4 16.7 78.8 400 100 18.4 14.3 67.3 Description The results of the use of catalyst X are as follows: the NH3 decomposition rate is higher at 93.40/〇 (@350 °C), but the N20 production rate is higher at 16.6%, so the N2 yield is lower. 75.1%. Also, after 1800 hours of treatment, the decomposition rate was greatly reduced to 23.1% (@350 °C). (Refer to Table 5A, Fig. 3 and Fig. 4) The catalyst Y-based ammonia decomposition rate is 1%, and it has excellent durability in terms of decomposition activity, but the production rate of NOx or the like is high, and the yield is high. The lower catalyst is not suitable for the purpose of the present invention. (Refer to Table 5B, Fig. 3 and Fig. 4) <Example 1> 136838.doc -31 - 200936240 Initial activity and wealth of catalyst C-1 (comparative example) and catalyst El (catalyst of the present invention) The results of the evaluation and the results measured by the evaluation conditions 2 shown in Table 2 are shown in Table 6A (catalyst C-1 of the comparative example) and Table 6B (catalyst E-la of the example). [Table 6A] Table 6A Activity of Catalyst C-1 Comparative Example: Catalyst < ------- Temperature, °c NH3 Decomposition Rate, % NOx Formation Rate, % N2〇 Formation Rate, % n2 Yield % New Catalyst 300 100.0 T4 一―~~ ------— 3.3 ος ^ 350 100.0 2.3 To Q4 7 400 100.0 4.1 ΤΊ ~ 91.8 After 1800 hours, 300 4.0 Α Λ ~~~ V/^Lf 0.0 4 350 4.1 0.0 " - 0.0 A 1 400 14.2 0.1 0.0 ΛΛ 1 After 5000 hours of treatment 300 10.1 0.0 ~αο ————~~ ln.1 10.1 350 10.2 uu 0.0 in 9 400 21.1 0.0 ' "αδ ~~ ~~ 21.1 •丨一- [Table 6B] Table 6B Activity of Catalyst E-la Example: Catalyst E-fi 'temperature, °C NH3 decomposition rate % N〇x generation rate, % N2〇 generation rate, % New catalysts are processed after 1800 hours and after 500 stone hours

說明： <觸媒C-1之活性> 136838.doc -32· 200936240 參照表6Α、圖1、圖3及圖4 : (初始活性）ΝΗ3分解率在300〜400°C下發揮出100%之活性。 (耐久性）藉由實用設備使用1800小時後，nh3分解率降低至 4.1%(@350。〇、14.2%(@400。〇。〈觸媒E -1 a之活性> 參照表6B、圖2、圖3及圖4參照：Explanation: <Activity of Catalyst C-1> 136838.doc -32· 200936240 Refer to Table 6Α, Fig. 1, Fig. 3 and Fig. 4: (Initial Activity) 分解3 decomposition rate is 100 at 300~400 °C % activity. (Durability) After 1800 hours of use, the nh3 decomposition rate was reduced to 4.1% (@350.〇, 14.2% (@400.〇. <Activity of Catalyst E -1 a>> Refer to Table 6B, Figure 2. Refer to Figure 3 and Figure 4:

Φ (初始活性）ΝΑ分解率較高為^(^(^ 350¾及400t)， NO等之生成率較小，結果n2產率較高為94〜95%，而表現出優異之活性。 (耐久性）藉由實用設備對水蒸汽濃度為5〇容量。/(>之含氨排氣進行長時間處理後，NH3分解率在350。(：下亦維持較高為100%(@ 1800小時後）之活性。即與觸媒相比，含p之觸媒E-1 a即使在過於苛刻之條件下使用，活性之降低亦極少’並發揮出較高之耐久性。 (NOj^NA之生成率）含磷之觸媒E-la與不含磷之觸媒相比，分解率如以下所示，可見到NOx&N2〇之生成率（以Ν〇χ與N2〇之總計表示）減少之效果。 35〇°C_40Q°c 觸媒E-1 a : 觸媒C-1 : 〈實施例2> 4·5% 5.5% 5·3% 8.2% 對於不含磷之觸媒以及含磷之觸媒，藉由表2所示之評 136838.doc -33- 200936240 價條件2評價初始活性以及處理1800小時後之活性，結果示於表7。 [表7] 表7 活性(註1) 觸媒名是否含磷除磷以外之觸媒組成(註2) 新觸媒處理1800 @350〇C 小時後 @350〇C 觸媒C-2 無 CuO(15)、ZSM-5(85)、 100 氺氺氺 (比較例） Pt(O.l)' Ti02(15) 6.5 (註3) 觸媒Ε-2 有 100 100 (實施例） 4.9 3.9 觸媒C-3 無 CuO(15)、Mor.(85)、 100 52 (比較例） Pt(0.5)、Ti02(15) 1.6 0.2 觸媒Ε-3 有 100 92.5 (實施例） 2.1 1.6 觸媒C-4 無 CuO (15)、Mor.(85)、 100 35.9 (比較例） Pt(O.l)、Zr02(15) 19.9 0.3 觸媒Ε-4 有 100 95 (實施例） 13.8 5.9 觸媒C-5 無 CuO (5)、Mor.(95)、 100 氺氺氺 (比較例） Pt(0.1)、Ti02(15) 17.7 觸媒Ε-5 有 100 氺氺氺 (實施例） 11.6 觸媒C-6 有 CuO (0)、Mor.(100)、 100 氺氺氺 (比較例） Pt(0.1)、Ti02(15) 48.5 觸媒Ε-6 有 CuO (30)、Mor.(70)、 100 氺氺木 (實施例） Pt(0.2)、TiO2(30) 4.3 ❹ 註1 :上欄：分解率(％);下攔：NOx與N20之生成率總計(％) 註2 : Mor.表示絲光沸石。註3 : *表示由於未實施耐久試驗故而無測定值。 - 說明： (1) 不含磷之觸媒（例如觸媒C-3及觸媒C-4)雖然初始活性較高，但使用1 800小時後之分解活性大幅度降低。 (2) 相對於此，含磷之本發明之觸媒（例如觸媒Ε-3、觸 136838.doc -34- 200936240 媒E-4)之初始活性較高，且處理1 800小時後分解率之降低亦極少，並持續較高活性。 (3) 不含氧化銅之觸媒C-6雖然氨分解率較高，但^^(^等 (特別是N2〇)之生成率較高，因此N2之產率較低，而無法實現本發明之目的。 (4) 整體而言，含磷之觸媒（例如觸媒E-2)與不含磷之觸媒（例如觸媒C-2)相比，^^(^及N20之生成率較低，且結果 N2產率較高。 @ <實施例3> 對將鉑化合物直接添加至漿料中而製備之觸媒E-7及 Pt/Si02粒子進行混合，使用混合而製備之觸媒E-8，藉由表2之評價條件1對活性進行評價，結果示於表8。 [表8] 表8 活性(註1) 觸媒名是否含磷除磷以外之觸媒組成新觸媒 @350〇C 處理1800 小時後 @350〇C 觸媒E-7 有 CuO(15)、Mor..(85)、 99.8 71.9 (實施例） Pt(0.05) 3.4 1.3 觸媒E-8 有 CuO(15)、Mor..(85)、 100 84.5 (實施例） Pt(0.05)、Si02(15) 3.9 1.5 觸媒E-la 有 CuO(15)、Mor..(85)、 100 100 (實施例） Pt(O.l) 4.5 3.8 觸媒E-2 有 CuO(15)、ZSM5(85)、 100 100 (實施例） Pt(O.l) 5.0 3.9 註1 :上攔：分解率(％);下攔：NOx與N20之生成率總計(％) 說明藉由在漿料中添加Pt化合物而製備之觸媒E-7具有充分 136838.doc •35· 200936240 高之初始活性、然而，若長期使用，則與承載於無機氧化物粒子上、含有Pt而製備使用的觸媒（例如觸媒E—丨幻相比，活性降低稍大。使用承載有Pt之Ti〇2粒子的觸媒（例如觸媒E_la、觸媒E_ 2)與使用承載有Pt之Si〇2粒子而製備的觸媒E_8相比，活性降低較少。藉由選擇觸媒E-7及觸媒E-8’同時選擇適用之排氣的組成或處理條件’而具有可充分令人滿意之活性。 <實施例4> 觸媒E-9之製備在去離子水中分散上述（觸媒C4之製備）H型絲光沸石 1〇5 g、上述氧化銅粉末18 g、上述Pt(21)/Ce〇2.Zr〇2粒子 1 8 g以及作為黏合劑的二氧化矽溶膠，而製作漿料，與在觸媒C-1下使用該漿料之情況相同，薄塗於菫青石製蜂窩載體上，繼而進行乾燥以及煅燒，而製備每丨[蜂窩承載〇 I20 g觸媒層之蜂寫狀觸媒C·9。繼而，將其浸潰於磷酸水溶液中，以與上述觸媒E_i相同之條件進行乾燥以及煅燒，而獲得磷含量（P)為2.0重量％的蜂窩狀觸媒E_9(本發明之觸媒）。該觸媒E-9具有以下組成：The Φ (initial activity) ΝΑ decomposition rate is higher (^(^ 3503⁄4 and 400t), and the production rate of NO and the like is small, and the yield of n2 is higher as 94 to 95%, and the activity is excellent. (Sexuality) The concentration of water vapor is 5 〇 by the practical equipment. After the long-term treatment of the ammonia-containing exhaust gas, the decomposition rate of NH3 is 350. (The temperature is also maintained at 100% (@ 1800 hours). After the activity of the catalyst, the p-containing catalyst E-1 a is used under severe conditions, and the activity is reduced to a minimum, and the durability is high. (NOj^NA Formation rate) The phosphorus-containing catalyst E-la has a decomposition rate as shown below, and it can be seen that the generation rate of NOx & N2〇 (expressed as the total of Ν〇χ and N2〇) is reduced. Effect: 35〇°C_40Q°c Catalyst E-1 a : Catalyst C-1 : <Example 2> 4·5% 5.5% 5.3% 8.2% For catalysts containing no phosphorus and phosphorus The catalyst was evaluated for initial activity and activity after 1800 hours by the evaluation of 136838.doc -33-200936240 price condition 2 shown in Table 2. The results are shown in Table 7. [Table 7] Table 7 Activity (Note 1) Does the media name contain Composition of catalyst other than phosphorus (Note 2) New catalyst treatment 1800 @350〇C hours @350〇C Catalyst C-2 No CuO(15), ZSM-5(85), 100 氺氺氺 (Comparative Example) Pt(Ol)' Ti02(15) 6.5 (Note 3) Catalyst Ε-2 has 100 100 (Example) 4.9 3.9 Catalyst C-3 No CuO (15), Mor. (85), 100 52 ( Comparative Example) Pt(0.5), Ti02(15) 1.6 0.2 Catalyst Ε-3 has 100 92.5 (Example) 2.1 1.6 Catalyst C-4 No CuO (15), Mor. (85), 100 35.9 (Comparative Example) ) Pt(Ol), Zr02(15) 19.9 0.3 Catalyst Ε-4 has 100 95 (Example) 13.8 5.9 Catalyst C-5 No CuO (5), Mor. (95), 100 氺氺氺 (Comparative Example) ) Pt(0.1), Ti02(15) 17.7 Catalyst Ε-5 has 100 氺氺氺 (Example) 11.6 Catalyst C-6 has CuO (0), Mor. (100), 100 氺氺氺 (Comparative Example) Pt(0.1), Ti02(15) 48.5 Catalyst Ε-6 has CuO (30), Mor. (70), 100 eucalyptus (Example) Pt (0.2), TiO2 (30) 4.3 ❹ Note 1: Upper column: decomposition rate (%); lower barrier: total production rate of NOx and N20 (%) Note 2: Mor. indicates mordenite. Note 3: * indicates that there is no measured value because the endurance test has not been carried out. - Description: (1) Phosphorus-free catalysts (such as Catalyst C-3 and Catalyst C-4) have a high initial activity, but their decomposition activity after 1 800 hours is greatly reduced. (2) In contrast, the phosphorus-containing catalyst of the present invention (e.g., catalyst Ε-3, 136838.doc -34-200936240 medium E-4) has a high initial activity and a decomposition rate after 1 800 hours of treatment. The reduction is also minimal and continues to be highly active. (3) Catalyst C-6 without copper oxide has a high ammonia decomposition rate, but the yield of ^^(^ (especially N2〇) is high, so the yield of N2 is low, and this cannot be achieved. The purpose of the invention. (4) In general, the phosphorus-containing catalyst (for example, the catalyst E-2) is compared with the phosphorus-free catalyst (for example, the catalyst C-2), and the generation of ^^(^ and N20) The rate is low, and as a result, the yield of N2 is high. @<Example 3> Catalyst E-7 and Pt/SiO2 particles prepared by directly adding a platinum compound to a slurry are mixed and prepared by mixing. Catalyst E-8, the activity was evaluated by the evaluation condition 1 of Table 2, and the results are shown in Table 8. [Table 8] Table 8 Activity (Note 1) Whether the catalyst name contains phosphorus or phosphorus other than the catalyst composition Catalyst @350〇C After 1800 hours of treatment @350〇C Catalyst E-7 has CuO(15), Mor..(85), 99.8 71.9 (Example) Pt(0.05) 3.4 1.3 Catalyst E-8 Yes CuO (15), Mor.. (85), 100 84.5 (Example) Pt (0.05), SiO 2 (15) 3.9 1.5 Catalyst E-la has CuO (15), Mor.. (85), 100 100 ( EXAMPLES Pt(Ol) 4.5 3.8 Catalyst E-2 with CuO(15), ZSM5(85), 100 100 (Example) Pt(Ol) 5.0 3.9 Note 1: Upper barrier: decomposition rate (%); lower barrier: total yield of NOx and N20 (%) indicates that the catalyst E-7 prepared by adding Pt compound to the slurry has sufficient 136838.doc •35· 200936240 High initial activity, however, if used for a long period of time, the activity is slightly reduced compared to the catalyst (for example, catalyst E-丨幻) which is supported on inorganic oxide particles and contains Pt. The catalyst carrying the Pt Ti〇2 particles (for example, the catalyst E_la, the catalyst E_2) has less activity than the catalyst E_8 prepared by using the Pt-loaded Si〇2 particles. The medium E-7 and the catalyst E-8' simultaneously select the composition or processing conditions of the applicable exhaust gas to have sufficiently satisfactory activity. <Example 4> Preparation of the catalyst E-9 in deionized water Dispersing the above (preparation of catalyst C4) H mordenite 1〇5 g, 18 g of the above copper oxide powder, the above Pt(21)/Ce〇2.Zr〇2 particles of 18 g, and cerium oxide as a binder The sol is used to prepare a slurry which is thinly coated on a cordierite honeycomb carrier as in the case of using the slurry under the catalyst C-1. Followed by drying and calcining to prepare each Shu [square bee honeycomb carrier catalyst layers I20 g write shaped catalyst C · 9. Then, it was immersed in an aqueous solution of phosphoric acid, and dried and calcined under the same conditions as those of the above-mentioned catalyst E_i to obtain a honeycomb catalyst E_9 (catalyst of the present invention) having a phosphorus content (P) of 2.0% by weight. The catalyst E-9 has the following composition:

CuO(15)-Pt/Ce02(15)-Mor(85)-P(2) 觸媒E-10之製備於去離子水中分散上述氧化銅粉末15 g、H型絲光沸石粉末85 g、上述Pd(5)/Mor粒子20 g以及作為黏合劑的二氧化矽溶膠，而製作漿料，與在觸媒(：：_〗下使用該漿料之情 136838.doc •36· 200936240 況相同，薄塗於菫青石製蜂窩載體上，繼而進行乾燥以及煅燒，而製備每1 L蜂窩承載12〇 g觸媒層之蜂窩狀觸媒C· 10。繼而，將其浸漬於磷酸水溶液中，以與上述觸媒] 相同之條件進行乾燥以及煅燒，而獲得磷含量（p)為2〇重量％的蜂窩狀觸媒E_10(本發明之觸媒p該觸媒E_l〇具有以下之組成：Preparation of CuO(15)-Pt/Ce02(15)-Mor(85)-P(2) Catalyst E-10 Disperse 15 g of the above copper oxide powder, 85 g of H-type mordenite powder, and the above Pd in deionized water. (5) /Mor particles 20 g and a cerium oxide sol as a binder, and a slurry is prepared, which is the same as the use of the slurry under the catalyst (:: _ 136838.doc • 36· 200936240) Applying to a cordierite-made honeycomb carrier, followed by drying and calcining, to prepare a honeycomb catalyst C·10 carrying 12 μg of the catalyst layer per 1 L of the honeycomb. Then, immersing it in an aqueous phosphoric acid solution to The catalyst is dried and calcined under the same conditions to obtain a honeycomb catalyst E_10 having a phosphorus content (p) of 2% by weight (the catalyst p of the present invention) has the following composition:

CuO(15)-Pd/Mor(l 5)-Mor(85)-P(2)CuO(15)-Pd/Mor(l 5)-Mor(85)-P(2)

註：該觸媒E-1係使用絲光沸石作為無機氧化物，包含於其上承餘之粒子，it而使用絲光沸石作為沸石而獲得之觸媒。 <實施例5> 使用觸媒E-9以及E-10，藉由上述評價條件2(參照表2)評價對氨之分解活性。評價結果示於表9。 [表9] 表9Note: The catalyst E-1 is a catalyst obtained by using mordenite as an inorganic oxide and containing particles which are supported thereon, and using mordenite as a zeolite. <Example 5> Using the catalysts E-9 and E-10, the decomposition activity against ammonia was evaluated by the above evaluation condition 2 (refer to Table 2). The evaluation results are shown in Table 9. [Table 9] Table 9

如表9所示可明確：本發明之觸媒E_9及即使在水蒸汽漢度為50容量。/。之過度苛刻之條件下，亦發揮出對氨: 分解率為100%，且Ns選擇性亦極高之性能。【圖式簡單說明】 136838.doc •37- 200936240 圖1表示觸媒C-1(比較例）之新觸媒及處理1800小時後之分解活性。圖2表示觸媒E-la(本發明）之新觸媒及處理1800小時後之分解活性。圖3表示於300°C、350°C、400°C下新觸媒之活性。圖4表示於300°C、350°C、400°C下使用1800小時後之活性。As shown in Table 9, it is clear that the catalyst E_9 of the present invention has a capacity of 50% even in water vapor. /. Under the conditions of excessive harshness, it also exerts the performance of ammonia: the decomposition rate is 100%, and the Ns selectivity is also extremely high. [Simple description of the drawing] 136838.doc •37- 200936240 Figure 1 shows the new catalyst of Catalyst C-1 (Comparative Example) and the decomposition activity after 1800 hours of treatment. Fig. 2 shows the new catalyst of the catalyst E-la (invention) and the decomposition activity after 1800 hours of treatment. Figure 3 shows the activity of a new catalyst at 300 ° C, 350 ° C, and 400 ° C. Figure 4 shows the activity after 1800 hours of use at 300 ° C, 350 ° C, and 400 ° C.

136838.doc -38-136838.doc -38-

Claims

200936240 十、申請專利範圍： 1· 一種氨分解觸媒其係 (a) 對含氨排氣進行處理之觸媒， (b) 含有氧化銅(成分υ、沸石(成分2)、貴金屬(成分 3)、及磷（成分4) ’ ()相對於氧化銅與上述沸石之總計1〇〇重量份，氧化銅之含量為2〜40重量份，200936240 X. Patent application scope: 1. An ammonia decomposition catalyst system (a) Catalyst for treating ammonia-containing exhaust gas, (b) Containing copper oxide (ingredient bismuth, zeolite (ingredient 2), precious metal (ingredient 3) And phosphorus (ingredient 4) ' () with respect to a total of 1 part by weight of copper oxide and the above zeolite, the content of copper oxide is 2 to 40 parts by weight,

(d)相對於氧化銅與沸石之重量和 0.01重量％〜5重量％。 ’磷含量以P計為 2. 如請求们之氨分解觸媒，其中相對於氧化銅與沸石之重量和’磷含量以P計為0.05〜5重量％。 3. 如請求項⑷之氨分解_，其中相對於氧化銅與沸石重量和，貝金屬含量為1〇重量ppm〜5〇〇〇重量卯爪。 4. :請求項丨至3中任一項之氨分解觸媒，其中貴金屬係選自Pt及Pd中之至少1種。(d) with respect to the weight of the copper oxide and the zeolite and 0.01% by weight to 5% by weight. The phosphorus content is in terms of P. 2. The ammonia decomposition catalyst as claimed, wherein the weight and the phosphorus content relative to the weight of the copper oxide and the zeolite are 0.05 to 5% by weight in terms of P. 3. The ammonia decomposition _ of claim (4), wherein the shell metal content is 1 〇 ppm by weight to 5 〇〇〇 weight 卯 claws relative to the weight of the copper oxide to the zeolite. 4. The ammonia decomposition catalyst according to any one of claims 3 to 3, wherein the noble metal is selected from at least one of Pt and Pd.

5.如請求項中任—項之氣分解觸媒，其相對於上述< 化銅與滞石之總計1〇〇重量份’以Μ重量份之比例i 而含有選自Ti〇2、ZK)2、Si〇2 '及Ce〇2.Zr〇2中之至少種無機氧化物（成分5 )。 6.如請求項！至5中任-項之氨分解觸媒，其含有預先承_ 有Pt及Pd中之至少！種的選自由Ti〇2、&〇2、μ%』 Ce〇rZr〇2所組成群中之至少i種無機氧化物粒子。1 2 > 7· 一種氨分解觸媒，其係 (a)對含氨排氣進行處理之觸媒， 136838.doc 200936240 (b)含有氧化銅（成分1}、沸石（成分2)、貴金屬（成分 3)、磷（成分4)、以及選自Ti〇2、Zr〇2、以〇2及Ce〇2 Zr〇2 中之至少1種無機氧化物（成分5)， Ο)相對於氧化銅與上述沸石之總計_重量份，氧化銅含篁為2〜40重量份，以及 ⑷相對於氧化銅與彿石之重量和，磷含量以p計為 0.0 1重量。/〇〜5重量％。 8. 如請求項7之氨分解觸媒，其相對於上述氧化銅與沸石之總計100重量份，以1〜50重量份之比例含有無機氧化物。 9. 如凊求項7至8中任一項之氨分解觸媒，其中相對於氧化銅與沸石之重量和，磷含量以p計為〇〇5重量％〜5重量 %。 10. 如请求項7至9中任一項之氨分解觸媒，其中相對於氧化銅與沸石之重量和，貴金屬含量為10重量ppm〜5000重量 ppm 〇 11. 如請求項7至10中任一項之氨分解觸媒，其係混合預先承載有Pt及Pd中之至少1種的選自由Ti〇2、Zr〇2、Si〇2及 Ce〇2_Zr〇2所組成群中之至少丨種而成。 12. 如請求項7至11中任一項之氨分解觸媒，其含有預先承載有PtiTi〇2粒子、或預先承載有Pt之Zr〇2粒子、或預先承載有Pd之絲光沸石（Mordenite)粒子、或預先承載有 Pt之 Ce〇2 Zr〇2粒子。 13. 如請求項7至12中任一項之氨分解觸媒，其中作為處理 136838.doc 200936240 對象之含氨排氣係實質上由氨'水蒸汽以及氮所構成，並視需要自外部供給氧或含氧氣體而成的氣體。 14. 一種排氣處理方法，其包括：使如請求項1至13中任一項之氨分解觸媒與含氨排氣接觸，而將氨分解成氮與水之步驟。 15. 如請求項14之排氣處理方法，其中含氨排氣係水蒸汽濃度為10〜70容量％之氣體。 16. 如請求項丨5之排氣處理方法，其中含氨排氣係水蒸汽濃度為20〜70容量％之氣體。 ❿ 136838.doc5. The gas decomposition catalyst according to any one of the claims, which is selected from the group consisting of Ti〇2 and ZK in relation to the above-mentioned <a total of 1 part by weight of the copper and the stagnation stone. 2, at least one of the inorganic oxides (ingredient 5) of Si〇2' and Ce〇2.Zr〇2. 6. As requested! To the 5th - the ammonia decomposition catalyst, which contains the pre-supported _ with at least Pt and Pd! At least one type of inorganic oxide particles selected from the group consisting of Ti〇2, & 〇2, and μ%′′ Ce〇rZr〇2. 1 2 > 7· An ammonia decomposition catalyst, which is (a) a catalyst for treating ammonia-containing exhaust gas, 136838.doc 200936240 (b) contains copper oxide (ingredient 1}, zeolite (ingredient 2), precious metal (Component 3), phosphorus (Component 4), and at least one inorganic oxide (component 5) selected from the group consisting of Ti〇2, Zr〇2, 〇2 and Ce〇2 Zr〇2, Ο) relative to oxidation The total amount of copper and the above zeolite is _ part by weight, the copper oxide contains ruthenium in an amount of 2 to 40 parts by weight, and (4) the phosphorus content is 0.011 by weight based on the weight of the copper oxide and the fluorite. /〇~5 wt%. 8. The ammonia decomposition catalyst according to claim 7, which contains an inorganic oxide in an amount of from 1 to 50 parts by weight based on 100 parts by weight of the total of the copper oxide and the zeolite. 9. The ammonia decomposition catalyst according to any one of items 7 to 8, wherein the phosphorus content is 〇 5% by weight to 5% by weight based on the weight of the copper oxide to the zeolite. 10. The ammonia decomposition catalyst according to any one of claims 7 to 9, wherein the precious metal content is from 10 ppm by weight to 5000 ppm by weight relative to the weight of the copper oxide to the zeolite. 〇11. An ammonia decomposition catalyst mixed with at least one selected from the group consisting of Ti〇2, Zr〇2, Si〇2, and Ce〇2_Zr〇2, which is preliminarily supported by at least one of Pt and Pd. Made. 12. The ammonia decomposition catalyst according to any one of claims 7 to 11, which comprises Zr〇2 particles pre-loaded with PtiTi〇2 particles or pre-loaded with Pt, or mordenite (Mordenite) pre-loaded with Pd Particles, or Ce〇2 Zr〇2 particles pre-loaded with Pt. 13. The ammonia decomposition catalyst according to any one of claims 7 to 12, wherein the ammonia-containing exhaust system which is the object of the treatment 136838.doc 200936240 consists essentially of ammonia 'water vapor and nitrogen, and is supplied externally as needed. A gas made of oxygen or an oxygen-containing gas. An exhaust gas treatment method comprising the steps of: contacting an ammonia decomposition catalyst according to any one of claims 1 to 13 with an ammonia-containing exhaust gas to decompose ammonia into nitrogen and water. 15. The exhaust gas treatment method according to claim 14, wherein the ammonia-containing exhaust gas has a water vapor concentration of 10 to 70% by volume. 16. The exhaust gas treatment method according to claim 5, wherein the ammonia-containing exhaust gas has a water vapor concentration of 20 to 70% by volume. ❿ 136838.doc